CN103756228B - Self-driven light modulating device and preparation method thereof - Google Patents
Self-driven light modulating device and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of self-driven light modulating device and preparation method thereof, the method comprises the steps: (1) refrigerates after mixing 1:10:10000 ~ 100000 in mass ratio by photosensitizers, thermosensitizing agent and water; (2) gelifying agent is mixed 1:100 ~ 200 in mass ratio with water; (3) mixed solution that mixed solution step (1) obtained and step (2) obtain mixes 1:1 ~ 10 by volume, after thoroughly stirring, pours in transparent mould, and cooling forming after encapsulation, obtains self-driven light modulating device.This device comprises light modulation layer and two photic zones, described light modulation layer between described two photic zones, the polymer gel that described light modulation layer is made up of photosensitizers, thermosensitizing agent, gelifying agent and water.This device can realize light modulation, heat insulation or heat insulation function automatically, and effective, can normally work without any need for additional power source, safe, energy-conservation, cost is low, and it is simple to produce assembling, has higher industrial applications and is worth.
Description
Technical field
The invention belongs to optical sensing technical field, more specifically, relate to a kind of self-driven light modulating device and preparation method thereof.
Background technology
Current under the environment of energy growing tension, be save energy, reduce greenhouse gas emission, the research and development of heat-insulating heat-preserving material and device is had very important significance.Heat-insulation and heat-preservation facility, not only for reducing the loss of heat winter, also can be used for reducing solar radiation, avoiding room temp too high summer, thus reduces the power consumption of the cooling installations such as air-conditioning.
Mainly adopt curtain, dividing plate etc. to block to high light at present, mainly insulating layer material is adopted to high temperature, shading and heat insulation limited efficiency.Recently, come out for the Protection Product of dazzling light, and be applied to automotive sunshade panel, mainly adopt electrochromic material, to reduce solar radiation.If the liquid crystal digital adjusting light screen on automobile is exactly adopt solar cell for supplying power to drive liquid crystal color-changing to reach the object of blocking high light.This device needs manual control, and needs external energy powered operation, and cost is higher.
Summary of the invention
For above defect or the Improvement requirement of prior art, the invention provides a kind of self-driven light modulating device and preparation method thereof, this device can realize light modulation, heat insulation or heat insulation function automatically, and it is effective, can normally work without any need for additional power source, safe, energy-conservation, cost is low, it is simple to produce assembling, has higher industrial applications and is worth.
For achieving the above object, according to one aspect of the present invention, provide a kind of preparation method of self-driven light modulating device, it is characterized in that, comprise the steps: that photosensitizers, thermosensitizing agent and water refrigerate after mixing 1:10:10000 ~ 100000 by (1) in mass ratio; (2) gelifying agent is mixed 1:100 ~ 200 in mass ratio with water; (3) mixed solution that mixed solution step (1) obtained and step (2) obtain mixes 1:1 ~ 10 by volume, after thoroughly stirring, pours in transparent mould, and cooling forming after encapsulation, obtains self-driven light modulating device.
Preferably, the visible and near infrared light of described photosensitizers Absorbable rod 400 ~ 1500nm wavelength.
Preferably, described photosensitizers is metal Nano structure, transition metal, precious metal, heavy metal or rare-earth oxide nanostructure, transition metal, precious metal, heavy metal or rare earth metal chalcogenide nanostructure, organic dye, carbon material, or organic molecule switch.
Preferably, described photosensitizers is gold nanorods, gold nano grain, perylene diimide or Graphene.
Preferably, described thermosensitizing agent is PNIPAM, PNIPAM binary or terpolymer, polymethyl acrylic acid N, N dimethylamine base ethyl ester, or polymethyl acrylic acid N, N dimethylamine base methacrylate copolymers.
Preferably, described thermosensitizing agent is PNIPAM or N-isopropylacrylamide-acrylamide copolymer.
Preferably, described gelifying agent is agarose, polyacrylamide gel or gelatin.
