CN115304953A - Radiant heat photon control material and preparation method thereof - Google Patents
Radiant heat photon control material and preparation method thereof Download PDFInfo
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- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
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Abstract
The invention provides a radiant heat photon control material and a preparation method thereof; the material comprises a polymer porous matrix and micro-nano inorganic particles. The average reflectivity of the material in a visible near-infrared band is up to 96.7%, the average emissivity in a middle-infrared atmospheric window band (8-13 mu m) is up to 93.8%, and the radiation cooling at 8 ℃ can be realized in the daytime. Meanwhile, the material is prepared by a 3D printing technology, a porous polymer structure embedded with micro-nano inorganic particles is formed in one step based on a non-solvent induced phase separation principle, the high-precision customization requirement of a complex three-dimensional structure can be met, and the material has a wide application prospect in the fields of cold chain transportation, buildings and personal electronic equipment heat management.
Description
Technical Field
The invention relates to the technical field of functional composite materials, in particular to a radiant heat control photon material and a preparation method thereof.
Background
With the development of civilians and the increasing desire for good life, the demand for space and food refrigeration in summer is also increasing. Traditional cooling techniques based on vapor compression and fluid cooling need to be driven by large scale fossil energy consumption and cause severe emissions of hydrocarbons, carbon dioxide and black carbon, which is a driving force for global warming and the exacerbation of urban heat island effects. At present, 36 hundred million refrigeration devices are estimated to be in use globally, and the power consumption accounts for 10-15% of the global power consumption. Research shows that the space in 1990-2018 produces CO 2 The discharge amount is increased by more than two times, and reaches 11.3 hundred million tons. According to the comprehensive reports on the discharge and policy of the refrigeration system commonly issued by the environmental planning agency and the international energy agency of the united nations, the global climate-friendly refrigeration transformation can avoid the discharge of up to 4600 hundred million tons of greenhouse gases in the future 40 years and ensure that the global temperature rise is controlled within 1.5 ℃ at the end of the century. Therefore, the development of new cooling systems and the development of new cooling materials are significant challenges to reduce carbon emissions, climate degradation, and energy consumption.
Radiant heat control is a new effective passive cooling means without external energy input. The radiation heat exchange is one of the main forms of heat exchange, the energy radiated by an object at normal temperature is mainly concentrated in a middle infrared band, and the infrared transparency of the atmosphere in a band of 8-13 mu m is high, so that the heat radiated by the object on the ground can be transferred to the space through the atmosphere transparent window almost without loss. Considering the temperature difference between the earth surface temperature and the background temperature of the universe environment, which is nearly 300 ℃, the universe environment can be regarded as a 'refrigeration house' which is efficient and stable and is used for cooling earth surface objects. In order to fully realize the passive cooling, the radiant heat control material reduces the sunlight absorption amount to the maximum extent and improves the radiant rate of the intermediate infrared band, so that the radiant heat control material can realize the self temperature lower than the ambient air temperature. Compared with the current mainstream refrigeration system and refrigeration materials, the radiant heat control material does not need energy consumption and the carbon emission is almost zero, so that the method is an environment-friendly passive cooling mode with great development potential. Documents related to bolometric control materials have been reported, for example, chinese patent CN 112342792A, with the name: the technical characteristic of the patent is to provide the construction method of the fabric surface with the passive daytime radiation heat control function and the special wettability function, and the impregnation method is adopted to combine the potassium titanate whisker and the polydimethylsiloxane with the micro-nano structure of the fabric surface, so that the high mid-infrared emissivity and the good super-hydrophobic property can be realized. However, the material prepared by the technology has low reflectivity in a visible wave band, and the radiant heat control effect needs to be further improved. For another example, chinese patent CN 112460836A, entitled "passive radiation cooling composite material film", has the technical characteristics of providing a radiative heat control structure of metal-bonded patterned polydimethylsiloxane, and the material includes an infrared light emitting layer made of polydimethylsiloxane as a planar metal reflecting layer sequentially arranged from bottom to top, and a one-dimensional