CN114672094A - Modified nanometer VO of intelligence window2High polymer composite membrane and preparation method thereof - Google Patents

Modified nanometer VO of intelligence window2High polymer composite membrane and preparation method thereof Download PDF

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CN114672094A
CN114672094A CN202210352991.4A CN202210352991A CN114672094A CN 114672094 A CN114672094 A CN 114672094A CN 202210352991 A CN202210352991 A CN 202210352991A CN 114672094 A CN114672094 A CN 114672094A
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polymer composite
high polymer
modified
composite membrane
preparation
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刘相
王蓓
于桂琴
刘莉君
李静
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Huaian High Technology Institute Of Lanzhou University
Lanzhou University
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Huaian High Technology Institute Of Lanzhou University
Lanzhou University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

The invention relates to the technical field of organic films, in particular to a modified nano VO of an intelligent window2High polymer composite membrane and preparation method thereof, and modified VO2The high polymer composite membrane comprises the following raw materials in parts by weight: modified VO21-8 parts of nanoparticles; 70-80 parts of an adhesive; 10-20 parts of a surfactant. The composite film prepared by the invention has good photochromic effect, and VO is prepared2The nano particles are wrapped in the polymer adhesive, so that potassium, sodium, calcium and magnesium ions in glass can be well isolated, and acidic substances and water vapor in the air are prevented from influencing VO2Further improve the weather resistance of the composite film and prolong the service lifeThe coating can be applied to the fields of glass preparation of intelligent windows and building exterior walls, heat insulation coatings, film sticking and the like, and has the characteristics of intelligence controllability, low cost, environmental friendliness and the like.

Description

Modified nanometer VO of intelligence window2High polymer composite membrane and preparation method thereof
Technical Field
The invention relates to the technical field of organic films, in particular to a modified nano VO of an intelligent window2A high polymer composite membrane and a preparation method thereof.
Background
Modern houses adopt large-area glass curtain walls for pursuing the comfort of indoor lighting and the brightness of outdoor light, and for buildings, the heat energy transmitted through the glass windows is far higher than that of other enclosure bodies, so that the great loss of the energy of the whole house is caused. The intelligent glass has intelligent characteristics and can have a sensing function (namely a signal sensing function), so that the development of intelligent glass with a large energy-saving system, intelligent energy-saving glass with electrochromism and photochromism and the like is rapidly developed in recent years.
The wave band of the sunlight is divided into ultraviolet light (200-. When sunlight irradiates the surface of an object, the object mainly absorbs the energy of near infrared light, so that the surface temperature of the object is increased. In summer, when sunlight irradiates on the surface of a metal plate or a building, the surface temperature can reach 70-80 ℃, and infrared light needs to be reflected to reduce the surface temperature of the object.
The transmission range of the common glass is 300-500 nm, wherein the transmittance of visible light and near infrared light exceeds 80%, and the transmittance of the common glass in a middle infrared band is near 10%. This transmission range coincides exactly with the solar radiation spectral region, so the solar radiation transmitted through the glass is very strong.
The glass used in common use can be classified into flat glass and special glass. The plate glass has the advantages of good light transmission performance and low manufacturing cost, can be applied to the building industry on a large scale, but has large sun shading coefficient (0.99), poor blocking capability to solar radiation, needs air conditioning refrigeration indoors in summer, easily radiates indoor heat in winter, and causes unnecessary energy consumption. The special glass can be divided into hollow glass, laminated glass, coated glass and the like, the laminated glass is formed by bonding two or more pieces of flat glass by plastic linings such as polyvinyl butyral and the like, the impact resistance and the heat resistance are good, the viscoelasticity of an interlayer material in the glass has a high damping effect on sound transmission, the sound insulation effect of the glass is good, the heat conductivity of the glass is low, and the heat insulation performance is certain.
In 2004, the university of london, england invented a new type of heat resistant glass. When the temperature exceeds a certain limit value, the glass can automatically block infrared rays in sunlight and only allows visible light to irradiate into a room, so that the function of automatically blocking heat is achieved. The glass can ensure that the indoor temperature is not too high and the indoor temperature is not too dark when the sun is hot. It was found that when the critical temperature of 70 ℃ is reached, the electronic arrangement of vanadium dioxide itself changes, changing it from semiconductor to conductor, and blocking infrared rays.