According to another aspect of the present invention, provide self-driven light modulating device prepared by a kind of aforesaid method, it is characterized in that, comprise light modulation layer and two photic zones, described light modulation layer between described two photic zones, the polymer gel that described light modulation layer is made up of photosensitizers, thermosensitizing agent, gelifying agent and water.
Preferably, described photic zone is unorganic glass, synthetic glass or flexible transparent plastic.
Preferably, described photic zone is polyimide.
In general, the above technical scheme conceived by the present invention compared with prior art, has following beneficial effect:
(1) light modulation, heat insulation or heat insulation function can automatically be realized, and effective.With photosensitizers and thermosensitizing agent synthesis light control material, photosensitizers produces photic intensification under high light effect, and thermosensitizing agent makes light control material condense under high temperature action, form the polymer nano granules of tens to several thousand nanometers, make light control material become opaque, realize resistance light or heat insulation, vice versa.
(2) can normally work without any need for additional power source, safe, energy-conservation, cost is low.
(3) produce assembling simple, there is higher industrial applications and be worth, the fields such as architectural lighting insulation, intelligent curtain, intelligent curtain wall, intelligent automobile side window, intelligent skylight can be widely used in.
Accompanying drawing explanation
Fig. 1 is the self-driven light modulating device schematic diagram of the embodiment of the present invention;
Fig. 2 is the change curve of temperature with illumination switch of self-driven light modulating device prepared by the embodiment of the present invention 1;
Fig. 3 be the transmittance of self-driven light modulating device prepared of the embodiment of the present invention 1 with illumination switch reversible change cyclic curve;
Fig. 4 is the uv-visible absorption spectra figure of the embodiment of the present invention 1 gold nanorods used.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.In addition, if below in described each embodiment of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
As shown in Figure 1, the self-driven light modulating device of the embodiment of the present invention comprises: photic zone 1 and light modulation layer 2.Light modulation layer 2 is between two photic zones 1.
Photic zone 1 can be unorganic glass, as normal silicate glass; Also can be synthetic glass, as polymethylmethacrylate, poly hydroxy ethyl acrylate; Can also be flexible transparent plastic, as polyimide, epoxy resin, silicone resin, silicon rubber, polyethylene, polypropylene, polyvinyl chloride, polystyrene, poly(lactic acid), polycaprolactone, polyethylene glycol succinate, polyethylene terephthalate.
The polymer gel that light modulation layer 2 is made up of photosensitizers, thermosensitizing agent, gelifying agent and water.
Under high light conditions, photosensitizers produces photic intensification, and thermosensitizing agent is under high temperature action, make polymer agglomerates, form the polymer nano granules that particle diameter is tens to several thousand nanometers, make light modulation layer 2 become opaque, produce strong scattering of light, stop sunlight through; Under low-light condition, light modulation layer 2 is vitreous state, significantly improves the transmissivity of light.
Similarly, when envrionment temperature is higher, thermosensitizing agent makes polymer agglomerates under high temperature action, makes light modulation layer 2 become opaque, stops light, heat, realizes heat insulating function; When envrionment temperature is lower, light modulation layer 2 is vitreous state, significantly improves the transmissivity of light, realizes heat insulation function.
Photosensitizers is metal Nano structure, transition metal, precious metal, heavy metal or rare-earth oxide nanostructure, transition metal, precious metal, heavy metal or rare earth metal chalcogenide nanostructure, organic dye, carbon material, or organic molecule switch.
Particularly, metal Nano structure comprises: golden nanometer particle, gold nanorods, gold nanoshell, gold nanometer cage, gold nano shuttle, nanowires of gold, silver nanoparticle cube, Silver nanorod, nano silver wire etc.
Particularly, transition metal, precious metal, heavy metal or rare-earth oxide comprise: zinc oxide, cupric oxide, Red copper oxide, ferric oxide, iron protoxide, Z 250, nickel oxide, stannic oxide, tin protoxide, cobalt oxide, aluminum oxide, chromic oxide, Cadmium oxide, plumbous oxide, Indium sesquioxide, tin indium oxide, silver suboxide, palladous oxide, ruthenium oxide, Tungsten oxide 99.999, molybdenum oxide etc.
