CN113400750B - A liquid metal flexible composite film and its preparation method and application - Google Patents
A liquid metal flexible composite film and its preparation method and application Download PDFInfo
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- CN113400750B CN113400750B CN202110511895.5A CN202110511895A CN113400750B CN 113400750 B CN113400750 B CN 113400750B CN 202110511895 A CN202110511895 A CN 202110511895A CN 113400750 B CN113400750 B CN 113400750B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
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- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3428—Cathode assembly for sputtering apparatus, e.g. Target using liquid targets
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
- C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
- E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
- B32B2255/205—Metallic coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/416—Reflective
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2419/00—Buildings or parts thereof
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
- E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
- E04B2001/7691—Heat reflecting layers or coatings
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Abstract
本发明提供一种液态金属柔性复合薄膜及其制备方法与应用，所述液态金属柔性复合薄膜，由上至下依次包括：高辐射层；液态金属层；封装保护层。本发明提供的液态金属柔性复合薄膜不仅可以将极大部分阳光及近红外波反射回大气层，而且可以通过“大气窗口”与外太空(太空中的平均温度为‑270.3℃)进行热量交换，从而实现空间的被动致冷效果。本发明提供的液态金属柔性复合薄膜可以应用在各种房屋建筑等致冷空间表面，对于建筑节能等领域具有极大的应用潜力。The present invention provides a liquid metal flexible composite film and a preparation method and application thereof. The liquid metal flexible composite film comprises, from top to bottom, a high radiation layer; a liquid metal layer; and an encapsulation protection layer. The liquid metal flexible composite film provided by the present invention can not only reflect most of the sunlight and near-infrared waves back to the atmosphere, but also exchange heat with outer space (the average temperature in space is ‑270.3°C) through an "atmospheric window", thereby achieving a passive cooling effect in space. The liquid metal flexible composite film provided by the present invention can be applied to the surfaces of cooling spaces such as various housing buildings, and has great application potential in fields such as building energy conservation.
Description
Technical Field
The invention relates to the technical field of passive refrigeration, in particular to a liquid metal flexible composite film, a preparation method and application thereof.
Background
Passive refrigeration is a technique for reducing the temperature of a passive refrigerated space without the use of an external driving force. Compared to conventional cooling techniques, such as air conditioning or evaporative cooling, the compressor and fan are operated mechanically or electrically to force cooling of the space. Such external driving force sources mostly come from the combustion of fossil fuels. The passive cooling technology does not need external driving force, reduces the absorption of illumination through the design of a building structure or an external coating, and the like, increases the radiation to space, and ensures that the heat absorption capacity of the passive cooling space is smaller than the heat release capacity, thereby realizing the passive cooling of the passive cooling space. The interior of the passive cryogen space is maintained comfortable by reducing unnecessary heat from direct sunlight into the passive cryogen space.
Under the influence of secondary factors such as non-radiation items, the basic principle of radiation refrigeration can be simply summarized as that the atmospheric window (mainly 8-13 μm) emits enough infrared radiation energy to the cosmic space with the temperature close to absolute zero degree to release heat, and simultaneously, the energy from a solar spectrum wave band (mainly researching 0.2-4 μm, because the wave band accounts for more than 98% of the whole solar energy) is reflected or scattered as much as possible, so that the object self cooling purpose is achieved. Because passive refrigeration research may be partially or entirely avoided, the energy conservation strategy of the expense of cooling technology driven by power equipment such as fans or compressors may also reduce the burning of environmentally hazardous waste byproducts by reducing the need to burn non-renewable fuels. The development of high performance passive refrigeration materials or structures has gained active participation by many researchers.
As a unique advanced material with high fluidity, high conductivity and low toxicity, liquid metal has been widely and intensively studied in the fields of 3D printing, printed electronics, wearable skin electronics, biomedical devices, etc. due to its flexibility and stretchability. The liquid metal has extremely high reflection performance on full-band electromagnetic waves, the application of the liquid metal in energy is generally limited in heat conduction and heat convection heat dissipation, and the application of the radiation heat dissipation characteristic of the liquid metal in the heat dissipation field is rarely studied.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a liquid metal flexible composite film, and a preparation method and application thereof.
