CN109575797B - Color development adjustable vanadium dioxide-based thermochromic composite material and application thereof - Google Patents
Color development adjustable vanadium dioxide-based thermochromic composite material and application thereof Download PDFInfo
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Abstract
The invention relates to a color development adjustable vanadium dioxide-based thermochromic composite material and application thereof, wherein the vanadium dioxide-based thermochromic composite material comprises a vanadium dioxide-based thermochromic material and an ultraviolet photochromic material, and the mass ratio of the vanadium dioxide-based thermochromic material to the ultraviolet photochromic material is 1 (0.1-2), preferably 5: 1-2: 1.
Description
Technical Field
The invention relates to a vanadium dioxide-based thermochromic composite material with adjustable color development and application thereof, in particular to adjustment and application of color development of a vanadium dioxide-based thermochromic material film, and belongs to the technical field of composite films.
Background
The global energy shortage problem is increasingly serious, the environment is increasingly worsened due to excessive carbon emission, and energy conservation and emission reduction become the primary tasks of all countries at present. The building energy consumption is estimated to be more than 1/3 of the total social energy consumption, so that the promotion of building energy conservation is one of key measures for energy conservation, emission reduction and sustainable development realization. Most of building energy consumption is used for air conditioning, and the glass window is used as a main channel for heat exchange between the building and the outside and becomes a main way for air conditioning energy loss. Therefore, various types of energy-saving windows are used, the energy consumption can be effectively reduced, and the purposes of energy conservation and environmental protection are achieved.
The mainstream products of the energy-saving window in the existing market are Low-emissivity (Low-E) glass, heat-reflecting glass and the like, and the energy-saving window is widely applied to building energy conservation due to mature technology, Low price and good heat-insulating property. However, the optical performance of the energy-saving window cannot be changed due to seasonal changes and artificial requirements, and the energy-saving window is difficult to adapt to the energy-saving requirements of most of the winter-cold and summer-hot areas in China and the requirements of people on higher and higher comfort degree of living environment. Therefore, a new energy-saving product called an intelligent energy-saving window is produced at the same time, and becomes a new generation of energy-saving glass product following Low-E.
The intelligent energy-saving window uses the photochromic material with variable optical performance, and achieves the purpose of controllable regulation of indoor environment photo-thermal by utilizing the change of the photochromic material to the transflection performance and the like generated by various physical stimuli. Obviously, the intelligent energy-saving window can meet the requirements of most of areas and different climatic conditions, and the indoor living environment is more suitable for people. According to the physical stimulation type and the color changing mechanism, the intelligent energy-saving window has multiple types of intelligent energy-saving windows such as electrochromism, gasochromism, photochromism, thermochromism and the like. Among various types of intelligent energy-saving windows, the thermochromic energy-saving window developed by utilizing the semiconductor-metal reversible phase change principle near the room temperature of vanadium dioxide has the remarkable advantages of simple structure, small material consumption, capability of following the change of environmental temperature without switch or artificial energy control to realize automatic photo-thermal regulation and the like, and is paid attention to and developed in succession in various countries. The temperature-control intelligent energy-saving film pasting technology using the nano vanadium dioxide is a breakthrough in China at first, and the prepared vanadium dioxide-based temperature-control intelligent energy-saving film pasting is about to be put on the market. However, as the main inventors of the above technology, the following drawbacks of the vanadium dioxide temperature-controlled intelligent energy-saving window are still noticed: (1) the solar radiation infrared band has higher adjusting amplitude, but has almost no adjusting effect on the visible light band which accounts for 50% of the total solar radiation energy, and the total solar radiation adjusting rate is reduced as a result; (2) because the visible light wave band has no obvious regulation function, enough visual change can not be generated by utilizing the regulation, so that the strong regulation effect demonstration of customers can not be facilitated, and the decisive adverse effect is caused on the propaganda and popularization of products; (3) has strong absorption effect on short-wave-band visible light, and leads the film to develop yellow color. No mature technology has been known to date to fundamentally solve several of the above problems.
