CN115651470A - Grey passive radiation refrigeration material, preparation method and application - Google Patents
Grey passive radiation refrigeration material, preparation method and application Download PDFInfo
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Abstract
The invention belongs to the technical field of passive radiation refrigeration materials, and aims to solve the technical problem that a passive radiation material in the prior art cannot simultaneously meet the sunlight reflection requirement and the diversified color tone requirement, the embodiment of the invention provides a gray passive radiation refrigeration material, a preparation method and an application, wherein the gray passive radiation refrigeration material comprises the following components: the paint comprises a silicone-acrylic emulsion, a high-reflection filler, nano silicon oxide, hollow glass beads, an auxiliary agent, an organic solvent and a gray composite dye which selectively absorbs visible light waves of 400 to 700nm, wherein the high-reflection filler is a compound with a wide band gap. The embodiment of the invention realizes the equal proportion uniform absorption of the full-wave band of visible light of 400 to 700nm, simultaneously has no absorbed gray appearance of other wave bands, and gives consideration to aesthetic requirements and the requirement of realizing the reflectivity of passive radiation refrigeration.
Description
Technical Field
The invention belongs to the technical field of passive radiation refrigeration materials, and particularly relates to a gray passive radiation refrigeration material, a preparation method and application.
Background
The passive radiation refrigeration can realize the passive radiation refrigeration effect that the surface temperature is constantly lower than the ambient temperature in summer illumination, and is a coating which can extremely change the functionality. The solar energy heat exchanger efficiently reflects the energy of sunlight, and transmits the residual heat to the outer space by means of infrared radiation, so that the temperature of the outer wall of a building and the heat entering the indoor space are greatly reduced, the indoor thermal comfort is improved, and the refrigeration energy consumption of an air conditioner is reduced. However, passive radiation refrigeration coatings have been developed that are substantially white and rarely address both decorative and architectural aesthetic needs. A wide range of single white colors not only causes aesthetic fatigue, but also has potential glare and light pollution problems, thus limiting the application of passive radiation refrigeration coatings to urban civil buildings to some extent.
The passive radiation refrigeration material must possess extremely high solar reflectivity and infrared emissivity. More than 90% of solar short-wave radiation needs to be reflected, and more than 90% of heat can be emitted to the atmosphere and the outer space in the form of infrared radiation, so that the passive radiation refrigeration effect that the surface temperature is lower than the ambient temperature is realized. The solar reflectivity of the passive radiation refrigeration material is greatly influenced due to the inevitable introduction of absorption in a visible light wave band, so that the solar reflectivity is lower than a reflectivity threshold value required for realizing passive radiation refrigeration, and the effect is lost under the illumination in the daytime where refrigeration is most needed. Thus, in previous studies, there have been few reports of colored, especially gray, passively radiating refrigerant materials.
Disclosure of Invention
In order to solve the technical problem that a passive radiation material in the prior art cannot simultaneously meet the requirements on sunlight reflection and diversified color tones, the embodiment of the invention provides a gray passive radiation refrigeration material, a preparation method and application.
The embodiment of the invention is realized by the following technical scheme:
in a first aspect, an embodiment of the present invention provides a gray passive radiation refrigeration material, including the following components: the paint comprises a silicone-acrylic emulsion, a high-reflection filler, nano silicon oxide, hollow glass beads, an auxiliary agent, an organic solvent and a gray composite dye which selectively absorbs visible light waves of 400 to 700nm, wherein the high-reflection filler is a compound with a wide band gap.
Further, the gray passive radiation refrigeration material comprises the following components in percentage by mass: 20-25% of silicone-acrylic emulsion, 55-65% of high-reflection filler, 1.0-1.5% of nano silicon oxide, 2.0-2.5% of hollow glass bead, 3-4% of auxiliary agent, 1.8-1.95% of organic solvent and 0.05-0.2% of gray composite dye capable of selectively absorbing visible light waves with wavelength of 400-700nm.
Further, the gray composite dye selectively absorbing 400 to 700nm visible light waves is prepared by overlapping a plurality of red, yellow and blue three primary colors dyes with spectrum selectivity or compounding a yellow dye and a metachromatic purple dye.
Further, the organic solvent comprises one or more of N, N-dimethylformamide, dimethyl sulfoxide and ethanol.
Further, the secondary violet dye comprises one of Lanxess MACROLEX 3R anthraquinone dye violet and Clariant Savinyl R acid violet;
the red, yellow and blue dyes comprise red dyes, yellow dyes and blue dyes;
the Red dye comprises one of a visible light spectrum selective metal complex Red dye, BASF Orosol Ciba Red, clariant Savinyl Fire Red GLS solvent Red 89, lanxess Macrolex dye Red, red fluorescent dye BASF Lumogen F Red 305 and Red 300 fluorescent Red;
the Yellow dye comprises one of metal complex dye BASF Orosol Ciba Yellow, monoazo dye BASF Orosol 251 orange, clariant Savinyl 2GLS 01 metal complex dye solvent Yellow 79, clariant Savinyl RLS Yellow high transparent dye solvent Yellow, BASF Lumogen F Yellow 083 fluorescent Huang Hexiang coumarin 6;
the Blue dye comprises one of metal complex Blue dye with visible light spectrum selectivity, BASF Orosol BL Blue, GL Blue, lanxess Macrolex solvent Blue and CLARIANT Solvaperm Blue 2B anthraquinone Blue.
