CN113495369A - Thermochromic light modulation device and manufacturing method thereof - Google Patents
Thermochromic light modulation device and manufacturing method thereof Download PDFInfo
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/0009—Materials therefor
- G02F1/009—Thermal properties
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- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
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- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention provides a thermochromic dimming device and a manufacturing method thereof. The thermochromic dimming device can achieve temperature control of thermochromic materials in the color changing layer by electrifying and heating the electric heating layer, so that the device can actively dim light at will.
Description
Technical Field
The invention belongs to the field of intelligent dimming, and particularly relates to a thermochromic dimming device and a manufacturing method thereof.
Background
The color-changing glass is a device with a dimming function, which is composed of base materials such as glass or transparent plastics and the like and color-changing materials, and can meet partial requirements of energy conservation or privacy protection by adjusting the transmittance of visible light and infrared light. The color-changing glass mainly has photochromism, thermochromism, electrochromism and the like.
Photochromic refers to a compound that, by chemical reaction at a specific wavelength, produces another compound with different structural and spectral properties that reversibly produces the former compound upon irradiation with another wavelength. However, no matter which compound is made of photochromic glass, different positions generate different light intensities under the influence of the environment, and color differences of different colors occur, so that the consistency of the curtain wall glass is damaged.
Thermochromic discoloration refers to a phenomenon in which the transmission or absorption characteristics of incident light are changed by a change in ambient temperature. Thermochromic glass is generally formed by coating a layer of reversible thermochromic material on common toughened glass. The temperature-sensitive color-changing materials are more, and the thin film coating based on the vanadium oxide is the hot spot of the current research. The VO film has high low-temperature transmittance and low high-temperature transmittance. The main problems existing at the present stage are two points: (1) the phase transition temperature of VO is 68 ℃, and the phase transition temperature of the VO film must be reduced to be near room temperature by doping or changing a preparation method and the like. (2) The prior research shows that the visible light transmittance of the VO film is lower no matter before and after phase change, and most of the VO film is less than 40 percent. Therefore, it is necessary to improve the visible light transmittance of VO to ensure indoor lighting. In addition, the conventional thermochromic device is a phenomenon that the transmission or absorption characteristics of incident light are changed through ambient temperature, and the color change of the thermochromic device cannot be opened or closed at will, so that the thermochromic device is relatively passive.
Electrochromism utilizes reversible electrochemical oxidation reaction of materials, and the color changes. The electrochromic glass which is applied in small batches in the market is EC glass, the basic structure of the electrochromic glass is composed of two glass substrates and five layers of thin film materials clamped in the two glass substrates, the five layers of thin films are respectively a transparent electric heating layer, an electrochromic layer, an ion conductor layer, an ion storage layer and another transparent electric heating layer, and a commonly adopted transparent conductive film is Indium Tin Oxide (ITO). Electrochromic technology barriers are relatively high, especially for all-solid-state electrochromic glass, and small-lot commercial applications do not begin until the end of 2012. In addition, the cost of the material is high, so that the price of the material is always high.
Based on the analysis of the prior art, it is necessary to develop an active color-changing light-adjusting device with simple process and low cost.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a thermochromic light modulating device and a method for manufacturing the same.
The invention provides a thermochromic dimming device which comprises a first transparent substrate layer, a second transparent substrate layer, a color changing layer and an electrothermal layer, wherein the color changing layer and the electrothermal layer are clamped between the first transparent substrate layer and the second transparent substrate layer, and the color changing layer comprises thermochromic materials.
According to one embodiment of the invention, the light transmittance of the electric heating layer is more than or equal to 70%, and the surface resistance is 60-2000 omega/sq; preferably, the light transmittance is more than 80%, and the area resistance is 300-2000 Ω/sq.
According to another embodiment of the present invention, the electrothermal layer comprises one or more selected from metal oxide, graphene, nano silver wire, polyaniline, polythiophene; preferably, the electric heating layer is a metal oxide or graphene film; preferably, the metal oxide is selected from SnO2、InO2One or more of ITO, AZO and IZO.
According to another embodiment of the present invention, the thickness of the electrothermal layer is 0.3nm to 120 nm; preferably, the thickness of the electrothermal layer is 0.8-2.0 nm.