Patent 1 (chinese publication No. CN105694615A) discloses that Ligand converter Thermochromic (LETC) materials are compounded with vanadium dioxide-based Thermochromic materials, so as to realize reversible adjustment of visible light and infrared light spectra at high and low temperatures, but the LETC materials contain volatile components such as organic alcohols, which are easily volatilized and lose efficacy in production, preparation and daily use, thereby affecting the Thermochromic performance of the composite materials, and in addition, the LETC materials change color depending on thermal driving. Patent 2 (chinese publication No. CN108300002A) discloses a method of replacing organic alcohol with ionic liquid, which makes the LETC containing hydroxyl group ionic liquid have the advantages of non-volatility, high heat resistance and good chemical stability, but the ionic liquid is in liquid state at room temperature or near room temperature, also called as low temperature molten salt, and can not be solidified, thus severely limiting its application in practical use.
Disclosure of Invention
Aiming at the problems, the invention adopts the ultraviolet photochromic material and the vanadium dioxide-based thermochromic material to form the vanadium dioxide-based thermochromic composite material for the first time, and provides the vanadium dioxide-based thermochromic composite film and the preparation method thereof.
In a first aspect, the invention provides a color-developing adjustable vanadium dioxide-based thermochromic composite material, which comprises a vanadium dioxide-based thermochromic material and an ultraviolet photochromic material, wherein the mass ratio of the vanadium dioxide-based thermochromic material to the ultraviolet photochromic material is 1 (0.1-2), and preferably 5: 1-2: 1.
According to the invention, the vanadium dioxide-based thermochromic material and the ultraviolet photochromic material are compounded, and the visible and near-infrared bands of sunlight can be regulated and controlled by physically combining the vanadium dioxide-based thermochromic material and the ultraviolet photochromic material and matching the two materials in a spectrum. The ultraviolet photochromic material is changed in structure after absorbing ultraviolet rays (namely, the ultraviolet photochromic material is changed in color by the initiation of ultraviolet rays), so that different bands of visible light are absorbed; the vanadium dioxide-based thermochromic material has the infrared light regulation capability along with the temperature change, so that the ultraviolet irradiation resistance stability and the solar energy regulation rate of the vanadium dioxide-based thermochromic material can be improved.
Preferably, the vanadium dioxide-based thermochromic material is vanadium dioxide, preferably rutile phase dioxideVanadium or/and monoclinic phase vanadium dioxide; the particle size of the vanadium dioxide-based thermochromic material is 10 nm-10 mu m, and preferably 20-80 nm. Wherein the vanadium dioxide-based thermochromic material is doped and/or undoped rutile phase (space group is P4)2At mm) and/or monoclinic phase (space group P2)1V) vanadium dioxide, and vanadium dioxide particles with or without a coating.
Preferably, the ultraviolet photochromic material is a material which can generate a cyclotomic reaction, an alkoxy migration reaction and an isomerization reaction under ultraviolet irradiation to show red, blue and purple colors, and is preferably at least one of spiropyrans, spirooxazines, benzospiropyrans, fulgides, azo compounds, diarylethenes, aniline derivatives, polycyclic quinones and viologens. The ultraviolet photochromic material can be in a liquid state or a solid state, and can be dissolved or coordinated into the resin to form transparent liquid.
In a second aspect, the invention provides a vanadium dioxide-based thermochromic composite film with adjustable color development, wherein the vanadium dioxide-based thermochromic composite film is an organic polymer composite film formed by the vanadium dioxide-based thermochromic composite material.
Preferably, the mass ratio of the vanadium dioxide-based thermochromic material to the organic polymer is 1: (1 to 100), preferably 1: (3-50).
Preferably, the thickness of the vanadium dioxide-based thermochromic composite film is 1-200 μm.
Preferably, the organic polymer is at least one of a carbon chain polymer, a heterochain polymer and an element organic polymer, and is preferably at least one of a polycrystalline resin, a silicone resin, a polyacrylic acid resin, a polyethylene glycol resin, a polyvinyl butyral resin and a polyvinyl alcohol resin.
In a third aspect, the invention also provides a vanadium dioxide-based thermochromic composite film, which comprises an organic polymer film containing the vanadium dioxide-based thermochromic material and an organic polymer film containing the ultraviolet photochromic material, which are sequentially formed on the surface of the substrate.
