CN113782061A - Optical information encryption thin layer with wetting response and preparation method thereof - Google Patents
Optical information encryption thin layer with wetting response and preparation method thereof Download PDFInfo
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- CN113782061A CN113782061A CN202110835191.3A CN202110835191A CN113782061A CN 113782061 A CN113782061 A CN 113782061A CN 202110835191 A CN202110835191 A CN 202110835191A CN 113782061 A CN113782061 A CN 113782061A
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- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
- G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers
Abstract
The invention provides a wetting response optical information encryption thin layer and a preparation method thereof, wherein the method comprises the following steps: preparing an opal structure template, wherein a plurality of gaps are formed on the opal structure template; filling the precursor liquid into the gaps of the opal structure template; calcining the opal structure template filled with the precursor liquid to obtain an inverse opal structure thin layer; and adding an organic hydrophobic agent into the inverse opal structure thin layer for coating treatment to obtain the hydrophobic inverse opal structure thin layer. The IOS-T/H thin layer is simple to prepare and low in cost, information compiling is rapid, the hydrophilic/hydrophobic gradient difference with patterns is formed on the thin layer by using controllable ultraviolet irradiation, the color change response condition in the information display process is simple, the requirement on equipment is low, and the effect of low cost is achieved.
Description
Technical Field
The invention relates to the field of optical information encryption, in particular to a wetting response optical information encryption thin layer and a preparation method thereof.
Background
Structural color plays a crucial role in camouflage, signaling, and recognition, and thus it is widely present in organisms such as insects, birds, and plants. Which is generated when incident light interacts with microscopic or submicroscopic structures on a reflective material. The microstructures have certain periodicity and can be processed into one-dimensional, two-dimensional or three-dimensional ordered structures. Nowadays, structural colors have the advantages of resistance to photochemical degradation and flexibility in color programmability, which has stimulated many fields of application, such as colorants, optics, sensors and anti-counterfeiting technologies. Particularly in the field of optical information encryption, which requires that visually macroscopic color changes can be triggered under certain induction conditions, the intelligent response structural color system caused by the induction conditions is more competitive than the system based on chemical coloring in the aspects of easy synthesis, various types, sensitive reaction and the like.
The optical information encryption system in the prior art generally comprises three basic components of a revealing system, an induction factor and a compiling mode. The disclosed system provides a substrate (e.g., block copolymer, colloidal crystal, amorphous array, or cellulose nanocrystal, etc.) that interferes with light of a selected wavelength in the pre/post decryption state, i.e., provides a substrate that changes color. Induction factors refer to conditions (e.g., liquid, heat, change of viewing angle, or polarized light, etc.) that trigger the revealing system. Finally, compiled form refers to the method of editing (e.g., ink jet printing, ultraviolet, photolithography, or spray coating) or storing information in a material system. In recent years, various color changing mechanisms based on smart response structural colors are applied in optical information encryption systems, and many potential optical information display and encryption models are developed. Among a plurality of color change mechanisms (such as electric response, magnetic response, thermal response, ion response and the like), the wetting response color change mechanism triggered by swelling and permeation is widely used, and a convenient and effective strategy is provided for manufacturing visual color difference of decoding and encoding information.
The existing optical information display and encryption has the problems of complex preparation and higher cost in the aspects of preparation and response conditions, easy information distortion, poorer information accuracy, lower information storage capacity, poor durability and the like in the aspects of optical information display, encryption and durable functions.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a wet-response optical information encryption thin layer and a method for manufacturing the same, and aims to solve the problem that the existing optical information display and encryption manufacturing is complicated and the cost is high.
