CN110387751B - Radiation self-cooling functional fiber fabric and preparation method thereof - Google Patents
Radiation self-cooling functional fiber fabric and preparation method thereof Download PDFInfo
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
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- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/047—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with fluoropolymers
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- D06M2101/16—Synthetic fibres, other than mineral fibres
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- D06M2101/16—Synthetic fibres, other than mineral fibres
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Abstract
The invention relates to a radiation self-cooling functional fiber fabric and a preparation method thereof, and is characterized in that the functional fiber fabric is formed by sequentially coating a high-reflection aluminum-silver layer and an infrared strong selective radiation absorption coating with the thickness of 8-14 mu m on the surface of the fiber fabric; the 8-14 mu m infrared strong selective radiation absorption coating consists of an active nano functional composition and a fluorine-containing polymer resin solution, wherein the active nano functional composition is prepared by mixing nano silicon dioxide, a rare earth silicate compound and a molybdate compound according to the mass ratio of 1 (0.5-2) to (0.5-2) and modifying by using a silane coupling agent; the mass of the solid component of the fluorine-containing polymer resin solution accounts for 10-80% of the mass of the infrared strong selective radiation absorbing coating with the thickness of 8-14 mu m. The functional fiber fabric provided by the invention can play a high-efficiency radiation self-cooling function in the environment of sunlight and no illumination, and can be widely applied to the fields of buildings, outer layer hanging of high-power equipment, manufacturing of self-cooling tents, functional clothes and the like.
Description
Technical Field
The invention relates to a radiation self-cooling functional fiber fabric and a preparation method thereof, belonging to the technical field of functional composite fiber fabrics and heat radiation.
Background
With the continuous development of global economy, the energy demand of human society is increasing, novel energy-saving materials and technologies are developed, the energy consumption is reduced to the maximum extent, the environmental load is reduced, and the energy-saving material has important economic and social values. Radiation self-cooling is a physical mechanism by which ground objects transfer heat to outer space through an infrared atmospheric window, thereby reducing the temperature of the ground objects. Under solar lighting conditions, the reduction of the surface temperature of an object is closely related to several aspects: firstly, absorbing the sunlight energy, wherein the surface of an object needs to reflect sunlight with the thickness of 0.3-2.5 mu m as high as possible; second, absorption of atmospheric infrared radiant energy requires that the surface of the object have as low an absorption of atmospheric infrared energy in the surrounding environment in the non-atmospheric infrared window region as possible; thirdly, discharging infrared radiation into the atmospheric environment through an infrared window, wherein the surface of the object is required to have high radiation to infrared energy of 8-14 microns; fourth, heat convection and heat conduction under natural air.
From the prior published reports, under the condition of no solar illumination, the object self-cooling can be well realized by using a radiation cooling mechanism, but the radiation self-cooling performance of the radiation cooling material under the daytime illumination condition does not meet the practical requirement yet. The preparation of the existing radiation self-cooling material mainly comprises the following modes: the radiation cooler with the nanometer micro-scale structure is constructed by applying the nanometer photoetching and plasma deposition technology, and although the self-cooling performance of the radiation cooler is good, the manufacturing process is complex, the difficulty is high, the requirement is high, and the large-scale and low-cost production is difficult. In addition, the structure has the defects of low strength, easy damage and the like; and secondly, uniformly mixing anatase titanium dioxide micropowder, glass microspheres and other inorganic functional substances with polymer resin, and compounding a high-reflection metal aluminum or silver film with a certain thickness on one side surface of the anatase titanium dioxide micropowder, the glass microspheres and other inorganic functional substances to prepare the radiation self-cooling device.
At present, most of common radiation self-cooling materials are radiation self-cooling coatings, the requirements for painting a substrate are high, and some objects with rough surfaces and low reflectivity are difficult to effectively apply. Therefore, it is necessary and urgent to develop a fabric with a self-cooling function by radiation, which can be used in the daytime and at night, and can be produced in a large scale at a low cost.
Disclosure of Invention
The invention aims to provide a radiation self-cooling functional fiber fabric capable of solving the defects in the prior art, and the invention also aims to provide a preparation method of the radiation self-cooling functional fiber fabric.
