CN114940769B - Angle-dependence-free electric response film based on structural color and preparation method and application thereof - Google Patents
Angle-dependence-free electric response film based on structural color and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a structural color-based angle-independent electric response film, a preparation method and application thereof. The angle-independent electric response film based on structural color is of a reverse template structure, and compared with the small ball stacking structure of the existing positive template or the composite structure of the polymer filled with the positive template, the angle-independent electric response film based on structural color has the advantages of larger volume change rate, larger porosity, smaller material transmission resistance, better electric response performance, and suitability for the fields of display, sensing, camouflage and the like.
Description
Technical Field
The invention relates to the technical field of electrochromic materials, in particular to an angle-independent electric response film based on structural color, and a preparation method and application thereof.
Background
Electrochromic materials have the advantages of good controllability, high response speed and the like, and are particularly interesting. However, the traditional electrochromic materials are based on chemical colors, the color change process involves chemical reactions, the response speed is low, the materials are especially faded after a period of time, the color change effect cannot be maintained for a long time, and the types of the materials are very limited.
The photonic crystal can regulate the propagation of light of a specific wavelength, thereby presenting a specific color, i.e., structural color. The structural color has the advantages of permanent color fastness, cleanness, environmental protection and the like, and particularly, the structural color can be flexibly regulated and controlled, so that the structural color material has wide application prospect in the fields of display, decoration, anti-counterfeiting and the like. According to the generation principle of the structural color, the structural color of the photonic crystal mainly has two adjustment ways, one is to adjust the refractive index of a medium forming the photonic crystal, and the adjustment can be realized by changing the material type or the coloring state of the medium; the other is to adjust the periodic structure size of the photonic crystal, which can be achieved by changing the size (e.g., volume expansion or contraction) of any of the media components.
In the aspect of realizing the adjustment of the structural color of the photonic crystal by using electric stimulation, colleges and universities and research institutes at home and abroad have actively explored, such as Chinese patent document CN201510121404.0, but the structural color of the long-range ordered photonic crystal has iridescence effect, namely the color has angle dependence. Although this feature makes the material look colorful and more attractive, it becomes a fatal disadvantage for specific application fields such as display, sensing, camouflage, etc., and thus it is required to eliminate the angular dependence of colors by structural design.
Currently, there are several approaches to achieve no angular dependence of structural color, where the construction of short-range ordered, long-range disordered quasicrystal structures using spray techniques has significant advantages: the preparation efficiency is high, the preparation method is suitable for various rigid or flexible substrates, has lower requirements on equipment and technology, has low cost and is suitable for expansion production. For example, chinese patent document CN202010162215.9 discloses a method for constructing a positive template quasicrystal structure with no or low angle dependence by using spray coating technology. However, when used in electrically responsive materials, such positive templates have important limitations: firstly, the volume change rate is small, so that the color change range is limited; second, the porosity of the material is small, impeding the mass transfer process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and particularly provides a structural color-based angle-independent electric response film with large volume change rate, small substance transmission resistance and good electric response performance, and a preparation method and application thereof, aiming at the limitations of the existing angle-independent structural color material in the aspect of electric response.
In order to solve the technical problems, the invention adopts the following technical scheme.
The preparation method of the angle-independent electric response film based on the structural color comprises the following steps:
spraying a monodisperse colloidal bead dispersion liquid onto a substrate, wherein the monodisperse colloidal bead comprises one or more of a monodisperse polystyrene colloidal bead, a monodisperse polymethyl methacrylate colloidal bead and a monodisperse silica colloidal bead, and the temperature of the substrate is 65-85 ℃ to form a colloidal quasicrystal template; mixing a monomer, a cross-linking agent, an initiator and a solvent, wherein the monomer is an electric response monomer and a comonomer or the monomer is an electric response monomer, and the mass of the cross-linking agent accounts for 0.9-10% of the mass of the monomer, so as to obtain a precursor solution as a growth mother solution; and (3) dropwise adding the growth mother liquor into the colloidal quasi-crystal template, adsorbing the growth mother liquor into gaps among the monodisperse colloidal spheres through capillary action, and removing the template through illumination polymerization or heating polymerization to obtain the structure-color-based angle-free electric response film.