Particularly, transition metal, precious metal, heavy metal or rare earth metal chalcogenide comprise: zinc sulphide, cupric sulfide, cuprous sulfide, iron sulphide, Iron sulfuret, nickelous sulfide, tin sulfide, stannous sulfide, cobaltous sulfide, aluminium sulfide, chromic sulfide, Cadmium Sulfide, lead sulfide, indium sulfide, indium sulfide tin, silver sulfide, palladium sulfide, sulfuration ruthenium, tungsten sulfide, moly-sulfide, zinc selenide, copper selenide, selenkupfer, ferrous selenide, FeSe, nickelous selenide, Tin diselenide, Tin monoselenide, cobaltous selenide, aluminum selenide, selenizing chromium, cadmium selenide, lead selenide, indium selenide, indium selenide tin, silver selenide, selenizing palladium, selenizing ruthenium, tungsten selenide, selenizing molybdenum, zinc telluridse, telluride copper, cuprous telluride, telluride iron, ferrous telluride, telluride nickel, telluride tin, the sub-tin of telluride, cobaltous telluride, telluride aluminium, telluride chromium, cadmium telluride, lead telluride, telluride indium, telluride indium tin, silver telluride, telluride palladium, telluride ruthenium, telluride tungsten, telluride molybdenum etc.
Particularly, organic dye comprises: rhodamine B, rhodamine 6G, fluorescein, perylene diimide, cyanine dyes etc.
Particularly, carbon material comprises: Graphene, graphene oxide, graphene nanobelt, graphene nanometer sheet, carbon nanotube, soccerballene etc.
Particularly, organic molecule switch comprises: spiro-pyrans, spirooxazine, two fragrant alkene, six aryl bisglyoxalines etc.
Thermosensitizing agent is PNIPAM, PNIPAM binary or terpolymer or polymethyl acrylic acid N, N dimethylamine base ethyl ester or its multipolymer.
Particularly, PNIPAM binary and terpolymer comprise: N-isopropylacrylamide-acrylamide copolymer, N-isopropylacrylamide-acrylic copolymer, N-isopropylacrylamide-Sipacril 2739OF, N-isopropylacrylamide-acrylate copolymer, N-isopropylacrylamide-alkylmethacrylate polymer, N-isopropylacrylamide-styrol copolymer, N-isopropylacrylamide-hydroxyethyl methylacrylate multipolymer etc.
Particularly, polymethyl acrylic acid N, N dimethylamine base methacrylate copolymers comprises: methacrylic acid N, N dimethylamine base ethylacrylate-acrylic acid multipolymer, methacrylic acid N, N dimethylamine base ethyl ester-Sipacril 2739OF, methacrylic acid N, N dimethylamine base ethylacrylate-acrylic acid ester copolymer, methacrylic acid N, N dimethylamine base ethyl ester-alkylmethacrylate polymer, methacrylic acid N, N dimethylamine base lacrylate-styrene multipolymer etc.
Gelifying agent can be Native Gel agent, as agarose, gelatin, starch gel; Also can be synthesis high-molecular gel, as polyacrylamide gel, chitosan gel rubber, Lalgine gel, modified-cellulose gel.
The preparation method of self-driven light modulating device of the present invention comprises the steps:
(1) photosensitizers, thermosensitizing agent and water are refrigerated after mixing 1:10:10000 ~ 100000 in mass ratio.Wherein, the visible and near infrared light of photosensitizers Absorbable rod 400 ~ 1500nm wavelength.
(2) gelifying agent is mixed 1:100 ~ 200 in mass ratio with water.
(3) mixed solution that mixed solution step (1) obtained and step (2) obtain mixes 1:1 ~ 10 by volume, after thoroughly stirring, pours in transparent mould, and cooling forming after encapsulation, obtains self-driven light modulating device.
