CN113061274B - Multi-structure color-changing intelligent optical film driven by multi-shape memory and preparation method and application thereof - Google Patents
Multi-structure color-changing intelligent optical film driven by multi-shape memory and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials
- G02B1/005—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials made of photonic crystals or photonic band gap materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2301/04—Oxycellulose; Hydrocellulose
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- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
Abstract
The invention belongs to the technical field of optical intelligent materials, and discloses a multi-shape memory-driven intelligent optical film with multiple structural color transformations, and a preparation method and application thereof. Dissolving cellulose nano microcrystalline powder in deionized water, performing ultrasonic treatment at room temperature, and adjusting the pH value to 5-7 to prepare a CNCs suspension; dripping the CNCs suspension onto a glass sheet substrate, and drying at room temperature to obtain a self-assembled cellulose nano microcrystalline film; then the organic solution of amorphous polymer is evenly dripped and transferred to the surface of the self-assembled cellulose nano microcrystalline film and is solidified under vacuum at 40-80 ℃. The intelligent optical film has the polymorphic shape memory performance under the multiple stimulation of heat, water and moisture, and simultaneously has the adjustable multiple structural color transformation performance. Not only the chiral nematic structure of the cellulose nano-microcrystal is kept, but also the thermal stability, the mechanical strength, the flexibility and the like are obviously improved.
Description
Technical Field
The invention belongs to the technical field of optical intelligent materials, and particularly relates to a multi-shape memory-driven intelligent optical film with multiple structural color transformations, and a preparation method and application thereof.
Background
Polymorphic Shape Memory Polymers (Multi-Shape Memory Polymers) are an important class of intelligent Polymers that have two or more temporary deformations to achieve three or more Shape transitions in a particular flow. Studies of polymorphic shape memory polymers have focused primarily on shape memory elastic networks comprising two distinct temperature transitions, such as two Ts g Or two T m Or a T g A T m The two temperature transitions are respectively used as a switching mechanism, and when the external temperature is triggered, the transition of a plurality of temporary shapes is sequentially realized under the action of entropy elasticity. In addition, a wide Tg transition may also serve as a multiple step type temperature responsive switch. The research of polymorphic shape memory still has 2 problems at present: firstly, the research focuses on the response of thermal stimulation, and the research on the pleomorphic effect under the response of heterogeneous multi-stimulation simultaneously containing the stimulation such as thermal stimulation, water-moisture and the like is less; in addition, many polymorphic shape memory polymers are not transparent, and optical properties under polymorphic shape memory actuation are currently less studied.
Cellulose nano-crystallites are widely used for mechanical reinforcement of polymer composite systems. The early report shows that the cellulose nano-microcrystal can construct a stress transfer network structure based on reversible hydrogen bond action in the polymer, and can realize reversible transformation of modulus in a dry-wet state. As a response switch of water and moisture, under the interaction of water molecules and a hydrogen bond percolation transfer network, the modulus of the polymer composite material is reversibly transformed by 1 to 3 orders of magnitude under a dry-wet condition. When the nanocomposite is in a dry state, the modulus can be reduced by 1 to 3 orders of magnitude within seconds when encountering water or moisture, thereby achieving Mechanical adaptivity (Mechanical adaptivity).
