Deposition of ceramic material to polymer substrate

Abstract

Polymer-ceramic composites and methods of making such materials are provided. The polymer-ceramic material includes a polymer substrate and a ceramic located within an interior volume of the polymer substrate and on a polymer surface.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefits of U.S. Provisional Application No. 63 / 467,403, filed May 18, 2023, and U.S. Provisional Application No. 63 / 560,512, filed March 1, 2024, both of which are incorporated herein by reference in their entirety. Technical Field

[0003] This invention relates to the deposition of ceramics on polymer substrates (particularly without the use of resin or paint), and to polymer-ceramic composites. Background Technology

[0004] Applying ceramics to polymer surfaces typically requires adhesives and resins for adhesion. Directly applying ceramics to polymer surfaces presents challenges in terms of mechanical and thermal durability. Most applications of ceramic materials to polymers involve suspending the ceramic material in a varnish or other resin and then coating the resulting suspension onto the polymer. This approach typically covers the ceramic with resin and reduces the usable surface area of ​​the ceramic material. Furthermore, this creates a distinct interface between the resin and the polymer, which can act as a failure point for the ceramic coating (such as delamination). Improved methods for depositing ceramic materials onto polymer substrates are needed. Summary of the Invention

[0005] This article provides polymer-ceramic composites and methods for manufacturing said composites.

[0006] In one aspect, a polymer-ceramic composite is provided. The composite comprises: a polymer substrate having an outer surface and an internal volume; and ceramic. The polymer-ceramic composite includes ceramic on the outer surface of the polymer substrate, and the ceramic or inorganic element at least partially occupies the internal volume of the polymer substrate.

[0007] In some embodiments, the polymer-ceramic composite is in the form of fibers or films. For example, the composite may be in the form of fibers with an average diameter of less than about 5 mm or less than about 1 mm. For example, the polymer-ceramic composite may be in the form of films with an average polymer layer thickness of less than about 5 mm or less than about 3 mm.

[0008] In some embodiments, the polymer-ceramic composite is a fiber, laminate, film, textile material, paper, or a combination thereof. In some embodiments, the polymer substrate includes polyester, polyamide, polyolefin, substituted polyolefin, polyurethane, polyol, vinyl polymer, acrylate polymer, polycarbonate, polyether, cotton, wool, paper, cellulose material, or a combination thereof. For example, the polymer substrate may include polyethylene terephthalate (PET), nylon, polyethylene, polypropylene, polyvinyl chloride (PVC), polyvinyl alcohol (PVOH), polyvinyl acetate (PVAc), polyvinylpyrrolidone, polyethylene glycol (PEG), polymethyl methacrylate (PMMA), cellulose, or mixtures thereof.

[0009] In some embodiments, the ceramic in the polymer-ceramic composite comprises a transition metal, an alkali metal, or an alkaline earth metal. In some embodiments, the ceramic comprises one or more of oxides, hydroxides, phosphates, layered double hydroxides, sulfates, carbonates, and oxalates of transition metals, alkali metals, or alkaline earth metals. In some embodiments, the ceramic comprises one or more of manganese oxide, iron oxide, calcium carbonate, hydroxyapatite, calcium phosphate, calcium oxalate, magnesium carbonate, calcium sulfate, titanium oxysulfate, and magnesium sulfate. In some embodiments, the ceramic in the polymer-ceramic composite comprises calcium, sodium, potassium, sulfur, chlorine, manganese, iron, nickel, magnesium, titanium, lithium, or zinc.

[0010] In some embodiments, the polymer-ceramic composite is in fibrous form and is formed into or incorporated into a fabric. For example, forming or incorporating the polymer-ceramic composite fibers as described herein may be achieved by chemical, mechanical, heat application or one or more solvents, or other physical means of knitting, weaving, bonding, or entanglement.

[0011] In some embodiments, the polymer matrix of the polymer-ceramic composite includes one or more of polyesters, polyamides, polyolefins, substituted polyolefins, polyurethanes, polyols, vinyl polymers, acrylate polymers, polycarbonates, and polyethers. For example, the polymer matrix may include one or more of polyethylene terephthalate (PET), nylon, polyethylene, polypropylene, polyvinyl chloride (PVC), polyvinyl alcohol (PVOH), polyvinyl acetate (PVAc), polyvinylpyrrolidone, polyethylene glycol (PEG), polymethyl methacrylate (PMMA), or mixtures thereof.