According to the invention, the ultraviolet photochromic material is changed in structure after absorbing ultraviolet rays (namely, the ultraviolet photochromic material is changed in color by ultraviolet light), so that different bands of visible light are absorbed, the ultraviolet photochromic material is covered on the vanadium dioxide-based thermochromic film layer, ultraviolet rays in sunlight are absorbed by the ultraviolet photochromic layer to change color, the visible light region in the sunlight is adjusted, the lower vanadium dioxide-based thermochromic film layer has infrared light adjusting capability along with temperature change, and therefore, the ultraviolet radiation resistance stability and the solar energy adjusting rate of the vanadium dioxide-based thermochromic film can be improved.
Preferably, the mass ratio of the vanadium dioxide-based thermochromic material to the ultraviolet photochromic material is 1 (0.1-2), and preferably 5: 1-2: 1.
Preferably, the mass ratio of the vanadium oxide-based thermochromic material to the organic polymer in the organic polymer film containing the vanadium dioxide-based thermochromic material is 1: (1 to 100), preferably 1: (3-50); the mass ratio of the ultraviolet photochromic material to the organic polymer in the organic polymer film containing the ultraviolet photochromic material is 1: (10-1000), preferably 1: (50-200).
Preferably, the thickness of the organic polymer film containing the vanadium dioxide-based thermochromic material or the organic polymer film containing the ultraviolet photochromic material is 1-100 μm.
Preferably, the vanadium dioxide-based thermochromic material is vanadium dioxide; preferably, the vanadium dioxide is rutile phase vanadium dioxide or/and monoclinic phase vanadium dioxide. For example, doped and/or undoped rutile phase (space group P4)2At mm) and/or monoclinic phase (space group P2)1V) vanadium dioxide, and vanadium dioxide particles with or without a coating.
Preferably, the particle size of the vanadium dioxide-based thermochromic material is 10 nm-10 μm, and preferably 20-80 nm.
Preferably, the ultraviolet photochromic material is a substance which can generate a pericyclic reaction, an alkoxy migration reaction and an isomerization reaction under the irradiation of ultraviolet light to show red, blue and purple, and is preferably at least one of spiropyrans, spirooxazines, benzospiropyrans, fulgides, azo compounds, diarylethenes, aniline derivatives, polycyclic quinones and viologens; the ultraviolet photochromic material can be in a liquid state or a solid state, and can be dissolved or coordinated into the resin to form a transparent liquid.
Preferably, the organic polymer used in the organic polymer film is at least one of a carbon chain polymer, a heterochain polymer and an element organic polymer, and is preferably at least one of a polycrystalline resin, a silicone resin, a polyacrylic acid resin, a polyethylene glycol resin, a polyvinyl butyral resin and a polyvinyl alcohol resin.
In a fourth aspect, the present invention also provides a method for preparing the vanadium dioxide-based thermochromic composite membrane (single-layer composite membrane) according to the above, comprising:
uniformly dispersing the vanadium dioxide-based thermochromic composite material in a solvent to obtain a mixed dispersion liquid;
adding an organic polymer to the obtained mixed dispersion to obtain slurry;
and coating the surface of the substrate with the obtained slurry, and curing to obtain the vanadium dioxide-based thermochromic composite film.
Preferably, the solvent is at least one of toluene, xylene, ethanol and acetone; the concentration of the mixed dispersion liquid is 0.1-10 wt%.
In a fifth aspect, the present invention also provides a method for preparing the vanadium dioxide-based thermochromic composite film (layered composite film) according to the above, comprising:
respectively and uniformly dispersing a vanadium dioxide-based thermochromic material and an ultraviolet photochromic material in a solvent to obtain a mixed dispersion liquid 1 and a mixed dispersion liquid 2;
adding an organic polymer into the obtained mixed dispersion liquid 1 and the mixed dispersion liquid 2 respectively to obtain slurry 1 and slurry 2;
coating the obtained slurry 1 on the surface of a substrate, and curing to obtain a vanadium dioxide-based thermochromic material layer;
and coating the slurry 2 on the surface of the obtained vanadium dioxide-based thermochromic material layer, and then carrying out secondary curing to obtain the vanadium dioxide-based thermochromic composite film.
