CN110527505A - A kind of thermal response photonic crystal and preparation method thereof with color switch function becoming color system based on heat - Google Patents
A kind of thermal response photonic crystal and preparation method thereof with color switch function becoming color system based on heat Download PDFInfo
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- CN110527505A CN110527505A CN201910702905.6A CN201910702905A CN110527505A CN 110527505 A CN110527505 A CN 110527505A CN 201910702905 A CN201910702905 A CN 201910702905A CN 110527505 A CN110527505 A CN 110527505A
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Abstract
The present invention relates to a kind of thermal response photonic crystals with color switch function for becoming color system based on heat, in particular to the preparation method for becoming the thermal response photonic crystal with color switch function of color system based on heat, belongs to the preparation field of responsiveness material and chromogenic materials.A kind of thermal response photonic crystal with color switch function becoming color system based on heat, the material is made of anti-albumen photonic crystal and the thermo-color system material being filled in the anti-protein structure hole of anti-albumen photonic crystal, wherein, the thermo-color system material is made of procrypsis agent, color developing agent and phase-change material.Resulting materials of the present invention realize the responsiveness to extraneous thermostimulation, by external thermostimulation, realize the mutual conversion of schemochrome and pigmentary color.
Description
Technical field
The present invention relates to a kind of thermal response photonic crystals with color switch function for becoming color system based on heat, especially relate to
And based on heat become color system the thermal response photonic crystal with color switch function preparation method, belong to responsiveness material and
The preparation field of chromogenic materials.
Background technique
Photonic crystal is divided into opal structural and counter opal structure.Counter opal structure is due to its large specific surface area, electricity
Lotus transmittability is strong and size is controllable, and materials more obtain the attention of more researchers extensively.In general, counter opal structure
It is made by template, using opal structural as template, presoma is filled into the hole of opal structural, then removes mould
Corresponding counter opal structure can be obtained in plate.The advantages of based on counter opal structure, can satisfy more application fields,
Such as such as, the Song Hongwei research of Jilin University prepares the In of Au modification2O3Anti- protein structure is for detecting diabetes.(R.Xing,
Q.Li,L.Xia,J.Song,L.Xu,J.Zhang,Y.Xie,and H.Song,Au-modified three-dimensional
In2O3 inverseopals:synthesis and improved performance foracetone sensing
toward diagnosis of diabetes,Nanoscale,2015,7,13051-13060)；Univ cambridge uk
Jeremy J.Baumberg et al. introduces BiVO by the ZnO counter opal structure for adulterating Al4Water is improved in optoelectronic pole
Efficiency (L.Zhang, E.Reisner, and J.J.Baumberg, Al-doped ZnO the inverse opal of oxidation
networks as efficient electron collectors in BiVO4 photoanodes for solar
water oxidation,Energy Environ.Sci.,2014,7,1402-1408)。
Similar to opal structural, counter opal structure equally has periodic structure.Pass through its microstructure and light
Interaction, such as interference, diffraction, scattering and generate color.The periodic structure of anti-protein structure, so that it prohibits with photon
Band, the light fallen in forbidden photon band can not be propagated to any direction, it will thus be seen that arriving color.Responsive photonic crystals are usual
It is by being realized based on the variation of the reflection wavelength of Bragg diffraction.However, changing caused by being relied on due to inherent angle
Responsiveness result can be had an impact, be difficult to differentiate between color change caused by responsiveness.Therefore, it avoids being caused by viewing angle
Color change seem most important for Responsive photonic crystals.
Summary of the invention
In order to preferably utilize photonic crystal structure color, the present invention provides a kind of opening with color based on heat change color system
The thermal response photonic crystal of function is closed, heat is become color system and is sufficient filling in anti-albumen photon crystal material by such material, real
Existing thermo-responsive.By external thermostimulation, the mutual conversion of schemochrome and pigmentary color is realized.Utilize anti-albumen photonic crystal
The interdependent characteristic of low angle, so that color change caused by thermostimulation is protruded.This method is low in cost, simple and easy, In
Anti-fake and Information hiding field has broad application prospects.