[0012] In some embodiments, the polymer matrix of the polymer-ceramic composite comprises one or more copolymers. For example, the polymer matrix may include one or more of the following: polyether-polyurea copolymers, nylon copolymers (such as copolymers of nylon 12, nylon 6, nylon 6 / 6 and / or nylon 6 / 12), copolyesters, acrylonitrile butadiene styrene (ABS), styrene / butadiene copolymers (SBR), nitrile rubber, styrene-acrylonitrile, styrene-isoprene-styrene (SIS), and ethylene-vinyl acetate, or other copolymers formed by chain growth polymerization or stepwise growth polymerization.

[0013] In some embodiments, the polymer matrix of the polymer-ceramic composite includes hydrocolloids, such as (but not limited to) polysaccharides.

[0014] In some embodiments, the polymer matrix of the polymer-ceramic composite includes one or more of locust bean gum, starch, carrageenan, pectin, chitosan, xanthan gum, cellulose, and carboxymethyl cellulose.

[0015] In some embodiments, the polymer matrix of the polymer-ceramic composite includes one or more of wool, cotton, hemp, animal hair, collagen, keratin, silk, chitin, flax, and jute.

[0016] In some embodiments, the polymer-ceramic composite is in the form of fibers, and the ceramic concentration relative to the polymer matrix increases radially from the center of the interior volume of the polymer matrix within the fibers to the outer surface of the polymer matrix. In some embodiments, the polymer-ceramic composite is in the form of a membrane or thin film, and the ceramic concentration relative to the polymer matrix increases from the center of the interior volume of the polymer matrix within the membrane to the outer surface of the polymer matrix. In some embodiments, the polymer-ceramic composite is in the form of a laminate, and the ceramic concentration relative to the polymer matrix increases in the outermost layer of the laminate relative to the inner layers. In some embodiments, the polymer-ceramic composite contains a polymer core and a shell comprising a ceramic composite material. In some embodiments, the polymer-ceramic composite is a textile containing polyamide, polyester, polyolefin, polyurethane, polyol, vinyl, cotton, wool, cellulose material, or combinations thereof. In some embodiments, the polymer-ceramic composite is in the form of a membrane, and the ceramic concentration relative to the polymer matrix increases on one side of the membrane relative to the opposite side of the outer surface of the membrane. In some embodiments, the polymer-ceramic composite contains a core material comprising a thermoplastic, wherein the thermoplastic is composed of polyester, polyamide, polyurethane, acrylic, polyolefin, polyol, ABS, polyvinyl alcohol, or combinations thereof. In some embodiments, the polymer-ceramic composite contains a core material comprising cotton, wool, or cellulose materials, blends of natural and synthetic fibers, or combinations thereof.

[0017] In some embodiments, more than about 20% by weight of the ceramic in the polymer-ceramic composite protrudes from the outer surface of the polymer matrix, i.e., outside the surface of the polymer substrate. For example, the composite may include a ceramic layer on the outer surface of the polymer matrix, and the thickness of this layer may be less than about 1 µm or less than about 100 nm. The average thickness of the ceramic layer is the distance from the outer surface of the polymer substrate to the outer surface of the ceramic layer. For example, the ceramic layer may be nanostructured and may have at least one feature size with a dimension less than about 100 nm. In some embodiments, both the ceramic layer on the outer surface and the ceramic in the internal volume of the composite may be nanostructured, for example, having at least one feature size with a dimension less than about 100 nm. In some embodiments, both the ceramic layer on the outer surface and the ceramic in the internal volume of the composite may include additional inorganic elements, such as (but not limited to) potassium, sodium, magnesium, chlorine, sulfur, phosphorus, or other ionic elements or compounds.

