CN117341310A - Dual-band refrigeration film for plant growth and preparation method thereof - Google Patents
Dual-band refrigeration film for plant growth and preparation method thereof Download PDFInfo
- Publication number
- CN117341310A CN117341310A CN202210739348.7A CN202210739348A CN117341310A CN 117341310 A CN117341310 A CN 117341310A CN 202210739348 A CN202210739348 A CN 202210739348A CN 117341310 A CN117341310 A CN 117341310A
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- CN
- China
- Prior art keywords
- film
- layer
- plant growth
- dual
- thickness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000008635 plant growth Effects 0.000 title claims abstract description 55
- 238000005057 refrigeration Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000010410 layer Substances 0.000 claims abstract description 251
- 239000000758 substrate Substances 0.000 claims abstract description 40
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- 229920006254 polymer film Polymers 0.000 claims abstract description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 238000002834 transmittance Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
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- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004568 cement Substances 0.000 claims description 6
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 5
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- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
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- 238000005566 electron beam evaporation Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 3
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
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- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims 2
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- 241000196324 Embryophyta Species 0.000 abstract description 23
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- 229910010413 TiO 2 Inorganic materials 0.000 description 17
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 3
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B32—LAYERED PRODUCTS
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
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- 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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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
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- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3639—Multilayers containing at least two functional metal 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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
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- 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
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
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- 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
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
- C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
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- 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
- B32B2307/40—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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- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
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- C03C2217/00—Coatings on glass
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- C03C2217/00—Coatings on glass
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Abstract
The invention provides a dual-band refrigeration film for plant growth and a preparation method thereof. The refrigeration film comprises a packaging layer, a coating layer and a substrate layer which are sequentially arranged from outside to inside; the packaging layer is a high-molecular polymer film layer with high emission characteristic; the coating layer comprises at least 4 layers of film layers with the thickness of 1-300nm which are sequentially laminated, the film layers comprise metal film layers, oxide film layers and fluoride film layers, and the metal film layers cannot be arranged on the outermost layers; the film layers are alternately arranged according to the refractive index. The refrigeration film can obtain maximum refrigeration power on the premise of meeting the normal growth of plants, reduces the temperature of plant leaves, reduces the transpiration rate of plants, and solves the problems of overheat and water shortage of plants in summer in traditional agriculture.
Description
Technical Field
The invention relates to the technical field of refrigeration films, in particular to a dual-band refrigeration film for plant growth and a preparation method thereof.
Background
With the increasing population of the world, the rapid industrialized development and the increasing increase of towns, the effective planting area of crops and forestry is rapidly reduced, and further the problems of food shortage and desertification are increasingly serious. In order to solve the problem of food shortage, besides increasing the acre yield, finding new land available for planting is a more effective and convenient way, so that the development and utilization of land in some extreme areas become vital. Meanwhile, as global warming is increasingly serious, the global average air temperature is increased year by year and high-temperature weather frequently occurs, so that summer planting is particularly difficult. Summer planting obviously aggravates the consumption of water resources, which runs counter to the idea of saving water. In order to reduce the consumption of water resources, some refrigerating systems such as air conditioners and the like can be used for cooling; however, the refrigerating system represented by the air conditioner has high energy consumption and large economic loss, and the generated greenhouse gas can be further discharged to influence the growth of plants, so that the method is not acceptable by the traditional planting industry. Therefore, the passive solar spectrum regulation and control energy-consumption-free film which can provide a proper temperature and humidity environment for plant growth in summer is researched, the use of an active refrigeration device and the consumption of a large amount of water resources can be effectively reduced, the economic cost is reduced, and the environment-friendly concept is met.
For any object on the earth's surface, the energy transfer calculation that it receives during the day is: p (P) net ＝P rad -P atm -P solar -P non-radiative Wherein P is net Refers to the refrigeration power obtained by an object, P rad Refers to the radiation power of an object to the environment, P atm Refers to the radiation power of the environment to an object, P solar Refers to the incident power of sunlight, P non-radiative Refers to convective conduction power. From the above equation, in order to obtain as high a cooling power as possible, it is necessary to apply the heat energy to P atm 、P solar And P non-radiative Effective regulation and control are carried out, wherein P solar The solar spectrum is effectively regulated and controlled to reduce the incident energy of the solar spectrum, so that the solar spectrum has great implementation significance.
