CN103756228A - Self-driven dimming device and preparation method thereof - Google Patents
Self-driven dimming device and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a self-driven dimming device and a preparation method thereof. The method comprises the steps of: (1) mixing a photosensitizer, a heat sensitizer and water in a mass ratio of 1:10:10000-100000, and then conducting refrigeration; (2) mixing a gel with water in a mass ratio of 1:100-200; (3) mixing the mixed solution obtained in step (1) with the mixed solution obtained in step (2) in a volume ratio of 1:1-10, stirring them evenly and thoroughly, then conducting perfusion to a transparent mold, performing encapsulation and then carrying out cooling molding, thus obtaining the self-driven dimming device. The device includes a dimming layer and two transparent layers, and the dimming layer is located between the two transparent layers. The dimming layer is a polymer gel composed of the photosensitizer, the heat sensitizer, the gel and water. The device can automatically dimming, heat insulation or heat preservation functions, and can achieve good effects. Without any external power, the device can work normally, and has the advantages of safety, energy saving, low cost, simple production assembly, and high industrial application value.
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 summer, avoids room temp too high, thereby reduces the power consumption of the cooling installations such as air-conditioning.
To high light, mainly adopt curtain, dividing plate etc. to block at present, high temperature is mainly adopted to insulating layer material, shading and heat insulation effect are limited.Recently, for the Protection Product of dazzling light, come out, 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 to 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
Above defect or Improvement requirement for prior art, the invention provides a kind of self-driven light modulating device and preparation method thereof, this device can be realized light modulation, heat insulation or heat insulation function automatically, and effective, without any need for additional power source, can normally work, safe, energy-conservation, cost is low, produces assembling simple, there is higher industrial applications and be 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, comprised the steps: that (1) 1:10:10000～100000 refrigerates photosensitizers, thermosensitizing agent and water in mass ratio after mixing; (2) gelifying agent is mixed 1:100～200 in mass ratio with water; (3) mixed solution step (1) being obtained mixes 1:1～10 by volume with the mixed solution that step (2) obtains, and after thoroughly stirring, in transparent mould, pours into, and cooling forming after encapsulation, obtains self-driven light modulating device.
Preferably, described photosensitizers can absorb the visible and near infrared light of 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 ethyl ester multipolymer.
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, a kind of self-driven light modulating device of preparing with aforesaid method is provided, 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 comprised 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 of conceiving by the present invention compared with prior art, has following beneficial effect:
(1) can automatically realize light modulation, heat insulation or heat insulation function, and effective.With photosensitizers and the synthetic light control material of thermosensitizing agent, photosensitizers produces photic intensification under high light effect, and thermosensitizing agent makes light control material cohesion 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) without any need for additional power source, can normally work, safe, energy-conservation, cost is low.
(3) produce assembling simply, there is higher industrial applications and be worth, can be widely used in the fields such as architectural lighting insulation, intelligent curtain, intelligent curtain wall, intelligent automobile side window, intelligent skylight.
Accompanying drawing explanation
Fig. 1 is the self-driven light modulating device schematic diagram of the embodiment of the present invention;
Fig. 2 is that the temperature of self-driven light modulating device of the embodiment of the present invention 1 preparation is with the change curve of illumination switch;
Fig. 3 be the transmittance of self-driven light modulating device of the embodiment of the present invention 1 preparation 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 clearer, 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, is not intended to limit the present invention.In addition,, in each embodiment of described the present invention, involved technical characterictic just can not combine mutually as long as do not form each other conflict.
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.
The polymer gel that light modulation layer 2 is comprised of photosensitizers, thermosensitizing agent, gelifying agent and water.
Under intense light irradiation condition, photosensitizers produces photic intensification, and thermosensitizing agent is under high temperature action, make polymkeric substance cohesion, forming particle diameter is the polymer nano granules of tens to several thousand nanometers, makes light modulation layer 2 become opaque, produce strong scattering of light, stop that sunlight sees through; Under weak illumination condition, light modulation layer 2 is vitreous state, obviously improves optical transmission rate.
Similarly, when envrionment temperature is higher, thermosensitizing agent makes polymkeric substance cohesion 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, obviously improves optical transmission rate, 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 nanoparticle rod, 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, selenizing tungsten, selenizing molybdenum, zinc telluridse, tellurium copper, cuprous telluride, tellurium iron, ferrous telluride, tellurium nickel, tellurium tin, the sub-tin of telluriumization, cobaltous telluride, tellurium aluminium, tellurium chromium, cadmium telluride, lead telluride, tellurium indium, tellurium indium tin, silver telluride, tellurium palladium, tellurium ruthenium, tellurium tungsten, tellurium 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 ethyl ester multipolymer comprises: methacrylic acid N, N dimethylamine base ethyl ester-acrylic copolymer, methacrylic acid N, N dimethylamine base ethyl ester-Sipacril 2739OF, methacrylic acid N, N dimethylamine base ethyl ester-acrylate copolymer, methacrylic acid N, N dimethylamine base ethyl ester-alkylmethacrylate polymer, methacrylic acid N, N dimethylamine base ethyl ester-styrol copolymer etc.
