CN103073941B - Vanadium dioxide powder slurry and preparation method thereof - Google Patents
Vanadium dioxide powder slurry and preparation method thereof Download PDFInfo
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- CN103073941B CN103073941B CN201210017917.3A CN201210017917A CN103073941B CN 103073941 B CN103073941 B CN 103073941B CN 201210017917 A CN201210017917 A CN 201210017917A CN 103073941 B CN103073941 B CN 103073941B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
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Abstract
The invention relates to vanadium dioxide powder slurry and a preparation method thereof. The invention relates to vanadium dioxide powder slurry comprising vanadium dioxide composite powder. The vanadium dioxide composite powder comprises vanadium dioxide nano-powder with a chemical composition of V1-xMxO2, and organic modification long-chain molecules are grafted on the surface of the vanadium dioxide nano-powder. M is a doping element, and x is no smaller than 0 and no greater than 0.5. According to the invention, the surface of the vanadium dioxide nano-powder is subjected to organic modification, such that chemical stability and dispersibility of the vanadium dioxide powder and the slurry thereof are greatly improved.
Description
Technical field
The present invention relates to a kind of hypovanadic oxide powder slurry and preparation method thereof, be mainly used in and prepare intelligent energy-saving coating, also can be used for the heat insulation occasions such as glass and exterior wall.
Background technology
The building energy consumption of China has accounted for 27.8% of social total energy consumption, and wherein the energy consumption of heating and air-conditioning accounts for 55% of building total energy consumption.In modern building, it is increasing that glass accounts for the area ratio of exterior wall, and the heat of being undertaken by glass port according to measuring and calculating is delivered in winter and summer and accounts for respectively 48% and 71%.If adopt air-conditioning to regulate room temp, refrigeration temperature improves 2 ℃, and cooling load reduces approximately 20%; Heat temperature and turn down 2 ℃, heating load and reducing approximately 30%, by sticking thermal isolation film or coating heat insulating coat can significantly reduce energy consumption on glass.
Current thermal isolation film or coating on the market mainly still be take and intercepted infrared property as main, can not change by response environment, they only have the function of reflects infrared light, and at low temperatures through ultrared effect, can not play the effect of intelligent surge chamber internal-external temperature difference, need to find and a kind ofly can intelligence regulate the material of solar heat, thereby realize effect cool in summer and warm in winter.
Vanadium dioxide material has first-order phase transition characteristic, can induced environment temperature variation, and this variation of intelligent response realizes the band selective of sunlight is seen through or covered.Conventionally in envrionment temperature during lower than transformation temperature, the film that contains vanadium dioxide or coating are almost completely penetrating to the visible ray in sunlight and mid-infrared light; When temperature surpasses semi-conductor-metal phase change temperature of vanadium dioxide, vanadium dioxide undergoes phase transition and is converted into R phase, and now material can, to the blocking of mid-infrared light selectivity, reach the object of transparent (visible ray sees through) thermal resistance.Semi-conductor-the metal phase change of vanadium dioxide is thermoinducible reversible change, and its temperature switch effect can be used to the ultrared break-make of centering and carries out intelligent control.Utilize low under infrared light district high temperature of vanadium dioxide to see through and low temperature under high transmission, can prepare the Energy Saving Windows port system of complete intelligence.
Optical computing shows (S.-Y.Li, a_G.A.Niklasson, and C.G.Granqvist Nanothermochromics:Calculations for VO
2nanoparticles in dielectric hosts show much improved luminous transmittance and solar energy transmittance modulation, JOURNAL OF APPLIED PHYSICS 108,0635252010) if vanadium dioxide nano powder can be scattered in to other matrix, as transparent polymer, can retain on the basis of vanadium dioxide optics performance of control, improve visible light transmissivity to realistic scale, can carry out reducing energy consumption to the outside surface of the transportation means such as in commission glass, metope and car and boat.By vanadium dioxide material being accomplished to nano-scale and can being prepared a kind of intelligent temperature control coating with organically-modified Material cladding, but because nanoparticle specific surface area is little and surface free energy is high, between particle, be easy to reunite, this specific character has determined direct vanadium dioxide nano particle to be joined in coating, be difficult to the performance of real performance nano material, and easily reunite, affect optical property and the outward appearance of coating, thereby limited the application of material on adhering film to glass and transparent glass.As mentioned a kind of vanadium dioxide intelligent temperature control coating in Chinese Patent Application No. 200410051965, but its vanadium dioxide particle of mentioning belongs to unmodified vanadium dioxide particle, do not relate to the pre-treatment of particle, the vanadium dioxide particle that particularly the present invention mentions carries out front dispersion treatment, and particularly organically-modified processing is for the raising of its dispersing property and chemical stability performance.
Chinese Patent Application No.: 200610117027.4 mention a kind of preparation method of hypovanadic oxide suspensoid, the dispersion treatment that wherein relates to hypovanadic oxide powder, but what it adopted is inorganic modified method, the organically-modified scheme of taking from the present invention is prepared vanadium dioxide composite particles the different of essence, and in invention, adopt acidity or alkaline condition, can destroy the structure of vanadium dioxide.
Chinese Patent Application No.: mentioned the surface treatment of light modulation paint particles in 200980123044.0 thermo-color microparticals and dispersion liquid thereof and manufacture method and light modulation coating, light modulation film, light modulation ink, but it does not propose concrete method of modifying, and this invention processing is that titanium dioxide and the vanadium dioxide composite particles vanadium dioxide composite granule related from this patent summary of the invention have the different of essence.