At present, effective regulation and control of solar spectrum are performed to achieve a refrigeration effect, and scientists have done a great deal of work: the first category is the development of radiation refrigeration materials, and the 2014 foreign research group passes through SiO 2 /HfO 2 The design of the multi-layer film photonic crystal is realized in a solar wave band (the sunlight reaching the ground surface ranges from 0.2 to 2.5 μm) reaches 97%, and simultaneously, heat is highly emitted in the form of electromagnetic wave of middle infrared (8-13 μm), thus realizing the cooling effect of 4.9 ℃ and 40W/m in daytime for the first time 2 Is used for the cooling power of the air conditioner; later, some other researchers realize the polymer-based daytime radiation refrigeration film through different methods, the preparation cost is rapidly reduced, and the process is simple, thereby being beneficial to large-scale preparation and application. The second type is a transparent refrigeration film, which is widely used in the automobile industry, and compared with a radiation refrigeration material, the film transmits visible light wave band (0.4-0.7 μm) and reflects near infrared light (0.7-2.5 μm) generating heat effect as far as possible, so that the energy injection is reduced as far as possible under the premise of not affecting the normal vision of people, and the refrigeration purpose is achieved.
Although the two modes are effective in regulating sunlight, the photosynthesis of plants is generally based on 0.6-0.7 mu m red light and 0.4-0.5 mu m blue-green light (0.5-0.6 mu m light plants do not need to generate heat), so that the required materials cannot totally reflect sunlight like the traditional radiation refrigerating materials and do not need to fully transmit the sunlight in the wide wave band of 0.4-0.7 mu m like a transparent refrigerating film, and the two existing refrigerating materials have limitations when applied to the field of plant cultivation. Therefore, the light with the wave bands of 0.4-0.5 mu m and 0.6-0.7 mu m required by photosynthesis of plants is only allowed to pass, and the light with other wave bands is reflected; meanwhile, the refrigerating material which carries out high emission on heat in the form of electromagnetic waves of middle infrared rays, namely, the maximum refrigerating power is obtained on the premise of meeting the normal growth of plants, is a problem to be solved urgently.
In view of the foregoing, there is a need for an improved dual-band refrigeration film for plant growth and method of making the same that addresses the above-described problems.
Disclosure of Invention
The invention aims to provide a dual-band refrigeration film for plant growth and a preparation method thereof, wherein the dual-band refrigeration film has more than 70% of transmittance in the wave bands of 0.4-0.5 mu m and 0.6-0.7 mu m and has more than 70% of reflectance in the wave bands of 0.5-0.6 mu m and 0.7-2.5 mu m by arranging oxide film layers and fluoride film layers which are alternately laminated with each other in refractive index and controlling the thickness and the position relation of different film layers; and a high-molecular polymer film layer with high emission characteristic is laminated on the film coating layer, so that heat can be transferred to a cosmic space in an electromagnetic wave mode of medium infrared (8-13 mu m) to realize the transmission of more than 90%, and the cooling of an object is realized.
In order to achieve the aim of the invention, the invention provides a dual-band refrigeration film for plant growth, which comprises a packaging layer, a coating layer and a substrate layer which are sequentially arranged from outside to inside; the packaging layer is a high-molecular polymer film layer with high emission characteristic; the film coating layer comprises at least 4 film layers with the thickness of 1-300nm, wherein the film layers comprise a metal film layer, an oxide film layer and a fluoride film layer, and the metal film layer cannot be arranged on the outermost layer; the film layers are alternately arranged according to the refractive index; when sunlight is incident, the light transmission of the wave bands of 0.4-0.5 mu m and 0.6-0.7 mu m and the reflection of the light of other wave bands can be realized, and meanwhile, the heat can realize high emission in the form of electromagnetic waves of middle infrared.
As a further improvement of the present invention, the coating layer includes 4-12 laminated film layers.
As a further improvement of the invention, the thickness of the metal film layer is 1-50nm; the thickness of the oxide film layer is 10-300nm, and the thickness of the fluoride film layer is 10-200nm.
As a further improvement of the invention, the metal film layer comprises one of aluminum, silver and gold; the oxide film layer comprises one of titanium dioxide, silicon dioxide, hafnium dioxide and zinc oxide; the fluoride film layer comprises one of magnesium difluoride, calcium difluoride, barium difluoride and aluminum trifluoride.
As a further improvement of the present invention, the high molecular polymer film layer includes one of PDMS, PET, PEO; the thickness is 10-500 μm.
As a further improvement of the invention, a glue layer is arranged between the packaging layer and the coating layer, the glue layer is high-transparency OCA optical glue, and the thickness is 1-30 mu m.