[0018] In another aspect, a method for manufacturing a polymer-ceramic composite as described herein is provided. The method comprises: (a) contacting a polymer substrate with at least one solution comprising a metal salt or a metal-organic complex and optionally an oxidant, amine, ammonia, a penetrant, surfactant, release agent, or other reactive precursor (such as, but not limited to, a catalyst in a solvent) or a combination thereof, wherein the solution is at least partially absorbed into the polymer matrix; (b) heating or otherwise ensuring that the temperature of the polymer substrate produced in step (a) reaches a temperature sufficient to remove the solvent from the polymer substrate, sufficient to drive a ceramic formation reaction with one or more metal salts, or sufficient to decompose or react the metal-organic complex, thereby forming a polymer-ceramic composite; and (c) optionally coating the polymer-ceramic composite produced in step (b) with one or more functional layers or molecules.

[0019] In some embodiments, the metal salt in step (a) may include one or more of the following: transition metal nitrates, transition metal chlorides, transition metal sulfates, alkali metal nitrates, alkaline earth metal nitrates, alkali metal chlorides, alkaline earth metal chlorides, alkali metal sulfates, and alkaline earth metal sulfates. 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.

[0020] In some implementations, the heating in step (b) can be performed at a temperature of about 30°C to about 200°C.

[0021] In some embodiments, the functional layer in step (c) may include a monolayer chemical, wherein the functional layer is substantially a monolayer with a thickness of less than about 5 nm. The average thickness of the functional layer is the distance from the outer surface of the ceramic layer to the external thickness of the functional layer. For example, the monolayer chemical may include silanes, siloxanes, phosphonic acids, phosphonates, sulfonates, sulfonic acids, carboxylic acids, carboxylic esters, carbamates, vinyl groups, or acrylates, or molecules having head and tail groups. In some embodiments, the monolayer chemical includes molecules having head and tail groups, wherein the head group includes silyl, phosphonate, phosphonic acid, carboxylic acid, vinyl, alcohol, hydroxide, thiolate, thiol, and / or ammonium groups, and wherein the tail group includes hydrocarbon, fluorocarbon, vinyl, phenyl, epoxy (epoxide group), acrylic (acrylic group), acrylate, hydroxy, carboxylic acid, thiol, and / or quaternary ammonium groups. For example, the head group may include an ammonium group, such as a quaternary ammonium group.

[0022] In some embodiments, the functional layer in step (c) may include, for example, a polymeric chemical with an average thickness of less than about 500 nm. The average thickness of the functional layer is the distance from the outer surface of the ceramic layer to the outer thickness of the functional layer. For example, the functional layer chemical may include functional molecules comprising silanes, siloxanes, phosphonic acids, phosphonates, sulfonates, sulfonic acids, carboxylic acids, carboxylic esters, carbamates, vinyl groups, or acrylates, or molecules having head and tail groups. In some embodiments, the polymeric chemical includes crosslinking agent molecules to improve mechanical and chemical properties. In some embodiments, the polymeric chemical includes molecules having head and tail groups, wherein the head group includes silyl, phosphonate, phosphonic acid, carboxylic acid, vinyl, alcohol, hydroxyl, thiol ester, thiol, and / or ammonium groups, and wherein the tail group includes hydrocarbon, fluorocarbon, vinyl, phenyl, epoxy, acrylic (acrylic group), acrylate, hydroxyl, carboxylic acid, thiol, and / or quaternary ammonium groups. For example, the head group may include an ammonium group, such as a quaternary ammonium group.

[0023] In some embodiments, the method includes forming a polymer-ceramic composite on a first substrate in steps (a) and (b), wherein the polymer-ceramic composite on the first substrate is in the form of an interconnected nanostructured layer on the first substrate, and the method further includes contacting a second substrate with the polymer-ceramic composite, such that at least a portion of the interconnected nanostructured layer is transferred to the second substrate, thereby forming a second substrate-ceramic composite. Optionally, the second substrate-ceramic composite may be coated with one or more functional layers or molecules. In some embodiments, the first substrate and the second substrate are contacted under suitable pressure according to standard methods (such as ASTM D3359). For example, the polymer-ceramic composite on the first substrate may be contacted with the second substrate by a roll lamination process or by hot pressing at a temperature of about 40°C to about 200°C and a pressure of about 0.1 MPa to about 10 MPa. In some embodiments, more than about 50%, more than about 60%, more than about 70%, more than about 80%, or more than about 90% of the interconnected nanostructured layer is transferred to the second substrate. In some embodiments, more than 50%, more than 60%, more than 70%, more than 80%, or more than 90% of the transferred nanostructured layers are continuous. In some embodiments, more than 50%, more than 60%, more than 70%, more than 80%, or more than 90% of the transferred nanostructured layers remain interconnected.