The invention provides a wetting response optical information encryption thin layer and a preparation method thereof, wherein an opal structure template is obtained by self-assembling organic nano microspheres with various sizes under the assistance of heat, and then TiO is used for preparing the opal structure template2The precursor liquid is fully filled in gaps in the opal structure template, and the opal structure template is removed by high-temperature calcination to obtain hydrophilic porous TiO2An inverse opal structure lamina (IOS-T); finally, treating the mixture with an organic hydrophobic agent to obtain IOS-T/H. And placing an information mask corresponding to the information to be compiled on the thin layer, and then carrying out ultraviolet irradiation treatment. The technical scheme of the invention is as follows:
the invention provides a preparation method of a wetting-response optical information encryption thin layer, which comprises the following steps:
preparing an opal structure template, wherein a plurality of gaps are formed on the opal structure template;
filling the precursor liquid into the gaps of the opal structure template;
calcining the opal structure template filled with the precursor liquid to obtain an inverse opal structure thin layer;
adding an organic hydrophobic agent to the inverse opal structure thin layer for coating treatment to obtain a hydrophobic inverse opal structure thin layer;
and placing an information mask above the optical information encryption thin layer for ultraviolet irradiation to obtain a hydrophobic inverse opal structure thin layer containing compiling information.
The opal structure template is a nano microsphere opal structure template; the step of preparing the opal structure template comprises:
and carrying out heat-assisted assembly treatment on the organic microspheres to obtain the nano microsphere opal structure template.
The preparation method of the optical information encryption thin layer with the wetting response comprises the following steps of (1) preparing a precursor liquid, wherein the precursor liquid is a titanium dioxide precursor liquid; the precursor solution is obtained by adopting the following method:
and mixing titanate with a solvent, adding an antioxidant, and uniformly stirring to obtain the titanium dioxide precursor solution.
The preparation method of the optical information encryption thin layer with the wetting response comprises the steps of preparing a titanium titanate, and preparing an antioxidant, wherein the titanium titanate is at least one of tetrabutyl titanate, tetraethyl titanate and tetraisopropyl titanate, the solvent is an organic solvent capable of uniformly dissolving the titanate, and the antioxidant is acetic acid or diethanol amine.
The preparation method of the optical information encryption thin layer with the wetting response comprises the following steps of (1) filling precursor liquid into the opal structure template, and then filling the precursor liquid into the opal structure template; the step of filling the precursor liquid into the gaps of the opal structure template comprises the following steps:
fixing the nano-microsphere opal structure template on a spin coater, dropwise adding a titanium dioxide precursor solution on the nano-microsphere opal structure template until the nano-microsphere opal structure template is covered, and fully filling the titanium dioxide precursor solution in gaps of the nano-microsphere opal structure template through rotation of the spin coater to obtain the nano-microsphere opal structure template filled with the precursor solution.
The preparation method of the optical information encryption thin layer with the wetting response comprises the following steps of calcining the opal structure template filled with the precursor liquid to obtain the inverse opal structure thin layer:
and exposing the nano-microsphere opal structure template filled with the precursor liquid in the air for 3-6h, placing the template in a muffle furnace, heating the muffle furnace to 500 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2h, cooling, and taking out the template from the muffle furnace to obtain the titanium dioxide inverse opal structure thin layer.
The preparation method of the optical information encryption thin layer with the wetting response comprises the following steps that the organic hydrophobic agent is used for hydrophobicity and can be degraded by titanium dioxide under ultraviolet irradiation; the organic hydrophobic agent is obtained by adopting the following method:
dissolving any one of micromolecular long-chain silane, fluorine-containing hydrophobic agent and macromolecular hydrophobic agent in normal hexane to obtain the organic hydrophobic agent.
The preparation method of the optical information encryption thin layer with the wetting response comprises the following steps of (1) preparing a hydrophobic inverse opal structure thin layer by using a hydrophobic titanium dioxide inverse opal structure thin layer; the step of adding an organic hydrophobizing agent to the inverse opal structure thin layer for coating treatment to obtain a hydrophobic inverse opal structure thin layer comprises the following steps:
placing the titanium dioxide inverse opal structure thin layer on the spin coater, dropwise adding the organic hydrophobic agent on the titanium dioxide inverse opal structure thin layer and covering the titanium dioxide inverse opal structure thin layer, fully filling the organic hydrophobic agent in the titanium dioxide inverse opal structure thin layer through rotation of the spin coater, and drying to obtain the hydrophobic titanium dioxide inverse opal structure thin layer.