In order to achieve the purpose, the invention is realized by the following technical scheme: a radiation self-cooling functional fiber fabric is characterized in that a high-reflection aluminum silver layer and an 8-14 mu m infrared strong selective radiation absorption coating are sequentially coated on the surface of the fiber fabric; the 8-14 mu m infrared strong selective radiation absorption coating comprises an active nano functional composition which is transparent to visible-near infrared sunlight and has strong selective radiation absorption characteristics in an 8-14 mu m infrared atmospheric window and a fluorine-containing polymer resin solution which is transparent in a non-infrared atmospheric window area, wherein the active nano functional composition is prepared by mixing nano silicon dioxide, a rare earth silicate compound and a molybdate compound according to the mass ratio of 1 (0.5-2) to 0.5-2 and modifying by a silane coupling agent; the mass of the solid component of the fluorine-containing polymer resin solution accounts for 10-80% of the mass of the infrared strong selective radiation absorbing coating with the thickness of 8-14 mu m.
Preferably, the thickness of the high-reflection aluminum silver layer is 5-20 μm, and the thickness of the infrared strong selective absorption/radiation coating is 10-30 μm.
Preferably, the fiber fabric is polyester fiber fabric, polyamide fiber or polyurethane fiber. The light reflection of the high-reflection aluminum silver layer is more than 80 percent, and the high-reflection aluminum silver layer is commercially available.
The silicon dioxide, the rare earth silicate compound and the molybdate compound respectively have strong infrared selective absorption/radiation characteristics within the ranges of 8-10 microns, 9-12 microns and 10-14 microns. Wherein the rare earth silicate satisfies the stoichiometric ratio SiO2-(0.5～2)RE2O3-(0～0.5)Na2O, RE is La, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Y or Sc; the molecular formula of the alkaline earth molybdate is RMoO4And R is Mg, Ca, Sr or Ba.
Preferably, the nano rare earth silicate oxide has strong selective absorption/radiation characteristics (the infrared radiation absorption coefficient is more than 0.8) in an infrared spectral region of 9-12 mu m, and is prepared by the following method: accurately weighing nano silicon dioxide, rare earth nitrate and sodium nitrate according to the stoichiometric ratio of the rare earth silicate compound, and mixing and dispersing the nano silicon dioxide, the rare earth nitrate and the sodium nitrate into an ethanol-water mixed solution; evaporating the solvent under the condition of stirring in a water bath at the temperature of 70-80 ℃ to obtain gel; and after low-temperature pre-sintering treatment at 120-150 ℃ for 3-6 hours, performing heat treatment at 600-900 ℃ for 3-12 hours to obtain the rare earth silicate compound.
Preferably, the nano molybdate compound has strong selective absorption/radiation characteristics (the infrared radiation absorption coefficient is more than 0.8) in an infrared spectrum region of 10-14 μm, and is prepared by the following method: according to the stoichiometric ratio of the molybdate compound, accurately weighing ammonium molybdate and alkaline earth metal nitrate, and dissolving the ammonium molybdate and the alkaline earth metal nitrate into deionized water; preparing a citric acid solution with the mass concentration of 5-10%, stirring and dripping the citric acid solution into the solution, adjusting the pH to 3.0-4.0, and evaporating the solvent under the condition of stirring in a water bath at the temperature of 70-80 ℃ to obtain gel; and pre-sintering at the low temperature of 120-150 ℃ for 3-6 hours, and then performing heat treatment at the temperature of 800-1000 ℃ for 3-12 hours to obtain the molybdate compound.
Preferably, the fluoropolymer resin solution is any one of polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), Polytetrafluoroethylene (PTFEDE), Polytetrafluoroethylene (PTFE) or polyvinylidene fluoride-hexafluoropropylene (P (VDF-HFP)) resin solution; the mass solid content of the fluorine-containing polymer resin solution is 30-60%.
The invention also provides a method for preparing the radiation self-cooling functional fiber fabric, which comprises the following specific steps:
a. weighing a certain amount of nano silicon dioxide, rare earth silicate compound and alkaline earth molybdate compound powder and a silane coupling agent with the mass of 0.01-0.2% of that of the nano functional composition according to the mass proportion of the nano functional composition, adding the powder and the silane coupling agent into a high-speed grinding dispersion machine, and treating for 2-6 hours under the condition of 300-400 r/min to obtain the required active nano functional composition;
b. weighing the active nano functional composition and the fluorine-containing polymer resin solution according to the mass ratio of solid components of the fluorine-containing polymer resin solution to the mass of the infrared strong selective radiation absorbing coating of 8-14 mu m, and adding the active nano functional composition and the fluorine-containing polymer resin solution into a nano grinding dispersion machine for grinding and dispersing for 3-12 hours at 300-400 r/min to obtain the infrared strong selective radiation absorbing coating of 8-14 mu m;
c. and (3) adopting a spraying or coating process, sequentially coating a high-reflection aluminum silver layer and an 8-14 mu m infrared strong selective radiation absorption coating with a certain thickness on the surface of the fiber fabric, and naturally drying to obtain the radiation self-cooling functional fiber fabric.