Further, the high-reflection filler comprises one or more of nano barium sulfate and nano magnesium fluoride.
Furthermore, the auxiliary agent comprises a dispersing agent, a wetting agent, a defoaming agent, a thickening and leveling agent, an anti-settling agent and a film-forming auxiliary agent.
In a second aspect, an embodiment of the present invention provides a preparation method of the gray passive radiation refrigeration material, including:
uniformly dispersing the gray composite dye and an organic solvent to obtain a micromolecular dye solution;
adding the micromolecular dye solution into a part of silicone-acrylate emulsion for primary dispersion and uniform mixing to obtain pre-dispersion color paste;
adding the high-reflection filler, the nano silicon oxide, the hollow glass beads, the water, the dispersing agent, the wetting agent and the defoaming agent into the rest silicone-acrylate emulsion for secondary dispersion and uniform mixing to obtain a dispersion liquid;
and adding the pre-dispersing color paste into the dispersion liquid to carry out three-time dispersing and uniformly mixing, adding the thickening and leveling agent, the anti-settling agent and the film-forming assistant to carry out four-time dispersing and uniformly mixing after the three-time dispersing and uniformly mixing, and obtaining the gray passive radiation refrigeration material.
Further, the conditions of the primary dispersion and uniform mixing are as follows: stirring and dispersing at normal temperature, wherein the rotating speed is 500-1000 r/min, and the stirring time is 20-30min;
the conditions for secondary dispersion and uniform mixing are as follows: stirring and dispersing at normal temperature and normal pressure, wherein the stirring speed is 1500-2000 r/min, and the stirring time is 2 hours;
the conditions for dispersing and uniformly mixing for the third time are as follows: continuously stirring for 1h at normal temperature and normal pressure, wherein the stirring speed is 1500-2000 r/min;
the conditions for dispersing and uniformly mixing for four times are as follows: the stirring speed is 500r/min, and the stirring time is 30-60 min.
In a third aspect, embodiments of the present invention provide a use of a gray passive radiation refrigeration material as a coating.
Compared with the prior art, the embodiment of the invention has the following advantages and beneficial effects:
according to the gray passive radiation refrigeration material, the preparation method and the application, the full-wave band equal-proportion uniform absorption of visible light of 400 to 700nm is realized through the silicone-acrylic emulsion, the high-reflection filler, the nano silicon oxide, the hollow glass beads, the auxiliary agent, the organic solvent and the gray composite dye selectively absorbing the visible light of 400 to 700nm, meanwhile, the gray appearance without absorption of other wave bands is realized, and both aesthetic requirements and the requirement for realizing the reflectivity of passive radiation refrigeration are taken into consideration; the preparation method further ensures the combination and the dispersibility of the dye micromolecules in the film forming phase material of the whole coating through the sequence of pre-dissolving and color mixing, pre-dispersing and orderly adding, ensures the uniformity of the color and avoids the unwanted color cast and color difference.
Drawings
In order to more clearly illustrate the technical solutions of the exemplary embodiments of the present invention, the drawings that are required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and that those skilled in the art may also derive other related drawings based on these drawings without inventive effort.
Fig. 1 is a diagram of a radiation refrigeration paint refrigeration effect test apparatus that can be used for different color refrigeration paint template tests.
FIG. 2 is a graph showing the spectral reflectance curve, spectral reflectance and total solar reflectance of the gray passive radiation refrigeration coating and highly reflective white coating slurry of example 1, wherein the light absorption range in FIG. 2 is 360-690nm, the main absorption peak is 370-545nm, and the solar reflectance is 90.7%.
Fig. 3 is a schematic comparison of the surface temperature of a gray passive radiation refrigeration coating chiller and the ambient air temperature of example 1.
FIG. 4 is a graph showing the spectral reflectance curves, spectral reflectances, and total solar reflectances of the gray passive-radiation refrigeration coating and the highly reflective white coating slurry of example 2, in FIG. 4, the light absorption range is 388-678nm, the main absorption peak is 470-570nm, and the solar reflectance is 91.4%.
Fig. 5 is a schematic comparison of the surface temperature of a gray passive radiation refrigeration coating chiller and the ambient air temperature of example 2.
Reference numbers and corresponding part names in the figures:
1-a shutter box, 2-a test box and 3-a sample plate.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one of ordinary skill in the art that: it is not necessary to employ these specific details to practice the present invention. In other instances, well-known structures, circuits, materials, or methods have not been described in detail so as not to obscure the present invention.
Throughout the specification, reference to "one embodiment," "an embodiment," "one example," or "an example" means: the particular features, structures, or characteristics described in connection with the embodiment or example are included in at least one embodiment of the invention. Thus, the appearances of the phrase "one embodiment," "an embodiment," "one example" or "an example" in various places throughout this specification are not necessarily all referring to the same embodiment or example. Furthermore, the particular features, structures, or characteristics may be combined in any suitable combination and/or sub-combination in one or more embodiments or examples. Further, those of ordinary skill in the art will appreciate that the illustrations provided herein are for illustrative purposes and are not necessarily drawn to scale. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the description of the present invention, the terms "front", "rear", "left", "right", "upper", "lower", "vertical", "horizontal", "upper", "lower", "inner", "outer", etc. indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and therefore, should not be construed as limiting the scope of the present invention.