The preparation method of the optical information encryption thin layer with the wetting response comprises the following steps that the hydrophobic inverse opal structure thin layer containing coding information is a hydrophobic titanium dioxide inverse opal structure thin layer containing coding information; the step of placing an information mask above the hydrophobic inverse opal structure thin layer for ultraviolet irradiation to obtain the hydrophobic inverse opal structure thin layer containing compiling information comprises the following steps:
and placing an ultraviolet light source above the hydrophobic titanium dioxide inverse opal structure thin layer, and placing the information mask between the hydrophobic titanium dioxide inverse opal structure thin layer and the ultraviolet light source for ultraviolet irradiation to obtain the hydrophobic titanium dioxide inverse opal structure thin layer containing compiled information.
The invention also provides a wetting-response optical information encryption thin layer which is prepared by adopting the preparation method of any one of the wetting-response optical information encryption thin layers.
Has the advantages that: the invention provides a preparation method of a wetting-response optical information encryption thin layer, which comprises the following steps: preparing an opal structure template, wherein a plurality of gaps are formed on the opal structure template; filling the precursor liquid into the gaps of the opal structure template; calcining the opal structure template filled with the precursor liquid to obtain an inverse opal structure thin layer; and adding an organic hydrophobic agent into the inverse opal structure thin layer for coating treatment to obtain the hydrophobic inverse opal structure thin layer. The IOS-T/H thin layer is simple to prepare and low in cost, information compiling is rapid, the hydrophilic/hydrophobic gradient difference with patterns is formed on the thin layer by using controllable ultraviolet irradiation, the color change response condition in the information display process is simple, the requirement on equipment is low, and the effect of low cost is achieved.
Drawings
Fig. 1 is a flow chart of a method of manufacturing a wet-responsive optical information encryption layer according to the present invention.
FIG. 2 is a diagram illustrating a compiling method according to the invention.
FIG. 3 is a schematic illustration of the wetting response optical mechanism of the present invention as a function of gradient wetting and diffuse reflectance reduction.
Detailed Description
The invention provides a wetting response optical information encryption thin layer and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It will be understood that when an element is referred to as being "secured to" or "disposed on" another element, it can be directly on the other element or be indirectly on the other element. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or be indirectly connected to the other element.
It should also be noted that the same or similar reference numerals in the drawings of the embodiments of the present invention correspond to the same or similar components; in the description of the present invention, it should be understood that if there is an orientation or positional relationship indicated by the terms "upper", "lower", "left", "right", etc. based on the orientation or positional relationship shown in the drawings, it is only for convenience of describing the present invention and simplifying the description, but it is not intended to indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and therefore, the terms describing the positional relationship in the drawings are only used for illustrative purposes and are not to be construed as limiting the present patent, and the specific meaning of the terms may be understood by those skilled in the art according to specific circumstances.