As a further improvement of the invention, the substrate layer is a high molecular polymer film or inorganic glass, and the thickness is 0.1-1.5mm; the high polymer film is one of PET, PMMA, PDMS, and the inorganic glass is silica glass.
As a further improvement of the present invention, the dual-band refrigerating film for plant growth has a transmittance of 70% for light of the 0.4-0.5 μm and 0.6-0.7 μm bands, a reflectance of more than 70% for light of the 0.5-0.6 μm and 0.7-2.5 μm bands, and heat achieves an emissivity of 90% in the form of electromagnetic waves of mid-infrared.
In order to achieve the above object, the present invention further provides a method for preparing the above dual-band refrigeration film for plant growth, comprising the steps of:
s1, laminating corresponding film layers on a substrate layer according to a preset sequence by utilizing a film coating technology, and forming a film coating layer on the substrate layer;
s2, coating optical cement on the coating layer obtained in the step S1, and forming a cement layer on the coating layer after heat treatment;
s3, compounding a packaging layer on the adhesive layer obtained in the step S2 to obtain a dual-band refrigerating film for plant growth;
the film coating layer comprises at least 4 film layers with the thickness of 1-300nm, wherein the film layers comprise a metal film layer, an oxide film layer and a fluoride film layer, and the metal film layer cannot be arranged on the outermost layer; the film layers are alternately arranged according to the refractive index; the packaging layer is a high-molecular polymer film layer with high emission characteristic.
As a further improvement of the present invention, in step S1, the plating technique includes one or more of electron beam evaporation, resistive thermal evaporation, magnetron sputtering plating.
The beneficial effects of the invention are as follows:
(1) According to the invention, the metal film layer, the oxide film layer and the fluoride film layer are arranged on the substrate layer, the film layers are alternately arranged according to the refractive index, meanwhile, the thickness and the position relation of different film layers are controlled, the thickness and the refractive index difference of each film layer are utilized to realize the fine regulation and control of each wave band of the solar spectrum, sunlight is reflected and refracted between different film layers, different degrees of interference occur between the reflected and refracted light rays, the light transmission of light in wave bands of 0.4-0.5 mu m and 0.6-0.7 mu m and the light reflection of other wave bands are finally realized through the superposition or weakening of the light rays, only the light required by plants is transmitted, and the light reflection of other wave bands is realized, so that the damage of redundant light rays to the plants is avoided, and the heat generated by other light rays is reduced. Meanwhile, the invention also stacks a high polymer film layer with high emission characteristic on the film coating layer, firstly, the high polymer with a special structure is utilized to absorb heat and convert the heat into an electromagnetic wave form of middle infrared rays (8-13 mu m) in the energy level transition process, and then the electromagnetic wave form is transferred to a cosmic space to realize the cooling of an object; and then, the selective transmission and reflection of sunlight are further realized by utilizing the synergistic effect of the packaging layer and the coating layer. The refrigerating film can reduce total energy incidence only through light required by plant growth under normal incidence conditions of sunlight, can obtain maximum refrigerating power on the premise of meeting normal growth of plants, reduces the temperature of plant leaves, reduces the transpiration rate of plants, solves the problems of overheat and water shortage of plants in summer in traditional agriculture, can be applied to products such as plant greenhouses or greenhouses, and can effectively reduce the temperature of a cavity and improve the survival rate and yield of the plants while not influencing the normal growth of the plants.
(2) The refrigerating film prepared by the invention has more than 70% transmittance in the wave bands of 0.4-0.5 mu m and 0.6-0.7 mu m, and has more than 70% reflectivity in the wave bands of 0.5-0.6 mu m and 0.7-2.5 mu m; at the same time, the refrigerating film can transfer heat to the space in the form of electromagnetic wave of middle infrared (8-13 μm) with emissivity of more than 90%, 900W/m in noon 2 Compared with the traditional transparent greenhouse and commercial transparent refrigeration film, the temperature of the solar energy irradiation is reduced by 5-10 ℃, the object is cooled, and the solar energy irradiation has excellent minimum effective energy transmission and highest energy output, so that the excellent radiation refrigeration effect is realized. The refrigeration film greatly reduces the consumption of water resources, and saves nearly 20% compared with the traditional greenhouse film; in addition, the electric quantity consumption of the greenhouse in summer is reduced, and the crop yield is increased. The preparation of the inventionThe refrigerating film is an environment-friendly passive refrigerating device which does not consume energy and has the highest refrigerating power.
