CN108318943A - A kind of Responsive photonic crystals elastomeric film material, it is prepared and application - Google Patents
A kind of Responsive photonic crystals elastomeric film material, it is prepared and application Download PDFInfo
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- CN108318943A CN108318943A CN201810216897.XA CN201810216897A CN108318943A CN 108318943 A CN108318943 A CN 108318943A CN 201810216897 A CN201810216897 A CN 201810216897A CN 108318943 A CN108318943 A CN 108318943A
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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
Abstract
The invention belongs to Functionally structure field, more particularly to a kind of response, can selfreparing, display non-angular rely on photonic crystal elastomer film, preparation method and application.The Responsive photonic crystals elastomeric film material of the present invention, including cross-linked polymer matrix material, modified Nano particle and extinction nano material；The molar ratio of the cross-linked polymer, modified Nano particle and extinction nano material is (1~200)：100:(0~5)；The modified Nano particle and extinction nano material are dispersed in the structural arrangement of shortrange order in the cross-linked polymer matrix material, the color of the photonic crystal elastomeric film material does not change with viewing angle, it can be repaired automatically mechanical damage occurs, there is elasticity in drawing process.
Description
Technical field
The invention belongs to the invention in Functionally structure field, relate more specifically to a kind of response, can selfreparing, aobvious
Show that non-angular relies on photonic crystal elastomer film, preparation method and application.
Background technology
Photonic crystal is a kind of material with periodic nano-structure, in sensing, display, detection, nano impression, intelligence
The fields such as material have good application prospect.Photonic crystal has long range ordered structure so that crystal film with photon generally has
Dependence of angle, and its colour stable is required in use in order to observe and detect, therefore prepare non-angular and rely on
Photonic crystal membrane material have important application value.Meanwhile photonic crystal membrane material will not only have when in use convenient for seeing
The color examined also needs to have certain elasticity and has response to environmental stimuli, could realize in this way to light, heat, electricity, magnetic, from
The response of son etc., to widen its use scope.Traditional Responsive photonic crystals film mainly using basis material or is received
The property of rice corpuscles itself realizes its response to environmental stimuli；Be difficult to reach restore after response, duplicate responses and recovery
Purpose.Side particularly important to the practical application of photonic crystal membrane material, and traditional at present is replied and recycled to stimuli responsive
Method also cannot be satisfied the requirement.
Although selfreparing crystal film with photon is it has been reported that but in the photonic crystal of processing machinery (as stretched) response
It is low, frangible using the most intensity of photonic crystal membrane material of prior art preparation in terms of film, it cannot be satisfied the need of practical application
It asks.In addition, crystal film with photon preparation process prepared by conventional method is complicated, stretching is difficult to reuse, and cannot achieve selfreparing
With the purpose of reuse.The defect of the above photonic crystal membrane material and the insufficient practical application for strongly limiting the material.
Invention content
For the disadvantages described above or Improvement requirement of the prior art, the present invention provides a kind of response, can selfreparing, display
Non-angular relies on photonic crystal elastomer film, preparation method and application, fully combines photonic crystal elastomeric film material
Feature and demand, specific aim assembles the polymer material type of weight to photon crystal material and nano-particle type carries out again
Selection, and the other parameters such as key parameter such as component proportion, component dissolubility are designed, correspondingly obtain a kind of sound
Ying Xing, can selfreparing, display non-angular rely on photonic crystal elastomer film, thus solve the prior art photonic crystal membrane material
Most intensity is low, frangible, and demand and the preparation process that cannot be satisfied practical application are complicated, and stretching is difficult to reuse, can not
The technical issues of purpose of realization selfreparing and reuse.
To achieve the above object, according to one aspect of the present invention, a kind of Responsive photonic crystals elastomer film is provided
Material, including cross-linked polymer matrix material, modified Nano particle and extinction nano material；The cross-linked polymer, modification are received
The molar ratio of rice corpuscles and extinction nano material is (1~200)： 100:(0~5)；The modified Nano particle and the extinction
Nano material is dispersed in the structural arrangement of shortrange order in the cross-linked polymer matrix material, the photonic crystal elastomer film
The color of material does not change with viewing angle, can be repaired automatically after mechanical damage occurs, and has elasticity in drawing process.
Preferably, the size of the modified Nano particle is 100~500nm；The size of the extinction nano material is 10
~100nm.
Preferably, the cross-linked polymer passes through generation coordination, host-guest between crosslinking agent and the functional group of polymer
Interaction, hydrogen bond or chemical crosslink reaction and the cross-linked polymer with network structure formed, the polymer for it is transparent,
The refraction index of flexible functionalized polymer, the polymer is 1.2~2.0；The functionalized polymer contains
At least one of amino, pyridine groups, imidazoles, azobenzene, cyclodextrin, hydroxyl, sulfydryl, boric acid or adamantane double bond, it is described
The glass transition temperature of polymer is less than 25 DEG C；The molar ratio of the polymer and the crosslinking agent is 0.05:1~6:1.
Preferably, the polymer is functionalized dimethyl silicone polymer (PDMS) or functionalized polyacrylic acid fourth
Ester.
Preferably, the crosslinking agent is selected from metal ion, cyclodextrin, boric acid, polyalcohol, multi-thiol and diolefin.
Preferably, the metal ion is alkaline-earth metal ions, transition metal ions or rare earth metal with unoccupied orbital
Ion.
Preferably, the metal ion is Ce3+、Zn2+、Cu2+、Ni2+Or Co2+One or more of.
Preferably, the nano-particle of the modification carries out cross-linking modified obtain by nano-particle under the action of modifying agent
It arrives, the nano-particle is does not dissolve in organic solvent, and medicine ball or nucleocapsid knot of the size within the scope of 100-500nm
Structure spheroidal particle；The modifying agent is the oil-soluble polymers that molecular weight is less than 40000g/mol.
Preferably, the nano-particle is SiO2Nano-particle, polystyrene nanoparticle or polymethylacrylic acid nanometer
Particle.
Preferably, the modifying agent is the oil-soluble polymers that molecular weight is 600~30000g/mol.
Preferably, the modified Nano particle has the degree of cross linking more than 40%.
Preferably, the extinction nano material is selected from carbon black, CNT, graphene, fullerene, PbS and CuS.