A kind of thermal response photonic crystal with color switch function becoming color system based on heat, the material is by anti-albumen
Photonic crystal and the thermo-color system material being filled in the anti-protein structure hole of anti-albumen photonic crystal composition,
Wherein, wherein the thermo-color system material is made of procrypsis agent, color developing agent and phase-change material.
It is of the present invention that the thermal response photonic crystal with color switch function of color system is become by anti-opalescence based on heat
Sub- crystal and the compound gained of thermo-color system material, wherein anti-albumen photonic crystal is as backing material, thermal change color system conduct
Packing material is applied in anti-protein structure.
Thermo-color system material of the present invention is made of procrypsis agent, color developing agent and phase-change material.When initial, three kinds of raw materials
It is present in the anti-protein structure hole of anti-albumen photonic crystal with the state of physical mixed, but is regulated and controled by temperature, electronics occurs to turn
Shifting causes dye structure to change and change colour, and chemical change occurs at this time.When temperature is lower than phase transition temperature, procrypsis agent occurs
Ring-opening reaction, colour developing.When temperature is higher than phase transition temperature, ring-closure reaction occurs for procrypsis agent, becomes colorless and transparent.
Further, the thermo-color system material is 1:2~3 by procrypsis agent, color developing agent and phase-change material in mass ratio:
50~100 compositions.
Further, the thermo-color system material is 1:2 by procrypsis agent, color developing agent and phase-change material in mass ratio:
50~100 compositions.
Further, the thermo-color system material is 1:3 by procrypsis agent, color developing agent and phase-change material in mass ratio:
50~100 compositions.
Anti- albumen photonic crystal of the present invention is preferably the anti-albumen photonic crystal of stannic oxide, the anti-opalescence of titanium dioxide
The anti-albumen photonic crystal of sub- crystal, zinc oxide, the anti-albumen photonic crystal of zirconium oxide, the anti-albumen photonic crystal of cerium oxide, five oxidations
The anti-albumen photonic crystal of two tantalums, the anti-albumen photonic crystal of niobium oxide.
Further, the aperture of the anti-protein structure hole of anti-albumen photonic crystal is 200~400nm.
Further, the procrypsis agent is that temperature-sensitive is red, temperature-sensitive is green, temperature-sensitive is black, crystal violet lactone, peacock green lactone, cresols
It is red；The color developing agent is bisphenol-A, benzyl p-hydroxybenzoate, 4 hydroxy coumarin, caproic acid, octanoic acid, stearic acid, terephthaldehyde
Acid；The phase-change material is lauryl alcohol, tetradecyl alchohol, hexadecanol, octadecyl alcolol.
Further, preferably procrypsis agent is the red TF-R of temperature-sensitive2, color developing agent is bisphenol-A, and phase-change material is hexadecanol.
Anti- albumen photonic crystal of the present invention is preferably made using following methods: using opal structural as template, by not
Same filling mode, presoma is filled, such as liquid phase infiltration method, electrochemical deposition method, electrophoretic deposition, spray pyrolysis
Method, vapour deposition process, atomic layer deposition method.(A.Stein,B.E.Wilson,and S.G.Rudisill.Design and
functionality of colloidal-crystal-templated materials-chemical applications
of inverse opals.ChemSoc Rev.2013；42:2763-2803.)
It is a further object of the present invention to provide the above-mentioned thermal response light with color switch function for becoming color system based on heat
The preparation method of sub- crystal.
A kind of preparation method for the thermal response photonic crystal with color switch function becoming color system based on heat, including under
State step:
1. preparing anti-albumen photonic crystal structure color film using template；
2. being in mass ratio that 1:2~3:50~100 mix by procrypsis agent, color developing agent and phase-change material, thermal change is prepared
Colour solid based material；
3. make step 2. gained thermal change color system be filled into step 1. gained albumen photonic crystal structure color film anti-albumen
In structure hole；
4. removing solvent to get brilliant to a kind of thermal response photon with color switch function for becoming color system based on heat
Body.
In above-mentioned preparation method, the step 1. the method specifically: the mono-dispersion microballoon of template will be used for, as PS,
PMMA、SiO2Etc. being assembled, anti-albumen presoma is filled into and is assembled in resulting opal structural hole, then by forging
It burns or chemical attack removes template, obtain the anti-protein structure of target.
