CN107285640A - Enhanced intelligent temperature control vanadium dioxide laminated film of a kind of infrared light regulating power and preparation method thereof - Google Patents

Enhanced intelligent temperature control vanadium dioxide laminated film of a kind of infrared light regulating power and preparation method thereof Download PDF

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Publication number
CN107285640A
CN107285640A CN201710427087.4A CN201710427087A CN107285640A CN 107285640 A CN107285640 A CN 107285640A CN 201710427087 A CN201710427087 A CN 201710427087A CN 107285640 A CN107285640 A CN 107285640A
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laminated film
vanadium dioxide
temperature control
regulating power
infrared light
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赵丽
王超
梁子辉
董兵海
王世敏
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Hubei University
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Hubei University
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    • 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
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/113—Deposition methods from solutions or suspensions by sol-gel processes
    • 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
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation

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  • 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)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to a kind of enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power, it is composited by vanadium dioxide film layer and silica coating, and silica coating is located at top layer；Silica coating is the SiO that hydrophobic group is carried by surface2The nano-porous structure that particle is piled up, SiO2Grain diameter is 10nm 50nm；Vanadium dioxide film layer is by irregular VO2Particle deposition composition, VO2Grain diameter is 20nm 150nm；Preparation method is that silica dioxide gel is coated on into vanadium dioxide film surface, is made annealing treatment in atmosphere of inert gases.Intelligent temperature control vanadium dioxide laminated film of the present invention substantially increases the infrared regulating power of laminated film while excellent optical property, self-cleaning function is kept.

Description

A kind of enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power and its Preparation method
Technical field
The present invention relates to thermal induced phase transition material and automatically cleaning festival energy Material Field, and in particular to a kind of infrared light adjusts energy Enhanced intelligent temperature control vanadium dioxide laminated film of power and preparation method thereof.
Background technology
With the large-scale application of glass curtain wall, glass roof, glass structure in skyscraper, the cleaning problems of glass Increasingly protrude, clean that glass is not only uneconomical but also inconvenience using window cleaning equipment, seek a kind of glass with self-cleaning function Focus and difficult point that countries in the world are studied are turned into.Traditional wetting is self-cleaning and machinery it is self-cleaning be difficult to meet reality cleaning will Ask.Ecology direction is the trend of building glass development, actually the human nature of the direction of environmental protection and raising comfort level Change direction.The Main way of functional glass development has 3：(1) there is energy-conservation, sound insulation, heat-insulated glass；(2) can be with antifouling, anti- The glass of mist, self-cleaning and environment purification；(3) it can utilize and control the glass of sunshine or solar energy.Vanadium dioxide has good Good thermal induced phase transition property, this function can be widely used on intelligent window material.When thin film phase change temperature is higher than room temperature, The crystal structure of vanadium dioxide is monoclinic structure, and infrared light and visible ray have a higher transmitance, indoor temperature with The entrance of light and gradually rise；When thin film phase change temperature is less than room temperature, the crystal formation of vanadium dioxide becomes the red stone of tetragonal Structure, it is seen that light transmission rate is constant and infrared light transmittance is substantially reduced, the heat that infrared light is produced cannot be got in, from And smart window is realized according to indoor temperature the selectivity of different wave length light is passed through, what this process extraneous need not be added Other energy, realize the intelligent control to temperature.
The research that vanadium dioxide film or coating are used to save intelligent glass is had been achieved for into many achievements, China is public Open patent of invention CN102241482A and disclose one kind wet chemistry method and combined with sol/gel method and be prepared for a kind of intelligent temperature control Vanadium dioxide nano laminated film and preparation method thereof, complex thin film structure is ensureing VO2It is while film temperature control performance The visible region transmitance of film is improved, the regulating power of near-infrared region is not improved.The open patent of invention of China CN103042754A discloses adjustable heat stagnation discoloration hypovanadic oxide-based composite film of a kind of contact angle and preparation method thereof, and this is answered Thin-film integration heat stagnation discoloration coating and automatic cleaning coating advantage are closed, VO is improved2The visible light transmissivity of film, but it is compound The visible light transmissivity of film is still very low, there was only 40% or so under low temperature, does not also have to the regulating power of near-infrared region in addition It is improved.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of infrared light for the deficiency that above-mentioned prior art is present Enhanced intelligent temperature control vanadium dioxide laminated film of regulating power and preparation method thereof, is keeping excellent optical property, automatically cleaning The infrared regulating power of laminated film is substantially increased while function.