Summary of the invention
Application hypovanadic oxide powder and hypovanadic oxide powder and the compound film of preparing of other materials, method is simple, is convenient to large-scale operation, not only can transform for the energy-saving of original glass port, and can be coated on different substrates, expands the applicability of vanadium dioxide.But when hypovanadic oxide powder is prepared into vanadium dioxide slurries, formation film and coating, require hypovanadic oxide powder to there is excellent dispersing property and chemical stability.
At this, the invention provides a kind of vanadium dioxide composite granule, comprise that chemical constitution is V
1-xm
xo
2vanadium dioxide nano powder, vanadium dioxide nano powder surface connects organically-modified long chain molecule, wherein M is doped element, 0≤x≤0.5.
Vanadium dioxide composite granule of the present invention, organically-modified to the surface process of vanadium dioxide and Dope nano-power thereof.It is different from the hypovanadic oxide powder of general unmodified or inorganic parcel and modification, and the mode by organic modifiers makes vanadium dioxide surface connect organically-modified long chain molecule, thereby greatly improves chemical stability and the dispersiveness of hypovanadic oxide powder.Apply vanadium dioxide composite granule stability provided by the invention and good dispersity, can preserve for a long time use, can be used as intelligent heat insulation powder and be applied to prepare intelligent energy-saving coating or coating, also can be used for the heat insulation occasions such as glass and exterior wall.It is different from general lagging material, and it can significantly intercept infrared light when transformation temperature is above, and can highly see through lower than transformation temperature infrared rays, and this variation is reversible, and the intelligence that can realize solar heat regulates.
Preferably, in vanadium dioxide composite granule of the present invention, the content of organically-modified long chain molecule is 0.1～50%.More preferably, organically-modified long chain molecule content is 1～10%.Organically-modified long chain molecule content is too small, cannot realize the abundant parcel of powder surface; Organically-modified long chain molecule content is excessive, can cause mutually tangling between organic molecule, affects on the contrary dispersion effect.
Preferably, organically-modified long chain molecule chain length is at 0.1nm～100nm.
The present invention relates to the organic surface modifying of vanadium dioxide nano particle, can effectively improve the dispersiveness of vanadium dioxide and Dope nano-power thereof and the chemical stability of powder.
Organically-modified long chain molecule is for comprising the functionalized organic long-chains such as chain alkyl, polyacrylic acid group, polyvinyl alcohol group, epoxide group, chain alkyl amine groups, halogenation chain alkyl, carboxylated chain alkyl.
Vanadium dioxide composite granule of the present invention, grafting by organically-modified properties-correcting agent on hypovanadic oxide powder surface, be wrapped in hypovanadic oxide powder surface, thereby can change the surface property of vanadium dioxide, according to the difference of selected group, can increase the dispersing property of vanadium dioxide composite particles in different solvents, expand the purposes of vanadium dioxide particle in intelligent temperature control coating or coating.
Preferably, the vanadium dioxide nano powder in vanadium dioxide composite granule of the present invention is Rutile Type, and phase transition temperature is adjustable at-20～70 ℃.The shared ratio of rutile phase hypovanadic oxide can, up to 80%, even can reach 100%.This vanadium dioxide nano powder has first-order phase transition characteristic, can induced environment temperature variation, and this variation of intelligent response realizes the band selective of sunlight is seen through or covered.Conventionally in envrionment temperature during lower than transformation temperature, the film that contains vanadium dioxide or coating are almost completely penetrating to the visible ray in sunlight and mid-infrared light; When temperature surpasses semi-conductor-metal phase change temperature of vanadium dioxide, vanadium dioxide undergoes phase transition and is converted into R phase, and now material can, to the blocking of mid-infrared light selectivity, reach the object of transparent (visible ray sees through) thermal resistance.Semi-conductor-the metal phase change of vanadium dioxide is thermoinducible reversible change, and its temperature switch effect can be used to the ultrared break-make of centering and carries out intelligent control.
The doped element M of regulation can be or arbitrary combination in the elements such as near 21～30 transition element vanadium in the periodic table of elements, tin and near element thereof and tungsten, molybdenum, ruthenium, niobium in the present invention.Wherein, near 21～30 transition element in the periodic table of elements vanadium comprise scandium, titanium, chromium, manganese, iron, cobalt, nickel, copper and zinc, and described tin and near element thereof comprise indium, antimony, tin, gallium, germanium, lead and bismuth.Preferred doped element is tungsten, molybdenum, bismuth, tin, iron, zinc and titanium.
Adopt above-mentioned doped element, can controlled doping hypovanadic oxide powder size and pattern, doped element used equally also can regulate and control the phase transition temperature of vanadium dioxide.
In the present invention, doped vanadium dioxide powder is preferably particulate state, and the length-to-diameter ratio of particle is 1: 1～10: 1, is preferably 1: 1～5: 1, more preferably 1: 1～2: 1.Particle size is not more than 1um at least one dimension, preferably at least one dimension, is not more than 100nm, more preferably in three dimensions, is all not more than 100nm, most preferably in three dimensions, is all not more than 70nm.Described particulate state can be such as subsphaeroidal, oval, snowflake shape, cube, sheet shape etc.
The dispersiveness of hypovanadic oxide powder with above-mentioned size and pattern is better.The dispersiveness of the composite granule after modification also will be further enhanced.