In addition, negatively charged sulfonate or carboxylate groups are generated as a result of treatment of the cellulose fibers with acids or oxidizing agents. The electrostatic repulsive force of the surface charges enables the cellulose nanocrystals to form a stable colloidal dispersion system in water, and the cellulose nanocrystals can be self-assembled under the induction of water evaporation. When the concentration is higher than the critical concentration, the cellulose nanocrystals spontaneously organize into chiral nematic lyotropic liquid crystals, and after the water is completely evaporated, the structure is remained in the cellulose nanocrystal film. The structural characteristic of the chiral nematic phase is that the cellulose nanocrystalline layers are stacked and twisted and rotated, and the chiral nematic phase is a one-dimensional photonic crystal material. According to the Bragg equation of lambda = nPsin theta (wherein n is the average refractive index, P is the pitch of the chiral nematic phase, and theta is the included angle between the propagation direction of the incident light and the vertical direction of the spiral shaft), the nano-cellulose self-assembly film has selective reflection to the light with a specific wavelength determined by the size of the pitch, so that the nano-cellulose self-assembly film has a certain structural color. Because the pitch of the ordered structure is in the visible wavelength range, the cellulose nano-crystallites can self-assemble into a chiral nematic structure under the induction of solvent evaporation to realize the structural color of which the reflection spectrum is concentrated in a blue light region.
At present, although structural colors formed by the self-assembly behavior of cellulose nanocrystals have been widely studied, most of them are self-assembled by blending with water-soluble molecules, so that the structural color is changed by the pitch change of the chiral nematic structure under the external water/moisture stimulation by utilizing the swelling effect behavior of the polymer (see Wan, hao, li, xiaofeng, zhang, & Liang et al (2018). The research of polymorphic shape memory still has two problems at present: firstly, the research focuses on the response of thermal stimulation, and the research on pleomorphic effect under the response of heterogeneous multi-stimulation containing the stimulation of thermal stimulation, water-moisture and the like is less; in addition, many polymorphic shape memory polymers are not transparent, and optical properties under polymorphic shape memory actuation are currently less studied.
Disclosure of Invention
In order to solve the problems of the prior art that the method for preparing the cellulose optical film mainly utilizes the solvent effect of the water-soluble polymer to adjust the pitch and the single stimulation method, the invention provides a polymorphic shape memory-driven multiple-structure color-transition intelligent optical film.
The invention also aims to provide a preparation method of the polymorphic shape memory driven multiple structure color transition intelligent optical film.
It is still another object of the present invention to provide applications of the above-mentioned multiple structure color-transition intelligent optical film driven by multi-shape memory.
The purpose of the invention is realized by the following technical scheme:
an intelligent optical film with multiple structural color changes and driven by polymorphic shape memory is characterized in that cellulose nano microcrystal powder is dissolved in deionized water, ultrasonic treatment is carried out at room temperature, and the pH value is adjusted to 5-7 to prepare CNCs suspension; dripping the CNCs suspension onto a glass sheet substrate, and drying at room temperature to obtain a self-assembled cellulose nano microcrystalline film; then the amorphous polymer organic solution is evenly dripped and transferred to the surface of the self-assembled cellulose nano microcrystalline film and is solidified under vacuum at 40-80 ℃.
Preferably, the mass concentration of the CNCs suspension is 0.5-10%.
Preferably, the amorphous polymer is one or more of Tg type shape memory polyurethane, polytetrahydrofuran or polystyrene, and the molecular weight of the amorphous polymer is 10000 to 100000.
Preferably, the organic solvent in the organic solution of the amorphous polymer is one or more of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, and dichloromethane.
Preferably, the organic solution of the amorphous polymer has a mass concentration of 5 to 50%.
The preparation method of the polymorphic shape memory-driven multiple-structure color-transformation intelligent optical film comprises the following specific steps:
s1, dissolving cellulose nano microcrystalline powder in deionized water, performing ultrasonic treatment at room temperature, and adjusting the pH value to 5-7 to prepare a CNCs suspension;
s2, dripping the CNCs suspension onto a glass sheet substrate, and drying at room temperature to form a semitransparent self-assembled ordered structure to prepare a self-assembled cellulose nano microcrystalline film;
s3, dissolving the amorphous polymer in an organic solvent to prepare a solution, uniformly dripping and transferring the solution to the surface of the self-assembled cellulose nano microcrystalline film, and curing at 40-80 ℃ under vacuum to prepare the polymorphic shape memory driven intelligent optical film with multiple structural color conversion
Preferably, the time of the ultrasound in step S1 is 30 to 120min.