Specifically, the invention provides the following technical scheme:
the invention provides a liquid metal flexible composite film, which sequentially comprises the following components from top to bottom:
a high emissivity layer;
a liquid metal layer;
And packaging the protective layer.
The invention discovers that the high-radiation layer can transmit electromagnetic waves with visible light and near infrared wavelength and has high radiation characteristic to the thermal infrared wave band of an atmospheric window. The liquid metal layer has high reflectivity for electromagnetic waves with visible light and near infrared wavelengths, so that the electromagnetic waves with the visible light and near infrared wavelengths transmitted by the high-radiation layer are reflected back to the high-radiation layer, and the high transmissivity of the high-radiation layer can ensure that the electromagnetic waves with the visible light and near infrared wavelengths reflected back from the liquid metal layer are reflected back to the atmosphere. Meanwhile, the liquid metal layer also has good heat conduction property, and can transfer the heat of the passive refrigeration space to the high-radiation layer so as to radiate to space. By compounding the liquid metal layer and the high-emissivity layer, not only the high reflection characteristic of the liquid metal and the high emissivity of the high-emissivity layer can be fully exerted, but also the high heat conduction characteristic of the liquid metal can be exerted, so that an excellent passive refrigeration effect is realized.
Further, the material of the high-radiation layer is selected from any one of PDMS (polydimethylsiloxane), PE (polyethylene), PVF (polyvinyl fluoride), PVC (polyvinyl chloride) and TPX (poly 4-methylpentene-1).
Or the material of the high-emissivity layer is prepared by compounding high-emissivity micro-nano particles and a transparent high polymer material, wherein the high-emissivity micro-nano particles are selected from one or more of cordierite, transition metal oxide, silicon carbide, titanium dioxide, silicon dioxide, aluminum oxide and hafnium oxide, and the transparent high polymer material is selected from any one of PDMS, polyethylene, cellulose and PVF, PVC, TPX, PVA (polyvinyl alcohol). As an example, the transition metal oxide may be ZnMn 2O4、NiCr2O4、CoFeO4、NiFe2O4 or the like. Further, the particle size of the high-emissivity micro-nano particles is 1 nm-500 μm. The high-emissivity micro-nano particles have very high absorption characteristics on electromagnetic waves of atmospheric window wave bands, namely, electromagnetic waves with more wavelengths in the atmospheric window can be radiated, so that the radiation performance of the high-emissivity layer in the atmospheric window can be greatly improved by being mixed in the transparent high polymer material.
Further, the thickness of the high-emissivity layer is 1-2 mm, preferably 10-500 mu m.
Further, the material of the liquid metal layer is selected from one or more of gallium, gallium indium alloy, gallium indium tin zinc alloy and bismuth indium tin zinc alloy.
Further, the thickness of the liquid metal layer is 1 nm-500 μm, preferably 50 nm-200 μm.
The invention also discovers that the thickness of the high-radiation layer has great influence on the reflectivity of the liquid metal flexible composite film in the visible light and near infrared bands and the emissivity of the atmospheric window, the reflectivity of the liquid metal flexible composite film in the visible light and near infrared bands becomes low due to the overlarge thickness, and the emissivity of the liquid metal flexible composite film in the atmospheric window becomes low due to the overlarge thickness. Meanwhile, the thickness of the liquid metal layer has great influence on the reflectivity of the liquid metal flexible composite film in the visible light and near infrared bands, and the too thin liquid metal layer can cause electromagnetic waves in the visible light and near infrared bands to directly penetrate through the liquid metal film and cannot be reflected back to the high-radiation layer. Through a great deal of experimental study, the inventor finds that when the thicknesses of the high-radiation layer and the liquid metal layer are simultaneously in the preferable range, the obtained liquid metal flexible composite film has higher reflectivity to visible light and near infrared bands, has lower reflectivity to an atmospheric window, namely higher radiation rate, and further realizes more excellent passive refrigeration effect.