The technical scheme that the present invention is used by solution the problem of set forth above for：
A kind of enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power, it is by vanadium dioxide film layer and two Membranous layer of silicon oxide is composited, and silica coating is located at top layer；Silica coating is with hydrophobic group by surface SiO2The nano-porous structure that particle is piled up, thickness range is 30-300nm, SiO2Grain diameter is 10nm-50nm；Dioxy It is by irregular VO to change vanadium film layer2Particle deposition composition, thickness is 100-1000nm, VO2Grain diameter is 20nm-150nm.
The preparation method of the enhanced intelligent temperature control vanadium dioxide laminated film of above-mentioned infrared light regulating power, it is main to include such as Lower step：
1) tetravalence vanadium source, solvent alcohol are well mixed, are subsequently added polyethylene pyrrole network alkanone (PVP), and use acid for adjusting pH For 1-3, continue to stand aging after stirring, obtain precursor solution；
2) gained precursor solution is coated on substrate, then made annealing treatment in atmosphere of inert gases, obtained Vanadium dioxide film；
3) tetravalence silicon source, solvent alcohol are well mixed, first acidification 3-48h, then Re-boostering test processing 10-72h passes through Aging is stood, the silica dioxide gel that surface carries hydrophobic group has been obtained；
4) by step 3) obtained by silica dioxide gel be scattered in solvent alcohol, be then coated with step 2) gained titanium dioxide Vanadium film surface, then by being made annealing treatment in atmosphere of inert gases, obtain the enhanced intelligence control of infrared light regulating power Warm vanadium dioxide laminated film.
By such scheme, step 1) in, the molar concentration of tetravalent vanadium ion is 0.1-0.2mol/L in precursor solution, is gathered The concentration of ethene pyrrole network alkanone is in 1%-5%.
By such scheme, step 1) in, tetravalence vanadium source is in vanadic sulfate, vanadyl oxalate, vanadyl acetylacetonate etc. One or more of mixtures in any proportion.
By such scheme, step 1) in, one or more of the acid in hydrochloric acid, oxalic acid, sulfuric acid, nitric acid etc. press any ratio The mixture of example.
By such scheme, step 1) in, it is 3500,5500,8000,10100 that polyethylene pyrrole network alkanone, which can select molecular weight, One or more of mixtures in any proportion in equimolecular quantity, preferred molecular weight is 5500~10000.
By such scheme, step 1) in, mixing time is 12-96h, preferably 12-48h；Standing ageing time is 12-96h, It is preferred that 48-72h.
By such scheme, step 3) in, the silicon source described in tetravalence silicon source is selected from MTMS, the ethoxy of methyl three One kind in the silane couplers such as base silane, hexamethyldisilazane, three/aminopropyl triethoxysilane, trim,ethylchlorosilane Or several mixtures in any proportion.
By such scheme, step 1) and 3), 4) in, solvent alcohol is selected from ethanol, isopropanol, methanol, propane diols, glycerine One or more of mixtures in any proportion in.
By such scheme, step 3) in, the mol ratio (0.1-0.5) of tetravalence silicon source and solvent alcohol：1.