The invention provides a wetting-response optical information encryption thin layer and a preparation method thereof, wherein TiO2The properties of the crystal and an Inverse Opal Structure (IOS) can be mutually enhanced, and TiO2Providing photodegradation properties, the ordered porous structure of the IOS not only provides structural color, but also enhances TiO2The photodegradability of (c). TiO not prepared as IOS multilayer porous structure2Has high opacity, refractive index and whiteness, which result in strong scattering and limit the utilization of light, while IOS-T can obtain light blue instead of white, which greatly improves the information identification capability, and when TiO is used2When the surface area is higher, the photodegradation activity is greatly improved. In addition, the principle of information display of IOS-T/H is to change the effective refractive index by water penetration, reduce diffuse reflection to induce a fast wetting response, by simple regulation: ultraviolet (UV) irradiation duration to create a wetting gradient, thereby obtaining a visualized color gradient; the visual color gradient of the IOS-T/H enables the IOS-T/H to have four-variable combination of 'dark color-light color-colorless' and pattern change, more information combinations are provided, the information storage capacity is greatly improved, and therefore multi-layer encryption is achieved. Thin TiO layer of IOS-T/H2The framework also provides good chemical and shape stability under severe conditions such as strong acid/alkaline environments or extreme temperatures, can store information well after compiling, and can ensure that accurate patterns and colors do not cause distortion to cause misleading of information under long-term use. In addition, titanium dioxide excites free radicals to degrade partial organic matters under UV irradiation, so that the thin layer has self-cleaning performance, and can be reused after being polluted through UV self-cleaning. In addition, after the use is finished, the thin layer can be erased in a whole piece through ultraviolet rays, and the hydrophobic agent is coated again, so that new information can be compiled, and the reutilization rate is high.
Referring to fig. 1-3, a method for preparing a wet-response optical information encryption thin layer includes the following steps:
s10, preparing an opal structure template, wherein the opal structure template is provided with a plurality of gaps.
Step S10 is specifically to obtain a nano-microsphere opal structure template by thermally assisted assembly of the organic microspheres.
The organic microspheres can be removed by calcination (i.e., the organic microspheres are dispersed in the air in a molecular or atomic manner after calcination), and include monodisperse Polystyrene (PS) nanoparticles and polymethyl methacrylate (PMMA) nanoparticles.
Preferably, Polystyrene (PS) microspheres with the average particle size of 260-310nm are ultrasonically dispersed in deionized water and ethanol in equal volume ratio and diluted to an emulsion with the solid content of 0.2-0.5%. Placing the cut glass slide in a 65 ℃ oven for preheating for 30min, sucking a proper amount of the diluted and dispersed emulsion in the step (1) by using a dropper, slowly dripping the diluted and dispersed emulsion on the glass slide until 80% of the area of the glass slide is covered, and then slightly scratching the emulsion on the glass slide by using a dropper head to spread the emulsion as much as possible; after being spread, the PS microspheres are continuously put in an oven environment of 65 ℃ for 1 hour to finish the self-loading of the PS microspheres. Taking out the glass slide, and enabling a lighting PS microsphere opal structure thin layer to be visible on the glass slide; and then placing the glass slide in an oven at 80 ℃ for 30min to reinforce the connection strength between the microspheres and dry moisture. Uniformly mixing titanate and a solvent in a mass ratio of 1:6, adding 2-5 wt% of antioxidant to slow down the oxidation speed of titanate in the air, and violently stirring for 1h at room temperature by magnetic force to obtain TiO2The precursor liquid, wherein the titanate type comprises titanium-containing esters such as tetrabutyl titanate, tetraethyl titanate and tetraisopropyl titanate; the solvent can be any organic solvent capable of uniformly dissolving titanate; the antioxidant is acetic acid or diethanolamine.
And S20, filling the precursor liquid into the gaps of the opal structure template.
Step S20 specifically includes fixing the polystyrene opal structure template on a spin coater, dropping a titanium dioxide precursor solution on the polystyrene opal structure template until covering the polystyrene opal structure template, and rotating the spin coater to fully fill the titanium dioxide precursor solution in the gaps of the polystyrene opal structure template, thereby obtaining the polystyrene opal structure template filled with the precursor solution.
Preferably, the glass slide with the template of the PS opal structure is fixed on a table-type spin coater, the rotation speed of the spin coater is set to be 20 thousand revolutions per minute, and the spin time is 3 s. Taking a proper amount of TiO by using a rubber head dropper2And (3) slightly dropping the precursor solution on the template, starting a rotary button, taking down the glass slide with the template, exposing the glass slide in the air for 5min, and repeating for 1-2 times.
