Water repellent polymer textiles

Abstract

Polymer substrates, such as textiles, with durable water repellent properties, and methods of manufacture thereof, are provided. Urethane and / or acrylic matrix containing coating compositions that impart durable water repellency are described. Composites that include a polymer substrate, a urethane and / or acrylic containing water repellent layer, and optionally a ceramic, are described.

Description

[0001] WATER REPELLENT POLYMER TEXTILES

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003]

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 721 ,926, filed on November 18, 2024, which is incorporated by reference herein in its entirety.

[0004] FIELD OF THE INVENTION

[0005]

[0002] The invention relates to water repellent polymer textiles and methods of manufacture thereof.

[0006] BACKGROUND

[0007]

[0003] Application of water repellent chemistries to fabrics to generate water repellent polymer textiles results in textiles which prevent water intrusion. Fluorine free chemistries have been developed, but often do not provide durable performance for multiple washing cycles or fouling by soils, oils, dirt and debris. New water repellent compositions with improved durability are needed.

[0008] BRIEF SUMMARY OF THE INVENTION

[0009]

[0004] Urethane matrix based and / or acrylic matrix based water repellent compositions and methods of making and applying these compositions to substrates, such as polymer substrates, for example, polymer textiles, are provided.

[0010]

[0005] In one aspect, a composite is provided. The composite includes: a polymer substrate, which includes a polymer matrix that has an external surface and an internal volume; and a water repellent urethane matrix and / or acrylic matrix containing functional layer on the external surface of the substrate polymer matrix. In some embodiments, the composite further includes a ceramic on the external surface of the polymer matrix and ceramic or inorganic elements at least partially occupy the internal volume of the polymer matrix. In some embodiments, a ceramic is deposited on the substrate, and then the water repellent functional layer is deposited over the ceramic.

[0011]

[0006] In some embodiments, the composite retains at least about 30% of its original thickness after 24 hours of continuous washing according to AATCC LP1-2021, Home Laundering: Machine Washing, and the water repellent layer contains less than 1% fluorine element. In some embodiments, the water repellent layer retains at least about 50% of its original silicon concentration [Si] after 24 hours of continuous washing according to AATCC LP1-2021 , Home Laundering: Machine Washing, and the water repellent layer contains less than 100 ppm fluorine element.

[0007] In some embodiments, more than 30% of the water repellent layer is block isocyanate derived urethane or acrylic matrix.

[0012]

[0008] In some embodiments, the water repellent layer includes both an acrylate rich region of about 10 nm to about 200 nm in thickness and a silicon rich region of about 2 nm to about 20 nm in thickness as measured by transmission electron microscopy (TEM). In some embodiments, the water repellent coating layer has a thickness of about 20 nm to about 50 nm, and wherein the silicon rich region has a peak silicon content of about 5 atomic percent to about 30 atomic percent. In some embodiments, the acrylate rich region is proximal to the external surface of the substrate and the silicon rich region is distal to the external surface of substrate. In some embodiments, an outermost region of about 25 nm of the water repellent layer includes silicon rich regions interspersed with acrylate rich regions. In some embodiments, the water repellent layer includes silicon rich regions interspersed within an acrylic matrix.

[0013]

[0009] In some embodiments, the water repellent layer includes calcium phosphate (Cax(PO4)yrich regions, wherein the concentration of calcium phosphate is greater than in the bulk material. In some embodiments, at least a portion of the calcium phosphate regions include lattice spacings of about 2.1 nm to about 1.9 nm as measured by Selective Area Electron Diffraction (SAED) or a Fourier Transform of a high-resolution transmission electron microscopy (HRTEM) Image. In some embodiments, at least a portion of the calcium phosphate domains are located proximal to the external surface of the substrate.

[0014]

[0010] In some embodiments, the water repellent layer includes a glycol ether.

[0015]

[0011] In some embodiments, the substrate is a ripstop textile or fabric. For example, the substrate may be a textile or fabric that includes synthetic fibers, wherein at least a portion of the urethane and / or acrylic structure lies within the synthetic fibers as measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS). In some embodiments, the substrate is a textile or fabric, wherein storage modulus as measured in warp and weft directions by dynamic mechanical analysis (DMA) is increased by about 1.1 to about 3.5 times in comparison to an identical textile or fabric that does not include the water repellent layer. In some embodiments, the substrate is a textile or fabric, wherein tensile modulus as measured in a warp direction by dynamic mechanical analysis (DMA) is increased by about 1.5 to about 3.0 times in comparison to an identical textile or fabric that does not include the water repellent layer. In some embodiments, the substrate is a textile or fabric, wherein storage modulus as measured on an axial surface by instrumented nanoindentation is increased by about 2.0 times to about 10.0 times at 10nm of contact depth in comparison to an identical textile or fabric that does not include the water repellent layer. In some embodiments, the substrate is a textile or fabric, wherein the composite is further processed to reduce the surface roughness or reduce the air permeability of the textile or fabric. In some embodiments, the substrate is a textile or fabric, wherein the composite is further processed to form an assembly by additional coating applications of urethanes or laminations to additional membrane materials to form a multilayer composite.

[0016]

[0012] In some embodiments, the composite is in the form of a fiber or a film with an applied urethane and / or acrylic matrix coating layer. For example, the substrate may be in the form of a polymer fiber with a mean diameter less than about 5 millimeters or less than about 1 millimeter and a urethane and / or acrylic matrix coating layer with a thickness of less than 500 nm. For example, the substrate may be in the form of a film with a mean thickness less than about 5 millimeters or less than about 3 millimeters and a urethane and / or acrylic matrix coating layer with a thickness of less than 500 nm.

[0017]

[0013] In some embodiments, ceramic is included in the composite. For example, the ceramic may include an alkali metal, or an alkaline earth metal. In some embodiments, the ceramic includes one or more of an oxide, a hydroxide, a phosphate, a layered double hydroxide, a sulfate, a carbonate, and an oxalate of an alkali metal, or an alkaline earth metal. In some embodiments, the ceramic includes one or more of manganese oxide, iron oxide, calcium carbonate, hydroxyapatite, calcium phosphate, calcium oxalate, magnesium carbonate, calcium sulfate, titanium oxysulfate, and magnesium sulfate.

[0018]

[0014] In some embodiments, the composite is in the form of a fiber, which may be formed into or incorporated into a textile. For example, the forming or incorporating the composite fibers into a textile may include knitting, weaving, bonding, or entangling of fibers, either chemically, mechanically, by applying heat or one or more solvent(s), or by other physical means.

[0019]

[0015] In some embodiments, the polymer matrix of the composite includes one or more of a polyester, a polyamide, a polyolefin, a substituted polyolefin, a polyurethane, a polyol, and a polyether. For example, the polymer matrix may include one or more of polyethylene terephthalate (PET), a nylon, polyethylene, polypropylene, polyvinyl chloride (PVC), polyvinyl alcohol (PVOH), polyvinyl acetate (PVAc), polyvinylpyrrolidone (PVP), and polyethylene glycol (PEG).

[0020]

[0016] In some embodiments, the polymer matrix of the composite includes one or more copolymer. For example, the polymer matrix may include one or more of polyetherpolyurea copolymer, a nylon copolymer such as a copolymer of nylon 12, nylon 6, nylon 6 / 6, and / or nylon 6 / 12, a copolyester, acrylonitrile butadiene styrene (ABS), styrene / butadiene co-polymer (SBR), nitrile rubber, styrene-acrylonitrile, styrene-isoprene- styrene (SIS) and ethylene-vinyl acetate (EVA), or other co-polymers, e.g., formed by chain-growth polymerization or step-growth polymerization.

[0021]

[0017] In another aspect, a chemical solution is provided for functionalization of substrates as described herein by immersion. In some embodiments, the chemical solution includes a non-fluorinated cationic acrylate copolymer emulsion, a blocked isocyanate crosslinker, and an organic solvent additive containing glycol, wherein the total solids content in the chemical solution is about 1% to about 5%. In some embodiments, the chemical solution includes a non-fluorinated cationic acrylate copolymer emulsion, a non-fluorinated silicone emulsion, a blocked isocyanate crosslinker, and an organic solvent additive containing glycol, wherein the total solids content in the chemical solution is about 1% to about 5%. In some embodiments, the ratio of silicone and acrylic to other added solids is about 0.5:1 to about 5: 1 and wherein the ratio of acrylic solids to silicone solids is about 1 : 1 to about 10:1.

[0022]

[0018] In another aspect, a method of manufacturing a composite as described herein is provided. The method includes: (a) contacting a polymer substrate with one or more functional chemicals that include urethane and / or acrylate groups and removing excess liquid; and (b) heating the functionalized polymer substrate produced in step (b) to a temperature sufficient to drive a crosslinking reaction within the functional layer, thereby generating a urethane matrix and / or acrylic matrix containing functional coating layer. In some embodiments, the substrate is cleaned prior to step (a), which improves overall uniform performance of the composite.

[0023]

[0019] In another aspect, a method of manufacturing a composite as described herein is provided. The method includes: (a) contacting a polymer substrate with at least one first solution comprising a metal salt ora metal-organic complex, and optionally, an oxidizing agent, an amine, ammonia, or other reactive precursor(s) (such as, but not limited to, a catalyst in a solvent), wherein the first solution is at least partially absorbed into the polymer matrix; (b) removing excess liquid from the polymer substrate; (c) contacting the polymer substrate with at least one second solution comprising a metal salt or a metalorganic complex, and optionally, an oxidizing agent, an amine, ammonia, or other reactive precursor(s) (such as, but not limited to, a catalyst in a solvent), wherein said solution is at least partially absorbed into the polymer matrix; (d) removing excess liquid from the polymer substrate; (e) heating to a temperature sufficient to remove the solvent from said polymer substrate, sufficient to drive a ceramic-forming reaction with the metal salt, or sufficient to decompose or react the metal-organic complex, thereby forming a polymerceramic composite; (f) contacting the polymer substrate treated with the first and second solutions produced in step (e) with one or more functional chemicals containing urethane and / or acrylate groups and removing excess liquid; and (g) heating the polymer-ceramic composite to a temperature sufficient to drive a crosslinking reaction, thereby generating a water repellent urethane and / or acrylic matrix containing functional layer. In some embodiments, the substrate is cleaned prior to step (a), which improves overall uniform performance of the composite.

[0024]

[0020] In some embodiments, the metal salt in step (a) may include one or more of an alkali metal nitrate, an alkaline earth metal nitrate, an alkali metal chloride, an alkaline earth metal chloride, an alkali metal sulfate, and an alkaline earth metal sulfate. In some embodiments, the metal-organic complex in step (a) may include a metal-amine complex. In some embodiments, the amine in step (a) may include a free amine.

[0025]

[0021] In some embodiments, the heating in step (b) may be at a temperature of about 70°C to about 170°C.

[0026]

[0022] In some embodiments, the functional chemicals that include urethane groups include a non-fluorinated cationic acrylate copolymer emulsion, a blocked isocyanate crosslinker, and an organic solvent or glycol additive. In some embodiments, the functional chemicals that include urethane groups include a non-fluorinated silicone emulsion, a blocked isocyanate crosslinker, and an organic solvent or glycol additive. In some embodiments, the functional chemicals that include urethane groups include a non-fluorinated cationic acrylate copolymer emulsion, a non-fluorinated cationic silicone emulsion, a blocked isocyanate crosslinker, and an organic solvent additive. In some embodiments, the blocked isocyanate crosslinker has a deblocking temperature of about 70°C to about 160°C, about 80°C to about 140°C, about 90°C to about 130°C.

[0027]

[0023] In some embodiments, the urethane functional layer may include a polymer chemistry, for example, with a mean thickness of about 20 nm to about 500 nm. The mean thickness of the functional layer is the distance from the external surface of the of the ceramic layer to the external thickness of the functional layer. For example, the functional layer chemistry may include a silane, siloxane, phosphonic acid, phosphonate, sulfonate, sulfonic acid, carboxylic acid, carboxylate, urethane, vinyl group, or acrylate, or a molecule with a head group and a tail group. In some embodiments, polymer chemistry includes a crosslinker molecule to improve mechanical and chemical properties. In some embodiments, the polymer chemistry includes a molecule with a head group and a tail group, wherein the head group includes a silane group, a phosphonate group, a phosphonic acid group, a carboxylic acid group, a vinyl group, an alcohol group, a hydroxide group, a thiolate group, a thiol group, and / or an ammonium group, and wherein the tail group includes a hydrocarbon group, a fluorocarbon group, a vinyl group, a phenyl group, an epoxide group, an acrylic group, an acrylate group, a hydroxyl group, a carboxylic acid group, a thiol group, and / or a quaternary ammonium group. For example, the head group may include an ammonium group, such as a quaternary ammonium group.

[0028]

[0024] In some embodiments, the urethane and / or acrylic matrix containing functional layer contains less than 1% fluorine element. In some embodiments, the urethane and / or acrylic matrix containing functional layer contains less than 0.1% [1000 ppm] or less than 0.01% [100 ppm] fluorine element.

[0029]

[0025] In some embodiments, the urethane and / or acrylic matrix containing functional layer has a block isocyanate derived urethane structure of more than about 30% or more than about 35% by volume. In some embodiments, the urethane and / or acrylic matrix containing functional layer has an acrylic matrix structure of more than about 30% or more than about 35% by volume. The water repellent functional layer may contain many urethane groups (R(-NH-CO-O)-)R) in the makeup of the layer. In some embodiments, the functional layer includes both an acrylate rich region of about 20 nm to about 200 nm in thickness and a silicon rich region of about 2 nm to about 20 nm thickness. Acrylate rich is defined as having a greater concentration of acrylate groups than the bulk sample and silicon rich is defined as having a greater concentration of silicon than the bulk sample. In some embodiments, the functional layer includes an acrylate rich region ( / .e., the concentration of acrylate groups is greater than in the bulk sample) adjacent to the substrate surface and a silicon rich region adjacent to the external surface of the functional layer. In some embodiments, the external surface of the functional layer includes silicon rich regions interspersed with acrylate rich regions. In some embodiments, the functional layer includes silicon rich regions interspersed within an acrylate matrix. In some embodiments, at least a portion of the urethane structure lies within the substrate as measured by TOF-SIMS.

[0030]

[0026] In some embodiments, the water repellent functional layer includes calcium / phosphate domains. In some embodiments, the water repellent functional layer includes Ca / P domains with at least a portion having lattice spacings of about 2.1 nm and about 1.9 nm. In some embodiments, at least a portion of the Ca / P domains are located adjacent to the substrate surface.

[0031]

[0027] In some embodiments, the mass of ceramic, as a percentage of mass of the total coating layer composition (ceramic plus water repellent urethane functional layer), is less than about 10%. In some embodiments, the ceramic contains less than about 10 grams per square meter of nominal geometric surface area of the coating layer composition.

[0028] In some embodiments, the water repellent functional layer has a thickness of less than about 500 nm and retains at least about 30% of its original thickness after 24 hours of continuous washing compliant with the AATCC LP1-2021, Home Laundering: Machine Washing, with washing under the Normal / Cotton Sturdy Washing Cycle, with a Group (III) Washing Temperature.

[0032]

[0029] In some embodiments, the silicon (Si) content of the water repellent functional layer (e.g., urethane- and / or acrylate-containing water repellent functional layer) is more than about 200 ppm or 150 ppm initially and retaining more than 50% of the initial value after 24 hours of continuous washing.

[0033]

[0030] In some embodiments, the chlorine (Cl) content of the water repellent functional layer (e.g., urethane- and / or acrylate-containing water repellent functional layer) is more than about 1000 ppm initially and more than about 500 ppm after 24 hours of continuous washing.

[0034]

[0031] In some embodiments, the water repellent functional layer (e.g., urethane- and / or acrylate-containing water repellent functional layer) has an increased storage modulus relative to the uncoated substrate material. In some embodiments, the storage modulus as measured by dynamic mechanical analysis, as measured in the warp and weft directions by dynamic mechanical analysis (DMA), is increased in comparison to uncoated substrate. In some embodiments, the storage modulus, as measured by dynamic mechanical analysis in the warp direction by dynamic mechanical analysis (DMA) is increased in comparison to uncoated substrate. In some embodiments, the storage or tensile moduli are measured by tensile testing, nanoindentation, or dynamic mechanical analysis.

[0035]

[0032] In some embodiments, at least a portion of the composite has a sessile drop water contact angle greater than about 90 degrees.

[0036]

[0033] In some embodiments, the polymer substrate is a textile material, a thin film, a laminate, or a combination thereof. In some embodiments, the polymer substrate is a textile material. In some embodiments, the substrate is a textile material that includes a polyamide, a polyester, a polyolefin, a substituted polyolefin, a polyurethane, a polyol, a vinyl, cotton, wool, a cellulosic material, or a combination thereof.

[0037]

[0034] In some embodiments, tear strength, tensile strength, gas permeability, vapor permeability, and / or abrasion resistance is improved relative to the polymer substrate. In some embodiments, tear strength, tensile strength, gas permeability, vapor permeability, and / or abrasion resistance is improved in comparison to an identical substrate that does not include the functional molecule. In some embodiments, the tear strength is greater than about 1000 gF.