Other side according to the invention provides a kind of preparation side of Responsive photonic crystals elastomeric film material
Method includes the following steps：
(1) preparation of modified Nano particle：Nano-particle is passed through into sol-gal process under the action of modifying agent
Learn and be modified, then in organic solvent by modified nano-particle dispersion, wherein the mass concentration of modified Nano particle be 1%~
50%；The nano-particle is will not dissolve in organic solvent, and medicine ball or nucleocapsid of the size within the scope of 100-500nm
Structure spheroidal particle；The modifying agent is the oil-soluble polymers that molecular weight is less than 40000g/mol；
(2) preparation of cross-linked polymer：It will be obtained containing poly- after transparent, elastic functionalized polymer dissolving or melting
Close the organic solution of object, then crosslinking agent be added dropwise in the organic solution containing polymer, the polymer with it is described
The molar ratio of crosslinking agent is 0.05:1~6:1；Be coordinated by generation between the crosslinking agent and the functional group of the polymer,
Host-guest interactions, hydrogen bond or chemical crosslink reaction and to form the crosslinking with self-repair function with network structure poly-
Close object；The cross-linked polymer water white transparency, refraction index are 1.2~2.0；The functionalized polymer contain amino,
At least one of pyridine groups, imidazoles, azobenzene, cyclodextrin, hydroxyl, sulfydryl, boric acid or adamantane double bond；The polymer
Glass transition temperature be less than room temperature (25 DEG C)；The crosslinking agent is selected from metal ion, cyclodextrin, boric acid, polyalcohol, polynary
Mercaptan and diolefin；In organic solvent by the cross-linked polymer prepared dispersion, the mass concentration of wherein cross-linked polymer is
1%~65%；
(3) preparation of photonic crystal elastic film material：By the modified Nano grain of step (1) dispersion in organic solvent
Son disperses the cross-linked polymer in organic solvent according to mass ratio 100 with extinction nano material and step (2)：(0~
5)：(1~200), preferred mass ratio are 100：(0~2)：(1~200), in hydrophobic and organic solvent-resistant material surface or appearance
Device internal mix obtains Hybrid assembling body, and organic solvent under the conditions of 20~70 DEG C in Hybrid assembling body described in fast eliminating obtains
To photonic crystal elastic film material, wherein the removing rate of the organic solvent is more than 0.4ml/min；Or by the mixing group
Dress body is placed in spraying container, is sprayed into the hydrophobic material surface and is obtained photonic crystal elastic film material；
Wherein, step (1) modifying agent and the Flory-Huggin of step (2) described cross-linked polymer interact
Parameter is not more than 0.5, it is ensured that modified Nano particle described in step (3) can dissolve each other with the cross-linked polymer.
Preferably, the nano-particle is SiO2Nano-particle, polystyrene nanoparticle or polymethylacrylic acid nanometer
Particle.
Preferably, the modifying agent is the oil-soluble polymers that molecular weight is 600~30000g/mol.
Preferably, the modified Nano particle has the degree of cross linking more than 40%.
Preferably, the organic solvent is selected from tetrahydrofuran, chloroform, dichloromethane, hexamethylene, DMSO, DMF, benzene, first
Alcohol, ethyl alcohol, isopropanol, pyridine, toluene, ethyl acetate and acetone.
Preferably, the molecular weight of step (2) described polymer is 5000~1,000,000g/mol
Other side according to the invention provides a kind of application of the photonic crystal elastic membrane, is applied to anti-
Pseudo-, wearable, fingerprint recognition, sensor, coating or paint field.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect：
(1) present invention realizes the preparation of cross-linked polymer by selecting particular kind of polymer and crosslinking agent.The present invention
Selecting has the polymer of higher elasticity and modulus, and the molar ratio by regulating and controlling polymer and crosslinking agent regulates and controls cross-linked polymer
The degree of cross linking, to being adjusted to obtain film strength according to use demand.
(2) cross-linked polymer that the present invention uses contains reversible crosslink structure, is the selfreparing of photonic crystal elastomer film
Provide a good platform, after the film is destroyed in use can the selfreparing within the regular hour, be convenient for material
Material is used for multiple times.
(3) the present invention provides a kind of preparation methods of photonic crystal elastomer film, real by quickly volatilizing or spraying
The preparation of non-angular dependence crystal film with photon is showed, preparation time is short, easy to operate, and repeatability is strong, convenient for extensive system
It is standby.
(4) present invention introduces the extinctions nano material such as carbon black in photonic crystal elastomer film preparation process, is conducive to
It stretches or observes its color when compressing, be conducive to it in context of detection application.
(5) the schemochrome non-angular dependence of photonic crystal elastomer provided by the invention has preferable elasticity and has
Standby self-healing properties.This photonic crystal elastomer is interacted with functionalized polymer and additional third substance, that is, crosslinking agent
Cross-linked structure is formed, then the modified nano-particle of oleophylic and extinction nano material are dispersed in cross-linked polymer ultrasonic mixing
In specific solvent, after by modes such as spraying, spin coatings control solvent evaporation rate and prepare and form a film.This method is easy to operate, at
This is low and is prepared convenient for extensive.Obtained photonic crystal elastomer film also has one other than having specific schemochrome
Fixed fluorescent characteristic can be used for anti-fake, wearable device, fingerprint recognition, sensor, selfreparing colour-wash, intelligent toy etc.
Field.
(6) it is provided by the invention can photonic crystal elastomer film its area of selfreparing and display non-angular dependence can root
According to arbitrarily adjustment, the spraying technology used is needed advantage is provided for the large area preparation of the film.Can meet it is anti-fake, can wear
It wears, the size requirement in the applications such as fingerprint recognition, sensor or even coating, paint to photonic crystal elastomer, is expected to realize light
Practical application of the sub- crystal film in above-mentioned field.
Description of the drawings
Fig. 1 is the scanning electricity for four kinds of various sizes of Nano particles of silicon dioxide that embodiment 1 is synthesized according to the method
Mirror picture.Fig. 1 (a) prepare blue photons film thus improved silica nano-particle；Fig. 1 (b) prepares green photon film institute
With improved silica nano-particle；Fig. 1 (c) prepare the sub- film of yellow colour thus improved silica nano-particle；Fig. 1
(d) prepare yellow photons film thus improved silica nano-particle the case where disperseing in PDMS.
Fig. 2 is four kinds of various sizes of improved silica nano-particles and the crosslinking of embodiment 2-6 the methods synthesis
The digital photograph (Fig. 2 (a)) and spectrogram (Fig. 2 (b)) for the crystal film with photon that polymer is prepared after being blended.The sample exists
Shown in the variation relation such as Fig. 2 (c) of the maximum absorption band of different angle with angle, this illustrates that the sample does not have dependence of angle.
Fig. 2 (d) is cross-linked polymer and adds the drawing of the crystal film with photon prepared after four kinds of various sizes of Nano particles of silicon dioxide
Stretch curve.
Fig. 3 be four kinds of different colours photonic crystal elastomer films preparing of embodiment 1-6 different angle (0 °, 15 °,
30 °, 45 °, 60 °, 75 °) observation when obtained spectrogram：Fig. 3 (a) blue photons crystal films, Fig. 3 (b) green photon crystal films,
Fig. 3 (c) yellow photons crystal films, Fig. 3 (d) red photon crystal films.
Fig. 4 be embodiment 2 prepare crystal film with photon, surface have cut (blade is scratched) afterwards (Fig. 4 (a)) at 60 DEG C
The digital photograph of (Fig. 4 (b)) after lower placement 48h.
It is the crystal film with photon after being scratched with knife that Fig. 5, which is embodiment 2, and 60 DEG C are repaired certain time (6 h, for 24 hours, 48h)
Extension test data afterwards.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
It does not constitute a conflict with each other and can be combined with each other.
The photon crystal material of the prior art cannot meet simultaneously response, can selfreparing, reuse, display non-angular
Dependence and sufficient intensity, the present invention provides a kind of Responsive photonic crystals elastomeric film materials, including cross-linked polymer base
Body material, modified Nano particle and extinction nano material；The cross-linked polymer, modified Nano particle and extinction nano material
Molar ratio is (1~200)：100:(0~5)；The modified Nano particle and extinction nano material are arranged with the structure of shortrange order
Row are dispersed in the cross-linked polymer matrix material, and the color of the photonic crystal elastomeric film material does not become with viewing angle
Change, can be repaired automatically mechanical damage occurs, there is elasticity in drawing process.The size of the modified Nano particle is
100-500nm；The size 10-100nm of the extinction nano material.