By such scheme, step 3) in, pH is 3-5 during acidification, using the molten of the acid such as hydrochloric acid, sulfuric acid, nitric acid, oxalic acid One or more of mixtures in liquid, the concentration range of acid solution is 0.001-0.1mol/L；Acidificatoin time is 3-96h, preferably 10-48h。
By such scheme, step 3) in, pH is 8-9 during basification, using one in the aqueous slkalis such as ammoniacal liquor, sodium hydroxide Plant or two kinds of mixtures, the concentration range of aqueous slkali is 0.001-0.1mol/L；Alkalization time is 10-96h, preferably 24-48h.
By such scheme, step 2) and 4) in, coating method is selected from blade coating, spraying, spin coating and Best-Effort request etc., preferably just Formula is spin coating, rate-determining steps 2) in spin coating thickness range be 30-300nm, step 4) in spin coating thickness be 100-1000nm, after Thickness is basically unchanged after continuous annealing steps.It is further preferred that spin coating be divided at a slow speed with quick two step, 800- is mainly used at a slow speed 1000r/min, spin coating 8-10s realizes the separation of sol particle and solvent；Quickly mainly use 2500-5000r/min, spin coating 20-40s realizes the homogenization that sol particle is distributed on substrate.
By such scheme, step 2) in, annealing temperature is 200-800 DEG C, and annealing time is 0.5-5h, preferably annealing temperature For 400-800 DEG C, annealing time is 0.5-5h；Step 4) in, annealing temperature is 300-600 DEG C, and annealing time is 0.5-3h.
Compared with prior art, the beneficial effects of the invention are as follows：
1st, intelligent temperature control vanadium dioxide laminated film provided by the present invention has excellent optical characteristics switching, Ke Yigen According to the transmitance of the regulation and control infrared light of environment temperature intelligence, and infrared regulating power and solar energy regulation energy is greatly enhanced Power, light transmittance difference up to 39.5% is obtained before and after phase transformation at wavelength 2000nm, and the visible light transmissivity of laminated film is higher than 60%, the need for meeting building to glass lighting.
2nd, the SiO on intelligent temperature control vanadium dioxide laminated film top layer provided by the present invention2Grain diameter is about 10nm- 50nm, far smaller than visible ray wavelength, greatly reduce light loss of energy, in addition also pile up and construct laminated film table The micro-nano structure in face, makes laminated film surface have excellent super-hydrophobic effect, and surface water contact angle is more than 150 °, served very Good antifog, dust-proof, automatically cleaning effect.
Brief description of the drawings
In Fig. 1, (a) is the VO prepared by embodiment 12Film and SiO2/VO2The UV collection of illustrative plates of laminated film, (b) is implementation VO prepared by example 22Film and SiO2/VO2The UV collection of illustrative plates of laminated film, (c) is the VO prepared by comparative example 12Film and SiO2/ VO2The UV collection of illustrative plates of laminated film, (d) is the VO prepared by comparative example 22Film and SiO2/VO2The UV collection of illustrative plates of laminated film.
Fig. 2 is the VO prepared by embodiment 12Film (a) and SiO2/VO2The SEM figures of laminated film (b), (c).
Fig. 3 is the VO prepared by embodiment 12Film (a) and SiO2/VO2The surface water contact angle collection of illustrative plates of laminated film (b).
Fig. 4 is the VO prepared by embodiment 12Film (a) and SiO2/VO2The XRD spectrum of laminated film (b).
Fig. 5 is the SiO prepared by comparative example 12/VO2Laminated film obtains SEM spectrum.
Fig. 6 is the SiO prepared by embodiment 12/VO2The surface water contact angle collection of illustrative plates of laminated film.
Embodiment
For a better understanding of the present invention, with reference to embodiment and the accompanying drawing content that the present invention is furture elucidated, but this Invention is not limited solely to the following examples.