According to another embodiment of the present invention, the color changing layer comprises a thermochromic material and a polymer material, wherein the thermochromic material is selected from the group consisting of a transition metal ion thermochromic material, a polyol ligand compound thermochromic material, and organic nitrogen N (R)3Compound thermochromic material, organic phosphorus P (R)3One or more of compound temperature-sensitive color-changing materials, wherein the high polymer material is selected from one or more of polysiloxane, polyvinyl alcohol ester, polyacrylate and epoxy resin.
According to another embodiment of the present invention, the thermochromic material is contained in the color-changing layer in an amount of 0.3 to 10%
According to another embodiment of the present invention, the color changing layer comprises two or more thermochromic materials, and the color changing temperature of each thermochromic material is different.
According to another embodiment of the present invention, the discoloration temperature of the discoloration layer is-5 ℃ to 70 ℃, preferably 30 ℃ to 60 ℃; the thickness is 0.02mm to 2mm, preferably 0.5mm to 1.5 mm.
The invention also provides a manufacturing method of the thermochromic dimming device, which comprises the following steps: providing a first transparent substrate layer; forming an electrothermal layer on the first transparent substrate layer to form a first transparent substrate/electrothermal composite layer; forming a color changing layer; providing a second transparent substrate layer; and laminating the first transparent substrate/electrothermal composite layer, the discoloration layer and the second transparent substrate layer.
According to an embodiment of the present invention, the color-changing layer is obtained by mixing a crosslinkable polymer, a crosslinking agent, and a thermochromic material, defoaming in vacuum, and then crosslinking and curing.
The thermochromic dimming device can achieve temperature control of thermochromic materials in the color changing layer by electrifying and heating the electric heating layer, so that the device can actively dim light at will. Furthermore, color-changing materials with different color-changing temperatures can be selected to manufacture color-changing devices with different temperatures. And the temperature sensing color changing materials with different color changing temperatures can be adopted to realize continuous color changing or multi-section color changing. Furthermore, the electric heating layer, especially the graphene film, which is preferably used as the electric heating layer, has the characteristics of good electric heating conversion efficiency, high transparency, stable resistance under the condition of hot oxygen and the like, and is long in service life. The technical scheme of the invention has the advantages of simple manufacturing process and lower material cost.
Drawings
The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings.
Fig. 1 is a schematic diagram of a structure of a dimming device of the present invention.
Fig. 2 is a schematic view of an electrothermal layer of the dimming device of the present invention.
Fig. 3 is a plan view of the electrothermal layer shown in fig. 2.
Wherein the reference numerals are as follows:
1-a first transparent substrate layer; 2-a second transparent substrate layer; 3-a color-changing layer; 4-electric heating layer; 5, 6-electrodes; 7, 8-conductor
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
As shown in fig. 1, the light modulation device of the present invention includes a first transparent substrate layer 1, a second transparent substrate layer 2, a color changing layer 3, and an electrothermal layer 4. The color-changing layer and the electro-thermal layer 4 are sandwiched between the first transparent substrate layer 1 and the second transparent substrate layer 2. The color changing layer 3 includes a temperature sensitive color changing material. According to the dimming device, the electric heating layer 2 is heated, and when the temperature reaches the color change temperature of the temperature sensing color change material in the color change layer 3, the temperature sensing color change material changes color, so that the purpose of active dimming is achieved. The light modulation device can realize that the color and the transparency of the device change along with the change of temperature according to the desire of people, and the color changes from colorless to colored, from colored to colorless or from colored to other colors.
The first and second transparent substrate layers 1,2 play a role of supporting and protecting the electrothermal layer 4 and the color-changing layer 4, and simultaneously have certain transmittance to satisfy the light transmission effect. Preferably, the first and second transparent substrate layers 1 and 2 are made of glass, hard temperature-resistant transparent resin sheets, or the like, and the thickness is preferably 1.1mm to 5 mm.
