CN117799273A - Radiation cooling film with micro-nano cell structure and preparation method and application thereof - Google Patents

Radiation cooling film with micro-nano cell structure and preparation method and application thereof Download PDF

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Publication number
CN117799273A
CN117799273A CN202311802910.7A CN202311802910A CN117799273A CN 117799273 A CN117799273 A CN 117799273A CN 202311802910 A CN202311802910 A CN 202311802910A CN 117799273 A CN117799273 A CN 117799273A
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micro
nano
film
cell structure
layer
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CN117799273B (en
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翟文涛
王俞舒
王泽林
赵丹
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Sun Yat Sen University
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Sun Yat Sen University
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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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B32B5/20—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material foamed in situ
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • 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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
    • 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
    • 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
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
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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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
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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
    • 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
    • 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
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    • B32—LAYERED PRODUCTS
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    • B32B2266/00—Composition of foam
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    • B32B2266/025—Polyolefin
    • 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
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
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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
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    • B32B2266/0278—Polyurethane
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to a radiation cooling film with a micro-nano cell structure, and a preparation method and application thereof, and belongs to the technical field of radiation cooling. The radiation cooling film with the micro-nano cell structure comprises at least 2 micro-nano composite layers and at least 1 functional layer arranged on the whole surface of the micro-nano composite layers; the micro-nano pore composite layer comprises micro-pores and nano-pores, wherein the aperture of the micro-pores is 10-80 mu m, the aperture of the nano-pores is 10-100 nm, and the porosity of the micro-nano pore composite layer is 50-90%; the functional layer includes a metal nanomaterial. The radiation cooling film with the micro-nano cell structure has the characteristics of light weight, softness, long service life, excellent radiation cooling effect, good antibacterial property and the like, and can be applied to the passive cooling fields of high-temperature operators or food transportation and the like.

Description

Radiation cooling film with micro-nano cell structure and preparation method and application thereof
Technical Field
The invention belongs to the technical field of radiation cooling, and particularly relates to a radiation cooling film with a micro-nano cell structure, and a preparation method and application thereof.
Background
At present, the energy consumed by refrigeration and cooling each year accounts for 14.6% of the total global energy consumption, and the environmental problems such as greenhouse effect and the like can be generated while huge energy consumption is caused, so that huge burden is caused to the earth environment. Therefore, it is urgent to seek a more environmentally friendly and efficient cooling method. The radiation cooling technology can scatter or reflect most solar spectrum (0.3-2.5 μm), and meanwhile, utilizes the special spectral characteristics of the earth surface atmosphere, is highly transparent to infrared radiation in an atmosphere window of 8-13 μm, and exchanges own heat with cold cosmic space, thereby realizing the passive cooling function without external input. As a novel cooling technique, radiation cooling materials have various forms to realize different application scenarios.
In general, polymers possess good external radiation capability in atmospheric windows, but often have absorption effects far greater than reflection effects in the solar band, which presents a great challenge for their application in radiation cooling. To cope with this problem, the preparation of porous polymeric materials by pore-forming in a polymeric matrix is a straightforward, simple and efficient method of imparting radiation cooling functionality thereto.
However, most of the existing cooling porous membranes mainly adopt a strategy of constructing a pore structure on the surface of the membrane to form a rough surface and increase diffuse reflection so as to further improve the reflectivity of the porous membrane and realize the cooling effect. The method has limited cooling effect and can only be effective under outdoor illumination, and cannot realize all-wave band all-weather multi-environment cooling effect; meanwhile, common porous films are prepared by adopting methods such as electrostatic spinning, a template method, a phase separation method and the like, so that the cost is high, and the large-area production is difficult to realize due to the limitation of a preparation means; in addition, the porous membrane for cooling produced at present is often made of polyethylene and other materials, has poor air permeability, flexibility and the like, is widely used for cooling buildings, cooling vehicle covers and the like, and cannot be applied to human body thermal management in a wearable mode.
Therefore, it is of great importance to develop radiant cooling materials that can be used for thermal management of humans.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a radiation cooling film with a micro-nano cell structure, and a preparation method and application thereof.