[0035] In some embodiments, the water repellent functional layer additionally includes a siloxane, an acrylate, a phosphonate, a sulfonate, a urethane, or a combination thereof. In some embodiments, the functional coating layer further includes a silicone polymer, an alkyl-terminated silane, or an alkyl-terminated siloxane. In some embodiments, the functional coating layer further includes an alkyl-terminated functional group, such as, but not limited to, an alkyl- terminated functional group that includes an alkyl group greater than three carbon atoms. In some embodiments, the functional coating layer further includes an isocyanate or an isocyanate-terminated polymer.

[0038]

[0036] In some embodiments, the functional layer includes an additive. In some embodiments, the additive may include water or may include an alcohol, acetone, dimethyl carbonate, methyl acetate, tert-butyl acetate, propylene carbonate, acetic acid, methyl ethyl ketone, or mixtures thereof. In some embodiments, the additive includes an alcohol, such as, but not limited to, ethanol, methanol, isopropanol, butanol, isobutanol, propylene glycol, glycol ether, 2-ethylhexanol, 2-butoxyethanol, or mixtures thereof. In some embodiments, the functional layer additive includes one or more cosolvents. In some embodiments, the one or more cosolvents include an alcohol, a ketone, a dialkyl carbonate, an alkyl carboxylic acid, an alkyl ester of an alkyl carboxylic acid, an alkyl diol, an ether, or mixtures thereof. In some embodiments, the alcohol includes methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-butoxyethanol, 2- ethylhexanol, or mixtures thereof. In some embodiments, the alcohol includes methanol. In some embodiments, the ketone includes acetone and / or methyl ethyl ketone. In some embodiments, the dialkyl carbonate includes dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, or mixtures thereof. In some embodiments, the alkyl carboxylic acid includes formic acid, acetic acid, propionic acid, or mixtures thereof. In some embodiments, the alkyl ester of an alkyl carboxylic acid includes methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, sec-butyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, or mixtures thereof. In some embodiments, the alkyl diol includes ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, or mixtures thereof. In some embodiments, the ether includes tetrahydrofuran, ethylene glycol butyl ether [HO(CH2)2O(CH2)3CH3, 2-butoxyethanol, EGBE], diethylene glycol [HO(CH2)2O(CH2)2OH], diethylene glycol monobutyl ether, [2-(2-butoxyethoxy)ethan-1-ol, HO(CH2)2O(CH2)2O(CH2)3CH3, DEGBE], a diethylene glycol monoalkyl ether, HO(CH2)2O(CH2)2O(CH2)nCH3, where n = 0, 1 , 2, or 4, or mixtures thereof. In some embodiments, the ether includes EGBE. In some embodiments, the ether includes DEGBE. In some embodiments, the ether includes a mixture of EGBE and DEGBE.

[0037] In some embodiments in which the composite includes a ceramic, at least a portion of the ceramic is interconnected. In one embodiment, more than 50% of the ceramic on a particle basis is interconnected.

[0039]

[0038] In some embodiments in which the composite includes a ceramic, the ceramic includes crystalline domains, and in some embodiments, one or more of the crystalline domains include crystalline particles. In some embodiments, the crystalline domains are embedded in an amorphous matrix. For example, the amorphous matrix may contain at least two elements not including carbon, hydrogen, oxygen or nitrogen, that are present in the crystalline domains. In some embodiments, the amorphous matrix contains three common elements not including carbon, hydrogen, oxygen, or nitrogen, with the crystalline particles or crystalline domains. In some embodiments, the crystalline domains range in size from about 2nm in nominal dimension to about 200nm in nominal dimension. In some embodiments, the crystalline domains include an alkali metal, an alkaline earth metal, or a combination thereof, such as, but not limited to, Ca, Li, Mg, K, Na, ora combination thereof. In some embodiments, the crystalline domains include a phosphate group (e.g., a polyphosphate, a pyrophosphate, a hydrogen phosphate, a dihydrogen phosphate, an orthophosphate, ora combination thereof), a carbonate group, a sulfate group, or a combination thereof. In some embodiments, the amorphous matrix includes calcium and / or phosphorus. In some embodiments, the crystalline domains include octacalcium phosphate, hydroxyapatite, monetite, brushite, calcium triphosphate, calcium pyrophosphate, and / or hydrates thereof.

[0040]

[0039] In another aspect, an assembly of composites is provided that contains a plurality of composites as described herein. In some embodiments, at least a portion of the composites are in the form of fibers, which in certain embodiments may be assembled into yarns, woven textiles, knit textiles, or non-woven textiles.

[0041] BRIEF DESCRIPTION OF THE DRAWINGS

[0042]

[0040] Figure 1 shows a tomographic representation of prominence and isolation.

[0043]

[0041] Figure 2 shows a transmission electron microscopy (TEM) cross section of a composition as described herein after focused ion beam (FIB) cross section.

[0044] DETAILED DESCRIPTION

[0045]

[0042] Urethane matrix and / or acrylic matrix (urethane matrix, acrylic matrix, or urethane and acrylic matrix) containing durable water repellent coating compositions are provided herein. Composites that include the urethane and / or acrylic matrix containing coating on substrates, such as polymer substrates, e.g., textiles, are provided, and methods of manufacture thereof are also provided. In some embodiments, a thin coating layer of less than about 500 nm thickness of the water repellent urethane and / or acrylic matrix containing composition is desirable to maintain the design properties of a substrate such as a fiber, textile, or fabric. The water repellent urethane and / or acrylic matrix containing coating may be deposited directly on the substrate, or it may be deposited over a ceramic composition on the substrate.

[0046] Definitions

[0047]

[0043] Numeric ranges provided herein are inclusive of the numbers defining the range.

[0048]

[0044] Unless otherwise indicated, nucleic acids are written left to right in 5' to 3' orientation; amino acid sequences are written left to right in amino to carboxy orientation, respectively.

[0049]

[0045] Numeric ranges provided herein are inclusive of the numbers defining the range.

[0050]

[0046] “A,” “an,” and “the” include plural references unless the context clearly dictates otherwise.

[0051]

[0047] The term “about” as used herein when referring to a measurable value such as an amount, a temporal duration, and the like, is meant to encompass variations of ±10%, ±5%, ±1%, or ±0.1% from the specified value, as such variations are appropriate to perform the disclosed methods or in connection with a disclosed composition. In some embodiments, may be used to mean plus or minus ten percent (10%) of a value; for example, “about 100” refers to any number between 90 and 110. Unless otherwise stated, average values herein refer to number averages.

[0052]

[0048] The phrase “and / or,” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Additional elements may optionally be present other than the elements specifically identified by the “and / or” clause, whether related or unrelated to those elements specifically identified, unless clearly indicated to the contrary. Thus, as a non-limiting example, a reference to “A and / or B,” when used in conjunction with open ended language such as “comprising” can refer, in one embodiment, to A without B (optionally including elements other than B); in another embodiment, to B without A (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.

[0049] “O-dimensional materials’’ are materials where all the dimensions of the material are less than about 100 nm and typically boundary or edge properties are important. Example materials are quantum dots.

[0053]

[0050] “Agglomerate” or ’’agglomerated” refers to a collection of previously discrete particles or materials which when contacted remain connected and undergo some degree of coalescence, relative incorporation, or growth.

[0054]

[0051] “Aggregate” or ’’aggregated” refers to a collection of previously discrete particles or materials that when contacted remain connected but do not appear to undergo an additional coalescence, relative incorporation, or growth.

[0055]

[0052] “Air permeability” is the rate of air transmission through a textile or fabric according to ASTM D737 or similar methods. The rate is reported in volumetric flow per unit time, typically in cubic feet per minute per square foot (cfm per square foot).

[0056]

[0053] “Atomic percentage” refers to the number of atoms of one or more specifically named elements as a percentage of the total number of atoms present within a specified area or volume.

[0057]

[0054] A “ceramic” or “ceramic material” refers to a solid material including an inorganic compound of a metal or a metalloid, and a non-metal, with ionic or covalent bonds. In this context, “ceramics” may include amorphous inorganic glasses, glass-ceramics, polycrystalline materials, and combinations thereof. Ceramics may contain at least one type of functional crystalline phase and a residual glass phase with the volume fraction crystallized may vary from ppm to almost 100%. A “non-metal” may include oxygen (oxide ceramic), or carbon (carbide) or nitrogen (nitride) (non-oxide ceramics). A “metal” may include a non-hydrogen element of Group 1 of the periodic table, an element of Groups 2-12 of the periodic table, or an element from the p-block (Groups 12-17 of the periodic table), e.g., Al, Ga, In, Tl, Sn, Pb, Bi, or combinations thereof. A “metalloid” may include B, Si, Ge, As, Sb, Se, Te, or Po, or combinations thereof.

[0058]

[0055] “Complementary inorganic element” refers to an element present in a counterion, where a ceramic precursor includes one or more ions incorporated into the ceramic and one or more counterions that are not incorporated into the ceramic. For example, in some embodiments, the ceramic precursors include calcium chloride and / or calcium nitrate, calcium ions are incorporated into the ceramic, the counterions chloride and nitrate are not incorporated into the ceramic, and the complementary inorganic elements include chlorine, nitrogen, and / or oxygen. In a further example, in some embodiments, the ceramic precursors include ammonium dihydrogen phosphate, dihydrogen phosphate ions are incorporated into the ceramic, the counterion ammonium is not incorporated into the ceramic, and the complementary inorganic elements include nitrogen and / or hydrogen.

[0059]

[0056] "Contact angle” refers to the angle measured through a liquid from the surface and to the liquid-vapor interface at the contacting surface. The sessile drop method is the standard method of contact angle measurement in which the droplet used to characterize the surface is stationary.

[0060]

[0057] "Hydraulic diameter” refers to a value that is 4 times the cross-sectional area divided by the perimeter of the cross-sectional area. In the case of a nominally cylindrical fiber of circular cross section, the hydraulic diameter is 2 times the radius of the circular cross-section.

[0061]

[0058] "Hydrophilic” refers to a surface that has a high affinity for water. Contact angles can be very low (j.e., less than 30 degrees as measured from the surface through the liquid water in the presence of air) and / or immeasurable.

[0062]

[0059] "Interconnected” refers to a network or matrix of ceramic material, wherein ceramic material in the network is in physical contact with (connected to) other ceramic material in the network, i.e., a majority of ceramic material is adjoined to other ceramic material resulting in a scaffolded structure either free-standing or supported on a substrate. The interconnected ceramic network described herein is a continuous ceramic phase over an area or volume defined by lengths greater than 100 mean particle diameters, and may contain pores (open spaces) with an accessible pore volume, which may be filled, or partially filled, with another material, such as, but not limited to, a polymer.

[0063]

[0060] "Laminate” refers to a structure or composite that includes one or more thin layers affixed to other thin layers, to membranes, to other textiles or fabrics, or to structural layers, or to a substrate.

[0064]

[0061] "Layered double hydroxide” refers a class of ionic solids characterized by a layered structure with the generic sequence [AcB Z AcB]n, where c represents layers of metal cations, A and B are layers of hydroxide anions, and Z are layers of other anions and / or neutral molecules (such as water). Layered double hydroxides are also described in PCT Application No. PCT / US2017 / 052120, which is incorporated by reference herein in its entirety.

[0065]

[0062] "Matrix” refers to a volume of material that is comprised of many material subunits, where the volume can optionally enclose or embed additional materials such as ceramics. Subunits may be, but are not necessarily ordered as observed in a crystal lattice. The subunits may comprise one or more chemical compositions such as is observed in a copolymer having two or more chemical compositions (polymers). Within the matrix, regions may have different average chemical compositions than the bulk of the matrix.

[0066]

[0063] "Mean” refers to the arithmetic mean or average.

[0067]

[0064] "Mean” refers to the arithmetic mean or average.

[0068]

[0065] A “nanostructured” coating refers to a coating composition that has a feature in at least one dimension that is less than 100 nanometers.

[0069]

[0066] "Nominal” is used to refer to approximate sizes or dimensions of a material; the actual dimensions may be larger or smaller than the nominal dimension. When nominal dimensions are used to describe nanomaterials, the nominal dimension is the largest single dimension of the nanomaterial, such as the diameter of a sphere, or the length of a plate. When nominal is used to describe materials such as fabrics, the term nominal is used to refer to the approximate value or measurement of the most prevalent feature, but not necessarily the exact measurement. An example is the nominal surface area of a fabric. The nominal surface area is defined by the length multiplied by the width of the fabric, and does not account for any increase in surface area as would be provided the fibers that make up the fabric.

[0070]

[0067] "Non-fluorinated” refers to chemical compositions and formulations where fluorine content is less than 50 mg / kg as measured by test method EN 14582:2016 or less than about 2 mg / L for dilute water samples using EPA Standard Methods for the Examination of Water and Wastewater, 4500-F B & D.

[0071]

[0068] "Storage modulus” refers to elasticity of a material, i.e., the energy the material can store and release when deformed.

[0072]

[0069] "Surface roughness” or “roughness factor” is the measurement of the relative smoothness of a surface’s profile, calculated via the deviations (macroscopic or microscopic) in a surface’s true or ideal form. The larger the deviation from the ideal form, the larger the surface roughness. A surface roughness factor commonly used is Ra which is defined as the arithmetic average of profile height deviations from the mean line. This is the term used throughout this application when not otherwise specified.

[0073]

[0070] "Textile” is a term that includes various fiber-based materials including fibers, yarns, filaments, and / or threads that are combined or manufactured to create a flexible polymeric film, garment, or fabric. Textiles or textile materials can be described as woven or nonwoven, whereas fabrics are a subset of textiles which include only woven fibers, yarns, filaments and / or threads.

[0074]

[0071] "Thickness” of a material (e.g., the first or second material as described herein) refers to the nominal distance between top and bottom edges or surfaces of a material, such as the surface defined by the edge of the interfacial layer in contact with the substrate or first material in the case of a second material, and the nominal top surface of the layer of surface modification material.

[0075]

[0072] “Water repellent” refers to materials and chemical treatments of substrates which provide a delay to the intrusion of water from the substrate exterior to or through the internal substrate volume. Applied water droplets may bounce, roll, slide, or bead up on the surface of a water repellent substrate.

[0076] Water Repellent Composites

[0077]

[0073] Water repellent composites are provided. A composite as described herein includes: a polymer substrate, which includes a polymer matrix that has an external surface and an internal volume; a water repellent functional layer, e.g., a water repellent urethane matrix and / or acrylic matrix containing functional layer, on the substrate, and optionally, a ceramic.

[0078]

[0074] In some embodiments, the composite includes ceramic on the external surface of the polymer matrix and the ceramic and / or inorganic elements (e.g., salts and / or excess reagents) at least partially occupies the internal volume of the polymer matrix, i.e., occupies at least a portion of the polymer matrix interior volume.

[0079]

[0075] In some embodiments, the substrate of the composite is in the form of a fiber or a film. In some embodiments, the substrate is in the form of a fiber with a mean diameter less than about 5 millimeters or less than about 1 millimeter. In some embodiments, the substrate of the water repellent composite is in the form of a film with a mean thickness less than about 5 millimeters or less than about 3 millimeters.

[0080]

[0076] In some embodiments in which the composite includes a ceramic, greater than about 10%, or greater than about 20%, or greater than about 30%, or greater than about 40%, or greater than about 50%, or greater than about 60%, or greater than about 70%, or greater than about 80%, or greater than about 90% of total ceramic in the composite protrudes through the polymer substrate surface.

[0081]

[0077] In some embodiments in which the composite includes a ceramic, the ceramic in the composition (i.e., the composite) is nanostructured and includes structures or features such as plates, rods, spheroids or agglomerates, which are geometrically similar and which have at least one dimension that is less than 100 nanometers.

[0082]

[0078] In some embodiments, the composite is functionalized with a thin film which has a thickness of less than about 500 nanometers (nm), or less than about 200 nm, or less than about 150 nm, or less than about 100 nm, or less than about 50 nm, about 20 nm to about 50 nm, or less than about 20 nm, or less than about 10 nm. In some embodiments, the composite is coated with a silane, a siloxane, a urethane, an acrylate, or with a molecule with a head group and a tail group (for example, wherein the head group includes a silane group, a phosphonate group, a phosphonic acid group, a carboxylic acid group, a vinyl group, an alcohol group, a hydroxide group, a thiolate group, a thiol group, and / or an ammonium group (e.g., a quaternary ammonium group), and wherein the tail group includes a hydrocarbon group, a fluorocarbon group, a vinyl group, a phenyl group, an epoxide group, an acrylic group, an acrylate group, a hydroxyl group, a carboxylic acid group, a thiol group, and / or a quaternary ammonium group.

[0083]

[0079] In some embodiments, the composite has a surface roughness greater than 1.1.