Preferably, the drying time in step S2 is 1 to 4 days.
Preferably, the curing time in step S3 is 2 to 12 hours.
The polymorphic shape memory-driven multiple-structure color-transformation intelligent optical film is applied to the field of optical encryption.
The self-assembled cellulose nano microcrystalline film provided by the invention has a one-dimensional photonic crystal film with a chiral nematic structure. Self-assembled cellulose nanocrystals play two roles simultaneously in polymer composite membranes: as a tunable photonic crystal layer to produce structural color transition and a hydro-entangled response reversible hydrogen bonding network switch. The shape memory-driven multiple structural color transformation means that the optical film is sequentially deformed and restored under the triggering of external thermal stimulation and multiple stimulation of water-moisture, and the reflection spectrum peak area of the optical film is blue-shifted. On the adjustable optical layer, the multi-structure color transformation with multi-shape memory drive is realized, namely, the reflection spectrum peak area is correspondingly transformed from colorless transparency to a red light area and then to a blue light area along with the change of the thread pitch of the photonic crystal layer in the deformation drive process.
The invention utilizes the shape memory effect of macromolecules and adjusts the pitch of the chiral nematic structure under the drive of heat. Specifically, a periodically arranged chiral nematic structure is formed on the basis of an aqueous solution of cellulose nanocrystals under evaporation-induced self-assembly of an aqueous solvent. The surface of the composite film is coated with a macromolecule solution with multiple shape memory effect by drop coating, and the prepared composite film presents a cross-linked network structure of a polymer and a chiral nematic phase. Wherein, the change of the screw pitch of the chiral nematic phase structure in the shape memory deformation process of the thermally driven macromolecule is the main factor for generating the color transition of multiple structures.
According to the invention, water evaporation is carried out on a CNCs aqueous solution at room temperature, and an ordered chiral nematic structure is formed under the induction of evaporation, so that the self-assembled cellulose nano microcrystalline film is prepared; then, the amorphous shape memory polymer solution is dripped on the surface of the cellulose nano microcrystal film in a dripping mode and is solidified into the intelligent optical film under vacuum. The intelligent optical film has adjustable and controllable multiple structural color transformation performance, the structural color transformation driven by the shape memory is a brand new adjusting and controlling mechanism, the polymorphic shape memory recovery can be controllably generated under the external stimulus, and the blue shift is generated on the structural color reflection spectrum, namely from a forbidden band transparent area to a red light area and to a blue light area. At the same time, the swelling effect counteracts the structural color control in order to avoid water-moisture triggering. In addition, the shape memory polymer adopted by the invention has extremely low water absorption performance, and the water absorption rate in a saturated state is less than 1%. This avoids the reverse increase of the pitch of the ordered structure of the cellulose nanocrystallite self-assembly due to the swelling effect when the deformation is recovered under the trigger of water-moisture. In addition, the amorphous polymorphic shape memory polymer can not be crystallized between the sheets of the spiral structure, and the influence of the crystallization and melting transformation on the thread pitch under the stimulation of high and low temperature is avoided. The optical transition of the present invention is derived to the greatest extent from the change in pitch caused by the shape memory drive recovery.
The mechanism of structural color transition of the invention: in the previous optical research on the self-assembled cellulose nano-microcrystal, the water-soluble polymer and the cellulose nano-microcrystal are assembled together, and the polymer chain segment layer is inserted into the lamellar structure with an ordered structure. This results in a large pitch and a red shift of the reflectance spectrum; further, due to the water-moisture stimulus, a "swelling effect" is produced, making the pitch further larger. By optimizing the water solubility and crystallization property of the high molecular chain segment, the red shift range can be optimized to 400nm, and the red shift is reversible in a dry-wet state. In conclusion, the pitch will only increase under external stimuli, the spectrum will only red-shift, and the stimulus is removed, with a blue-shift.
