CN112225939A - Humidity response type composite inverse opal photonic crystal film and preparation method thereof - Google Patents
Humidity response type composite inverse opal photonic crystal film and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of photonic crystals, and relates to construction and a preparation method of a photonic crystal film with invisible encryption information, which has stable mechanical properties and response color change performance to polar and non-polar solvents, in particular to a humidity response type composite inverse opal photonic crystal film and a preparation method thereof. The method uses an opal photonic crystal structure as a template, obtains a polymer inverse protein photonic crystal structure by filling high-stability polymer precursor liquid, then permeates a hydrophilic agent into an inverse protein pore channel, obtains a metallic luster structure color film with invisible encryption information after free radical polymerization, and can realize local structure color response color change decryption under the stimulation of solvents with different polarities. The method has the advantages of simple operation, strong stability and low cost; decryption of information can be achieved in solvents of different polarities. The film prepared by the invention can be widely applied to the fields of chemical sensing, anti-counterfeit labels and the like.
Description
Technical Field
The invention belongs to the technical field of photonic crystals, and relates to construction and a preparation method of a photonic crystal film with invisible encryption information, which has stable mechanical properties and response color change performance to polar and non-polar solvents, in particular to a humidity response type composite inverse opal photonic crystal film and a preparation method thereof.
Background
Photonic crystals are widely studied because of their unique photonic band gap characteristics. When the frequency of the incident light is matched to the photonic band gap, light cannot penetrate the photonic crystal structure, thereby exhibiting structural color. Since the mechanism for producing such a color is due to the microstructure itself, the structural color does not fade as compared to conventional pigment coloration, and different colors are observed when the same photonic crystal material is viewed from different angles.
Compared with the conventional photonic crystal with the photonic band gap position being fixed and unchanged, the photonic band gap of the stimulus-type response photonic crystal can be changed by changing the lattice parameter of the photonic crystal structure through external stimulus, and the direct expression form is the change of the structural color.
Researchers at home and abroad carry out a great deal of research on the stimulus response type photonic crystal and obtain certain achievements. Zhang Shufen et al (see Qi Y, Chu L, Niu W, et al.. Advanced Functional Materials,2019,29(40),1903743.) in SiO2The opal photonic crystal is used as a template, polyethylene glycol (glycol) diacrylate and acrylic acid are filled in gaps of the photonic crystal, the template is removed after ultraviolet polymerization to obtain an inverse opal structure responding to an ethanol solvent, decryption and hiding of encrypted information can be realized through impregnation and volatilization of the solvent, however, a photonic crystal film obtained by the method has the problems of poor mechanical performance and easy abrasion. Koen Clays et al (Zhong K, Li J, Liu L, et al. Advanced Materials,2018,30(25),1707246.) use plasma techniques on SiO2Pattern hydrophilization treatment is carried out on the surface of the opal photonic crystal, and different hidden patterns are displayed by controlling the humidity of air flow. However, this type of opal photonic crystal structure must be attached to a substrate to be formed, and further expansion of applications is difficult. Therefore, the above method has problems that affect the application of the responsive photonic crystal material. At present, no report is found on the research of preparing the self-supporting stimulus response photonic crystal film with high mechanical property stability. The problem that the prepared response color-changing photonic crystal structure is unstable in mechanical property or cannot be self-supported exists at present, and practical application of the response color-changing photonic crystal structure is limited.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a self-supporting stimulus-responsive humidity-responsive composite inverse opal photonic crystal film with stable mechanical properties and a preparation method thereof.