Red, yellow and blue are three primary colors for color development, any two of the three primary colors are added to form secondary colors, for example, red plus yellow forms orange, red plus blue forms purple, and yellow plus blue forms green. The three primary colors are superposed according to a certain proportion to form black, and mixed with white to form gray, and simultaneously, color gray with color cast can be prepared according to different contents of the three primary colors. Therefore, the color development of the color gray is closely related to the trichromatic color developing materials used. The materials commonly used for color development are small dye molecules and pigment particles, which have completely different mechanisms for color development. Most of the pigments are inorganic compounds or polymer-coated dye clusters, and are granulated into particles. The pigment presents color because of selective absorption of visible light by outer layer valence electrons in the molecular structure, and because the formed compound can reflect and transmit light, the pigment is the result of combined action of chemical absorption and physical scattering and diffraction. The color development of the dye small molecule is determined by the selective absorption of visible light by the valence electrons in the chromophoric group. Wherein, the more chromophoric groups, the darker the color, and the chromophoric groups do not absorb at more than 200 nm. Therefore, compared with pigment particles, the dye micromolecule has the characteristics of bright color, less introduced extra absorption amount and the like.
In order to solve the technical problem that a passive radiation material in the prior art cannot simultaneously meet the requirements on sunlight reflection and diversified color tones, the embodiment of the invention provides a gray passive radiation refrigeration material, a preparation method and application.
In a first aspect, an embodiment of the present invention provides a gray passive radiation refrigeration material, including the following components: the paint comprises a silicone-acrylic emulsion, a high-reflection filler, nano silicon oxide, hollow glass beads, an auxiliary agent, an organic solvent and a gray composite dye which selectively absorbs visible light waves of 400 to 700nm, wherein the high-reflection filler is a compound with a wide band gap.
The material of the embodiment of the invention can realize the passive radiation refrigeration effect that the surface temperature is slightly lower than the ambient temperature and the all-weather surface temperature is constantly lower than the ambient temperature under the condition of the vertical incidence of sunlight. Compared with the white passive radiation refrigeration coating, the coating can realize colored appearance and ensure aesthetic requirements; compared with the color gray paint prepared by pigment particles, the color gray paint does not introduce other absorption except the visible light wave band, so the whole reflectivity is higher, and the passive radiation refrigeration effect can be ensured.
Therefore, the embodiment of the invention realizes the equal-proportion uniform absorption of the whole wave band of visible light of 400 to 700nm through the silicone-acrylic emulsion, the high-reflection filler, the nano silicon oxide, the hollow glass beads, the auxiliary agent, the organic solvent and the gray composite dye which selectively absorbs the visible light of 400 to 700nm, simultaneously realizes the gray appearance without absorption of other wave bands, and gives consideration to the aesthetic requirements and the requirement on the reflectivity of realizing passive radiation refrigeration.
Further, the grey passive radiation refrigeration material comprises the following components in percentage by mass: 20 to 25 percent of silicone-acrylic emulsion, 55 to 65 percent of high-reflection filler, 1.0 to 1.5 percent of nano silicon oxide, 2.0 to 2.5 percent of hollow glass bead, 3 to 4 percent of auxiliary agent, 1.8 to 1.95 percent of organic solvent and 0.05 to 0.2 percent of gray composite dye selectively absorbing visible light waves of 400 to 700nm.
Further, the gray composite dye selectively absorbing 400 to 700nm visible light waves is prepared by overlapping a plurality of red, yellow and blue three primary colors dyes with spectrum selectivity or compounding a yellow dye and a metachromatic purple dye.
For the former, the yellow dye can absorb blue-violet light with a peak near 450nm, the yellow dye can absorb yellow-green light with a peak near 550nm, and the blue dye can absorb red light with a peak near 650nm, so that uniform high-proportion absorption of visible light wave bands is realized, and black is presented. In the latter case, the violet dye itself has a high absorption for visible light of 500nm or less, and the addition of the yellow dye introduces absorption in the wavelength range of 400 to 500nm, thereby realizing absorption in the entire visible light wavelength range.
Further, the organic solvent comprises one or more of N, N-dimethylformamide, dimethyl sulfoxide and ethanol.
Further, the secondary violet dye comprises one of Lanxess MACROLEX 3R anthraquinone dye violet and Clariant Savinyl R acid violet;
the red, yellow and blue three-primary-color dyes comprise red dyes, yellow dyes and blue dyes;
the Red dye comprises one of a visible light spectrum selective metal complex Red dye, BASF Orosol Ciba Red, clariant Savinyl Fire Red GLS solvent Red 89, lanxess Macrolex dye Red, red fluorescent dye BASF Lumogen F Red 305 and Red 300 fluorescent Red;
the Yellow dye comprises one of metal complex dye BASF Orosol Ciba Yellow, monoazo dye BASF Orosol 251 orange, clariant Savinyl 2GLS 01 metal complex dye solvent Yellow 79, clariant Savinyl RLS Yellow high transparent dye solvent Yellow, BASF Lumogen F Yellow 083 fluorescent Huang Hexiang coumarin 6;
the Blue dye comprises one of metal complex Blue dye with visible light spectrum selectivity, BASF Orosol BL Blue, GL Blue, lanxess Macrolex solvent Blue and CLARIANT Solvaperm Blue 2B anthraquinone Blue.
Further, the high-reflection filler comprises one or more of nano barium sulfate and nano magnesium fluoride.