Drawings
Fig. 1 is a schematic structural view of a dual-band refrigerating film for plant growth according to the present invention.
FIG. 2 is a graph showing spectral transmittance of solar light in a wavelength band of the substrate layer according to example 1 of the present invention.
Fig. 3 is a graph showing spectral transmittance of solar light wave bands of the dual-band refrigerating film for plant growth prepared in example 1 of the present invention.
Fig. 4 is a representation of the mid-infrared band spectral emissivity of the dual-band refrigeration film for plant growth prepared in example 1 of the present invention.
FIG. 5 is a schematic diagram of an apparatus for testing the cooling performance of a material.
FIG. 6 is a graph of temperature profiles for different film materials.
Fig. 7 is a graph showing spectral transmittance of solar light wave bands of a dual-band refrigerating film for plant growth prepared in example 2 of the present invention.
Fig. 8 is a graph showing spectral transmittance of solar light wave bands of the dual-band refrigerating film for plant growth prepared in comparative example 1 of the present invention.
Fig. 9 is a graph showing spectral transmittance of solar light wave bands of the dual-band refrigerating film for plant growth prepared in comparative example 2 of the present invention.
Reference numerals
1-an encapsulation layer; 2-an adhesive layer; 3-coating film layer; 4-a substrate layer; 5-a film to be measured; 6-thermocouple; 7-plants; 8-foam.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Referring to fig. 1, the invention provides a dual-band refrigeration film for plant growth, which comprises a packaging layer 1, a coating layer 3 and a substrate layer 4 which are sequentially arranged from outside to inside. The packaging layer 1 is a high-molecular polymer film layer with high emission characteristic; the coating layer 3 comprises at least 4 layers of film layers with the thickness of 1-300nm which are sequentially laminated, specifically, the film layers comprise a metal film layer, an oxide film layer and a fluoride film layer, and the metal film layer cannot be arranged on the outermost layer; the film layers are alternately arranged according to the refractive index, and the refractive index difference between the adjacent film layers is more than 0.5. When sunlight is incident, the solar energy packaging film can realize the transmission of light with wave bands of 0.4-0.5 mu m and 0.6-0.7 mu m and the reflection of light with other wave bands under the synergistic effect of the packaging layer 1 and the film coating layer 3, and simultaneously, the heat can realize high emission in the form of electromagnetic waves of middle infrared.
The packaging layer 1 meets the requirements that the sunlight wave band has high permeability and the mid-infrared light region has high emissivity. Preferably, the high molecular polymer film layer comprises one of PDMS (polydimethylsiloxane), PET (polyethylene terephthalate) and PEO (polyethylene oxide) with a thickness of 10-500 μm. The high polymers with high emission characteristics absorb heat and convert the heat into electromagnetic wave forms of medium infrared rays (8-13 mu m) in the energy level transition process, and then the electromagnetic wave forms are transferred to a cosmic space to realize the cooling of objects.
Preferably, the coating layer 3 comprises 4-12 laminated film layers, wherein the metal film layer comprises one of aluminum, silver and gold, and has a thickness of 1-50nm; the oxide film layer comprises one of titanium dioxide, silicon dioxide, hafnium dioxide and zinc oxide, the thickness is 10-300nm, and the fluoride film layer comprises one of magnesium difluoride, calcium difluoride, barium difluoride and aluminum trifluoride, and the thickness is 10-200nm. The film layers are alternately arranged according to the refractive index, the high refractive index film layers and the low refractive index film layers are alternately arranged, and the metal film layers are intercalated in the film layers or positioned at the bottom layer, but cannot be positioned at the top layer, mainly because the metal film layers have higher reflectivity and can be easily oxidized to cause the optical property change if positioned at the top layer, so that the effective transmission of sunlight cannot be realized. When sunlight irradiates the coating layer 3 through the packaging layer 1, light rays are reflected and refracted between different film layers according to the thickness and refractive index difference of each film layer, interference of different degrees occurs between the reflected and refracted light rays, and finally, the light rays are overlapped or weakened to finally realize the transmission of light in the wave bands of 0.4-0.5 mu m and 0.6-0.7 mu m and the reflection of light in other wave bands. In this way, only the light required by the plants is transmitted, and the light in other wave bands is reflected, so that on one hand, the damage of redundant light to the plants is avoided, and on the other hand, the heat generated by other light is reduced.