The application also provides a kind of preparation method of vanadium dioxide composite granule, comprises that operation (1) is scattered in vanadium dioxide nano powder in dispersion medium, obtains mixture A; (2) in described mixture A, add dispersing auxiliary and the organic modifiers that is used to form hypovanadic oxide powder surface organic modification long chain molecule, be stirred to and fully mix to obtain mixture B; (3) mixture B is dried and makes organically-modified vanadium dioxide composite granule.
Hypovanadic oxide powder can be rutile phase hypovanadic oxide nanoparticle or doped rutile phase hypovanadic oxide nanoparticle.Can be the method preparation providing according to publication 2010PA011267CN, can be also rutile phase hypovanadic oxide nanoparticle or doped rutile phase hypovanadic oxide nanoparticle prepared by other known methods.Powder granule gravel size decision is below 200nm.The pattern of powder can be particle, nanometer rod and flakes particle.If prepare doped rutile phase hypovanadic oxide nanoparticle, before doped element, can adopt alkaline reagents to process presoma (the tetravalent vanadium ion aqueous solution), can obtain the controlled hypovanadic oxide powder size of size and pattern (being not more than 1um at least one dimension) and pattern (particulate state, length-to-diameter ratio is not more than 10: 1), the hypovanadic oxide powder grain-size of preparation is little, uniform particle diameter, and stable crystal form, it is at water, for example, in dispersion agent (polyvinylpyrrolidone) good dispersity, be easy to be coated on the matrixes such as glass, be suitable for preparing film and the coating of hypovanadic oxide powder.
The preparation method of vanadium dioxide composite granule provided by the invention, the dispersing auxiliary adding in operation (2) can be polyvinyl alcohol, one or more in polyvinylpyrrolidone, organic modified polyorganosiloxane dipropylene glycol monomethyl ether solution, organic silicon surfactant or fluorochemical surfactant or the dispersing auxiliary known altogether in the industry.
The preparation method of vanadium dioxide composite granule provided by the invention, the organic modifiers adding in operation (2) can be the organic modifiers such as stearic acid, polyacrylic acid, silane coupling agent, aluminate coupling agent or titanate coupling agent.Be preferably the silane coupling agent of pbz polymer long-chain.
Mode by coupling agent can make vanadium dioxide surface connect organic long-chain molecule, thereby greatly improves chemical stability and the dispersiveness of hypovanadic oxide powder.
In the preparation method of vanadium dioxide composite granule provided by the invention, dispersion medium used can be ethanol, one or more in the inert solvents such as Virahol, chloroform, dimethyl formamide, dimethyl sulfoxide (DMSO) ethylene dichloride or acetone.
In inert media, carry out organically-modifiedly, can prevent the sex change of vanadium dioxide, improve the chemical stability of powder.
The preparation method of vanadium dioxide composite granule provided by the invention, preparation technology's innovation, by the organic surface modifying process of organic modifiers, can effectively improve dispersiveness and the chemical stability of vanadium dioxide (vanadium dioxide) and Dope nano-power thereof.
In addition, the present invention also provides a kind of hypovanadic oxide powder slurry that comprises vanadium dioxide composite granule of the present invention.
Wherein, hypovanadic oxide powder slurry provided by the invention can possess, (1) vanadium dioxide composite granule, and it comprises that chemical constitution is V
1-xm
xo
2vanadium dioxide nano powder, and described powder surface connects organically-modified long chain molecule, wherein M is doped element, 0≤x≤0.5; And (2) dispersion medium.
In hypovanadic oxide powder slurry of the present invention, vanadium dioxide composite granule and dispersion medium weight ratio can be 1: 1～1: 1000.Preferably, the weight ratio of vanadium dioxide composite granule and dispersion medium is 1: 5～1: 500.It is more preferably 1: 10～1: 100.The vanadium dioxide composite granule of preparing by the present invention can effectively disperse within the scope of 0～50 % by weight.If from the application point of smart coat, the scope of 0.5～10 % by weight more preferably.Too high levels can affect the transmittance of coating, the too low intelligent effect of heat insulation that is difficult to bring into play coating.
Can select one or more in deionized water, ethanol, propyl alcohol, Virahol, ethyl acetate, toluene, butanone as the dispersion medium in hypovanadic oxide powder slurry of the present invention again.
In addition, vanadium dioxide composite granule slurry of the present invention can also comprise dispersing auxiliary, this dispersing auxiliary can be to be selected from polyacrylate, polyacrylamide, polyphosphoric acid salt, polyvinyl alcohol, polyvinylpyrrolidone, modified poly ester, one or more in modified polyurethane and modified acroleic acid dispersion agent.
In addition, the present invention is also provided for preparing the preparation method of hypovanadic oxide powder slurry of the present invention.
In the preparation method of hypovanadic oxide powder slurry provided by the invention, can first vanadium dioxide composite granule be added and in dispersion medium, carry out pre-dispersedly, then add described dispersion agent, mix and make described hypovanadic oxide powder slurry.
Vanadium dioxide composite granule of the present invention and the hypovanadic oxide powder slurry that comprises this powder, can be applicable to prepare intelligent energy-saving coating or coating, the coating transparency of preparation is high, low, the ageing-resistant ability of mist degree is strong, be mainly used in film, the flexible materialss such as cloth, also can be used for the heat insulation occasions such as glass and exterior wall.
Accompanying drawing explanation
Fig. 1 is that hypovanadic oxide powder surface is without the transmission electron microscope picture of organically-modified hypovanadic oxide powder;
Fig. 2 is that hypovanadic oxide powder surface is through the transmission electron microscope picture of organically-modified vanadium dioxide composite granule.