[0024] In another aspect, a polymer-ceramic composite is provided, comprising a polymer substrate and a ceramic, wherein the polymer substrate has an outer surface and an internal volume of the polymer matrix, a first portion of the ceramic is on the outer surface, and a second portion of the ceramic occupies at least a portion of the internal volume of the polymer matrix.

[0025] In some embodiments, the second portion of the ceramic penetrates from the outer surface into the internal volume of the polymer matrix by more than about 10 nanometers. In some embodiments, the second portion of the ceramic penetrates from the outer surface of the polymer substrate into the internal volume of the polymer matrix by less than about 90% of its hydraulic diameter. In some embodiments, the ceramic concentration decreases when measured from the outer surface of the polymer substrate into the internal volume of the polymer matrix. For example, the ceramic concentration may decrease from the outer surface of the polymer substrate into the internal volume of the polymer matrix at a certain decreasing rate. For example, the ceramic concentration may decrease from the surface into the internal volume of the polymer matrix in an exponential decay manner, such as an exponential decay constant greater than about 0.01.

[0026] In some embodiments, the second portion of the ceramic accounts for at least about 1% of the mass of the ceramic and / or the first portion of the ceramic accounts for less than about 99% of the mass of the ceramic.

[0027] In some embodiments, the ceramic comprises a metal, and the atomic molar percentage of the metal within the polymer matrix volume is greater than about 0.1% at a depth of about 10 nm from the outer surface to the inner volume of the polymer matrix. In some embodiments, the ceramic comprises a metal, and the atomic molar percentage of the metal is discontinuous at the outer surface of the polymer substrate when measured from the outer surface to the inner volume of the polymer matrix. In some embodiments, the inner volume of the polymer matrix includes both convex Gaussian geometry and concave Gaussian geometry, the ceramic comprises a metal, and the atomic molar percentage of the metal in the convex features is equal to or greater than the atomic molar percentage of the metal in the concave features. In some embodiments, the ceramic comprises a metal, and the diffusion length of the metal within the inner volume of the polymer matrix is ​​greater than about 1 µm. In some embodiments, the ceramic comprises a metal, and the diffusion coefficient of the metal within the inner volume of the polymer matrix is ​​less than about 10. -8 m 2 / Second.

[0028] In some embodiments, the ceramic mass accounts for less than about 10% of the mass of the polymer-ceramic composite. In some embodiments, the ceramic accounts for less than about 10 grams per square meter of the nominal geometric surface area of ​​the polymer-ceramic composite.

[0029] In some embodiments, the polymer-ceramic composite further includes functional molecules. For example, functional molecules may include silanes, siloxanes, phosphonic acids, phosphonates, sulfonates, sulfonic acids, carboxylic acids, carboxylic esters, carbamates, vinyl groups, acrylates, or molecules having head and tail groups. In some embodiments, functional molecules include molecules having head and tail groups, wherein the head group includes silyl, phosphonate, phosphonic acid, carboxylic acid, vinyl, alcohol, hydroxyl, thiol ester, thiol, and / or ammonium (e.g., quaternary ammonium) groups, and wherein the tail group includes hydrocarbon, fluorocarbon, vinyl, phenyl, epoxy, acrylic (acrylic group), acrylate, hydroxyl, carboxylic acid, thiol, and / or quaternary ammonium groups.

[0030] In some embodiments, at least a portion of the functional molecule occupies the internal volume of the polymer matrix. In some embodiments, the functional molecule penetrates more than 10 nanometers into the internal volume of the polymer matrix.

[0031] In some embodiments, the concentration of functional molecules decreases when measured from the outer surface of the polymer substrate into the internal volume of the polymer matrix. In one embodiment, the concentration of functional molecules decreases at a certain rate from the outer surface of the polymer substrate into the internal volume of the polymer matrix. In one embodiment, the distance the functional molecules travel into the internal volume of the polymer matrix is ​​shorter compared to the same polymer substrate without ceramics. In one embodiment, the diffusion coefficient of the functional molecules in the internal volume of the polymer matrix is ​​more than about 5% smaller than the diffusion coefficient of the functional molecules in the same polymer substrate without ceramics.