Wherein, cross-linked polymer is mutual by generation coordination, master-object between crosslinking agent and the functional group of polymer
Effect, hydrogen bond or chemical crosslink reaction and the cross-linked polymer with network structure formed, the polymer and the crosslinking
The molar ratio of agent is 0.05:1~6:1；The cross-linked polymer water white transparency, refraction index are 1.2~2.0；It is wherein described
Polymer is transparent, elastic functionalized polymer, and the glass transition temperature of the polymer is less than room temperature (25 DEG C), institute
It states functionalized polymer and preferably comprises amino, pyridine groups, imidazoles, azobenzene, cyclodextrin, hydroxyl, sulfydryl, boric acid or Buddha's warrior attendant
At least one of alkane double bond；The polymer is preferably functionalized dimethyl silicone polymer (PDMS) or functionalized poly-
Butyl acrylate；The crosslinking agent is preferably selected from metal ion, cyclodextrin, boric acid, polyalcohol, multi-thiol and diolefin.Gold
It is alkaline-earth metal ions, transition metal ions or rare earth ion with unoccupied orbital, preferably Ce to belong to ion3+、Zn2+、Cu2 +、Ni2+Or Co2+One or more of.
When polymer is the polymer containing amino, pyridine groups or imidazole group, crosslinking agent is metal ion.Polymerization
Object is coordinated by occurring with crosslinking agent by forms the cross-linked polymer with network structure.The selection gist of metal ion is to ensure
Polymer after crosslinking does not have deeper color, does not influence the colour developing of photonic crystal.
When polymer is polymer containing groups such as polyalcohol, multi-thiol, amido bonds, crosslinking agent be polyalcohol,
Polyacid, amido bond form cross-linked polymer between polymer and crosslinking agent with hydrogen bond action.
When polymer and crosslinking agent are polymer isostructural containing azobenzene, crosslinking agent, which is cyclodextrin etc., can pass through master-
Object interacts and forms the cross-linked polymer with network structure.
When polymer be containing hydroxyl, polyol structure polymer when, crosslinking agent is boric acid, and polymer is logical with crosslinking agent
It crosses chemical crosslink reaction and forms the cross-linked polymer with network structure.
The present invention polymerize species to obtain the photonic crystal of the cross-linked polymer of clear, colorless and then acquisition clear, colorless
The selection of class and the selection of type of crosslinking agent are most important, and polymer and crosslinking agent are both preferably clear, colorless, at least want
Ask its refraction index of the cross-linked polymer to be formed in 1.2~2.0 ranges.On the other hand, in order to have after obtaining mechanical damage
Can restore deformation realization cycling and reutilization after self-repair function, stretching repairs photonic crystal, by especially selecting to have
Certain functionalized polymer of elasticity is crosslinked with suitable crosslinking agent, and the cross-linked polymer of formation is because of its framework material
For polysiloxanes, butyl polyacrylate etc. there is the polymer compared with low Tg, polymer chain to have preferable flexibility, gather
It closes and act as reversible action between object and crosslinking agent, when connection (coordinate bond, the host-guest phase between polymer and crosslinking agent
The corresponding chemical bond of interaction, hydrogen bond or the corresponding chemical bond of chemical crosslinking) disconnect after, and can be again coupled to, i.e., it is of the invention
Cross-linked polymer contain reversible crosslink structure, restore deformation after tension failure or when surface abrasion, realize that cycle is sharp again
With.
Modified nano-particle carried out under the action of modifying agent by nano-particle it is cross-linking modified obtain, the nanoparticle
Son is does not dissolve in organic solvent, and medicine ball or nucleocapsid spheroidal particle of the size within the scope of 100-500nm, described
Nano-particle is preferably SiO2Nano-particle, polystyrene nanoparticle or polymethylacrylic acid nano-particle；It is preferred that nanoparticle
Son is SiO2Nano-particle, preferred size range 170-270nm；Modifying agent is that molecular weight is molten less than the oil of 40000g/mol
Property polymer, preferably molecular weight be 600~30000g/mol oil-soluble polymers；By using small molecule oil-soluble polymerization
Object is cross-linking modified to nano-particle progress, and its object is to enhance modified Nano particle and the crosslinking with supramolecular network structure
The compatibility of polymer.Modified Nano particle preferably has greater than 40% degree of cross linking, correspondingly, modified Nano particle and crosslinking
Polymer has better compatibility.Nano-particle is modified using modifying agent, makes modified nano-particle and crosslinking
Polymer has good dissolving compatibility, should by selecting the Flory-Huggin interaction parameters with cross-linked polymer
What parameter mainly characterized two kinds of polymer is mutually dissolved performance, can pass through solubility meter of the two kinds of polymer in same solvent
It calculates, when value is not more than 0.5, modified Nano particle has well mutually when being mixed with photon crystal film with cross-linked polymer
It is molten, be not in macro when realizing that the specific requirement well dissolved each other mixes for the two with cross-linked polymer to modified Nano particle here
See phase separation when rheology testing (i.e., the frequency scanning curve under different temperatures meets time temperature equivalence principle of stacking).
Extinction nano material is selected from carbon black, CNT, graphene, fullerene, PbS and CuS.
The present invention provides the preparation methods of above-mentioned Responsive photonic crystals elastomeric film material, include the following steps：
(1) preparation of modified Nano particle：Nano-particle is handed under the action of modifying agent by sol-gal process
Connection is modified, and specific method is：Then modified nano-particle is disperseed in organic solvent, wherein the quality of modified Nano particle
A concentration of 1%~50%；The nano-particle is that will not dissolve in organic solvent, and size is within the scope of 100-500nm
Medicine ball or nucleocapsid spheroidal particle；The nano-particle is preferably SiO2Nano-particle, polystyrene nanoparticle or poly-
Methacrylic acid nano-particle；The modifying agent is that molecular weight is less than 40000, and preferred molecular weight is 600~30000g/mol's
Oil-soluble polymers, the modified Nano particle preferably have greater than 40% degree of cross linking.
(2) preparation of cross-linked polymer：By transparent, elastic functionalized polymer using organic solvent carry out dissolving or
The organic solution containing polymer is obtained after melting, and then crosslinking agent is added dropwise in the organic solution containing polymer,
The molar ratio of the polymer and the crosslinking agent is 0.05:1~6:1；The crosslinking of polymer is controlled by controlling the molar ratio
Degree, and the degree of cross linking should not it is too high can not be too low, too high crystal film with photon elasticity is too low, the too low photonic crystal film-strength of the degree of cross linking
Not enough.By the way that coordination, host-guest interactions or chemical crosslinking occurs between the crosslinking agent and the functional group of the polymer
It reacts and forms the cross-linked polymer with self-repair function with network structure；The cross-linked polymer water white transparency, folding
Optical index is 1.3~1.8；The functionalized polymer preferably comprise amino, pyridine groups, imidazoles, azobenzene, cyclodextrin,
The glass transition temperature of at least one of hydroxyl, sulfydryl, boric acid or adamantane double bond, the polymer is less than room temperature (25
℃)；The crosslinking agent is preferably selected from metal ion, cyclodextrin, boric acid, polyalcohol, multi-thiol and diolefin；Point of polymer
Son amount is 5000~1,000,000g/mol.The cross-linked polymer prepared is disperseed in organic solvent, wherein cross-linked polymeric
The mass concentration of object is 1%~65%；The concentration of cross-linked polymer cannot be too high, otherwise assembling prepare photonic crystal be cannot
The defect sturcture of shortrange order is formed, on the other hand, concentration is too high, and spraying may be blocked when preparing photonic crystal using spray coating method
Rifle.The polymer is preferably functionalized dimethyl silicone polymer (PDMS) or functionalized butyl polyacrylate；The friendship
Connection agent is preferably selected from metal ion, cyclodextrin, boric acid, polyalcohol, multi-thiol and diolefin.Metal ion is with unoccupied orbital
Alkaline-earth metal ions, transition metal ions or rare earth ion, preferably Ce3+、Zn2+、Cu2+、Ni2+Or Co2+In one
Kind is a variety of.