Embodiment
Below, with reference to accompanying drawing, and further illustrate the present invention in conjunction with subordinate's embodiment.
Vanadium dioxide material has first-order phase transition characteristic, can induced environment temperature variation, and this variation of intelligent response realizes the band selective of sunlight is seen through or covered.Vanadium dioxide nano powder is scattered in to other matrix, as transparent polymer, can retain on the basis of vanadium dioxide optics performance of control, improve visible light transmissivity to realistic scale, can carry out reducing energy consumption to the outside surface of the transportation means such as in commission glass, metope and car and boat.But because nanoparticle specific surface area is little and surface free energy is high, between particle, be easy to reunite, this specific character has determined direct vanadium dioxide nano particle to be joined in coating, be difficult to the performance of real performance nano material, and easily reunite, affect optical property and the outward appearance of coating, thereby limited the application of material on adhering film to glass and transparent glass.The present invention relates to the organic surface modifying process of vanadium dioxide nano particle, can effectively improve the dispersiveness of vanadium dioxide and Dope nano-power thereof and the chemical stability of powder.
In the preparation method of vanadium dioxide composite granule of the present invention, comprise, vanadium dioxide nano powder is scattered in dispersion medium, obtain the operation of mixture A; In described mixture A, add dispersing auxiliary and be used to form the organic modifiers of hypovanadic oxide powder surface organic modification long chain molecule, be stirred to and fully mix to obtain the operation of mixture B; By the dry operation that makes organically-modified vanadium dioxide composite granule of mixture B.
The preparation method of above-mentioned vanadium dioxide composite granule, particularly, the first high-speed stirring dispersing and mixing of the hypovanadic oxide powder that can be 1～50% by weight percent content and 50～99% dispersion medium, and the ultrasonic mixture that disperses to obtain, in mixture, add again afterwards dispersing auxiliary and organic modifiers, at 0～200 ℃ of constant temperature, stir, by modes such as ultrasonic, sand milling or ball millings, disperse, then centrifugation, under certain temperature, vacuum-drying obtains organically-modified vanadium dioxide composite granule.
Wherein, in the operation that vanadium dioxide nano powder is mixed with dispersion medium, the weight ratio of vanadium dioxide nano powder and dispersion medium can be 1: 1～1: 1000.Preferably, the weight ratio of vanadium dioxide nano powder and dispersion medium is 1: 5～1: 100.When weight ratio is too small, hypovanadic oxide powder is low with organic modifiers contact probability, jitter time that need to be longer and larger properties-correcting agent consumption; Weight ratio is excessive, is unfavorable for the abundant dispersion of powder in dispersion medium and wetting, affects the modified effect in later stage.
In above-mentioned vanadium dioxide nano powder surface organic modification, organic modifiers can be the organic modifiers such as stearic acid, polyacrylic acid, silane coupling agent, aluminate coupling agent or titanate coupling agent, is preferably the silane coupling agent of pbz polymer long-chain.It can be 0.05～5 % by weight that organic modifiers adds the amount in mixture; Be preferably 0.1～2 % by weight.Organically-modified long chain molecule content is too small, cannot realize the abundant parcel of powder surface; Organically-modified long chain molecule content is excessive, can cause mutually tangling between organic molecule, affects on the contrary dispersion effect.Mode by coupling agent can make vanadium dioxide surface connect organic long-chain molecule, thereby greatly improves chemical stability and the dispersiveness of hypovanadic oxide powder.In addition, dispersing auxiliary used can be polyvinyl alcohol, one or more in polyvinylpyrrolidone, organic modified polyorganosiloxane dipropylene glycol monomethyl ether solution, organic silicon surfactant or fluorochemical surfactant or the dispersing auxiliary known altogether in the industry.Dispersing auxiliary is mainly used in reducing the surface tension of solution, and raising solvent is wetting powder surface, thereby improves dispersion effect.It can be 0.02～2 % by weight that dispersing auxiliary adds the amount in mixture; Be preferably 0.05～1 % by weight.Few add-on can reach needed dispersion effect.Add the surface organic modification process that too much can affect on the contrary powder.
The preparation method of hypovanadic oxide powder slurry provided by the invention, particularly, it is pre-dispersed that the hypovanadic oxide powder that can be 1～50% by weight percent content adds the middle and high speed of 40～99% dispersion medium to stir to carry out, in mixture, add again afterwards dispersing auxiliary, the hypovanadic oxide powder slurry that high-speed stirring must mix.Can described slurry be mixed by dispersing method such as ultrasonic, ball milling and/or sand millings in addition.
In the present invention, no matter be in the preparation process of vanadium dioxide composite granule or in the preparation process of composite granule slurry, the rotating speed of high-speed stirring can be 1000～3000rad/min.Ultrasonic power can be 50～5000W, and frequency is 21KHz.In addition, drum's speed of rotation can be chosen as 10～2000rad/min.Again, the rotating speed of sand mill can be 10～2000rad/min.Grinding medium can be selected zirconia balls, and particle diameter, at 0.02mm～50mm, is preferably the grinding medium of small particle size.
Should be understood that the above-mentioned embodiment that the present invention describes in detail, and following examples only for being described, the present invention being not used in and limiting the scope of the invention.The raw material adopting, reagent can be synthesized and be made by purchase marketable material or traditional chemical transform mode.Unless otherwise defined or described herein, the familiar same meaning of all specialties used herein and scientific words and those skilled in the art.In addition any method and material similar to described content or that be equal to all can be applicable in the inventive method.Other aspects of the present invention, due to disclosure herein, are that appearance is intelligible to those skilled in the art.