[0032] In some embodiments, the ceramic of the polymer-ceramic composite includes transition metals, alkali metals, or alkaline earth metals, such as (but not limited to) calcium, manganese, phosphorus, iron, nickel, magnesium, titanium, lithium, or zinc. In some embodiments, the ceramic contains oxides, hydroxides, layered double hydroxides, phosphates, oxalates, sulfates, or carbonates of transition metals, alkali metals, or alkaline earth metals, or combinations thereof.

[0033] In some embodiments, at least a portion of the outer surface of the polymer substrate does not include a first portion of ceramic; for example, at least a portion of the outer surface of the polymer substrate is free of ceramic.

[0034] In some embodiments, at least a portion of the polymer-ceramic composite has a sessile drop water contact angle greater than about 90°. In some embodiments, at least a portion of the polymer-ceramic composite has a rugosity ratio greater than about 1.3.

[0035] In some embodiments, the polymer substrate is a textile material, a film, a laminate, or a combination thereof. In some embodiments, the polymer substrate is a textile material. In some embodiments, the polymer-ceramic composite is a textile material comprising polyamide, polyester, polyolefin, substituted polyolefin, polyurethane, polyol, vinyl, cotton, wool, cellulose material, or a combination thereof.

[0036] In some embodiments, tear strength, tensile strength, air permeability, vapor permeability, and / or abrasion resistance are improved relative to the polymer substrate. In some embodiments, tear strength, tensile strength, air permeability, vapor permeability, and / or abrasion resistance are improved compared to the same polymer-ceramic composite that does not include functional molecules. In some embodiments, the tear strength is greater than about 1000 gF.

[0037] In some embodiments, the polymer-ceramic composite has a core-shell structure, comprising a polymer substrate having an outer surface and an internal volume as the core, and a ceramic comprising ceramic on the outer surface of the polymer substrate and a ceramic or inorganic element occupying at least partially the internal volume of the polymer substrate as the shell. In some embodiments, the polymer-ceramic composite has a film and coating structure, comprising a polymer substrate having an outer surface and an internal volume as the film, and a ceramic comprising ceramic on the outer surface of the polymer substrate and a ceramic or inorganic element occupying at least partially the internal volume of the polymer substrate as the coating applied to one or more outer surfaces of the polymer substrate.

[0038] In another embodiment, a polymer-ceramic composite is provided, comprising a core and a shell, wherein the core comprises a polymer and the shell comprises ceramic. In some embodiments, the thickness of the shell is less than 20% of the hydraulic diameter of the core. In some embodiments, the thickness of the shell is less than about 1 micrometer. In some embodiments, the diameter or thickness of the core is greater than about 1 micrometer.

[0039] In some embodiments, the core contains a thermoplastic, such as (but not limited to) polyester, polyamide, polyurethane, acrylic (polyacrylate), polyolefin, polyol, acrylonitrile butadiene styrene (ABS), or combinations thereof. In some embodiments, the core contains cotton, wool, or cellulose materials.

[0040] In some embodiments, the cross-section of the core is a circle with a roundness greater than or greater than about 0.7, or a semicircle with ...

[0041] In some embodiments, the ceramic in the shell comprises a transition metal, alkali metal, or alkaline earth metal, such as (but not limited to) iron, magnesium, zinc, manganese, calcium, nickel, titanium, lithium, or combinations thereof. In some embodiments, the transition metal, alkali metal, or alkaline earth metal is in the form of oxides, hydroxides, phosphates, carbonates, sulfates, oxalates, layered double hydroxides, or combinations thereof, such as (but not limited to) manganese oxide, iron oxide, calcium carbonate, hydroxyapatite, calcium phosphate, calcium oxalate, magnesium carbonate, calcium sulfate, magnesium sulfate, or combinations thereof.

[0042] In some embodiments, the ceramic in the shell has a weight fraction of less than about 0.9. In some embodiments, at least one dimension of the ceramic is less than about 100 nanometers. In some embodiments, the ceramic in the shell has a 0-dimensional, 1-dimensional, or 2-dimensional morphology.

