Conventional textiles for personal cooling by active cooling techniques tend to be bulky, heavyweight, and expensive. For example, infrared-transparent textiles made of nanoporous polymer membranes feature high transparency (˜90%) in the mid-IR region, allowing radiative heat dissipation to the environment. However, they cannot realize sub-ambient cooling in the daytime with solar irradiation due to the inherent tradeoff between solar reflectance and mid-IR transparency. Solar-reflected and Infrared-emissive textile requires the addition of very high-concentration ceramic nanoparticles, which increases the cost and processing difficulty.
Over the past years, a broad variety of textiles for personal cooling have been explored, including:
Phase-change thermoregulation garment (U.S. Pat. Nos. 9,062,913B2; 3,950,789A)
Problem: This system storages cold energy by the use of the latent energy of the phase-change material. It should accumulate cold again after latent heat release. The application of phase-change material will lead to heavy weight and high cost.
Air-cooling or liquid-cooling garment (U.S. Pat. Nos. 9,204,674B2; 7,117,687B2)
Problem: The cooling system is equipped with air fans or water pumps. The garment is heavy, bulky, and expensive for daily use.
Portable vapor compression or thermoelectric system (US 20110048048A1; U.S. Pat. No. 6,915,641B2)
Problem: The total system is often very heavy. The system should be maintained horizontally to ensure the safe running of the compressor. The refrigerant is generally flammable (i.e., R290, R32) or harmful to the environment.
Infrared-transparent textile (US20190008217A1; US20190239586A1)
Problem: To maintain enough infrared transmittance, the thickness of the infrared-transparent textile is highly restricted to less than 150 μm. Solar heating blockage and structural toughness become challenging at this thickness level.
Solar-reflected and Infrared-emissive textile (WO2021203867A1)
Problem: The high solar reflection originates from the very high-concentration ceramic particles, which have a much higher cost than polymers. And the high-concentration particles also largely reduce the elongation of fibers.
Hence, there still exists the need for a convenient, effective, and low-cost personal cooling strategy.
Systems and methods of the present disclosure may provide numerous advantages over conventional fabric technology of the prior art, including the following:
Without wishing to be bound by any particular theory, there may be discussion herein of beliefs or understandings of underlying principles relating to the devices and methods disclosed herein. It is recognized that regardless of the ultimate correctness of any mechanistic explanation or hypothesis, an embodiment of the invention can nonetheless be operative and useful.
In an embodiment, a polymer-based composite fiber comprises a matrix (e.g., a continuous matrix) comprising one or more polymers; a plurality of voids formed in the continuous matrix; and a plurality of solid particles, each particle of the plurality of solid particles being disposed in a respective void of the plurality of voids; wherein each void of the plurality of voids has a respective long axis, each long axis being a line that extends through a longest dimension of the void; and wherein each long axis extends in a direction parallel to a length of the fiber.
In an embodiment, each void of the plurality of voids in the polymer-based composite fiber has an interior space, each interior space being isolated from an ambient environment. In an embodiment each void of the plurality of voids has a void interior surface, and wherein each particle of the plurality of solid particles is completely encapsulated by a respective void interior surface.
In an embodiment, each void has an aspect ratio of at least 3, the void aspect ratio being defined as the longest dimension of a respective void divided by a width of the void. In an embodiment, for each respective void of the plurality of voids, the width of the void is less than or equal to an effective diameter of the particle disposed within the void. In an embodiment, for each respective void, the particle is disposed in the void such that the particle divides the void into two separate sub-voids.
In an embodiment, each void may have a total volume defined as the volume of the empty space in the void plus the volume of the particle. In an embodiment, the total volume of each void may be at least two times the volume of the respective particle within the void. In an embodiment, the total volume of each void may be at least three times the volume of the respective particle within the void. In an embodiment, the total volume of each void is less than 1000 times the volume of the respective particle within the void. In an embodiment, the total volume of each void is less than 100 times the volume of the respective particle within the void. In an embodiment, the total volume of each void is less than 50 times the volume of the respective particle within the void.
In an embodiment, the diameter of the polymer-based composite fiber is selected from the range of 100 nm to 1000 microns. In an embodiment, the polymer-based composite fiber has a ratio of a weight of the plurality of particles to a weight of the continuous polymer matrix of 5% to 50%. In an embodiment, the polymer-based composite fiber has a ratio of a weight of the plurality of particles to a weight of the continuous polymer matrix of 5% to 65%.