The technical scheme of the invention is as follows:
a humidity response type composite inverse opal photonic crystal film comprises a polymer substrate and a hydrophilic agent which are combined into a whole through physical action; the polymer base material is one or the mixture of more than two of polyfluorovinyl, polyvinyl, polypropylene, polyethersulfone, acrylonitrile-butadiene-styrene copolymer, polyurethane, polyaniline, polyether ether ketone, polyarylsulfone and polyphenylene sulfide with stable mechanical property; the hydrophilic agent comprises a monomer, a cross-linking agent and an initiator, wherein: the monomer is acrylamide (N-hydroxyethyl acrylamide, N-isopropyl acrylamide, etc.), acrylic acid (acrylic acid, methacrylic acid, etc.), acrylate (ethoxylated trimethylolpropane triacrylate, polyethylene glycol acrylate, hydroxyethyl methacrylate, butyl acrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, isoborneol acrylate, ethoxylated 1.6 hexanediol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, propoxylated trihydroxy acrylate, diethylene glycol diacrylate phthalate, triethylene glycol diacrylate, 1,4 butanediol diacrylate, polyethylene glycol diacrylate, ethoxylated ethyl acrylate, etc.), One or more of ethylene glycol (polyethylene glycol, etc.) and vinyl alcohol (polyvinyl alcohol, etc.); the cross-linking agent is one or more of polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, N' -dimethylene bis (acrylamide), tetramethylethylenediamine, dihydroxyethylene and glutaraldehyde; the initiator is one or more of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-dimethoxy-2-phenylacetophenone, azobis (4-cyanovaleric acid), ammonium persulfate, potassium persulfate and azobisisobutyronitrile.
A preparation method of a humidity response type composite inverse opal photonic crystal film comprises the steps of selecting a polymer with stable mechanical property to prepare a polymer precursor liquid, filling the polymer precursor liquid into a gap of an opal photonic crystal template under the action of capillary force, volatilizing a solvent to obtain a polymer inverse opal structure, and then selecting a hydrophilic agent to chelate with the polymer inverse opal, so that hydrophilic treatment is carried out on the polymer inverse opal structure, the hydrophilic property of a hydrophilic agent and the hydrophilic property of a polymer inverse opal chelate part are improved, the hydrophilic property of other parts is unchanged, so that invisible encryption information is formed in the film, and structural color response to solvents with different polarities is realized.
The method comprises the following specific steps:
step (1), selecting monodisperse microspheres with uniform particle size as construction units of opal photonic crystal template
The monodisperse microsphere is one or more of polystyrene microsphere, polymethyl methacrylate microsphere, polysulfide resin microsphere, silicon dioxide microsphere, titanium dioxide microsphere, cadmium sulfide microsphere, zinc oxide microsphere, zinc sulfide microsphere, copper sulfide microsphere and cuprous oxide microsphere.
Step (2) preparing a construction unit dispersion liquid of an opal photonic crystal template
Dispersing microspheres of the construction unit of the opal photonic crystal template selected in the step (1) into a solvent to obtain a construction unit dispersion liquid, wherein the concentration of the microspheres in the solvent is 1-20 wt%, and the solvent is one or more of water, methanol, ethanol, propanol, butanol, ethylene glycol, dimethylformamide and dimethyl sulfoxide.
Step (3), construction of opal photonic crystal template
Assembling the construction unit dispersion liquid obtained in the step (2) on a substrate (such as glass) at the temperature of 20-100 ℃ by adopting a gravity settling, pulling or spin coating method to obtain the opal photonic crystal template.
Step (4), selection and preparation of polymer precursor liquid
Dissolving a polymer or a mixture of the polymer and carbon black in an organic solvent, carrying out ultrasonic treatment until the polymer is uniformly dispersed, and then standing and defoaming to obtain a polymer precursor liquid, wherein the concentration of the polymer is 0.5-20 wt%, and the concentration of the carbon black is 0-10 wt%.
The organic solvent is one or more of dimethyl formamide, dimethyl sulfoxide or N-methyl pyrrolidone.
The polymer is organic solvent with stable mechanical property, poor hydrophilic property and easy dissolution at high boiling point, and can be selected from one or more of polyvinyl, polyvinyl fluoride, polypropylene, polyether sulfone, acrylonitrile-butadiene-styrene copolymer, polyurethane, polyaniline, polyether ether ketone, polyarylsulfone and polyphenylene sulfide.
Step (5), preparation of polymer inverse opal photonic crystal film
Drying the opal photonic crystal template obtained in the step (3) at the temperature of 20-150 ℃, and uniformly spreading the polymer precursor liquid obtained in the step (4) on the surface of the opal photonic crystal template, wherein the coverage of the polymer precursor liquid is 0.02-0.15mL/cm-2(ii) a Standing until the polymer precursor solution is completely filled in the photonic crystal template, and drying at 60-150 ℃ for 2-8h to obtain a polymer composite photonic crystal film; and then removing the microspheres in the opal photonic crystal template through calcination or acid corrosion to obtain the polymer inverse opal photonic crystal film.