The invention is realized by the following technical scheme:
the invention provides a radiation cooling film with a micro-nano cell structure, which comprises at least 2 micro-nano pore composite layers and at least 1 functional layer arranged on the whole surface of the micro-nano pore composite layers; the micro-nano pore composite layer comprises micro-pores and nano-pores, wherein the aperture of the micro-pores is 10-80 mu m, the aperture of the nano-pores is 10-100 nm, and the porosity of the micro-nano pore composite layer is 50-92%; the functional layer includes a metal nanomaterial.
The radiation cooling film comprises a micro-nano composite layer containing micro-holes and nano-holes, and the radiation cooling effect is maximally realized by constructing graded pore diameters in the porous film, wherein the nano-holes can greatly reduce the path and transmission of average scattering through a material, thereby further enhancing the scattering of shorter visible wavelength. At the same time, the coincidence of micro-and nano-holes can provide sharp refractive index transitions across the film-air boundary and produce efficient solar scattering. The invention is also provided with a functional layer on the surface of the micro-nano porous composite layer, and the functional layer can reflect sunlight, thereby improving the reflectivity of the radiation cooling film. The radiation cooling film has the characteristics of good spectral selectivity, high reflectivity and high emissivity, can obviously cool in hot outdoor environment in summer, has the reflectivity of more than or equal to 85% in the wave band of 0.3-2.5 mu m of sunlight and has the emissivity of more than or equal to 85% in the wave band of 8-13 mu m of an atmospheric window.
Preferably, the micro-nano porous composite layer is an integrated structure, and the layers of the micro-nano porous composite layer are combined through lamination or multilayer coextrusion.
The micro-nano porous composite layer is obtained by lamination or multi-layer coextrusion and foaming, molecular chain diffusion fusion occurs between layers, the layers are not needed to be bonded, no interface holes exist, and the micro-nano porous composite layer has the advantages of light weight, soft texture, water resistance, moisture permeability and antibacterial property, can be produced in a large scale, and has high processing efficiency.
Preferably, the pore structures of different layers of the micro-nano pore composite layer are different.
As a preferred embodiment of the radiation cooling film with the micro-nano cell structure, the thickness of the radiation cooling film with the micro-nano cell structure is 0.1mm-5mm.
Preferably, the thickness of the functional layer is 0.4mm-0.6mm.
As a preferred embodiment of the radiation cooling film with the micro-nano cell structure, the average pore diameter of the micro-nano pore composite layer is 0.1-60 μm.
Preferably, the micro-nano porous composite layer has an average pore size of 10 μm to 60 μm.
Preferably, the porosity of the micro-nano porous composite layer is 80% -90%.
Preferably, the functional layer is capable of reflecting sunlight.
As a preferred embodiment of the radiation cooling film with the micro-nano cell structure, the micro-nano cell composite layer respectively and independently comprises the following components in parts by weight: 50-100 parts of polymer, 0-20 parts of inorganic oxide, 0-3 parts of lubricant, 0-1 part of cross-linking agent and 0-0.5 part of antioxidant.
As a preferred embodiment of the radiation cooling film with micro-nano cell structure, the polymer comprises at least one of thermoplastic elastomer and cross-linked elastomer.
Preferably, the inorganic oxide comprises SiO 2 、TiO 2 、CrO 2 At least one of silicon nitride, aluminum phosphate, and aluminum oxide; the lubricant comprises at least one of fatty acid amide lubricant, hydrocarbon lubricant and siloxane lubricant; the cross-linking agent comprises at least one of bis-tert-butylperoxyisopropyl benzene (BIPB) and dicumyl peroxide (DCP); the antioxidant comprises at least one of amine antioxidants and p-phenylenediamine derivative antioxidants.
Preferably, the thermoplastic elastomer comprises at least one of polyurethane thermoplastic elastomer, thermoplastic polyester elastomer, nylon elastomer; the crosslinked elastomer comprises at least one of EVA crosslinked elastomer, polyolefin crosslinked elastomer, styrene crosslinked elastomer, vulcanized rubber and vulcanized rubber compound.
As a preferred embodiment of the radiation cooling film with micro-nano cell structure of the present invention, the metal nanomaterial comprises at least one of metal nanowires or metal nanoparticles; the metal nanowire comprises at least one of a silver nanowire, an aluminum nanowire and a dysprosium nanowire; the metal nanoparticles include silver nanoparticles.
The functional layer has good reflectivity and antibacterial function, and can enhance the cooling effect and antibacterial property of the radiation film.