And S30, calcining the opal structure template filled with the precursor liquid to obtain an inverse opal structure thin layer.
Step S30 specifically comprises the steps of exposing the polystyrene opal structure template filled with the precursor liquid in air for 3-6 hours, placing the template in a muffle furnace, heating the muffle furnace to 500 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2 hours, cooling, and taking out the template from the muffle furnace to obtain the titanium dioxide inverse opal structure thin layer.
Preferably, the glass slide with the template is taken down and placed on a plane to stand overnight, the glass slide with the template is placed in a muffle furnace, the temperature is raised to 500 ℃ from room temperature at the speed of 5 ℃/min and is kept for 2h, and the glass slide is cooled along with the furnace; and taking out to obtain the IOS-T.
It should be noted that, titanic acid is fully oxidized in air to form titanium dioxide solid, and after oxidation, the titanium dioxide solid exists in the gaps of the PS microspheres in a solid form, so that incomplete or collapse of a pore structure can be reduced in the calcining process.
S40, adding an organic hydrophobic agent to the inverse opal structure thin layer for coating treatment to obtain the hydrophobic inverse opal structure thin layer.
Step S40 is specifically to dissolve any one of micromolecule long-chain silane, fluorine-containing hydrophobic agent and macromolecule hydrophobic agent in normal hexane to obtain organic hydrophobic agent; placing the titanium dioxide inverse opal structure thin layer on the spin coater, dropwise adding the organic hydrophobic agent on the titanium dioxide inverse opal structure thin layer and covering the titanium dioxide inverse opal structure thin layer, fully filling the organic hydrophobic agent in the titanium dioxide inverse opal structure thin layer through rotation of the spin coater, and drying to obtain the hydrophobic titanium dioxide inverse opal structure thin layer.
The organic hydrophobic agent is used for hydrophobicity and is degraded by titanium dioxide under ultraviolet irradiation; the organic hydrophobic agent comprises any one of micromolecular long-chain silane, fluorine-containing hydrophobic agent and high-molecular hydrophobic agent, and n-hexane can be other soluble organic solvents, and the concentration of the n-hexane can be properly adjusted according to the difficulty of the n-hexane in being degraded by titanium dioxide.
Specifically, heptadecafluorodecyltrimethoxysilane is dissolved in normal hexane and diluted to the concentration of 1-12 wt%; fixing the IOS-T on a table type spin coater, setting the rotating speed to be 20 thousand revolutions per minute and the spin coating time to be 3 s; and (3) taking a proper amount of hydrophobic agent by using a rubber head dropper, lightly dripping the hydrophobic agent on the IOS-T, starting a rotary button, repeating the operation for 1-2 times to obtain the IOS-T/H, and putting the glass slide with the IOS-T/H into an oven to be dried for 30min at the temperature of 60 ℃.
It is to be noted that the organic hydrophobic agent is long-chain fluorine-containing siloxane dissolved in n-hexane, and diluted to a concentration which can be degraded by titanium dioxide within 30min, such as heptadecafluorodecyltrimethoxysilane, wherein the concentration of 1-4 wt% can be degraded within about 10min, 5-7 wt% can be degraded within about 15min, and 9-12 wt% can be degraded within about 30 min; after the solvent of the hydrophobic agent is dried and removed, the dissolved long-chain fluorine-containing silane can be attached to a porous framework of titanium dioxide, the titanium dioxide has photocatalytic performance, and radicals can be excited to degrade partial organic matters under ultraviolet irradiation, so that the self-cleaning agent is realized.
And S50, placing an information mask above the hydrophobic inverse opal structure thin layer for ultraviolet irradiation to obtain the hydrophobic titanium dioxide inverse opal structure thin layer containing compiling information.