Further, the material of the packaging protection layer is any substrate material which can be coated by liquid metal, preferably any one of PDMS, polyethylene, PVF, PVC, glass, wood board and metal sheet. The packaging protection layer mainly protects the liquid metal layer from overflowing, and simultaneously transfers heat of the passive refrigeration space to the liquid metal layer.
Further, the surface roughness of the encapsulation protection layer is smaller than Ra 6.3. Therefore, a liquid metal layer with more uniform thickness is obtained, so that the liquid metal layer has higher reflectivity for full-band light waves.
Further, the thickness of the packaging protection layer is 100 mu m-10 mm. The high-radiation layer and the liquid metal layer which are matched with the packaging protection layer in the thickness range have the advantages that the obtained liquid metal flexible composite film has more excellent passive refrigeration effect.
The invention also provides a preparation method of the liquid metal flexible composite film, which comprises the following steps:
1) Forming a liquid metal layer on one surface of the high-radiation layer/packaging protective layer through liquid-phase magnetron sputtering or spin coating adhesion transfer printing;
2) And forming a packaging protection layer/high-radiation layer on one surface of the liquid metal layer, which is far away from the high-radiation layer/packaging protection layer.
Further, in step 2), an encapsulation protection layer/high-emissivity layer is formed on a surface of the liquid metal layer, which is far away from the high-emissivity layer/encapsulation protection layer, in a bonding or adhesive sealing manner.
Specifically, the preparation method of the liquid metal flexible composite film comprises the following steps:
1) Adding liquid metal into an acidic solution to remove a surface oxide film, wherein the acidic solution can be hydrochloric acid, sulfuric acid and the like, and the concentration is 0.1 mol/L-2 mol/L;
2) Immersing one side of a processed conventional metal target material into an acid solution to be in contact with liquid metal, wherein the conventional metal target material can be iron, nickel, copper, silver, gold and the like, immersing for 1-2 hours, and then taking out the metal target material to obtain a metal target material with a surface coated with a layer of liquid metal;
3) Placing the metal target with the surface coated with the liquid metal on a spin coater for spin coating, wherein the rotating speed of the spin coater is 50-10000 r/min, the spin coating operation time is 10-10 min, the liquid-phase magnetron sputtering metal target with the surface coated with uniform liquid metal can be obtained after the spin coating is finished, and the thickness of a liquid metal layer on the liquid-phase magnetron sputtering metal target after the spin coating is 200-500 mu m;
4) Placing the liquid-phase magnetron sputtering metal target material obtained in the step 3) in a magnetron sputtering instrument, taking the high-radiation layer (or packaging protection layer) which is left white by the protection of the outermost adhesive tape as a sputtering substrate, and obtaining the high-radiation layer (or packaging protection layer) with a certain uniform thickness liquid metal layer after the magnetron sputtering time is 10 min-24 h;
5) The liquid metal flexible composite film is obtained by removing the outermost protective white adhesive tape of the high-emissivity layer (or the packaging protective layer) with a certain uniform thickness and then bonding or adhering and sealing with the packaging protective layer (or the high-emissivity layer). The bonding is performed by a plasma treatment process for 5-60 s, the adhesion and sealing are performed by an adhesive bonding mode, and the adhesive can be instant adhesive, epoxy resin bonding, anaerobic adhesive, UV adhesive (ultraviolet light curing), hot melt adhesive, pressure sensitive adhesive, emulsion and the like.
Or the preparation method of the liquid metal flexible composite film comprises the following steps:
1) Preparing PDMS mixed solution, pouring the PDMS mixed solution into a container in which a polished silicon wafer is placed in advance, then placing the container on a heating plate at 60-85 ℃ for 2.5-0.5 h, and stripping the PMDS from the silicon wafer after PMDS is solidified to obtain the PDMS with an extremely smooth surface;
2) Placing PDMS in a plasma processor for surface treatment, directly dipping the surface-treated PDMS in liquid metal, placing the liquid metal surface on a spin coater at a rotating speed of 50-10000 r/min, and spin-coating for 10-10 min to obtain a liquid metal film with a thickness of 1-5 mu m;
3) And (3) attaching and adhering the PDMS with the surface coated with the liquid metal film to the high-radiation layer (or the packaging protective layer), so that a uniform liquid metal layer with halved thickness can be obtained on the high-radiation layer (or the packaging protective layer).