Preferably, the silane coupling agent is KH560 or KH 570.
Has the advantages that:
according to the radiation self-cooling functional fiber fabric provided by the invention, through multi-layer functional composite assembly, a common fiber fabric has excellent visible-near infrared sunlight reflection and strong infrared selective absorption/radiation characteristics of 8-14 mu m, and further can play a high-efficiency radiation self-cooling function in the solar illumination and non-solar illumination environments, so that a new technical approach is provided for zero-energy-consumption self-cooling of various buildings and high-power equipment and manufacturing of self-cooling tents, clothes and the like, and the application in the energy-saving field is wide.
Drawings
FIG. 1 is an infrared absorption/radiation spectrum of the nano-silica of example 1;
FIG. 2 is an infrared absorption/radiation spectrum of a rare earth silicate compound of example 1;
FIG. 3 is a graph of the visible-IR absorption/radiation spectrum of the calcium molybdate compound of example 1.
Detailed Description
In order to better understand the present invention, the following examples are given as specific examples to illustrate the present invention, but the present invention is by no means limited to the following examples.
The fluoropolymer resin solution used in the following examples was a polytetrafluoroethylene PTFE concentrated dispersion (HGF-1, 60% solid content) and a commercial aqueous polyvinylidene fluoride-hexafluoropropylene P (VDF-HFP) resin (relative molecular weight 4.7X 10)540% solid content manufactured by Suwei corporation of America(ii) a The nano silicon dioxide is a product sold in the market of Mecline, and the average grain diameter is 30 nanometers or 50 nanometers; the high-reflection aluminum silver layer material is silver arrow waterborne floating type silver paste.
In the following examples, the nano-functional composition used was prepared using the following preparation process:
1) accurately weighing a certain amount of raw materials such as nano silicon dioxide, soluble rare earth nitrate, sodium nitrate and the like according to the stoichiometric ratio of the rare earth silicate compound, uniformly mixing and dispersing the raw materials into the ethanol-water mixed solution; evaporating the solvent in a water bath at 70 ℃ under stirring to obtain a gel; after low-temperature presintering treatment for 6 hours at 120 ℃, heat treatment is carried out for 12 hours at 800 ℃ to obtain the rare earth silicate compound.
2) Accurately weighing a certain amount of ammonium molybdate ((NH) according to the molecular formula of the molybdate compound4)2MoO4) And a soluble alkaline earth metal nitrate raw material, uniformly mixing and dissolving into deionized water; preparing a 10% citric acid solution, dropwise adding the citric acid solution into the solution while violently stirring, adjusting the pH to 3.0 by using ammonia water, and evaporating the solvent to obtain gel under the stirring condition of 80 ℃ in a water bath; after 3 hours of low-temperature presintering treatment at 150 ℃, heat treatment is carried out for 6 hours at 1000 ℃ to obtain the molybdate compound.
Example 1
A preparation method of a radiation self-cooling functional fiber fabric comprises the following steps:
1) weighing 30g of nano silicon dioxide (infrared absorption/radiation spectrogram is shown in figure 1) and 30g of rare earth silicate compound SiO according to the mass ratio of 1:1:1 of the nano functional composition2-La2O3-0.5Na2O (Infrared absorption/radiation spectrum shown in FIG. 2) and 30g of calcium molybdate CaMoO4The powder (infrared absorption/radiation spectrum is shown in figure 3), and 0.045g of silane coupling agent HK560 (mass is 0.05% of the nano functional composition), are added into a high-speed grinding dispersion machine, and are treated for 6 hours at 300 r/min, so as to prepare the active nano functional composition.
2) And (2) weighing 50g of the active nano functional composition prepared in the step (1) and 225g of PTFE fluorine-containing polymer resin solution according to the mass ratio of 60% of the fluorine-containing resin solid content in the infrared strong selective absorption/radiation coating, adding the active nano functional composition and the PTFE fluorine-containing polymer resin solution into a nano grinding dispersion machine together, and treating for 12 hours at 300 r/min to obtain the radiation self-cooling fluorine-containing polymer functional coating required for preparing the infrared strong selective absorption/radiation coating.
3) The surface of a common polyester fiber fabric (terylene) is sequentially sprayed with a 5 mu m thick high-reflection aluminum silver layer and a 25 mu m thick infrared strong selective absorption/radiation coating, and the required radiation self-cooling functional fiber fabric can be obtained after natural drying.