Gelifying agent can be natural gelifying agent, as agarose, gelatin, starch gel; Also can be synthetic 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, photosensitizers can absorb the visible and near infrared light of 400～1500nm wavelength.
(2) gelifying agent is mixed 1:100～200 in mass ratio with water.
(3) mixed solution step (1) being obtained mixes 1:1～10 by volume with the mixed solution that step (2) obtains, and after thoroughly stirring, in transparent mould, pours into, and cooling forming after encapsulation, obtains self-driven light modulating device.
For making those skilled in the art understand better the present invention, below in conjunction with specific embodiment, the preparation method of self-driven light modulating device of the present invention is elaborated.
Take gold nanorods as photosensitizers, 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 refrigeration at 4 ℃.
(2) after 1:100 mixes in mass ratio at 80 ℃ with water by agarose, be cooled to 50 ℃.
(3) mixed solution that mixed solution step (1) being obtained obtains with step (2) by volume 1:1 mixes, and after thoroughly stirring, in unorganic glass mould, pours into, and cooling forming after encapsulation, obtains self-driven light modulating device.
Fig. 2 be the temperature of the self-driven light modulating device prepared of the present embodiment with the change curve of illumination switch, Fig. 3 be the transmittance of the self-driven light modulating device prepared of the embodiment of the present invention with illumination switch reversible change curve.From Fig. 2 and Fig. 3, illumination is opened, and the prolongation in time of the temperature of self-driven light modulating device is risen, thermosensitizing agent makes light control material cohesion under high temperature action, the polymer nano granules that forms tens to several thousand nanometers, declines the transmittance of self-driven light modulating device gradually, realizes resistance light or heat insulation.
Particularly, gold nanorods and PNIPAM preparation as follows respectively.
The preparation of gold nanorods: to the silver nitrate solution that adds 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 to cause gold nanorods growth, as shown in Figure 4, gold nanorods can absorb the near infrared light of 600～900nm wavelength to the uv-visible absorption spectra of the gold nanorods making again.
Wherein, the preparation method of gold colloid seed solution is as follows: to the chlorauric acid solution that adds 2.5 milliliters of 0.0005mol/L in the CTAB solution of 2.5 milliliters of 0.2mol/L, the sodium borohydride that adds again 0.3 milliliter of 0.01mol/L, shake up and standing 1 minute, then be placed in 40 ℃ of water-baths 15 minutes, normal temperature is preserved.
The preparation of PNIPAM: by 5 grams of the good monomer N-isopropylacrylamide of 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, continuation is stirred 24 hours under 80 ℃ of conditions, reaction head product is dissolved in methylene dichloride, then slowly drips and precipitate in anhydrous diethyl ether, vacuum-drying throw out obtains white solid.Through nuclear-magnetism and Infrared Characterization, prove that the synthetic white solid of the method is PNIPAM, transformation efficiency is 60%.By gel permeation chromatography (GPC), measure, this polymkeric substance number-average molecular weight Mn=50000, dispersion coefficient is 2.4.
Take gold nanorods as photosensitizers, 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 refrigeration at 4 ℃.
(2) after 1:200 mixes in mass ratio at 80 ℃ with water by agarose, be cooled to 50 ℃.
(3) mixed solution that mixed solution step (1) being obtained obtains with step (2) by volume 1:10 mixes, and after thoroughly stirring, in synthetic glass mould, pours into, and cooling forming after encapsulation, obtains self-driven light modulating device.
The preparation method of gold nanorods and PNIPAM and embodiment 1 are same.
Embodiment 3
Take gold nanorods as photosensitizers, 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 refrigeration at 4 ℃.
(2) after 1:200 mixes in mass ratio at 80 ℃ with water by agarose, be cooled to 50 ℃.
(3) mixed solution that mixed solution step (1) being obtained obtains with step (2) by volume 1:10 mixes, and after thoroughly stirring, in polyimide mould, pours into, and cooling forming after encapsulation, obtains self-driven light modulating device.
The preparation method of gold nanorods and PNIPAM and embodiment 1 are same.
Embodiment 4
Take gold nanorods as photosensitizers, take N-isopropylacrylamide-acrylamide copolymer 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, N-isopropylacrylamide-acrylamide copolymer and water, and refrigeration at 4 ℃.Wherein, the molecular weight of N-isopropylacrylamide-acrylamide copolymer is 42000.
(2) after 1:200 mixes in mass ratio at 80 ℃ with water by agarose, be cooled to 50 ℃.
(3) mixed solution that mixed solution step (1) being obtained obtains with step (2) by volume 1:10 mixes, and after thoroughly stirring, in unorganic glass mould, pours into, and cooling forming after encapsulation, obtains self-driven light modulating device.