Furthermore, the auxiliary agent comprises a dispersing agent, a wetting agent, a defoaming agent, a thickening and leveling agent, an anti-settling agent and a film-forming auxiliary agent.
In a second aspect, an embodiment of the present invention provides a preparation method of the gray passive radiation refrigeration material, including:
uniformly dispersing the gray composite dye and an organic solvent to obtain a micromolecular dye solution;
adding the micromolecular dye solution into a part of silicone-acrylic emulsion for primary dispersion and uniform mixing to obtain pre-dispersion color paste;
adding the high-reflection filler, the nano silicon oxide, the hollow glass beads, the water, the dispersing agent, the wetting agent and the defoaming agent into the rest silicone-acrylate emulsion for secondary dispersion and uniform mixing to obtain a dispersion liquid;
and adding the pre-dispersing color paste into the dispersion liquid to carry out three-time dispersing and uniformly mixing, adding the thickening and leveling agent, the anti-settling agent and the film-forming assistant to carry out four-time dispersing and uniformly mixing after the three-time dispersing and uniformly mixing, and obtaining the gray passive radiation refrigeration material.
Further, the conditions of the primary dispersion and uniform mixing are as follows: stirring and dispersing at normal temperature, wherein the rotating speed is 500-1000 r/min, and the stirring time is 20-30min;
the conditions for secondary dispersion and uniform mixing are as follows: stirring and dispersing at normal temperature and normal pressure, wherein the stirring speed is 1500-2000 r/min, and the stirring time is 2h;
the conditions for dispersing and uniformly mixing for the third time are as follows: continuously stirring for 1h at normal temperature and normal pressure, wherein the stirring speed is 1500-2000 r/min;
the conditions for dispersing and uniformly mixing for four times are as follows: the stirring speed is 500r/min, and the stirring time is 30-60 min.
The preparation method further ensures the combination and the dispersity of the dye micromolecules in the whole coating film-forming phase material through the sequence of pre-dissolving and color mixing, pre-dispersing and orderly adding, ensures the color uniformity and avoids unnecessary color cast and color difference.
The color matching method of the gray coating provided by the embodiment of the invention has the advantages of simple process and good dispersibility. The gray paint has adjustable color, and the corresponding color gray refrigeration paint can be obtained by adjusting the content of a certain dye. The color mixing method is simple and accurate, and the color gray with smaller color deviation value can be prepared and produced by mixing the gray color paste without color deviation in advance and then adding a trace amount of other color pastes.
In a third aspect, embodiments of the present invention provide a use of a gray passive radiation refrigeration material as a coating.
Example 1
The gray passive radiation refrigeration coating provided by the embodiment of the invention comprises the following components in percentage by mass: 65% of high-reflection filler (wherein the barium sulfate is 60%, and the magnesium fluoride is 5%), 1.0% of nano silicon oxide, 2.0% of hollow glass microsphere, 20% of silicone-acrylic emulsion, 3% of auxiliary agent, 7% of water, 0.5% of DMF (dimethyl formamide), 0.5% of DMSO (dimethyl sulfoxide), and 0.8% of ethanol; the gray color paste is prepared by compounding red, yellow and blue dyes with the following proportions: metal complex dye BASF Orosol yellow 0.08%, metal complex BASF Orosol BL blue 0.05%, clariant Savinyl Fire Red GLS solvent Red 89.07%. The specific operation steps are as follows:
1) Weighing a solvent according to the formula amount, placing the solvent into a conical flask, weighing a dye according to the formula amount, sequentially adding the dye into the solvent, magnetically stirring at normal temperature, wherein the stirring speed is 500-800 r/min, the stirring time is 2 hours, and preparing a dye micromolecule solution after the dye is completely dissolved;
2) Adding the dye solution into a silicone-acrylic emulsion weighed according to 10% of the formula amount, putting the mixture into a small dispersion kettle, stirring at normal temperature at the stirring speed of 500-1000 r/min for 20-30min, and preparing a pre-dispersion emulsion color paste;
3) Weighing the rest silicone-acrylic emulsion according to the formula amount, putting the silicone-acrylic emulsion into a dispersion kettle, continuously weighing the high-reflection filler, the nano silicon oxide, the hollow glass beads, the water and the auxiliaries except the thickening and leveling agent, the film-forming auxiliary and the anti-settling agent according to the formula amount, sequentially adding the materials into the dispersion kettle, stirring and dispersing at normal temperature and normal pressure, wherein the stirring speed is 1500-2000 r/min, and the stirring time is 2 hours, so as to prepare high-reflection white coating slurry;
4) Slowly adding the pre-dispersed emulsion color paste in the step 2 into the high-reflection white coating slurry prepared in the step 3, and continuously stirring for 1h at the stirring speed of 1500-2000 r/min;
5) Adding the thickening and leveling agent, the film forming aid and the anti-settling agent according to the formula amount, reducing the rotating speed to 500r/min, continuously stirring at a low speed for 30-60 min, discharging and packaging.