VO2The phenomenon of thermochromism was discovered in 1958 by f.j.morin of bell laboratories, and as the temperature decreases, some compounds undergo a sudden transition (MST) from metallic to non-metallic (or semiconducting) properties in a certain temperature range, accompanied by a crystal transformation to a less symmetrical structure. And VO2Has a phase transition temperature of 341K (68 ℃), which is closest to room temperature, and thus has received extensive attention from researchers.
VO2When the transition from low-temperature phase semiconductor to high-temperature phase metal occurs, the crystal structure is changed from monoclinic to tetragonal, meanwhile, the resistance is suddenly changed in a nanosecond range, and the near infrared light is changed from high transmittance to high reflectance. The mutation of the performance before and after the phase change is VO2Has the function of photoelectric conversion switch. Such photoelectric conversion is widely used in the fields of thermochromic and photochromic devices, such as electronic scanning lasers, optical storage, gas sensors, thermally triggered electrical converters, transparent conductors, and the like. In the construction field, VO2The material is also researched in solar temperature control devices, energy-saving coatings and intelligent energy-saving window materials.
Existing VO2The fluorescent probe capable of detecting cadmium ions by the membrane is generally complex in molecular structure, unstable in property in a complex environment, complex to operate, long in corresponding time during identification, and poor in selectivity and sensitivity.
Disclosure of Invention
The invention aims to provide a modified nano VO of an intelligent window2A polymer composite membrane and a method for preparing the same, which solve the problems of the background art.
The invention is realized by the following technical scheme:
modified nanometer VO of intelligence window2Modified nano VO of/high polymer composite film and intelligent window2The high polymer composite membrane is characterized in that the modified VO2The high polymer composite membrane comprises the following raw materials in parts by weight:
modified VO21-8 parts of nanoparticles;
70-80 parts of an adhesive, wherein the adhesive comprises ethylene-vinyl acetate EVA or polyvinyl butyral PVB, and also comprises at least one of an epoxy resin adhesive, polyurethane, phenolic resin, polyvinyl chloride, an ethylene copolymer and chloroprene rubber;
10-20 parts of a surfactant, wherein the surfactant is selected from sodium dodecyl benzene sulfonate and/or ammonium cetyl benzyl chloride.
Preferably, the content of the vinyl acetate in the ethylene-vinyl acetate is 5-45%.
Preferably, the modified VO2The nanoparticles comprise VO2Nanometer superfine powder and doped modified VO2Nanometer superfine powder.
As a further embodiment of the invention, the doping modified VO2The nanometer superfine powder is selected from VO doped with F, O, W or Mo2And (3) microparticles.
Preferably, the modified nano VO2The thickness of the high polymer composite film is 0.2-0.3 mm.
The invention also provides the modified nano VO2The preparation method of the high polymer composite membrane specifically comprises the following steps：
S1 preparation of VO by coprecipitation method2Nano-particles: with VOSO4Adding ammonia water as a vanadium source, and blending to obtain VO2Precipitating the precursor, and performing heat treatment at 400-500 ℃ to obtain VO2Nanoparticles; taking a compound containing F or O or W or Mo as a source, adding ammonia water, and blending to obtain F-VO2Or O-VO2Or W-VO2Or Mo-VO2Performing high-temperature treatment on the precursor to obtain VO doped with F, O, W or Mo2Nanoparticles;
s2 preparation of modified nano VO by solution blending method2High polymer composite material: dissolving an adhesive and a surfactant in a toluene or ethanol solvent, and adding the F or O or W or Mo doped VO obtained in the step S12Carrying out ultrasonic-assisted dispersion on the nano particles to form a blending liquid;
s3, preparation of modified nano VO2High polymer composite membrane: taking glass or a metal plate as a substrate, dripping the blended liquid obtained in the step S2 on the substrate, leveling the blended liquid, and naturally airing to obtain the modified nano VO2High polymer composite membranes.
Preferably, the VO is characterized in that2The content of the nanoparticles is 1 to 8 wt%.
Preferably, the VO is characterized in that2The particle size of the nanoparticles is 10 to 40 nm.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method is simple, the prepared composite film has good photochromic effect, and VO is prepared2The nano particles are wrapped in the polymer adhesive, so that potassium, sodium, calcium and magnesium ions in glass can be well isolated, and acidic substances and water vapor in the air are prevented from influencing VO2And further improve the weather resistance of the composite film and prolong the service life.