Preferably, the solvent is at least one of toluene, xylene, ethanol and acetone; the concentration of the mixed dispersion liquid 1 and the mixed dispersion liquid 2 is 0.1-10 wt%.
The invention has the following beneficial effects: 1) the ultraviolet photochromic material is adopted to adjust the color development of the vanadium dioxide-based thermochromic film, and meanwhile, the adjustable range of the wave band of the product covers the whole solar spectrum including visible light, so that the ultraviolet photochromic film has higher total solar adjustment rate. Has decisive significance for the effect display and the propaganda popularization of products. 2) Because the ultraviolet photochromic material can absorb ultraviolet rays, the ultraviolet rays which are unfavorable to vanadium dioxide-based thermochromic absorption are reduced and even avoided, and the stability of ultraviolet irradiation resistance of the ultraviolet photochromic material is improved. 3) The preparation method is simple, is easy for mass production, can be used in the aspects of thermochromic intelligent energy-saving films and intelligent energy-saving windows for buildings and vehicles, and can realize the leap breakthrough of the application technology of the vanadium dioxide-based thermochromic energy-saving windows.
Drawings
Fig. 1 is a transmission spectrum of a vanadium dioxide-based thermochromic composite film and a vanadium dioxide-based thermochromic film prepared in example 1 at high and low temperatures;
FIG. 2 is a photo of the vanadium dioxide-based thermochromic composite film prepared in example 1 taken before and after solar irradiation;
FIG. 3 is a transmission spectrum of the vanadium dioxide-based thermochromic composite film prepared in example 2;
fig. 4 is a transmission spectrum of the vanadium dioxide-based thermochromic film prepared in comparative example 1;
fig. 5 is a transmission spectrum of the ultraviolet photochromic material film prepared in comparative example 2.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the disclosure, a vanadium dioxide-based thermochromic composite material is prepared by using a vanadium dioxide-based thermochromic material and an ultraviolet photochromic material. And forming a composite film by using an organic polymer uniform dispersion system containing vanadium dioxide solid-phase nano particles and an organic polymer containing an ultraviolet photochromic material, wherein the color of the composite film can be adjusted to red, blue and purple from intrinsic yellow color development.
In the invention, the vanadium dioxide-based thermochromic film can be developed from yellow to red, blue and purple and can be adjusted by mainly changing the absorption peak of the ultraviolet photochromic material. The mixture ratio of the two is changed to realize the shade adjustment of the color so as to meet different requirements of consumers on the color of the film. The solar energy regulation rate of the vanadium dioxide-based thermochromic film can be greatly improved, the photochromic layer absorbs ultraviolet rays harmful to the vanadium dioxide-based thermochromic film, and the photochemical stability of the vanadium dioxide-based thermochromic film is enhanced.
In one embodiment of the present invention, the vanadium dioxide-based thermochromic composite film is an organic polymer composite film comprising a vanadium dioxide-based thermochromic material and an ultraviolet photochromic material that absorbs ultraviolet rays and emits blue light, and the thermochromic behavior thereof is reversible at around 40 ℃. The color of the film can be adjusted from an intrinsic yellow coloration to red, blue and violet.
In an alternative embodiment, the mass ratio of the vanadium dioxide-based thermochromic material to the organic polymer can be 1:100 to 1:1, and preferably 1:50 to 1: 3.
In another embodiment of the invention, the organic polymer uniform dispersion system containing vanadium dioxide solid phase nano particles and the organic polymer containing ultraviolet photochromic material form a composite film, and the thermochromism of the composite film is reversibly carried out at the temperature of about 40 ℃. The color of the film can be adjusted from an intrinsic yellow coloration to red, blue and violet.