In the preparation method of the structure-color-based angle-independent electric response film, preferably, the mass fraction of the monodisperse colloidal globules in the monodisperse colloidal globule dispersion liquid is 5-15%, and the particle size of the monodisperse colloidal globules is 150-350 nm.
The above-mentioned method for producing a structure-color-based angle-independent electro-responsive film, preferably, the electro-responsive monomer includes one or more of an electrochromic monomer including aniline and/or 3, 4-ethylenedioxythiophene, a ferrocene-containing monomer including vinylferrocene and/or divinylferrocene, and an ionizable monomer including one or more of 1-vinyl, 3-propylimidazole bromide, 1, 6-bis (3-vinylimidazole) n-hexane bromide, and [3- (methacrylamido) propyl ] trimethyl hexafluorophosphate.
The above-mentioned method for preparing the structure-color-based angle-independent electric response film preferably includes one or more of methyl methacrylate, butyl methacrylate and hydroxyethyl methacrylate.
In the above method for preparing the structure-color-based angle-independent electric response film, the cross-linking agent preferably comprises one or more of ethylene glycol dimethacrylate, N' -methylenebisacrylamide and 1, 6-di (3-vinylimidazole) N-hexane bromide.
The above-mentioned method for preparing the structure-color-based angle-independent electric response film preferably comprises one or more of 2, 2-dimethoxy-2-phenylacetophenone, 2-azo diisobutylamidine dihydrochloride, azo diisobutyronitrile and azo diisoheptonitrile.
The above-mentioned method for preparing an angle-independent electric response film based on structural color, preferably, the solvent includes one or more of water, ethanol, chloroform and propylene carbonate.
In the preparation method of the structure color-based angle-independent electric response film, preferably, the mass of the electric response monomer accounts for 1-100% of that of the monomer, the mass of the initiator accounts for 1-3% of that of the monomer, and the concentration of the monomer in the precursor solution is 0.4-5 g/mL. When the monomers are electrically responsive monomers and comonomers, more preferably, the mass of the electrically responsive monomers is from 1% to 55% of the mass of the monomers.
In the preparation method of the structure-color-based angle-independent electric response film, preferably, the illumination polymerization time is 1-4 h, the heating polymerization temperature is 50-80 ℃, and the heating polymerization time is 8-24 h.
In the above preparation method of the structure-color-based angle-independent electro-responsive film, preferably, the template removing operation is as follows: when the template adopts a silicon dioxide template, the silicon dioxide template is treated by 0.5 to 4 weight percent of hydrofluoric acid for 5 to 20 minutes; when the template is an organic template, the organic template is treated with an organic solvent comprising one or more of chloroform, 1, 4-dioxane, N-dimethylformamide and tetrahydrofuran for 18 to 48 hours.
In the above method for producing an angle-independent electro-responsive film based on structural color, preferably, the monodisperse colloidal bead dispersion liquid is obtained by dispersing monodisperse colloidal beads in a solvent, and the solvent includes one or more of water, ethanol and methanol.
As a general technical concept, the invention also provides the structure-color-based angle-independent electric response film prepared by the preparation method of the structure-color-based angle-independent electric response film.
The invention also provides application of the structure color-based angle-independent electric response film in the display field, the sensing field or the camouflage field as a general technical concept.
In the invention, the supporting medium used for measuring the electric response is a non-medium, a phosphate buffer solution, a lithium perchlorate propylene carbonate solution, a lithium hexafluorophosphate ethylene carbonate/dimethyl carbonate mixed solution, an N, N-dimethylformamide/1, 4-dioxane mixed solution and the like, and the bias voltage applied by the electric response performance is measured to be 1V-10V.
In the invention, the substrate can be ITO glass, ITO film, graphite paper, metal plate, etc.