or two-dimensional micrometer-scale optical microstructure unit is arranged on the upper surface of the infrared light emitting layer, so that a visible near-infrared high reflectivity and a middle-infrared high emissivity can be simultaneously realized. However, the preparation cost of the technology is high, and the large-area preparation manufacturability needs to be further improved. For example, chinese patent CN 111455484A, which is named as 'a preparation method of a high-doped radiation refrigeration composite fiber and a fabric thereof', has the technical characteristics that a thermal drawing method is used for preparing a polymer fiber mixed with inorganic micro-nano particles, and the cross section shape and the macroscopic structure of the fiber can be designed to realize good radiation thermal control performance and mechanical property. However, the technique consumes a lot of energy during the preparation process, and the applicability to irregular surfaces needs to be improved. The currently studied bolometric control materials are almost served in the form of thin films or coatings, and are attached to the existing substrates. In cold chain transportation and building application, the block radiant heat control material with a complex shape meets the actual requirement, but related research and preparation processes are rarely reported.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a bolometric photon material and a preparation method thereof, wherein the bolometric photon material has high reflectivity in a sunlight wave band so as to reduce energy absorption, and simultaneously has high radiance in a middle infrared wave band so as to enhance radiative heat exchange efficiency and realize a passive cooling effect; meanwhile, the radiant heat control photon material is prepared by adopting a 3D printing technology, programmed construction of a complex three-dimensional shape can be realized, and personalized customization can be realized according to different application occasions and requirements.
The purpose of the invention is realized by the following technical scheme:
in a first aspect, the invention relates to a radiation thermal control photon material, which is formed by inlaying micro-nano inorganic particles in a porous polymer matrix, wherein the micro-nano inorganic particles are selected from one or more of aluminum oxide, silicon oxide, magnesium oxide, zinc oxide, boron nitride, yttrium oxide and titanium oxide, the diameter of the micro-nano inorganic particles is 50 nm-20 microns, the polymer is one of polyurethane, polyvinylidene fluoride, polystyrene, polymethyl methacrylate, polylactic acid, acrylonitrile-butadiene-styrene and polycaprolactone, and the average pore diameter of the pores is 0.5-5 microns.
The material selected by the invention has extremely low extinction coefficient in the sunlight wave band (0.3-2.5 mu m) so as to ensure the minimum sunlight absorption. The polymer porous matrix has strong light scattering efficiency and a low photon average transmission path, and can realize very high visible near infrared reflectivity. Meanwhile, the selected polymer has multiple absorption peaks in the middle infrared (2.5-20 mu m) due to abundant functional group resonance modes, and can realize higher middle infrared emissivity. The addition of the micro-nano inorganic particles can further improve the infrared emissivity of the whole structure by utilizing a phonon polarization resonance mode of the micro-nano inorganic particles, and maintain the high reflectivity of a visible near-infrared band. The polymers chosen may also provide good mechanical properties to achieve self-support of the entire photonic structure.
In a second aspect, the invention further relates to a 3D printing preparation method of the bolometric photonic material, where the 3D printing preparation method includes the following steps:
s1, mixing a polymer, a pore-forming agent and micro-nano inorganic particles in a polymer solvent to prepare a precursor solution used as printing ink;
s2, preparing a mixed solution of a polymer solvent and a non-solvent to be used as a coagulating bath;
s3, placing the printing ink in 3D printing equipment, extruding the ink by using air pressure, sinking a needle below the liquid level of the coagulating bath, controlling the programmed movement of the needle by using a G-code, extruding and printing fibers and stacking the fibers into a three-dimensional printing structure;
and S4, placing the three-dimensional printing structure in the coagulating bath for 0.5-2 h, and then drying at normal temperature to obtain the radiation heat control photon material.
As one embodiment of the present invention, in step S1, the mass fraction of the polymer is 10% to 40%, and the polymer solvent is one of N, N-dimethylformamide, acetone, dichloromethane, chloroform, acetyldimethylamine and dimethylsulfoxide. The polymer concentration in the above range is advantageous for the solution to maintain a better viscosity and to avoid collapse during 3D printing.
In step S1, the mass fraction of the pore-forming agent is 1% to 10%, the pore-forming agent is one or more of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, lithium chloride, sodium sulfate, and methylcellulose, and the pore-forming agent is used to adjust the pore size distribution and porosity of the porous matrix, so that the porous matrix has an optimal visible near-infrared reflectance.