In an embodiment, the polymer-based composite fiber has a porosity in the range of 10% to 50%. In an embodiment, the polymer-based composite fiber has a porosity in the range of 10% to 30%. In an embodiment, the polymer-based composite fiber has a porosity in the range of 10% to 20%.
In an embodiment, the plurality of solid particles comprises polyolefin and/or a mix of ceramic and/or metal oxide particles
In an embodiment, the plurality of solid particles comprises particles of: aluminium oxide (Al2O3), silicon dioxide (SiO2), barium sulfate (BaSO4), zinc oxide (ZnO), boron nitride (BN), yttrium oxide (Y2O3), zirconium oxide (ZrO2), titanium dioxide (TiO2), zinc sulfide (ZnS), magnesium oxide (MgO), and/or ytterbium oxide (Yb2O3).
In an embodiment, the plurality of solid particles comprises polyolefin particles having an effective diameter in the range of 30 to 5000 μm.
In an embodiment, the plurality of solid particles comprises particles having an effective diameter in the range of 0.1 to 100 μm.
In an embodiment, the linear density of the fiber is in the range of 1 denier to 200 denier and the diameter of the fiber is in the range of 10 to 1000 μm.
In an embodiment, the fiber has an aspect ratio of at least 10, the fiber aspect ratio being defined as the length of the fiber divided by a diameter of the fiber.
In an embodiment, a fabric may be assembled from the disclosed polymer-based composite fibers.
In an embodiment, a method of producing a solar reflective, polymer-based composite fiber comprises: mixing a plurality of particles and a polymer material at a preset ratio to prepare a composite master batch; heating the composite master batch in order to melt the polymer material of the composite master batch without melting the plurality of particles; forming the melted composite master batch into a precursor composite fiber, the precursor composite fiber comprising at least some of the plurality of particles surrounded by a continuous matrix of the polymer material; and drawing the precursor composite fiber, thereby forming the solar reflective, polymer-based composite fiber, wherein the drawing comprises: elongating the precursor composite fiber such that a plurality of voids are formed in the fiber via the particles in the fiber.
In an embodiment, the forming step comprises melt spinning the melted composite master batch to form the precursor composite fiber. In an embodiment, the heating step comprises heating the polymer to a temperature in the range of 100 to 400° C. In an embodiment, the drawing step comprises drawing the precursor composite fiber at a draw ratio in the range of of 2 to 6.
In an embodiment, the solar reflective, polymer-based composite fiber has an aspect ratio of at least 10, the fiber aspect ratio being defined as a length of the fiber divided by a diameter of the fiber; wherein each void of the plurality of voids has a respective long axis, each long axis being a line that extends through a longest dimension of the void; and wherein each long axis extends in a direction parallel to the length of the fiber
In an embodiment, a method of fabricating a cooling fabric comprises: producing a plurality of solar reflective, polymer-based composite; and weaving or knitting the solar reflective, polymer-based composite fibers into the cooling fabric.
Exemplary embodiments are illustrated in referenced figures of the drawings. It is intended that the embodiments and figures disclosed herein are to be considered illustrative rather than limiting.
In general, the terms and phrases used herein have their art-recognized meaning, which can be found by reference to standard texts, journal references and contexts known to those skilled in the art. The following definitions are provided to clarify their specific use in the context of the invention.
In an embodiment, a composition or compound of the invention, such as an alloy or precursor to an alloy, is isolated or substantially purified. In an embodiment, an isolated or purified compound is at least partially isolated or substantially purified as would be understood in the art. In an embodiment, a substantially purified composition, compound or formulation of the invention has a chemical purity of 95%, optionally for some applications 99%, optionally for some applications 99.9%, optionally for some applications 99.99%, and optionally for some applications 99.999% pure.
In the following description, numerous specific details of the devices, device components and methods of the present invention are set forth in order to provide a thorough explanation of the precise nature of the invention. It will be apparent, however, to those of skill in the art that the invention can be practiced without these specific details.