Example 2
The gray passive radiation refrigeration coating comprises the following components in percentage by mass: 65% of high-reflection filler (wherein the barium sulfate is 60%, and the magnesium fluoride is 5%), 1.0% of nano silicon oxide, 2.0% of hollow glass beads, 20% of silicone-acrylic emulsion, 3% of auxiliary agent, 7% of water, 0.5% of DMF (dimethyl formamide), 0.5% of DMSO (dimethyl sulfoxide), 0.8% of ethanol, and gray color paste is prepared by compounding a violet dye of a metachromatic system and a yellow dye for extinction, and the mixture ratio is as follows: the metal complex dye BASF Orosol Ciba yellow 0.02%, lanxess Macrolex 3R anthraquinone dye Violet 0.18%. The specific operation steps are as follows:
6) Weighing a solvent according to the formula amount, placing the solvent into a conical flask, weighing a dye according to the formula amount, sequentially adding the dye into the solvent, magnetically stirring at normal temperature, wherein the stirring speed is 500-800 r/min, the stirring time is 2 hours, and preparing a dye micromolecule solution after the dye is completely dissolved;
7) Adding the dye solution into a silicone-acrylic emulsion weighed according to 10% of the formula amount, putting the mixture into a small dispersion kettle, stirring at normal temperature at the stirring speed of 500-1000 r/min for 20-30min, and preparing a pre-dispersion emulsion color paste;
8) Weighing the rest silicone-acrylic emulsion according to the formula amount, putting the silicone-acrylic emulsion into a dispersion kettle, continuously weighing the high-reflection filler, the nano silicon oxide, the hollow glass beads, the water and the auxiliaries except the thickening and leveling agent, the film-forming auxiliary and the anti-settling agent according to the formula amount, sequentially adding the materials into the dispersion kettle, stirring and dispersing at normal temperature and normal pressure, wherein the stirring speed is 1500-2000 r/min, and the stirring time is 2 hours, so as to prepare high-reflection white coating slurry;
9) Slowly adding the pre-dispersed emulsion color paste obtained in the step 2 into the high-reflection white coating slurry obtained in the step 3, and continuously stirring for 1h at the stirring speed of 1500-2000 r/min;
10 Adding a thickening and leveling agent, a film-forming assistant and an anti-settling agent according to the formula amount, reducing the rotating speed to 500r/min, continuing stirring at a low speed for 30-60 min, discharging and packaging.
Gray radiation refrigeration coating optical and refrigeration effect test
And (3) testing optical performance: the prepared gray passive radiation refrigeration coating is sprayed on a smooth aluminum plate and a fiber cement plate of 3 cm X3 cm, and the solar spectral reflectivity and the infrared emissivity of the coating are respectively measured by an ultraviolet/visible light/near infrared spectrophotometer (Pekin-Elmer Lambda 950) and an integrated infrared radiance tester (AE 1, devices & Services Co., dallas, TX).
And (3) testing the refrigeration effect: uniformly spraying the gray passive radiation refrigeration coating on a smooth square aluminum plate with the width of 30cm and the thickness of 1mm by using a spraying machine, wherein a contact thermocouple is adhered to the back surface of the aluminum plate and used for testing the temperature of the lower surface of the aluminum plate sprayed with the coating; the thermocouple was connected to a daily LR8431 multichannel data recorder for recording the temperature data of the sample plate. The sample plate was placed on a heat-insulated box consisting of vacuum insulation panels of 5cm thickness to insulate the ground from conductive heat transfer from the surrounding environment. The upper edge of the box body is 2cm higher than the sample plate, and partial air convection heat transfer is isolated. The thermocouples were placed in a white louvre (fig. 1) to measure ambient air temperature, and the data was similarly transmitted and recorded on a day LR8431 multichannel data recorder. In fig. 1, a louver 1, a test box 2, and a sample plate 3 are shown.
Test results and analysis
Results and analysis of example 1
Referring to fig. 2, the gray passive radiation refrigeration coating of example 1 has a total infrared radiance of 92% and a total solar reflectance of 90.7%, the coating absorbs in a range of 360 to 590nm, an absorption peak range of 370 to 545nm, the absorption peak intensity is relatively uniform (about 72 to 74%), and the coating is light gray without color cast; compared with a white refrigeration coating, the gray coating of the embodiment has no other absorption in ultraviolet and near infrared bands, and the total introduced solar absorption is less, so that the extremely high reflectivity is still maintained. As can be seen from fig. 3, under the condition of sunlight vertical incidence in the daytime (11 to 15).
Results and analysis of example 2
Referring to fig. 4, the gray passive radiation refrigeration coating of example 2 has an overall infrared radiance of 92% and an overall solar reflectance of 91.4%, and the coating absorbs in a range of 388 to 678nm, has an absorption peak in a range of 470 to 570nm, and has a relatively uniform absorption peak intensity (about 74 to 76%); due to the existence of an absorption peak in a red light wave band of 570nm, the appearance of the paint is in bluish light gray; the grey coating of this example has no other absorption in the ultraviolet and near infrared bands, and overall introduces less solar absorption, yet maintains extremely high reflectivity. As can be seen from fig. 5, the slightly bluish light gray passive radiation refrigeration coating demonstrated in example 2 is constantly below ambient air temperature at all times. The surface temperature of the coating can be up to 2.1 ℃ below the ambient temperature in the daytime under the condition of vertical incidence of sunlight, and can be up to about 5 ℃ below the ambient temperature at night. The absorption of the gray refrigeration coating in a visible light wave band causes that a part of heat is accumulated under daytime illumination, so that the surface temperature is increased, and the refrigeration effect is reduced; when no light is emitted at night, the coating layer keeps obvious radiation refrigeration effect lower than the ambient temperature due to high infrared emissivity.