(3) preparation of photonic crystal elastic film material：By the modified Nano grain of step (1) dispersion in organic solvent
Son disperses the cross-linked polymer in organic solvent according to mass ratio 100 with extinction nano material and step (2)：(0~
5)：(1~200), preferred mass ratio are 100：(0~2)：(1~200), in hydrophobic and organic solvent-resistant material surface or appearance
Device internal mix obtains Hybrid assembling body, and organic solvent under the conditions of 20~70 DEG C in Hybrid assembling body described in fast eliminating obtains
To photonic crystal elastic film material, wherein the removing rate of the organic solvent is more than 0.4mL/min；Or by the mixing group
Dress body is placed in spraying container, is sprayed into the hydrophobic material surface and is obtained photonic crystal elastic film material.Extinction nano material
It can first mix with modified Nano particle, then be mixed with the organic solution of cross-linked polymer, three can be also carried out at the same time to mixing.
Wherein, step (1) modifying agent and the Flory-Huggin of step (2) described cross-linked polymer interact
Parameter is not more than 0.5, it is ensured that modified Nano particle described in step (3) can dissolve each other with the cross-linked polymer.Organic solvent
Selected from tetrahydrofuran, chloroform, dichloromethane, hexamethylene, DMSO, DMF, benzene, methanol, ethyl alcohol, isopropanol, pyridine, toluene, second
Acetoacetic ester and acetone.
In above-mentioned preparation method, cross-linked polymer, modified Nano particle and extinction nano material are being subjected to Hybrid assembling
When at photon crystal film material, the interaction of modified Nano particle and cross-linked polymer (ensures modified Nano particle and gathers
Conjunction is mutually dissolved) and the evaporation rate of organic solvent be to directly influence the photon crystal film being finally prepared to develop the color
Two key factors, not requiring nothing more than cross-linked polymer and modified Nano particle has good compatibility, and compatibility is too poor to be led
It causes the phase separation of large-size and then the elastomer film of preparation is made not have color；And the evaporation rate of organic solvent is had to
Soon, to ensure that modified Nano particle forms the package assembly of shortrange order in the polymer.Extinction nano material is in Hybrid assembling
Mass fraction in body also should not be too high, and otherwise the color of light absorbent can cover the colour developing of photonic crystal.Using spraying legal system
When standby photon crystal film, spraying rate cannot be too high, and otherwise organic solvent has little time to volatilize, and leads to that photon crystalline substance cannot be formed
Body, rational spraying rate mainly pass through nitrogen pressure when spraying, control as 0.03MPa~0.5MPa.For the ease of that will make
Standby obtained photon crystal film is removed, is taken out from preparing in container, it should be noted that selection hydrophobicity is good and resistance to has
The material of solvent (not dissolving in organic solvent), adhesion polymer, the currently preferred container material quality for preparing is polytetrafluoroethyl-ne
Sheet glass, silicon chip, the mica sheet etc. of alkene, Kynoar, polypropylene, polyethylene or hydrophobically modified.
The application of above-mentioned photonic crystal elastic membrane provided by the invention, at the same have response, can selfreparing, repeat make
With, display non-angular rely on and sufficient intensity, can be widely applied to anti-fake, wearable, fingerprint recognition, sensor, coating or
Paint field.
It is embodiment below：
Embodiment 1
(1) synthesis and modification of Nano particles of silicon dioxide：By 8mL ammonium hydroxide, 4mL water dissolutions in the ethyl alcohol of 100mL,
After stirring ten minutes, the TEOS of 3mL is added dropwise, quickly stirring 15min is added dropwise, reduces mixing speed, 30 DEG C of reaction 5- afterwards
6h is centrifuged with the rotating speed of 8 000rpm after the completion of reaction, is washed, centrifuged with ethanol solution hydrochloride, water and ethyl alcohol successively
Nano-particle is dried in vacuo at 50 DEG C and obtains white solid.Then by the Nano particles of silicon dioxide ultrasonic disperse of 1g 85
In mL ethyl alcohol, the lower ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol) that ammonium hydroxide is added dropwise, 40 stirring 1h are stirred, then by molecule
The ethanol solution for the PDMS that the triethoxy that amount is 600-900g/mol blocks is slowly dropped in above-mentioned solution, and addition finishes anti-
Should for 24 hours, product centrifuges to obtain the silica of a diameter of 170nm with the rotating speed of 7 000rpm, uses ethanol solution hydrochloride, water successively
It is washed with ethyl alcohol, white solid is obtained after centrifugal vacuum drying (50 DEG C).Finally, Nano particles of silicon dioxide ultrasonic disperse is existed
In tetrahydrofuran solution (10wt%), and suitable carbon black particle (0.5 wt%) is added in the solution, ultrasonic disperse is uniformly standby
With.
(2) preparation of cross-linked polymer solution：The PDMS that molecular weight is 5 000g/mol is dissolved in tetrahydrofuran, it is dense
Degree is 15wt%.In methyl alcohol (0.01-0.2g/mL) by cerium chloride dissolving, the methanol solution of cerium chloride is slowly dripped under stirring
It is added in polymer solution, is stirred overnight at room temperature, it is spare.
(3) preparation of selfreparing photonic crystal elastomer film：Take the cross-linked polymer and silica nanometer of certain volume
Particle solution, with volume ratio 1：1 mixing ultrasound 1h, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/
For the solution of silica/carbon black by the method for spray gun spraying, control spraying nitrogen pressure used is 0.03MPa, is quickly volatilized
Solvent prepares the crystal film with photon that non-angular relies on.The volume of its membrane area solution used in spraying and spraying reception device
Size codetermines.