Compared with the prior art, the invention has the advantages that:
(1) According to the preparation method, the electric response polymer and the colloid quasicrystal structure are coupled, the quick and controllable construction of the colloid quasicrystal template without angle dependence is realized through a spraying technology, so that the problem of angle dependence of structure colors is solved, and the space-limited growth of the electric response polymer is realized by controlling the preparation process, the substrate temperature, the dosage of a cross-linking agent and other conditions, so that the electric response film without angle dependence is obtained.
In the process of preparing the structure-color-based angle-free electric response film, key technical conditions are required to be strictly controlled to obtain a relatively ideal quasi-crystal inverse template structure, otherwise, the conditions that the film does not form a hole structure, the template is not removed cleanly, the film is fragile, the structure color is uneven, the angle dependence cannot be eliminated and the like can occur. According to the invention, the film is formed into an expected inverse template structure by controlling the conditions of a preparation flow, the dosage of a cross-linking agent and the like, and the characteristic of no angle dependence is obtained by controlling the conditions of the temperature of a substrate and the like.
(2) The angle-independent electric response film based on structural color is of a reverse template structure, a continuous porous flexible framework is arranged in the reverse template structure, a flexible electric response polymer framework is arranged in a continuous phase, spherical hole structures with uniform sizes are distributed in the reverse template structure, and compared with a small ball stacking structure of a positive template or a composite structure of a polymer filled with the positive template, the angle-independent electric response film based on structural color has the advantages of larger volume change rate, larger porosity, smaller material transmission resistance and easy obtainment of good electric response performance, and is suitable for the fields of display, sensing, camouflage and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a structural color-based, angle-independent, electro-responsive film according to example 1 of the present invention.
FIG. 2 is an electrical response spectrum of the structure color-based angle-independent electrical response film of example 1 of the present invention.
FIG. 3 is a scanning electron micrograph of a structural color-based, angle-independent, electro-responsive film according to example 2 of the present invention.
FIG. 4 is an electrical response spectrum of the structure color-based, angle-independent electrical response film of example 2 of the present invention.
FIG. 5 is a scanning electron micrograph of a structural color-based, angle-independent, electro-responsive film according to example 3 of the present invention.
FIG. 6 is an electrical response spectrum of a structural color-based, angle-independent, electrical response film in example 3 of the present invention.
FIG. 7 is a scanning electron micrograph of the polymer film of comparative example 1.
FIG. 8 is a scanning electron micrograph of the polymer film of comparative example 2.
FIG. 9 is a scanning electron micrograph of the polymer film of comparative example 3.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby. The materials and instruments used in the examples below are all commercially available.
Example 1:
the preparation method of the structure color-based angle-independent electric response film comprises the following steps:
(1) Dispersing 0.4g of monodisperse polystyrene colloid beads with the particle size of 300nm in 5mL of water to obtain polystyrene colloid bead dispersion liquid, spraying the polystyrene colloid bead dispersion liquid onto a substrate at the substrate temperature of 75 ℃ to form a colloid quasicrystal template.
(2) 0.035g of acrylic acid, 2.5g of hydroxyethyl methacrylate, 0.025g of ethylene glycol dimethacrylate and 0.075g of 2, 2-dimethoxy-2-phenylacetophenone were dissolved in 0.6mL of water to form a precursor solution as a growth mother solution, which was then dropped into the above colloidal quasi-crystal template by a microinjector, adsorbed into the gaps between polystyrene beads by capillary action, and irradiated under a 100W UV lamp for 3 hours. After the reaction is finished, the obtained film is soaked in chloroform for 24 hours to remove a colloid quasicrystal template, and the angle-independent electric response film based on structural color is obtained.
As shown in FIG. 1, the structure color-based angle-independent electro-responsive film prepared in the embodiment is of an inverse template structure, the continuous phase is of an electro-responsive polymer, and uniformly-sized holes are distributed, and the structure is convenient for substance transmission and has large volume change under the electrical stimulation.