[0084]

[0080] In some embodiments in which the composite includes a ceramic, at least a portion of the ceramic is interconnected. In some embodiments, the substrate includes a polymer film or polymer film layer of a laminate and a deposition including a ceramic on at least one side of the film. In some embodiments, the deposited ceramic has a thickness less than 20% or less than about 20% of the mean thickness of the polymer film. In some embodiments, the deposited ceramic has a thickness less than about 1 micrometer. In some embodiments, the polymer film substrate has a thickness greater than about 1 micrometer. In some embodiments, the polymer film substrate contains a thermoplastic. In nonlimiting examples, the thermoplastic is a polyester, a polyamide, a polyurethane, an acrylic (acrylate polymer), a polyolefin, a polyol, acrylonitrile butadiene styrene (ABS), a polyvinyl alcohol, or a combination thereof. In some embodiments, the polymer film substrate contains cellulosic material, or cellulosic derived material. In some embodiments, the deposited ceramic includes an alkaline earth metal. In some embodiments, the alkaline earth metal is magnesium, or calcium. In some embodiments, the alkaline earth metal is in the form of an oxide, a hydroxide, a phosphate, a carbonate, a sulfate, or a combination thereof. In some embodiments, the ceramic fraction in the deposited ceramic is less than about 0.9. In some embodiments, the deposited ceramic includes morphologies with at least one dimension less than 100 nanometers. In some embodiments, the deposited ceramic includes 0-dimensional or 2-dimensional morphology. In some embodiments, the deposited ceramic includes a siloxane, an acrylate, a phosphonate, a sulfonate, a urethane, or combination thereof. In some embodiments, the deposited ceramic includes a silicone polymer or an alkyl terminated silane or siloxane. In some embodiments, the deposited ceramic includes an alkyl terminated functional group. In some embodiments, the alkyl terminated functional group includes a saturated chain length longer than three carbons. In some embodiments, deposited ceramic includes an isocyanate or isocyanate terminated polymer. In some embodiments, the deposited ceramic is chemically bound to the polymer film material, e.g., by covalent, ionic or Van der Waals mechanisms. In some embodiments, the composition material has a surface roughness greater than 1.1. In some embodiments, at least a portion of the deposited ceramic is interconnected. In some embodiments, greater than about 50% of the ceramic on a particle basis is interconnected. In some embodiments, greater than about 20%, or greater than about 30%, or greater than about 40%, or greater than about 60%, or greater than about 70%, or greater than about 80%, or greater than about 90% of the ceramic on a particle basis is interconnected.

[0085]

[0081] In some embodiments, the ceramic includes crystalline domains. In some embodiments, the ceramic includes crystalline particles. In some embodiments, the crystalline domains or crystalline particles are embedded in an amorphous matrix. In some embodiments, the amorphous matrix includes at least one element that is included in the crystalline particles or crystalline domains. In some embodiments, the amorphous matrix includes two or more common elements with the crystalline particles or crystalline domains. In some embodiments, the crystalline domains range in size from about 2 nm in nominal dimension to about 200 nm in nominal dimension. In some embodiments, the crystalline domains or crystalline particles include metal(s) from metal salt(s) in the first and / or second contact solutions. In some embodiments, the crystalline domains or crystalline particles include a rare earth metal, a transition metal, an alkaline earth metal, or a combination thereof. In some embodiments, the ceramic contains crystalline domains which include Ca, Li, Mg, K, Na, or a combination thereof. In some embodiments, the ceramic contains crystalline domains which include phosphate, carbonate, or sulfate groups. In some embodiments, the phosphate is polyphosphate, pyrophosphate, hydrogen phosphate, dihydrogen phosphate, or orthophosphate. In some embodiments, the amorphous matrix contains calcium, phosphorus, and or oxygen. In some embodiments, the ceramic contains crystalline domains or crystalline particles that contain octacalcium phosphate, hydroxyapatite, monetite, brushite, calcium triphosphate, calcium pyrophosphate, and / or hydrates thereof.

[0086]

[0082] In some embodiments, substrates are sequentially contacted with liquid solutions by spraying, padding, or immersion. In these cases, a first solution in contact with the substrates is considered the first contact solution, a second solution in contact with the substrate after the first solution is considered the second contact solution, and so on.

[0087]

[0083] In some embodiments, the composite is an assembly of a plurality of water repellent composites as described herein, such as a plurality of fibers that are formed into the assembly. In some embodiments, composite fibers are assembled into yarns, woven textiles, knit textiles, or non-woven textile materials.

[0084] In some embodiments, the composite is functionalized, i.e., the optional ceramic, the polymer substrate, or both are functionalized, i.e., modified with one or more functional group or molecule to impart one or more desirable property. In some embodiments, the functionalized composite increases the hydrophobicity of the substrate compared to the unfunctionalized composite. In some embodiments the functionalized substrate and / or optional ceramic provides improved properties such as microbial resistance, ultraviolet light resistance, improved chemical resistance, improved tear strength, improved moisture vapor transmission rate (MVTR), light transmission, improved oil or stain resistance, improved wear durability, or improved wash durability. In some embodiments, the functional group or molecule improves these properties when compared to either the polymer substrate and water repellent functional layer or the ceramic and water repellent functional layer.

[0088]

[0085] In some embodiments, a composite as described herein has a tear strength, tensile strength, gas permeability, vapor permeability, and / or abrasion resistance that is maintained or improved relative to an identical untreated polymer substrate. In some embodiments, the composite is measured in accordance with test standard ASTM D1424 wherein the tear strength is greater than about than about 5000gF, or greater than about 2000gF, or greater than about 1OOOgF or greater than about 500gF or about 100gF greater than the uncoated material. In some embodiments, the composition (i.e., the composite) is measured in accordance with test standard ASTM D5034 wherein the breaking strength in gramForce (gF) or gF per width of textile or fabric, and / or elongation is measured and is about 1%, about 2%, about 5%, about 10%, about 25%, about 50%, about 100%, and about 250%, or more. Tensile strength may be determined and is typically reported in MPa. In some embodiments, the composition gas permeability is measured in accordance with test standard ASTM D1434. In some embodiments, the composition is measured in accordance with test standard ASTM E96 wherein the moisture vapor transport rate (MVTR) is measured and is reported in grams per area per time. In some embodiments, the MVTR is less than about 500 g / day / m2, about 500 g / day / m2to about 1000 g / day / m2, about 1000 g / day / m2to about 2500 g / day / m2, about 2500 g / day / m2to about 5000 g / day / m2, about 5000 g / day / m2to about 10000 g / day / m2, or greater than about 10000 g / day / m2. In some embodiments, the composition is measured in accordance with test standard ASTM D4966 wherein the abrasion resistance is measured and is reported according to the ratings outlined in the standard for about 500 cycles, about 1000 cycles, about 5000 cycles, about 10000 cycles, about 30000 cycles, about 50000 cycles, or more.

[0086] In some embodiments, a composite as described herein includes a polymer substrate, a ceramic, and a water repellent functional layer, wherein the polymer substrate has an external surface and a polymer matrix internal volume, a first portion of the ceramic is on the external surface, and a second portion of the ceramic occupies at least a portion of the polymer matrix internal volume, and wherein the second portion of the ceramic has a diffusion length more than about 10 nm, more than about 50 nm, or more than about 100 nm from the external surface into the polymer matrix internal volume at a temperature less than about 160°C and in a time period of less than about 90 minutes.

[0089]

[0087] In some embodiments, a composite as described herein includes a polymer substrate, a ceramic, and a water repellent functional layer, wherein the polymer substrate has an external surface and a polymer matrix internal volume, a first portion of the ceramic is on the external surface, and a second portion of the ceramic occupies at least a portion of the polymer matrix internal volume, and wherein the second portion of the ceramic penetrates less than about 90%, less than about 75% less than about 50% less than about 40% less than about 30% less than about 20%, less than about 10%, or less than about 5% of the hydraulic diameter of the polymer matrix, from the external surface into the polymer matrix internal volume.

[0090]

[0088] In some embodiments, a composite as described herein includes a polymer substrate, a ceramic, and a water repellent functional layer, wherein the polymer substrate has an external surface and a polymer matrix internal volume, a first portion of the ceramic is on the external surface, and a second portion of the ceramic occupies at least a portion of the polymer matrix internal volume, and wherein the mass of the ceramic, as a percentage of the mass of the polymer-ceramic composite, is less than about 10%.

[0091]

[0089] In some embodiments, a composite as described herein includes a polymer substrate, a ceramic, and a urethane matrix (e.g., polyurethane) and / or acrylic matrix (e.g., polyacrylate) functional layer, wherein the polymer substrate has an external surface and a polymer matrix internal volume, a first portion of the ceramic is on the external surface, and a second portion of the ceramic occupies at least a portion of the polymer matrix internal volume, and wherein the ceramic includes less than about 2 grams per square meter, less

[0090] than about 5 grams per square meter, less than about 10 grams per square meter, less than about 20 grams per square meter, less than about 50 grams per square meter, or less than about 100 grams per square meter of the nominal geometric surface area of the polymer-ceramic composite.

[0092]

[0091] In some embodiments, the composite including a polymer substrate, a ceramic and a water repellent functional layer can be described by the morphology or topology of the substrate surface. In some embodiments, the topological features may be described as having a smooth conformal surface which resembles closely the original polymer substrate. In some embodiments, the topological features may be described as having a smooth conformal surface which resembles closely the original polymer substrate but also contains a filmlike ceramic surface below the functional coating layer which may only be observed by fiber cross section investigations, chemical analysis or chemical composition interrogation such as time-of-flight secondary ion mass spectrometry (TOF-SIMS), energy dispersive X-ray analysis (EDX), or other means. The filmlike structures may be described as having a low prominence of about 5 nm to about 20nm from the surface with a large coverage area of about 75% of the original surface. In some embodiments, the topological features may be described as having a morphology that is largely conformal to the original polymer substrate but also contains large flat areas of ceramic surface features below the functional coating layer which may only be observed by fiber cross section investigations, chemical analysis or chemical composition interrogation such as TOF-SIMS, EDX, or other means. The large flat ceramic regions may be described as having a low prominence of about 5 nm to about 20nm from the surface with a large area of up to about 10um in critical dimension and a high isolation greater than about 20um in linear distance. In some embodiments, the topological features may be described as having a discrete barnacle-like morphology that includes identifiable structures having a discrete prominence of about 20 nm to about 100nm from the surface and an isolation greater than about 5mm in linear distance. In some embodiments, the topological features may be described as having a small range-like morphology that includes 2 to 20 identifiable peaks having a discrete prominence of about 10 nm to about 10Onm and an isolation less than about 5mm in linear distance. In some embodiments, the topological features may be described as having a large range-like morphology that includes 5 to 100 identifiable peaks having a discrete prominence of about 10 nm to about 50nm, the primary peak of the range having a prominence of about 10nm to about 100nm from the surface.

[0093]

[0092] In some embodiments, the functional layer has an increased storage modulus relative to the uncoated substrate material. In some embodiments, the storage modulus as measured by dynamic mechanical analysis, as measured in the warp and weft directions by dynamic mechanical analysis (DMA), is increased by about 1.1 to about 3.5 times in comparison to uncoated substrate. In some embodiments, the storage modulus, as measured by dynamic mechanical analysis in the warp direction by dynamic mechanical analysis (DMA) is increased by about 1.5 to about 3.0 times in comparison to uncoated substrate. In some embodiments, the tensile modulus of the uncoated substrate is about 25MPa to about 150MPa. In some embodiments, the storage modulus of the uncoated substrate is about 25MPa to about 250MPa.

[0094]

[0093] In some embodiments, the storage or tensile moduli are measured by tensile testing, nanoindentation, or dynamic mechanical analysis. In some embodiments, instrumented nanoindentation of axial locations was used to determine the storage modulus as a function of contact depth. A low temperature treated recycled nylon fiber, fiber temperature less than about 100°C, had a measured storage modulus about 0.5 to 1.0 gigapascal (GPa) across all contact depths from about 10nm to about 50nm. Composite samples including a polymer substrate, a ceramic, and a functional layer, processed on two different pieces of production equipment in a manner as described herein, had a measured storage modulus of about 3 to about 6 GPa at about 10nm of contact depth and about 1 to about 3 GPa at about 50nm of contact depth. Composite samples including a polymer substrate, a ceramic, and a functional layer, processed on two different pieces of production equipment in a manner as described herein, have storage modulus as measured on an axial surface by instrumented nanoindentation that is increased by about 2.0 times to about 10.0 times at 10nm of contact depth in comparison to an identical substrate (e.g., textile or fabric) that does not include the water repellent functional layer.

[0095]

[0094] In some embodiments, at least a portion of a composite as described herein has a sessile drop water contact angle greater than about 90 degrees, greater than about 100 degrees, greater than about 110 degrees, greater than about 115 degrees, than about 120 degrees, greater than about 125 degrees, greater than about 128 degrees, greater than about 130 degrees, greater than about 131 degrees, than about 132 degrees, greater than about 134 degrees, greater than about 136 degrees, greater than about 138 degrees, greater than about 140 degrees, greater than about 142 degrees, greater than about 144 degrees, greater than about 146 degrees, greater than about 148 degrees, greater than about 150 degrees, greater than about 155 degrees greater than about 160 degrees, greater than about 165 degrees, greater than about 170 degrees, greater than about 175 degrees, greater than about 178 degrees, or about 179 degrees.

[0096]

[0095] In some embodiments, the urethane or acrylate containing functional coating solution contains less than 1% fluorine element. In some embodiments, the urethane or acrylate containing functional coating solution contains less than 0.1% fluorine element. In some embodiments, the urethane or acrylate containing functional coating solution contains less than 0.01% fluorine element.

[0097]

[0096] In some embodiments, the water repellent functional layer (functional coating layer) may include a polymer chemistry, for example, with a mean thickness of about 20nm to about 500 nm. The mean thickness of the functional layer is the distance from the external surface of the of the ceramic layer to the external thickness of the functional layer. For example, the functional layer chemistry may include a silane, siloxane, phosphonic acid, phosphonate, sulfonate, sulfonic acid, carboxylic acid, carboxylate, urethane, vinyl group, or acrylate, or a molecule with a head group and a tail group. In some embodiments, polymer chemistry includes a crosslinker molecule to improve mechanical and chemical properties. In some embodiments, polymer chemistry includes a molecule with a head group and a tail group, wherein the head group includes a silane group, a phosphonate group, a phosphonic acid group, a carboxylic acid group, a vinyl group, an alcohol group, a hydroxide group, a thiolate group, a thiol group, and / or an ammonium group, and wherein the tail group includes a hydrocarbon group, a fluorocarbon group, a vinyl group, a phenyl group, an epoxide group, an acrylic group, an acrylate group, a hydroxyl group, a carboxylic acid group, a thiol group, and / or a quaternary ammonium group. For example, the head group may include an ammonium group, such as a quaternary ammonium group.

[0098]

[0097] In some embodiments, the functional coating layer has a block isocyanate derived urethane structure of more than about 30% by volume. In some embodiments, the functional coating layer has an acrylic matrix structure of more than about 30% by volume. In some embodiments, the functional coating layer includes both an acrylate rich region having a greater concentration of acrylate groups than the bulk sample) of about 20 nm to about 200 nm in thickness and a silicon rich region (having a greater concentration of silicon than the bulk sample) of about 2 nm to about 20 nm thickness. In some embodiments, the functional coating layer includes an acrylate rich region adjacent to the substrate surface and a silicon rich region adjacent to the urethane functional layer external surface. In some embodiments, the functional coating layer includes silicon rich domains interspersed with acrylate rich regions. In some embodiments, the functional coating layer includes silicon rich domains interspersed within an acrylate matrix. In some embodiments, at least a portion of the urethane and / or acrylic matrix structure lies within the substrate as measured by TOF-SIMS.

[0099]

[0098] In some embodiments, the functional coating layer has a block isocyanate derived urethane structure of more than about 30% by volume and a total layer thickness of about 25 nm to about 300 nm. In some embodiments, the functional coating layer has an acrylic matrix structure of more than about 30% by volume and a total layer thickness of about 10 nm to about 200 nm. In some embodiments, the functional coating layer thickness is about 10%, about 20%, about 30%, about 40%, about 50%, or about 100% greater in thickness after ceramic addition than an identical functional layer which does not contain added ceramic.

[0099] In some embodiments, the functional coating layer includes a siloxane, an acrylate, a phosphonate, a sulfonate, a urethane, or a combination thereof. In some embodiments, the functional coating layer further includes a silicone polymer, an alkyl-terminated silane, or an alkyl-terminated siloxane. In some embodiments, the functional coating layer further includes an alkyl-terminated functional group, such as, but not limited to, an alkyl-terminated functional group that includes an alkyl group greater than three carbon atoms. In some embodiments, the functional coating layer further includes an isocyanate or an isocyanate-terminated polymer.

[0100]

[0100] In some embodiments, the functional coating layer includes an additive. In some embodiments, the additive may include water or may include an alcohol, acetone, dimethyl carbonate, methyl acetate, tert-butyl acetate, propylene carbonate, acetic acid, methyl ethyl ketone, or mixtures thereof. In some embodiments, the additive includes an alcohol, such as, but not limited to, ethanol, methanol, isopropanol, butanol, isobutanol, propylene glycol, glycol ether, or2-ethylhexanol, 2-butoxyethanol, or mixtures thereof. In some embodiments, the functional layer additive includes one or more cosolvents. In some embodiments, the one or more cosolvents include an alcohol, a ketone, a dialkyl carbonate, an alkyl carboxylic acid, an alkyl ester of an alkyl carboxylic acid, an alkyl diol, an ether, or mixtures thereof. In some embodiments, the alcohol includes methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-butoxyethanol, 2- ethylhexanol, or mixtures thereof. In some embodiments, the alcohol includes methanol. In some embodiments, the ketone includes acetone and / or methyl ethyl ketone. In some embodiments, the dialkyl carbonate includes dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, or mixtures thereof. In some embodiments, the alkyl carboxylic acid includes formic acid, acetic acid, propionic acid, or mixtures thereof. In some embodiments, the alkyl ester of an alkyl carboxylic acid includes methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, sec-butyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, or mixtures thereof. In some embodiments, the alkyl diol includes ethylene glycol, propylene glycol, 1 ,2-butanediol, 1 ,3-butanediol, 1,4-butanediol, or mixtures thereof. In some embodiments, the ether includes tetrahydrofuran, ethylene glycol butyl ether [HO(CH2)2O(CH2)3CH3, 2-butoxyethanol, EGBE], diethylene glycol [HO(CH2)2O(CH2)2OH], diethylene glycol monobutyl ether, 2-(2-butoxyethoxy)ethan-1-ol, HO(CH2)2O(CH2)2O(CH2)3CH3, DEGBE, a diethylene glycol monoalkyl ether, HO(CH2)2O(CH2)2O(CH2)nCH3, where n = 0, 1, 2, or 4, or mixtures thereof. In some embodiments, the ether includes EGBE. In some embodiments, the ether includes DEGBE. In some embodiments, the ether includes a mixture of EGBE and DEGBE.