Embodiment 2
(1) synthesis and modification of Nano particles of silicon dioxide：By 8mL ammonium hydroxide, 4mL water dissolutions in the ethyl alcohol of 100mL,
After stirring ten minutes, the TEOS of 3mL is added dropwise, quickly stirring 15min is added dropwise, reduces mixing speed, 30 DEG C of reaction 5- afterwards
6h is centrifuged with the rotating speed of 8 000rpm after the completion of reaction, is washed, centrifuged with ethanol solution hydrochloride, water and ethyl alcohol successively
Nano-particle obtains white solid after being dried in vacuo at 50 DEG C.Then by the Nano particles of silicon dioxide ultrasonic disperse of 1g 85
In mL ethyl alcohol, the stirring lower ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol) that ammonium hydroxide is added dropwise, 40 DEG C of stirring 1h, then will divide
The ethanol solution for the PDMS that the triethoxy that son amount is 600-900g/mol blocks is slowly dropped in above-mentioned solution, and addition finishes
Reaction for 24 hours, product centrifuges to obtain the silica of a diameter of 170nm with the rotating speed of 7 000rpm, successively use ethanol solution hydrochloride,
Water, ethyl alcohol washing, centrifugal vacuum drying (50 DEG C) obtain white solid.Finally by Nano particles of silicon dioxide ultrasonic disperse four
In hydrogen tetrahydrofuran solution (10wt%), and suitable carbon black particle (1wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer solution：The PDMS that molecular weight is 50 000g/mol is dissolved in tetrahydrofuran,
A concentration of 10wt%.In methyl alcohol (0.01-0.2g/mL) by cerium chloride dissolving, under stirring that the methanol solution of cerium chloride is slow
It is added drop-wise in polymer solution, is stirred overnight at room temperature, it is spare.
(3) preparation of selfreparing photonic crystal elastomer film：Take the cross-linked polymer and silica nanometer of certain volume
Particle solution, with volume ratio 1：1 mixing ultrasound 1h, using the black polypropylene plate of 8cm*8cm as reception device, by polymer/
For the solution of silica/carbon black by the method for spray gun spraying, control spraying nitrogen pressure used is 0.08MPa, is quickly volatilized
Solvent prepares the crystal film with photon that non-angular relies on.The volume of its membrane area solution used in spraying and spraying reception device
Size codetermines.
Embodiment 3
(1) synthesis and modification of Nano particles of silicon dioxide：By 8mL ammonium hydroxide, 2mL water dissolutions in the ethyl alcohol of 100mL,
After stirring ten minutes, the TEOS of 3mL is added dropwise, quickly stirring 15min is added dropwise, reduces mixing speed, 30 DEG C of reaction 5- afterwards
6h is centrifuged with the rotating speed of 8 000rpm after the completion of reaction, is washed successively with ethanol solution hydrochloride, water, ethyl alcohol, what is centrifuged receives
Rice corpuscles is dried in vacuo at 50 DEG C and obtains white solid.Afterwards by the Nano particles of silicon dioxide ultrasonic disperse of 1g in 85mL second
In alcohol, the lower ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol) that ammonium hydroxide is added dropwise, 40 DEG C of stirring 1h are stirred, then by molecular weight
Ethanol solution for the PDMS of the triethoxy sealing end of 600-900g/mol is slowly dropped in above-mentioned solution, and addition finishes reaction
For 24 hours, product centrifuges to obtain the silica of a diameter of 200nm with the rotating speed of 7 000rpm, successively use ethanol solution hydrochloride, water,
Ethyl alcohol washs, and centrifugal vacuum drying (50 DEG C) obtains white solid.Finally by Nano particles of silicon dioxide ultrasonic disperse in tetrahydrochysene
In tetrahydrofuran solution (10wt%), and suitable carbon black particle (0.5wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer solution：The PDMS that molecular weight is 100 000g/mol is dissolved in tetrahydrofuran,
A concentration of 5wt%.In methyl alcohol (0.01-0.2g/mL) by cerium chloride dissolving, the methanol solution of cerium chloride is slowly dripped under stirring
It is added in polymer solution, is stirred overnight at room temperature, it is spare.
(3) preparation of selfreparing photonic crystal elastomer film：Take the cross-linked polymer and silica nanometer of certain volume
Particle solution, with volume ratio 1：1 mixing ultrasound 1h, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/
The solution of silica/carbon black sprays nitrogen pressure used and is by the method for spray gun spraying, quick solvent flashing, control
0.5MPa prepares the crystal film with photon that non-angular relies on.The volume and spraying reception device of its membrane area solution used in spraying
Size codetermine.
Embodiment 4
(1) synthesis and modification of Nano particles of silicon dioxide：By 8mL ammonium hydroxide, 2mL water dissolutions in the ethyl alcohol of 100mL,
After stirring ten minutes, the TEOS of 3mL is added dropwise, quickly stirring 15min is added dropwise, reduces mixing speed, 30 DEG C of reaction 5- afterwards
6h is centrifuged with the rotating speed of 8 000rpm after the completion of reaction, is washed successively with ethanol solution hydrochloride, water, ethyl alcohol, what is centrifuged receives
Rice corpuscles is dried in vacuo at 50 DEG C and obtains white solid.Then by the Nano particles of silicon dioxide ultrasonic disperse of 1g in 85 mL
In ethyl alcohol, the lower ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol) that ammonium hydroxide is added dropwise, 40 DEG C of stirring 1h are stirred, then by molecule
The ethanol solution for the PDMS that the triethoxy that amount is 600-900g/mol blocks is slowly dropped in above-mentioned solution, and addition finishes anti-
Should for 24 hours, product centrifuges to obtain the silica of a diameter of 200nm with the rotating speed of 7 000rpm, uses ethanol solution hydrochloride, water successively
It is washed with ethyl alcohol, white solid is obtained after centrifugal vacuum drying (50 DEG C).Finally Nano particles of silicon dioxide ultrasonic disperse is existed
In tetrahydrofuran solution (10wt%), and suitable carbon black particle (1wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer solution：The PDMS that molecular weight is 50 000g/mol is dissolved in tetrahydrofuran,
A concentration of 10wt%.In methyl alcohol (0.01-0.2g/mL) by zinc chloride dissolving, under stirring that the methanol solution of zinc chloride is slow
It is added drop-wise in polymer solution, is stirred overnight at room temperature, it is spare.
(3) preparation of selfreparing photonic crystal elastomer film：Take the cross-linked polymer and silica nanometer of certain volume
Particle solution, with volume ratio 1：1 mixing ultrasound 1h, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/
The solution of silica/carbon black prepares the photonic crystal that non-angular relies on by the method for spray gun spraying, quick solvent flashing
Film.The volume of its membrane area solution used in spraying and the size of spraying reception device codetermine.
Embodiment 5
(1) synthesis and modification of Nano particles of silicon dioxide：By 8mL ammonia solvents in the ethyl alcohol of 100mL, stirring is very
The TEOS of 3mL is added dropwise in Zhong Hou, and quickly stirring 15min is added dropwise, and reduces mixing speed afterwards, and 30 DEG C of reaction 5-6h have reacted
It is centrifuged, is washed successively with ethanol solution hydrochloride, water and ethyl alcohol, the nano-particle centrifuged exists with the rotating speed of 8 000rpm after
White solid is obtained after being dried in vacuo at 50 DEG C.Then by the Nano particles of silicon dioxide ultrasonic disperse of 1g in 85mL ethyl alcohol,
The stirring lower ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol) that ammonium hydroxide is added dropwise, 40 DEG C of stirring 1h, then by molecular weight be 600-
The ethanol solution of the PDMS of the triethoxy sealing end of 900g/mol is slowly dropped in above-mentioned solution, and addition finishes reaction for 24 hours, production
Object centrifuges to obtain the silica of a diameter of 270nm with the rotating speed of 7 000rpm, is washed successively with ethanol solution hydrochloride, water and ethyl alcohol
It washs, white solid is obtained after centrifugal vacuum drying (50 DEG C).Finally by Nano particles of silicon dioxide ultrasonic disperse in tetrahydrofuran
In solution (10wt%), and suitable carbon black particle (2wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer solution：The PDMS that molecular weight is 50 000g/mol is dissolved in tetrahydrofuran,
A concentration of 10wt%.In methyl alcohol by metal ion dissolving, metal ion is slowly dropped in polymer solution under stirring, room
Temperature is stirred overnight, spare.