Step S50 is specifically to place an ultraviolet light source above the hydrophobic titanium dioxide inverse opal structure thin layer, and place the information mask between the hydrophobic titanium dioxide inverse opal structure thin layer and the ultraviolet light source to perform ultraviolet irradiation, so as to obtain the hydrophobic titanium dioxide inverse opal structure thin layer containing compiled information.
Preferably, the glass slide with the IOS-T/H is placed at a position 15-20cm away from a light source of an ultraviolet lamp, the wavelength of the ultraviolet lamp is 365nm, an information mask is placed on the glass slide for local irradiation, and the color development depth can be regulated and controlled by regulating the concentration of the hydrophobing agent and the illumination time, wherein the concentration range is 1 wt% -10 wt%, and the illumination time range is 3min-180 min. Taking a proper amount of clear water by using a dropper, slowly dripping a small amount of clear water on the compiled sample, and generating target information of IOS-T/H under the condition of water wetting; after the water is volatilized, the information disappears, and after the information is wetted again by water, the information is displayed again.
The information mask is a common black polyester photomask capable of blocking the wave band of the UV light source; after once compiling, the whole piece of ultraviolet can be erased, the hydrophobic agent is coated again, and new information compiling is carried out.
The invention is further illustrated by the following specific examples:
k1, using Polystyrene (PS) microspheres with the average particle size of 260-310nm, ultrasonically dispersing in deionized water and ethanol in an equal volume ratio, and diluting to an emulsion with the solid content of 0.2-0.5% to form monodisperse Polystyrene (PS) microspheres.
K2, placing a cut glass slide with the length and width close to 1:1 in a 65 ℃ oven for preheating for 30min, sucking a proper amount of diluted and dispersed emulsion by a dropper, slowly dripping the diluted and dispersed emulsion on the glass slide until 80% of the area of the glass slide is covered, wherein the emulsion is high in liquid level and concentrated, relatively dispersing the concentrated emulsion in order to reduce the liquid level, slightly scratching the emulsion on the glass slide by a dropper head to spread the emulsion as much as possible, and carrying out the emulsion dripping process in the oven; after being spread, the PS microspheres are continuously placed in an oven environment of 65 ℃ for 1 hour to finish the self-assembly of the PS microspheres.
K3, taking out the glass slide from the oven, and enabling the PS microsphere opal structure thin layer with lighting to be visible to be positioned above; and then placing the glass slide in an oven at 80 ℃ for 30min to reinforce the connection strength between the microspheres and dry moisture to form the Polystyrene (PS) opal structure template.
K4, tetrabutyl titanate and organic solvent capable of uniformly dissolving titanate are uniformly mixed according to the mass ratio of 1:6, and 2-5 wt% of antioxidant is added to slow down the oxidation rate of titanate in airThen stirred vigorously at room temperature for 1h by magnetic force to prepare titanium dioxide (TiO)2) A precursor liquid.
K5, fixing the glass slide with the template with the PS opal structure on a table type spin coater, setting the spin speed of the spin coater at 20 thousand revolutions per minute and the spin time at 3s, and taking a proper amount of TiO by using a rubber head dropper2And (3) slightly dropping the precursor liquid on the PS opal structure template, and then starting a rotary button to form the Polystyrene (PS) opal structure template after spin coating.
K6, taking down the glass slide 13 with the template with the structure of the Polystyrene (PS) opal after spin coating, exposing the glass slide in the air for 5min, and repeatedly dripping TiO2And (3) performing a rotation process for 1-2 times, in order to fully oxidize titanic acid into titanium dioxide solid in the air, enabling the titanic acid to exist in gaps of the PS microspheres in a solid form after oxidation, protecting the integrity of a pore structure in the subsequent calcination process, taking down the pore structure, placing the pore structure on a plane, exposing the pore structure in the air, and standing for 3-6 hours to form a Polystyrene (PS) opal structure template with the gaps filled with the titanium dioxide solid.