Example 3
The embodiment of the invention provides a gray passive radiation refrigeration material which comprises the following components in parts by mass: 20% of silicone-acrylic emulsion, 65% of high-reflection filler, 1.0% of nano silicon oxide, 2.0-2.5% of hollow glass microsphere, 3% of auxiliary agent, 1.8% of organic solvent and 0.05% of gray composite dye selectively absorbing 400-700nm visible light waves.
The gray composite dye selectively absorbing 400 to 700nm visible light waves is prepared by superposing a plurality of spectrally selective red, yellow and blue three-primary-color dyes or compounding a yellow dye and a secondary-color purple dye.
The organic solvent comprises one or more of N, N-dimethylformamide, dimethyl sulfoxide and ethanol.
The metachromatic violet dye comprises one of Lanxess MacroLEX 3R anthraquinone dye violet and Clariant Savinyl R acid violet;
the red, yellow and blue three-primary-color dyes comprise red dyes, yellow dyes and blue dyes;
the Red dye comprises one of a visible light spectrum selective metal complex Red dye, BASF Orosol Ciba Red, clariant Savinyl Fire Red GLS solvent Red 89, lanxess Macrolex dye Red, red fluorescent dye BASF Lumogen F Red 305 and Red 300 fluorescent Red;
the Yellow dye comprises one of metal complex dye BASF Orosol Ciba Yellow, monoazo dye BASF Orosol 251 orange, clariant Savinyl 2GLS 01 metal complex dye solvent Yellow 79, clariant Savinyl RLS Yellow high-transparency dye solvent Yellow, BASF Lumogen F Yellow 083 fluorescent Huang Hexiang soy 6;
the Blue dye comprises one of metal complex Blue dye with visible light spectrum selectivity, BASF Orosol BL Blue, GL Blue, lanxess Macrolex solvent Blue and CLARIANT Solvaperm Blue 2B anthraquinone Blue.
The high-reflection filler comprises one or more of nano barium sulfate and nano magnesium fluoride.
The auxiliary agent comprises a dispersing agent, a wetting agent, a defoaming agent, a thickening and leveling agent, an anti-settling agent and a film-forming auxiliary agent.
The preparation method of the grey passive radiation refrigeration material comprises the following steps:
uniformly dispersing the gray composite dye and an organic solvent to obtain a micromolecular dye solution;
adding the micromolecular dye solution into a part of silicone-acrylate emulsion for primary dispersion and uniform mixing to obtain pre-dispersion color paste; the conditions of primary dispersion and uniform mixing are as follows: stirring and dispersing at normal temperature, wherein the rotating speed is 500r/min, and the stirring time is 20min;
adding the high-reflection filler, the nano silicon oxide, the hollow glass beads, the water, the dispersing agent, the wetting agent and the defoaming agent into the rest of the silicone-acrylate emulsion for secondary dispersion and uniform mixing to obtain a dispersion liquid; the conditions of secondary dispersion and uniform mixing are as follows: stirring and dispersing at normal temperature and normal pressure, wherein the stirring speed is 2000r/min, and the stirring time is 2h; the conditions for three times of dispersing and uniformly mixing are as follows: continuously stirring for 1h at normal temperature and normal pressure, wherein the stirring speed is 1500r/min;
adding the pre-dispersion color paste into the dispersion liquid to carry out three-time dispersion and uniform mixing, adding the thickening and leveling agent, the anti-settling agent and the film-forming assistant after the three-time dispersion and uniform mixing to carry out four-time dispersion and uniform mixing to obtain the gray passive radiation refrigeration material, wherein the four-time dispersion and uniform mixing conditions are as follows: the stirring speed is 500r/min, and the stirring time is 30min.
Example 4
The embodiment of the invention provides a gray passive radiation refrigeration material which comprises the following components in parts by mass: 25% of silicone-acrylic emulsion, 55% of high-reflection filler, 1.5% of nano silicon oxide, 2.5% of hollow glass bead, 4% of auxiliary agent, 1.8-1.95% of organic solvent and 0.2% of gray composite dye selectively absorbing 400-700nm visible light waves.
The gray composite dye selectively absorbing 400 to 700nm visible light waves is prepared by superposing a plurality of spectrally selective red, yellow and blue three-primary-color dyes or compounding a yellow dye and a secondary-color purple dye.
The organic solvent comprises one or more of N, N-dimethylformamide, dimethyl sulfoxide and ethanol.
The metachromatic violet dye comprises one of Lanxess Macrolex 3R anthraquinone dye violet and Clariant Savinyl R acid violet;
the red, yellow and blue three-primary-color dyes comprise red dyes, yellow dyes and blue dyes;
the Red dye comprises one of a visible light spectrum selective metal complex Red dye, BASF Orosol Ciba Red, clariant Savinyl Fire Red GLS solvent Red 89, lanxess Macrolex dye Red, red fluorescent dye BASF Lumogen F Red 305 and Red 300 fluorescent Red;
the Yellow dye comprises one of metal complex dye BASF Orosol Ciba Yellow, monoazo dye BASF Orosol 251 orange, clariant Savinyl 2GLS 01 metal complex dye solvent Yellow 79, clariant Savinyl RLS Yellow high transparent dye solvent Yellow, BASF Lumogen F Yellow 083 fluorescent Huang Hexiang coumarin 6;
the Blue dye comprises one of metal complex Blue dye with visible light spectrum selectivity, BASF Orosol BL Blue, GL Blue, lanxess Macrolex solvent Blue and CLARIANT Solvaperm Blue 2B anthraquinone Blue.