[0043] In some embodiments, the shell further comprises a siloxane, acrylate, phosphonate, sulfonate, carbamate, or a combination thereof. In some embodiments, the shell further comprises an organosilicon polymer, an alkyl-terminated silane, or an alkyl-terminated siloxane. In some embodiments, the shell further comprises an alkyl-terminated functional group, such as (but not limited to) an alkyl-terminated functional group comprising an alkyl group with more than three carbon atoms. In some embodiments, the shell further comprises an isocyanate or an isocyanate-terminated polymer.

[0044] In some implementations, the shell is chemically bonded to the core.

[0045] In some embodiments, the surface roughness of the polymer-ceramic composite is greater than 1.1.

[0046] In some implementations, at least a portion of the ceramic is interconnected. In one implementation, based on particles, more than 50% of the ceramic is interconnected.

[0047] In some embodiments, the ceramic includes crystalline domains, and in some embodiments, one or more 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 present in the crystalline domains, excluding carbon, hydrogen, oxygen, or nitrogen. In some embodiments, the amorphous matrix and the crystalline particles or crystalline domains contain three common elements excluding carbon, hydrogen, oxygen, or nitrogen. In some embodiments, the size of the crystalline domains ranges from a nominal size of about 2 nm to a nominal size of about 200 nm. In some embodiments, the crystalline domains include rare earth metals, transition metals, alkali metals, alkaline earth metals, or combinations thereof, such as (but not limited to) Ca, Zn, Ni, Li, Mg, Ti, Mn, or combinations thereof. In some embodiments, the crystalline domains include phosphate groups (e.g., polyphosphate, pyrophosphate, hydrogen phosphate, dihydrogen phosphate, orthophosphate, or combinations thereof), carbonate groups, sulfate groups, or combinations thereof. In some embodiments, the amorphous matrix includes calcium and / or phosphorus. In some embodiments, the crystalline domains include octacalcium phosphate, hydroxyapatite, triclinic calcium phosphate, calcium phosphate, calcium triphosphate, calcium pyrophosphate, and / or their hydrates.

[0048] In another embodiment, a composite assembly is provided comprising a variety of polymer-ceramic composites as described herein. In some embodiments, at least a portion of the polymer-ceramic composite is in fibrous form, and in other embodiments, it can be assembled into yarns, woven fabrics, knitted fabrics, paper, or nonwoven fabrics. Attached Figure Description

[0049] Figures 1a-1b show the deposition results of the structured ceramics as described in Example 1 on a nylon substrate. Figure 1a: SEM image of the fiber cross-section. Figure 1b: SEM-EDS profile of the fiber cross-sections of carbon (top left), silicon (top right), calcium (bottom left), and phosphorus (bottom right).

[0050] Figures 2a-2b show the evaluation results of the spray rating of the polymer-ceramic composite structure prepared as described in Example 1. Figure 2a: Contact angle measurement. Figure 2b: AATCC 22 spray rating as a function of total solution contact based on immersion time before and after household washing (3 times).

[0051] Figure 3 This displays an SEM image of a cross-section of a processed fabric sample.

[0052] Figures 4a-4f show the analysis of the calcium phosphate polymer-ceramic composite sample. Figure 4a: FIB cross-section of the EDS region of interest. Figure 4b: Cross-section of the Ga sample after FIB. Figure 4c: 67 nm FOV image showing domains and lattice spacing. Figure 4d: 67 nm FOV image showing domains and lattice spacing. Figure 4e: EDS profile. Figure 4f: EDS plot - potassium (K).

[0053] Figures 5a-5c show cross-sections of the fiber samples. Figure 5a: 1. Cross-section of the cyclic fiber. Figure 5b: 3. Cross-section of the cyclic fiber. Figure 5c: 5. Cross-section of the cyclic fiber.

[0054] Figure 6 Display example SEM images.

[0055] Figure 7 The EDS overlay plot of the fabric cross-section shows the Ca (top) and Ti (bottom) values ​​of the single-cycle sample (left) and the three-cycle sample (right).