Preferably, the diameter of the metal nanowire is5 μm-30nm, and the length is 10 μm-40 μm; the particle size of the metal nano particles is 0.05-10 mu m.
The invention further aims to provide a preparation method of the radiation cooling film with the micro-nano cell structure, which comprises the following steps of:
(1) Drying, mixing, multi-layer co-extrusion, casting, rolling and cooling the components according to the proportion to obtain an integrated thermoplastic elastomer multi-layer composite film; or mixing the components, and carrying out open mill, extrusion casting, film lamination and heating vulcanization to obtain an integrated crosslinked elastomer multilayer composite film;
(2) Immersing the thermoplastic elastomer multilayer composite film or the crosslinked elastomer multilayer composite film obtained in the step (1) in supercritical fluid, releasing pressure to normal pressure after saturation, and then heating and foaming to obtain a multilayer micro-nano porous composite layer;
(3) And (3) carrying out hot pressing or cooling shaping on the multi-layer micro-nano hole composite layer obtained in the step (2), and then coating a metal nano material on the surface of the micro-nano hole composite layer to form a functional layer, thereby obtaining the radiation cooling film with the micro-nano cell structure.
According to the invention, all components are subjected to fusion lamination, supercritical fluid foaming, shaping and surface coating to prepare the radiation cooling film with the micro-nano cell structure, and reflection and infrared wave emission of the composite film to sunlight in different wave bands are realized by controlling the lamination structure, the cell structure, the functional filler types, the functional filler content and the dispersion state, so that the microporous elastomer radiation cooling composite film with good all-band solar radiation cooling effect, light weight and softness is obtained. In the step (2), the composite membrane is nucleated to form micropores during pressure relief, and is nucleated again to form nanopores during the heating foaming process, so as to obtain the micro-nano porous composite layer containing nanopores and micropores.
In step (1), if the component contains an inorganic oxide, it is preferable to prepare a polymer/inorganic oxide nano-powder master batch by melt-extruding the inorganic oxide and the polymer.
Preferably, in the step (3), the functional layer, the metal nanomaterial accounts for 1wt% to 15wt% of the functional layer.
In the step (1), the integrated crosslinked elastomer multilayer composite film is prepared by adopting film preparation, film lamination and hot press vulcanization, so that components in layers, component collocation between layers and multilayer structure design are easier to control. The radiation cooling film with the integrated micro-nano cell structure, which has compact and orderly distributed structure, can be prepared by optimizing the components of each layer of the film, the preparation temperature and the vulcanization temperature and controlling the crosslinking process of the elastomer.
As a preferred embodiment of the method for preparing a radiation cooling film with a micro-nano cell structure, in the step (1), the high mixing temperature is 90 ℃ to 130 ℃, and the heating and vulcanizing temperature is 160 ℃ to 190 ℃.
Sunlight includes ultraviolet rays, visible rays, infrared rays, etc., which are light waves having a wavelength of 0.3 to 2.5 mm. When a light wave enters a medium, it may reflect, refract, and scatter at the interface as it propagates through the non-uniform medium. Microcellular foaming forms a large number of closed cells in a transparent or translucent polymer, and microcellular foamed materials appear white and exhibit increased whiteness with decreasing cell size and increasing porosity. When the size of the bubble hole is equal to the wavelength of the light wave, the bubble hole of the microporous polymer can cause the sunlight to generate a remarkable scattering phenomenon, and the white microporous polymer presents a diffuse reflection phenomenon to the sunlight. The invention can lead the microporous polymer to show good reflectivity and emissivity by limiting the size and porosity of the cells of the microporous polymer.
Preferably, in the step (1), each layer of the multi-layer composite film has a different hardness or modulus and has a different foaming behavior at the same temperature.
The expansion behaviour of supercritical fluid micro-foaming processes of elastomers is affected by hardness or modulus, in general, the foaming temperature of high hardness or modulus plastic elastomers is higher, while the foaming temperature of low hardness or modulus elastomers is lower. In order to realize the micro-nano composite cell structure and different cell sizes of different layers so as to realize a multi-angle propagation path, the multi-diffuse reflection is realized, the reflectivity is improved, the passive radiation cooling function is endowed to the micro-nano composite cell structure, and the resin of each layer has similar types but different hardness or modulus and different foaming behaviors at the same temperature.