In above-mentioned preparation method, the step 3. in, " filling " can for nature fill, i.e., by thermal change color system according to
Mass ratio 1:1 is dissolved in dehydrated alcohol, is then added dropwise on anti-albumen photonic crystal structure color film, 70 DEG C of solvent flashings.
The invention has the benefit that thermal change color system is sufficient filling in anti-albumen photonic crystal, it is compound to be based on
The thermal response photonic crystal with color switch function of thermal change color system.Resulting materials realize the response to extraneous thermostimulation
Property, by external thermostimulation, realize the mutual conversion of schemochrome and pigmentary color.When ambient temperature is higher than the phase transformation of phase transformation system
When temperature, pigment decoloration shows schemochrome.When temperature is lower than phase transition temperature, it may appear that pigmentary color, and knot is hidden therewith
Structure color.Due to the low angle interdependence of anti-protein structure, so that color change caused by thermostimulation is protruded.It is basic herein
On, the display to counter opal pattern is realized using its thermo-responsive and is hidden.Invention also provides one kind based on heat
The preparation method of the thermal response photonic crystal with color switch function of variable color system.It is prepared instead by template first
Then albumen photonic crystal refills thermal change color system.This method preparation has the function of color switch based on heat change color system
Thermal response photonic crystal, it is low in cost, simple and easy, provide more possibility in practical applications for schemochrome material,
Especially have broad application prospects in anti-fake, field of information encryption.
Detailed description of the invention
Fig. 1 (a) is the resulting anti-albumen photon crystal surface topography scan electron microscope of embodiment 1；
Fig. 1 (b) is Fourier's variation diagram of the resulting anti-albumen photonic crystal of embodiment 1；
Fig. 2 is the different detection angles reflectance spectrum figures of the resulting anti-albumen photonic crystal of embodiment 1；
Fig. 3 is the DSC curve figure of the thermal change color system of embodiment 1；
Fig. 4 is Discoloration mechanism figure of the 1 thermal change color system of embodiment under thermostimulation；
Fig. 5 (a) is number of the Patterned Sample (maple leaf shape) of 1 thermal response photonic crystal of embodiment in crystalline state
Photo；
Fig. 5 (b) is number of the Patterned Sample (maple leaf shape) of 1 thermal response photonic crystal of embodiment in melting state
Photo.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Embodiment 1
1. by template, the anti-egg white films of stannic oxide that preparation aperture is 368nm, specifically: before stannic oxide
It drives body to be added drop-wise on polystyrene moulding, penetrate into naturally；It is placed in Muffle furnace and is calcined after the solvent is volatilized, obtain anti-albumen
Schemochrome film,
The polystyrene moulding is prepared by the method for emulsion polymerization, specifically the preparation method comprises the following steps: weighing 0.016g
Lauryl sodium sulfate is dissolved in 135ml deionized water, and 300r/min is stirred in 250ml three-necked flask；Heating water bath is to 85 DEG C
After stabilization, 15g styrene monomer is added；After 15min, 0.15g potassium peroxydisulfate is added, 85 DEG C, is stirred to react 5 hours；By gained
Lotion carries out heating convection current self assembly in 70 DEG C of heating plates, and opal structural template can be obtained.
2. by procrypsis agent (the red TF-R of temperature-sensitive2), color developing agent (bisphenol-A), phase-change material (hexadecanol) is 1:2 in mass ratio:
100 carry out 90 DEG C of dissolution mixing, prepare thermal change color system.
3. heat is become color system to be filled into the anti-protein structure of stannic oxide, using nature fill method, heated in 70 DEG C
It is filled on plate, the thermal response photon with color switch function to obtain becoming color system based on heat after solvent volatilization
Crystal.