[0056] Figures 8a-8e show exemplary SEM images of interconnected nanostructured layers formed on a polymer (cellulose) substrate. Figure 8e shows the interconnected nanostructured layer retained on the polymer (cellulose) substrate after tape adhesion. Figure 8f is an exemplary SEM image of an interconnected nanostructured layer transferred from the polymer (cellulose) substrate to the polymer substrate. Detailed Implementation

[0057] This paper describes a method for preparing a polymer-ceramic composite by depositing ceramics onto a polymer substrate without using resins or varnishes. The polymer-ceramic composite includes one or more ceramics deposited on the outer surface of a polymer substrate. The ceramics deposited on the polymer substrate typically also penetrate the internal volume of the polymer substrate, i.e., are integrated within the internal volume of the polymer matrix, thereby increasing durability and adhesion compared to ceramic coatings that are only or mostly adhered to the outer surface of the polymer substrate. In some embodiments, one or more complementary inorganic elements penetrate the ceramics on the polymer substrate and the internal volume of the polymer matrix. In some embodiments, one or more complementary inorganic elements penetrate the ceramics. In some embodiments, one or more complementary inorganic elements penetrate the ceramics on the polymer substrate. In some embodiments, one or more complementary inorganic elements penetrate the ceramics on the outer surface of the polymer substrate. In some embodiments, one or more complementary inorganic elements penetrate the ceramics occupying at least a portion of the internal volume of the polymer matrix. In some embodiments, one or more complementary inorganic elements penetrate the ceramics on the outer surface of the polymer substrate and occupy at least a portion of the internal volume of the polymer matrix. In some embodiments, one or more complementary inorganic elements penetrate the internal volume of the polymer matrix. In some embodiments, one or more complementary inorganic elements penetrate the ceramics and the internal volume of the polymer matrix. In some embodiments, the complementary inorganic elements include potassium, magnesium, chlorine, bromine, iodine, phosphorus, sulfur, nitrogen, oxygen, carbon, hydrogen, manganese, aluminum, titanium, sodium, calcium, or combinations thereof.

[0058] In some embodiments, ceramics are added to a polymer substrate prior to melting, extruding, stretching, or spinning the polymer, or other processing methods as described herein. The ceramics are typically in powder or particulate form and can be added to modify the functional properties of the polymer, such as (but not limited to) color, optical properties, electrical conductivity, catalytic or photocatalytic properties, or to provide or enhance the antimicrobial properties of the base polymer. Generally, the methods described herein involve the reaction of chemicals in the presence of a polymer substrate to generate ceramic material in situ and conformally around and within the polymer substrate, i.e., on the outer surface and occupying a portion of the internal volume of the polymer matrix, thereby improving adhesion without melting or pressing the ceramic into the polymer substrate.

[0059] The method described herein can be implemented on polymer substrates that have previously incorporated ceramics (such as by blending, stretching, casting or other mechanical addition methods), or on polymer substrates that do not contain previously incorporated ceramic materials.

[0060] definition

[0061] The numerical ranges provided in this article include those within the defined range.

[0062] Unless the context clearly indicates otherwise, “a,” “an,” and “the” include multiple indicators.

[0063] Unless otherwise stated, the average values ​​in this article refer to the quantity average.

[0064] As used herein in the specification and claims, the phrase “and / or” should be understood to mean “any one or both” of the elements so combined, that is, elements that exist together in some cases and separately in others. Unless explicitly indicated otherwise, additional elements may optionally exist, whether related to or unrelated to those specifically identified by the “and / or” clause. Thus, as a non-limiting example, when used in conjunction with open-ended language such as “comprising”, a reference to “A and / or B” may in one embodiment refer to A without B (optionally including elements other than B); in another embodiment, it may refer to B without A (optionally including elements other than A); in yet another embodiment, it may refer to both A and B (optionally including other elements); and so on.

[0065] "Zero-dimensional materials" are materials in which all dimensions are less than about 100 nm and whose boundary or edge properties are typically critical. An example material is a quantum dot.

[0066] An "agglomerate" or "agglomerate" refers to a collection of previously discrete particles or materials that remain connected upon contact and undergo a degree of aggregation, relative incorporation, or growth.

[0067] An "aggregate" or "aggregated" refers to a collection of previously discrete particles or materials that remain connected upon contact but do not appear to undergo additional coalescence, relative incorporation, or growth.

[0068] "Air permeability" is the rate at which air passes through a fabric according to ASTM D737 or a similar method. This rate is reported as volumetric flow rate per unit time, typically in cubic feet per minute or cfm.