Embodiment 1
A kind of preparation method of the enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power, specific steps are such as Under：
1) take 1g vanadyl acetylacetonates, 30ml methanol in beaker, be placed on magnetic stirring apparatus and stir, then successively 0.2g PVP, 0.5ml (11.2mol/L) hydrochloric acid solution (now system pH=3) is added, 24h is then persistently stirred, aging is stood 48h, is obtained without the uniform navy blue precursor solution of precipitation；
2) by step 1) gained precursor solution drop in the Quartz glass surfaces rotated in sol evenning machine, with 800r/min at a slow speed Turn 9s, the rotating speed that high speed 2500r/min turns 30s carries out spin coating, after vacuum drying in argon gas atmosphere, tubular type Muffle furnace Anneal 1h at 650 DEG C, that is, obtains VO2Film；
3) 1.08g MTMSs, 0.5ml (0.001mol/L) oxalic acid, 8.72g methanol are taken in 25ml beakers (now system pH=5), is placed in strong stirring 3h on magnetic stirring apparatus, then adds 0.6ml (11.2mol/L) ammoniacal liquor (now System pH=8) continue strong stirring 30min, aging 24h is stored at room temperature, the silica that surface carries hydrophobic group is obtained Gel；
4) by step 4) gained SiO2Gel dispersion turns 9s, high speed 3000r/ in 25ml methanol with 1000r/min at a slow speed The rotating speed that min turns 30s is spin-coated on step 2) gained VO2Film surface, after vacuum drying under an argon atmosphere, tubular type Muffle Anneal 1h in stove at 450 DEG C, that is, obtains the SiO of the enhanced intelligent temperature control of infrared light regulating power2/VO2Laminated film.
From Fig. 2 (a), (b)：Vanadium dioxide film layer is by irregular VO2Particle deposition composition, VO2Grain diameter is 20nm-150nm；Silica coating is the SiO that hydrophobic group is carried by surface2The nanoporous knot that particle is piled up Structure, SiO2Grain diameter is 10nm-50nm, and this nano-porous structure constitutes rough surface so that laminated film surface has There is good super-hydrophobic effect；By Fig. 2 (c) as can be seen that VO2The thickness of film is about 70nm, and the thickness of laminated film is about For 500nm.
From Fig. 1 (a)：SiO2/VO2The infrared regulating power of laminated film is greatly enhanced, at 2000nm, VO2Film It is 31.7% in the near-infrared transmitance change difference of 20 DEG C of 90 DEG C of high temperature and low temperature, and SiO2/VO2Laminated film is in high temperature 90 DEG C and 20 DEG C of low temperature near-infrared transmitance change difference then brought up to 39%, the infrared regulating power of laminated film is relative VO2Film improves 22.1%；Meanwhile, solar energy modulation capability has also brought up to 5.9% from 4.8%, relative to improve 22.9%, and the visible light transmissivity of laminated film is higher than 60%, meets the daylighting requirement to ecology glass.
As shown in Figure 3：VO2Film is hydrophilic, SiO2Film is hydrophobic, and laminated film top layer is SiO2Film is thin Film surface just becomes super-hydrophobic by super hydrophilic, possesses good super-hydrophobic effect.
As shown in Figure 4：SiO2/VO2Laminated film and VO2Film is respectively provided with VO2(011) characteristic peak of crystal face, illustrates compound Film is relative to VO2Film crystal formation does not change, it is often more important that other barium oxides does not occur and produces.