[0101] In some embodiments the functionalized molecule applied in the functionalization step is one or more of a silane, a siloxane, a urethane, an acrylate, or a molecule with a head group and a tail group (for example, wherein the head group includes a silane group, a phosphonate group, a phosphonic acid group, a carboxylic acid group, a vinyl group, an alcohol group, a hydroxide group, a thiolate group, a thiol group, and / or an ammonium group (e.g., a quaternary ammonium group), and wherein the tail group includes a hydrocarbon group, a fluorocarbon group, a vinyl group, a phenyl group, an epoxide group, an acrylic group, an acrylate group, a hydroxyl group, a carboxylic acid group, a thiol group, and / or a quaternary ammonium group. In some embodiments the functional molecule is dissolved in a solvent such as water, an alcohol, such as but not limited to isopropanol, methanol, or ethanol, an alkane such as a hexane or a heptane, or an aromatic hydrocarbon, such as, but not limited to a xylene or toluene. In some embodiments the functionalized polymer ceramic is cured at elevated temperatures to stabilize the functional molecule.

[0101]

[0102] In some embodiments, the substrate is immersed in a functional chemical solution to deposit the water repellent urethane and / or acrylic matrix functional layer on the substrate. In some embodiments, the total solids content of the functional chemical solution as used in the immersion step is about 1% to about 5%, or about 1%, about 1.25%, about 1.5%, about 1.75%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, or about 5%. In some embodiments, the ratio of silicone and acrylic to other added solids (optionally including glycol) is about 0.5:1, about 1:1, about 1.5:1, about 2:1 , about 3:1 , about 4:1, about 5:1 , about 6:1 , or about 8:1 , about 10:1 , or about 20:1. In some embodiments, the ratio of acrylic solids to silicone solids is about 1:1 to about 10:1, about 1:1, about 2:1, about 2.5:1, about 3:1, about 4:1, about 5:1, about 7.5:1, or about 10:1.

[0102]

[0103] In some embodiments, the total solids content of the individual functional chemical solutions as used in the immersion step is about 1% to about 5%, or about 1%, about 1.25%, about 1.5%, about 1.75%, about 2%, about 2.5%, about 3%, about 3.5%, about 4%, or about 5%. The individual functional chemical solutions may be a non-fluorinated cationic acrylate copolymer emulsion, a blocked isocyanate crosslinker, an organic solvent or glycol additive, a non-fluorinated silicone emulsion, or a blended non-fluorinated cationic acrylate copolymer emulsion and a non-fluorinated cationic silicone emulsion, or combinations thereof. In some embodiments, the ratio of silicone and acrylic to other added solids (optionally including glycol) after mixing is about 0.5:1, about 1:1, about 1.5:1, about 2:1, about 3:1, about 4:1, about 5:1, about 6:1, or about 8:1, about 10:1, or about 20:1. In some embodiments, the ratio of acrylic solids to silicone solids after mixing is about 1:1 to about 10:1, about 1:1, about 2:1 , about 2.5:1, about 3:1 , about 4:1, about 5:1 , about 7.5:1, or about 10:1.

[0103]

[0104] In some embodiments, the total solids content of the functional chemical solution is a concentrate that is diluted at the time of use in the immersion equipment. The chemical solution, or individual solutions have total solids contents about 20x, about 15x, about 10x, about 7.5x or about 5x the concentration of the solids content of the chemical solution used in the immersion step.

[0104] Polymer substrates

[0105]

[0105] The water repellent composites described herein include a polymer substrate.

[0106]

[0106] In some embodiments, the polymer substrate of the composite as described herein is hydrophilic. For example, the hydrophilic polymer may include one or more hydroxide group(s).

[0107]

[0107] In some embodiments, the polymer substrate of the composite as described herein is hydrophobic. In some embodiments, the hydrophobic polymer substrate includes one or more acrylic, amide, imide, carbonate, diene, ester, ether, fluorocarbon, olefin, styrene, and / or vinyl group(s). In some embodiments, the hydrophobic polymer substrate includes one or more arylalkyl groups, e.g., the monomer used to form the polymer substrate contains styrene or a substituted styrene, a nonlimiting example of which is exemplified by forming the polymer substrate by polymerizing styrene and the resulting substrate containing phenylalkyl groups. In some embodiments, the hydrophobic polymer substrate includes one or more ester groups, e.g., the monomer used to form the polymer substrate contains a carboxylic acid ester of vinyl alcohol or a carboxylic acid ester of a substituted vinyl alcohol, a nonlimiting example of which is exemplified by forming the polymer substrate by polymerizing vinyl acetate and the resulting substrate containing the polyacetate of a polyalcohol. In some embodiments, the hydrophobic polymer substrate includes one or more ester groups, e.g., the monomer used to form the polymer substrate contains an ester of acrylic acid or of a substituted acrylic acid, a nonlimiting example of which is exemplified by forming the polymer substrate by polymerizing methyl acrylate and the resulting substrate containing the polymethylester of a polyalkylcarboxylic acid. In some embodiments, the hydrophobic polymer substrate includes one or more olefin groups, e.g., the monomer used to form the polymer substrate includes a diene or a substituted diene, a nonlimiting example of which is exemplified by forming the polymer substrate by polymerizing 1,3-butadiene and the resulting substrate containing alkyl chains or sidechains containing olefinic groups.

[0108] In some embodiments, the polymer substrate of the composite as described herein is a copolymer. For example, the copolymer may be amphiphilic. In some embodiments, the amphiphilic copolymer includes one or more polymer compound(s), such as polyethylene glycol)-block-poly(lactic acid) (PEG-PLA).

[0108]

[0109] In some embodiments, the polymer substrate of the composite as described herein includes a polymer blend. In some embodiments, the polymer blend is a blend of two or more homopolymers. In some embodiments, the polymer blend is a blend of two or more copolymers. In some embodiments, the polymer blend is a blend of one or more homopolymers and one or more copolymers.

[0109]

[0110] In some embodiments, the polymer substrate of the composite as described herein is at least partially composed of an elastomer. For example, the substrate may include a styrene elastomer fiber, a polyester elastomer fiber, or a nylon elastomer fiber.

[0110]

[0111] In some embodiments, the polymer substrate of the composite as described herein is at least partially composed of a resin. For example, the substrate may include a liquid crystal polymer, an acrylic resin fiber, or other resin based fiber.

[0111]

[0112] In some embodiments, the polymer substrate of the composite as described herein includes a manufactured fiber, e.g., spun from a liquid-crystal polymer (LCP). For example, in one embodiment, the substrate may include Vectran®, an aromatic polyester produced by the polycondensation of 4-hydroxybenzoic acid and 6-hydroxynaphthalene-2-carboxylic acid.

[0112]

[0113] In some embodiments, the polymer substrate of the composite as described herein is composed of fully drawn or oriented filaments or multifilament yarns (FDY). In some embodiments, the polymer substrate of the composite as described herein is composed of partially drawn or oriented filaments or multifilament yarns (PDY). In some embodiments, the polymer substrate of the composite as described herein is composed of drawn textured yarns (DTY). In some embodiments, the polymer substrate of the composite as described herein is composed of staple fibers.

[0113]

[0114] In some embodiments, the polymer substrate includes a polyester such as, but not limited to, polyethylene terephthalate (PET), a polyamide such as, but not limited to, a nylon, a polyvinyl chloride (PVC), a polyolefin such as, but not limited to, polyethylene or polypropylene, a polyurethane, a polyvinyl alcohol (PVOH), a polyvinyl acetate (PVAc), a polyvinylpyrrolidone, a polyol, a polyethylene glycol (PEG), or mixtures and / or copolymers thereof. In some embodiments, the nylon is nylon-6, nylon-6, 6, or nylon-12, or copolymers thereof. In some embodiments the nylon is nylon-6, 6. In some embodiments the polyamide is the product of condensation of hexamethylenediamine and terephthalic acid or the condensation of paraphenylenediamine and terephthalic acid. In some embodiments, the polymer is a copolymer of more than one monomer such as, but not limited to, nylon, acrylonitrile butadiene styrene (ABS), styrene / butadiene copolymer (SBR), nitrile rubber, styrene-acrylonitrile, styrene-isoprene-styrene (SIS), or mixtures thereof. In other embodiments, the polymer substrate includes a hydrocolloid, such as, but not limited to, a polysaccharide. In some embodiments, the polymer substrate includes locust bean gum, a starch, carrageenan, pectin, chitosan, xanthan gum, cellulose, or carboxymethyl cellulose, or mixtures thereof. In some embodiments, the polymer includes wool, cotton, hemp, animal hair, collagen, keratin, silk, chitin, flax, or jute, or mixtures thereof.

[0114]

[0115] In some embodiments, the polymer substrate includes one or more copolymers. In some embodiments, the copolymer includes a polyether-polyurea copolymer, a polyamide copolymer, a polyester copolymer, an acrylonitrile butadiene styrene (ABS) copolymer, a styrene / butadiene copolymer (SBR), a nitrile rubber, a styrene-acrylonitrile copolymer, a styrene-isoprene-styrene (SIS) copolymer, an ethylene-vinyl acetate (EVA) copolymer, or combinations thereof. In some embodiments, the substrate includes a copolymer formed by chain-growth polymerization and / or a copolymer formed by step-growth polymerization.

[0115]

[0116] In some embodiments, a polyamide copolymer is formed by condensation polymerization of two or more dicarboxylic acids and a diamine, a dicarboxylic acid and two or more diamines, or two or more dicarboxylic acids and two or more diamines. In some embodiments, the dicarboxylic acid(s) is / are selected from adipic acid, sebacic acid, 1,12-dodecanedioic acid, terephthalic acid, and isophthalic acid. In some embodiments, the diamine(s) is / are selected from 1,4-diaminobutane, 1 ,5-diaminopentane, 2-methylpentamethylenediamine, hexamethylenediamine (1,6-diaminohexane), metaxylenediamine, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 4,4'-methylenedi(cyclohexan-1 -amine), and trimethylhexamethylenediamine.

[0116]

[0117] In some embodiments, a polyamide copolymer is formed by condensation polymerization of one or more aminocarboxylic acids or the corresponding lactams, one or more dicarboxylic acids, and one or more diamines. In some embodiments, the aminocarboxylic acid or the corresponding lactam is selected from caprolactam, 11-aminoundecanoic acid, and co-aminolauric acid. In some embodiments, the dicarboxylic acid is selected from adipic acid, sebacic acid, dodecanedioc acid, terephthalic acid, and isophthalic acid, and wherein the diamine is selected from 1,4-diaminobutane, 1,5-diaminopentane, 2-methylpentamethylene-diamine, hexamethylenediamine (1,6-diaminohexane), meta-xylenediamine, 1,9-diaminononane, 1,10-diaminodecane, 1,12- diaminododecane, 4,4'-methylenedi(cyclohexan-1-amine), and trimethylhexamethylenediamine.

[0117]

[0118] In some embodiments, a polyamide copolymer is formed by condensation polymerization of two or more aminocarboxylic acids or the corresponding lactams. In some embodiments, the aminocarboxylic acids or the corresponding lactams are selected from caprolactam, 11-aminoundecanoic acid, and ro-aminolauric acid.

[0118]

[0119] In some embodiments, a polyamide copolymer is formed by condensation polymerization of caprolactam and 11-aminoundecanoic acid. In some embodiments, the polyamide copolymer is formed by condensation polymerization of caprolactam and ro-aminolauric acid. In some embodiments, the polyamide copolymer is formed by condensation polymerization of caprolactam, adipic acid, and hexamethylenediamine. In some embodiments, the polyamide copolymer is formed by condensation polymerization of cD-aminolauric acid, adipic acid, and hexamethylenediamine. In some embodiments, the polyamide copolymer is formed by condensation polymerization of caprolactam, <o-aminolauric acid, adipic acid, and hexamethylenediamine.

[0119]

[0120] In some embodiments, the polymer substrate includes a blend of one or more polymer and / or copolymer. In some embodiments, the blend includes a blend of two or more polyamides, or two or more nylons. In some embodiments, the blend of two or more polyamides is composed of any two or more of the polyamides that could be derived from caprolactam (nylon-6), 11-aminoundacanoic acid (nylon-11), o-aminolauric acid (nylon-12), adipic acid and hexamethylenediamine (nylon-6, 6), sebacic acid and hexamethylenediamine (nylon-6, 10), dodecanedioic acid and hexamethylenediamine (nylon-6, 12), terephthalic acid and hexamethylenediamine, isophthalic acid and hexamethylenediamine, adipic acid and 2-methylpentamethylenediamine, terephthalic acid and 2-methylpentamethylenediamine, isophthalic acid and 2-methylpentamethylenediamine, sebacic acid and 1 ,5-diaminopentane (nylon-5, 10), adipic acid and 1 ,4-diaminobutane (nylon-4, 6), sebacic acid and 1,4-diaminobutane (nylon-4, 10), terephthalic acid and 1,4-diaminobutane, terephthalic acid and 1 ,9-diaminononane, terephthalic acid and 1 ,10-diaminodecane, terephthalic acid and 1 ,12-diaminododecane, terephthalic acid and trimethylhexamethylenediamine, adipic acid and meta-xylenediamine, sebacic acid and 1 ,10-diaminodecane (nylon-10,10), dodecanedioic acid and 1,12-diaminododecane (nylon-12, 12), or dodecanedioic acid and 4,4'-methylenedi(cyclohexan-1-amine). In some embodiments, the blend of two or more polyamides is composed of any two or more of nylon-6, nylon-6, 6, or nylon-12. In some embodiments, the blend of two or more polyamides includes nylon-6 and nylon-6, 6. In some embodiments, the blend of two or more polyamides includes nylon-6 and nylon-12. In some embodiments, the blend of two or more polyamides includes nylon-6, 6 and nylon-12.

[0120]

[0121] In some embodiments, the polymer substrate is a woven textile, a nonwoven textile, leather, a synthetic leather, or an artificial leather. In some embodiments, the polymer substrate is made by impregnating non-woven or woven textiles, e.g., made of nylon or polyester, with a resin, such as a polyurethane resin, and then soaking the textiles in water or a solvent mixture to harden them. In some embodiments, the method of solidifying polymer elasticity by wet method includes, for example, immersion in a solidifying solution at about 20°C to about 60°C for about 1 to about 60 minutes, which contains a polyurethane solvent, such as N,N-dimethylformamide, dimethylacetamide, orN-methylpyrrolidone, and water. The method of coagulation includes immersion in a coagulating solution, for example, at about 20°C to about 60°C for about 1 minute to about 60 minutes. In some embodiments, the polymer substrate is made by laminating a layer of polyurethane resin onto a surface such as artificial leather. In some embodiments, the base yarns of non-woven textiles or fabrics are composed of ultrafine fibers, for example, with fiber diameters of about 0.1 micrometers (pm) to any of about 0.5 pm, about 1 pm, about 2 pm, about 4 pm, about 10 pm, about 20 pm, or about 50 pm.

[0121]

[0122] In some embodiments, the polymer substrate includes a combination of synthetic and natural fibers, such as, for example, a cotton-polyester blend, or a cotton-nylon blend.

[0122]

[0123] In some embodiments, the polymer substrate is in the form of a fiber. For example, the polymer substrate may be extruded into a fiber, prior to or after formation of the composite. In some embodiments, the fiber is knit or woven into a textile. In other embodiments, the fiber is assembled into a nonwoven textile. In some embodiments, the fiber diameter ( / .e., number average diameter) ranges from about 10 pm to about 100 pm, from about 50 pm to about 250 pm, from about 100 pm to about 300 pm, from about 300 pm to about 500 pm, or from about 100 pm to about 500 pm. In some embodiments, the mean fiber diameter ranges from about 5 pm to about 20 pm, or from about 2 pm to about 10 pm, or from about 1 pm to about 5 pm. In some embodiments, the mean fiber diameter ranges from about 0.1 pm to about 4 pm. In some embodiments, the mean fiber diameter is less than about 1000 pm, less than about 900 pm, less than about 800 pm, less than about 700 pm, less than about 600 pm, less than about 500 pm, less than about 400 pm, less than about 300 pm, less than about 200 pm, less than about 100 pm, less than about 90 pm, less than about 80 pm, less than about 70 pm, less than about 60 pm, less than about 50 pm, less than about 40 pm, less than about 30 pm, less than about 20 pm, less than about 10 m, less than about 5 pm, less than about 2 pm less than about 1 pm, or less than about 0.5 pm.