For making those skilled in the art understand the present invention better, below in conjunction with specific embodiment, the preparation method to self-driven light modulating device of the present invention is described in detail.
Embodiment 1
Be photosensitizers with gold nanorods, take PNIPAM as thermosensitizing agent, the preparation method of the self-driven light modulating device of the embodiment of the present invention comprises the steps:
(1) by the 1:10:100000 mixing in mass ratio of gold nanorods, PNIPAM and water, and refrigerate at 4 DEG C.
(2), after 1:100 mixes in mass ratio at 80 DEG C with water by agarose, 50 DEG C are cooled to.
(3) mixed solution that mixed solution step (1) obtained and step (2) obtain by volume 1:1 mixes, and after thoroughly stirring, pours in mineral glass mold, and cooling forming after encapsulation, obtains self-driven light modulating device.
Fig. 2 is the change curve of temperature with illumination switch of self-driven light modulating device prepared by the present embodiment, Fig. 3 be the transmittance of self-driven light modulating device prepared by the embodiment of the present invention with illumination switch reversible change curve.From Fig. 2 and Fig. 3, illumination is opened, and the temperature prolongation in time of self-driven light modulating device is risen, thermosensitizing agent makes light control material condense under high temperature action, form the polymer nano granules of tens to several thousand nanometers, the transmittance of self-driven light modulating device is declined gradually, realize resistance light or heat insulation.
Particularly, gold nanorods and PNIPAM are prepared respectively as follows.
The preparation of gold nanorods: the silver nitrate solution adding 0.06 milliliter of 0.01mol/L in Cetrimide (CTAB) solution of 3.0 milliliters of 0.2mol/L, the chlorauric acid solution of 0.3 milliliter of 0.01mol/L, and the ascorbic acid solution of 0.046 milliliter of 0.1mol/L.Add 0.1 milliliter of gold colloid seed solution again and cause gold nanorods growth, the uv-visible absorption spectra of obtained gold nanorods as shown in Figure 4, the near infrared light of gold nanorods Absorbable rod 600 ~ 900nm wavelength.
Wherein, the preparation method of gold colloid seed solution is as follows: the chlorauric acid solution adding 2.5 milliliters of 0.0005mol/L in the CTAB solution of 2.5 milliliters of 0.2mol/L, add the sodium borohydride of 0.3 milliliter of 0.01mol/L again, shake up and leave standstill 1 minute, then be placed in 40 DEG C of water-baths 15 minutes, normal temperature is preserved.
The preparation of PNIPAM: by monomer N-isopropylacrylamide 5 grams good for purifying and initiator Diisopropyl azodicarboxylate in molar ratio 800:1 add in round-bottomed flask, add 20 milliliters of toluene, load onto reflux condensing tube, under agitation logical nitrogen deoxygenation 30 minutes, continue to stir 24 hours under 80 DEG C of conditions, be dissolved in methylene dichloride by reaction head product, then slowly drip and precipitate in anhydrous diethyl ether, vacuum-drying throw out obtains white solid.Through nuclear-magnetism and Infrared Characterization, prove that the white solid that the method is synthesized is PNIPAM, transformation efficiency is 60%.Measured by gel permeation chromatography (GPC), this polymkeric substance number-average molecular weight Mn=50000, dispersion coefficient is 2.4.
Embodiment 2
Be photosensitizers with gold nanorods, take PNIPAM as thermosensitizing agent, the preparation method of the self-driven light modulating device of the embodiment of the present invention comprises the steps:
(1) by the 1:10:10000 mixing in mass ratio of gold nanorods, PNIPAM and water, and refrigerate at 4 DEG C.
(2), after 1:200 mixes in mass ratio at 80 DEG C with water by agarose, 50 DEG C are cooled to.
(3) mixed solution that mixed solution step (1) obtained and step (2) obtain by volume 1:10 mixes, and after thoroughly stirring, pours in synthetic glass mould, and cooling forming after encapsulation, obtains self-driven light modulating device.