Below, by embodiment, the present invention is described in more details.
As shown in Figure 1, without the pattern of organically-modified vanadium dioxide particle, diameter of particle 10～100nm not etc., is not that agglomerating particles exists but comparatively loose between particle.
Embodiment 1
(1) surface organic modification of vanadium dioxide nano powder:
Get each constituent mass as follows:
Vanadium dioxide nano powder (Doped Tungsten, particle diameter 20～100nm), 20g
Ethanol (dispersion medium), 80g
Silane coupling agent (containing polyvinyl alcohol group, organic modifiers), 1g
Polyvinylpyrrolidone (dispersing auxiliary), 0.05g;
First by vanadium dioxide nano powder and dispersion medium, high-speed stirring under 1500rad/min is disperseed 30min, and ultrasonic dispersion 30min, again dispersing auxiliary and silane coupling agent are added wherein, on homogenizer, at 70 ℃ of constant temperature, stir 2h, centrifugation again, vacuum-drying obtains the vanadium dioxide composite granule of organo-silicon coupling agent modification at 60 ℃;
(2) preparation of vanadium dioxide composite granule slurry:
Get each constituent mass as follows:
The vanadium dioxide composite granule making in the present embodiment (1), 3g
Deionized water, 97.95g
Modified acroleic acid dispersion agent, 0.05g
Organic modified nano powder is added to the pre-dispersed 5min of deionized water high-speed stirring, then add the ultrasonic dispersion of dispersion agent 30min, stir process 1h on homogenizer, obtains vanadium dioxide and Dope nano-power slurry thereof;
In the present embodiment, the salient features of resulting vanadium dioxide composite granule and slurry thereof is in Table 1.
As shown in Figure 2, through the pattern of the vanadium dioxide composite granule of organic surface modifying, not etc., powder is not because be coated with machine group for diameter of particle 10～100nm, and the more not organically-modified particle of particle diameter increases slightly, but presents dispersion state between powder.
Embodiment 2
(1) surface organic modification of vanadium dioxide nano powder:
Get each constituent mass as follows:
Vanadium dioxide nano powder (undoping, particle diameter 20～60nm), 10g
Ethanol (dispersion medium), 90g
Stearic acid, 1g
Polyvinyl alcohol (dispersing auxiliary), 0.05g
First by vanadium dioxide nano powder and dispersion medium, high-speed stirring under 1500rad/min is disperseed 30min, and ultrasonic dispersion 30min, again dispersing auxiliary and stearic acid are added wherein, on homogenizer, at 60 ℃ of constant temperature, stir 2h, centrifugation again, vacuum-drying obtains stearic acid modified vanadium dioxide nano composite granule at 60 ℃;
(2) preparation of vanadium dioxide composite granule slurry:
Get each constituent mass as follows:
The vanadium dioxide composite granule making in the present embodiment (1), 1g
Virahol, 95g
Polyacrylic acid dipersant, 0.05g
Organic modified nano powder is added to the pre-dispersed 10min of deionized water high-speed stirring, then add the ultrasonic dispersion of dispersion agent 30min, stir process 1h on homogenizer, obtains vanadium dioxide composite granule slurry;
In the present embodiment, the salient features of resulting vanadium dioxide composite granule and slurry thereof is in Table 1.
Embodiment 3
(1) surface organic modification of vanadium dioxide nano powder:
Get each constituent mass as follows:
Vanadium dioxide nano powder (Doped Tungsten, particle diameter 20～100nm), 15g
Virahol (dispersion medium), 85g
Silane coupling agent (containing chain alkyl, organic modifiers), 1g
Organic modified polyorganosiloxane dipropylene glycol monomethyl ether solution (dispersing auxiliary), 0.08g
First by vanadium dioxide nano powder and dispersion medium, high-speed stirring under 1000rad/min is disperseed 20min, and ultrasonic dispersion 60min, again dispersing auxiliary and silane coupling agent are added wherein, on homogenizer, at 80 ℃ of constant temperature, stir 2h, centrifugation again, vacuum-drying obtains the vanadium dioxide nano composite granule that surface is connected to chain alkyl at 60 ℃;
(2) preparation of vanadium dioxide composite granule slurry:
Get each constituent mass as follows:
The vanadium dioxide composite granule making in the present embodiment (1), 15g
Ethyl acetate, 75g
Modified poly ester dispersion agent, 2.5g
Organic modified nano powder is added to the pre-dispersed 5min of deionized water high-speed stirring, then add the ultrasonic dispersion of dispersion agent 20min, stir process 1h on homogenizer, obtains vanadium dioxide composite granule slurry;
In the present embodiment, the salient features of resulting vanadium dioxide composite granule and slurry thereof is in Table 1.