In the disclosure, regardless of the composite form of the organic polymer composite film formed by the vanadium dioxide-based thermochromic material and the ultraviolet photochromic material, the two materials are directly mixed or the multilayer film is compounded, or the vanadium dioxide-based thermochromic composite material is adopted, the mass ratio of the vanadium dioxide particles to the ultraviolet photochromic material can be preferably 1: 0.1-1: 1, and if the content of the vanadium dioxide-based thermochromic material is low, the energy regulation rate of the obtained composite film in an infrared region is too low, so that the composite film is inconvenient to use; if the content of the ultraviolet photochromic material is low, the color change effect is not obvious, and the effect of color development regulation cannot be achieved, and the preferable ratio is 5: 1-2: 1.
In the present disclosure, the vanadium dioxide particles are in the doped and/or undoped rutile phase (space group P4)2At mm) and/or monoclinic phase (space group P2)1V) vanadium dioxide, and vanadium dioxide particles with or without a coating. Wherein the particle size range of the vanadium dioxide particles can be 10 nm-10 μm, and preferably 20-80 nm.
In an optional embodiment, the thickness of the cured film layer can be 1-200 μm when the vanadium dioxide-based thermochromic material and the ultraviolet photochromic material are directly mixed. When the vanadium dioxide-based thermochromic material and the ultraviolet photochromic material are respectively prepared into films and compounded, the thickness of each film after curing can be 1-100 mu m.
In an alternative embodiment, the ultraviolet photochromic material is a substance that can exhibit a color of red, blue or purple by undergoing a cyclotomic reaction, an alkoxy group transfer reaction or an isomerization reaction under irradiation of ultraviolet light, and is preferably at least one of spiropyrans, spirooxazines, benzospiropyrans, fulgides, azo compounds, diarylethylenes, aniline derivatives, polycyclic quinones and viologens, and is preferably a spiropyrans or spirooxazines ultraviolet photochromic material. The organic polymer material has certain film forming property and certain bonding strength after curing, and is at least one of carbon chain polymer, heterochain polymer and element organic polymer. The ultraviolet photochromic material can be in a liquid state or a solid state and can be dissolved or coordinated into the resin to form transparent liquid.
The vanadium dioxide-based thermochromic composite film disclosed by the invention is low in preparation cost, simple and reliable, and easy to realize large-scale production. The method for preparing the vanadium dioxide-based thermochromic composite film is exemplarily described below.
The vanadium dioxide-based thermochromic composite material is uniformly dispersed in an organic polymer to form stable slurry. And then coating the prepared slurry on the surface of a substrate (such as a light-transmitting object of glass, PET, PMMA polyester and the like), and curing to form an organic polymer composite film capable of absorbing visible light with a specific wavelength under ultraviolet irradiation. Wherein, the slurry also comprises a solvent which can be at least one of toluene, xylene, ethanol and acetone.
Or, the vanadium dioxide-based thermochromic material and the ultraviolet photochromic material are respectively uniformly dispersed in the organic polymer to form the stable slurry 1 and the stable slurry 2. And then coating the prepared slurry 1 on the surface of the substrate, curing the slurry, coating the slurry 2, and performing secondary curing to finally form the organic polymer composite film emitting blue light under ultraviolet irradiation. Wherein, the slurry 1 and the slurry 2 also comprise a solvent, and the solvent can be at least one of toluene, xylene, ethanol and acetone.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below. In the following examples, unless otherwise specified, the particle diameter of the vanadium dioxide particles is 30 to 60 nm; the photosensitive powder for absorbing the ultraviolet light changing blue is OP pink/blue/purple, and YS-316 produced by the company Limited in research chemical engineering of Dongguan can be dissolved in polycrystalline resin to form transparent liquid.
Example 1
Weighing 0.1g of vanadium dioxide particles (with the particle size of 30-60 nm) and ultrasonically dispersing the particles in 2g of ethanol to form 5 wt% of dispersion liquid, then adding 4g of silicone resin into the dispersion liquid, forming uniform slurry through magnetic stirring, coating the uniform slurry on a substrate (such as glass) in a blade coating mode, standing at room temperature for 2 hours until the uniform slurry is cured (or putting the uniform slurry into an oven to heat and accelerate the curing), and obtaining the vanadium dioxide-based thermochromic film which is yellow and has the thickness of 80 mu m.
