Patent ID: 12210146

DETAILED DESCRIPTION

Referring now toFIG.1A, some aspects of the disclosed subject matter include a structured material100including a substrate102and a polymer layer104. In some embodiments, substrate102is a building material, glass, plastic, metal, textile, siding, roofing, decking, or combinations thereof. In some embodiments, substrate102is light-permeable. In some embodiments, substrate102is flexible. In some embodiments, polymer layer104is a porous structured polymer layer including a plurality of voids106. In some embodiments, polymer layer104is freestanding and/or self-supporting. In some embodiments, polymer layer104is flexible. Polymer layer104has a high hemispherical reflectance of light in the solar wavelengths, i.e., about 0.35 micrometers to about 2.5 micrometers. In some embodiments, the hemispherical reflectance of polymer layer104is from about 50% to about 99% in the solar wavelengths. In some embodiments, the hemispherical reflectance of polymer layer104is from about 78 to 95%, from about 81% to about 93%, from about 83% to about 90%, from about 85% to about 89%, or about 87% in the solar wavelengths. Polymer layer104also has a high hemispherical emittance in the thermal wavelengths, i.e., greater than about 7 micrometers). In some embodiments, the hemispherical thermal emittance of polymer layer104is at least about 75% for radiation having a wavelength from about 8 to about 13 micrometers or longer. In some embodiments, the hemispherical thermal emittance of polymer layer104is at least about 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or even about 99% for radiation having a wavelength from about 8 to about 13 micrometers or longer. In some embodiments, polymer layer104has a hemispherical reflectance from about 50% to about 99% and a hemispherical thermal emittance of at least about 75%. In some embodiments, polymer layer104has a hemispherical reflectance from about 75% to about 99% and a hemispherical thermal emittance of at least about 75%. Referring now toFIG.1B, in some embodiments, polymer layer104has a bright white appearance under typical lighting conditions. Polymer layer104effectively scatters light ranging from the solar to thermal wavelengths. For example, in the solar wavelengths (e.g., 0.35-2.5 micrometers), where the polymer has negligible intrinsic absorption, this may result in back-scattering and high reflectivity, which can result in a white appearance of the film. At the same time, in the thermal wavelengths (e.g., 2.5-40 micrometers) where the polymer is intrinsically absorptive or emissive, this can lead to a high absorbance (black appearance) or emittance (glowing appearance) for the film. The structure can also introduce a refractive index gradient and lower the effective refractive index of the layer for longer thermal wavelengths, reducing the reflection of light and further enhancing the absorbance or emittance. In some embodiments, polymer layer104includes a colorant, such as a dye or pigment. In some embodiments, the colorant is a visible dye, infrared reflective dye, visible pigment, infrared reflective pigment, or combinations thereof. In some embodiments, the colorant is one or a combination of sudan blue, brilliant blue FCF, unisol blue, indigo carmine, sudan yellow, yellow 5, hansa yellow, titanium dioxide white, zinc oxide white, paliogen black, and chromium iron oxide black. In some embodiments, the colorant absorbs only a desired wavelength of light, e.g., blue and green if red color is desired, or green and red if blue is desired, and not others. In some embodiments, the colorant does not absorb the infrared component of the solar wavelengths, i.e., 0.7 to 2.5 micron. In some embodiments, polymer layer104includes additives to enhance mechanical strength. Referring now toFIG.1C, in some embodiments, polymer layer104has an additional top-coating108. In some embodiments, top-coating108includes one or more colorants. In some embodiments, top-coating108includes a material that provides protection from weather or moisture. Referring now toFIG.1D, in some embodiments, polymer layer104is deployed as a coating104A on substrates, e.g., copper, as a freestanding sheet104B suitable for use as fabrics or tarpaulins, or combinations thereof.