As an embodiment of the invention, in the step S1, the mass fraction of the micro-nano inorganic particles is 2% to 30%, and the mass fraction of the micro-nano inorganic particles in the above range is favorable for further enhancing the radiance of the bolometric photon control material, and simultaneously ensures that the whole structure has a certain mechanical strength.
In step S2, the non-solvent is one or more of deionized water, ethanol, methanol and propanol, the volume percentage of the polymer solvent in the coagulation bath is 0-70%, and the polymer solvent is in the above ratio range, which is beneficial to improving the surface morphology of the printed fiber and making the pore size distribution in the three-dimensional printed structure more uniform.
As an embodiment of the present invention, in step S3, the tip diameter of the printing nozzle of the 3D printing device is 100 μm to 600 μm, the printing air pressure is 0.05 MPa to 0.6MPa, and the needle running speed is 4 mm/S to 10mm/S.
In step S3, the G-code is written according to the created model.
The preparation process principle of the invention is that in the printing process, the exchange of polymer solvent and non-solvent occurs in the printing fiber, the polymer is induced to have the non-solvent induced phase separation process, and then a porous matrix is formed and solidified. The exchange rate of the polymer solvent and the non-solvent can be further promoted by adjusting the quality and the molecular weight of the pore-making agent, and the final pore morphology is improved.
Compared with the prior art, the invention has the following beneficial effects:
1. the bolometric photon material has strong visible near-infrared reflectivity and strong mid-infrared radiance, the average reflectivity of a single-layer 3D printing structure with the thickness of 350 mu m to sunlight can be up to 96.7 percent, the average radiance in a mid-infrared atmospheric window (within 8-13 mu m) can be up to 93.8 percent, and the bolometric photon material can be in a range of 1000W/m 2 The highest temperature of the glass is reduced by 8 ℃ under the sunlight;
2. the bolometric photon control material breaks through the single two-dimensional service form of the existing bolometric photon control material, realizes the construction of three-dimensional bolometric photon control materials with different customized shapes at room temperature for the first time, and has wide application prospect in the fields of cold chain transportation, building, personal electronic equipment cooling and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts. Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a schematic structural diagram of a composition of a bolometric photonic material;
fig. 2 is an optical photograph of a three-dimensional printing structure of a bolometric photonic material obtained in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of a three-dimensional printed fiber of a bolometric photonic material obtained in example 1 of the present invention;
FIG. 4 is a partial magnified scanning electron micrograph of a three-dimensional printed fiber of a bolometric photonic material obtained in example 1 of the present invention;
FIG. 5 shows the spectral reflectance of the bolometric photonic material obtained in example 1 of the present invention in the visible near-infrared band;
fig. 6 shows the spectral radiance of the bolometric photonic material obtained in example 1 of the present invention in the atmospheric window band.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
Firstly, preparing printing ink, dissolving 20% of polyurethane, 4% of polyvinyl alcohol and 5% of alumina particles in N, N-dimethylformamide by mass fraction, and magnetically stirring for 4 hours to uniformly mix the solution. The alumina used had an average particle size of 500nm. Preparing a coagulation bath containing 50% of N, N-dimethylformamide, and selecting deionized water as a non-solvent. The printing ink was loaded into a plastic cartridge equipped with a 600 μm inner diameter needle and mounted into the nozzle slot of a 3D printer, clamped with a clamp and then loaded with compressed air to prepare for printing. The printing air pressure is set to be 0.2MPa, and the running speed of the needle head is set to be 6mm/s. And printing a corresponding 3D structure according to the three-dimensional model under the guidance of the G-code. And after printing is finished, standing the printed structure in a coagulating bath for 1h, and drying at normal temperature to obtain the three-dimensional radiation thermal control photon material structure. The prepared radiation thermal control photon material has a composition structure shown in figure 1, and comprises a porous polymer matrix 1 and micro-nano inorganic particles 2 embedded in the porous polymer matrix. The optical photograph of the printed structure is shown in fig. 2, and it can be seen from the figure that the structure obtained by 3D printing has different shapes, which indicates that the bolometric photon control material prepared by the 3D printing method has the characteristic of high-precision customization. Scanning electron micrographs of the printed fibers are shown in fig. 3 and 4, and as can be seen from fig. 3 and 4, the prepared polymer has compact micropore arrangement and uniform size, and the micro-nano inorganic particles are uniformly dispersed in the porous matrix without serious agglomeration, thereby greatly contributing to the improvement of mechanical properties and radiation heat control properties.