(3) preparation of selfreparing crystal film with photon：Take cross-linked polymer and the Nano particles of silicon dioxide of certain volume molten
Liquid, with volume ratio 1：1 mixing ultrasound 1h, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/titanium dioxide
The solution of silicon/carbon black prepares the crystal film with photon that non-angular relies on by the method for spray gun spraying, quick solvent flashing.Its film
The volume of area solution used in spraying and the size of spraying reception device codetermine.
Embodiment 6
(1) synthesis modification of polymer nano-particle：It is prepared by the method that polymer nano-particle mainly uses emulsion polymerization, with
Illustrate for the preparation of the polystyrene PHEMA balls of nucleocapsid.First polypyrrole alkanone (6.5g) is dissolved in 135g water,
Styrene (6.5g) 1,4-butanediol diacrylate (BDDA) is added dropwise after stirring and dissolving, is heated to 90 DEG C, is then slowly added dropwise
A certain amount of potassium persulfate solution, reaction are added HEMA, double fork acrylamides, potassium peroxydisulfate after 1.5 hours, are reacted after being added dropwise
It two hours, finally adds and the PDMS containing allyl double bonds and KPS carries out oleophylic modification to nanoparticle surface.Reaction
It is centrifuged after the completion with the speed of 9000rpm, washing obtains polymer nano-particle drying.Finally nano-particle ultrasonic disperse is existed
In tetrahydrofuran solution (10wt%), and suitable carbon black particle (2wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer solution：The PDMS that molecular weight is 50 000g/mol is dissolved in tetrahydrofuran,
A concentration of 10wt%.In methyl alcohol by metal ion dissolving, metal ion is slowly dropped in polymer solution under stirring, room
Temperature is stirred overnight, spare.
(3) preparation of selfreparing photonic crystal elastomer film：Take the cross-linked polymer and silica nanometer of certain volume
Particle solution, with volume ratio 1：1 mixing ultrasound 1h, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/
The solution of silica/carbon black prepares the photonic crystal that non-angular relies on by the method for spray gun spraying, quick solvent flashing
Film.The volume of its membrane area solution used in spraying and the size of spraying reception device codetermine.
Embodiment 7
(1) synthesis and modification of Nano particles of silicon dioxide：By 8mL ammonia solvents in the ethyl alcohol of 100mL, stirring is very
The TEOS of 3mL is added dropwise in Zhong Hou, and quickly stirring 15min is added dropwise, and reduces mixing speed afterwards, and 30 DEG C of reaction 5-6h have reacted
It is centrifuged, is washed successively with ethanol solution hydrochloride, water, ethyl alcohol, the nano-particle centrifuged exists with the rotating speed of 8 000rpm after
Vacuum drying obtains white solid at 50 DEG C.Afterwards by the Nano particles of silicon dioxide ultrasonic disperse of 1g in 85mL ethyl alcohol, stirring
It is lower be added dropwise ammonium hydroxide ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol), 40 DEG C stirring 1h, then by molecular weight be 600-
The ethanol solution of the PDMS of the triethoxy sealing end of 900g/mol is slowly dropped in above-mentioned solution, and addition finishes reaction for 24 hours, production
Object centrifuges to obtain the silica of a diameter of 270nm with the rotating speed of 7 000rpm, is washed successively with ethanol solution hydrochloride, water, ethyl alcohol
It washs, white solid is obtained after centrifugal vacuum drying (50 DEG C).Finally by Nano particles of silicon dioxide ultrasonic disperse in tetrahydrofuran
In solution (10wt%), and suitable graphene (2wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer：Cross-linked polymer preparation method in preceding embodiment 1-6 is suitble to physical crosslinking poly-
The preparation for closing object, for then needing to realize under conditions of melting when chemical crosslinking, with the crosslinking of hydroxy-end capped PDMS and boric acid
For illustrate, reaction bulb is dried before reactions, is heated after mixing PDMS and boric acid in certain proportion after sample drying
It melts, the viscosity of system significantly increases after stirring 6h, and polymer is dissolved in tetrahydrofuran after completion of the reaction, removes unreacted
Boric acid, the PDMS being chemically crosslinked, revolving remove tetrahydrofuran weigh after polymer is dissolved in it is spare in tetrahydrofuran.
(3) preparation of selfreparing photonic crystal elastomer film：Take the cross-linked polymer and silica nanometer of certain volume
Particle solution, with volume ratio 1：1 mixing ultrasound 1h, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/
The solution of silica/carbon black prepares the photonic crystal that non-angular relies on by the method for spray gun spraying, quick solvent flashing
Film.The volume of its membrane area solution used in spraying and the size of spraying reception device codetermine.
Embodiment 8
(1) synthesis and modification of Nano particles of silicon dioxide：By 8mL ammonia solvents in the ethyl alcohol of 100mL, stirring is very
The TEOS of 3mL is added dropwise in Zhong Hou, and quickly stirring 15min is added dropwise, and reduces mixing speed afterwards, and 30 DEG C of reaction 5-6h have reacted
It is centrifuged, is washed successively with ethanol solution hydrochloride, water, ethyl alcohol, the nano-particle centrifuged exists with the rotating speed of 8 000rpm after
Vacuum drying obtains white solid at 50 DEG C.Afterwards by the Nano particles of silicon dioxide ultrasonic disperse of 1g in 85mL ethyl alcohol, stirring
It is lower be added dropwise ammonium hydroxide ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol), 40 DEG C stirring 1h, then by molecular weight be 600-
The ethanol solution of the PDMS of the triethoxy sealing end of 900g/mol is slowly dropped in above-mentioned solution, and addition finishes reaction for 24 hours, production
Object centrifuges to obtain the silica of a diameter of 270nm with the rotating speed of 7 000rpm, is washed successively with ethanol solution hydrochloride, water, ethyl alcohol
It washs, white solid is obtained after centrifugal vacuum drying (50 DEG C).Finally by Nano particles of silicon dioxide ultrasonic disperse in tetrahydrofuran
In solution (10wt%), and suitable carbon black particle (2wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer：Cross-linked polymer preparation method in preceding embodiment 1-6 is suitble to physical crosslinking poly-
The preparation for closing object blocks PDMS and cyclodextrin for then needing to realize under conditions of melting when chemical crosslinking with azobenzene
Illustrate for crosslinking (host-guest interactions), the PDMS that the azobenzene that molecular weight is 50 000g/mol blocks is dissolved in four
In hydrogen furans, a concentration of 10 wt%.Beta-cyclodextrin is dissolved in tetrahydrofuran, can suitably heat, stir to improve its dissolubility
Mix it is lower beta-cyclodextrin is slowly dropped in polymer solution, be stirred at room temperature 36h or more, both ensure that fully effect, solution are protected
It deposits spare.