Embodiment 4
(1) surface organic modification of vanadium dioxide nano powder:
Get each constituent mass as follows:
Vanadium dioxide nano powder (doping molybdenum, particle diameter 20～100nm), 25g
Virahol (dispersion medium), 75g
Titanate coupling agent (containing epoxide group, organic modifiers), 1g
Polyvinyl alcohol (dispersing auxiliary), 0.15g
First by vanadium dioxide nano powder and dispersion medium, high-speed stirring under 1500rad/min is disperseed 20min, and ultrasonic dispersion 60min, again dispersing auxiliary and titanate coupling agent are added wherein, on homogenizer, at 80 ℃ of constant temperature, stir 2h, centrifugation again, vacuum-drying obtains the vanadium dioxide nano composite granule that surface is connected to epoxide group at 70 ℃;
(2) preparation of vanadium dioxide composite granule slurry:
Get each constituent mass as follows:
The vanadium dioxide composite granule making in the present embodiment (1), 4g
Deionized water, 96g
Modified acroleic acid dispersion agent, 0.5g
Organic modified nano powder is added to the pre-dispersed 5min of deionized water high-speed stirring, then add the ultrasonic dispersion of dispersion agent 60min, stir process 2h on homogenizer, obtains vanadium dioxide composite granule slurry;
In the present embodiment, the salient features of resulting vanadium dioxide composite granule and slurry thereof is in Table 1.
Embodiment 5
(1) surface organic modification of vanadium dioxide nano powder:
Get each constituent mass as follows:
Vanadium dioxide nano powder (doping molybdenum, particle diameter 20～100nm), 5g
Virahol (dispersion medium), 95g
Aluminate coupling agent (containing chain alkyl, organic modifiers), 0.7g
Polyvinylpyrrolidone (dispersing auxiliary), 0.04g
First by vanadium dioxide nano powder and dispersion medium, high-speed stirring under 1500rad/min is disperseed 20min, and ultrasonic dispersion 60min, again dispersing auxiliary and aluminate coupling agent are added wherein, on homogenizer, at 80 ℃ of constant temperature, stir 2h, centrifugation again, vacuum-drying obtains the vanadium dioxide nano powder that surface is connected to chain alkyl at 60 ℃;
(2) preparation of vanadium dioxide composite granule slurry:
Get each constituent mass as follows:
The vanadium dioxide composite granule making in the present embodiment (1), 15g
Deionized water, 75g
Modified polyurethane dispersion agent, 2.5g
Organic modified nano powder is added to the pre-dispersed 5min of deionized water high-speed stirring, then add the ultrasonic dispersion of dispersion agent 60min, stir process 2h on homogenizer, obtains vanadium dioxide composite granule slurry;
In the present embodiment, the salient features of resulting vanadium dioxide composite granule and slurry thereof is in Table 1.
Embodiment 6
(1) surface organic modification of vanadium dioxide nano powder:
Get each constituent mass as follows:
Vanadium dioxide nano powder (Doped Tungsten, particle diameter 20～100nm), 8g
Virahol (dispersion medium), 92g
Silane coupling agent (containing halogenation chain alkyl, organic modifiers), 1g
Organic silicon surfactant (dispersing auxiliary), 0.06g
First by vanadium dioxide nano powder and dispersion medium, high-speed stirring under 1500rad/min is disperseed 20min, and ultrasonic dispersion 60min, again dispersing auxiliary and silane coupling agent are added wherein, on homogenizer, at 80 ℃ of constant temperature, stir 2h, centrifugation again, vacuum-drying obtains the vanadium dioxide nano powder that surface is connected to halogenation chain alkyl at 60 ℃;
(2) preparation of vanadium dioxide composite granule slurry:
Get each constituent mass as follows:
The vanadium dioxide composite granule making in the present embodiment (1), 20g
Toluene, 80g
Modified polyurethane dispersion agent, 3g
Organic modified nano powder is added to the pre-dispersed 5min of deionized water high-speed stirring, then add the ultrasonic dispersion of dispersion agent 60min, stir process 2h on homogenizer, obtains vanadium dioxide composite granule slurry;
In the present embodiment, the salient features of resulting vanadium dioxide composite granule and slurry thereof is in Table 1.
Embodiment 7
(1) surface organic modification of vanadium dioxide nano powder:
Get each constituent mass as follows:
Vanadium dioxide nano powder (Doped Tungsten, particle diameter 20～100nm), 10g
Ethanol (dispersion medium), 90g
Silane coupling agent (containing epoxy-functional, organic modifiers), 1g
Fluorochemical surfactant (dispersing auxiliary), 0.06g
First by vanadium dioxide nano powder and dispersion medium, high-speed stirring under 1500rad/min is disperseed 20min, and ultrasonic dispersion 60min, again dispersing auxiliary and silane coupling agent are added wherein, on homogenizer, at 80 ℃ of constant temperature, stir 2h, centrifugation again, vacuum-drying obtains the vanadium dioxide nano powder that surface is connected to epoxy-functional at 60 ℃;
(2) preparation of vanadium dioxide composite granule slurry:
Get each constituent mass as follows:
The vanadium dioxide composite granule making in the present embodiment (1), 5g
Deionized water, 95g
Modified acroleic acid dispersion agent, 1.5g
Organic modified nano powder is added to the pre-dispersed 5min of deionized water high-speed stirring, then add the ultrasonic dispersion of dispersion agent 60min, stir process 2h on homogenizer, obtains vanadium dioxide composite granule slurry;
In the present embodiment, the salient features of resulting vanadium dioxide composite granule and slurry thereof is in Table 1.
Comparative example 8
Get the vanadium dioxide nano powder of the non-modified of using in above-described embodiment 7 (1), 5g
Deionization, 95g
Modified acroleic acid dispersion agent, 1.5g
To have nano-powder to add the pre-dispersed 5min of deionized water high-speed stirring, then add the ultrasonic dispersion of dispersion agent 60min, stir process 2h on homogenizer, obtains vanadium dioxide nano powder slurry;
The salient features of the prepared vanadium dioxide nano powder slurry of this comparative example is in Table 1.