Step (6), selection of hydrophilic agent pre-polymerization liquid
The hydrophilic agent has excellent hydrophilic performance, and the pre-polymerization solution of the hydrophilic agent comprises a monomer, a cross-linking agent, an initiator and a solvent, wherein the concentrations of the monomer, the cross-linking agent and the initiator are respectively 1-98.9 wt%, 1-10 wt% and 0.1-1 wt%.
The monomer is acrylamide (N-hydroxyethyl acrylamide, N-isopropyl acrylamide, etc.), acrylic acid (acrylic acid, methacrylic acid, etc.), acrylate (ethoxylated trimethylolpropane triacrylate, polyethylene glycol acrylate, hydroxyethyl methacrylate, butyl acrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, isoborneol acrylate, ethoxylated 1,6 hexanediol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, propoxylated trihydroxy acrylate, diethylene glycol diacrylate phthalate, triethylene glycol diacrylate, 1,4 butanediol diacrylate, polyethylene glycol diacrylate, ethoxylated ethyl acrylate, etc.), One or more of ethylene glycol (polyethylene glycol, etc.) and vinyl alcohol (polyvinyl alcohol, etc.);
the cross-linking agent is one or more of polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, N' -dimethylene bis (acrylamide), tetramethylethylenediamine, dihydroxyethylene and glutaraldehyde;
the initiator is one or more than two of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-dimethoxy-2-phenylacetophenone, azobis (4-cyanovaleric acid), ammonium persulfate, potassium persulfate and azobisisobutyronitrile;
the solvent is one or more of water, methanol, ethanol, propanol and butanol.
Step (7), preparation of response type composite inverse opal photonic crystal film
In order to prepare the humidity-responsive composite inverse opal photonic crystal structure containing encrypted information, masks with different encrypted information are flatly placed on the surface of the polymer inverse opal photonic crystal film prepared in the step (5), the hydrophilic agent pre-polymerization liquid selected in the step (6) is injected into a gap between the mask and the polymer inverse opal photonic crystal film, the hydrophilic agent pre-polymerization liquid permeates into the film through capillary force, and monomers in the hydrophilic agent pre-polymerization liquid are polymerized in an ultraviolet light, thermal polymerization or laser-assisted polymerization mode so as to be chelated with the surface of the polymer inverse opal photonic crystal, so that the humidity-responsive composite inverse opal photonic crystal film is obtained.
Under normal environment, the polymer inverse opal photonic crystal part chelated with the hydrophilic agent has the same structural color with the unchelated part. After the polymer inverse opal photonic crystal is contacted with a polar solvent such as water, due to the fact that the hydrophilicity of the polymer inverse opal photonic crystal position chelated with a hydrophilic agent is enhanced, water molecules easily substitute for air to permeate into gaps of an inverse opal structure, the average refractive index of the inverse opal photonic crystal is improved, according to the Bragg reflection law, the structural color is red-shifted, and after water is volatilized, the structural color is recovered; the hydrophilic performance of the part which is not chelated with the hydrophilic agent is unchanged, water molecules cannot enter the gaps of the inverse opal structure, and the structural color is unchanged, so that the decryption of the encrypted information is realized. The color change range of the invisible encryption information of the prepared response type composite inverse opal photonic crystal film is 200-2000 nm.
The invention has the beneficial effects that:
the invention realizes the encryption of the invisible information by compounding a proper amount of hydrophilic agent and a polymer inverse opal photonic crystal film; the encrypted hydrophilic information is displayed and decrypted under the water-impregnated condition, the structural color of the substrate which is not modified by hydrophilization is not changed, and the pattern is hidden after the water is volatilized; the structure color of the encrypted hydrophilic information is unchanged under the condition of non-polar solvent infiltration, the structure color of the hydrophobic substrate is red-shifted, and the information is hidden after the solvent is volatilized, so that the information encryption and decryption are realized. In the method, the hydrophilic agent is introduced into the hydrophobic mechanical stability polymer photonic crystal, which is innovative and meaningful, and the encrypted information can be decrypted under the soaking condition of different polar solvents. The hydrophilic/hydrophobic response polymer inverse opal photonic crystal film can be widely applied to the fields of label anti-counterfeiting, chemical sensing and the like.