The preparation method comprises the steps of ball-milling photosensitive powder absorbing ultraviolet light changing blue by using toluene as a solvent to form 3 wt% of dispersion liquid, taking 2g of the dispersion liquid, adding 2.5g of polycrystalline resin and 1g of silicon resin into the dispersion liquid, carrying out magnetic stirring to form uniform slurry, carrying out blade coating on the uniform slurry to obtain a vanadium dioxide-based thermochromic film prepared in advance, and carrying out curing to obtain the effect that the film (the total thickness is 200 mu m) develops color from turning blue under the irradiation of sunlight.
Example 2
Adding vanadium dioxide particles and photosensitive powder in a mass ratio of 2:1 into a ball mill, adding toluene as a solvent and a proper dispersant to obtain a mixed dispersion liquid containing the vanadium dioxide-based thermochromic composite material, wherein the concentrations of the mixed dispersion liquid are 5 wt% and 2.5 wt%, respectively, then taking 2g of the dispersion liquid, adding 4g of silicon resin into the dispersion liquid, forming uniform slurry through magnetic stirring, coating the uniform slurry on a substrate in a blade coating manner, and curing the uniform slurry to obtain the vanadium dioxide-based thermochromic composite film with the thickness of 120 mu m.
Example 3
A vanadium dioxide-based thermochromic film was prepared as in example 1, having a thickness of 80 μm;
and (2) carrying out ball milling on photosensitive powder absorbing ultraviolet light changing blue by using methylbenzene as a solvent to form 3 wt% of dispersion liquid, respectively taking 0.5 g, 1g, 3 g and 4g of dispersion liquid, adding 2.5g of polycrystalline resin and 1g of silicon resin, carrying out magnetic stirring to form uniform slurry, and carrying out blade coating on the uniform slurry to obtain a vanadium dioxide-based thermochromic film (the total thickness is 200 mu m) with adjustable color changing depth.
Example 4
A vanadium dioxide-based thermochromic film was prepared as in example 1, having a thickness of 80 μm;
the method comprises the steps of enabling photosensitive powder capable of absorbing ultraviolet light to be changed into red and purple respectively to be ball-milled by using methylbenzene as a solvent to form 3 wt% of dispersion liquid, taking 2g of the dispersion liquid, adding 2.5g of polycrystalline resin and 1g of silicon resin into the dispersion liquid, carrying out magnetic stirring to form uniform slurry, and carrying out blade coating on the uniform slurry to obtain the effect that the color of a film (the total thickness is 200 mu m) under the irradiation of sunlight is changed from yellow to red and purple.
Table 1 shows the comparison of the transmittance, solar adjustment and adjustment at 1300nm of the composite film prepared in example 1 with the properties of the vanadium dioxide-based thermochromic film not compounded in comparative example 1:
table 2 shows the transmittance, solar energy adjustment rate and adjustment rate at 1300nm of the composite film prepared in example 2:
| sample (I) | Light transmittance Tlum/％ | Solar energy regulation rate delta Tsol | ΔT1300nm |
| Composite film of two mixed materials | 72.6 | 7.4 | 20.0 |
。
FIG. 1 is a graph showing transmission spectra at high and low temperatures of a composite film prepared in example 1 and a vanadium dioxide-based thermochromic film in comparative example 1, from which it can be seen that the transmission spectra in both visible and near infrared regions at low temperatures are substantially similar; under high-temperature illumination, the near-infrared light transmittance of the vanadium dioxide-based thermochromic film is reduced, the change of a visible light region is small, the composite film not only shows the near-infrared adjusting characteristic of the vanadium dioxide-based thermochromic film, but also generates an absorption peak in the visible light region and is positioned in a yellow light region, and the composite film is blue;
FIG. 2 is a photograph of the composite film prepared in example 1 taken before and after solar irradiation, from which it can be seen that the color of the composite film becomes darker after the irradiation than before the irradiation, which indicates that the composite film is sensitive to light and absorbs visible light;
FIG. 3 is a graph showing the transmittance spectra of the composite film prepared in example 2 and the vanadium dioxide-based thermochromic film in comparative example 1, in which it can be seen that the transmittance spectra of the two films substantially coincide with each other at a low temperature, and the mixed film has a relatively weak absorption in the visible light region; the reduction degree of the near-infrared light transmittance of the mixed film at high temperature is smaller than that of the vanadium dioxide-based thermochromic film, which shows that the direct mixing with the ultraviolet photochromic material can reduce the solar energy regulation rate of the vanadium dioxide-based thermochromic material;
FIG. 4 is a transmission spectrum of a vanadium dioxide-based thermochromic film prepared in comparative example 1, in which reference numeral "1" is a test result at a high temperature and reference numeral "2" is a test result at a room temperature, and it can be seen from the graph that the visible light transmission spectra are substantially similar, and strong absorption is observed in a blue region, indicating that the film shows yellow, and the transmittance is decreased with an increase in temperature in a near infrared region, indicating thermochromic properties;
FIG. 5 is a transmission spectrum of the UV photochromic material film prepared in comparative example 2, from which it is known that its transmittance in the UV wavelength band becomes low, indicating absorption of light in this wavelength band, while it has a very high transmittance in the visible light region of 450-700nm, indicating that the film is nearly colorless and transparent before it is discolored.