[0123]

[0124] In some embodiments, a light weight woven textile or fabric, having a density of about 20 g / m2to about 200 g / m2, or about 30 g / m2to about 75 g / m2, comprising or consisting of or consisting essentially of polyester, a polyester blend, nylon, recycled nylon, and / or a nylon blend, is used as the polymer substrate for the formation of a composite as described herein.

[0124]

[0125] In some embodiments the polymer substrate is in the form of a film. For example, the polymer substrate may be formed into a film, prior to or after formation of the composite. In some embodiments, the film has an average thickness of less than about 5 millimeters (mm), less than about 4 mm, less than about 3 mm, less than about 2 mm, or less than about 1 mm. In some embodiments, the film has an average thickness of from about 10 pm to about 100 pm, from about 10 pm to about 500 pm, from about 100 pm to about 500 pm, from about 500 pm to about 1000 pm, or from about 1000 pm to about 5000 pm.

[0125]

[0126] In some embodiments the polymer substrate is formed into a structural element, cast into a shape, printed or otherwise deposited from a melt and nozzle arrangement, or photocured from a melt to form a complex structure, prior to or after formation of the composite.

[0126]

[0127] In some embodiments the polymer substrate is chemically altered, such as by a cross-linking reaction, with different parts of the polymer chain, or a functional group on the polymer chain is reacted with one or more chemical substance to form a different polymer, such as, but not limited to the formation of vinylon from polyvinyl alcohol. In some embodiments, the polymer substrate is chemically altered prior to or after formation of the composite.

[0127]

[0128] In some embodiments a polymer melt is formed by heating the polymer to a temperature above its melting point or by dissolving the polymer in a suitable solvent. The melt can then be extruded to form a filament or fibers, or cast into a shape or film, or printed or otherwise deposited to form a melt and nozzle arrangement forming a polymer substrate. These steps can be completed prior to or after formation of the composite.

[0128] Functional coating layer

[0129]

[0129] The composites described herein include a water repellent functional layer coated on the substrate.

[0130]

[0130] In some embodiments, the functional layer includes more than about 30% or about 35% by volume of a block isocyanate derived urethane structure. The urethane structure includes urethane groups, for example, a urethane bonded to an acrylic group, or a polyurethane containing (adjacent) urethane groups, or large regions of acrylic (polyacrylic) adjacent to regions of urethanes (polyurethanes). In some embodiments, the functional layer includes more than about 30% or about 35% by volume of an acrylic matrix structure. In some embodiments, the functional layer includes both an acrylate rich region of about 20 nm to about 200 nm in thickness and a silicon rich region of about 2 nm to about 20 nm thickness. In some embodiments, the functional layer includes an acrylate rich region adjacent to the substrate, e.g., fiber surface and a silicon rich region adjacent to the external surface of the functional layer. In some embodiments, the external surface of the functional layer includes silicon rich domains interspersed with acrylate rich regions. In some embodiments, the functional layer includes silicon rich domains interspersed within an acrylate matrix. In some embodiments, at least a portion of the urethane and / or acrylic matrix structure lies within the substrate, e.g., synthetic fiber, as measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS).

[0131]

[0131] In some embodiments, the functional layer includes urethane groups and / or acrylate groups formed from a mixed chemical emulsion, including a non-fluorinated cationic acrylate copolymer emulsion, a blocked isocyanate crosslinker, and an organic solvent or glycol additive. In some embodiments, the functional layer includes urethane groups and silicone groups formed from a mixed chemical emulsion, including a nonfluorinated silicone emulsion, a blocked isocyanate crosslinker, and an organic solvent or glycol additive. In some embodiments, the functional layer includes urethane groups and / or acrylate groups, and silicone groups formed from a mixed chemical emulsion, including a non-fluorinated cationic acrylate copolymer emulsion, a non-fluorinated cationic silicone emulsion, a blocked isocyanate crosslinker, and an organic solvent additive. In some embodiments, the blocked isocyanate crosslinker has a deblocking temperature of about 70°C to about 160°C, about 80°C to about 140°C, or about 90°C to about 130°C.

[0132]

[0132] In some embodiments, the functional layer includes a siloxane, an acrylate, a phosphonate, a sulfonate, a urethane, or a combination thereof. In some embodiments, the functional layer further includes a silicone polymer, an alkyl-terminated silane, or an alkyl-terminated siloxane. In some embodiments, the functional layer further includes an alkyl-terminated functional group, such as, but not limited to, an alkyl- terminated functional group that includes an alkyl group greater than three carbon atoms. In some embodiments, the functional layer further includes an isocyanate or an isocyanate-terminated polymer.

[0133]

[0133] In some embodiments, the functional layer (e.g., water repellent functional layer) includes an acrylic matrix. In some embodiments, the functional layer includes both an acrylate rich region of about 10 nm to about 200 nm in thickness and a silicon rich region of about 5nm to about 40nm in thickness. In some embodiments, within the functional layer, the acrylate rich region is proximal to the external surface of the substrate and the silicon rich region is distal to the external surface of substrate. In some embodiments, the outermost region of about 25 nm of the functional layer includes silicon rich regions interspersed with acrylate rich regions. In some embodiments, the functional layer includes silicon rich regions interspersed within an acrylic matrix.

[0134]

[0134] In some embodiments, the functional layer includes an additive. In some embodiments, the additive may include water or may include an alcohol, acetone, dimethyl carbonate, methyl acetate, tert-butyl acetate, propylene carbonate, acetic acid, methyl ethyl ketone, or mixtures thereof. In some embodiments, the additive includes an alcohol, such as, but not limited to, ethanol, methanol, isopropanol, butanol, isobutanol, propylene glycol, glycol ether, or2-ethylhexanol, 2-butoxyethanol, or mixtures thereof. In some embodiments, the additive includes one or more cosolvents. In some embodiments, the one or more cosolvents include an alcohol, a ketone, a dialkyl carbonate, an alkyl carboxylic acid, an alkyl ester of an alkyl carboxylic acid, an alkyl diol, an ether, or mixtures thereof. In some embodiments, the alcohol includes methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-butoxyethanol, 2- ethylhexanol, or mixtures thereof. In some embodiments, the alcohol includes methanol. In some embodiments, the ketone includes acetone and / or methyl ethyl ketone. In some embodiments, the dialkyl carbonate includes dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, or mixtures thereof. In some embodiments, the alkyl carboxylic acid includes formic acid, acetic acid, propionic acid, or mixtures thereof. In some embodiments, the alkyl ester of an alkyl carboxylic acid includes methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, sec-butyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, or mixtures thereof. In some embodiments, the alkyl diol includes ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, or mixtures thereof. In some embodiments, the ether includes tetrahydrofuran, ethylene glycol butyl ether [HO(CH2)2O(CH2)3CH3, 2-butoxyethanol, EGBE], diethylene glycol [HO(CH2)2O(CH2)2OH], diethylene glycol monobutyl ether, [2-(2-butoxyethoxy)ethan-1 -ol, HO(CH2)2O(CH2)2O(CH2)3CH3, DEGBE], or a diethylene glycol monoalkyl ether, HO(CH2)2O(CH2)2O(CH2)nCH3, where n = 0, 1 , 2, or 4, or mixtures thereof. In some embodiments, the ether includes EGBE. In some embodiments, the ether includes DEGBE. In some embodiments, the ether includes a mixture of EGBE and DEGBE.

[0135] Ceramic

[0135] In some embodiments, a ceramic is deposited onto the polymer substrate of a composite as described herein, e.g., prior to addition of a functional layer (e.g., water repellent functional layer), e.g., a urethane- and / or acrylate-containing (urethane and / or acrylic matrix containing) functional layer, as described herein. For example, the ceramic may include an alkali metal oxide, an alkaline earth oxide, an alkali carbonate, an alkaline earth carbonate, an alkali oxalate, an alkaline earth oxalate, an alkali phosphate, an alkaline earth phosphate, an alkali sulfate, an alkaline earth sulfate, or combinations thereof. In some embodiments, the ceramic includes a metal oxide, a metal hydroxide, a layered double hydroxide, a metal carbonate, a metal oxalate, a metal phosphate, a metal sulfate, or mixtures thereof. In some embodiments, the ceramic includes a metal oxide, a metal hydroxide, a layered double hydroxide, a metal carbonate, a metal oxalate, a metal phosphate, a metal sulfate, or mixtures thereof, wherein the metal is an alkali metal or an alkaline earth metal.

[0136]

[0136] In some embodiments, the ceramic includes an alkali metal or an alkaline earth metal. In some embodiments, the ceramic includes calcium, potassium, lithium, magnesium, sodium, or mixtures thereof. In some embodiments, the ceramic includes oxygen, phosphorus, sulfur, carbon, or mixtures thereof. In some embodiments, the ceramic includes hydroxyapatite, calcium carbonate, magnesium carbonate, calcium sulfate, octacalcium phosphate, calcium phosphate, or mixtures or hydrates thereof. In some embodiments, wherein the ceramic includes phosphate, the phosphate is present in partially protonated, partially hydrated, hydrated, partially dehydrated, and / or dehydrated forms. In some embodiments, wherein the ceramic includes calcium phosphate, the calcium phosphate includes hydroxyapatite [Ca5(PO4)3OH], brushite [Ca(PO3OH)2*H2O], monetite [Ca(PO3OH)], or mixtures thereof. In some embodiments, wherein the ceramic includes sulfate, the sulfate is present in partially protonated, partially hydrated, and / or partially dehydrated forms. In some embodiments, the functional layer (e.g., water repellent functional layer) includes calcium phosphate (Cax(PO4)yrich regions wherein the concentration of calcium phosphate is greater than the bulk material. For example, (Cax(PO4)ymay be, but is not limited to, triclinium phosphate (x=3, y=2), octacalcium phosphate (x-8,y=6), tetracalcium phosphate (x=4, y=2), or apatite (x = 10, y = 6).

[0137]

[0137] In some embodiments, one or more additional inorganic elements, inorganic compounds, and / or ionic compounds may also penetrate the ceramic deposited onto the polymer substrate as well as the substrate polymer matrix internal volume. In some embodiments, the inorganic elements, compounds and / or ionic compounds are contained within an amorphous, inorganic glass phase. In some embodiments, the inorganic elements, compounds and / or ionic compounds are contained within a crystalline or a multicrystalline domain or phase. In some embodiments, the inorganic elements, compounds and / or ionic compounds are contained within a crystalline domain in an ordered manner. In some embodiments, the inorganic elements, compounds and / or ionic compounds are distributed or contained along crystalline domain boundaries, grain boundaries, defects, or pores. In some embodiments, the inorganic elements, compounds and / or ionic compounds are distributed along the polymer substrate exterior surface. In some embodiments, the inorganic elements, compounds and / or ionic compounds are distributed into the polymer substrate interior volume. In some embodiments, the inorganic elements, compounds and / or ionic compounds are distributed among the ceramic deposited onto the polymer substrate, along the polymer substrate exterior surface, within the polymer substrate interior volume, or combinations thereof.

[0138]

[0138] In some embodiments, one or more complementary inorganic elements also penetrate the ceramic deposited onto the polymer substrate as well as the substrate polymer matrix internal volume. In some embodiments, the complementary inorganic elements are contained within an amorphous, inorganic glass phase. In some embodiments, the complementary inorganic elements are contained within a crystalline, or multi-crystalline domain or phase. In some embodiments, the complementary inorganic elements are contained within a crystalline domain in an ordered manner. In some embodiments, the complementary inorganic elements are distributed or contained along crystalline domain boundaries, grain boundaries, defects, or pores. In some embodiments, the complementary inorganic elements are distributed along the polymer substrate exterior surface. In some embodiments, the complementary inorganic elements are distributed into the polymer substrate interior volume. In some embodiments, the complementary inorganic elements are distributed among the ceramic deposited onto the polymer substrate, along the polymer substrate exterior surface, within the polymer substrate interior volume, or combinations thereof.

[0139]

[0139] In some embodiments, the complementary inorganic element includes potassium, magnesium, chlorine, bromine, iodine, phosphorus, sulfur, nitrogen, oxygen, carbon, hydrogen, manganese, aluminum, titanium, sodium, calcium, or a combination thereof. In some embodiments, the complementary inorganic element is present as a counterion, present in a counterion, or present as a component of a counterion. In some embodiments, the counterion is a cation or an anion. In some embodiments, the counterion is a cation. In some embodiments, the complementary inorganic element is present in a potassium cation, a magnesium cation, a manganese cation, an aluminum cation, a titanium cation, a sodium cation, a calcium cation, an ammonium cation, ora combination thereof. In some embodiments, the complementary inorganic element is present in a cation comprising potassium, magnesium, manganese, aluminum, titanium, sodium, calcium, nitrogen, or a combination thereof. In some embodiments, the complementary inorganic element is present as K+1, Mg+2, Mn+2, Mn+3, Mn+5, Mn+7, Al+3, Ti+4, Na+1, Ca+2, NH4+1, or a combination thereof. In some embodiments, the cation is hydrated. In some embodiments, the hydrated cation is partially dehydrated. In some embodiments, the hydrated cation is partially deprotonated. In some embodiments, the hydrated cation is partially deprotonated, and the degree of deprotonation is dependent on the effective pH of the immediate environment of the hydrated cation. In some embodiments, the counterion is an anion. In some embodiments, the complementary inorganic element is nitrogen, which may be present in nitrate (NO31), nitrite (NO21), nitride (N3), amide (NH21), or a combination thereof. In some embodiments, the complementary inorganic element is oxygen, which may present in hydroxide (OH1), oxide (O2), peroxide (O22), hydroperoxide (HO21), or a combination thereof. In some embodiments, the complementary inorganic element is chlorine, which may be present in chloride (Cl1), perchlorate (CIO41), chlorate (CIO3‘1), chlorite (CIO2-1), hypochlorite (CIO1), or a combination thereof. In some embodiments, the complementary inorganic element is bromine, which may be present in bromide (Br1), perbromate (BrO4-1), bromate (BrO31), bromite (BrO21), hypobromite (BrO1), or a combination thereof. In some embodiments, the complementary inorganic element is iodine, which may be present in iodide (I1), periodate (IO41), iodate (IO31), iodite (IO21), hypoiodite (IO1), or a combination thereof. In some embodiments, the complementary inorganic element is phosphorus, which may be present in phosphate (PO43), hydrogen phosphate (HPO42), dihydrogen phosphate (H2PO41), or a combination thereof. In some embodiments, the complementary inorganic element is sulfur, which may be present in sulfate (SO42), hydrogen sulfate (HSO41), sulfite (SO32), hydrogen sulfite (HSO31), sulfide (S2), thiosulfate (S2O32), thiocyanate (SCN1) or a combination thereof. In some embodiments, the complementary inorganic element is carbon or nitrogen, which may be present in cyanate (OCN1), thiocyanate (SCN1), or a combination thereof. In some embodiments, the anion is permanganate (MnO4-1) or hydride (H1). In some embodiments, the anion is permanganate (MnO41). In some embodiments, the complementary inorganic element is carbon and present in carbonate (CO3-2), hydrogen carbonate (HCO31), or a combination thereof. In some embodiments, the complementary inorganic element is carbon, which may be present in a carboxylate anion. In some embodiments, the carboxylate anion is formate, acetate, propionate, butyrate, isobutyrate, or a combination thereof. In some embodiments, the complementary inorganic element is carbon, which may be present in a dicarboxylate anion. In some embodiments, the dicarboxylate anion is succinate, malonate, oxalate, or a combination thereof. In some embodiments the dicarboxylate anion is partially protonated. In some embodiments the dicarboxylate anion is partially protonated, and the degree of deprotonation is dependent on the effective pH of the immediate environment of the dicarboxylate anion. In some embodiments, the complementary inorganic element is present in an anion including chlorine, bromine, iodine, phosphorus, sulfur, nitrogen, oxygen, carbon, hydrogen, manganese, ora combination thereof.

[0140]

[0140] In some embodiments, ceramic precursors are soluble chemical salts used individually or collectively in the formation of insoluble ceramic materials. In some embodiments, the ceramic precursors include calcium nitrate and potassium phosphate, the counterions include nitrate and potassium, and the complementary inorganic elements include nitrogen, oxygen, and / or potassium. In some embodiments, the ceramic precursors include calcium nitrate and potassium phosphate, the counterions include nitrate and potassium, the complementary inorganic elements include nitrogen, oxygen, and / or potassium, and nitrogen, oxygen, potassium, or a combination thereof penetrate the ceramic and / or the substrate polymer matrix internal volume.

[0141]

[0141] In some embodiments, the ceramic precursors include calcium nitrate and sodium oxalate dihydrate, the counterions include nitrate and sodium, and the complementary inorganic elements include nitrogen, oxygen, and / or sodium. In some embodiments, the ceramic precursors include calcium nitrate and sodium oxalate dihydrate, the counterions include nitrate and sodium, the complementary inorganic elements include nitrogen, oxygen, and / or sodium, and nitrogen, oxygen, sodium, ora combination thereof penetrate the ceramic and / or the substrate polymer matrix internal volume.

[0142]

[0142] In some embodiments, the ceramic precursors include calcium nitrate and / or calcium chloride and ammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate, and / or sodium dihydrogen phosphate, the counterions include nitrate and / or chloride and ammonium, potassium, and / or sodium, and the complementary inorganic elements include nitrogen, chlorine, oxygen, potassium and / or sodium. In some embodiments, the ceramic precursors include calcium nitrate and / or calcium chloride and ammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate, and / or sodium dihydrogen phosphate, the counterions include nitrate and / or chloride and ammonium, potassium, and / or sodium, the complementary inorganic elements include nitrogen, chlorine, oxygen, potassium and / or sodium, and nitrogen, chlorine, oxygen, potassium, sodium, or a combination thereof penetrate the ceramic and / or the substrate polymer matrix internal volume.