(3) preparation of selfreparing photonic crystal elastomer film：Take the cross-linked polymer and silica nanometer of certain volume
Particle solution, with volume ratio 1：1 mixing ultrasound 1h, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/
The solution of silica/carbon black prepares the photonic crystal that non-angular relies on by the method for spray gun spraying, quick solvent flashing
Film.The volume of its membrane area solution used in spraying and the size of spraying reception device codetermine.
Embodiment 9
(1) synthesis and modification of Nano particles of silicon dioxide：By 8mL ammonia solvents in the ethyl alcohol of 100mL, stirring is very
The TEOS of 3mL is added dropwise in Zhong Hou, and quickly stirring 15min is added dropwise, and reduces mixing speed afterwards, and 30 DEG C of reaction 5-6h have reacted
It is centrifuged, is washed successively with ethanol solution hydrochloride, water, ethyl alcohol, the nano-particle centrifuged exists with the rotating speed of 8 000rpm after
Vacuum drying obtains white solid at 50 DEG C.Afterwards by the Nano particles of silicon dioxide ultrasonic disperse of 1g in 85mL ethyl alcohol, stirring
It is lower be added dropwise ammonium hydroxide ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol), 40 DEG C stirring 1h, then by molecular weight be 600-
The ethanol solution of the PDMS of the triethoxy sealing end of 900g/mol is slowly dropped in above-mentioned solution, and addition finishes reaction for 24 hours, production
Object centrifuges to obtain the silica of a diameter of 270nm with the rotating speed of 7 000rpm, is washed successively with ethanol solution hydrochloride, water, ethyl alcohol
It washs, white solid is obtained after centrifugal vacuum drying (50 DEG C).Finally by Nano particles of silicon dioxide ultrasonic disperse in tetrahydrofuran
In solution (10wt%), and suitable carbon black particle (2wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer：Cross-linked polymer preparation method in preceding embodiment 1-6 is suitble to physical crosslinking poly-
The preparation for closing object, for then needing to realize under conditions of melting when chemical crosslinking, with the friendship of hydroxy-end capped PDMS and polyalcohol
Illustrate for connection (interaction of hydrogen bond), the PDMS for the side chain hydroxyl that molecular weight is 50 000g/mol is dissolved in tetrahydrochysene furan
In muttering, a concentration of 10wt%.Polyhydroxy small molecule is dissolved in tetrahydrofuran, polymer solution is slowly dropped under stirring
In, it is stirred overnight at room temperature, solution saves backup.
(3) preparation of selfreparing photonic crystal elastomer film：Take the cross-linked polymer and silica nanometer of certain volume
Particle solution, with volume ratio 1：1 mixing ultrasound 1h, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/
The solution of silica/carbon black passes through the method for spray gun spraying, quick solvent flashing (solvent evaporation rate is more than 20mL/h), system
The crystal film with photon that standby non-angular relies on.The volume of its membrane area solution used in spraying and the size of spraying reception device are common
It determines.
Embodiment 10
(1) synthesis and modification of Nano particles of silicon dioxide：By 8mL ammonia solvents in the ethyl alcohol of 100mL, stirring is very
The TEOS of 3mL is added dropwise in Zhong Hou, and quickly stirring 15min is added dropwise, and reduces mixing speed afterwards, and 30 DEG C of reaction 5-6h have reacted
It is centrifuged, is washed successively with ethanol solution hydrochloride, water and ethyl alcohol, the nano-particle centrifuged exists with the rotating speed of 8 000rpm after
White solid is obtained after being dried in vacuo at 50 DEG C.Then by the Nano particles of silicon dioxide ultrasonic disperse of 1g in 85mL ethyl alcohol,
The stirring lower ethanol solution 30mL (88mL ammonium hydroxide/320mL ethyl alcohol) that ammonium hydroxide is added dropwise, 40 DEG C of stirring 1h, then by molecular weight be 600-
The ethanol solution of the PDMS of the triethoxy sealing end of 900g/mol is slowly dropped in above-mentioned solution, and addition finishes reaction for 24 hours, production
Object centrifuges to obtain the silica of a diameter of 270nm with the rotating speed of 7 000rpm, is washed successively with ethanol solution hydrochloride, water and ethyl alcohol
It washs, white solid is obtained after centrifugal vacuum drying (50 DEG C).Finally by Nano particles of silicon dioxide ultrasonic disperse in tetrahydrofuran
In solution (10wt%), and suitable carbon black particle (2wt%) is added in the solution, ultrasonic disperse is uniformly spare.
(2) preparation of cross-linked polymer solution：Molecular weight is molten for the amino-terminated butyl polyacrylate of 50 000g/mol
Solution is in tetrahydrofuran, a concentration of 10wt%.In methyl alcohol (0.05-2g/mL) by cerium chloride dissolving, by cerium chloride under stirring
Methanol solution is slowly dropped in polymer solution, is stirred overnight at room temperature, spare.
(3) preparation of selfreparing crystal film with photon：Take cross-linked polymer and the Nano particles of silicon dioxide of certain volume molten
Liquid, with volume ratio 1：1 mixing ultrasound 1h, using the black polypropylene plate of 8cm × 8cm as reception device, by polymer/titanium dioxide
The solution of silicon/carbon black prepares the crystal film with photon that non-angular relies on by the method for spray gun spraying, quick solvent flashing.Its film
The volume of area solution used in spraying and the size of spraying reception device codetermine.
Fig. 1 is the scanning electricity for four kinds of various sizes of Nano particles of silicon dioxide that embodiment 1 is synthesized according to the method
Mirror picture.Fig. 1 (a) prepare blue photons film thus improved silica nano-particle；Fig. 1 (b) prepares green photon film institute
With improved silica nano-particle；Fig. 1 (c) prepare the sub- film of yellow colour thus improved silica nano-particle；Fig. 1
(d) prepare red photon film thus improved silica nano-particle the case where disperseing in PDMS.As can be seen from the figure
Nano-particle has apparent monodispersity, and forms shot-range ordered structure in the polymer.Embodiment only gives a kind of ruler
The synthetic method of very little nano-particle, because the synthetic method of nano-particle is identical, the amount of concentration and water by changing ammonium hydroxide
The size that nano-particle can be changed, by regulate and control nano-particle size can prepare the crystal film with photon of different colours with
Meet requirement.In addition from as can be seen that when silica disperses in PDMS matrixes, a part is in close in Fig. 1 (d)
The structure of accumulation, and wherein also have larger gap, this illustrates that Nano particles of silicon dioxide forms short distance in crystal film with photon
Ordered structure, this, which is also crystal film with photon, does not have the reason of dependence of angle.
Fig. 2 is four kinds of various sizes of improved silica nano-particles and the crosslinking of embodiment 2-6 the methods synthesis
The digital photograph (Fig. 2 (a)) and spectrogram (Fig. 2 (b)) for the crystal film with photon that polymer is prepared after being blended.The sample exists
Shown in the variation relation such as Fig. 2 (c) of the maximum absorption band of different angle with angle, this illustrates that the sample does not have dependence of angle.
Fig. 2 (d) is cross-linked polymer and adds the drawing of the crystal film with photon prepared after four kinds of various sizes of Nano particles of silicon dioxide
Curve is stretched, after adding various sizes of improved silica nano-particle in cross-linked polymer as seen from the figure, is broken
It splits elongation to significantly improve, shows preferable tensile property, sample has preferable elasticity.