Comparative example 1
Only a vanadium dioxide-based thermochromic film was prepared on the surface of the substrate with reference to example 1, and exhibited a yellow color and a thickness of 80 μm.
Comparative example 2
Only a film of the ultraviolet photochromic material was prepared at the surface of the substrate with a thickness of 80 μm with reference to example 1.
The above examples are only for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and the non-essential modifications and adaptations of the present invention by those skilled in the art based on the foregoing descriptions are within the scope of the present invention.
Claims (4)
1. The color development adjustable vanadium dioxide-based thermochromic composite film is characterized by comprising an organic polymer film containing a vanadium dioxide-based thermochromic material and an organic polymer film containing an ultraviolet photochromic material, which are sequentially formed on the surface of a substrate;
the ultraviolet photochromic material is a substance which can generate a pericyclic reaction, an alkoxy migration reaction and an isomerization reaction under the irradiation of ultraviolet light to show red, blue and purple colors, and is selected from at least one of spiropyrans, spirooxazines, benzospiropyrans, fulgides, azo compounds, diarylethenes, aniline derivatives, polycyclic quinones and viologens;
the vanadium dioxide-based thermochromic material is vanadium dioxide, and the particle size is 20-80 nm;
the mass ratio of the vanadium dioxide-based thermochromic material to the organic polymer in the organic polymer film containing the vanadium dioxide-based thermochromic material is 1: (1-100);
the mass ratio of the ultraviolet photochromic material to the organic polymer in the organic polymer film containing the ultraviolet photochromic material is 1: (10-1000);
the mass ratio of the vanadium dioxide-based thermochromic material to the ultraviolet photochromic material is 5: 1-1: 1;
the organic polymer used by the organic polymer film is at least one of carbon chain polymer, heterochain polymer and element organic polymer.
2. The vanadium dioxide-based thermochromic composite film according to claim 1, wherein the mass ratio of the vanadium dioxide-based thermochromic material to the organic polymer in the organic polymer film containing the vanadium dioxide-based thermochromic material is 1: (3-50); the mass ratio of the ultraviolet photochromic material to the organic polymer in the organic polymer film containing the ultraviolet photochromic material is 1: (50-200).
3. The vanadium dioxide-based thermochromic composite film according to claim 1, wherein the thickness of the organic polymer film containing the vanadium dioxide-based thermochromic material or the organic polymer film containing the ultraviolet photochromic material is 1 to 100 μm.
4. The vanadium dioxide-based thermochromic composite membrane according to claim 1, wherein the vanadium dioxide-based thermochromic material is rutile-phase vanadium dioxide or/and monoclinic-phase vanadium dioxide.
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| CN113185140A (en) * | 2021-05-11 | 2021-07-30 | 济南大学 | Vanadium dioxide-based thermochromic composite film and preparation method thereof |
| WO2024040429A1 (en) * | 2022-08-23 | 2024-02-29 | 中国科学院深圳先进技术研究院 | Electromagnetic shielding composite material with temperature response characteristic, and preparation method therefor and application thereof |
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