In some embodiments, a glue layer 2 is disposed between the encapsulation layer 1 and the coating layer 3, where the glue layer 2 is a high-transparency OCA optical glue. The OCA optical adhesive is a special adhesive, has the advantages of no color, transparency, light transmittance of more than 90 percent and good cementing strength, and can be cured at room temperature or medium temperature. By the arrangement, light passes through the adhesive layer 2 and is hardly attenuated, so that the performance of the dual-band refrigeration film for plant growth prepared by the invention is not affected.
The substrate layer 4 may be a hard substrate such as quartz glass, or a flexible substrate, and mainly has a supporting function, so that it needs to satisfy a certain mechanical strength, but more importantly, needs to satisfy an optical characteristic of high transmittance in the solar spectrum, so that the effective light injection is not affected. The thickness of the substrate layer 4 is 0.1-1.5mm; the hard substrate is inorganic glass, preferably silica glass; the flexible substrate is a high molecular polymer film, preferably one of polyethylene terephthalate (PET), polymethyl methacrylate (PMMA) and Polydimethylsiloxane (PDMS).
The invention also provides a preparation method of the dual-band refrigeration film for plant growth, which comprises the following steps:
s1, preparation of a coating layer
Selecting a proper substrate layer 4, and laminating corresponding film layers on the substrate 4 according to a preset sequence by utilizing a film coating technology, namely firstly forming a first film layer on the substrate layer 4 by utilizing the film coating technology, and then forming a second film layer on the formed first film layer by utilizing the film coating technology; and continuously repeating until the required last film layer is plated to form a planar photonic crystal, and finally forming a coating layer 3 on the substrate layer 4.
The coating technology comprises one or more methods of electron beam evaporation, resistance type thermal evaporation and magnetron sputtering coating.
The coating layer 3 comprises at least 4 layers with the thickness of 1-300nm which are sequentially laminated, wherein the layers comprise a metal film layer, an oxide film layer and a fluoride film layer, and the metal film layer cannot be arranged on the outermost layer; the film layers are alternately arranged according to the refractive index, and the refractive index difference of the adjacent film layers is more than 0.5; different high refractive index film materials may be substituted for each other, and different low refractive index film materials may be substituted for each other.
In the whole preparation process, the cleaning of the surface of the substrate layer 4 is critical, the cleaning is strictly performed according to the traditional three-step method, the ultrasonic treatment is performed for 10min through acetone soaking, the ultrasonic treatment is replaced for 10min through ethanol soaking, finally the ultrasonic treatment is performed for 10min through water soaking, and oil stains and impurities on the surface of the substrate layer 4 are removed as much as possible, so that a clean and flat surface is obtained. Next, the substrate layer 4 is fixed at the center of the substrate by using the copper adhesive, so that the bonding degree of the substrate layer 4 and the substrate is improved to increase the thermal conductivity, and meanwhile, the non-uniformity of the sample caused by the curling of the substrate layer 4 is avoided. And then carrying out normal coating operation, replacing source materials, respectively placing the used coating materials into different crucibles, placing samples, closing a cabin door and vacuumizing. When the vacuum degree reaches 5x10 -4 Setting the rotation speed of the substrate to be 15r/min below Pa, starting an electron gun and an electron gun baffle plate to perform pre-sputtering, observing through a crystal oscillator plate, adjusting current to control the coating speed, stabilizing the coating speed indication at 5A/s, and starting the substrate baffle plate to perform coating. In the film plating process, the number indicating runout of the crystal oscillator plate is observed at any time, the current is finely adjusted to stabilize the crystal oscillator plate, the crucible is replaced for sputtering after the first film layer is plated, the second film layer is plated, and the operation is repeatedAnd stopping vacuum to take out the sample until all the film layers are plated, so as to prepare the film coating layer 3.
S2, preparation of an adhesive layer
And (3) coating optical cement on the coating layer 3 obtained in the step (S1), and forming a cement layer 2 on the coating layer 3 after heat treatment. The temperature of the heat treatment is 40 ℃, and the thickness of the obtained adhesive layer 2 is 1-30 mu m.
S3, preparation of dual-band refrigeration film for plant growth
And (2) compounding a packaging layer 1 with the thickness of 10-500 mu m on the adhesive layer 2 obtained in the step (S2) to obtain the dual-band refrigerating film for plant growth.
The obtained dual-band refrigerating film for plant growth has a transmittance of 70% for light in the 0.4-0.5 μm and 0.6-0.7 μm bands, a reflectance of more than 70% for light in the 0.5-0.6 μm and 0.7-2.5 μm bands, and heat achieves an emissivity of 90% in the form of electromagnetic waves of mid-infrared.