Embodiment 2
A kind of preparation method of the enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power, specific steps are such as Under：
1) take 1g vanadyl acetylacetonates, 30ml methanol in beaker, be placed on magnetic stirring apparatus and stir, then successively 0.4g PVP, 1ml (11.2mol/L) oxalic acid solution (now system pH=2) is added, 48h is persistently stirred, aging 96h is stood, obtains To without the uniform navy blue precursor solution of precipitation；
2) precursor solution is dropped in the Quartz glass surfaces rotated in sol evenning machine, 9s is turned with 800r/min at a slow speed, at a high speed The rotating speed that 2500r/min turns 30s carries out spin coating, by vacuum drying, is annealed in argon gas atmosphere, tubular type Muffle furnace at 500 DEG C 3h, that is, obtain VO2Film；
3) 1.08g MTMSs, 0.5ml (0.001mol/L) oxalic acid, 8.72g methanol are taken in 25ml beakers (now system pH=5), is placed in strong stirring 6h on magnetic stirring apparatus, then adds 0.6ml (11.2mol/L) ammoniacal liquor and continues strong Power stirring 30min (now system pH=8), is stored at room temperature aging 24h, and surface carries the silica dioxide gel of hydrophobic group；
4) by SiO2Gel dispersion turns 9s in 25ml methanol with 1000r/min at a slow speed, and high speed 3000r/min turns 30s's The VO of rotating speed spin coating after the high-temperature anneal2Film surface, by vacuum drying, under an argon atmosphere, 400 DEG C in tubular type Muffle furnace Lower annealing 1.5h, that is, obtain the enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power.
From Fig. 1 (b)：SiO2/VO2The infrared regulating power of laminated film is equally greatly enhanced, at 2000nm, VO2 Film is 30% in the near-infrared transmitance change difference of 20 DEG C of 90 DEG C of high temperature and low temperature, and SiO2/VO2Laminated film is in high temperature The near-infrared transmitance change difference of 90 DEG C and 20 DEG C of low temperature has then brought up to 35.5%, the infrared regulating power phase of laminated film To VO2Film improves 13.9%；Meanwhile, solar energy modulation capability has also brought up to 5.1% from 4.6%, relative to improve 10.9%, and the visible light transmissivity of laminated film is equally higher than 60%, meets the daylighting requirement to ecology glass.
Embodiment 3
A kind of preparation method of the enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power, specific steps are such as Under：
1) take 1g vanadyl acetylacetonates, 30ml methanol in beaker, be placed on magnetic stirring apparatus and stir, then successively 0.4g PVP, 0.5ml (11.2mol/L) hydrochloric acid solution (now system pH=2) is added, 24h is persistently stirred, aging 48h is stood, Obtain without the uniform navy blue precursor solution of precipitation；
2) precursor solution is dropped in the Quartz glass surfaces rotated in sol evenning machine, 9s is turned with 800r/min at a slow speed, at a high speed The rotating speed that 2500r/min turns 30s carries out spin coating, by vacuum drying, is annealed in argon gas atmosphere, tubular type Muffle furnace at 500 DEG C 1.5h, that is, obtain VO2Film；
3) take 0.54g MTMSs, 0.64g HMDSs, 0.5ml (0.001mol/L) oxalic acid, 8.72g methanol (now system pH=5) in 25ml beakers, is placed in strong stirring 6h on magnetic stirring apparatus, then adds 0.6ml (11.2mol/L) ammoniacal liquor continues strong stirring 30min (now system pH=8), is stored at room temperature aging 48h, obtains surface and carry The silica dioxide gel of hydrophobic group；
4) by SiO2Gel dispersion in methyl alcohol, 9s is turned with 1500r/min at a slow speed, and high speed 4000r/min turns 30s rotating speed The VO of spin coating after the high-temperature anneal2Film surface, by vacuum drying, is moved back at 450 DEG C under an argon atmosphere, in tubular type Muffle furnace Fiery 1h, that is, obtain the enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power.