4) The liquid metal flexible composite film is obtained by removing the outermost protective white adhesive tape of the high-emissivity layer (or the packaging protective layer) with a certain uniform thickness and then bonding or adhering and sealing with the packaging protective layer (or the high-emissivity layer). The bonding is performed by a plasma treatment process for 5-60 s, the adhesion and sealing are performed by an adhesive bonding mode, and the adhesive can be instant adhesive, epoxy resin bonding, anaerobic adhesive, UV adhesive (ultraviolet light curing), hot melt adhesive, pressure sensitive adhesive, emulsion and the like.
The invention also provides application of the liquid metal flexible composite film in passive radiation refrigeration.
The invention has the beneficial effects that:
the liquid metal flexible composite film provided by the invention not only reflects most sunlight and near infrared waves back to the atmosphere, but also can exchange heat with the outer space (average temperature in the space is-270.3 ℃) through the high radiation of the atmosphere window, thereby realizing the refrigeration effect of the passive refrigeration space. The liquid metal flexible composite film provided by the invention can be applied to the surfaces of refrigeration spaces such as various buildings and the like, and has a great application space in the fields of building energy conservation and the like.
Drawings
Fig. 1 is a schematic structural diagram of a liquid metal flexible composite film provided by the invention.
Fig. 2 is a schematic illustration of the principle of radiative cooling of a liquid metal flexible composite film in accordance with the present invention.
Fig. 3 is a basic principle of passive radiation refrigeration.
The reference sign is 1, high radiation layer, 2, liquid metal layer, 3, encapsulation protective layer.
Detailed Description
The terms "upper" and "lower" are based on the orientation or positional relationship shown in the drawings, and are merely for convenience of description and to simplify the description, and do not indicate or imply that the apparatus or elements referred to must have a particular orientation, be constructed and operate in a particular orientation, and therefore should not be construed as limiting the invention. The specific techniques or conditions are not identified in the examples, and the reagents or apparatus used, which are not identified in the manufacturer, are conventional products commercially available, either in accordance with the techniques or conditions described in the literature in this field or in accordance with the specifications of the product.
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The liquid metal is prepared according to the following technical scheme, taking GaIn24.5 as an example:
(a) Weighing gallium and indium with the purity of 99.9% according to the mass ratio of 75.5:24.5, and then placing the gallium and indium into a beaker;
(b) Placing the beaker on a heating constant-temperature magnetic stirrer, setting the heating temperature to be 80 ℃ and the rotating speed to be 200r/min, and simultaneously placing a magnetic stirrer;
(c) After the indium block is dissolved, stirring the metal liquid for 10min continuously to ensure that the metal liquid is completely mixed into homogeneous phase.
Other liquid metal alloys can be prepared by changing the mass ratio of gallium to indium and the same operation.
Example 1
A liquid metal flexible composite film is composed of a sandwich structure of an upper high radiation layer 1, a middle liquid metal layer 2 and a lower packaging protection layer 3.
Wherein, the high radiation layer is PDMS with the thickness of 100 mu m;
a liquid metal layer, namely liquid metal GaIn24.5 with the thickness of 50 nm;
and encapsulating the protective layer, namely PDMS with the thickness of 200 mu m.
The preparation method of the liquid metal flexible composite film comprises the following steps:
1) Adding liquid metal GaIn24.5 into an acidic solution to remove a surface oxide film, wherein the acidic solution is hydrochloric acid solution with the concentration of 1 mol/L;
2) Immersing one side of the processed copper target into hydrochloric acid solution to be in contact with liquid metal, and taking out the copper target after immersing for 10min, so as to obtain the copper target with the surface coated with a layer of liquid metal;
3) Placing the copper target with the surface coated with the liquid metal on a spin coater for spin coating, wherein the rotating speed of the spin coater is 500r/min, the spin coating running time is 60s, the liquid-phase magnetron sputtering copper target with the surface coated with the uniform liquid metal can be obtained after the spin coating is finished, and the thickness of a liquid metal layer on the liquid-phase magnetron sputtering metal target after the spin coating is 50 mu m;
4) Placing the liquid-phase magnetron sputtering copper target material obtained in the step 3) in a magnetron sputtering instrument, taking the PDMS packaging protection layer which is protected by the outermost adhesive tape and left white as a sputtering substrate, and obtaining the packaging protection layer with a 50nm thick liquid metal layer after magnetron sputtering for 20 min;
5) And (3) removing the outermost protective white adhesive tape of the packaging protective layer, and then bonding and sealing with PDMS of the high-radiation layer, wherein the bonding is performed by adopting a plasma treatment process for 20s, so that the liquid metal flexible composite film can be obtained.