As shown in fig. 2, when the external pressure is increased from 0V to 4V in the phosphate buffer solution, the reflection spectrum of the film is significantly blue shifted by about 70nm, which indicates that the film can realize a wide range of color gamut change at a lower voltage.
Example 2:
the preparation method of the structure color-based angle-independent electric response film comprises the following steps:
(1) 0.4g of monodisperse polymethyl methacrylate colloid pellets with the particle size of 280nm are dispersed in 5mL of water to obtain polymethyl methacrylate colloid pellet dispersion liquid, the substrate temperature is 70 ℃, and the polymethyl methacrylate colloid pellet dispersion liquid is sprayed on the substrate to form a colloid quasicrystal template.
(2) 0.3g of 1-vinyl, 3-propylimidazole bromide, 0.03g of 1, 6-bis (3-vinylimidazole) n-hexane bromide, and 0.0045g of 2, 2-azobisisobutylaminidine dihydrochloride were dissolved in 0.4mL of water to form a precursor solution as a growth mother liquor, which was then added dropwise to the above colloidal quasi-crystal template with a microinjector, adsorbed into the gaps between polymethyl methacrylate pellets by capillary action, and irradiated under a 100W UV lamp for 2.5 hours. After the reaction is finished, the obtained film is placed in a 1, 4-dioxane for soaking for 36 hours to remove a colloid quasicrystal template, and the structure-color-based angle-free electric response film is obtained, and a scanning electron microscope photo is shown in figure 3. As shown in FIG. 4, when the external pressure is increased from 0V to 6V in the N, N-dimethylformamide/1, 4-dioxane mixed solution, the reflection spectrum of the film is significantly blue shifted around 110 nm.
Example 3:
the preparation method of the structure color-based angle-independent electric response film comprises the following steps:
(1) 0.6g of monodisperse silica gel beads with the particle size of 260nm are dispersed in 5mL of ethanol to obtain ethanol dispersion liquid of the silica gel beads, the temperature of the substrate is 80 ℃, and the ethanol dispersion liquid of the silica gel beads is sprayed on the substrate to form a colloidal quasicrystal template.
(2) 0.49g of [3- (methacrylamido) propyl ] trimethylhexafluorophosphate, 0.45g of hydroxyethyl methacrylate, 0.015g of N, N' -methylenebisacrylamide and 0.0141g of azobisisobutyronitrile were dissolved in 2mL of propylene carbonate to form a precursor solution as a growth mother liquor, which was then added dropwise to the colloidal quasi-crystalline template by a microinjector, adsorbed by capillary action into the interstices between silica pellets and polymerized by heating at 60℃for 12 hours. After the reaction, the obtained film was immersed in 1wt% hydrofluoric acid for 20 minutes to remove the colloidal quasicrystal template, and an angle-independent electroresponse film based on structural color was obtained, and a scanning electron microscope photograph was shown in fig. 5. As shown in FIG. 6, when the external pressure was increased from 0V to 8V in the N, N-dimethylformamide/1, 4-dioxane mixed solution, the reflectance spectrum of the film was significantly blue shifted by about 80 nm.
Comparative example 1:
a method of preparing a polymer film comprising the steps of:
0.4g of monodisperse polystyrene colloid beads with the particle size of 300nm are dispersed in 5mL of water, and a colloid quasicrystal template is prepared by a spraying technology, wherein the substrate temperature is 75 ℃. 0.035g of acrylic acid, 2.5g of hydroxyethyl methacrylate, 0.015g of ethylene glycol dimethacrylate and 0.075g of 2, 2-dimethoxy-2-phenylacetophenone were dissolved in 0.6mL of water to form a precursor solution as a mother solution, and then the growth mother solution was dropped into the above colloidal quasi-crystal template using a microinjector, adsorbed into the gaps between polystyrene beads by capillary action, and irradiated under a 100W UV lamp for 3 hours. After the completion of the reaction, the obtained film was immersed in chloroform for 24 hours, as shown in FIG. 7, without forming a pore structure.