[0143]

[0143] In some embodiments, the ceramic precursors include manganese nitrate and sodium hydroxide, the counterions include nitrate and sodium, and the complementary inorganic elements include nitrogen, oxygen, and / or sodium. In some embodiments, the ceramic precursors include manganese nitrate and sodium hydroxide, the counterions include nitrate and sodium, the complementary inorganic elements include nitrogen, oxygen, and / or sodium, and nitrogen, oxygen, sodium, ora combination thereof penetrate the ceramic and / or the substrate polymer matrix internal volume.

[0144]

[0144] In some embodiments, the ceramic precursors include manganese sulfate and potassium persulfate and / or ammonium hydroxide, the counterions include sulfate and ammonium and / or potassium, and the complementary inorganic elements include sulfur, oxygen, nitrogen, and / or potassium. In some embodiments, the ceramic precursors include manganese sulfate and potassium persulfate and / or ammonium hydroxide, the counterions include sulfate and ammonium and / or potassium, the complementary inorganic elements include sulfur, oxygen, nitrogen, and / or potassium, and nitrogen, oxygen, sodium, or a combination thereof penetrate the ceramic and / or the substrate polymer matrix internal volume.

[0145]

[0145] The ceramic that is deposited onto the polymer substrate may be in the form of discrete particulates or smaller aggregates. In some embodiments, the size of the discrete particulates or smaller aggregates, i.e., the average particle size of the ceramic (e.g., mean diameter), is from about 0.05 pm to about 5 pm, from about 0.5 pm to about 10 pm, or from about 0.1 pm to about 0.5 pm. In some embodiments, the average particle size (e.g., mean diameter) is less than about 10 pm, less than about 5 pm, less than about 1 pm, less than about 0.5 pm, less than about 0.1 pm, or less than about 0.05 pm. In some embodiments, the ceramic deposited onto the polymer may be in the form of networked particulates, agglomerations or aggregates. In some embodiments, the ceramic may be nanostructured and have geometrically similar features or structures such as plates, rods, spheroids or agglomerates which have at least one dimension that is less than about 100 nm.

[0146]

[0146] In some embodiments, the ceramic that is deposited onto the polymer substrate has an average thickness of from about 0.05 pm to about 5 pm, or from about 0.05 pm to about 10 pm, or from about 0.1 pm to about 0.5 pm, or less than about 10 pm, or less than about 5 pm, or less than about 1 pm, or less than about 0.5 pm, or less than about 0.25 pm, or less than about 0.2 pm, or less than about 0.15 pm, or less than about 0.1 pm, or less than about 0.075 pm, or less than about 0.05 pm outside of the polymer, i.e., as measured from the external surface of the polymer substrate. The mean thickness of the ceramic is the average distance from the external surface of the polymer substrate to the external surface of the ceramic.

[0147]

[0147] In some embodiments, the ceramic that is deposited onto the polymer substrate has a secondary structure, such as in the form of plates or a platelike morphology on the outer surface of the ceramic, i.e., the surface of the ceramic that is not in contact with the substrate.

[0148]

[0148] In some embodiments, the ceramic is crystalline. In other embodiments the ceramic is amorphous. In some embodiments, the ceramic contains an aggregate of crystalline domains.

[0149] Methods of manufacture

[0150]

[0149] Methods are provided for production of water repellent composites as described herein.

[0151]

[0150] In some embodiments, a method of manufacturing a composite as described herein includes: (a) contacting a polymer substrate with one or more functional chemicals, e.g., one or more functional chemicals that include urethane and / or acrylate groups and removing excess liquid; and (b) heating the functionalized polymer substrate produced in step (b) to a temperature sufficient to drive a crosslinking reaction within the functional layer, thereby generating afunctional coating layer, e.g., a urethane- and / or acrylate-containing (urethane and / or acrylic matrix) functional coating layer. In some embodiments, the substrate is cleaned prior to step (a), which improves overall uniform performance of the composite.

[0152]

[0151] In some embodiments, a method of manufacturing a composite as described herein includes: (a) contacting a polymer substrate with at least one first solution comprising a metal salt or a metal-organic complex, and optionally, an oxidizing agent, an amine, ammonia, or other reactive precursor(s), wherein the first solution is at least partially absorbed into the polymer matrix; (b) removing excess liquid from the polymer substrate; (c) contacting the polymer substrate with at least one second solution comprising a metal salt or a metal-organic complex, and optionally, an oxidizing agent, an amine, ammonia, or other reactive precursor(s), wherein said solution is at least partially absorbed into the polymer matrix; (d) removing excess liquid from the polymer substrate; (e) heating to a temperature sufficient to remove the solvent from said polymer substrate, sufficient to drive a ceramic-forming reaction with the metal salt, or sufficient to decompose or react the metal-organic complex, thereby forming a polymer-ceramic composite; (f) contacting the polymer substrate treated with the first and second solutions produced in step (e) with one or more functional chemicals, e.g., one or more functional chemicals containing urethane and / or acrylate groups and removing excess liquid; and (g) heating the polymer-ceramic composite to a temperature sufficient to drive a crosslinking reaction, thereby generating a water repellent functional layer, e.g., a urethane- and / or acrylate-containing (urethane and / or acrylic matrix) functional layer. In some embodiments, the substrate is cleaned prior to step (a), which improves overall uniform performance of the composite.

[0153]

[0152] In some embodiments in which a ceramic is included in the composite, the polymer substrate material absorbs metal salts or precursors, and the ceramic is produced in situ on the polymer substrate. In some embodiments, these ceramic precursors or salts are dissolved into a solvent or solvent mixture that is absorbed into the polymer substrate. In some embodiments, the metal salts or precursors include a metal nitrate, a metal acetate, a metal sulfate, a metal chloride, or mixtures thereof. The solvent may include, but is not limited to, an alcohol, acetone, dimethyl carbonate, methyl acetate, tert-butyl acetate, propylene carbonate, acetic acid, methyl ethyl ketone, or mixtures thereof, and / or any other solvent described herein, supra. In other embodiments, the metal salts or precursors include a phosphate, a carbonate, an oxalate, a hydroxide, a sulfate, or mixtures thereof. In some embodiments, the metal salts or precursors include the components of the ceramic. In some embodiments, the metal salts or precursors include metal organic complexes, such as, but not limited to, transition metal amine complexes, transition metal amide complexes, alkaline earth metal amine complexes, alkaline earth metal amide complexes, and coordination complexes of transition metals and amines. In some embodiments, the precursors include an oxidizing agent such as a permanganate, a persulfate, hydrogen peroxide, a chlorate, a perchlorate, or a hypochlorite which accelerates the formation of the ceramic on the polymer substrate. In other embodiments, the precursors include an amine, an amide, or ammonia which accelerates the formation of the ceramic on the polymer substrate. In some embodiments, the precursors include a catalyst which accelerates the precipitation of a ceramic on the substrate. In some embodiments, the precursors provide multiple benefits. In some embodiments the ceramic precursors include one or more of a metal salt, components of the ceramic, metal organic complexes, an oxidizing agent, an amine, an amide or ammonia.

[0154]

[0153] Other nonlimiting examples of materials which may be added to the reactive solutions or rinses in order to provide process or operational benefits are penetrants and solvents, wetting agents, surfactants and dispersants, pH modifiers, anti-scaling chemicals, colorants, and defoaming agents.

[0154] In some embodiments, the metal salts or precursors are dissolved or dispersed into a solvent. In some embodiments, the polymer substrate is contacted with the solution that includes the metal salts or ceramic precursors and solvent. In some embodiments, the solution is absorbed into the polymer substrate.

[0155]

[0155] In some embodiments, the polymer substrate is contacted or absorbed with multiple solutions (i.e., two or more solutions) that contain different metal salts or precursors. For example, the multiple solutions may contain the same or different solvents. In some embodiments, the multiple solutions, if mixed, react to form a precipitant, such as the ceramic. In some embodiments, the reaction between these multiple solutions results in a double replacement reaction to form products that include at least one precipitant.

[0156]

[0156] In some embodiments, the polymer substrate is contacted or absorbed with one solution that contains the one or more metal salt and / or one or more ceramic precursor.

[0157]

[0157] In some embodiments, multiple solutions are used, which if exposed to a change in pH, would react under the new pH condition to form a precipitant, such as a ceramic. In some embodiments, the reaction between these solutions results in a double replacement reaction. In some embodiments, the products include at least one precipitant. In some embodiments, a single solution is used which contains the metal salts and / or ceramic precursors.

[0158]

[0158] In some embodiments, the polymer substrate with absorbed solution that contains metal salts or ceramic precursors and solvent is heated. The heating may cause solvent evaporation and / or precipitation of ceramic. In some embodiments, there is a chemical reaction upon heating, such as, for example, precipitation of ceramic due to supersaturation, and / or migration of ceramic precipitant to the external surface of the polymer substrate. In some embodiments, at least a portion of the ceramic precipitant remains within the interior volume of the polymer matrix.

[0159]

[0159] In some embodiments, the polymer substrate is dipped or submerged into a solution that includes a first metal salt and then dipped or submerged into a solution that includes a second metal salt, wherein the solutions absorb into the polymer or swell the polymer. In some embodiments, the polymer includes metal salts within the interior volume and / or on the external surface of the polymer substrate. In some embodiments, the polymer substrate is then heated to evaporate the solvent, react the salts, or a combination thereof. In some embodiments, the solutions migrate to the external surface of the polymer substrate during heating. In some embodiments, ceramic precipitates within the interior volume of the polymer matrix, on the external surface of the polymer substrate, or a combination thereof. In some embodiments, the ceramic protrudes outward from the external surface of the polymer substrate.

[0160]

[0160] In some embodiments, the polymer substrate is contacted with a solution that includes a first metal salt, and then is contacted with a solution that includes a second metal salt, wherein the polymer substrate absorbs at least a portion of one or both of the solutions or swells upon being contacted with one or both of the solutions, and the solutions that independently include water or water and one or more cosolvents such as EGBE or DEGBE. In some embodiments, the polymer substrate is contacted with a combination of a first metal salt and a second metal salt, wherein the polymer substrate is first contacted with the first metal salt and then contacted with the second metal salt, the first metal salt includes one or more first ionic compounds, nonlimiting examples of which are calcium nitrate tetrahydrate or magnesium nitrate hexahydrate, and the second metal salt includes one or more second ionic compounds, nonlimiting examples of which are potassium phosphate dibasic or sodium oxalate dihydrate. In some embodiments, the contacting includes dipping the polymer substrate into one or more of the solutions, submerging the polymer substrate in one or more of the solutions, spraying the polymer substrate with one or more of the solutions, or a combination thereof.

[0161]

[0161] In some embodiments, the polymer substrate is pre-treated before contacting with the solution that includes the one or more first ionic compounds. In some embodiments, the pre- treatment includes one or more of contacting the polymer substrate with a solution of sodium hydroxide from about 0.25% (w / w) to about 5% (w / w) for about 15 seconds to about 30 minutes, rinsing the polymer substrate with water or a solvent that includes water and a cosolvent, mechanically dewatering the polymer substrate, drying the polymer substrate under the ambient atmosphere at a temperature from about ambient temperature (e.g., about 20°C) to about 140°C, and / or equilibrating the polymer substrate against ambient conditions. The solvent may include, but is not limited to, an alcohol, acetone, dimethyl carbonate, methyl acetate, tert-butyl acetate, propylene carbonate, acetic acid, methyl ethyl ketone, or mixtures thereof, and / or any other solvent described herein, supra. In some embodiments, the cosolvent may include, but is not limited to, an alcohol, a ketone, a dialkyl carbonate, an alkyl carboxylic acid, an alkyl ester of an alkyl carboxylic acid, an alkyl diol, an ether, or mixtures thereof, and / or another other cosolvent described herein, supra.

[0162]

[0162] In some embodiments, the polymer substrate is further treated after contacting with the solution that includes the one or more first ionic compounds and before contacting with the solution that includes the one or more second ionic compounds. In some embodiments, the further treatment includes one or more of mechanically dewatering the polymer substrate and / or drying the polymer substrate under ambient atmosphere at a temperature from about ambient temperature (e.g., about 20°C) to about 140°C.

[0163]

[0163] In some embodiments, the solution that includes the one or more first ionic compounds and the solution that includes the one or more second ionic compounds independently include water or a solvent that includes water and one or more cosolvents. In some embodiments where the solvent includes water and one or more cosolvents, the ratio of water to the total of one or more cosolvents is from about 1 :99 (v / v) to about 999: 1 (v / v). In some embodiments where the solvent includes water and one or more cosolvents, the ratio of water to the total of one or more cosolvents is from about 1 :99 (w / 2) to about 999:1 (w / w). In some embodiments, the solvent is water. In some embodiments, the solvent is from about 0.25% (w / w) to about 50% EGBE in water (w / w). In some embodiments, the solvent is from about 0.5% (w / w) to about 5% EGBE in water (w / w) . In some embodiments, the solvent is from about 1% (w / w) to about 2% EGBE in water (w / w) . In some embodiments, the solvent is from about 0.25% (w / w) to about 50% DEGBE in water (w / w) . In some embodiments, the solvent is from about 0.5% (w / w) to about 5% DEGBE in water (w / w). In some embodiments, the solvent is from about 1% (w / w) to about 2% DEGBE in water (w / w).

[0164]

[0164] In some embodiments, the polymer substrate is dipped or submerged into a solution that includes a metal organic complex. In some embodiments, the polymer substrate includes the metal organic complex within the interior volume of the polymer matrix and / or on the external surface of the polymer substrate. In some embodiments, the polymer substrate is then heated to evaporate the solvent, decompose or react with the metal organic complex, or a combination thereof. In some embodiments, the heating decomposes the metal-organic complex into ceramic. In some embodiments, the solutions migrate to the external surface of the polymer substrate during heating. In some embodiments, ceramic precipitates within the interior volume of the polymer matrix, on the external surface of the polymer substrate, or a combination thereof. In some embodiments, the ceramic protrudes outward from the external surface of the polymer substrate.

[0165]

[0165] In some embodiments the polymer substrate is dipped or submerged into a solution that includes a metal organic complex. In some embodiments, the polymer substrate includes the metal organic complex within the interior volume of the polymer matrix and / or on the external surface of the polymer substrate. In some embodiments, the polymer substrate is then contacted with a pH adjustment solution and / or with a catalyst containing solution to form a precipitate of ceramic. In some embodiments, the solutions migrate into the polymer substrate. In some embodiments, ceramic precipitates within the interior volume of the polymer matrix, on the external surface of the polymer substrate, or a combination thereof. In some embodiments, the ceramic protrudes outward from the external surface of the polymer substrate.

[0166]

[0166] In some embodiments, the polymer substrate is dipped or submerged into a solution that contains a metal salt and an oxidizing agent such as, but not limited to, oxygen, halogens, hydrogen peroxide, ozone, strong acids including but not limited to nitric acid and sulfuric acid, potassium permanganate, potassium dichromate, or hypochlorites. In some embodiments, the polymer substrate includes the metal salt and / or the oxidizing agent within the interior volume of the polymer matrix and / or on the external surface of the polymer substrate. In some embodiments, the polymer substrate is dipped sequentially into a solution containing a metal salt, followed by a solution containing an oxidizing agent. In some embodiments, the polymer substrate is first dipped into a solution containing an oxidizing agent followed by a solution containing a metal salt. In some embodiments, the oxidizing agent oxidizes the metal ions in solution and forms a ceramic precipitate within the interior volume of the polymer matrix and / or on the external surface of the polymer substrate. In some embodiments the ceramic protrudes outward from the external surface of the polymer substrate.

[0167]

[0167] In some embodiments, the polymer substrate is contacted by a solution that contains a metal salt and an oxidizing agent by spraying, flooding, padding, or gravure coating. In some embodiments, the polymer substrate includes the metal salt and / or the oxidizing agent within the interior volume of the polymer matrix and / or on the external surface of the polymer substrate. In some embodiments, the polymer substrate is sequentially contacted by spraying, flooding, padding, or gravure coating with a solution containing a metal salt, followed by a solution containing an oxidizing agent. In some embodiments, the polymer substrate is first sprayed, flooded, padded, or gravure coated into a solution containing an oxidizing agent followed by a solution containing a metal salt. In some embodiments, the oxidizing agent oxidizes the metal ions in solution and forms a ceramic precipitate within the interior volume of the polymer matrix and / or on the external surface of the polymer substrate. In some embodiments the ceramic protrudes outward from the external surface of the polymer substrate.

[0168]

[0168] In some embodiments the substrate is functionalized via spraying, immersing, dipping, vapor depositing, spin coating, gravure coating, knife coating, or roll coating the substrate with a functionalization or functional coating solution.

[0169] In some embodiments, the metal salt in step (a) may include one or more of an alkali metal nitrate, an alkaline earth metal nitrate, an alkali metal chloride, an alkaline earth metal chloride, an alkali metal sulfate, and an alkaline earth metal sulfate. In some embodiments, the metal-organic complex in step (a) may include a metal-amine complex. In some embodiments, the amine in step (a) may include a free amine. Representative amines include, but are not limited to, methylamine, ethylamine, n-butylamine, aniline, diethylamine, methylisopropylamine, triethylamine, trimethylamine, N-methylphenethylamine, monoethanolamine (MEA), diethanolamine (DEA), diglycolamine (DGA), and / or hexamine.