Drawings
FIG. 1 is a scanning electron microscope image of a polyacrylic acid/polyether sulfone responsive composite inverse opal photonic crystal film obtained by using a transparent pattern mask and a photonic crystal prepared from silica microspheres with the particle size of 200nm as a template.
FIG. 2 is a scanning electron microscope image of a polyacrylic acid/polyether sulfone responsive composite inverse opal photonic crystal film obtained by masking a transparent pattern with a photonic crystal prepared from silica microspheres with a particle size of 330nm as a template.
FIG. 3 is a scanning electron microscope image of a polyacrylic acid/polyethersulfone responsive composite inverse opal photonic crystal film obtained by using a photonic crystal prepared from silica microspheres with a particle size of 330nm as a template and using a local light-transmitting pattern on an opaque mask.
Detailed Description
The invention is further illustrated by the following figures and examples.
Example 1 preparation and encrypted information decryption of a polyethersulfone-based humidity-responsive composite inverse opal photonic crystal film with structural colors in a blue wavelength region:
firstly, the 200nm monodisperse SiO is prepared by stober synthesis method2And dispersing the microspheres into ethanol with the concentration of 20 wt%, and assembling the construction unit on the surface of the glass sheet substrate at 70 ℃ by a thermogravimetric self-assembly method after complete dispersion, wherein the assembly thickness is controlled by adjusting the number of the lifting layers.
Preparation of polymer precursor solution: dissolving polyether sulfone and carbon black in N-methyl pyrrolidone at concentrations of 2 wt% and 0.1 wt%, performing ultrasonic treatment until the polyether sulfone and the carbon black are uniformly dispersed, and standing for defoaming.
Preparation of polymer inverse opal crystal film: placing opal photonic crystal template at 80 deg.C for 1h, and collecting appropriate amount of polymer precursor solution (0.02 mL/cm)-2) Uniformly spreading on the surface of a template, standing for 2h, and drying at 120 ℃ for 4h to obtain SiO2And (3) compounding the polymer with the photonic crystal film, and removing the template microspheres through acid corrosion to finally obtain the polyether sulfone inverse opal photonic crystal film with different structural colors.
Preparation of responsive inverse opal photonic crystal: firstly, preparing polyacrylic acid pre-polymerization liquid, wherein a solvent is a mixed solvent of deionized water and normal propyl alcohol in a volume ratio of 1: 1; the monomer is acrylic acid with the concentration of 1 wt%; the cross-linking agent is N, N' -dimethylenebis (acrylamide) with the concentration of 10 wt%; the initiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone with the concentration of 1 wt%. And flatly placing the transparent mask on the surface of the polymer inverse opal photonic crystal film, injecting a proper amount of polyacrylic acid pre-polymerization liquid (4uL) into a gap between the mask and the photonic crystal film, permeating the polyacrylic acid precursor solution into the film through capillary force, and obtaining the polyacrylic acid/polyether sulfone response type composite inverse opal photonic crystal film in an ultraviolet polymerization mode, wherein the polymerization time is 60 s.
The responsive composite inverse opal photonic crystal thin film obtained in this example is shown in fig. 1. Respectively contacting a polyacrylic acid/polyether sulfone composite photonic crystal membrane with water and absolute ethyl alcohol, wherein after the polyacrylic acid/polyether sulfone composite photonic crystal membrane is contacted with the water, the hydrophilic property of a polyacrylic acid and polyether sulfone chelating part is enhanced, water molecules penetrate into gaps, the average refractive index of an inverse opal photonic crystal structure is improved, the structural color is subjected to red shift, and the structural color is recovered after the water is volatilized; the hydrophilicity of the polyether sulfone inverse opal structure at the position which is not chelated with polyacrylic acid is unchanged, water molecules cannot enter gaps, and the structural color is kept unchanged. After the polyacrylic acid and the polyether sulfone are contacted with ethanol, the hydrophilic property of the chelating part of the polyacrylic acid and the polyether sulfone is enhanced, so that ethanol molecules are not easy to permeate into gaps, and the structural color is not changed; the polyether sulfone inverse opal structure at the position not chelated with polyacrylic acid has weaker hydrophilicity, ethanol molecules easily permeate into gaps, the average refractive index of the inverse opal photonic crystal structure is improved, the structural color is red-shifted, and the structural color is recovered after water is volatilized. The decryption and encryption of the information are realized through the above process.