The reflectivity of the bolometric photon material prepared by the embodiment in the visible near infrared is 96.7%, as shown in fig. 5, and the infrared emissivity in the atmospheric window band is 93.8%, as shown in fig. 6, and the bolometric photon material can reach the cooling temperature of 8 ℃ at most in the daytime.
Example 2
Firstly, preparing printing ink, dissolving polystyrene with the mass fraction of 20%, polyvinyl alcohol with the mass fraction of 4% and alumina particles with the mass fraction of 5% in N, N-dimethylformamide, and stirring for 4 hours by magnetic force to uniformly mix the solution. The alumina used had an average particle size of 500nm. Preparing a coagulation bath containing 50% of N, N-dimethylformamide, and selecting deionized water as a non-solvent. The printing ink was loaded into a plastic cartridge equipped with a 600 μm inner diameter needle and mounted into the nozzle slot of a 3D printer, clamped with a clamp and then loaded with compressed air to prepare for printing. The printing air pressure is set to be 0.2MPa, and the running speed of the needle head is set to be 6mm/s. And printing a corresponding 3D structure according to the three-dimensional model under the guidance of the G-code. And after printing is finished, standing the printed structure in a coagulating bath for 1h, and drying at normal temperature to obtain the three-dimensional radiation thermal control photon material structure.
The reflectivity of the radiant heat control photon material prepared by the embodiment in the visible near infrared is 96.2%, the infrared emissivity in an atmospheric window wave band is 91%, and the maximum temperature of the material can be reduced by 5 ℃ in the daytime.
Example 3
Firstly, preparing printing ink, dissolving 20% of acrylonitrile-butadiene-styrene, 4% of polyvinyl alcohol and 5% of alumina particles in dichloromethane, and stirring for 4 hours by magnetic force to uniformly mix the solution. The alumina used had an average particle size of 500nm. A coagulation bath containing 50% dichloromethane was prepared, and ethanol was selected as the non-solvent. The printing ink was loaded into a plastic cartridge equipped with a 600 μm inner diameter needle and mounted into the nozzle slot of a 3D printer, clamped with a clamp and then loaded with compressed air to prepare for printing. The printing air pressure is set to be 0.2MPa, and the running speed of the needle head is set to be 6mm/s. And printing a corresponding 3D structure according to the three-dimensional model under the guidance of the G-code. And after printing is finished, standing the printed structure in a coagulating bath for 1h, and drying at normal temperature to obtain the three-dimensional radiation thermal control photon material structure.
The reflectivity of the radiant heat control photon material prepared by the embodiment in visible near infrared is 95.8%, the infrared emissivity in an atmospheric window wave band is 90%, and the maximum temperature can be reduced by 4.8 ℃ in the daytime.
Example 4
Firstly, preparing printing ink, dissolving 20% of polyurethane, 4% of polyvinylpyrrolidone and 10% of silicon oxide particles in N, N-dimethylformamide, and magnetically stirring for 4h to uniformly mix the solution. The average particle size of the silicon oxide used was 100nm. A coagulation bath containing 50% of N, N-dimethylformamide was prepared, and deionized water was selected as a non-solvent. The printing ink was loaded into a plastic cartridge equipped with a 600 μm inner diameter needle and mounted into the nozzle slot of a 3D printer, clamped with a clamp and then loaded with compressed air to prepare for printing. The printing air pressure is set to be 0.2MPa, and the running speed of the needle head is 6mm/s. And printing a corresponding 3D structure according to the three-dimensional model under the guidance of the G-code. And after printing is finished, standing the printed structure in a coagulating bath for 1h, and drying at normal temperature to obtain the three-dimensional radiation thermal control photon material structure.
The reflectivity of the radiant heat control photon material prepared by the embodiment in visible near infrared is 96%, the infrared emissivity in an atmospheric window wave band is 92%, and the maximum temperature can be reduced by 5.5 ℃ in the daytime.