K7, placing the glass slide with the Polystyrene (PS) opal structure template filled with titanium dioxide solid in the gap in a muffle furnace, heating to 500 ℃ from room temperature at a heating rate of 5 ℃/min, keeping the temperature for 2h, cooling along with the furnace, and taking out to obtain TiO2An inverse opal structure lamina (IOS-T).
K8, dissolving heptadecafluorodecyltrimethoxysilane in n-hexane, diluting to a concentration of 3 wt%, and stirring uniformly under magnetic stirring.
Adding TiO into the mixture2Fixing an inverse opal structure thin layer (IOS-T) on a table type spin coater, setting the rotating speed to be 20 thousand revolutions per minute and the spin coating time to be 3 s; and (3) lightly dropping a proper amount of hydrophobizing agent on the IOS-T by using a rubber head dropper, covering the solution, starting a rotary button, and repeating the operation for 1-2 times to obtain the hydrophobic titanium dioxide inverse opal structure thin layer (IOS-T/H).
K9, putting the glass slide 13 with the hydrophobic titanium dioxide inverse opal structure thin layer (IOS-T/H) into an oven to be dried for 30min at 60 ℃, putting the glass slide with the hydrophobic titanium dioxide inverse opal structure thin layer (IOS-T/H) under a light source which is 15-20cm away from an ultraviolet lamp (with the wavelength of 365nm), and putting a common black polyester photomask which can block the wave band of the UV light source on the glass slide to carry out local irradiation to obtain the hydrophobic titanium dioxide inverse opal structure thin layer containing compiled information, wherein the color depth can be controlled by controlling the concentration of a hydrophobizing agent and the illumination time, the concentration range is 1-10 wt%, and the illumination time range is 3-180 min.
K10, taking a proper amount of clear water by using a dropper, slowly dripping a small amount of clear water on the hydrophobic titanium dioxide inverse opal structure thin layer containing the compiled information, and generating target information on the hydrophobic titanium dioxide inverse opal structure thin layer containing the compiled information under the condition of water wetting; after the water is volatilized, the information disappears, and after the information is wetted again by water, the information is displayed again.
In summary, the present invention provides a method for preparing a wet-response optical information encryption thin layer, the method comprising: preparing an opal structure template, wherein a plurality of gaps are formed on the opal structure template; filling the precursor liquid into the gaps of the opal structure template; calcining the opal structure template filled with the precursor liquid to obtain an inverse opal structure thin layer; and adding an organic hydrophobic agent into the inverse opal structure thin layer for coating treatment to obtain the hydrophobic inverse opal structure thin layer. The IOS-T/H thin layer is simple to prepare, low in cost and fast in information compiling, hydrophilic/hydrophobic gradient differences with patterns are formed on the thin layer by using controllable ultraviolet irradiation, the color change response condition in the information display process is simple, the IOS-T/H thin layer can provide more information combinations, the information storage capacity is improved, the information display function is maintained under severe conditions, the information can be recovered by ultraviolet self-cleaning after being polluted by pollutants, and the recycling rate is high.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A method of making a wet-responsive optical information encryption laminate comprising the steps of:
preparing an opal structure template, wherein a plurality of gaps are formed on the opal structure template;
filling the precursor liquid into the gaps of the opal structure template;
calcining the opal structure template filled with the precursor liquid to obtain an inverse opal structure thin layer; adding an organic hydrophobic agent to the inverse opal structure thin layer for coating treatment to obtain a hydrophobic inverse opal structure thin layer;
and placing an information mask above the hydrophobic inverse opal structure thin layer for ultraviolet irradiation to obtain the hydrophobic inverse opal structure thin layer containing compiled information.
2. The method for manufacturing a wet-response optical information encryption thin layer according to claim 1, wherein the opal structure template is a nano-microsphere opal structure template; the step of preparing the opal structure template comprises:
and carrying out heat-assisted assembly treatment on the organic microspheres to obtain the nano microsphere opal structure template.