[0169]

[0170] In some embodiments, the heating in step (b) may be at a temperature of about 70°C to about 170°C.

[0170]

[0171] In some embodiments, the functional chemicals that include urethane include a non-fluorinated cationic acrylate copolymer emulsion, a blocked isocyanate crosslinker, and an organic solvent or glycol additive. In some embodiments, the functional chemicals that include urethane groups include non-fluorinated silicone emulsion, a blocked isocyanate crosslinker, and an organic solvent or glycol additive. In some embodiments, the functional chemicals that include urethane groups include a non-fluorinated cationic acrylate copolymer emulsion, a non-fluorinated cationic silicone emulsion, a blocked isocyanate crosslinker, and an organic solvent additive. In some embodiments, the blocked isocyanate crosslinker has a deblocking temperature of about 70°C to about 160°C, about 80°C to about 140°C, about 90°C to about 130°C.

[0171]

[0172] In some embodiments, the functional chemical chemicals that include urethane groups are prepared by mixing individual solutions of non-fluorinated cationic acrylate copolymer emulsion, non-fluorinated cationic silicone emulsion, blocked isocyanate crosslinker, and organic solvent additive containing glycol to form a concentrated functional chemical solution. Within about 2 days, or about 3 days, or about 1 week, or about 1 month, or about 3 months, or about 6 months, or longer of controlled storage, the concentrated functional chemical solution is used. Controlled storage requires no direct sunlight or UV exposure and a temperature of about 5°C to about 30°C. The concentrated functional chemical solution is then added to the production equipment where the immersion is to be carried out and diluted to a final target functional chemical solution.

[0172]

[0173] In some embodiments, the functional chemicals that include acrylate include a non-fluorinated cationic acrylate copolymer emulsion, a blocked isocyanate crosslinker, and an organic solvent or glycol additive that are used to form a functional layer that includes an acrylic matrix. In some embodiments, the functional chemicals that include acrylic groups include non-fluorinated silicone emulsion, a blocked isocyanate crosslinker, and an organic solvent or glycol additive that are used to form a functional layer that includes an acrylic matrix. In some embodiments, the functional chemicals that include acrylate groups include a non-fluorinated cationic acrylate copolymer emulsion, a non-fluorinated cationic silicone emulsion, a blocked isocyanate crosslinker, and an organic solvent additive that are used to form a functional layer that includes an acrylic matrix. Some nonlimiting examples of acrylate monomers and esters include acrylic acid, methyl acrylate, ethyl acrylate, 2-Ethylhexyl acrylate, 2-hydroxyethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, and 2-hydroxypropyl acrylate. Polymerization of acrylate monomers and copolymers result in the formation of polyacrylate materials, acrylate polymers or acrylic matrixes. Nonlimiting examples of acrylic matrix compositions include polyalkyl acrylates such as poly(methyl acrylate) (PMA), poly(ethyl acrylate) (PEA), poly(butyl acrylate) (PBA), cyanoacrylates, polyacrylamides, or polyglycolic acrylates such as Polyethylene Glycol Monomethyl Ether Acrylate or Polyethylene Glycol Diacrylate (PEGDA).

[0173]

[0174] In some embodiments, the functional chemicals that include acrylate groups are prepared by mixing individual solutions of non-fluorinated cationic acrylate copolymer emulsion, non-fluorinated cationic silicone emulsion, blocked isocyanate crosslinker, and organic solvent additives containing glycols, a glycol functional groups or glycol ethers to form a concentrated functional chemical solution. Within about 2 days, or about 3 days, or about 1 week, or about 1 month, or about 3 months, or about 6 months, or longer of controlled storage, the concentrated functional chemical solution is used. Controlled storage requires no direct sunlight or UV exposure and a temperature of about 5°C to about 30°C. The concentrated functional chemical solution is then added to the production equipment where the immersion is to be carried out and diluted to a final target functional chemical solution to form a functional layer that includes an acrylic matrix.

[0174]

[0175] In some embodiments, the functional layer applied to the substrate forms a water repellent composite material. In some embodiments, the substrate of the water repellent composite material is a textile or fabric or a ripstop textile or fabric. In some embodiments, the water repellent composite material is further processed to reduce the surface roughness or reduce the air permeability of the textile or fabric. Processes used to reduce the surface roughness or reduce the air permeability of the textile or fabric may include calendering, heat setting, cire treatment, or heat pressing.

[0175]

[0176] In some embodiments, the water repellent composite is further processed to form a water repellent composite assembly by additional coating applications of urethanes, such as, but not limited to, polyurethanes or thermoplastic urethane (TPU), or laminations to additional membrane materials to form a multilayer water repellent composite textile or fabric.

[0176] EXAMPLES

[0177]

[0177] The following examples are intended to illustrate, but not limit, the invention.

[0178] Example 1

[0179]

[0178] A light weight (~2 oz / yd), 50D (denier), rip-stop nylon was used as the polymer substrate for the formation of a composite. The polymer substrate material was cleaned with a scouring process by immersion in 2% NaOH solution for about 10 minutes, rinsed with water, mechanically dewatered, air-dried at a temperature of about 105°C, and conditioned to laboratory ambient conditions.

[0180]

[0179] The cleaned substrates were then processed via batch solution contact by immersion in alternating 25 mM solutions of a calcium source ( / .e., calcium nitrate tetrahydrate) and a phosphate source ( / .e., ammonium phosphate dibasic) at a temperature of about 20°C for about 30 seconds (sec) per stage. The substrates were then treated by up to three sequential solution contacts in the same 25 mM solutions by immersion to generate more uniformly deposited structures and particulates. Samples were dewatered with mechanical rollers to increase uniformity and reduce particulate formation that occurred in the immersion baths. The samples were air-dried at room temperature after the solution contact by immersion cycles until dry and then annealed at a temperature of about 140°C for about 10 minutes. The result was the deposition of a structured ceramic on the nylon substrate. The deposit structure was imaged to assess uniformity and characterize the material.

[0181]

[0180] A representative fiber from a three solution contact process was cross-sectioned and imaged with a scanning electron microscope (SEM) and the concentration of elements was measured along the radius of the fiber with energy dispersive x-ray spectroscopy (EDS).

[0182]

[0181] The processed deposit structure was further functionalized to impart hydrophobic properties via batch solution contact by immersion in a mixed water emulsion comprising a non-fluorinated cationic acrylate copolymer emulsion, a silicone containing emulsion, a blocked isocyanate crosslinker, and an organic solvent additive containing glycol. The samples were removed from the functionalization solution and dried at about 140°C for about 5 minutes.

[0182] The composite was evaluated by Inductively Coupled Mass Spectroscopy (ICP-MS) to determine the concentration of [Si], The composite had a [Si] concentration of greater than 200 ppm.

[0183]

[0183] The samples were tested and evaluated to AATCC 22 standards for spray rating to assess resistance to wetting by water, and were observed to possess water resistance by spray ratings greater than 90. Household wash resistance was measured by washing the material in a household washer for 3 wash / dry cycles. Extended wash resistance was measured by washing the material in a AATCC LP1-2021 , Home Laundering: Machine Washing, compatible washer for a period of 24 hours

[0184] ( https: / / me bers .aatcc. orq / store / l p001 Z2212, . The samples from each washing condition were re-tested and rated to AATCC 22 standards and were observed to possess spray ratings greater than 80. Air permeability was measured according to ASTM D737 after processing and remained within 25% of the untreated textile condition, after processing and after washing.

[0185]

[0184] The composite was evaluated by ICP-MS to determine the concentration of [Si] after the extended wash. After washing, the composite had a [Si] concentration of greater than 100 ppm.

[0186] Example 2

[0187]

[0185] A light weight (~2 ozZyd), 50D (denier), rip-stop nylon was used as the polymer substrate for the formation of a composite.

[0188]

[0186] The substrates were processed via continuous processing methods in a pilot scale production line. The 300mm wide substrates were placed on an unwinder spool and placed into contact by immersion in alternating 25 mM solutions of a calcium source ( / .e., calcium nitrate tetrahydrate) and a phosphate source ( / .e., ammonium phosphate dibasic) at a temperature of about 20°C for about 30 seconds (sec) per stage. Samples were mechanically dewatered after each immersion stage to generate more uniformly deposited structures and particulates. The samples were dried and then annealed at a fabric temperature of about 140°C for about 5 minutes. The samples were rewound onto a rewinder spool under tension control. The result was the deposition of a structured ceramic on the nylon substrate. The deposit structure was imaged to assess uniformity and characterize the material.

[0189]

[0187] The processed deposit structure was further functionalized to impart hydrophobic properties via batch solution contact by immersion in a mixed water emulsion comprising a non-fluorinated cationic acrylate copolymer emulsion, a silicone containing emulsion, a blocked isocyanate crosslinker, and an organic solvent additive containing glycol. The samples were removed from the functionalization solution and dried at about 140°C for about 5 minutes.

[0190]

[0188] The composite was evaluated by Inductively Coupled Mass Spectroscopy (ICP-MS) to determine the concentration of [Si], The composite had a [Si] concentration of greater than 200 ppm.

[0191]

[0189] The samples were tested and evaluated to AATCC 22 standards for spray rating and were observed to possess water resistance by spray ratings greater than 90.

[0192] Household wash resistance was measured by washing the material in a household washer for 3 wash / dry cycles. Extended wash resistance was measured by washing the material in a AATCC Monograph 6 compatible washer for a period of 24 hours. The samples from each washing condition were re-tested and rated to AATCC 22 standards and were observed to possess spray ratings greater than 80. Air permeability was measured according to ASTM D737 after processing and remained within 25% of the untreated textile condition, after processing and after washing.

[0193]

[0190] The composite was evaluated by ICP-MS to determine the concentration of [Si] after the extended wash. After washing, the composite had a [Si] concentration of greater than 100 ppm.

[0194] Example 3

[0195]

[0191] A light weight (~2 oz / yd), 50D (denier), rip-stop nylon was used as the polymer substrate for the formation of a composite.

[0196]

[0192] The substrates were processed via continuous processing methods in a manufacturing scale production line. The 1500mm wide substrates were placed on a leader fabric and bin and placed into contact by immersion in alternating 25 mM solutions of a calcium source ( / .e., calcium nitrate tetrahydrate) and a phosphate source ( / .e., ammonium phosphate dibasic) at a temperature of about 30°C for about 1-15 seconds (sec) per stage. Samples were mechanically dewatered after each immersion stage to generate more uniformly deposited structures and particulates. The samples were dried in a pin clamp mounted tenter frame in a first heated zone and then annealed at an elevated temperature zone. The overall drying and curing time was about 2-3 minutes with fabric temperatures ranging from 100°C to about 160°C at the exit. The samples were cooled by air and placed into a bin. The result was the deposition of a structured ceramic on the nylon substrate. The deposit structure was imaged to assess uniformity and characterize the material.

[0193] The 1500mm wide substrates were fed from the bin and the processed deposit structure was further functionalized to impart hydrophobic properties via continuous solution contact by immersion in a mixed water emulsion containing a non-fluorinated cationic acrylate copolymer emulsion, a silicone containing emulsion, a blocked isocyanate crosslinker, and an organic solvent additive containing glycol. The total immersion time was about 1-15 seconds. The samples were continuously removed from the functionalization solution, dried, and cured in a two zone tenter for about 1 minute. Fabric temperatures in the tenter ranged from about 100°C to about 160°C at the exit. Several line speed and tenter conditions were evaluated, reducing the fabric exit temperature to about 155°C, about 150°C, about 145°C, about 140°C, about 135°C, about 130°C, about 125°C, about 120°C, about 115°C and about 110°C.

[0197]

[0194] The composites were evaluated by ICP-MS to determine the concentration of [Si], The composites had [Si] concentrations of greater than 150 ppm.

[0198]

[0195] The samples were tested and evaluated to AATCC 22 standards for spray rating and were observed to possess water resistance by spray ratings greater than 90.

[0199] Household wash resistance was measured by washing the material in a household washer for 3 wash / dry cycles. Extended wash resistance was measured by washing the material in a AATCC LP1-2021 , Home Laundering: Machine Washing, compatible washer for a period of 24 hours. The samples from each washing condition were re-tested and rated to AATCC 22 standards and were observed to possess spray ratings greater than 80. Air permeability was measured according to ASTM D737 after processing and remained within 25% of the untreated textile condition, after processing and after washing.

[0200]

[0196] The composites were evaluated by ICP-MS to determine the concentration of [Si] after the extended wash. After washing, the composites had a [Si] concentration of greater than 100 ppm.

[0201] Example 4

[0202]

[0197] A light weight (~2 oz / yd), 50D (denier), polyester was used as the polymer substrate for the formation of a composite.

[0203]

[0198] These substrates were then processed via continuous processing methods in a manufacturing scale production line. The 1500mm wide substrates were placed on a leader fabric and bin and placed into contact by immersion in alternating 25 mM solutions of a calcium source ( / .e., calcium nitrate tetrahydrate) and a similar concentration of a phosphate source ( / .e., ammonium phosphate dibasic) at a temperature of about 30°C for about 1-15 seconds (sec) per stage. Samples were mechanically dewatered after each immersion stage to generate more uniformly deposited structures and particulates. The samples were dried in a pin clamp mounted tenter frame in a first heated zone and then annealed at an elevated temperature zone. The overall drying and curing time was about 2-3 minutes with fabric temperatures ranging from 100°C to about 160°C at the exit. The samples were cooled by air and placed into a bin. The result was the deposition of a structured ceramic on the nylon substrate. The deposit structure was imaged to assess uniformity and characterize the material.

[0204]

[0199] The 1500mm wide substrates were fed from the bin The processed deposit structure was further functionalized to impart hydrophobic properties via continuous solution contact by immersion in a mixed water emulsion containing a non-fluorinated cationic acrylate copolymer emulsion, a silicone containing emulsion, a blocked isocyanate crosslinker, and an organic solvent additive containing glycol. The total immersion time was about 1-15 seconds. The samples were continuously removed from the functionalization solution, dried and cured in a two zone tenter for about 1 minute. Fabric temperatures in the tenter ranged from about 100°C to about 160°C at the exit. Several line speed and tenter conditions were evaluated reducing the fabric exit temperature to about 155°C, about 150°C, about 145°C, about 140°C, about 135°C, about 130°C, about 125°C, about 120°C, about 115°C and about 110°C.

[0205]

[0200] The composites were evaluated by ICP-MS to determine the concentration of [Si], The composites had [Si] concentrations of greater than 150 ppm.

[0206]

[0201] The samples were tested and evaluated to AATCC 22 standards for spray rating and were observed to possess water resistance by spray ratings greater than 90.

[0207] Household wash resistance was measured by washing the material in a household washer for 3 wash / dry cycles. Extended wash resistance was measured by washing the material in a AATCC LP1-2021 , Home Laundering: Machine Washing, compatible washer for a period of 24 hours. The samples from each washing condition were re-tested and rated to AATCC 22 standards and were observed to possess spray ratings greater than 80. Air permeability was measured according to ASTM D737 after processing and remained within 25% of the untreated textile condition, after processing and after washing.

[0208]

[0202] The composites were evaluated by ICP-MS to determine the concentration of [Si] after the extended wash. After washing, the composites had a [Si] concentration of greater than 75 ppm.

[0209] Example 5

[0203] Light weight recycled nylon rip stop textiles having wet pick up values of 67% and 109%, respectively, were used as polymer substrates for the formation of a composite.

[0210]

[0204] The substrates were processed by placing the fabrics into contact with chemical functionalization solutions of a non-fluorinated cationic acrylate copolymer emulsion, a blocked isocyanate crosslinker, and an organic solvent additive containing glycol at total solids contents of 1.4%, 1.7%, 2% and 2.6% for about 10 seconds, and mechanically dewatered. The samples were then dried and cured at 140°C for 10 minutes. The ratio of acrylic copolymer solids to other added solids (containing glycol) of the solution after mixing was about 0.75:1, 1.1:1, 1.5:1, and a2.25:1.

[0211]

[0205] The resulting composites were then tested for chlorine content [Cl] as an indicator of acrylic content using X-ray fluorescence (XRF) before and after a 24h extended wash. The results are shown in Table 1.

[0212] Table 1

[0213] > > > >

[0214]

[0215] > > > >

[0216] Example 6

[0217]

[0206] A light weight recycled nylon rip stop textile having wet pick up value of 67% was used as the polymer substrate for the formation of a composite.

[0218]

[0207] The substrates were processed by placing the fabric into contact with chemical functionalization solution of a non-fluorinated silicone emulsion, a non-fluorinated cationic acrylate copolymer emulsion, a blocked isocyanate crosslinker, an organic solvent additive containing glycol at total solids contents of about 2% for about 10 seconds and mechanically dewatered. The samples were then dried and cured for about 2 minutes, reaching a fabric temperature of about 150°C . The ratio of acrylic copolymer solids to silicone emulsion solids was about 3:1.

[0219]

[0208] The resulting composites were then mounted and coated with a gold layer and a protective carbon layer. A focused ion beam was used to cross section the materials for examination by the Scanning Transmission Electron Microscopy (STEM) technique of High-angle annular dark-field imaging (HAADF) with Energy Dispersive X-Ray Spectroscopy (EDS). The results can be seen in Figure 2.