Fig. 1 (a) is the surface topography scanning electron microscope (SEM) photograph of the resulting anti-protein structure color material of embodiment 1, and Fig. 1 (b) is Fig. 1
(a) Fourier's variation, the spatial information of reaction structure, as shown in it, material surface pattern are the more of presentation FCC form arrangement
Pore structure；Fig. 2 is the different angle reflectance spectrum figure of the resulting anti-albumen photonic crystal of embodiment 1, shows resulting materials not
There is no variations substantially for forbidden band peak position under same detection angles；Fig. 3 is the DSC curve of the thermal change color system of embodiment 1,
Phase transition temperature is 49.9 DEG C；Fig. 4 is Discoloration mechanism of the 1 thermal change color system of embodiment under thermostimulation, the red work in bisphenol-A of temperature-sensitive
Under, in the state of cooling (<49.9 DEG C), dyestuff lactonic ring is opened, and becomes red by colourless, and in a heated state (>49.9
DEG C), then it is red to disappear.Fig. 5 (a) is digital photograph of the Patterned Sample of 1 thermal response photonic crystal of embodiment in crystalline state
Piece；Fig. 5 (b) is digital photograph of the Patterned Sample in melting state.When temperature is lower than phase transition temperature, at thermal change color system
In crystalline state, pigmentary color is showed at this time, and anti-protein structure pattern is hidden completely.When temperature is higher than phase transition temperature, heat
Variable color system is in melting state, becomes colourless transparent liquid, pigment decoloration and show schemochrome so that anti-albumen
Pattern (maple leaf shape) displays.
Embodiment 2-7
It is brilliant that the anti-albumen photonic crystal of stannic oxide is changed to the anti-albumen photon of the anti-albumen photonic crystal of titanium dioxide, zinc oxide
The anti-albumen photonic crystal of body, zirconium oxide, the anti-albumen photonic crystal of cerium oxide, the anti-albumen photonic crystal of tantalum pentoxide, niobium oxide
Anti- albumen photonic crystal, other conditions and embodiment 1 are consistent.
Embodiment 8
The red temperature-sensitive that is changed to of temperature-sensitive in embodiment 1 is green, and other conditions and embodiment 1 are consistent.
Embodiment 9-14
It is brilliant that the anti-albumen photonic crystal of stannic oxide is changed to the anti-albumen photon of the anti-albumen photonic crystal of titanium dioxide, zinc oxide
The anti-albumen photonic crystal of body, zirconium oxide, the anti-albumen photonic crystal of cerium oxide, the anti-albumen photonic crystal of tantalum pentoxide, niobium oxide
Anti- albumen photonic crystal, other conditions and embodiment 8 are consistent.
Embodiment 15
The red temperature-sensitive that is changed to of temperature-sensitive in embodiment 1 is black, and other conditions and embodiment 1 are consistent.
Embodiment 16-21
It is brilliant that the anti-albumen photonic crystal of stannic oxide is changed to the anti-albumen photon of the anti-albumen photonic crystal of titanium dioxide, zinc oxide
The anti-albumen photonic crystal of body, zirconium oxide, the anti-albumen photonic crystal of cerium oxide, the anti-albumen photonic crystal of tantalum pentoxide, niobium oxide
Anti- albumen photonic crystal, other conditions and embodiment 15 are consistent.
Embodiment 22-24
Hexadecanol in embodiment 1 is changed to one of lauryl alcohol, tetradecyl alchohol, octadecyl alcolol, other conditions and embodiment 1
Unanimously.
Embodiment 16-21
It is brilliant that the anti-albumen photonic crystal of stannic oxide is changed to the anti-albumen photon of the anti-albumen photonic crystal of titanium dioxide, zinc oxide
The anti-albumen photonic crystal of body, zirconium oxide, the anti-albumen photonic crystal of cerium oxide, the anti-albumen photonic crystal of tantalum pentoxide, niobium oxide
Anti- albumen photonic crystal, other conditions and embodiment 15 are consistent.
Embodiment 22-24
Hexadecanol in embodiment 8 is changed to one of lauryl alcohol, tetradecyl alchohol, octadecyl alcolol, other conditions and embodiment 8
Unanimously.
Embodiment 25-27
Hexadecanol in embodiment 15 is changed to one of lauryl alcohol, tetradecyl alchohol, octadecyl alcolol, other conditions and embodiment
15 is consistent
Above embodiments are only intended to help to better understand core of the invention thought and technical method, but cannot be with this
It limits the scope of the invention.It should be pointed out that for those of ordinary skill in the art, on basis according to the principle of the invention
On, certain improvement and expansion can also be carried out to the present invention, these improve and expand also in the protection of the claims in the present invention
In range；It is all any equivalent transformation or modification made according to the spirit of the present invention, should all cover in claim guarantor of the invention
It protects in range.