3. The method for producing a wet-response optical information encryption sheet as claimed in claim 2, wherein the precursor liquid is a titanium dioxide precursor liquid; the precursor solution is obtained by adopting the following method: and mixing titanate with a solvent, adding an antioxidant, and uniformly stirring to obtain the titanium dioxide precursor solution.
4. The method of manufacturing a wet-response optical information encryption thin layer according to claim 3, wherein the titanate is at least one of tetrabutyl titanate, tetraethyl titanate, and tetraisopropyl titanate, the solvent is an organic solvent capable of uniformly dissolving titanate, and the antioxidant is acetic acid or diethanolamine.
5. The method for preparing a wet response optical information encryption thin layer as claimed in claim 3, wherein the opal structure template after being filled with the precursor liquid is a nanosphere opal structure template after being filled with the precursor liquid; the step of filling the precursor liquid into the gaps of the opal structure template comprises the following steps:
fixing the nano-microsphere opal structure template on a spin coater, dropwise adding a titanium dioxide precursor solution on the nano-microsphere opal structure template until the nano-microsphere opal structure template is covered, and fully filling the titanium dioxide precursor solution in gaps of the nano-microsphere opal structure template through rotation of the spin coater to obtain the nano-microsphere opal structure template filled with the precursor solution.
6. The method for preparing a wet-response optical information encryption thin layer according to claim 5, wherein the step of calcining the opal structure template filled with the precursor liquid to obtain the inverse opal structure thin layer comprises:
and exposing the nano-microsphere opal structure template filled with the precursor liquid in the air for 3-6h, placing the template in a muffle furnace, heating the muffle furnace to 500 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2h, cooling, and taking out the template from the muffle furnace to obtain the titanium dioxide inverse opal structure thin layer.
7. The method for producing a wet-response optical information encryption thin layer according to claim 6, wherein the organic water repellent agent is used to be hydrophobic and is degradable by titanium dioxide under ultraviolet irradiation; the organic hydrophobic agent is obtained by adopting the following method:
dissolving any one of micromolecular long-chain silane, fluorine-containing hydrophobic agent and macromolecular hydrophobic agent in normal hexane to obtain the organic hydrophobic agent.
8. The method of manufacturing a wet-response optical information encryption sheet as claimed in claim 7, wherein the hydrophobic inverse opal structure sheet is a hydrophobic titanium dioxide inverse opal structure sheet; the step of adding an organic hydrophobizing agent to the inverse opal structure thin layer for coating treatment to obtain a hydrophobic inverse opal structure thin layer comprises the following steps:
placing the titanium dioxide inverse opal structure thin layer on the spin coater, dropwise adding the organic hydrophobic agent on the titanium dioxide inverse opal structure thin layer and covering the titanium dioxide inverse opal structure thin layer, fully filling the organic hydrophobic agent in the titanium dioxide inverse opal structure thin layer through rotation of the spin coater, and drying to obtain the hydrophobic titanium dioxide inverse opal structure thin layer.
9. The method of manufacturing a wet-response optical information encryption sheet as claimed in claim 8, wherein the hydrophobic inverse opal structure sheet containing compiled information is a hydrophobic titanium dioxide inverse opal structure sheet containing compiled information; the step of placing an information mask above the hydrophobic inverse opal structure thin layer for ultraviolet irradiation to obtain the hydrophobic inverse opal structure thin layer containing compiling information comprises the following steps:
and placing an ultraviolet light source above the hydrophobic titanium dioxide inverse opal structure thin layer, and placing the information mask between the hydrophobic titanium dioxide inverse opal structure thin layer and the ultraviolet light source for ultraviolet irradiation to obtain the hydrophobic titanium dioxide inverse opal structure thin layer containing compiled information.
10. A wet-response optical information encryption sheet produced by the method for producing a wet-response optical information encryption sheet according to any one of claims 1 to 9.
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