[0220] Example 7

[0209] A light weight recycled nylon rip stop textile having wet pick up value of 67% was used as the polymer substrate for the formation of a composite.

[0221]

[0210] The substrates were processed by placing the fabric into contact with chemical functionalization solution of a non-fluorinated silicone emulsion, a non-fluorinated cationic acrylate copolymer emulsion, a blocked isocyanate crosslinker in varying amounts as shown in Table 2, an organic solvent additive containing glycol at total solids contents of about 2% for about 30 seconds and mechanically dewatered. The samples were then dried and cured for about 10 minutes as outlined below. The ratio of acrylic copolymer solids to silicone emulsion solids was about 3:1. Results are shown in Table 2.

[0222] Table 2

[0223] < <

[0224]

[0225] > >

[0226]

[0211] The resulting composite samples A, C, and E were tested by instrumented nanoindentation along the axial direction of the fiber in the fabric from about 5nm of contact depth to about 50nm of contact depth. The measured storage modulus for samples C and E decreased with increasing contact depth. The measured storage modulus for sample A was relatively consistent in the range of 0.5-1.0 GPa across the contact depth range of about 5 nm to about 50 nm.

[0227] Example 8

[0228]

[0212] A light weight (~2 oz / yd), 50D (denier), rip-stop nylon was used as the polymer substrate for the formation of a composite.

[0229]

[0213] The substrates were processed via continuous processing methods in a manufacturing scale production line. The 1500 mm wide substrates were placed on a leader fabric and bin and placed into contact by immersion in alternating 25 mM solutions of a calcium source ( / .e., calcium nitrate tetrahydrate) and a phosphate source ( / .e., ammonium phosphate dibasic) at a temperature of about 30°C for about 1-15 seconds (sec) per stage. Samples were mechanically dewatered after each immersion stage to generate more uniformly deposited structures and particulates. The samples were dried in a pin clamp mounted tenter frame in a first heated zone and then annealed at an elevated temperature zone. The overall drying and curing time was about 2-3 minutes with fabric temperatures ranging from 100°C at the inlet to exit temperatures ranging from about 120°C to about 150°C at the exit. The samples were cooled by air and placed into a bin. The result was the deposition of a structured ceramic on the nylon substrate. The deposit structure was imaged to assess uniformity and characterize the material.

[0230]

[0214] The 1500mm wide substrates were fed from the bin and the processed deposit structure was further functionalized to impart hydrophobic properties via continuous solution contact by immersion in a mixed water emulsion containing a non-fluorinated cationic acrylate copolymer emulsion, a blocked isocyanate crosslinker, and an organic solvent additive containing glycol. The total solids content of the mixed water emulsion is about 2-3%. The total immersion time was about 1-15 seconds. The samples were continuously removed from the functionalization solution, dried, and cured in a two zone tenter for about 1 minute. Fabric temperatures in the tenter ranged from about 100°C to about 160°C at the exit. Several line speed and tenter conditions were evaluated, reducing the fabric exit temperature to about 155°C, about 150°C, about 145°C, about 140°C, about 135°C, about 130°C, about 125°C, about 120°C, about 115°C, and about 110°C.

[0231]

[0215] The composites were evaluated by ICP-MS to determine the concentration of [Si], The composites had [Si] concentrations of about 100 ppm to about 300 ppm.

[0232]

[0216] The samples were tested and evaluated to AATCC 22 standards for spray rating and were observed to possess water resistance by spray ratings greater than 90.

[0233] Household wash resistance was measured by washing the material in a household washer for 3 wash / dry cycles. Extended wash resistance was measured by washing the material in a AATCC LP1-2021 , Home Laundering: Machine Washing, compatible washer for a period of 24 hours. The samples from each washing condition were re-tested and rated to AATCC 22 standards and were observed to possess spray ratings greater than 80. Air permeability was measured according to ASTM D737 after processing and remained within 25% of the untreated textile condition, after processing and after washing.

[0234]

[0217] The composites were evaluated by ICP-MS to determine the concentration of [Si] after the extended wash. After washing, the composites had a [Si] concentration of greater than about 50% of the initial value.

[0235] Example 9

[0236]

[0218] A light weight recycled nylon rip stop textile was used as the polymer substrate for the formation of a composite.

[0219] The substrates were processed by sequential by immersion in alternating 25 mM solutions of a calcium source ( / .e., calcium nitrate tetrahydrate) and a phosphate source (J.e., ammonium phosphate dibasic) at a temperature of about 20°C for about 30 seconds (sec) per stage. Samples were mechanically dewatered after each immersion stage to generate more uniformly deposited structures and particulates. The samples were dried at 130°C oven for about 10 minutes. Samples were then placing into contact with (a) chemical functionalization solution of a non-fluorinated silicone emulsion, a non-fluorinated cationic acrylate copolymer emulsion, a blocked isocyanate crosslinker, an organic solvent additive containing glycol at total solids contents of about 2% for about 10 seconds and mechanically dewatered or (b) chemical functionalization solution of a non-fluorinated cationic acrylate copolymer emulsion, a blocked isocyanate crosslinker, an organic solvent additive containing glycol at total solids contents of about 2% for about 10 seconds and mechanically dewatered. The samples were then dried and cured for about 10 minutes, reaching a textile temperature of about 140°C .

[0237]

[0220] The resulting composites were then mounted and coated with a gold layer and a protective carbon layer. A focused ion beam was used to cross section the materials for examination by the Scanning Transmission Electron Microscopy (STEM) technique of Energy Dispersive X-ray Spectroscopy (EDS). In these cases, a water repellent layer was observed, having a thickness of 20-50 nm and a silicon content of about 1 atomic % was identified. The silicon content at a penetration depth of about 50 nm from the surface was measured at about 0.1 to about 0.2 atomic %. An EDS line scan identified a maximum atomic percentage of about 15-30% at the water repellent layer outer surface.

[0238] Example 10

[0239]

[0221] A light weight recycled nylon rip stop textile was used as the polymer substrate for the formation of a composite.

[0240]

[0222] The substrates were processed by sequential by immersion in alternating 25 mM solutions of a calcium source ( / .e., calcium nitrate tetrahydrate) and a phosphate source ( / .e., ammonium phosphate dibasic) at a temperature of about 20°C for about 30 seconds (sec) per stage. Samples were mechanically dewatered after each immersion stage to generate more uniformly deposited structures and particulates. The samples were dried at 130°C oven for about 10 minutes. Samples were then placing into contact with (a) chemical functionalization solution of a non-fluorinated cationic acrylate copolymer emulsion, a blocked isocyanate crosslinker, an organic solvent additive containing glycol at total solids contents of about 2% for about 10 seconds and mechanically dewatered or (b) chemical functionalization solution of a non-fluorinated cationic acrylate copolymer emulsion, a blocked isocyanate crosslinker, an organic solvent additive containing glycol at total solids contents of about 2% for about 10 seconds and mechanically dewatered. The samples were then dried and cured for about 10 minutes, reaching a temperature of about 140°C as measured by a surface mounted temperature indicating strip .

[0241]

[0223] The resulting composites were then mounted and coated with a gold layer and a protective carbon layer. A focused ion beam was used to cross section the materials for examination by the Scanning Transmission Electron Microscopy (STEM) with Energy Dispersive X-ray Spectroscopy (EDS). In these cases, a water repellent layer was observed, having a thickness of 20-50 nm and a silicon content of about 1 atomic % was identified. The silicon content at a penetration depth of about 50 nm from the surface was measured at about 0.1 to about 0.2 atomic %. An EDS line scan identified a maximum atomic percentage of about 5-10% at the water repellent layer outer surface.

[0242] Example 11

[0243]

[0224] Light weight woven textiles, having a fabric density of about 20 g / m2to about 200 g / m2, composed of polyester, polyester blends, nylon, recycled nylon, and nylon blends, were used as the polymer substrates for the formation of a composite. The substrates were processed according to the procedures outlined in Example 3 and Example 10. The resulting textiles showed good water repellency having a ISO9865 Bundesmann score after 10 minutes of 4 or greater, maintained an air permeability as measured by ASTM D737 within 25% of the untreated substrate. Extended wash resistance was measured by washing the material in a AATCC LP1-2021 , Home Laundering: Machine Washing, compatible washer for a period of 24 hours. The samples from each washing condition were re-tested and rated to ISO9865 Bundesmann score after 10 minutes of 3 or greater.

[0244] Example 12

[0245]

[0225] Nylon textiles, having a fabric density of about 30 g / m2to about 75 g / m2, were used as the polymer substrate for the formation of a composite. The substrates were processed according to the procedures outlined in Example 10. The resulting fabrics showed good water repellency having an ISO 9865 Bundesmann score after 10 minutes of 4 or greater, maintained an air permeability as measured by ASTM D737 within 25% of the untreated substrate. Extended wash resistance was measured by washing the material in a AATCC LP1-2021 , Home Laundering: Machine Washing, compatible washer for a period of 24 hours. The samples from each washing condition were re-tested and rated to ISO9865 Bundesmann score after 10 minutes of 3 or greater.

[0246]

[0226] Nylon fabric substrates, on which a water repellent composite was formed, were further processed to form a water repellent composite fabric by additional coating applications of urethanes.

[0247] Example 13

[0248]

[0227] Nylon textiles, having a fabric density of 30-75 g / m2, were used as the polymer substrate for the formation of a composite. The substrates were processed according to the procedures outlined in Example 10. The resulting fabrics showed good water repellency having an ISO 9865 Bundesmann score after 10 minutes of 4 or greater, maintained an air permeability as measured by ASTM D737 within 25% of the untreated substrate. Extended wash resistance was measured by washing the material in a AATCC LP1-2021 , Home Laundering: Machine Washing, compatible washer for a period of 24 hours. The samples from each washing condition were re-tested and rated to ISO9865 Bundesmann score after 10 minutes of 3 or greater.

[0249]

[0228] Nylon substrates, on which a water repellent composite was formed, were further processed to form a water repellent composite assembly by an additional lamination to polyurethane membrane materials to form multilayer water repellent composite fabrics.

[0250]

[0229] Although the foregoing invention has been described in some detail by way of illustration and examples for purposes of clarity of understanding, it will be apparent to those skilled in the art that certain changes and modifications may be practiced without departing from the spirit and scope of the invention, which is delineated in the appended claims. Therefore, the description should not be construed as limiting the scope of the invention, which is delineated in the appended claims.

[0251]

[0230] All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entireties for all purposes and to the same extent as if each individual publication, patent, or patent application were specifically and individually indicated to be so incorporated by reference.

Claims

CLAIMSWe claim:

1. A water repellent composite, comprising a water repellent layer on a substrate that comprises an external surface, wherein the water repellent layer is deposited on the external surface of the substrate, and wherein the water repellent layer has a thickness of less than about 500 nm.

2. The water repellent composite according to claim 1 , wherein said composite retains at least about 30% of its original thickness after 24 hours of continuous washing according to AATCC LP1-2021, Home Laundering: Machine Washing, and wherein the water repellent layer contains less than 1% fluorine element.

3. The water repellent composite according to claim 2, wherein the water repellent layer retains at least about 50% of its original silicon concentration [Si] after 24 hours of continuous washing according to AATCC LP1-2021 , Home Laundering: Machine Washing, and wherein the water repellent layer contains less than 100 ppm fluorine element.

4. The water repellent composite according to claim 1 , wherein more than 30% of the water repellent layer is block isocyanate derived urethane or an acrylic matrix.

5. The composite according to claim 4, wherein the water repellent layer comprises both an acrylate rich region of about 10 nm to about 200 nm in thickness and a silicon rich region of about 2 nm to about 20 nm in thickness as measured by transmission electron microscopy (TEM).

6. The water repellent composite according to claim 5, wherein the water repellent coating layer comprises a thickness of about 20 nm to about 50 nm, and wherein the silicon rich region comprises a peak silicon content of about 5 atomic percent to about 30 atomic percent.

7. The water repellent composite according to claim 6, wherein the acrylate rich region is proximal to the external surface of the substrate and the silicon rich region is distal to the external surface of substrate.

8. The water repellent composite according to claim 7, wherein an outermost region of about 25 nm of the water repellent layer comprises silicon rich regions interspersed with acrylate rich regions.

9. The water repellent composite according to claim 4, wherein the water repellent layer comprises silicon rich regions interspersed within an acrylic matrix.

10. The water repellent composite according to claim 4, wherein the water repellent layer comprises calcium phosphate (Cax(PO4)y) rich regions, wherein the concentration of calcium phosphate is greater than in the bulk material.

11. The water repellent composite according to claim 10, wherein at least a portion of the calcium phosphate regions comprise lattice spacings of about 2.1 nm to about 1.9 nm as measured by Selective Area Electron Diffraction (SAED) or a Fourier Transform of a high-resolution transmission electron microscopy (HRTEM) Image.

12. The water repellent composite according to claim 10, wherein at least a portion of the calcium phosphate domains are located proximal to the external surface of the substrate.

13. The water repellent composite according to claim 4, wherein the water repellent layer comprises a glycol ether.

14. The water repellent composite according to any of claims 1 to 13, wherein the substrate is a ripstop textile.

15. The water repellent composite according to claim 4, wherein the substrate is a textile that comprises synthetic fibers, and wherein at least a portion of the urethane and / or acrylic structure lies within the synthetic fibers as measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS).

16. The water repellent composite according to any of claims 1 to 13, wherein the substrate is a textile, and wherein storage modulus as measured in warp and weft directions by dynamic mechanical analysis (DMA) is increased by about 1.1 to about 3.5 times in comparison to an identical textile that does not comprise the water repellent layer.

17. The water repellent composite according to any of claims 1 to 13, wherein the substrate is a textile, and wherein tensile modulus as measured in a warp direction by dynamic mechanical analysis (DMA) is increased by about 1.5 to about 3.0 times in comparison to an identical textile that does not comprise the water repellent layer.

18. The water repellent composite according to any of claims 1 to 13, wherein the substrate is a textile, and wherein storage modulus as measured on an axial surface by instrumented nanoindentation is increased by about 2.0 times to about 10.0 times at 10nm of contact depth in comparison to an identical textile that does not comprise the water repellent layer.

19. The water repellent composite according to any of claims 1 to 13, wherein the substrate is a textile, and wherein the water repellent composite is further processed toreduce the surface roughness or reduce the air permeability of the textile.

20. The water repellent composite according to any of claims 1 to 13, wherein the substrate is a textile and wherein the water repellent composite is further processed to form a water repellent composite assembly by additional coating applications of urethanes or laminations to additional membrane materials to form a multilayer composite.

21. A chemical solution for functionalization of substrates by immersion, comprising a non-fluorinated cationic acrylate copolymer emulsion, a blocked isocyanate crosslinker, and an organic solvent additive containing glycol, wherein the total solids content in the chemical solution is about 1% to about 5%.

22. A chemical solution for functionalization of substrates by immersion, comprising a non-fluorinated cationic acrylate copolymer emulsion, a non-fluorinated silicone emulsion, a blocked isocyanate crosslinker, and an organic solvent additive containing glycol, wherein the total solids content in the chemical solution is about 1% to about 5%.

23. A chemical solution according to claim 22, wherein the ratio of silicone and acrylic to other added solids is about 0.5:1 to about 5:1 and wherein the ratio of acrylic solids to silicone solids is about 1:1 to about 10:1.

24. A method of manufacturing a water repellent composite, said method comprising:(a) contacting a polymer substrate with one or more functional chemicals that include urethane and / or acrylate groups and removing excess liquid; and(b) heating the functionalized polymer substrate produced in step (b) to a temperature sufficient to drive a crosslinking reaction within the functional layer, thereby generating a urethane matrix and / or acrylic matrix containing functional coating layer.

25. A method of manufacturing a water repellent composite, said method comprising:(a) contacting a polymer substrate with at least one first solution comprising a metal salt or a metal-organic complex, and optionally, an oxidizing agent, an amine, ammonia, or other reactive precursor(s), wherein the first solution is at least partially absorbed into the polymer matrix;(b) removing excess liquid from the polymer substrate;(c) contacting the polymer substrate with at least one second solution comprising a metal salt or a metal-organic complex, and optionally, an oxidizing agent, an amine, ammonia, or other reactive precursor(s), wherein said solution is at least partially absorbed into the polymer matrix;(d) removing excess liquid from the polymer substrate;(e) heating to a temperature sufficient to remove the solvent from said polymer substrate, sufficient to drive a ceramic-forming reaction with the metal salt, or sufficient to decompose or react the metal-organic complex, thereby forming a polymer-ceramic composite;(f) contacting the polymer substrate treated with the first and second solutions produced in step (e) with one or more functional chemicals containing urethane and / or acrylate groups and removing excess liquid; and(g) heating the polymer-ceramic composite to a temperature sufficient to drive a crosslinking reaction, thereby generating a water repellent urethane matrix and / or acrylic matrix containing functional layer.

26. The method of claim 25, wherein the metal salt in step (a) comprises one or more of an alkali metal nitrate, an alkaline earth metal nitrate, an alkali metal chloride, an alkaline earth metal chloride, an alkali metal sulfate, and an alkaline earth metal sulfate.

27. The method of claim 25, wherein the metal-organic complex in step (a) comprises a metal-amine complex.

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