The liquid metal flexible composite film of the embodiment has the composite reflectivity of more than 85% for visible light and near infrared wavelength bands, the emissivity of more than 85% for the thermal infrared wavelength band of an atmospheric window, and the overall refrigeration power of about 50W/m 2 in a 25 ℃ outdoor environment.
Example 2
A liquid metal flexible composite film is composed of a sandwich structure of an upper high radiation layer 1, a middle liquid metal layer 2 and a lower packaging protection layer 3.
Wherein, the high radiation layer is polyethylene with the thickness of 50 mu m;
a liquid metal layer of liquid metal Ga with the thickness of 250 nm;
and packaging and protecting layer, namely polyethylene with the thickness of 100 mu m.
The preparation method of the liquid metal flexible composite film comprises the following steps:
1) Weighing 50g of polyethylene particles, adding the polyethylene particles into a stainless steel container, and then placing the container into a heating box at 120 ℃ and heating for 1 hour until the particles are completely melted;
2) After melting polyethylene particles, pouring the melted polyethylene into a polished silicon wafer, and then placing the silicon wafer on a spin coater for spin coating, wherein the rotation speed of the spin coater is 5000r/min, and the spin coating is operated for 1min, so that a polyethylene film with the thickness of 50 mu m can be obtained as an upper high-radiation layer;
3) Then after the polyethylene is completely solidified, the polyethylene film is peeled off from the silicon wafer, and the polyethylene film with the thickness of 50 mu m and even and smooth two sides can be obtained;
4) Repeating the step 2) and the step 3), wherein the rotating speed of a spin coater is 2000r/min, and spin coating is performed for 1min, so that a polyethylene film with the thickness of 100 mu m can be obtained as a lower packaging protective layer;
5) Preparing PDMS mixed solution, pouring the PDMS mixed solution into a container in which a polished silicon wafer is placed in advance, then placing the container on a heating plate at 75 ℃ for baking for about 1.5 hours, and stripping the PMDS from the silicon wafer after PMDS is solidified to obtain PDMS with even and smooth two sides;
6) Placing PDMS in a plasma processor for surface treatment, directly dipping the surface-treated PDMS in liquid metal, placing the liquid metal surface upwards on a spin coater at a rotating speed of 10000r/min, and spin-coating for 5min to obtain a liquid metal film with a thickness of 2 mu m;
7) Carrying out 3 times of adhesion and lamination on PDMS with a liquid metal film coated on the surface and a polyethylene film of a lower packaging protective layer to obtain the lower packaging protective layer with the 250nm thick liquid metal film on the surface;
8) And removing the outermost protective white-remaining adhesive tape of the lower packaging protective layer with the 250nm thick liquid metal film on the surface, and then bonding or bonding and sealing the protective white-remaining adhesive tape with the upper high-radiation layer by using polyethylene adhesive to obtain the liquid metal flexible composite film.
The liquid metal flexible composite film of the embodiment has the composite reflectivity of more than 80% in the visible light and near infrared wavelength bands and the emissivity of more than 85% in the thermal infrared band of an atmospheric window. The overall refrigeration power is about 40W/m 2 in a 25 ℃ outdoor environment.
Example 3
The liquid metal flexible composite film of this embodiment differs from embodiment 1 only in the thickness of the liquid metal layer. In this embodiment, the thickness of the liquid metal layer is 10nm, and other parameters and materials are unchanged.