The preparation method of gold nanorods and PNIPAM and embodiment 1 are together.
Embodiment 3
Be photosensitizers with gold nanorods, take PNIPAM as thermosensitizing agent, the preparation method of the self-driven light modulating device of the embodiment of the present invention comprises the steps:
(1) by the 1:10:10000 mixing in mass ratio of gold nanorods, PNIPAM and water, and refrigerate at 4 DEG C.
(2), after 1:200 mixes in mass ratio at 80 DEG C with water by agarose, 50 DEG C are cooled to.
(3) mixed solution that mixed solution step (1) obtained and step (2) obtain by volume 1:10 mixes, and after thoroughly stirring, pours in polyimide mould, and cooling forming after encapsulation, obtains self-driven light modulating device.
The preparation method of gold nanorods and PNIPAM and embodiment 1 are together.
Embodiment 4
Take gold nanorods as photosensitizers, with N-isopropylacrylamide-acrylamide copolymer for thermosensitizing agent, the preparation method of the self-driven light modulating device of the embodiment of the present invention comprises the steps:
(1) by the 1:10:10000 mixing in mass ratio of gold nanorods, N-isopropylacrylamide-acrylamide copolymer and water, and refrigerate at 4 DEG C.Wherein, the molecular weight of N-isopropylacrylamide-acrylamide copolymer is 42000.
(2), after 1:200 mixes in mass ratio at 80 DEG C with water by agarose, 50 DEG C are cooled to.
(3) mixed solution that mixed solution step (1) obtained and step (2) obtain by volume 1:10 mixes, and after thoroughly stirring, pours in mineral glass mold, and cooling forming after encapsulation, obtains self-driven light modulating device.
The preparation method of gold nanorods and embodiment 1 are together.
Embodiment 5
Be photosensitizers with gold nano grain, take PNIPAM as thermosensitizing agent, the preparation method of the self-driven light modulating device of the embodiment of the present invention comprises the steps:
(1) by the 1:10:100000 mixing in mass ratio of gold nano grain, PNIPAM and water, and refrigerate at 4 DEG C.
(2), after 1:100 mixes in mass ratio at 80 DEG C with water by agarose, 50 DEG C are cooled to.
(3) mixed solution that mixed solution step (1) obtained and step (2) obtain by volume 1:1 mixes, and after thoroughly stirring, pours in flexible transparent plastic mould, and cooling forming after encapsulation, obtains self-driven light modulating device.
The preparation method of gold nano grain is as follows: by 0.05 gram of hydrochloro-auric acid and 0.5 gram of polyvinyl alcohol soluble in water, be heated to 80 DEG C, add reductive agent fast, solution becomes redness a few second, can obtain the gold nano grain that polyvinyl alcohol is stable.Characterize through uv-visible absorption spectra, this gold nano grain absorbs visible-range 400 ~ 600nm, and maximum absorption band is 520 ~ 540nm.
The preparation method of PNIPAM and embodiment 1 are together.
Embodiment 6
Be photosensitizers Yi perylene diimide, take PNIPAM as thermosensitizing agent, the preparation method of the self-driven light modulating device of the embodiment of the present invention comprises the steps:
(1) Jiang the 1:10:100000 mixing in mass ratio of perylene diimide, PNIPAM and water, and refrigerates at 4 DEG C.The visible ray of perylene diimide Absorbable rod 400 ~ 700nm wavelength.
(2), after 1:100 mixes in mass ratio at 80 DEG C with water by agarose, 50 DEG C are cooled to.
(3) mixed solution that mixed solution step (1) obtained and step (2) obtain by volume 1:1 mixes, and after thoroughly stirring, pours in mineral glass mold, and cooling forming after encapsulation, obtains self-driven light modulating device.
The preparation method of PNIPAM and embodiment 1 are together.