Example 2
A preparation method of a radiation self-cooling functional fiber fabric comprises the following steps:
1) weighing 30g of nano silicon dioxide and 45g of rare earth silicate compound SiO according to the mass ratio of the nano functional composition of 1:1.5:0.52-0.5La2O3-1.0Na2O and 15g of MgMoO4The powder and 0.09g of silane coupling agent HK560 (the mass is 0.1 percent of the nano functional composition) are added into a high-speed grinding dispersion machine together and treated for 2 hours under the condition of 400 r/min, and the active nano functional composition is prepared.
2) And (2) adding 90g of the active nano functional composition prepared in the step (1) and 100g of PTFE fluorine-containing polymer resin solution into a nano grinding dispersion machine together according to the mass proportion of 40 percent of the fluorine-containing resin solid content in the infrared strong selective absorption/radiation coating, and treating for 8 hours at 350 r/min to obtain the radiation self-cooling fluorine-containing polymer functional coating required by preparing the infrared strong selective absorption/radiation coating.
3) A high-reflection aluminum-silver layer with the thickness of 10 mu m and an infrared strong selective absorption/radiation coating with the thickness of 20 mu m are sequentially compounded on the surface of a common polyamide fiber (nylon) fabric in a coating mode, and the required radiation self-cooling functional fabric can be obtained after natural drying.
Example 3
A preparation method of a radiation self-cooling functional fiber fabric comprises the following steps:
1) weighing 20g of nano silicon dioxide and 10g of rare earth silicate compound SiO according to the mass ratio of 1:0.5:1 of the nano functional composition2-0.5La2O3-0.1Gd2O3-0.5Na2O and 20g of calcium molybdate CaMoO4The powder and 0.05g of silane coupling agent HK560 (the mass is 0.1 percent of the nano functional composition) are added into a high-speed grinding dispersion machine together and treated for 4 hours under the condition of 350 revolutions per minute, and the active nano functional composition is prepared.
2) Adding 45g of the active nano functional composition prepared in the step (1) and 105g P (VDF-HFP) fluorine-containing polymer resin solution into a nano grinding dispersion machine together according to the mass ratio of 70 percent of the fluorine-containing resin solid content in the infrared strong selective absorption/radiation coating, and grinding and dispersing for 3 hours at 400 r/min to obtain the radiation self-cooling fluorine-containing polymer functional coating required by preparing the infrared strong selective absorption/radiation coating.
3) Coating a high-reflection aluminum-silver layer and a 30-micrometer infrared strong selective absorption/radiation coating on the surface of a common polyurethane fiber (spandex) fabric in a composite thickness of 15 micrometers in sequence by a spraying process, and naturally drying to obtain the required radiation self-cooling functional fiber fabric.
Example 4
A preparation method of a radiation self-cooling functional fiber fabric comprises the following steps:
4) weighing 20g of nano silicon dioxide and 40g of rare earth silicate compound SiO according to the mass ratio of 1:2:2 of the nano functional composition2-0.5La2O3-0.5Y2O3-1.0Na2O and 40g of calcium molybdate CaMoO4The powder and 0.1g of silane coupling agent HK560 (the mass is 0.1 percent of the nano functional composition) are added into a high-speed grinding dispersion machine together and treated for 4 hours under the condition of 350 revolutions per minute, and the active nano functional composition is prepared.
5) Adding 50g of the active nano functional composition prepared in the step (1) and 100g P (VDF-HFP) fluorine-containing polymer resin solution into a nano grinding dispersion machine together according to the mass ratio of 50% of the fluorine-containing resin solid content in the infrared strong selective absorption/radiation coating, and grinding and dispersing for 3 hours at 400 r/min to obtain the radiation self-cooling fluorine-containing polymer functional coating required by preparing the infrared strong selective absorption/radiation coating.
6) Coating a high-reflection aluminum silver layer and a 25-micron infrared strong selective absorption/radiation coating on the surface of a common polyurethane fiber (spandex) fabric in a composite thickness of 10 microns in sequence through a spraying process, and naturally drying to obtain the required radiation self-cooling functional fabric.
Claims (6)
1. A radiation self-cooling functional fiber fabric is characterized in that a high-reflection aluminum silver layer and an 8-14 mu m infrared strong selective radiation absorption coating are sequentially coated on the surface of the fiber fabric; the 8-14 mu m infrared strong selective radiation absorption coating comprises an active nano functional composition which is transparent to visible-near infrared sunlight and has strong selective radiation absorption characteristics in an 8-14 mu m infrared atmospheric window and a fluorine-containing polymer resin solution which is transparent in a non-infrared atmospheric window area, wherein the active nano functional composition is prepared by mixing nano silicon dioxide, a rare earth silicate compound and a molybdate compound according to the mass ratio of 1 (0.5-2) to 0.5-2 and modifying by a silane coupling agent; the mass of the solid component of the fluorine-containing polymer resin solution accounts for 10-80% of the mass of the infrared strong selective radiation absorbing coating with the thickness of 8-14 mu m; wherein the oxide SiO contained in the rare earth silicate compound2：RE2O3：Na2The stoichiometric ratio of O is 1: (0.5-2.0): (0-0.5), RE is La, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Y or Sc; the molecular formula of the molybdate compound is RMoO4And R is Mg, Ca, Sr or Ba.