The invention is described in detail below by means of several examples:
example 1
The preparation method of the dual-band refrigeration film for plant growth comprises the following steps:
s1, preparation of a coating layer
SiO 1mm thick is selected 2 As a result of characterizing the solar light band transmittance of the substrate layer 4 by using glass as the substrate layer 4, the substrate layer 4 can achieve a transmittance higher than 90% in the solar light band, as shown in fig. 2, and has good light transmittance.
SiO is made of 2 The glass is arranged with one side facing upwards, and TiO is filled in the electron beam cavity 2 、MgF 2 、Ag、HfO 2 And SiO 2 Target material, utilizing electron beam evaporation technology to make SiO 2 TiO with thickness of 190nm is laminated on glass in turn 2 Film layer, mgF with thickness of 70nm 2 Film layer, 140nm thick TiO 2 Film layer, mgF with thickness of 70nm 2 Film layer, 10nm thick Ag film layer, 207nm thick HfO 2 Film layer, 53nm thick MgF 2 Film layer, 88nm thick TiO 2 Film layer, 7nm thick Ag film layer, 25nm thick HfO 2 Film layer and 100nm thick SiO 2 A film layer formed on the substrate layer 4And (3) breaking vacuum and taking out the sample.
S2, preparation of an adhesive layer
And (2) coating acrylate pressure-sensitive adhesive on the coating layer of the uppermost layer of the coating layer 3 obtained in the step (S1) and drying to obtain a glue layer, namely forming a glue layer 2 on the coating layer 3. Wherein, the glue is LOCTITE DURO-TAK 8063 solvent type acrylic ester glue of Hangao of Germany.
S3, preparation of dual-band refrigeration film for plant growth
And (3) compounding a PDMS packaging layer 1 with the thickness of 300 mu m on the adhesive layer 2 obtained in the step (S2) to obtain the dual-band refrigerating film for plant growth.
The dual-band refrigeration film for plant growth was subjected to solar band transmittance characterization, and the results are shown in fig. 3. As can be seen from FIG. 3, the film has a transmittance of more than 70% in the wavelength bands of 0.4-0.5 μm and 0.6-0.7. Mu.m, and a reflectance of more than 70% in the wavelength bands of 0.5-0.6 μm and 0.7-2.5. Mu.m, and it is seen that the film transmits substantially only light required by plants and substantially totally reflects light not required by plants.
The dual-band refrigeration film for plant growth was subjected to mid-infrared band spectral emissivity characterization, and the results are shown in fig. 4. As can be seen from FIG. 4, the refrigerating film can transfer heat to the space in the form of electromagnetic waves of medium infrared (8-13 μm) to achieve the emissivity of more than 90%, so as to achieve the cooling of objects.
As can be seen from fig. 3 and 4, the refrigeration film has excellent minimum effective energy transmission and highest energy output, thereby achieving excellent radiation refrigeration effect.
To investigate the cooling effect of the dual-band refrigerating film for plant growth prepared in example 1 of the present invention, an apparatus as shown in fig. 5 was used for measurement. Wherein 5 represents a film to be measured; 6 represents a thermocouple; 7 represents a plant; and 5 represents foam. The plant 7 is placed in a cover-opening box made of acrylic glass plates, the periphery and the bottom are insulated by foam 8, the film 5 to be measured is placed at the top end of the box, and a thermocouple 6 is placed between the plant 7 and the film 5 to be measured for temperature measurement.
The film 5 to be measured was used for plant growth prepared in example 1 of the present inventionIs a dual-band refrigerating film, a commercial transparent heat-insulating film and a PE film, and is 900W/m 2 The temperature profile under solar irradiation is shown in figure 6. As can be seen from fig. 6, (1) the dual-band refrigerating film for plant growth prepared in example 1 of the present invention maintains the ambient temperature at substantially 25-30 ℃, which is suitable for plant growth; (2) commercial transparent insulating films to raise ambient temperature; (3) Under the action of the PE film, the ambient temperature rises to 35 ℃ and even the highest temperature exceeds 40 ℃, and the highest tolerance temperature of plants is far exceeded. Therefore, the refrigeration film prepared by the invention has better cooling effect, and can meet the normal growth of plants.
Examples 2 to 4
The preparation method of the dual-band refrigeration film for plant growth is different from that of the embodiment 1 in that the number of coating layers is reduced, but the same spectrum effect still exists, the specific film layers and structures are shown in the table 1, and the other film layers and structures are approximately the same as those of the embodiment 1, and are not repeated here.