Fig. 3 is that four kinds of different colours photonic crystal elastomer films prepared by embodiment 1-6 are obtained in different angle observations
The spectrogram arrived：Fig. 3 (a) blue photons crystal films, Fig. 3 (b) green photon crystal films, Fig. 3 (c) yellow photons crystal films, Fig. 3
(d) red photon crystal film.When observing sample from different perspectives, the maximum absorption band in the spectrogram of obtained crystal film with photon
Position and viewing angle relational graph, find out that the position of maximum absorption band is basically unchanged from figure, spectrum peak is also shown well
Monochromaticjty, this further illustrates that the crystal film with photon does not have dependence of angle.
Fig. 4 be embodiment 2 prepare crystal film with photon, surface have cut (blade is scratched) afterwards (Fig. 4 (a)) at 60 DEG C
The digital photograph of (Fig. 4 (b)) after lower placement 48h.Illustrating can the selfreparing within the regular hour after the film surface is impaired.
Fig. 5 be embodiment 2 be the crystal film with photon after being scratched with knife, at 60 DEG C repair certain time (6h, for 24 hours,
Extension test data after 48h) have preferable tensile property, with the selfreparing time repairing sample after a certain period of time
Extend, the sample of (the most deep curve of color) before the closer reparation of tensile property of sample.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all within the spirits and principles of the present invention made by all any modification, equivalent and improvement etc., should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of Responsive photonic crystals elastomeric film material, which is characterized in that received including cross-linked polymer matrix material, modification
Rice corpuscles and extinction nano material；The cross-linked polymer, modified Nano particle and extinction nano material molar ratio be (1~
200)：100:(0~5)；The modified Nano particle and the extinction nano material are dispersed in the cross-linked polymer matrix material
In material, the color of the photonic crystal elastomeric film material does not change with viewing angle, can be repaiied automatically after mechanical damage occurs
It is multiple, there is elasticity in drawing process.
2. photonic crystal elastomeric film material as described in claim 1, which is characterized in that the size of the modified Nano particle
For 100~500nm；The size of the extinction nano material is 10~100nm.
3. photonic crystal elastomeric film material as described in claim 1, which is characterized in that the cross-linked polymer is crosslinking agent
The tool formed by coordination, host-guest interactions, hydrogen bond or chemical crosslink reaction occurs between the functional group of polymer
It is transparent, flexible functionalized polymer, the folding of the polymer to have the cross-linked polymer of network structure, the polymer
Optical index is 1.2~2.0；The functionalized polymer contain amino, pyridine groups, imidazoles, azobenzene, cyclodextrin, hydroxyl,
At least one of sulfydryl, boric acid or adamantane double bond；The glass transition temperature of the polymer is less than 25 DEG C；The crosslinking
Agent is preferably selected from metal ion, cyclodextrin, boric acid, polyalcohol, multi-thiol and diolefin；The polymer and the crosslinking agent
Molar ratio be 0.05:1~6:1.
4. photonic crystal elastomeric film material as claimed in claim 3, which is characterized in that the metal ion is with empty rail
Alkaline-earth metal ions, transition metal ions or the rare earth ion in road.
5. photonic crystal elastomeric film material as described in claim 1, which is characterized in that the modified Nano particle is by receiving
Rice corpuscles carried out under the action of modifying agent it is cross-linking modified obtain, the nano-particle is not dissolve in organic solvent, and ruler
Very little medicine ball or nucleocapsid spheroidal particle within the scope of 100~500nm, the nano-particle is preferably SiO2Nanoparticle
Son, polystyrene nanoparticle or polymethylacrylic acid nano-particle；The modifying agent is molecular weight less than 40000g/mol's
Oil-soluble polymers.
6. photonic crystal elastomeric film material as described in claim 1, which is characterized in that the extinction nano material is selected from charcoal
Black, CNT, graphene, fullerene, PbS and CuS.
7. a kind of preparation method of Responsive photonic crystals elastomeric film material, which is characterized in that include the following steps：
(1) preparation of modified Nano particle：Nano-particle is carried out chemistry under the action of modifying agent by sol-gal process to change
Property, then in organic solvent by modified nano-particle dispersion, wherein the mass concentration of modified Nano particle be 1%~
50%；The nano-particle is will not dissolve in organic solvent, and medicine ball or core of the size within the scope of 100~500nm
Shell structure spheroidal particle；The modifying agent is the oil-soluble polymers that molecular weight is less than 40000g/mol；
(2) preparation of cross-linked polymer：It will be obtained containing polymer after transparent, elastic functionalized polymer dissolving or melting
Organic solution, then crosslinking agent is added dropwise in the organic solution containing polymer, the polymer and the crosslinking
The molar ratio of agent is 0.05:1~6:1；By the way that coordination, main-visitor occurs between the crosslinking agent and the functional group of the polymer
Body interaction, hydrogen bond or chemical crosslink reaction and form the cross-linked polymer with self-repair function with network structure；
The cross-linked polymer water white transparency, refraction index are 1.2~2.0；The functionalized polymer contains amino, pyridyl group
At least one of group, imidazoles, azobenzene, cyclodextrin, hydroxyl, sulfydryl, boric acid or adamantane double bond；The crosslinking agent is selected from gold
Belong to ion, cyclodextrin, boric acid, polyalcohol, multi-thiol and diolefin；The cross-linked polymer prepared is dispersed in organic solvent
In, wherein the mass concentration of cross-linked polymer is 1%~65%；
(3) preparation of photonic crystal elastic film material：By step (1) the dispersion modified Nano particle in organic solvent with
The cross-linked polymer of extinction nano material and step (2) dispersion in organic solvent is according to mass ratio 100：(0~5)：(1
~200) Hybrid assembling body, is obtained in hydrophobic and organic solvent-resistant material surface or container internal mix, in 20~70 DEG C of items
Organic solvent under part in Hybrid assembling body described in fast eliminating obtains photonic crystal elastic film material, wherein the organic solvent
Removing rate be more than 0.4ml/min；Or the Hybrid assembling body is placed in spraying container, it is sprayed into the hydrophobic material
Surface obtains photonic crystal elastic film material；
Wherein, the Flory-Huggin interaction parameters of step (1) modifying agent and step (2) described cross-linked polymer are not
More than 0.5, it is ensured that modified Nano particle described in step (3) can dissolve each other with the cross-linked polymer.
8. preparation method as claimed in claim 7, which is characterized in that the organic solvent is selected from tetrahydrofuran, chloroform, dichloro
Methane, hexamethylene, DMSO, DMF, benzene, methanol, ethyl alcohol, isopropanol, pyridine, toluene, ethyl acetate and acetone.
9. preparation method as claimed in claim 7, which is characterized in that the molecular weight of step (2) described polymer be 5000~
1,000,000g/mol。
10. the application of the photonic crystal elastic membrane as described in claim 1 to 6 any one, which is characterized in that be applied to anti-
Pseudo-, wearable, fingerprint recognition, sensor, coating or paint field.
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| CN114031946A (en) * | 2021-10-20 | 2022-02-11 | 安徽大学 | Photonic crystal film and preparation method and application thereof |
| CN115321829A (en) * | 2022-02-22 | 2022-11-11 | 江苏铁锚玻璃股份有限公司 | Fluoride-free and self-repairable super-hydrophobic glass and preparation method thereof |
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