Example 2 preparation and encrypted information decryption of a polyethersulfone-based humidity-responsive composite inverse opal photonic crystal film with structural colors in a red wavelength region:
firstly, preparing 330nm monodisperse SiO by stober synthesis method2Dispersing the microspheres into ethanol with the concentration of 3 wt%, and assembling the construction unit on the surface of the glass sheet substrate at 20-35 ℃ by a pulling self-assembly method after the microspheres are completely dispersed.
Preparation of polymer precursor solution: dissolving the selected polymer and carbon black in N-methyl pyrrolidone with the concentration of 20 wt% and 0.1 wt% respectively, performing ultrasonic treatment until the polymer and the carbon black are uniformly dispersed, standing and defoaming,
preparation of polymer inverse opal crystal film: placing opal photonic crystal template at 150 deg.C for 1h, and collecting appropriate amount of polymer precursor solution (0.1 mL/cm)-2) Uniformly spreading on the surface of a template, standing for 2h, and drying at 150 ℃ for 2h to obtain SiO2And (3) compounding the polymer with the photonic crystal film, and removing the template microspheres through acid corrosion to finally obtain the polymer inverse opal photonic crystal film with different structural colors.
Preparation of responsive inverse opal photonic crystal: firstly, preparing a polyacrylic acid precursor solution, wherein a solvent is a mixed solvent of deionized water and n-propanol with a volume ratio of 1: 1; the monomer is acrylic acid with the concentration of 50 wt%; the cross-linking agent is N, N' -dimethylenebis (acrylamide) with the concentration of 1 wt%; the initiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone with a concentration of 0.4 wt%. And flatly placing the transparent mask on the surface of the polymer inverse opal photonic crystal film, taking a proper amount of polyacrylic acid precursor solution (4uL) to inject into a gap between the mask and the photonic crystal film, permeating the polyacrylic acid precursor solution into the film through capillary force, and obtaining the polyacrylic acid/polymer response type composite inverse opal photonic crystal film in an ultraviolet polymerization mode, wherein the polymerization time is 30 s.
The responsive composite inverse opal photonic crystal thin film obtained in this example is shown in fig. 2. Respectively contacting a polyacrylic acid/polyether sulfone composite photonic crystal membrane with water and absolute ethyl alcohol, wherein after the polyacrylic acid/polyether sulfone composite photonic crystal membrane is contacted with the water, the hydrophilic property of a polyacrylic acid and polyether sulfone chelating part is enhanced, water molecules penetrate into gaps, the average refractive index of an inverse opal photonic crystal structure is improved, the structural color is subjected to red shift, and the structural color is recovered after the water is volatilized; the hydrophilicity of the polyether sulfone inverse opal structure at the position which is not chelated with polyacrylic acid is unchanged, water molecules cannot enter gaps, and the structural color is kept unchanged. After the polyacrylic acid and the polyether sulfone are contacted with ethanol, the hydrophilic property of the chelating part of the polyacrylic acid and the polyether sulfone is enhanced, so that ethanol molecules are not easy to permeate into gaps, and the structural color is not changed; the polyether sulfone inverse opal structure at the position not chelated with polyacrylic acid has weaker hydrophilicity, ethanol molecules easily permeate into gaps, the average refractive index of the inverse opal photonic crystal structure is improved, the structural color is red-shifted, and the structural color is recovered after water is volatilized. The decryption and encryption of the information are realized through the above process.
Example 3 preparation and encrypted information decryption of a polyethersulfone-based humidity-responsive composite inverse opal photonic crystal film with a structural color in a red wavelength region:
firstly, preparing 330nm monodisperse SiO by stober synthesis method2Dispersing the microspheres in 8 wt% ethanol, and dispersing completelyAnd assembling the construction unit on the surface of the glass sheet substrate at 20-35 ℃ by using a dip-coating and dip-coating instrument.