The electric heating layer 4 is used for heating the color changing layer 3 so as to change the color or transparency of the color changing layer 3 and realize the active dimming function. Meanwhile, the electric heating layer 4 should have good light transmittance to ensure that the transmittance of the device before and after the color change of the color changing layer 3 is not affected by the electric heating layer 4. Preferably, the light transmittance of the electric heating layer 4 is more than or equal to 70%, and the surface resistance is 60-2000 Ω/sq, and the light transmittance and the surface resistance in the above ranges can ensure good light transmittance of the device and enable the electric heating layer 4 to have a high electric heating conversion effect. More preferably, the light transmittance is more than 80%, and the area resistance is 100-. The electrothermal layer 4 may include one or more selected from metal oxide, graphene, nano silver wire, polyaniline, and polythiophene. More preferably, the electrothermal layer 4 is a metal oxide or graphene film, and the graphene film can maintain stable photoelectric properties under long-term high-temperature application. Metallic oxygenThe compound is selected from SnO2、InO2One or more of ITO, AZO, IZO and the like. The thickness of the electric heating layer 4 is 0.3nm-120nm, preferably the thickness of the electric heating layer 4 is 0.8-2.0nm, so that high light transmittance and good resistivity are ensured. Referring to fig. 2 and 3, the electrothermal layer 4 including a pair of electrodes 5 and 6 may be led out through wires 7 and 8 to facilitate connection to a power source.
The color changing layer 3 comprises a temperature sensing color changing material and a high polymer material. The temperature-sensitive color-changing material is selected from one or more of transition metal ion temperature-sensitive color-changing materials, polyalcohol ligand compound temperature-sensitive color-changing materials and organic nitrogen organic phosphorus compound temperature-sensitive color-changing materials. The high molecular material is selected from one or more of polysiloxane, polyvinyl alcohol ester, polyacrylate and epoxy resin. The mass content of the temperature-sensitive color-changing material in the color-changing layer 3 is 0.3-10%. When the content of the thermochromic material in the color changing layer 3 is lower than 0.3%, the color of the color changing layer is lighter, the color changing process is not obvious, when the content of the thermochromic material in the color changing layer 3 is higher than 10%, the color is too dark, the base color still exists after the dark color is changed to be lighter, and in addition, the structural strength of the matrix is damaged if the content is too high.
The color changing layer 3 may contain a thermochromic material, and the color changing layer 3 changes color when the temperature reaches a color changing temperature. The color-changing layer 3 may also contain two or more temperature-sensitive color-changing materials, and the color-changing temperature of each temperature-sensitive color-changing material is different. When the temperature reaches the color changing temperature of one temperature sensing color changing material, the color changing layer 3 changes color, when the temperature reaches the color changing temperature of another temperature sensing color changing material again, the color changing layer 3 changes color again, thereby realizing the effect of continuous or segmented color changing.
The color changing temperature of the color changing layer 3 is-5 ℃ to 70 ℃, preferably 30 ℃ to 60 ℃. The thickness is 0.02mm to 2mm, preferably 0.5mm to 1.5 mm.
The dimming device can be manufactured as follows: providing a first transparent substrate layer 1; forming an electrothermal layer 4 on the first transparent substrate layer 1 to form a first transparent substrate/electrothermal composite layer; forming a color changing layer 3; providing a second transparent substrate layer 2; and laminating the first transparent substrate/electrothermal composite layer, the discoloring layer 3 and the second transparent substrate layer 4.
The electrothermal layer 4 can be formed on the first transparent substrate layer 1 by selecting an appropriate manner according to the material of the electrothermal layer 4. For example, the graphene electrothermal layer 4 is manufactured by a chemical vapor deposition, growth method or transfer method, or the graphene electrothermal layer is manufactured by a coating method, or the metal oxide electrothermal layer 4 is manufactured by a magnetron sputtering method.
After the formation of the electrothermal layer 4, electrodes 5,6 are formed at both ends of the electrothermal layer 4. A coating method may be used, with different electrode materials depending on whether the device is shielded around. Preferably, when the periphery of the device is shielded, the electrodes 5 and 6 are made of conductive silver paste materials; when the periphery of the device is not shielded, the nano silver wires are coated to manufacture the transparent electrodes 5 and 6. And then led out through the leads 7, 8.
The color-changing layer 3 can be obtained by mixing the crosslinkable polymer, the crosslinking agent and the thermochromic material, defoaming in vacuum, and then crosslinking and curing.
And finally, after the layers are overlapped, the opposite side parts are packaged to form the dimming device.