2. The radiation self-cooling functional fiber fabric according to claim 1, wherein: the thickness of the high-reflection aluminum silver layer is 5-20 mu m, and the thickness of the infrared strong selective absorption radiation coating is 10-30 mu m.
3. The radiation self-cooling functional fabric according to claim 1, wherein the fabric is a polyester fabric, a polyamide fabric or a polyurethane fabric.
4. The radiation self-cooling functional fiber fabric according to claim 1, wherein: the fluorine-containing polymer resin solution is any one of polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, polytetrafluoroethylene or polyvinylidene fluoride-hexafluoropropylene resin solution; the mass solid content of the fluorine-containing polymer resin solution is 30-60%.
5. The method for preparing the radiation self-cooling functional fiber fabric as claimed in claim 1 comprises the following specific steps:
a. weighing a certain amount of nano silicon dioxide, rare earth silicate compound and molybdate compound powder and a silane coupling agent with the mass of 0.01-0.2% of that of the nano functional composition according to the mass proportion of the active nano functional composition, adding the weighed materials into a high-speed grinding dispersion machine, and treating for 2-6 hours under the condition of 300-400 r/min to obtain the required active nano functional composition;
b. weighing the active nano functional composition and the fluorine-containing polymer resin solution according to the mass ratio of solid components of the fluorine-containing polymer resin solution to the mass of the infrared strong selective radiation absorbing coating of 8-14 mu m, and adding the active nano functional composition and the fluorine-containing polymer resin solution into a nano grinding dispersion machine for grinding and dispersing for 3-12 hours at 300-400 r/min to obtain the infrared strong selective radiation absorbing coating of 8-14 mu m;
c. and (3) coating a high-reflection aluminum silver layer and an 8-14 mu m infrared strong selective radiation absorption coating on the surface of the fiber fabric according to a certain thickness by adopting a spraying or coating process, and naturally drying to obtain the radiation self-cooling functional fiber fabric.
6. The method according to claim 5, wherein the silane coupling agent is KH560 or KH 570.
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| JP6944013B2 (en) * | 2019-11-06 | 2021-10-06 | 寧波瑞凌新能源科技有限公司Ｎｉｎｇｂｏ Ｒａｄｉ−Ｃｏｏｌ Ａｄｖａｎｃｅｄ Ｅｎｅｒｇｙ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｃｏ．， Ｌｔｄ． | Radiative cooling fabrics and products |
| CN111155332A (en) * | 2020-01-20 | 2020-05-15 | 西安工程大学 | Radiation cooling passive cooling fabric and preparation method thereof |
| CN111607983B (en) * | 2020-05-15 | 2023-05-26 | 浙江理工大学 | Super-hydrophobic daytime passive radiation refrigeration fabric and preparation method thereof |
| CN112176720B (en) * | 2020-09-28 | 2023-04-25 | 安徽瑜合警用装备有限公司 | Photoluminescent finishing agent based on silica microspheres, preparation method and application thereof |
| CN112853771A (en) * | 2021-02-03 | 2021-05-28 | 南京大学 | Radiation cooling antibacterial fabric and preparation method thereof |
| CN113827079B (en) * | 2021-09-29 | 2023-03-24 | 浙江真爱毯业科技有限公司 | Outdoor blanket with day radiation refrigeration function |
| CN114525612B (en) * | 2022-02-22 | 2023-07-11 | 宁波瑞凌新能源科技有限公司 | Cooling fiber, preparation method thereof and textile |
| CN115573169B (en) * | 2022-09-26 | 2023-11-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Radiation cooling water-based spray, preparation method and application thereof |
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| US6037280A (en) * | 1997-03-21 | 2000-03-14 | Koala Konnection | Ultraviolet ray (UV) blocking textile containing particles |
| CN107663771A (en) * | 2017-08-10 | 2018-02-06 | 江苏新瑞贝科技股份有限公司 | A kind of fabric radiation agent and preparation method thereof |
| CN109988467B (en) * | 2019-03-29 | 2021-10-29 | 杭州瑞酷新材料有限公司 | Radiation cooling coating and preparation method and application thereof |
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