2. The composite film provided by the invention has an intelligent light control effect, can be applied to the fields of intelligent windows made of glass and building exterior walls, can also be applied to the fields of heat-insulating coatings, film sticking and the like, and has the characteristics of intelligence controllability, low cost, environmental friendliness and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used for describing the embodiments are briefly introduced below, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows VO obtained by the present invention2TEM images of the nanoparticles;
FIG. 2 is VO of the present invention2The variable temperature infrared absorption spectrum of the sample;
FIG. 3 is VO of the present invention2An ultraviolet-visible absorption spectrum chart of the/EVA composite membrane;
FIG. 4 is VO of the present invention2Ultraviolet-visible absorption spectrum of the/PVB composite film.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
this example provides a modified nano VO2The preparation method of the high polymer composite membrane specifically comprises the following steps:
s1 preparation of VO by coprecipitation method2Nano-particles:
VO2the reaction formula of the nanoparticles is VOSO4+2NH3·H2O＝VO2+(NH4)2SO4。
Measuring 80-120 mL VOSO with concentration of 0.1-0.2 mol/L4Adjusting the pH of the solution to 4.0-7.0 by using dilute ammonia water, wherein the solution is an off-white turbid liquid, and performing suction filtration to obtain off-white VO2Precipitating the precursor, and thermally treating VO at 500 deg.C2Precipitating the precursor for 5h to obtain a black blue powder product, namely VO2Nanoparticles.
Measuring 80-120 mL of F-containing compound solution with the concentration of 0.1-0.2 mol/L, adjusting the pH of the solution to 7.0 by using dilute ammonia water, and dissolvingThe liquid is gray suspension, and is filtered to obtain gray VO2Precipitating the precursor, and thermally treating VO at 500 deg.C2Precipitating the precursor for 5h to respectively obtain F-doped VO2And (3) a nanoparticle product.
S2, preparation of modified nano VO2High polymer solution:
weighing EVA and sodium dodecyl benzene sulfonate in a ratio into a conical flask, and adding toluene or ethanol solvent to dissolve the EVA and the sodium dodecyl benzene sulfonate to obtain an adhesive solution, wherein the ratio of the adhesive to the surfactant to the organic solvent is 1 g: 1 g: 10-20 mL. Weighing the F-doped VO obtained from S1 in proportion2Placing the nano particles into an agate mortar for fine grinding, and VO2The mass fraction of the relative pure adhesive is 1%, then an adhesive solution is added to continuously grind to obtain a blending solution, the blending solution is poured into a conical flask to be subjected to ultrasonic-assisted dispersion, and the VO is prepared2High polymer solution.
S3, preparation of modified nano VO2High polymer composite membrane:
respectively taking VO prepared in step S22The high polymer solution is dripped on a clean glass substrate by a dropper to ensure that the glass substrate is naturally leveled, and the glass substrate is placed in a bell jar in a room temperature environment to avoid air circulation from influencing the flatness of the composite membrane. When the composite film is semi-dry, the composite film is placed in an oven, dried at the temperature of 80-100 ℃, and then the film is taken off from the substrate to obtain the modified nano VO2High polymer composite membranes.
The embodiment also provides the F-doped nano VO prepared by the preparation method2The thickness of the composite film is 0.2 mm.
Example 2:
the difference between this embodiment and embodiment 1 is that in step S1, 80 to 120mL of 0.1 to 0.2mol/L O-containing compound solution is measured, diluted ammonia water is used to adjust the pH of the solution to 7.0, the solution is an off-white suspension, and filtration is performed to obtain off-white VO2Precipitating the precursor, and thermally treating VO at 500 deg.C2Precipitating the precursor for 5h to respectively obtain O-doped VO2A nanoparticle product; in step S2, the O-doped VO obtained in step S1 is weighed in proportion2The nano particles are put into an agate mortar for grindingFine, VO2The mass fraction of the relatively pure adhesive is 2%, then an adhesive solution is added to continuously grind to obtain a blending solution, the blending solution is poured into a conical flask to be subjected to ultrasonic-assisted dispersion, and the VO is prepared2A high polymer solution; step S3 corresponds to example 1.
The embodiment also provides O-doped nano VO prepared by the preparation method2The composite film has a thickness of 0.25 mm.