Compared with the prior art, the invention has the following beneficial effects:
1. the intelligent optical film has the polymorphic shape memory performance under the multiple stimulation of heat, water and moisture, and simultaneously has the adjustable multiple structural color transformation performance.
2. The polymorphic shape memory-driven multiple-structure color transition intelligent optical film not only keeps the chiral nematic structure of the cellulose nano microcrystal, but also overcomes the defects of easy cracking, brittleness and the like of the cellulose film, and obviously improves the aspects of thermal stability, mechanical strength, flexibility and the like.
3. The self-assembled cellulose nanofibers of the present invention have 2 functions simultaneously: (a) As a photonic crystal layer, the controllable transformation of structural color is realized (b) as a water-moisture switch, and the Tg transformation of the polymer is combined to be used as a thermal stimulus response switch, so that the three-shape memory performance of a hetero-double switch is realized
4. The invention develops a program, in the program, the intelligent optical film is firstly stretched under the conditions of heat and humidity and then fixed and temporarily deformed under the conditions of dry and cold; when the intelligent optical film is heated and stimulated, the intelligent optical film shrinks and changes from a temporary shape to a deformation and returns to 1, and the reflection spectrum of the optical film is changed from transparency to a red light area; further, the intelligent optical film is changed from deformation recovery 1 to deformation recovery 2 under the trigger of water and moisture, and the reflection spectrum of the optical film is transferred from red light to blue light. With the transformation of the three shapes, the structural color is also transformed from colorless and transparent, red light and blue light.
5. The preparation process is simple and controllable, and the polymer shape memory effect and the high mechanical modulus and self-assembly characteristics of the cellulose nano-crystallite are combined, so that the material can respond to various external stimuli such as water, heat, infrared light and the like, and the multifunctional requirement of the material can be met.
Drawings
FIG. 1 is a schematic flow chart of the present invention for preparing an intelligent optical film;
FIG. 2 is a schematic flow chart of the polymorphic shape memory multiple structure color transition of the present invention;
FIG. 3 is a graph of spectral shift for the polymorphic shape memory smart optical film drive of example 1.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. Dissolving cellulose nano microcrystal (CNCs) powder in deionized water to prepare an aqueous solution with the mass fraction of 3%, performing ultrasonic dispersion for 2 hours at room temperature, and adjusting the pH value to 5-7 to prepare a cellulose nano microcrystal suspension; and (3) dripping 0.5ml of CNCs dispersion liquid on a glass sheet substrate, slowly drying for 2 days at room temperature, and performing water evaporation induction to form a semitransparent self-assembled ordered structure to prepare the self-assembled cellulose nano microcrystalline film.
2. Dissolving amorphous high-molecular Tg type shape memory polyurethane in N, N-dimethylformamide to prepare a solution with the mass fraction of 20%. 5ml of the solution is uniformly dripped and transferred to the surface of the self-assembled cellulose nano microcrystalline film by a needle tube, and the solution is cured for 2 hours at 60 ℃ in vacuum to prepare the polymorphic shape memory driven multiple structure color transition intelligent optical film.
FIG. 1 is a schematic flow chart of the present invention for preparing an intelligent optical film. Wherein the SMP is a shape memory polymer, tg type shape memory polyurethane. As shown in FIG. 1, the composite material is obtained by embedding a self-assembled cellulose nano-crystallite ordered structure into a transparent, low water absorption amorphous thermally responsive shape memory polymer matrix. FIG. 2 is a schematic flow chart of the polymorphic shape memory multiple structure color transition of the present invention. Wherein, (a) is the initial state of the intelligent optical film, (b) is the temporary shape 1 obtained by pre-stretching, (c) is the temporary shape 2 obtained after the pre-stretching temporary shape is fixed, (the temporary shape 1 can shrink to a certain extent), (d) is the deformation recovery 1 obtained under the first thermal stimulation, and (e) is the deformation recovery 2 obtained under the second water stimulation. The polymorphic shape memory regulation process is divided into: (1) pre-stretching in hot water at 70-120 ℃; (2) carrying out shape fixation at room temperature; (3) Under the heating condition of 70-120 ℃, performing deformation recovery 1 (corresponding to (d) in the figure); (4) The deformation recovery 2 is carried out under water-moisture triggering conditions, i.e. hot water at 80-90 ℃ (corresponding to (e) in the figure).