Example 5
Firstly, preparing printing ink, dissolving 20 mass percent of polyurethane, 4 mass percent of polyvinylpyrrolidone and 10 mass percent of boron nitride particles in N, N-dimethylformamide, and magnetically stirring for 4 hours to uniformly mix the solution. The boron nitride used had an average particle size of 400nm. Preparing a coagulation bath containing 50% of N, N-dimethylformamide, and selecting deionized water as a non-solvent. The printing ink was loaded into a plastic cartridge equipped with a 600 μm inner diameter needle and mounted into the nozzle slot of a 3D printer, clamped in place and loaded with compressed air to prepare for printing. The printing air pressure is set to be 0.2MPa, and the running speed of the needle head is 6mm/s. And printing a corresponding 3D structure according to the three-dimensional model under the guidance of the G-code. And after printing is finished, standing the printed structure in a coagulating bath for 1h, and drying at normal temperature to obtain the three-dimensional radiation thermal control photon material structure.
The reflectivity of the radiant heat control photon material prepared by the embodiment in visible near infrared is 92%, the infrared emissivity in an atmospheric window wave band is 90%, and the temperature can be reduced by 3 ℃ at most in the daytime.
In the present specification, the embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
The foregoing description has described specific embodiments of the present invention. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. The bolometric photon control material is characterized by comprising a polymer porous matrix and micro-nano inorganic particles;
the polymer is any one of polyurethane, polyvinylidene fluoride, polystyrene, polymethyl methacrylate, polylactic acid, acrylonitrile-butadiene-styrene and polycaprolactone, and the average pore diameter of the porous polymer is 0.5-5 mu m;
the micro-nano inorganic particles are selected from any one or more of aluminum oxide, silicon oxide, magnesium oxide, zinc oxide, boron nitride, yttrium oxide and titanium oxide, and the diameter of the micro-nano inorganic particles is 50 nm-20 mu m.
2. A method of preparing a bolometric photonic material according to claim 1, comprising the steps of:
s1, mixing a polymer, a pore-forming agent and micro-nano inorganic particles in a polymer solvent to prepare a precursor solution used as printing ink;
s2, preparing a mixed solution of a polymer solvent and a non-solvent to be used as a coagulating bath;
s3, placing the printing ink in 3D printing equipment, extruding the ink by utilizing air pressure, sinking a needle head below the liquid level of the coagulating bath, controlling the movement of the needle head, extruding the printing fiber and stacking the printing fiber into a three-dimensional printing structure;
and S4, placing the three-dimensional printing structure in the coagulating bath for 0.5-2 h, and then drying to obtain the radiant heat photon control material.
3. The method for preparing the bolometric photonic material of claim 2, wherein in step S1, the polymer has a mass fraction of 10% to 40%.
4. The method of claim 2, wherein in step S1, the polymer solvent is one of N, N-dimethylformamide, acetone, dichloromethane, chloroform, acetyldimethylamine and dimethylsulfoxide.
5. The method for preparing the bolometric photon control material as claimed in claim 2, wherein in step S1, the mass fraction of the hole forming agent is 1-10%.
6. The method of claim 2, wherein in step S1, the pore-forming agent is one or more of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, lithium chloride, sodium sulfate, and methylcellulose.
7. The preparation method of the bolometric photon control material according to claim 2, wherein in step S1, the mass fraction of the micro-nano inorganic particles is 2% -30%.
8. The method of claim 2, wherein in step S2, the non-solvent is one or more of deionized water, ethanol, methanol, and propanol.
9. The method for preparing a bolometric photonic material according to claim 2, wherein in step S2, the volume percentage of the polymer solvent in the coagulation bath is 0-70%.
10. The method for preparing the bolometric photonic material of claim 2, wherein in step S3, the tip diameter of the printing nozzle of the 3D printing device is 100 μm to 600 μm, the printing pressure is 0.05 MPa to 0.6MPa, and the needle running speed is 4 mm/S to 10mm/S.
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| CN117488423A (en) * | 2023-11-02 | 2024-02-02 | 武汉格物感知信息科技有限公司 | Preparation method and application of passive cooling photo-thermal regulation fiber and fabric |
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