Table 1 film layer Structure of Dual band refrigeration films for plant growth prepared in examples 2-4
| Example 2 (9 layer structure) | Example 3 (6 layer structure) | Example 4 (4-layer structure) |
| 200nm SiO 2 | 100nm TiO 2 | 90nm HfO 2 |
| 80nm HfO 2 | 70nm SiO 2 | 80nm MgF 2 |
| 50nm SiO 2 | 220nm HfO 2 | 211nm TiO 2 |
| 240nm TiO 2 | 17nm Ag | 17nm Ag |
| 17nm Ag | 120nm MgF 2 | Substrate layer 4 |
| 100nm MgF 2 | 100nm HfO 2 | |
| 120nm TiO 2 | Substrate layer 4 | |
| 150nm SiO 2 | ||
| 90nm TiO 2 | ||
| Substrate layer 4 |
The refrigerating film prepared in example 2 was subjected to solar band transmittance characterization, and the result is shown in fig. 7. As can be seen from FIG. 7, the transmittance of the refrigerating film of example 2 in the wavelength bands of 0.4 to 0.5 μm and 0.6 to 0.7 μm and the reflectance in the wavelength bands of 0.5 to 0.6 μm and 0.7 to 2.5 μm are substantially similar to those of example 1. Similarly, the refrigerating films prepared in examples 3-4 are characterized by solar light wave band transmittance, the spectrum effect (namely, reflection and absorption of light in different wave bands) is similar to that of example 1, and the cooling effect corresponding to the refrigerating films prepared in examples 2-4 is similar to that of example 1.
Comparative example 1
A method for preparing a dual-band refrigerating film for plant growth is different from example 1 in that a 10nm thick Ag film layer in a film coating layer 3 is removed, and SiO is used as a material 2 TiO with thickness of 190nm is laminated on glass in turn 2 Film layer, mgF with thickness of 70nm 2 Film layer, 140nm thick TiO 2 Film layer, mgF with thickness of 70nm 2 Film layer, 207nm thick TiO 2 Film layer, 53nm thick MgF 2 Film layer, 88nm thick TiO 2 Film layer, 7nm thick Ag film layer, 25nm thick TiO 2 Film layer and 100nm thick SiO 2 The film layer is otherwise substantially the same as that of example 1, and will not be described here again.
The refrigerating film prepared in comparative example 1 was subjected to solar band transmittance characterization, and the result is shown in fig. 8. As can be seen from FIG. 8, the transmittance in the 0.4-0.5 μm wavelength band is significantly reduced, and the reflectance in the 0.5-0.6 μm and 0.7-2.5 μm wavelength bands is significantly reduced, so that more light in the 0.5-0.6 μm and 0.7-2.5 μm wavelength bands is transmitted, which seriously affects the dual transmission peak and the near infrared blocking effect, thus indicating that the Ag film layer is important. This is probably due to the fact that no Ag film exists, reflection and refraction of light rays between different films are affected, interference effects between different light rays are further affected, and the performance of the finally prepared refrigeration film is poor.
Comparative example 2
A method for preparing a dual-band refrigerating film for plant growth is different from example 1 in that a first layer of TiO 2 Film and second layer MgF 2 The sequence of the film layers is changed, and the film layers are formed on SiO 2 MgF with thickness of 70nm is laminated on glass in turn 2 Film layer, 190nm thick TiO 2 Film layer, 140nm thick TiO 2 Film layer, mgF with thickness of 70nm 2 Film layer, 10nm thick Ag film layer, 207nm thick HfO 2 Film layer, 53nm thick MgF 2 Film layer, 88nm thick TiO 2 Film layer, 7nm thick Ag film layer, 25nm thick HfO 2 Film layer and 100nm thick SiO 2 The film layer is otherwise substantially the same as that of example 1, and will not be described here again.
The refrigerating film prepared in comparative example 2 was subjected to solar band transmittance characterization, and the result is shown in fig. 9. As can be seen from fig. 9, the peak position is shifted to the right and the intensity is reduced, which seriously affects the peak position and the intensity of the dual-transmission peak, even the dual-band transmission can not occur, but the whole visible light band is transmitted, which indicates that the film sequence is critical, and needs to be performed according to the sequence of the refractive index alternation. At the same time, the thickness of the film layer is required to have strict requirements (if 190nm thick TiO 2 Film and 140nm thick TiO 2 The film layer is regarded as the same layer, and the thickness exceeds the standard).