Preparation of polymer precursor solution: dissolving the selected polymer and carbon black in N-methyl pyrrolidone with the concentration of 10 wt% and 0.1 wt% respectively, performing ultrasonic treatment until the polymer and the carbon black are uniformly dispersed, standing and defoaming,
preparation of polymer inverse opal crystal film: placing opal photonic crystal template at 20 deg.C for 5 hr, and collecting appropriate amount of polymer precursor solution (0.15 mL/cm)-2) Uniformly spreading on the surface of a template, standing for 2h, and drying at 60 ℃ for 8h to obtain SiO2And (3) compounding the polymer with the photonic crystal film, and removing the template microspheres through acid corrosion to finally obtain the polymer inverse opal photonic crystal film with different structural colors.
Preparation of responsive inverse opal photonic crystal: firstly, preparing a polyacrylic acid precursor solution, wherein a solvent is a mixed solvent of deionized water and n-propanol with a volume ratio of 1: 1; the monomer is acrylic acid with the concentration of 15 wt%; the cross-linking agent is N, N' -dimethylenebis (acrylamide) with the concentration of 1 wt%; the initiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone with a concentration of 0.4 wt%. Carving an opaque mask to obtain a hollow pattern, flatly placing the surface of a glass sheet on a polymer inverse opal photonic crystal film, injecting a proper amount of polyacrylic acid precursor solution (4uL) into a gap between the glass sheet and the photonic crystal film, permeating the polyacrylic acid precursor solution into the film through capillary force, and obtaining the polyacrylic acid/polymer response type composite inverse opal photonic crystal film in an ultraviolet polymerization mode, wherein the polymerization time is 50 s.
The responsive composite inverse opal photonic crystal film obtained in this example is shown in fig. 3. Respectively contacting a polyacrylic acid/polyether sulfone composite photonic crystal membrane with water and absolute ethyl alcohol, wherein after the polyacrylic acid/polyether sulfone composite photonic crystal membrane is contacted with the water, the hydrophilic property of a polyacrylic acid and polyether sulfone chelating part is enhanced, water molecules penetrate into gaps, the average refractive index of an inverse opal photonic crystal structure is improved, the structural color is subjected to red shift, and the structural color is recovered after the water is volatilized; the hydrophilicity of the polyether sulfone inverse opal structure at the position which is not chelated with polyacrylic acid is unchanged, water molecules cannot enter gaps, and the structural color is kept unchanged. After the polyacrylic acid and the polyether sulfone are contacted with ethanol, the hydrophilic property of the chelating part of the polyacrylic acid and the polyether sulfone is enhanced, so that ethanol molecules are not easy to permeate into gaps, and the structural color is not changed; the polyether sulfone inverse opal structure at the position not chelated with polyacrylic acid has weaker hydrophilicity, ethanol molecules easily permeate into gaps, the average refractive index of the inverse opal photonic crystal structure is improved, the structural color is red-shifted, and the structural color is recovered after water is volatilized. The decryption and encryption of the information are realized through the above process.
Example 4 preparation and encrypted information decryption of polyvinylidene fluoride-based humidity-responsive composite inverse opal photonic crystal film with structural color in green wavelength region:
firstly, the 245nm monodisperse SiO is prepared by adopting a stober synthesis method2And dispersing the microspheres into ethanol, wherein the concentration is 8 wt%, assembling the construction units on the bottom surface of the glass sheet substrate by a pulling method after the microspheres are completely dispersed, and controlling the assembling thickness by adjusting the number of pulling layers.
Preparation of polymer precursor solution: dissolving polyvinylidene fluoride and carbon black in N-methyl pyrrolidone with the concentrations of 10 wt% and 0.1 wt% respectively, performing ultrasonic treatment until the dispersion is uniform, and standing for defoaming.
Preparation of polymer inverse opal crystal film: placing opal photonic crystal template at 80 deg.C for 1h, and collecting appropriate amount of polymer precursor solution (0.02 mL/cm)-2) Uniformly spreading on the surface of a template, standing for 2h, and drying at 120 ℃ for 4h to obtain SiO2And (3) compounding the polymer with the photonic crystal film, and removing the template microspheres through acid corrosion to finally obtain the polyvinylidene fluoride inverse opal photonic crystal films with different structural colors.