Claims (8)
1. a kind of thermal response photonic crystal with color switch function for becoming color system based on heat, it is characterised in that: the material
Material is made of anti-albumen photonic crystal and the thermo-color system material being filled in the anti-protein structure hole of anti-albumen photonic crystal,
Wherein, the thermo-color system material is made of procrypsis agent, color developing agent and phase-change material.
2. material according to claim 1, it is characterised in that: the thermo-color system material by procrypsis agent, color developing agent and
Phase-change material is that 1:2~3:50~100 is formed in mass ratio.
3. material according to claim 1, it is characterised in that: the thermo-color system material by procrypsis agent, color developing agent and
Phase-change material is the composition of 1:2:50~100 or is in mass ratio 1:3:50 by procrypsis agent, color developing agent and phase-change material in mass ratio
~100 compositions.
4. material according to claim 1, it is characterised in that: the anti-albumen photonic crystal is the anti-opalescence of stannic oxide
The anti-albumen photonic crystal of sub- crystal, titanium dioxide, the anti-albumen photonic crystal of zinc oxide, the anti-albumen photonic crystal of zirconium oxide, oxidation
The anti-albumen photonic crystal of cerium, the anti-albumen photonic crystal of tantalum pentoxide, the anti-albumen photonic crystal of niobium oxide.
5. material according to claim 1 or 4, it is characterised in that: the anti-protein structure hole of the anti-albumen photonic crystal
The aperture of gap is 200~400nm.
6. material according to claim 1, it is characterised in that: the procrypsis agent is that temperature-sensitive is red, temperature-sensitive is green, temperature-sensitive is black, knot
Crystalviolet lactone, peacock green lactone, cresol red；The color developing agent be bisphenol-A, benzyl p-hydroxybenzoate, 4 hydroxy coumarin, oneself
Acid, octanoic acid, stearic acid, terephthalic acid (TPA)；The phase-change material is lauryl alcohol, tetradecyl alchohol, hexadecanol, octadecyl alcolol.
7. becoming the preparation side of the thermal response photonic crystal with color switch function of color system described in claim 1 based on heat
Method, it is characterised in that: include the following steps:
1. preparing anti-albumen photonic crystal structure color film using template；
2. being in mass ratio that 1:2~3:50~100 mix by procrypsis agent, color developing agent and phase-change material, thermal change colour solid is prepared
Based material；
3. make step 2. gained thermo-color system material be filled into step 1. gained albumen photonic crystal structure color film anti-albumen
In structure hole；
4. removing solvent to get a kind of thermal response photonic crystal with color switch function for becoming color system based on heat is arrived.
8. according to the method described in claim 7, it is characterized by: the step 3. in, it is described be filled with nature filling: will be hot
Variable color system material is dissolved in dehydrated alcohol according to mass ratio 1:1, is then added dropwise on anti-albumen photonic crystal structure color film, 70
DEG C solvent flashing is up to the thermal response photonic crystal with color switch function for becoming color system based on heat.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477290A (en) * | 2010-11-30 | 2012-05-30 | 北京华纺高新技术有限公司 | Thermo-sensitive discoloration material microcapsule and preparation method thereof |
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2019
- 2019-07-31 CN CN201910702905.6A patent/CN110527505A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477290A (en) * | 2010-11-30 | 2012-05-30 | 北京华纺高新技术有限公司 | Thermo-sensitive discoloration material microcapsule and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| QUAN MAOHUA等: "Simultaneous Microscopic Structure Characteristics of Shape-Memory Effects of Thermo-Responsive Poly(vinylidene fluoride-co-hexafluoropropylene) Inverse Opals", 《SCIENTIFIC REPORTS》 * |
| ZHANG YUQI等: "Fluorescence-enhancing film sensor for highly effective detection of Bi3+ ions based on SiO2 inverse opal photonic crystals", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
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Application publication date: 20191203 |