As the preparation method of the radiation cooling film with the micro-nano cell structure, the invention is preferableIn an embodiment, in the step (2), the supercritical fluid is CO 2 Fluid, N 2 At least one of the fluids; the solubility of the supercritical fluid in the multilayer composite film is 0.8wt% to 15wt%; the temperature of the heating foaming is 100-180 ℃ and the time is 1-3 min.
In the step (3), the microporous elastomer composite film can be subjected to thickness change to a certain extent through hot pressing or cooling, so that the radiation cooling film with controllable thickness size is obtained.
Preferably, in the step (3), the hot pressing temperature is 65 ℃ to 80 ℃, and the cooling temperature is 4 ℃ to 15 ℃.
The application performance of the micro-nano porous composite layer can be further improved through surface coating.
Preferably, in the step (3), a functional layer is coated on the surface of the microporous elastomer composite membrane through glue; the glue comprises at least one of anionic aqueous polyurethane glue, cationic aqueous polyurethane glue and nonionic aqueous polyurethane glue.
Preferably, in the step (3), glue coating is performed by padding.
It is still another object of the present invention to provide an application of the radiation cooling film with micro-nano cell structure or the radiation cooling film with micro-nano cell structure prepared by the preparation method thereof in the field of passive cooling.
The radiation cooling film with the micro-nano cell structure is soft and light in texture, and can be applied to various outdoor passive cooling fields in summer such as buildings, automobiles, clothes, tents, food transportation and the like.
According to the radiation cooling film with the micro-nano cell structure, the penetration of heat radiation in different wave bands can be limited under the condition that the micro-holes and the nano-holes exist at the same time, and the radiation cooling film is longer than the wave band limited by a single pore structure; the composite hole structure can change the propagation path of radiation, so that the radiation is difficult to penetrate through the composite film, therefore, the micro-nano composite hole structure has higher cooling effect and great application potential in the fields of passive cooling such as human body heat management, food transportation and the like.
The invention has the following beneficial effects:
the invention prepares the light-weight and soft radiation cooling film with a micro-nano cell structure by fusing and compounding a plurality of elastic bodies, micro-pore foaming and coating a functional layer on the surface to construct a reflecting layer, and provides the micro-pore elastic body composite film with high solar reflectance, high reflectance and good cooling effect and integrated structure by selecting and collocating the elastic body resin/layer, controlling the cell size and porosity of the elastic body film in the layer and limiting the type and content of the functional coating metal nano wire. The reflectivity of the radiation cooling film to sunlight with the wavelength of 0.3-2.5mm is more than or equal to 85%, preferably more than or equal to 92%, the emissivity of the radiation cooling film in an atmospheric window of 8-13mm is more than or equal to 85%, preferably more than or equal to 92%, and the radiation cooling film can cool to more than 10 ℃ in the direct solar irradiation environment (the environment temperature is 38-39 ℃ and the contrast environment temperature is 72 ℃) in Guangzhou summer, and has excellent radiation cooling effect.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples. It will be appreciated by persons skilled in the art that the specific embodiments described herein are for purposes of illustration only and are not intended to be limiting.
The test methods used in the examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are all commercially available.
The materials used in the examples and comparative examples are as follows:
thermoplastic polyurethane elastomer: TPU, HF-1385AX, huafeng;
thermoplastic polyester elastomer: TPEE,1028D, basf, germany;
EVA elastomer: EVA,360, dupont usa;
polybutylece ester elastomer: TPBA, duPont USA;
butanediol oxalate elastomer: PBAT, dow chemical company, usa;
polypropylene: PP, dupont usa;
polyethylene: PE, duPont U.S.;
functional layer: metal nanomaterial: silver nanowires, average diameter 20nm, length 30 μm, commercially available;
al NW has an average diameter of 18nm and a length of 25 μm, and is commercially available;
td NW, average diameter 28nm, length 30 μm, commercially available;
cu NW, average diameter 24nm, length 35 μm, commercially available;
crosslinking agent: BIPB, commercially available;
an antioxidant: antioxidant 1010, basf.
Examples and comparative examples
The composition and parts by weight of each layer of the radiation-cooled films having a micro-nano cell structure of examples 1 to 6 and comparative examples 1 to 5, the conditions at the time of preparation, and the performance parameters are shown in table 1.