For a better understanding of the present invention and the method of making the same, reference is made to the following detailed description of the invention taken in conjunction with the accompanying drawings.
Example 1
The embodiment provides an active thermochromic dimming device which comprises a first transparent substrate layer 1, a second transparent substrate layer 2, a color changing layer 3, an electric heating layer 4 and a pair of electrode leading- out wires 7 and 8. Wherein the first and second transparent substrate layers 1,2 are glass sheets.
1) Glass with a thickness of 1.1mm and 300mm by 300mm is selected as the first transparent substrate layer 1 and subjected to cleaning treatment.
2) A graphene thin film is directly grown on the glass by a Chemical Vapor Deposition (CVD) method as the electrothermal layer 4. The resistance of the graphene conductive film (the electrothermal layer 4) is about 1000 Ω/sq. The visible light transmittance of the graphene conductive glass (formed by directly growing the graphene conductive film on the glass) is 88%.
3) Printing a pair of nano-silver transparent electrodes 5 and 6 with the width of 4mm on the electric heating layer 4, putting the electric heating layer on a curing box or a heating plate at the temperature of 120 ℃ for heating for 20min for curing, and then welding two leads 7 and 8.
4) An organic reversible temperature-sensitive color-changing material (purchased from Shenzhen Shenjinli New Material Co., Ltd., model number H20, wherein the blue color at 45 ℃ changes to colorless, and the color at RTP 31 ℃ does not change to red) is selected: the temperature-sensitive color-changing material with the temperature-changing threshold value of 45 ℃ changing blue color into colorless color is prepared by mixing PDMS prepolymer, a cross-linking agent and the temperature-sensitive color-changing material in the proportion of 10: 1: mixing at a ratio of 0.5.
5) Coating the crosslinkable thermochromic material prepared in the step 4) on a clamped second transparent glass substrate 2, laminating the crosslinkable thermochromic material with the first transparent glass substrate 1 with the electrothermal layer 4 prepared in the step 3), and then heating the laminated material on a hot plate or in an oven at 80-100 ℃ for 60min for curing.
6) And finishing the edge packaging post-treatment.
When the temperature of the color changing layer is more than or equal to 45 ℃ (electrifying for 2min), the color of the color changing device is changed from blue to colorless; the color of the material can be changed from colorless to blue after the temperature is adjusted to be less than 45 ℃ or the power is cut off.
Example 2
The present embodiment provides a thermochromic dimmer device, which is different from embodiment 1 in that: the electric heating layer 4 is an ITO electric heating layer manufactured by a magnetron sputtering method, the resistance is 90 +/-10 omega/sq, and the visible light transmittance is 80 +/-1%; a pair of electrodes 5,6 made of conductive silver paste are arranged on the electrothermal layer 4, and lead wires 7,8 are used. The temperature-sensitive color-changing material is a red color-changing colorless temperature-sensitive color-changing material with a temperature-changing threshold value of 33 ℃ (the model number of H20, purchased from Shenzhen Shenjinli New Material Co., Ltd., blue color-changing colorless at 45 ℃ and colorless at RTP 31 ℃). The rest is the same as example 1.
When the temperature of the color changing layer is more than or equal to 33 ℃, the color of the color changing device is changed from colorless to red; the color can be changed from red to colorless after the temperature is adjusted to be less than 33 ℃ or the power is cut off.
Example 3
The embodiment provides a thermochromic dimming device which comprises a first transparent substrate layer 1, a second transparent substrate layer 2, a color changing layer 3, an electric heating layer 4 and a pair of electrode leading- out wires 7 and 8. Wherein the first and second transparent substrate layers 1,2 are glass sheets.
1) A glass substrate 1 with a thickness of 3mm and 300mm x 300mm is selected for cleaning treatment.
2) A graphene film is grown on the glass by a CVD method to be used as an electric heating layer 4. The resistance of the graphene conductive film (the electrothermal layer 4) is about 1000 +/-100 omega/sq. The visible light transmittance of the graphene conductive glass (formed by directly growing the graphene conductive film on the glass) is 88 +/-1%.