The multiple shape memory driven intelligent optical film has adjustable multiple structural color conversion performance, and the transmission spectrum of the optical film is transferred from red light to blue light. With the transformation of the three shapes, the structural color is also transformed from colorless transparency, red light and blue light. FIG. 3 is a graph of spectral shift for the polymorphic shape memory smart optical film drive of example 1. The intelligent optical film driven by multiple shape memories is pre-stretched by 20 percent after being soaked in water at 90 ℃ for 2min, and is cooled, dried and fixed at room temperature, and at the moment, the intelligent optical film is colorless and transparent. Reheating to 90 ℃ to trigger the first deformation recovery, wherein the recovery rate is 65%, the peak value of the transmission spectrum shifts from 1100nm to 834nm, and at the moment, the intelligent optical film is converted from colorless transparency to red light; and further dropwise adding hot water at the temperature of 80-90 ℃ for stimulation to trigger secondary deformation recovery, wherein the recovery rate is 93%, the peak value of the transmission spectrum shifts from 834nm to 450nm, and at the moment, the intelligent optical film is changed from red light to blue light. The multiple shape memory driven intelligent optical film has adjustable multiple structural color conversion performance, and the transmission spectrum of the optical film is transferred from red light to blue light.
Example 2
1. Dissolving the cellulose nano microcrystalline powder in deionized water to prepare a suspension solution with the mass fraction of 5%, ultrasonically dispersing for 2 hours at room temperature, and adjusting the pH value to be between 5 and 7. And (3) dropwise coating 2ml of CNCs suspension on a glass sheet substrate, slowly drying at room temperature for 2 days, and evaporating and inducing water to form a semitransparent self-assembled ordered structure to obtain the self-assembled cellulose nano microcrystalline film.
2. Dissolving amorphous high-molecular Tg type shape memory polyurethane in N, N-dimethylformamide to prepare a solution with the mass fraction of 20%. 5ml of the solution is uniformly dripped and transferred to the surface of the self-assembled cellulose nano microcrystalline film through a needle tube, and the self-assembled cellulose nano microcrystalline film is placed in an oven and cured for 2 hours at 60 ℃ under vacuum to prepare the intelligent optical film driven by multiple shape memories.
After the intelligent optical film is soaked in hot water at the temperature of 90 ℃ for 1min, the intelligent optical film is pre-stretched by 50 percent and is cooled, dried and fixed at room temperature. Heating to 90 ℃ again to trigger the first deformation recovery, wherein the recovery rate is 55%, and the peak value of the transmission spectrum shifts from 1000nm to 634nm; and further dropwise adding hot water at the temperature of 80-90 ℃ to stimulate and trigger secondary deformation recovery, wherein the recovery rate is 86%, and the peak value of the transmission spectrum shifts from 634nm to 550nm. The intelligent optical film has the performance of multiple shape memory driven structural color transformation.
Example 3
1. Dissolving cellulose nano microcrystalline powder in deionized water to prepare a suspension solution with the mass fraction of 5%, performing ultrasonic dispersion for 2 hours at room temperature, and adjusting the pH value to be between 5 and 7. And (3) dropwise coating 2ml of CNCs suspension on a glass sheet substrate, slowly drying at room temperature for 2 days, and evaporating and inducing water to form a semitransparent self-assembled ordered structure to obtain the self-assembled cellulose nano microcrystalline film.