In some embodiments, polymer layer104includes poly(vinylidene difluoride), poly(vinylidene difluoride-co-hexafluoropropene), poly(methyl methacrylate), poly(vinyl chloride), poly(vinyl fluoride), poly(styrene), poly(dimethyl siloxane), poly(vinyl alcohol), ethyl-cellulose, methyl-cellulose, cellulose acetate, or combinations thereof. In some embodiments, polymer layer104has a thickness between 50 micrometers to 2 mm. In some embodiments, polymer layer104has a thickness between 200 micrometers to 400 micrometers. In some embodiments, voids106have cross-sectional dimensions of less than 2 micrometers. In some embodiments, voids106have cross-sectional dimensions between 20 nm to 700 nm. In some embodiments, voids106have cross-sectional dimensions between about 20 to about 700 nm, between about 30 to about 670 nm, between about 40 to about 630 nm, between about 60 to about 600 nm, between about 80 to about 580 nm, between about 100 to about 550 nm, between about 150 to about 520 nm, between about 180 to about 490 nm, between about 200 to about 470 nm, between about 220 to about 440 nm, between about 250 to about 410 nm, between about 270 to about 380 nm, between about 290 to about 350 nm, between about 310 to about 340 nm, or about 330 nm. In some embodiments, voids106have cross-sectional dimensions between 3 micrometers to 20 micrometers. In some embodiments, voids106have cross-sectional dimensions between 5 micrometers to about 10 micrometers. In some embodiments, voids106have cross-sectional dimensions of about 5 about 6 about 7 about 8 about 9 or about 10 In some embodiments, voids106have cross-sectional dimensions of less than 2 micrometers and between 3 micrometers to 20 micrometers. Without wishing to be bound by theory, relatively smaller voids, e.g., less than about 2 micrometers in cross-section) more efficiently scatter smaller wavelengths of radiation while larger voids, e.g., from about 3 to about 20 micrometers more efficiently scatter larger wavelengths, so a polymer layer104including both the smaller and larger voids106should lead to more efficient radiative cooling performance.

Referring now toFIG.2, high reflectance and thermal emittance was demonstrated for a poly(vinylidene difluoride-co-hexafluoropropene) foam film according to some embodiments of the present disclosure. The graph portrays the variation in spectral reflectance (i.e., [1−spectral emittance]) as a function of wavelength. As shown, the reflectance is high (>90%) in the solar wavelengths, i.e., about 0.35 micrometers to about 2.5 micrometers, and the emittance is high in the thermal wavelengths (i.e., greater than about 7 micrometers. This leads to an efficient radiative cooling performance for the film, as the film is reflective of solar radiation and also emits heat efficiently in the thermal wavelengths.

Referring now toFIG.3A, some embodiments of the present disclosure are directed to a method of forming a structured material. In some embodiments, at302, a mixture including polymers, a solvent, and a non-solvent is, e.g., made into a layer. At304A, the solvent is evaporated. Referring now toFIG.3B, in some embodiments, at304B, the solvent is diluted and/or diffused out by immersion in a reservoir containing the non-solvent, followed by removal of the mixture from the reservoir at3043. Referring again toFIG.3A, at306, the non-solvent is evaporated. In some embodiments, the non-solvent is evaporated306after the solvent is evaporated304. In some embodiments, after completion of the above-identified steps, a structured polymer layer including a plurality of voids disposed therein is produced. At308, the structured polymer layer is disposed on a substrate. In some embodiments, the mixture is disposed on the substrate, e.g., via spraying, painting, or dipping, and the steps302-308are each allowed to proceed in situ to apply the structured polymer layer to the substrate.

Without being bound to any particular theory, during the drying process, the solvent evaporates first, causing the polymer and the non-solvent to form separate phases. Eventually, the non-solvent also evaporates, leaving air in its place. The result is a layer of structured polymer, with the morphology and porosity of the layer being tunable by, e.g., the choices of polymer, molecular weight of the polymer, ambient temperature, solvent, and non-solvent and their mass ratios.

In some embodiments, the solvent includes acetone, tetrahydrofuran, methanol, ethanol, propanol, isopropanol, hexane, benzene, toluene, or combinations thereof. In some embodiments, the non-solvent includes water, methanol, ethanol, propanol, isopropanol, or combinations thereof. In some embodiments, the mass ratio of the solvent (X) to polymer (Y) to non-solvent (Z) in the mixture is X>0.5, 0.5<Y<1.25, and 0.5<Z<1.25. In some embodiments, the mass ratio of the solvent (X) to polymer (Y) to non-solvent (Z) in the mixture is X>4, 0.5<Y<1.25, and 0.5<Z<1.25. In some embodiments, the mass ratio of the solvent (X) to polymer (Y) to non-solvent (Z) in the mixture is X>6, 0.5<Y<1.25, and 0.5<Z<1.25.

Methods of the present disclosure advantageously provide a porous polymer layer that can be deposited on wide variety of substrates and has a large scattering of light, resulting in a reflective film. As the optical properties provided by the composition and the voids of the polymer layer provide high reflectance and emittance, the layers are particularly advantageous for cool-roof coatings, enabling surfaces coated by the film to stay cool, even under strong sunlight. The performance of the layers is also tunable via addition of visible and infrared dyes to change the spectral absorbance.

Although the disclosed subject matter has been described and illustrated with respect to embodiments thereof, it should be understood by those skilled in the art that features of the disclosed embodiments can be combined, rearranged, etc., to produce additional embodiments within the scope of the invention, and that various other changes, omissions, and additions may be made therein and thereto, without parting from the spirit and scope of the present invention.