3) Printing a pair of conductive silver paste with the width of 4mm on the electric heating layer 4 to be used as electrodes 5 and 6, putting the electrodes on a curing box or a heating plate at the temperature of 120 ℃ for heating for 20min for curing, and then welding two leads 7 and 8.
4) The metal ion complex type reversible thermochromic material (Cu (ClO) is selected4)2-6H2O) -ethylene diamine): the thermochromic material with the temperature change threshold value of 52 ℃ capable of changing from colorless to blue is added into PVB resin in a weight ratio of 0.3%, fully stirred and uniformly dispersed, and the mixture is extruded into the color changing layer 3 by adopting the existing extrusion technology.
5) And (3) sandwiching the color-changing layer 3 between the first transparent glass substrate layer 1 and the second transparent glass substrate layer 2 with the electric heating layer 4, wherein the electric heating layer 4 is in direct contact with the color-changing layer 3, and then heating in an autoclave to obtain the laminated glass.
6) And finishing the edge packaging post-treatment.
Wherein the color-changing layer 3 is made of PVB (polyvinyl butyral) with the thickness of 0.4 mm.
When the temperature of the color changing layer is more than or equal to 52 ℃ (30V is electrified for 2min), the color of the color changing device is changed from colorless to blue; the color of the blue can be changed into colorless after the temperature is adjusted to be less than 52 ℃ or the power is cut off.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. The thermochromic dimming device is characterized by comprising a first transparent substrate layer, a second transparent substrate layer, a color changing layer and an electric heating layer, wherein the color changing layer and the electric heating layer are clamped between the first transparent substrate layer and the second transparent substrate layer, and the color changing layer comprises reversible temperature-sensitive color changing materials.
2. The thermochromic dimmer of claim 1, wherein the electrothermal layer has a light transmittance of 70% or more and a surface resistance of 60-2000 Ω/sq; preferably, the light transmittance is more than 80%, and the area resistance is 300-2000 Ω/sq.
3. The thermochromic dimmer of claim 2, wherein said electrically-heating layer comprises one or more selected from the group consisting of metal oxides, graphene, silver nanowires, polyaniline, polythiophene; preferably, the electric heating layer is a metal oxide or graphene film; preferably, the metal oxide is selected from SnO2、InO2One or more of ITO, AZO and IZO.
4. The thermochromic dimmer of claim 2, wherein said electrically-heating layer has a thickness of 0.3nm to 120 nm; preferably, the thickness of the electrothermal layer is 0.8-2.0 nm.
5. The thermochromic dimmer pack according to claim 1, wherein the color changing layer comprises a thermochromic material selected from one or more of a transition metal ion thermochromic material, a polyol ligand compound thermochromic material, an organic nitrogen compound thermochromic material, and an organic phosphorus compound thermochromic material, and a polymer material selected from one or more of polysiloxane, polyvinyl alcohol ester, polyacrylate, and epoxy resin.
6. The thermochromic dimmer of claim 5, wherein said thermochromic material in said color changing layer is present in an amount of 0.3% to 10% by weight.
7. The thermochromic dimmer apparatus of claim 5, wherein said color changing layer comprises two or more thermochromic materials, and the color changing temperature of each thermochromic material is different.
8. A thermochromic dimmer device as claimed in claim 1, wherein the color change temperature of the color change layer is from-5 ℃ to 70 ℃, preferably from 30 ℃ to 60 ℃; the thickness is 0.02mm to 2mm, preferably 0.5mm to 1.5 mm.
9. A manufacturing method of a thermochromic dimming device is characterized by comprising the following steps:
providing a first transparent substrate layer;
forming an electrothermal layer on the first transparent substrate layer to form a first transparent substrate/electrothermal composite layer;
forming a color changing layer;
providing a second transparent substrate layer; and
laminating the first transparent substrate/electrothermal composite layer, the discoloration layer, and the second transparent substrate layer.
10. The method of claim 9, wherein the color-changing layer is obtained by mixing a crosslinkable polymer, a crosslinking agent, and a thermochromic material, defoaming in vacuum, and then crosslinking and curing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202010202316.4A CN113495369A (en) | 2020-03-20 | 2020-03-20 | Thermochromic light modulation device and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010202316.4A CN113495369A (en) | 2020-03-20 | 2020-03-20 | Thermochromic light modulation device and manufacturing method thereof |
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