Preparation of responsive inverse opal photonic crystal: firstly, preparing polyacrylic acid pre-polymerization liquid, wherein acrylic acid is selected as a monomer, and the concentration is 98.9 wt%; the cross-linking agent is N, N' -dimethylenebis (acrylamide) with the concentration of 1 wt%; the initiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone with a concentration of 0.1 wt%. Flatly placing a transparent mask on the surface of the polymer inverse opal photonic crystal film, injecting a proper amount of polyacrylic acid pre-polymerized liquid (4uL) into a gap between the mask and the photonic crystal film, permeating a polyacrylic acid precursor solution into the film through capillary force, and obtaining the polyacrylic acid/polyvinylidene fluoride response type composite inverse opal photonic crystal film in an ultraviolet polymerization mode, wherein the polymerization time is 35 s.
Respectively contacting the polyacrylic acid/polyvinylidene fluoride composite photonic crystal film with water and absolute ethyl alcohol, wherein after the polyacrylic acid/polyvinylidene fluoride composite photonic crystal film is contacted with the water, the hydrophilic property of a chelating part of the polyacrylic acid and the polyvinylidene fluoride is enhanced, water molecules permeate into gaps, the average refractive index of the inverse opal photonic crystal structure is improved, the structural color is red-shifted, and after the water is volatilized, the structural color is recovered; the hydrophilicity of the polyvinylidene fluoride inverse opal structure at the position which is not chelated with polyacrylic acid is unchanged, water molecules cannot enter the gap, and the structural color is kept unchanged. After the polyacrylic acid is contacted with the ethanol, the hydrophilic property of the chelating part of the polyacrylic acid and the polyvinylidene fluoride is enhanced, so that ethanol molecules are not easy to permeate into gaps, and the structural color is not changed; the polyvinylidene fluoride inverse opal structure at the position not chelated with polyacrylic acid has weaker hydrophilicity, ethanol molecules easily permeate into gaps, the average refractive index of the inverse opal photonic crystal structure is improved, the structural color is red-shifted, and after water is volatilized, the structural color is recovered. The decryption and encryption of the information are realized through the above process.
Claims (3)
1. The humidity-responsive composite inverse opal photonic crystal film is characterized by comprising a polymer base material and a hydrophilic agent which are combined into a whole through physical action; the polymer base material is one or more of polyfluorovinyl, polyvinyl, polypropylene, polyether sulfone, acrylonitrile-butadiene-styrene copolymer, polyurethane, polyaniline, polyether ether ketone, polyarylsulfone and polyphenylene sulfide; the hydrophilic agent comprises a monomer, a cross-linking agent and an initiator, wherein: the monomer is one or a mixture of more than two of acrylamide, acrylic acid, acrylate, ethylene glycol and vinyl alcohol; the cross-linking agent is one or more of polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, N' -dimethylene bis (acrylamide), tetramethylethylenediamine, dihydroxyethylene and glutaraldehyde; the initiator is one or more of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-dimethoxy-2-phenylacetophenone, azobis (4-cyanovaleric acid), ammonium persulfate, potassium persulfate and azobisisobutyronitrile.