Comparative example 1
A kind of preparation method of the enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power, specific steps are such as Under：
1) take 1g vanadyl acetylacetonates, 30ml methanol in beaker, be placed on magnetic stirring apparatus and stir, then successively 48h is persistently stirred, aging 96h is stood, obtained without the uniform navy blue precursor solution of precipitation；
2) precursor solution is dropped in the Quartz glass surfaces rotated in sol evenning machine, 9s is turned with 800r/min at a slow speed, at a high speed The rotating speed that 2500r/min turns 30s carries out spin coating, by vacuum drying, is annealed in argon gas atmosphere, tubular type Muffle furnace at 550 DEG C 3h, that is, obtain VO2Film；
3) 1.08g MTMSs, 0.5ml (0.001mol/L) oxalic acid, 8.72g methanol are taken in 25ml beakers (now system pH=5), is placed in strong stirring 6h on magnetic stirring apparatus, then adds 0.6ml (11.2mol/L) ammoniacal liquor and continues strong Power stirring 30min (now system pH=8), is stored at room temperature aging 24h, and surface carries the silica dioxide gel of hydrophobic group；
4) by SiO2Gel dispersion turns 9s in 25ml methanol with 1000r/min at a slow speed, and high speed 3000r/min turns 30s's The VO of rotating speed spin coating after the high-temperature anneal2Film surface, by vacuum drying, under an argon atmosphere, 400 DEG C in tubular type Muffle furnace Lower annealing 1.5h, that is, obtain the enhanced intelligent temperature control vanadium dioxide laminated film of laminated film sun light transmission rate.
From Fig. 1 (c)：SiO2/VO2The sun light transmission rate of laminated film rises appreciably, but infrared regulating power is not There is change, at 2000nm, VO2Film is 38% in the near-infrared transmitance change difference of 20 DEG C of 90 DEG C of high temperature and low temperature, SiO2/VO2Laminated film has then brought up to 37.5% in the near-infrared transmitance change difference of 20 DEG C of 90 DEG C of high temperature and low temperature, multiple The infrared regulating power for closing film is almost unchanged；The visible light transmissivity of laminated film is equally higher than 60%.
As can be seen from Figure 5：The porosity on laminated film surface does not have big change, SiO2The size of nano particle is about 10- 50nm, SiO2The hydrophobic ability of film surface is not reduced, as shown in fig. 6, SiO2/VO2The surface water contact angle of laminated film according to So it is higher than 150 °.
Comparative example 2
A kind of preparation method of the enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power, specific steps are such as Under：
1) 1g vanadyl acetylacetonates, 0.2g PVP, 30ml methanol are taken in beaker, is placed on magnetic stirring apparatus and stirs equal It is even, 48h is then persistently stirred successively, aging 96h is stood, and is obtained without the uniform navy blue precursor solution of precipitation；
2) precursor solution is dropped in the Quartz glass surfaces rotated in sol evenning machine, 9s is turned with 800r/min at a slow speed, at a high speed The rotating speed that 2500r/min turns 30s carries out spin coating, by vacuum drying, is annealed in argon gas atmosphere, tubular type Muffle furnace at 550 DEG C 3h, that is, obtain VO2Film；
3) take 1.08g MTMSs, 0.5ml (0.001mol/L) oxalic acid (pH=5), 8.72g methanol in In 25ml beakers, strong stirring 6h on magnetic stirring apparatus is placed in, 0.6ml (11.2mol/L) ammoniacal liquor is then added and continues strongly to stir 30min (pH=8) is mixed, aging 24h is stored at room temperature, surface carries the silica dioxide gel of hydrophobic group；
4) by SiO2Gel dispersion turns 9s in 25ml methanol with 1000r/min at a slow speed, and high speed 3000r/min turns 30s's The VO of rotating speed spin coating after the high-temperature anneal2Film surface, by vacuum drying, under an argon atmosphere, 400 DEG C in tubular type Muffle furnace Lower annealing 1.5h, that is, obtain the enhanced intelligent temperature control vanadium dioxide laminated film of laminated film sun light transmission rate.
From Fig. 1 (d)：SiO2/VO2The sun light transmission rate of laminated film slightly increases, but infrared regulating power is not There is change, at 2000nm, VO2Film is 39.6% in the near-infrared transmitance change difference of 20 DEG C of 90 DEG C of high temperature and low temperature, SiO2/VO2Laminated film is then 39.2%, laminated film in the near-infrared transmitance change difference of 20 DEG C of 90 DEG C of high temperature and low temperature Infrared regulating power it is almost unchanged；The visible light transmissivity of laminated film is equally higher than 60%.