Referring to following table 1, from this table, organically-modified vanadium dioxide composite granule and the slurry thereof that method provided by the invention obtains can be described, its particle diameter is significantly less than unmodified powder, and BET specific surface area is greater than unmodified powder, and Stability of Slurry also will be significantly better than unmodified powdery pulp.By 300 ℃ of weightless data, can find out by surface organic modification process, can connect at nano powder surface 5～10% organic long-chain, thereby greatly improve chemical stability and the dispersiveness of hypovanadic oxide powder.
Table 1:
Industrial applicability: vanadium dioxide composite granule of the present invention can be applicable to prepare intelligent energy-saving coating or coating, the coating transparency of preparation is high, and low, the ageing-resistant ability of mist degree is strong, is mainly used in film, the flexible materialss such as cloth, also can be used for the heat insulation occasions such as glass and exterior wall.Also can be widely used in energy-saving and emission-reduction equipment, for example energy-conservation film, energy-saving coatings, sun power temperature control unit; Or energy information equipment, for example, micro photo electric switch device, thermistor, battery material and optical information storage part.The preparation method of vanadium dioxide composite granule provided by the invention, preparation technology's innovation, by the organic surface modifying process of organic modifiers, can effectively improve dispersiveness and the chemical stability of vanadium dioxide (vanadium dioxide) and Dope nano-power thereof.
Claims (13)
1. a preparation method for hypovanadic oxide powder slurry, is characterized in that, comprise,
The operation 1 of preparing vanadium dioxide composite granule, this operation 1 comprises that operation (1) is V by chemical constitution
1-xm
xo
2vanadium dioxide nano powder be scattered in dispersion medium A1, obtain mixture B1; Operation (2) adds dispersing auxiliary and is used to form the organic modifiers that vanadium dioxide nano powder surface connects organically-modified long chain molecule in described mixture B1, is stirred to and fully mixes to obtain mixture B2; And operation (3) is dried mixture B2 to make the vanadium dioxide composite granule that described vanadium dioxide nano powder surface connects organically-modified long chain molecule; Wherein M is doped element, 0≤x≤0.5, and the quality percentage composition of described organically-modified long chain molecule is described vanadium dioxide nano powder 0.1～50%; And
The vanadium dioxide composite granule of described operation 1 preparation is scattered in to the operation 2 that makes described hypovanadic oxide powder slurry in dispersion medium A2.
2. the preparation method of hypovanadic oxide powder slurry according to claim 1, is characterized in that, the quality percentage composition of described organically-modified long chain molecule is described vanadium dioxide nano powder 1～10%.
3. the preparation method of hypovanadic oxide powder slurry according to claim 1, is characterized in that, described organically-modified long chain molecule chain length is at 0.1nm～100nm.
4. according to the preparation method of the hypovanadic oxide powder slurry described in any one in claim 1-3, it is characterized in that, described organically-modified long chain molecule is functionalized organic long-chain or chain alkyl.
5. the preparation method of hypovanadic oxide powder slurry according to claim 4, it is characterized in that, described functionalized organic long-chain is, polyacrylic acid group, polyvinyl alcohol group, epoxide group, chain alkyl amine groups, halogenation chain alkyl and/or carboxylated chain alkyl.
6. according to the preparation method of the hypovanadic oxide powder slurry described in any one in claim 1～3, it is characterized in that, described vanadium dioxide nano powder is rutile phase hypovanadic oxide nano-powder, and transformation temperature is adjustable at-20～70 ℃.
7. the preparation method of hypovanadic oxide powder slurry according to claim 6, it is characterized in that, described doped element M is or arbitrary combination in scandium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, indium, antimony, tin, gallium, germanium, lead, bismuth, tungsten, molybdenum, ruthenium and niobium.
8. according to the preparation method of the hypovanadic oxide powder slurry described in any one in claim 1～3, it is characterized in that, the particle size of described vanadium dioxide nano powder is below 200nm.
9. a preparation method for the hypovanadic oxide powder slurry described in any one in claim 1～3, is characterized in that, in slurry, the weight ratio of vanadium dioxide composite granule and dispersion medium A2 is 1:1～1:1000.
10. the preparation method of hypovanadic oxide powder slurry according to claim 9, is characterized in that, in slurry, the weight ratio of vanadium dioxide composite granule and dispersion medium A2 is 1:10～1:100.
11. according to the preparation method of the hypovanadic oxide powder slurry described in any one in claim 1～3, it is characterized in that, described dispersion medium A2 comprises or several solvents of deionized water, ethanol, propyl alcohol, Virahol, ethyl acetate, toluene, butanone.
12. according to the preparation method of the hypovanadic oxide powder slurry described in any one in claim 1～3, it is characterized in that, the dispersing method by high-speed stirring, ultrasonic, ball milling and/or sand milling mixes described slurry.
13. 1 kinds of hypovanadic oxide powder slurries that make according to the preparation method described in any one in claim 1～12.