Example 3:
the difference between the embodiment and embodiment 1 is that in step S1, 80 to 120mL of W-containing compound solution with a concentration of 0.1 to 0.2mol/L is measured respectively, the pH of the solution is adjusted to 7.0 with dilute ammonia water, the solution is an off-white suspension, and filtration is performed to obtain off-white VO2Precipitating the precursor, and thermally treating VO at 500 deg.C2Precipitating the precursor for 5h to respectively obtain W-doped VO2A nanoparticle product; in step S2, the W-doped VO obtained in step S1 is weighed in proportion2Placing the nano particles into an agate mortar for fine grinding, and VO2The mass fraction of the relatively pure adhesive is 3-4%, then an adhesive solution is added, the mixture is continuously ground to obtain a blending solution, the blending solution is poured into a conical flask for ultrasonic-assisted dispersion, and VO is obtained through preparation2A high polymer solution; step S3 corresponds to example 1.
The embodiment also provides the W-doped nano VO prepared by the preparation method2The composite film has a thickness of 0.3 mm.
Example 4:
the difference between the embodiment and embodiment 1 is that in step S1, 80 to 120mL of Mo-containing compound solution with a concentration of 0.1 to 0.2mol/L is measured, the pH of the solution is adjusted to 7.0 with dilute ammonia water, the solution is an off-white suspension, and the off-white VO is obtained by suction filtration2Precipitating the precursor, and thermally treating VO at 500 deg.C2Precipitating the precursor for 5h to respectively obtain Mo-doped VO2A nanoparticle product; in the step S2, PVB and ammonium cetyl benzyl chloride are weighed in proportion in a conical flask, and Mo-doped VO obtained in the step S1 is weighed in proportion2Placing the nano particles into an agate mortar for fine grinding, and VO2The mass fraction of the relatively pure adhesive is 4%, then an adhesive solution is added to continuously grind to obtain a blending solution, the blending solution is poured into a conical flask to be subjected to ultrasonic-assisted dispersion, and the VO is prepared2A high polymer solution; step S3 corresponds to example 1.
The embodiment also provides Mo-doped nano VO prepared by the preparation method2The composite film has a thickness of 0.3 mm.
VO obtained by scanning examples using a transmission electron microscope2Nanoparticles, VO obtained in example 1, FIG. 12The morphology of the nanoparticles as shown in FIG. 1 is scanned by electron microscope, VO2The particle size of the nanoparticles is 10 to 40 nm.
VO obtained in example 1 by IR spectroscopy2The nanometer particles are analyzed and identified, and figure 2 is an infrared temperature-variable absorption spectrogram. 682cm, as shown in FIG. 2-1、527cm-1The absorption peak disappears when the temperature is increased to above 68 ℃, and reappears when the temperature is reduced to below 68 ℃, which shows that VO2The phase transition point of the nanoparticles was 68 ℃. The spectral lines before temperature rise and when the temperature is reduced to room temperature are completely consistent, which shows that the product has reversible phase change property and can be recycled for multiple times. Compared with the undoped nano vanadium dioxide, the phase change critical temperature of the F/O/W/Mo doped and modified nano vanadium dioxide ultrafine powder is reduced by about 10-40 ℃ from 68 ℃ before modification, and the F/O/W/Mo doped and modified nano vanadium dioxide ultrafine powder also has reversible phase change property and can be recycled for multiple times.
So as not to add VO2The blank/EVA film and blank/PVB film prepared by nano particles under the same condition are comparative examples, and modified nano VO obtained in examples 1-4 are respectively2The polymer composite film was subjected to the purple-visible absorption test, and the test results are shown in fig. 3 to 4. As can be seen from FIGS. 3-4, modified nano VO was added2After the particles are formed, the film has good absorption and shielding in an ultraviolet region (200-400nm), a visible light region (400-800nm) and an infrared region (800-1000nm), and the corresponding absorption is reduced by 30-70%, especially 3% wt VO2The UV ray at 350nm shielded by the EVA composite film can reach 70%, which shows that the modified nano VO2The high polymer composite film has excellent intelligent light control effect.
Example 5:
the invention also provides a modified nano VO2The application of the high polymer composite film in the color-changing laminated glass. After the surfaces of two pieces of glass with the same size were cleaned, one piece of the glass was used as a negative film, and any one of the modified nano VOs prepared in examples 1 to 4 was subjected to surface modification2The high polymer composite film is coated on the bottom glass, another piece of glass is coated on the bottom glass, one piece of glass is placed into the silica gel bag, and after exhausting for 10-30 minutes under the vacuum degree of 1.0-3.5 KPa, the temperature is kept for 10-40 minutes at 70-90 ℃; and flatly placing the glass in an autoclave for hot pressing for 25 minutes, setting the pressure to be 1-2 MPa and the heating temperature to be 100 ℃, and obtaining the color-changing laminated glass. The color-changing laminated glass prepared by the embodiment has an intelligent light control effect.