2. A preparation method of a humidity response type composite inverse opal photonic crystal film is characterized by comprising the following specific steps:
step (1), selecting monodisperse microspheres with uniform particle size as construction units of opal photonic crystal template
The monodisperse microspheres are one or more of polystyrene microspheres, polymethyl methacrylate-based microspheres, polysulfide resin microspheres, silicon dioxide microspheres, titanium dioxide microspheres, cadmium sulfide microspheres, zinc oxide microspheres, zinc sulfide microspheres, copper sulfide microspheres and cuprous oxide microspheres;
step (2) preparing a construction unit dispersion liquid of an opal photonic crystal template
Dispersing microspheres of the construction unit of the opal photonic crystal template selected in the step (1) into a solvent to obtain a construction unit dispersion liquid, wherein the concentration of the microspheres in the solvent is 1-20 wt%, and the solvent is one or more of water, methanol, ethanol, propanol, butanol, ethylene glycol, dimethylformamide and dimethyl sulfoxide;
step (3), construction of opal photonic crystal template
Assembling the construction unit dispersion liquid obtained in the step (2) on a substrate by adopting a gravity settling, pulling or spin coating method at the temperature of 20-100 ℃ to obtain an opal photonic crystal template;
step (4), selection and preparation of polymer precursor liquid
Dissolving a polymer or a mixture of the polymer and carbon black in an organic solvent, carrying out ultrasonic treatment until the polymer is uniformly dispersed, and then standing and defoaming to obtain a polymer precursor liquid, wherein the concentration of the polymer is 0.5-20 wt%, and the concentration of the carbon black is 0-10 wt%;
the organic solvent is one or more of dimethyl formamide, dimethyl sulfoxide or N-methyl pyrrolidone;
the polymer is one or more than two of polyvinyl, polyvinyl fluoride, polypropylene, polyether sulfone, acrylonitrile-butadiene-styrene copolymer, polyurethane, polyaniline, polyether ether ketone, polyarylsulfone and polyphenylene sulfide;
step (5), preparation of polymer inverse opal photonic crystal film
Drying the opal photonic crystal template obtained in the step (3) at the temperature of 20-150 ℃, and uniformly spreading the polymer precursor liquid obtained in the step (4) on the surface of the opal photonic crystal template, wherein the coverage of the polymer precursor liquid is 0.02-0.15mL/cm-2(ii) a Standing until the polymer precursor solution is completely filled in the photonic crystal template, and drying at 60-150 ℃ for 2-8h to obtain a polymer composite photonic crystal film; then removing the microspheres in the opal photonic crystal template through calcination or acid corrosion to obtain a polymer inverse opal photonic crystal film;
step (6), selection of hydrophilic agent pre-polymerization liquid
The hydrophilic agent comprises a monomer, a cross-linking agent, an initiator and a solvent, wherein the concentrations of the monomer, the cross-linking agent and the initiator are respectively 1-98.9 wt%, 1-10 wt% and 0.1-1 wt%;
the monomer is one or a mixture of more than two of acrylamide, acrylic acid, acrylate, ethylene glycol and vinyl alcohol;
the cross-linking agent is one or more of polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, N' -dimethylene bis (acrylamide), tetramethylethylenediamine, dihydroxyethylene and glutaraldehyde;
the initiator is one or more than two of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-dimethoxy-2-phenylacetophenone, azobis (4-cyanovaleric acid), ammonium persulfate, potassium persulfate and azobisisobutyronitrile;
the solvent is one or more of water, methanol, ethanol, propanol and butanol;
step (7), preparation of response type composite inverse opal photonic crystal film
Flatly placing masks with different encryption information on the surface of the polymer inverse opal photonic crystal film prepared in the step (5), injecting the hydrophilic agent pre-polymerization liquid selected in the step (6) into a gap between the masks and the polymer inverse opal photonic crystal film, enabling the hydrophilic agent pre-polymerization liquid to permeate into the film through capillary force, and polymerizing monomers in the hydrophilic agent pre-polymerization liquid in a mode of ultraviolet light, thermal polymerization or laser-assisted polymerization so as to chelate the surface of the polymer inverse opal photonic crystal, thereby obtaining the humidity-responsive composite inverse opal photonic crystal film.
3. The method for preparing a humidity-responsive composite inverse opal photonic crystal film according to claim 2, wherein in the step (6),
the acrylamide is N-hydroxyethyl acrylamide, acrylamide or N-isopropyl acrylamide;
the acrylic acid is acrylic acid or methacrylic acid;
the acrylate is ethoxylated trimethylolpropane triacrylate, polyethylene glycol acrylate, hydroxyethyl methacrylate, butyl acrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, isobornyl acrylate, ethoxylated 1,6 hexanediol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, propoxylated trihydroxy acrylate, diethylene glycol diacrylate phthalate, triethylene glycol diacrylate, 1,4 butanediol diacrylate, polyethylene glycol diacrylate or ethoxylated ethyl acrylate
The ethylene glycol is polyethylene glycol;
the vinyl alcohol is polyvinyl alcohol.
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