The preparation method of gold nanorods and embodiment 1 are same.
Embodiment 5
Take gold nano grain as photosensitizers, 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 refrigeration at 4 ℃.
(2) after 1:100 mixes in mass ratio at 80 ℃ with water by agarose, be cooled to 50 ℃.
(3) mixed solution that mixed solution step (1) being obtained obtains with step (2) by volume 1:1 mixes, and after thoroughly stirring, in flexible transparent plastic mould, pours into, and cooling forming after encapsulation, obtains self-driven light modulating device.
The preparation method of gold nano grain is as follows: 0.05 gram of hydrochloro-auric acid and 0.5 gram of polyvinyl alcohol is soluble in water, be heated to 80 ℃, and add fast reductive agent, solution becomes redness several seconds, can obtain the stable gold nano grain of polyvinyl alcohol.Through uv-visible absorption spectra, characterize, 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 same.
Embodiment 6
Take perylene diimide as photosensitizers, 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) is Jiang the 1:10:100000 mixing in mass ratio of perylene diimide, PNIPAM and water, and refrigeration at 4 ℃.Perylene diimide can absorb the visible ray of 400～700nm wavelength.
(2) after 1:100 mixes in mass ratio at 80 ℃ with water by agarose, be cooled to 50 ℃.
(3) mixed solution that mixed solution step (1) being obtained obtains with step (2) by volume 1:1 mixes, and after thoroughly stirring, in unorganic glass mould, pours into, and cooling forming after encapsulation, obtains self-driven light modulating device.
The preparation method of PNIPAM and embodiment 1 are same.
Embodiment 7
Take Graphene as photosensitizers, 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 refrigeration at 4 ℃.Graphene can absorb 400～1200nm as seen and the light of near-infrared wavelength.
(2) after 1:100 mixes in mass ratio at 80 ℃ with water by agarose, be cooled to 50 ℃.
(3) mixed solution that mixed solution step (1) being obtained obtains with step (2) by volume 1:1 mixes, and after thoroughly stirring, in synthetic glass mould, pours into, and cooling forming after encapsulation, obtains self-driven light modulating device.
The preparation method of PNIPAM and embodiment 1 are same.
The test result of self-driven light modulating device prepared by above-described embodiment shows, illumination is opened, and unit temp prolongation is in time risen, and when temperature rises to 31 degree left and right, transmittance declines suddenly, avoids the excessive irradiation of sunlight.Illumination is closed, and unit temp prolongation in time declines, and when temperature drops to 31 degree left and right, transmittance rises suddenly.Therefore, self-driven light modulating device of the present invention can be realized light modulation, heat insulation or heat insulation function automatically, and effective, without any need for additional power source, can normally work, safe, energy-conservation, cost is low, produces assembling simple, 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 modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
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;
(2) gelifying agent is mixed 1:100～200 in mass ratio with water;
(3) mixed solution step (1) being obtained mixes 1:1～10 by volume with the mixed solution that step (2) obtains, and after thoroughly stirring, in transparent mould, pours into, 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, described photosensitizers can absorb the visible and near infrared light of 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 the self-driven light modulating device as described in any one in claim 1 to 4, it is characterized in that, 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 ethyl ester multipolymer.
6. the preparation method of self-driven light modulating device as claimed in claim 5, is characterized in that, described thermosensitizing agent is PNIPAM or N-isopropylacrylamide-acrylamide copolymer.
7. the preparation method of self-driven light modulating device as claimed in claim 1, is characterized in that, described gelifying agent is agarose, polyacrylamide gel or gelatin.
8. the self-driven light modulating device of preparing by method described in any one in claim 1 to 7, 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 comprised of photosensitizers, thermosensitizing agent, gelifying agent and water.
9. self-driven light modulating device as claimed in claim 8, is characterized in that, described photic zone is unorganic glass, synthetic glass or flexible transparent plastic.
10. self-driven light modulating device as claimed in claim 9, is characterized in that, described photic zone is polyimide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108983527A (en) * | 2018-08-28 | 2018-12-11 | 上海幂方电子科技有限公司 | A kind of self-powered type electrochromic device and preparation process |
| CN111505842A (en) * | 2020-04-30 | 2020-08-07 | 温州激光与光电子协同创新中心 | Passive optical sensitive device for improving laser power stability and implementation and test method thereof |
| CN111505842B (en) * | 2020-04-30 | 2023-11-10 | 温州激光与光电子协同创新中心 | Passive photosensitive device for improving laser power stability and implementation and test method thereof |
| CN115232477A (en) * | 2022-05-16 | 2022-10-25 | 上海大学 | Temperature-sensitive dendronized gelatin fluorescent microsphere as well as preparation method and application thereof |
| CN115232477B (en) * | 2022-05-16 | 2023-05-16 | 上海大学 | Temperature-sensitive dendronized gelatin fluorescent microsphere, and preparation method and application thereof |
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