The high-reflection filler comprises one or more of nano barium sulfate and nano magnesium fluoride.
The auxiliary agent comprises a dispersing agent, a wetting agent, a defoaming agent, a thickening and leveling agent, an anti-settling agent and a film-forming auxiliary agent.
The preparation method of the grey passive radiation refrigeration material comprises the following steps:
uniformly dispersing the gray composite dye and an organic solvent to obtain a micromolecular dye solution;
adding the micromolecular dye solution into a part of silicone-acrylate emulsion for primary dispersion and uniform mixing to obtain pre-dispersion color paste; the conditions of primary dispersion and uniform mixing are as follows: stirring and dispersing at normal temperature, wherein the rotating speed is 1000r/min, and the stirring time is 30min;
adding the high-reflection filler, the nano silicon oxide, the hollow glass beads, the water, the dispersing agent, the wetting agent and the defoaming agent into the rest silicone-acrylate emulsion for secondary dispersion and uniform mixing to obtain a dispersion liquid; the conditions of secondary dispersion and uniform mixing are as follows: stirring and dispersing at normal temperature and normal pressure, wherein the stirring speed is 2000r/min, and the stirring time is 2h; the conditions for three times of dispersing and uniformly mixing are as follows: continuously stirring for 1h at normal temperature and normal pressure, wherein the stirring speed is 2000r/min;
adding the pre-dispersion color paste into the dispersion liquid to carry out three-time dispersion and uniform mixing, adding the thickening and leveling agent, the anti-settling agent and the film-forming assistant after the three-time dispersion and uniform mixing to carry out four-time dispersion and uniform mixing to obtain the gray passive radiation refrigeration material, wherein the four-time dispersion and uniform mixing conditions are as follows: the stirring speed is 500r/min, and the stirring time is 60min.
Example 5
The embodiment of the invention provides a gray passive radiation refrigeration material which comprises the following components in parts by mass: 22% of silicone-acrylic emulsion, 60% of high-reflection filler, 1.2% of nano silicon oxide, 2.2% of hollow glass microsphere, 3.5% of auxiliary agent, 1.9% of organic solvent and 0.1% of gray composite dye selectively absorbing visible light waves of 400 to 700nm.
The gray composite dye selectively absorbing 400 to 700nm visible light waves is prepared by overlapping a plurality of spectrally selective red, yellow and blue three-primary-color dyes or compounding a yellow dye and a secondary color purple dye.
The organic solvent comprises one or more of N, N-dimethylformamide, dimethyl sulfoxide and ethanol.
The metachromatic violet dye comprises one of Lanxess Macrolex 3R anthraquinone dye violet and Clariant Savinyl R acid violet;
the red, yellow and blue three-primary-color dyes comprise red dyes, yellow dyes and blue dyes;
the Red dye comprises one of a visible light spectrum selective metal complex Red dye, BASF Orosol Ciba Red, clariant Savinyl Fire Red GLS solvent Red 89, lanxess Macrolex dye Red, red fluorescent dye BASF Lumogen F Red 305 and Red 300 fluorescent Red;
the Yellow dye comprises one of metal complex dye BASF Orosol Ciba Yellow, monoazo dye BASF Orosol 251 orange, clariant Savinyl 2GLS 01 metal complex dye solvent Yellow 79, clariant Savinyl RLS Yellow high transparent dye solvent Yellow, BASF Lumogen F Yellow 083 fluorescent Huang Hexiang coumarin 6;
the Blue dye comprises one of metal complex Blue dye with visible light spectrum selectivity, BASF Orosol BL Blue, GL Blue, lanxess Macrolex solvent Blue and CLARIANT Solvaperm Blue 2B anthraquinone Blue.
The high-reflection filler comprises one or more of nano barium sulfate and nano magnesium fluoride.
The auxiliary agent comprises a dispersing agent, a wetting agent, a defoaming agent, a thickening and leveling agent, an anti-settling agent and a film-forming auxiliary agent.
The preparation method of the grey passive radiation refrigeration material comprises the following steps:
uniformly dispersing the gray composite dye and an organic solvent to obtain a micromolecular dye solution;
adding the micromolecular dye solution into a part of silicone-acrylate emulsion for primary dispersion and uniform mixing to obtain pre-dispersion color paste; the conditions of primary dispersion and uniform mixing are as follows: stirring and dispersing at normal temperature, wherein the rotating speed is 800r/min, and the stirring time is 25min;
adding the high-reflection filler, the nano silicon oxide, the hollow glass beads, the water, the dispersing agent, the wetting agent and the defoaming agent into the rest silicone-acrylate emulsion for secondary dispersion and uniform mixing to obtain a dispersion liquid; the conditions of secondary dispersion and uniform mixing are as follows: stirring and dispersing at normal temperature and normal pressure, wherein the stirring speed is 1700r/min, and the stirring time is 2h; the conditions for three times of dispersing and uniformly mixing are as follows: continuously stirring for 1h at normal temperature and normal pressure, wherein the stirring speed is 1800r/min;
adding the pre-dispersion color paste into the dispersion liquid to carry out three-time dispersion and uniform mixing, adding the thickening and leveling agent, the anti-settling agent and the film-forming assistant after the three-time dispersion and uniform mixing to carry out four-time dispersion and uniform mixing to obtain the gray passive radiation refrigeration material, wherein the four-time dispersion and uniform mixing conditions are as follows: the stirring speed is 500r/min, and the stirring time is 40min.