Embodiment 7
Be photosensitizers with Graphene, take PNIPAM as thermosensitizing agent, the preparation method of the self-driven light modulating device of the embodiment of the present invention comprises the steps:
(1) by the 1:10:100000 mixing in mass ratio of Graphene, PNIPAM and water, and refrigerate at 4 DEG C.The light of the visible and near-infrared wavelength of Graphene Absorbable rod 400 ~ 1200nm.
(2), after 1:100 mixes in mass ratio at 80 DEG C with water by agarose, 50 DEG C are cooled to.
(3) mixed solution that mixed solution step (1) obtained and step (2) obtain by volume 1:1 mixes, and after thoroughly stirring, pours in synthetic glass mould, and cooling forming after encapsulation, obtains self-driven light modulating device.
The preparation method of PNIPAM and embodiment 1 are together.
Show the test result of self-driven light modulating device prepared by above-described embodiment, illumination is opened, and unit temp prolongation is in time risen, and when temperature rises to about 31 degree, transmittance declines suddenly, avoids the excessive radiation of sunlight.Illumination is closed, and unit temp prolongation in time declines, and when being down to about 31 degree at temperature, transmittance rises suddenly.Therefore, self-driven light modulating device of the present invention can realize light modulation, heat insulation or heat insulation function automatically, and effective, can normally work without any need for additional power source, safe, energy-conservation, cost is low, and it is simple to produce assembling, has higher industrial applications and is worth.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a preparation method for self-driven light modulating device, is characterized in that, comprises the steps:
(1) photosensitizers, thermosensitizing agent and water are refrigerated after mixing 1:10:10000 ~ 100000 in mass ratio;
Described thermosensitizing agent is PNIPAM, PNIPAM binary or terpolymer, polymethyl acrylic acid N, N dimethylamine base ethyl ester, or polymethyl acrylic acid N, N dimethylamine base methacrylate copolymers;
(2) gelifying agent is mixed 1:100 ~ 200 in mass ratio with water;
Described gelifying agent is agarose, polyacrylamide gel or gelatin;
(3) mixed solution that mixed solution step (1) obtained and step (2) obtain mixes 1:1 ~ 10 by volume, after thoroughly stirring, pours in transparent mould, and cooling forming after encapsulation, obtains self-driven light modulating device.
2. the preparation method of self-driven light modulating device as claimed in claim 1, is characterized in that, the visible and near infrared light of described photosensitizers Absorbable rod 400 ~ 1500nm wavelength.
3. the preparation method of self-driven light modulating device as claimed in claim 1 or 2, it is characterized in that, described photosensitizers is metal Nano structure, transition metal, precious metal, heavy metal or rare-earth oxide nanostructure, transition metal, precious metal, heavy metal or rare earth metal chalcogenide nanostructure, organic dye, carbon material, or organic molecule switch.
4. the preparation method of self-driven light modulating device as claimed in claim 3, is characterized in that, described photosensitizers is gold nanorods, gold nano grain, perylene diimide or Graphene.
5. the preparation method of self-driven light modulating device as claimed in claim 1 or 2, is characterized in that, described thermosensitizing agent is PNIPAM or N-isopropylacrylamide-acrylamide copolymer.
6. with self-driven light modulating device prepared by method according to any one of claim 1 to 5, it is characterized in that, comprise light modulation layer and two photic zones, described light modulation layer between described two photic zones, the polymer gel that described light modulation layer is made up of photosensitizers, thermosensitizing agent, gelifying agent and water.
7. self-driven light modulating device as claimed in claim 6, is characterized in that, described photic zone is unorganic glass, synthetic glass or flexible transparent plastic.
8. self-driven light modulating device as claimed in claim 7, is characterized in that, described photic zone is polyimide.
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| CN102816340A (en) * | 2012-09-06 | 2012-12-12 | 北京理工大学 | Intelligent light adjusting film based on temperature-sensitive polymer hydrogel and preparation method of intelligent light adjusting film |
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| CN101382668A (en) * | 2007-09-04 | 2009-03-11 | 成都博深高技术材料开发有限公司 | Temperature sensitive light modulation material, method for making same and optical device composed of the same |
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