2. Dissolving amorphous high-molecular Tg type shape memory polyurethane in an N, N-dimethylformamide organic solvent to prepare a solution with the mass fraction of 20%. 5ml of the solution is uniformly dripped and transferred to the surface of the CNCs self-assembled film by a needle tube, and the CNCs self-assembled film is placed in an oven and cured for 2 hours at 60 ℃ under vacuum to prepare the intelligent optical film driven by multiple shape memories.
After the intelligent optical film is soaked in hot water at the temperature of 90 ℃ for 3min, the intelligent optical film is pre-stretched by 30 percent and is cooled, dried and fixed at room temperature. Heating to 90 ℃ again to trigger the first deformation recovery, wherein the recovery rate is 45%, and the peak value of the transmission spectrum shifts from 900nm to 700nm; further, the illumination intensity is 100mW/cm 2 The infrared lamp triggers the second deformation recovery, the recovery rate is 70%, and the peak value of the transmission spectrum shifts from 700nm to 500nm. The multiple shape memory driven intelligent optical film has the S performance of multiple shape memory driven structural color transition.
The self-assembled cellulose nano-crystallite plays two roles in a polymer composite film, namely, the self-assembled cellulose nano-crystallite is used as a controllable photonic crystal layer for generating structural color conversion and a hydro-entangled response reversible hydrogen bond network switch. The shape memory-driven multiple structural color transformation means that the optical film is sequentially deformed and restored under the triggering of external heat stimulation and multiple stimulation of water-moisture, and the transmission spectrum peak area of the optical film is subjected to blue shift.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes and modifications are intended to be included in the scope of the present invention.
Claims (6)
1. A preparation method of a polymorphic shape memory-driven multiple-structure color-transformation intelligent optical film is characterized by comprising the following specific steps:
s1, dissolving cellulose nano microcrystalline powder in deionized water, performing ultrasonic treatment at room temperature, and adjusting the pH value to 5~7 to prepare a CNCs suspension; the mass concentration of the CNCs suspension is 0.5 to 10 percent;
s2, dripping the CNCs suspension onto a glass sheet substrate, and drying at room temperature to form a semitransparent self-assembled ordered structure to prepare a self-assembled cellulose nano microcrystalline film;
s3, dissolving the amorphous polymer in an organic solvent to prepare a solution, uniformly dripping the solution on the surface of the self-assembled cellulose nano microcrystalline film, and curing at 40-80 ℃ in vacuum to prepare the polymorphic shape memory-driven multi-structure color-changing intelligent optical film; the amorphous polymer is more than one of Tg type shape memory polyurethane, polytetrahydrofuran or polystyrene, and the molecular weight of the amorphous polymer is 10000 to 100000; the organic solvent in the organic solution of the amorphous polymer is more than one of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran or dichloromethane; the mass concentration of the organic solution of the amorphous polymer is 5-50%.
2. The method for preparing the polymorphic shape memory-driven multiple structural color transition intelligent optical film according to claim 1, wherein the ultrasound time in step S1 is 30 to 120min.
3. The method as claimed in claim 1, wherein the drying time in step S2 is 1~4 days.
4. The method for preparing the polymorphic shape memory-driven multiple structural color transition intelligent optical film according to claim 1, wherein the curing time in the step S3 is 2 to 12h.
5. A polymorphic shape memory-driven intelligent optical film with multiple structural color transitions, wherein the intelligent optical film is prepared by the method of any one of claims 1-4.
6. The polymorphic shape memory-driven intelligent optical film with multiple structural color transitions, as claimed in claim 5, for use in the field of optical cryptography.
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| CN108795018A (en) * | 2018-06-22 | 2018-11-13 | 南京林业大学 | A kind of preparation method of polyurethane/fibrination functional configurations memory high molecular material |
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| CN109880134A (en) * | 2019-01-23 | 2019-06-14 | 齐鲁工业大学 | A kind of preparation method of the intelligent response composite material of chiral nematic phase structure |
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