Therefore, the gray passive radiation refrigeration coating disclosed by the embodiment of the invention has higher solar reflectivity, can be used as a refrigeration coating with a single structure, and can also be used in combination with a high-reflection base coat. The production and preparation process is simple and easy to construct. The development and application of the invention further develop the passive radiation refrigeration coating technology, can well meet the special application in the aspects of industry, civil use, military industry and the like which take refrigeration and aesthetic/camouflage requirements into consideration, and has good application prospect and economic benefit.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A gray passive radiation refrigeration material, which is characterized by comprising the following components: the paint comprises a silicone-acrylic emulsion, a high-reflection filler, nano silicon oxide, hollow glass beads, an auxiliary agent, an organic solvent and a gray composite dye which selectively absorbs visible light waves of 400 to 700nm, wherein the high-reflection filler is a compound with a wide band gap.
2. The grey passive radiation refrigeration material according to claim 1, comprising the following components in parts by mass: 20 to 25 percent of silicone-acrylic emulsion, 55 to 65 percent of high-reflection filler, 1.0 to 1.5 percent of nano silicon oxide, 2.0 to 2.5 percent of hollow glass bead, 3 to 4 percent of auxiliary agent, 1.8 to 1.95 percent of organic solvent and 0.05 to 0.2 percent of gray composite dye selectively absorbing visible light waves of 400 to 700nm.
3. The gray passive radiation refrigeration material as claimed in claim 1 or 2, wherein the gray composite dye selectively absorbing 400 to 700nm visible light waves is prepared by superposing a plurality of spectrally selective red-yellow-blue three primary colors dyes or is prepared by compounding a yellow dye and a secondary color purple dye.
4. The gray passive radiation refrigerant material of claim 3 wherein the organic solvent comprises one or more of N, N-dimethylformamide, dimethylsulfoxide and ethanol.
5. The gray passive radiation cooling material of claim 3, wherein the m-violet dye comprises one of Lanxess MACROLEX 3R anthraquinone dye violet and Clariant Savinyl R acid violet;
the red, yellow and blue three-primary-color dyes comprise red dyes, yellow dyes and blue dyes;
the Red dye comprises one of a visible light spectrum selective metal complex Red dye, BASF Orosol Ciba Red, clariant Savinyl Fire Red GLS solvent Red 89, lanxess Macrolex dye Red, red fluorescent dye BASF Lumogen F Red 305 and Red 300 fluorescent Red;
the Yellow dye comprises one of metal complex dye BASF Orosol Ciba Yellow, monoazo dye BASF Orosol 251 orange, clariant Savinyl 2GLS 01 metal complex dye solvent Yellow 79, clariant Savinyl RLS Yellow high-transparency dye solvent Yellow, BASF Lumogen F Yellow 083 fluorescent Huang Hexiang soy 6;
the Blue dye comprises one of metal complex Blue dye with visible light spectrum selectivity, BASF Orosol BL Blue, GL Blue, lanxess Macrolex solvent Blue and CLARIANT Solvaperm Blue 2B anthraquinone Blue.
6. The gray passive radiation refrigeration material of claim 1 wherein the highly reflective filler comprises one or more of nanoscale barium sulfate and nanoscale magnesium fluoride.
7. The gray passive radiation refrigeration material of claim 1, wherein the adjuvants comprise a dispersant, a wetting agent, a defoamer, a thickener leveling agent, an antisettling agent and a film forming adjuvant.
8. A method for preparing a gray passive radiation refrigeration material as claimed in any one of claims 1 to 7, comprising:
dispersing and uniformly mixing the gray composite dye and an organic solvent to obtain a micromolecular dye solution;
adding the micromolecular dye solution into a part of silicone-acrylate emulsion for primary dispersion and uniform mixing to obtain pre-dispersion color paste;
adding the high-reflection filler, the nano silicon oxide, the hollow glass beads, the water, the dispersing agent, the wetting agent and the defoaming agent into the rest silicone-acrylate emulsion for secondary dispersion and uniform mixing to obtain a dispersion liquid;
and adding the pre-dispersing color paste into the dispersion liquid to carry out three-time dispersing and uniformly mixing, adding the thickening and leveling agent, the anti-settling agent and the film-forming assistant to carry out four-time dispersing and uniformly mixing after the three-time dispersing and uniformly mixing, and obtaining the gray passive radiation refrigeration material.
9. The method for preparing the gray passive radiation refrigerating material according to claim 8, wherein the conditions for primary dispersion and uniform mixing are as follows: stirring and dispersing at normal temperature, wherein the rotating speed is 500-1000 r/min, and the stirring time is 20-30min;
the conditions for secondary dispersion and uniform mixing are as follows: stirring and dispersing at normal temperature and normal pressure, wherein the stirring speed is 1500-2000 r/min, and the stirring time is 2 hours;
the conditions for dispersing and uniformly mixing for the third time are as follows: continuously stirring for 1h at normal temperature and normal pressure, wherein the stirring speed is 1500-2000 r/min;
the conditions for dispersing and uniformly mixing for four times are as follows: the stirring speed is 500r/min, and the stirring time is 30-60 min.
10. Use of the grey passive radiation refrigeration material according to any of claims 1 to 7 or of the grey passive radiation refrigeration material prepared by the preparation method according to any of claims 8 to 9 as a coating.
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