The liquid metal flexible composite film of the embodiment has the composite reflectivity of more than 40% in the visible light and near infrared wavelength bands, the emissivity of more than 85% in the thermal infrared band of an atmospheric window, and the overall refrigeration power of about 1W/m 2 in a 25 ℃ outdoor environment.
Example 4
The liquid metal flexible composite film of this embodiment differs from embodiment 1 only in the thickness of the high-emissivity layer. The thickness of the high emissivity layer in this embodiment is 1mm. Other parameters and materials are unchanged.
The liquid metal flexible composite film of the embodiment has the composite reflectivity of more than 50% in the visible light and near infrared wavelength bands and the emissivity of more than 90% in the thermal infrared band of an atmospheric window. The overall cooling power is about 3W/m 2 in a 25 ℃ outdoor environment.
The above examples are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solution of the present invention should fall within the scope of protection defined by the claims of the present invention without departing from the spirit of the design of the present invention.
Claims (9)
1. The liquid metal flexible composite film is characterized by comprising the following components in sequence from top to bottom:
a high emissivity layer;
a liquid metal layer;
Packaging the protective layer;
the material of the high-radiation layer is selected from PDMS, PE, PVF, PVC, TPX or,
The material of the high-radiation layer is prepared by compounding high-radiation micro-nano particles and a transparent high polymer material, wherein the high-radiation micro-nano particles are selected from one or more of cordierite, transition metal oxide, silicon carbide, titanium dioxide, silicon dioxide, aluminum oxide and hafnium oxide, and the transparent high polymer material is selected from any one of PDMS, polyethylene, cellulose and PVF, PVC, TPX, PVA;
The particle size of the high-emissivity micro-nano particles is 1 nm-500 mu m;
The material of the liquid metal layer is one or more selected from gallium, gallium indium alloy, gallium indium tin zinc alloy and bismuth indium tin zinc alloy;
The packaging protection layer is made of any substrate material which can be coated by liquid metal, and the substrate material is any one of PDMS, polyethylene, PVF, PVC, glass, wood board and metal sheet;
the surface roughness of the packaging protection layer is smaller than Ra 6.3.
2. The liquid metal flexible composite film according to claim 1, wherein the high emissivity layer has a thickness of 1 μm to 2 mm.
3. The liquid metal flexible composite film according to any one of claims 1 or 2, wherein the high-emissivity layer has a thickness of 10 μm to 500 μm.
4. The liquid metal flexible composite film according to claim 3, wherein the thickness of the liquid metal layer is 1 nm to 500 μm.
5. The liquid metal flexible composite film according to any one of claims 1 or 4, wherein the thickness of the liquid metal layer is 50 nm to 200 μm.
6. The liquid metal flexible composite film according to claim 5, wherein the thickness of the encapsulation protection layer is 100 μm to 10 mm.
7. The method for preparing the liquid metal flexible composite film according to any one of claims 1 to 6, which is characterized by comprising the following steps:
1) Forming a liquid metal layer on one surface of the high-radiation layer/packaging protective layer through liquid-phase magnetron sputtering or spin coating adhesion transfer printing;
2) And forming a packaging protection layer/high-radiation layer on one surface of the liquid metal layer, which is far away from the high-radiation layer/packaging protection layer.
8. The method of manufacturing a liquid metal flexible composite film according to claim 7, wherein in step 2), a package protection layer/high radiation layer is formed on a side of the liquid metal layer away from the high radiation layer/package protection layer in a bonding or adhesive sealing manner.
9. Use of the liquid metal flexible composite film according to any one of claims 1 to 6 in passive radiation refrigeration.
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| TW201400289A (en) * | 2012-06-22 | 2014-01-01 | Ritedia Corp | Liquid metal composite material and method for fabricating the same |
| US10570659B2 (en) * | 2014-06-12 | 2020-02-25 | Bae Systems Plc | Method of making electro-optic window by sputtering material to fill channels of a grid |
| CN108891115A (en) * | 2018-08-24 | 2018-11-27 | 宁波瑞凌节能环保创新与产业研究院 | A kind of radiation refrigeration film of achievable passive cooling |
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| CN217671566U (en) * | 2021-05-11 | 2022-10-28 | 中国科学院理化技术研究所 | A liquid metal flexible composite film |
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