In summary, according to the dual-band refrigeration film for plant growth and the preparation method thereof provided by the invention, the metal film layer, the oxide film layer and the fluoride film layer are arranged on the substrate layer, the film layers are alternately arranged according to the refractive index, the thickness and the position relation of different film layers are controlled, and the transmittance of more than 70% in the wave bands of 0.4-0.5 mu m and 0.6-0.7 mu m and the reflectance of more than 70% in the wave bands of 0.5-0.6 mu m and 0.7-2.5 mu m are realized by utilizing the difference of the thickness and the refractive index of each film layer; the invention also stacks a high polymer film layer with high emission characteristic on the film coating layer, which can transfer heat to the space in an electromagnetic wave form of medium infrared (8-13 μm) to achieve the emissivity of more than 90%, thereby achieving the cooling of the object.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, 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 modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A dual-band refrigeration film for plant growth, characterized in that: comprises a packaging layer, a coating layer and a substrate layer which are sequentially arranged from outside to inside; the packaging layer is a high-molecular polymer film layer with high emission characteristic; the film coating layer comprises at least 4 film layers with the thickness of 1-300nm, wherein the film layers comprise a metal film layer, an oxide film layer and a fluoride film layer, and the metal film layer cannot be arranged on the outermost layer; the film layers are alternately arranged according to the refractive index; when sunlight is incident, the light transmission of the wave bands of 0.4-0.5 mu m and 0.6-0.7 mu m and the reflection of the light of other wave bands can be realized, and meanwhile, the heat can realize high emission in the form of electromagnetic waves of middle infrared.
2. The dual band cooling film for plant growth of claim 1, wherein: the coating layer comprises 4-12 laminated film layers.
3. The dual band cooling film for plant growth of claim 1, wherein: the thickness of the metal film layer is 1-50nm; the thickness of the oxide film layer is 10-300nm, and the thickness of the fluoride film layer is 10-200nm.
4. A dual band refrigeration film for plant growth as claimed in claim 3, wherein: the metal film layer comprises one of aluminum, silver and gold; the oxide film layer comprises one of titanium dioxide, silicon dioxide, hafnium dioxide and zinc oxide; the fluoride film layer comprises one of magnesium difluoride, calcium difluoride, barium difluoride and aluminum trifluoride.
5. The dual band cooling film for plant growth of claim 1, wherein: the high molecular polymer film layer comprises one of PDMS, PET, PEO; the thickness is 10-500 μm.
6. The dual band cooling film for plant growth of claim 1, wherein: an adhesive layer is arranged between the packaging layer and the coating layer, the adhesive layer is high-transparency OCA optical adhesive, and the thickness is 1-30 mu m.
7. The dual band cooling film for plant growth of claim 1, wherein: the substrate layer is a high molecular polymer film or inorganic glass, and the thickness is 0.1-1.5mm; the high polymer film is one of PET, PMMA, PDMS, and the inorganic glass is silica glass.
8. The dual band cooling film for plant growth of claim 1, wherein: the dual-band refrigerating film for plant growth has a transmittance of 70% for light in the 0.4-0.5 μm and 0.6-0.7 μm bands, a reflectance of more than 70% for light in the 0.5-0.6 μm and 0.7-2.5 μm bands, and heat achieves an emissivity of 90% in the form of electromagnetic waves of mid-infrared.
9. A method for producing a dual-band refrigerating film for plant growth as claimed in any one of claims 1 to 8, characterized by: the method comprises the following steps:
s1, laminating corresponding film layers on a substrate layer according to a preset sequence by utilizing a film coating technology, and forming a film coating layer on the substrate layer;
s2, coating optical cement on the coating layer obtained in the step S1, and forming a cement layer on the coating layer after heat treatment;
s3, compounding a packaging layer on the adhesive layer obtained in the step S2 to obtain a dual-band refrigerating film for plant growth;
the film coating layer comprises at least 4 film layers with the thickness of 1-300nm, wherein the film layers comprise a metal film layer, an oxide film layer and a fluoride film layer, and the metal film layer cannot be arranged on the outermost layer; the film layers are alternately arranged according to the refractive index; the packaging layer is a high-molecular polymer film layer with high emission characteristic.
10. The method for preparing a dual-band refrigerating film for plant growth according to claim 9, wherein: in step S1, the plating technique includes one or more methods of electron beam evaporation, resistive thermal evaporation, and magnetron sputtering plating.
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