Understood with reference to comparative example and embodiment：On the one hand, in VO2Acid solution adds in the preparation process of precursor solution Enter so that the laminated film of preparation is provided with enhanced infrared light regulating power, thus it is speculated that its reason is probably the salt due to addition Acid, which decomposes macromolecular PVP, becomes small molecule so that PVP serves good solubilizer effect so that after high annealing VO2Film surface has good compactness, while again due to being compounded with the SiO with anti-reflection effect2After film, VO2Nanometer Particle and SiO2Nano-particle produces nano-particle cooperative effect and enhances infrared light regulating power.On the other hand, due to compound The last high temperature anneal temperature of film is significantly larger than the temperature that organic matter is decomposed, solvent volatilizees, equivalent to VO2Film enters simultaneously Secondary high-temperature annealing is gone, it is therefore prevented that VO2Particle is oxidized, and has been effectively maintained VO2The excellent optical property of film.
Described above is only the preferred embodiment of the present invention, it is noted that come for one of ordinary skill in the art Say, without departing from the concept of the premise of the invention, some modifications and variations can also be made, these belong to the present invention's Protection domain.

Claims (10)

1. a kind of enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power, it is by vanadium dioxide film layer and dioxy SiClx film layer is composited, and silica coating is located at top layer；Silica coating is with hydrophobic group by surface SiO2The nano-porous structure that particle is piled up, SiO2Grain diameter is 10nm-50nm；Vanadium dioxide film layer is by irregular VO2Particle deposition composition, VO2Grain diameter is 20nm-150nm.
2. the preparation method of the enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power described in claim 1, its It is characterised by silica dioxide gel being coated on vanadium dioxide film surface, is made annealing treatment in atmosphere of inert gases, i.e., Obtain the enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power.
3. the preparation method of the enhanced intelligent temperature control vanadium dioxide laminated film of a kind of infrared light regulating power, it is characterised in that main Comprise the following steps：
1) tetravalence vanadium source, solvent alcohol are well mixed, are subsequently added polyethylene pyrrole network alkanone, and be 1-3 with acid for adjusting pH, continued Aging is stood after stirring, precursor solution is obtained；
2) gained precursor solution is coated on substrate, then made annealing treatment in atmosphere of inert gases, obtain dioxy Change vanadium film；
3) tetravalence silicon source, solvent alcohol are well mixed, first acidification 10-72h, Re-boostering test processing 24-96h, then by quiet Aging is put, the silica dioxide gel that surface carries hydrophobic group has been obtained；
4) by step 3) obtained by silica dioxide gel be scattered in solvent alcohol, be then coated with step 2) gained vanadium dioxide it is thin Film surface, then by being made annealing treatment in atmosphere of inert gases, obtain the enhanced intelligent temperature control two of infrared light regulating power Vanadium oxide composite film.
4. a kind of system of the enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power according to claim 3 Preparation Method, it is characterised in that step 1) in, the one kind of tetravalence vanadium source in vanadic sulfate, vanadyl oxalate, vanadyl acetylacetonate Or several mixtures in any proportion；One or more of the acid in hydrochloric acid, oxalic acid, sulfuric acid, nitric acid etc. are in any proportion Mixture；The molecular weight of polyethylene pyrrole network alkanone is 3500~10100.
5. a kind of system of the enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power according to claim 3 Preparation Method, it is characterised in that step 1) in, the molar concentration of tetravalent vanadium ion is 0.1-0.2mol/L, poly- second in precursor solution The concentration of alkene pyrrole network alkanone is in 1%-5%；Mixing time is 12-96h；Standing ageing time is 24-96h.
6. a kind of system of the enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power according to claim 3 Preparation Method, it is characterised in that step 3) in, the silicon source described in tetravalence silicon source is selected from MTMS, methyl triethoxy One kind in the silane couplers such as silane, hexamethyldisilazane, three/aminopropyl triethoxysilane, trim,ethylchlorosilane or Several mixtures in any proportion；Step 1) and 3) in, solvent alcohol is selected from ethanol, isopropanol, methanol, propane diols, the third three One or more of mixtures in any proportion in alcohol.