Comparative example 2:
a method of preparing a polymer film comprising the steps of:
0.4g of monodisperse polymethyl methacrylate colloid beads with the particle size of 280nm are dispersed in 5mL of water, and a colloid quasicrystal template is prepared by a spraying technology, wherein the substrate temperature is 70 ℃. 0.3g of 1-vinyl, 3-propylimidazole bromide, 0.03g of 1, 6-bis (3-vinylimidazole) n-hexane bromide, and 0.0045g of 2, 2-azobisisobutylaminidine dihydrochloride were dissolved in 0.4mL of water to form a precursor solution, and then the growth master was dropped into the above colloidal quasi-crystal template using a microinjector, adsorbed into the gaps between polymethyl methacrylate pellets by capillary action, and irradiated under a 100W UV lamp for 2.5 hours. After the reaction was completed, the resulting film was immersed in 1, 4-dioxane for 12 hours, as shown in FIG. 8, to remove the template pellets.
Comparative example 3:
a method of preparing a polymer film comprising the steps of:
0.6g of monodisperse silica gel beads with the particle size of 260nm are dispersed in 5mL of ethanol, and a gel quasicrystal template is prepared by a spraying technology, wherein the substrate temperature is 50 ℃. 0.49g of [3- (methacrylamido) propyl ] trimethylhexafluorophosphate, 0.45g of hydroxyethyl methacrylate, 0.015g of N, N' -methylenebisacrylamide and 0.0141g of azobisisobutyronitrile were dissolved in 2mL of propylene carbonate to form a precursor solution as a growth mother liquor, which was then added dropwise to the colloidal quasi-crystalline template by a microinjector, adsorbed by capillary action into the interstices between silica pellets and polymerized by heating at 60℃for 12 hours. After the reaction was completed, the obtained film was immersed in 1wt% hydrofluoric acid for 20 minutes to remove the colloidal quasicrystal template, as shown in fig. 9, and the obtained film partially formed a long-range order structure, failing to eliminate the angle dependence.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. While the invention has been described in terms of preferred embodiments, it is not intended to be limiting. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or equivalent embodiments using the method and technical solution disclosed above without departing from the spirit and technical solution of the present invention. Therefore, any simple modification, equivalent substitution, equivalent variation and modification of the above embodiments according to the technical substance of the present invention, which do not depart from the technical solution of the present invention, still fall within the scope of the technical solution of the present invention.
Claims (8)
1. The preparation method of the angle-independent electric response film based on the structural color is characterized by comprising the following steps of:
spraying a monodisperse colloidal bead dispersion liquid onto a substrate, wherein the monodisperse colloidal bead comprises one or more of a monodisperse polystyrene colloidal bead, a monodisperse polymethyl methacrylate colloidal bead and a monodisperse silica colloidal bead, and the temperature of the substrate is 65-85 ℃ to form a colloidal quasicrystal template; mixing a monomer, a cross-linking agent, an initiator and a solvent, wherein the monomer is an electric response monomer and a comonomer or the monomer is an electric response monomer, and the mass of the cross-linking agent accounts for 0.9-10% of the mass of the monomer, so as to obtain a precursor solution as a growth mother solution; dropwise adding the growth mother liquor into the colloidal quasi-crystal template, adsorbing the growth mother liquor into gaps among the monodisperse colloidal spheres through capillary action, and removing the template through illumination polymerization or heating polymerization to obtain the structure-color-based angle-free electric response film;
the electroresponse monomer is one or more of electrochromic monomers, ionic liquid monomers and ionizable monomers, wherein the electrochromic monomers comprise aniline and/or 3, 4-ethylenedioxythiophene, the ferrocene-containing monomers comprise vinylferrocene and/or divinylferrocene, the ionic liquid monomers comprise one or more of 1-vinyl, 3-propylimidazole bromine salt, 1, 6-bis (3-vinylimidazole) n-hexane bromine salt and [3- (methacrylamido) propyl ] trimethyl hexafluorophosphate, and the ionizable monomers comprise one or more of acrylic acid, methacrylic acid and 1-vinylimidazole;
the comonomer is one or more of methyl methacrylate, butyl methacrylate and hydroxyethyl methacrylate;
the template removing operation is as follows: when the template adopts a silicon dioxide template, the silicon dioxide template is treated by 0.5 to 4 weight percent of hydrofluoric acid for 5 to 20 minutes; when the template is an organic template, the organic template is treated with an organic solvent comprising one or more of chloroform, 1, 4-dioxane, N-dimethylformamide and tetrahydrofuran for 18 to 48 hours.