The preparation method of the radiation cooling film with the micro-nano cell structure in the examples 1-6 and the comparative examples 1-4 comprises the following steps:
(1) Drying and mixing the components in each layer according to the proportion in the table 1, performing coextrusion double-screw multilayer coextrusion, casting, rolling and cooling to obtain an integrated thermoplastic elastomer multilayer composite film, or respectively mixing the components in the micro-nano porous composite layer according to the proportion, and performing open mill, extrusion casting, film lamination and heating vulcanization to obtain an integrated crosslinked elastomer multilayer composite film; wherein the temperature of each temperature zone of the extruder is 110 ℃, 180 ℃, 190 ℃, 185 ℃ and 180 ℃ in sequence; or mixing each layer of components at 110 ℃ according to the proportion in table 1, and carrying out open mill, twin-screw extrusion casting, film lamination and heating vulcanization to obtain an integrated crosslinked elastomer multilayer composite film, wherein the heating vulcanization temperature is 175 ℃;
(2) Compounding the thermoplastic elastomer obtained in the step (1) into a plurality of layersThe membrane or the cross-linked elastomer multilayer composite membrane is placed into supercritical fluid CO 2 The medium dipping, the solubility is shown in table 1, the room temperature is saturated, the pressure is released to normal pressure after the saturation is achieved, and then the temperature is raised and the foaming is carried out for 2 minutes at 150 ℃ to obtain a multi-layer micro-nano porous composite layer;
(3) And (3) carrying out hot press shaping on the multi-layer micro-nano porous composite layer obtained in the step (2) at 75 ℃, then adopting a padding method, and coating a metal nano material on the surface of the micro-nano porous composite layer by glue according to the proportion shown in the table 1 to form a functional layer, thereby obtaining the radiation cooling film with the micro-nano cellular structure.
The preparation method of the comparative example 5 is different from examples 1-6 in that in the step (2), after the saturation is achieved and the pressure is released to normal pressure, the temperature rising foaming is not performed; the rest of the preparation method is the same as other examples and comparative examples.
The average pore diameter, porosity, solar reflectance and emissivity of the radiation cooling films with micro-nano cell structures obtained in the examples and the comparative examples are tested, and the test results are shown in table 1, and the test method is as follows:
porosity: the water drainage method is adopted for testing, and the standard is HG/T2872-2009.
Average pore diameter: and (3) adopting SEM to test the section of the micro-nano porous composite layer, and counting the average value of the cell sizes of more than 100.
Reflectivity: the standard is JG/T235-2014 according to the method of measuring the ultraviolet-visible spectrophotometer ball integration of LAMBDA 950.
Emissivity: the standard iS JG/T235-2014 according to the measurement of the ball integral test method of the Nicolet iS50 Fourier transform infrared spectrometer.
The porosity and average pore diameter are tested by the multi-layer micro-nano porous composite layer without the functional layer after hot pressing or cooling shaping in the step (3).
Table 1 (weight portions)
From the data in table 1, the radiation cooling film of the present invention has excellent radiation cooling effect. Compared with the example, in comparative example 1, since copper nanowires are used as the functional layer material and since the melting point of PE is lower than that of TPU, the average pore diameter of the radiation cooling film is increased at the same foaming temperature, resulting in deterioration of the cooling effect of the radiation cooling film; in comparative examples 2 and 3, no functional layer was provided, resulting in a decrease in radiation cooling effect; in comparative example 4, only one layer of TPU is used as the micro-nano composite layer, the average pore diameter is increased, and the radiation cooling effect is poor; in comparative example 5, step (2) did not foam by reheating, and the radiation cooling film did not contain nanopores, resulting in poor cooling effect of the radiation cooling film.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims (10)

1. The radiation cooling film with the micro-nano cell structure is characterized by comprising at least 2 micro-nano pore composite layers and at least 1 functional layer arranged on the whole surface of the micro-nano pore composite layers; the micro-nano pore composite layer comprises micro-pores and nano-pores, wherein the aperture of the micro-pores is 10-80 mu m, the aperture of the nano-pores is 10-100 nm, and the porosity of the micro-nano pore composite layer is 50-92%; the functional layer includes a metal nanomaterial.
2. The radiant cooling film having a micro-nano cell structure of claim 1, wherein the thickness of the radiant cooling film having a micro-nano cell structure is 0.1mm to 5mm.