In conclusion, the preparation method is simple, the provided composite film has an intelligent light control effect, is high in weather resistance and long in service life, can be applied to the fields of intelligent windows and building exterior walls made of glass, can also be applied to heat insulation coatings, film sticking and the like, and has the characteristics of intelligence controllability, low cost, environmental friendliness and the like.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (8)

1. Modified nanometer VO of intelligence window2The high polymer composite membrane is characterized in that the modified VO2The high polymer composite membrane comprises the following raw materials in parts by weight:
modified VO21-8 parts of nanoparticles;
70-80 parts of an adhesive, wherein the adhesive comprises ethylene-vinyl acetate and polyvinyl butyral, and also comprises at least one of an epoxy resin adhesive, polyurethane, phenolic resin, polyvinyl chloride, an ethylene copolymer and chloroprene rubber;
10-20 parts of a surfactant, wherein the surfactant is selected from sodium dodecyl benzene sulfonate and/or ammonium cetyl benzyl chloride.
2. Modified nano VO according to claim 12The high polymer composite membrane is characterized in that the content of vinyl acetate in the ethylene-vinyl acetate is 5-45%.
3. Modified nano VO according to claim 12The polymer composite membrane is characterized in that the modified VO2The nanoparticles comprise VO2Nanometer superfine powder and VO modified by doping2Nanometer superfine powder.
4. Modified nano VO of claim 32The high polymer composite membrane is characterized in that the doped and modified VO2The nanometer superfine powder is selected from VO doped with F, O, W or Mo2And (3) microparticles.
5. Modified nano VO according to claim 12The high polymer composite membrane is characterized in that the modified nano VO2The thickness of the high polymer composite film is 0.2-0.3 mm.
6. The modified nano VO of any one of claims 1 to 52The preparation method of the high polymer composite membrane is characterized by comprising the following steps:
s1 preparation of VO by coprecipitation method2Nano-particles: with VOSO4Adding ammonia water as a vanadium source, and blending to obtain VO2Precipitating the precursor, and performing heat treatment at 400-500 ℃ to obtain VO2Nanoparticles; taking a compound containing F or O or W or Mo as a source, adding ammonia water and blending to obtain F-VO2Or O-VO2Or W-VO2Or Mo-VO2The precursor is treated at high temperature to obtain F, O, W or MoHetero VO2Nanoparticles;
s2 preparation of modified nano VO by solution blending method2High polymer composite material: dissolving an adhesive and a surfactant in a toluene or ethanol solvent, and adding the F or O or W or Mo doped VO obtained in the step S12Carrying out ultrasonic-assisted dispersion on the nano particles to form a blending liquid;
s3, preparation of modified nano VO2High polymer composite membrane: taking glass or a metal plate as a substrate, dripping the blended liquid obtained in the step S2 on the substrate, leveling the blended liquid, and naturally airing to obtain the modified nano VO2High polymer composite membranes.
7. Modified nano VO of claim 62The preparation method of the/high polymer composite membrane is characterized in that the VO2The content of the nanoparticles is 1 to 8 wt%.
8. The modified nano VO of claim 62The preparation method of the/high polymer composite membrane is characterized in that the VO2The particle size of the nanoparticles is 10 to 40 nm.
CN202210352991.4A 2022-04-02 2022-04-02 Modified nanometer VO of intelligence window2High polymer composite membrane and preparation method thereof Pending CN114672094A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105540667A (en) * 2015-12-30 2016-05-04 山东海容节能新材料有限公司 Preparation method of doping modified vanadium dioxide powder with lower phase transition temperature
CN106750466A (en) * 2017-01-13 2017-05-31 广东韩亚薄膜科技有限公司 reversible thermochromic film and preparation method thereof
CN113185140A (en) * 2021-05-11 2021-07-30 济南大学 Vanadium dioxide-based thermochromic composite film and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105540667A (en) * 2015-12-30 2016-05-04 山东海容节能新材料有限公司 Preparation method of doping modified vanadium dioxide powder with lower phase transition temperature
CN106750466A (en) * 2017-01-13 2017-05-31 广东韩亚薄膜科技有限公司 reversible thermochromic film and preparation method thereof
CN113185140A (en) * 2021-05-11 2021-07-30 济南大学 Vanadium dioxide-based thermochromic composite film and preparation method thereof

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