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| PCT/CN2012/072019 WO2013107080A1 (en) | 2012-01-19 | 2012-03-07 | Vanadium dioxide powdery slurry and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103589195B (en) * | 2013-10-24 | 2015-05-06 | 陕西理工学院 | Preparation method of cinereous pigment capable of reflecting infrared rays and heat-insulating paint |
| CN104562278A (en) * | 2014-12-30 | 2015-04-29 | 佛山金智节能膜有限公司 | Vanadium dioxide uniformly-dispersed polyester fiber |
| CN106433219A (en) * | 2016-09-22 | 2017-02-22 | 深圳大学 | Tungsten/fluorine codoped vanadium dioxide nanometer heat insulation sizing agent, tungsten/fluorine codoped vanadium dioxide paint film by means of sizing agent and preparation method |
| CN107039099B (en) * | 2017-03-10 | 2019-09-27 | 宜兴市昱元能源装备技术开发有限公司 | A kind of Novel conductive paste and the method for preparing solar battery sheet main gate line with it |
| CN107189550B (en) * | 2017-06-22 | 2021-01-08 | 中国人民解放军国防科学技术大学 | Vanadium dioxide water-based ink for ink-jet printing and preparation method and application thereof |
| CN107604684A (en) * | 2017-09-21 | 2018-01-19 | 江西省新天汇实业有限公司 | A kind of environment-friendly type discoloration packaging leather and preparation method thereof |
| CN108084742A (en) * | 2017-11-22 | 2018-05-29 | 纳琳威纳米科技南通有限公司 | A kind of preparation method and purposes of the high heat conduction aluminium nitride dispersion liquid that insulate |
| CN108611089A (en) * | 2018-03-27 | 2018-10-02 | 纳琳威纳米科技南通有限公司 | A kind of organically-modified fluorescence nano raw powder's production technology and application |
| CN108751256B (en) * | 2018-05-15 | 2020-12-29 | 清华大学 | Preparation method of high-performance lithium ion battery cathode material vanadium oxide |
| CN115991807B (en) * | 2021-10-19 | 2023-12-19 | 万华化学集团股份有限公司 | Yellowing-resistant polyvinyl chloride resin and preparation method thereof |
| CN113773707A (en) * | 2021-10-29 | 2021-12-10 | 湖北大学 | Waterproof vanadium dioxide intelligent temperature control coating and preparation method thereof |
| CN116023800A (en) * | 2022-12-01 | 2023-04-28 | 成都先进金属材料产业技术研究院股份有限公司 | Modified vanadium dioxide nano powder and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1162949A (en) * | 1994-11-09 | 1997-10-22 | 杰夫科油漆公司 | Vanadium dioxide microparticles, method for preparing same, and use thereof, in particular for surface coating |
| JP2011136873A (en) * | 2009-12-28 | 2011-07-14 | Tsurumi Soda Co Ltd | Vanadium dioxide fine particles, manufacturing method and thermo-chromic film |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3744188B2 (en) * | 1998-03-16 | 2006-02-08 | 住友金属鉱山株式会社 | Heat ray shielding film forming coating solution and heat ray shielding film |
| CN100434486C (en) * | 2006-10-11 | 2008-11-19 | 上海师范大学 | Method for preparing hypovanadic oxide suspensoid |
| CN101007928A (en) * | 2007-01-24 | 2007-08-01 | 安徽创尼新型建筑材料有限公司 | Solar heat reflective insulated lacquer and its production method |
| JP5136976B2 (en) * | 2007-09-12 | 2013-02-06 | 独立行政法人産業技術総合研究所 | Vanadium oxide thin film pattern and manufacturing method thereof |
| JP5476581B2 (en) * | 2008-06-30 | 2014-04-23 | 独立行政法人産業技術総合研究所 | Thermochromic fine particles, dispersion thereof, production method thereof, and light control paint, light control film and light control ink |
| US8461758B2 (en) * | 2008-12-19 | 2013-06-11 | E I Du Pont De Nemours And Company | Buffer bilayers for electronic devices |
| US20110284809A1 (en) * | 2009-02-09 | 2011-11-24 | National Institute Of Advanced Industrial Science And Technology | Particles, method of producing particles, and coating material, film, and ink including particles |
| CN101993657A (en) * | 2009-08-14 | 2011-03-30 | 北京建筑技术发展有限责任公司 | Intelligent nano transparent insulating glass coating |
| DE102009029640A1 (en) * | 2009-09-21 | 2011-04-07 | Evonik Degussa Gmbh | Process for the surface modification of metal oxide particles |
| CN101982514B (en) * | 2010-11-01 | 2013-08-28 | 北京燕山润泽清洁能源技术开发有限公司 | Nano transparent thermal insulation coating |
| CN102120615B (en) * | 2011-01-21 | 2012-10-31 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide-doped powder and dispersion, and preparation method and application thereof |
-
2012
- 2012-01-19 CN CN201210017917.3A patent/CN103073941B/en not_active Expired - Fee Related
- 2012-03-07 WO PCT/CN2012/072019 patent/WO2013107080A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1162949A (en) * | 1994-11-09 | 1997-10-22 | 杰夫科油漆公司 | Vanadium dioxide microparticles, method for preparing same, and use thereof, in particular for surface coating |
| JP2011136873A (en) * | 2009-12-28 | 2011-07-14 | Tsurumi Soda Co Ltd | Vanadium dioxide fine particles, manufacturing method and thermo-chromic film |
Non-Patent Citations (2)
| Title |
|---|
| 二氧化钒智能控温材料的制备与性能研究;宋锵;《中国优秀硕士论文全文数据库工程科技Ⅰ辑》;20111015(第10期);第39-43页、49-50页、53-55页、57页、59-60页、 * |
| 宋锵.二氧化钒智能控温材料的制备与性能研究.《中国优秀硕士论文全文数据库工程科技Ⅰ辑》.2011,(第10期),第39-43页、49-50页、53-55页、57页、59-60页、. |
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