3. The radiant cooling film having a micro-nano cell structure according to claim 1, wherein the micro-nano porous composite layer has an average pore size of 0.1 μm to 60 μm.
4. The radiant cooling film having a micro-nano cell structure of claim 1, wherein the micro-nano cell composite layer each independently comprises the following components in parts by weight: 50-100 parts of polymer, 0-20 parts of inorganic oxide, 0-3 parts of lubricant, 0-1 part of cross-linking agent and 0-0.5 part of antioxidant.
5. The radiant cooling film having a micro-nano cell structure according to claim 4, wherein the polymer comprises at least one of a thermoplastic elastomer, a cross-linked elastomer.
6. The radiant cooling film having a micro-nano cell structure of claim 1, wherein the metallic nanomaterial comprises at least one of a metallic nanowire or a metallic nanoparticle; the metal nanowire comprises at least one of a silver nanowire, an aluminum nanowire and a dysprosium nanowire; the metal nanoparticles include silver nanoparticles.
7. A method of preparing a radiant cooling film having a micro-nano cell structure as set forth in any one of claims 1-6, comprising the steps of:
(1) Respectively drying, mixing, multi-layer co-extrusion, tape casting, rolling and cooling all the layers in the micro-nano porous composite layer according to the proportion to obtain an integrated thermoplastic elastomer multi-layer composite film; or mixing the components in the micro-nano porous composite layer according to the proportion, and carrying out open mill, extrusion casting, film lamination and heating vulcanization to obtain an integrated crosslinked elastomer multilayer composite film;
(2) Immersing the thermoplastic elastomer multilayer composite film or the crosslinked elastomer multilayer composite film obtained in the step (1) in supercritical fluid, releasing pressure to normal pressure after saturation, and then heating and foaming to obtain a multilayer micro-nano porous composite layer;
(3) And (3) carrying out hot pressing or cooling shaping on the multi-layer micro-nano hole composite layer obtained in the step (2), and then coating a metal nano material on the surface of the micro-nano hole composite layer to form a functional layer, thereby obtaining the radiation cooling film with the micro-nano cell structure.
8. The method for preparing a radiation-cooled film having a micro-nano cell structure according to claim 7, wherein in the step (1), the high mixing temperature is 90 ℃ to 130 ℃, and the heat vulcanization temperature is 160 ℃ to 190 ℃.
9. The method for preparing a radiation-cooled film having a micro-nano cell structure according to claim 7, wherein in the step (2), the supercritical fluid is CO 2 Fluid, N 2 At least one of the fluids; the solubility of the supercritical fluid in the multilayer composite film is 0.8wt% to 15wt%; the temperature of the heating foaming is 100-180 ℃ and the time is 1-3 min.
10. Use of the radiation-based cooling film having a micro-nano cell structure according to any one of claims 1 to 6 or the radiation-based cooling film having a micro-nano cell structure according to any one of claims 7 to 9 in the field of passive cooling.
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Publication number Priority date Publication date Assignee Title
CN110016213A (en) * 2019-03-21 2019-07-16 北京工商大学 A kind of polylactic acid foam material and preparation method thereof with micro-nano compound abscess
WO2020237813A1 (en) * 2019-05-31 2020-12-03 宁波瑞凌新能源科技有限公司 Composite radiant refrigeration film and application thereof, and composite radiant refrigeration film material
US10927244B1 (en) * 2019-08-21 2021-02-23 Shaanxi University Of Science & Technology Superhydrophobic and self-cleaning radiative cooling film and preparation method thereof
CN115260740A (en) * 2022-08-26 2022-11-01 电子科技大学长三角研究院(湖州) High-mechanical-property radiation refrigeration film with composite aperture, preparation method and application thereof
CN115610060A (en) * 2022-09-05 2023-01-17 华南理工大学 Radiation cooling film based on micro-pore and inorganic particle synergistic reflection and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN110016213A (en) * 2019-03-21 2019-07-16 北京工商大学 A kind of polylactic acid foam material and preparation method thereof with micro-nano compound abscess
WO2020237813A1 (en) * 2019-05-31 2020-12-03 宁波瑞凌新能源科技有限公司 Composite radiant refrigeration film and application thereof, and composite radiant refrigeration film material
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