In one aspect, the present disclosure provides a polymer-based fiber with self-formed eye-like air pores and its preparation method for daytime passive radiative cooling fabric. The fabrication of the fiber in this invention follows the industrial production of commercial fibers. The pre-mixed master batch comprises one or more polymers and particulate (solid) additives. The mixture may be baked for more than 24 hours before spinning to completely remove moisture. After the melting spinning and lubricating process, partially oriented yarns, which have relatively low crystallinity and mechanical strength, are collected on the cone. Generally, partially oriented yarns are not well suited to be used for weaving or knitting directly. The partially oriented yarn may be drawn on differential speed rollers with heating functions to improve its crystallinity and mechanical strength. Thus, fully oriented yarns may be produced. After twisting, the yarns can be used to produce fabrics by knitting or weaving.
Air pores, or voids, may be self-formed around the solid particulate additives during the drawing process of the fibers. The composite structure of the fiber, including a continuous polymer matrix, dispersed solid particles, and air pores associated with the solid particles in the fibers produces a large scattering efficiency and scattering cross section in the solar wavelength range, which enables fibers to scatter incident sunlight effectively, even at a low concentration of solid particulate additive. As a result, the prepared fabric can have high solar reflectivity and emissivity in the atmospheric window, and realize all-day passive radiative cooling.
The fabrication of fibers of the present disclosure may include spinning, drawing, and twisting, followed by weaving or knitting to make fabrics. The pre-mixed master batch may include polymer and solid particulate additives. In the drawing process, polymers will transition from a hard and relatively brittle glassy state into a viscous or rubbery state at the temperature above their glass transition temperatures. When the tensile stress in the x-axis σx overcomes the weak Van der Waals force, the interface between the matrix and the nanoparticle separates and pores form around the particle (
The pore-forming process of this method may be simulated by physics simulation software such as COMSOL. A particle is placed in the center of a polymer fiber. The composite fiber is solid at the initial state (
A polyethylene terephthalate/barium sulfate (PET/BaSO4) porous fabric for all-day passive radiative cooling is prepared following the procedures mentioned above. The pre-mixed master batch comprises PET and ceramic nanoparticles. A PET/BaSO4 composite master batch was prepared with a BaSO4 concentration of 60% in weight (35% in volume). The composite master batch includes PET at a mass ratio of 1 to 2. The mixture should be baked for more than 24 hours before spinning to completely remove moisture. After the melting, spinning and lubricating process, partially oriented yarns, which have relatively low crystallinity and mechanical strength, are collected on the cone. Generally, partially oriented yarns are poorly suited for weaving or knitting directly. The partially oriented yarn may be drawn on differential speed rollers with heating functions to improve its crystallinity and mechanical strength. Then fully oriented yarns are yielded. After twisting, the yarns can be used to produce fabrics by knitting or weaving.
The density measurement of the as-spun fiber and the drawn fiber is based on Archimedes' principle. First, some cut fibers were weighed to get the mass. Next, the fibers were submerged in distilled water. Thus, the increased volume of the fibers in the water as compared to the water alone can be obtained, wherein the increase in volume equals the volume of the submerged fibers. Then the density of these fibers can be calculated. The densities of PET and BaSO4 are 1.38 g cm−3 and 4.5 g cm −3 respectively. So the density of the as-spun fiber (ρsolid) should be 1.55 g cm −3 by calculation, which is very close to the measured value of 1.52 g cm−3. The measured density of the drawn fiber (ρporous) is 1.31 g cm−3. Then the porosity ϕ of the drawn fiber can be calculated by
which is 15.6%.
The SEM images of melt-spinning fibers are shown in
Tensile tests of ten specimens were conducted by a universal testing machine. As shown in
Due to the internal structure of the fibers, including particles within voids within the fibers, the resulting fabric made from the fibers has a solar reflectivity of 92.0% (
Field tests were conducted to evaluate the cooling performance of the PET fabric using the same setup as in
Further, simulated human skin was used to evaluate the skin cooling performance of the fabric when worn on the body as clothing (
Durability of the solar reflecting property of the presently disclosed fibers was tested against washing, abrasion, bending, and UV exposure. As shown by the before and after tests of
All references throughout this application, for example patent documents including issued or granted patents or equivalents; patent application publications; and non-patent literature documents or other source material; are hereby incorporated by reference herein in their entireties, as though individually incorporated by reference, to the extent each reference is at least partially not inconsistent with the disclosure in this application (for example, a reference that is partially inconsistent is incorporated by reference except for the partially inconsistent portion of the reference).