7. a kind of system of the enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power according to claim 3 Preparation Method, it is characterised in that step 3) in, the mol ratio of tetravalence silicon source and solvent alcohol is (0.1-0.5):1.
8. a kind of system of the enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power according to claim 3 Preparation Method, it is characterised in that step 3) in, pH is 3-5 during acidification, and the concentration range of acid solution is 0.001-0.1mol/L； Acidificatoin time is 3-48h；PH is 8-9 during basification, and the concentration range of aqueous slkali is 0.001-0.1mol/L；Alkalization time is 10-72h。
9. a kind of system of the enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power according to claim 3 Preparation Method, it is characterised in that step 2) and 4) in, coating method is spin coating, step 2) in spin coating thickness range be 30-300nm, Step 4) in spin coating thickness be 100-1000nm.
10. a kind of enhanced intelligent temperature control vanadium dioxide laminated film of infrared light regulating power according to claim 3 Preparation method, it is characterised in that step 2) annealing temperature be 400-800 DEG C, annealing time is 0.5-5h；Step 4) in, annealing temperature Spend for 300-600 DEG C, annealing time is 0.5-3h.
CN201710427087.4A 2017-06-08 2017-06-08 Enhanced intelligent temperature control vanadium dioxide laminated film of a kind of infrared light regulating power and preparation method thereof Pending CN107285640A (en)

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CN109231848A (en) * 2018-10-22 2019-01-18 中国科学院理化技术研究所 Composite film with thermochromic, antifogging and self-repairing functions and preparation method thereof
CN110937819A (en) * 2019-12-09 2020-03-31 东莞深圳清华大学研究院创新中心 Preparation method of transparent super-hydrophobic intelligent temperature control glass
CN111453999A (en) * 2020-03-26 2020-07-28 哈尔滨工业大学 Intelligent radiator and preparation method thereof
CN113105765A (en) * 2021-03-31 2021-07-13 东南大学 Intelligent heat-insulating composite coating with high visible light transmittance and preparation method thereof
CN114988717A (en) * 2022-07-01 2022-09-02 武汉理工大学 Monodisperse vanadium dioxide nanoparticle coating and preparation method thereof
CN115159860A (en) * 2022-07-20 2022-10-11 贵州民族大学 Preparation of H-SiO in mild aqueous environment 2 -VO 2 (M) method of coating

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CN106082697A (en) * 2016-06-22 2016-11-09 浙江大学 A kind of energy-conservation coated glass and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109231848A (en) * 2018-10-22 2019-01-18 中国科学院理化技术研究所 Composite film with thermochromic, antifogging and self-repairing functions and preparation method thereof
CN109231848B (en) * 2018-10-22 2021-06-25 中国科学院理化技术研究所 Composite film with thermochromic, antifogging and self-repairing functions and preparation method thereof
CN110937819A (en) * 2019-12-09 2020-03-31 东莞深圳清华大学研究院创新中心 Preparation method of transparent super-hydrophobic intelligent temperature control glass
CN111453999A (en) * 2020-03-26 2020-07-28 哈尔滨工业大学 Intelligent radiator and preparation method thereof
CN111453999B (en) * 2020-03-26 2022-04-01 哈尔滨工业大学 Preparation method of intelligent radiator
CN113105765A (en) * 2021-03-31 2021-07-13 东南大学 Intelligent heat-insulating composite coating with high visible light transmittance and preparation method thereof
CN114988717A (en) * 2022-07-01 2022-09-02 武汉理工大学 Monodisperse vanadium dioxide nanoparticle coating and preparation method thereof
CN115159860A (en) * 2022-07-20 2022-10-11 贵州民族大学 Preparation of H-SiO in mild aqueous environment 2 -VO 2 (M) method of coating

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