2. The method for preparing the structural color-based angle-independent electric response film according to claim 1, wherein the mass fraction of the monodisperse colloidal globules in the monodisperse colloidal globule dispersion liquid is 5% -15%, and the particle size of the monodisperse colloidal globules is 150-350 nm.
3. The method for preparing the structural color-based angle-independent electric response film according to claim 1, wherein the crosslinking agent comprises one or more of ethylene glycol dimethacrylate, N' -methylenebisacrylamide and 1, 6-bis (3-vinylimidazole) N-hexane bromide;
and/or the initiator comprises one or more of 2, 2-dimethoxy-2-phenylacetophenone, 2-azobisisobutylamidine dihydrochloride, azobisisobutyronitrile, and azobisisoheptonitrile;
and/or the solvent comprises one or more of water, ethanol, chloroform, and propylene carbonate.
4. The method for preparing the structure color-based angle-independent electric response film according to claim 1, wherein the mass of the electric response monomer is 1-100% of the mass of the monomer, the mass of the initiator is 1-3% of the mass of the monomer, and the concentration of the monomer in the precursor solution is 0.4-5 g/mL.
5. The method for preparing the structure-color-based angle-independent electric response film according to claim 1, wherein the time of the illumination polymerization is 1-4 h, the temperature of the heating polymerization is 50-80 ℃, and the time of the heating polymerization is 8-24 h.
6. The method for producing a structural color-based angle-independent electric response film according to any one of claims 1 to 5, wherein the monodisperse colloidal globule dispersion is obtained by dispersing monodisperse colloidal globules in a solvent comprising one or more of water, ethanol and methanol.
7. A structural color-based angle-independent electro-responsive film produced by the method for producing a structural color-based angle-independent electro-responsive film as claimed in any one of claims 1 to 6.
8. Use of the structure-color-based, angle-independent, electrically-responsive film of claim 7 in the display field, the sensing field or the camouflage field.
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| CN111548452A (en) * | 2020-04-13 | 2020-08-18 | 剑桥大学南京科技创新中心有限公司 | Preparation method of self-adaptive optical gel based on borate reversible covalent bond |
| CN113461985A (en) * | 2021-07-22 | 2021-10-01 | 燕山大学 | Preparation method of high-brightness high-adhesion low-angle-dependence structural color film |
| CN114621476A (en) * | 2022-04-22 | 2022-06-14 | 广东工业大学 | PH and temperature dual-stimulus responsive structural color film, preparation method thereof and application thereof in optical anti-counterfeiting |
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| CN109201438A (en) * | 2018-07-28 | 2019-01-15 | 华南理工大学 | A kind of colour generation has the recombination photons structural material and preparation method thereof of high brightness low angle dependence |
| CN111548452A (en) * | 2020-04-13 | 2020-08-18 | 剑桥大学南京科技创新中心有限公司 | Preparation method of self-adaptive optical gel based on borate reversible covalent bond |
| CN113461985A (en) * | 2021-07-22 | 2021-10-01 | 燕山大学 | Preparation method of high-brightness high-adhesion low-angle-dependence structural color film |
| CN114621476A (en) * | 2022-04-22 | 2022-06-14 | 广东工业大学 | PH and temperature dual-stimulus responsive structural color film, preparation method thereof and application thereof in optical anti-counterfeiting |
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