The terms and expressions which have been employed herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments, exemplary embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims. The specific embodiments provided herein are examples of useful embodiments of the present invention and it will be apparent to one skilled in the art that the present invention may be carried out using a large number of variations of the devices, device components, methods steps set forth in the present description. As will be obvious to one of skill in the art, methods and devices useful for the present methods can include a large number of optional composition and processing elements and steps.
As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural reference unless the context clearly dictates otherwise. Thus, for example, reference to “a cell” includes a plurality of such cells and equivalents thereof known to those skilled in the art. As well, the terms “a” (or “an”), “one or more” and “at least one” can be used interchangeably herein. It is also to be noted that the terms “comprising”, “including”, and “having” can be used interchangeably. The expression “of any of claims XX-YY” (wherein XX and YY refer to claim numbers) is intended to provide a multiple dependent claim in the alternative form, and in some embodiments is interchangeable with the expression “as in any one of claims XX-YY.”
When a group of substituents is disclosed herein, it is understood that all individual members of that group and all subgroups, including any isomers, enantiomers, and diastereomers of the group members, are disclosed separately. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure. When a compound is described herein such that a particular isomer, enantiomer or diastereomer of the compound is not specified, for example, in a formula or in a chemical name, that description is intended to include each isomers and enantiomer of the compound described individual or in any combination. Additionally, unless otherwise specified, all isotopic variants of compounds disclosed herein are intended to be encompassed by the disclosure. For example, it will be understood that any one or more hydrogens in a molecule disclosed can be replaced with deuterium or tritium. Isotopic variants of a molecule are generally useful as standards in assays for the molecule and in chemical and biological research related to the molecule or its use. Methods for making such isotopic variants are known in the art. Specific names of compounds are intended to be exemplary, as it is known that one of ordinary skill in the art can name the same compounds differently.
Certain molecules disclosed herein may contain one or more ionizable groups [groups from which a proton can be removed (e.g., —COOH) or added (e.g., amines) or which can be quaternized (e.g., amines)]. All possible ionic forms of such molecules and salts thereof are intended to be included individually in the disclosure herein. With regard to salts of the compounds herein, one of ordinary skill in the art can select from among a wide variety of available counterions those that are appropriate for preparation of salts of this invention for a given application. In specific applications, the selection of a given anion or cation for preparation of a salt may result in increased or decreased solubility of that salt.
Every device, system, formulation, combination of components, or method described or exemplified herein can be used to practice the invention, unless otherwise stated.
Whenever a range is given in the specification, for example, a temperature range, a time range, or a composition or concentration range, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure. It will be understood that any subranges or individual values in a range or subrange that are included in the description herein can be excluded from the claims herein.
All patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the invention pertains. References cited herein are incorporated by reference herein in their entirety to indicate the state of the art as of their publication or filing date and it is intended that this information can be employed herein, if needed, to exclude specific embodiments that are in the prior art. For example, when composition of matter are claimed, it should be understood that compounds known and available in the art prior to Applicant's invention, including compounds for which an enabling disclosure is provided in the references cited herein, are not intended to be included in the composition of matter claims herein.
As used herein, “comprising” is synonymous with “including,” “containing,” or “characterized by,” and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, “consisting of” excludes any element, step, or ingredient not specified in the claim element. As used herein, “consisting essentially of” does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. In each instance herein any of the terms “comprising”, “consisting essentially of” and “consisting of” may be replaced with either of the other two terms. The invention illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations which is not specifically disclosed herein.
One of ordinary skill in the art will appreciate that starting materials, biological materials, reagents, synthetic methods, purification methods, analytical methods, assay methods, and biological methods other than those specifically exemplified can be employed in the practice of the invention without resort to undue experimentation. All art-known functional equivalents, of any such materials and methods are intended to be included in this invention. The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention that in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.
This application claims the benefit of priority to U.S. Provisional Patent Application No. 63/578,666, filed Aug. 25, 2023, which is hereby incorporated by reference in its entirety.
Number | Date | Country | |
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63578666 | Aug 2023 | US |