[0069] "Atomic percentage" refers to the percentage of atoms of one or more specific named elements relative to the total number of atoms present in a specified area or volume.

[0070] "Ceramics" or "ceramic materials" refers to solid materials comprising inorganic compounds of metals or metalloids and nonmetals having ionic or covalent bonds. In this context, "ceramics" can 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 glassy phase, with the volume fraction of crystals varying from ppm to almost 100%. "Nonmetals" can include oxygen (oxide ceramics), carbon (carbides), or nitrogen (nitrides) (non-oxide ceramics). "Metals" can include non-hydrogen elements of Group 1 of the periodic table, elements of Groups 2–12 of the periodic table, or elements from the p-block (Groups 12–17 of the periodic table), such as Al, Ga, In, Tl, Sn, Pb, Bi, or combinations thereof. "Metalloids" can include B, Si, Ge, As, Sb, Se, Te, or Po, or combinations thereof.

[0071] "Circularity" has a value from 0 to 1 and is defined as 4. Cross-sectional area / perimeter 2 A perfect circle will have a roundness value of 1. A perfect semicircle has a roundness value of 0.5, and a semicircle in the range of 0 to 1 is defined as 8. Cross-sectional area / perimeter 2 Semi-circular fiber cross-sections can be formed by extrusion, asymmetric fiber drawing, calendering, or other thermomechanical methods.

[0072] "Complementary inorganic elements" refer to elements existing as relative ions, wherein the ceramic precursor includes one or more ions incorporated into the ceramic and one or more relative ions not incorporated into the ceramic. For example, in some embodiments, the ceramic precursor includes calcium chloride and / or calcium nitrate, with calcium ions incorporated into the ceramic, and the relative ions chloride and nitrate not incorporated into the ceramic, and the complementary inorganic element includes chlorine, nitrogen, and / or oxygen. In another example, in some embodiments, the ceramic precursor includes ammonium dihydrogen phosphate, with dihydrogen phosphate ions incorporated into the ceramic, and the relative ion ammonium not incorporated into the ceramic, and the complementary inorganic element includes nitrogen and / or hydrogen.

[0073] "Concave Gaussian geometry" refers to a geometric surface feature that is nominally penetrated into the surface of the substrate, is concave when viewed along a line of sight from above the surface, is nominally orthogonal to the surface, and can be described by a Gaussian expression.

[0074] "Convex Gaussian geometry" refers to a geometric surface feature that is nominally convex from the surface of the substrate, is convex when viewed along a line of sight from above the surface, is nominally orthogonal to the surface, and can be described by a Gaussian expression.

[0075] The contact angle is the angle measured from the liquid passing through the surface to the liquid-gas interface at the contact surface. The sessile drop method is the standard method for measuring the contact angle, in which the droplet used to characterize the surface is stationary.

[0076] "dtex" or deci-tex is a direct measure of linear density, defined as grams per 10,000 meters of yarn. dtex = 10 Tex = Denier / 0.9.

[0077] The "diffusion coefficient" is a physical constant that depends on the molecular size, the properties of the diffusing substance, temperature, and pressure, and is usually determined experimentally.

[0078] "Diffusion length" is a characteristic length that provides a measure of the distance a concentration travels in a single dimension over a given time period. A common equation for determining this is... ,in It is the diffusion coefficient, and It's time.

[0079] A "functional material layer" refers to a material layer that can act as the uppermost surface layer interacting with the surrounding environment or as an interface layer (an intermediate layer between two other material layers) for subsequent materials. The functional material layer imparts one or more desired functional properties to the underlying substrate and / or the materials deposited on it.

[0080] In this document, "gradient" refers to a quantitative increase or decrease in one or more physical or chemical properties of a material, which is observed spatially from one point to another along the surface of a substrate on which the material is located or fixed, and varies in the x, y, or z directions in the Cartesian coordinate system on or through the material. Non-limiting examples of gradient properties include thickness, density, hardness, ductility, pore size, pore size distribution, pore filling fraction, or chemical or physical composition, including (but not limited to) oxidation state, metal concentration, or crosslinking density, which, for example, lead to changes in isoelectric point, electrical conductivity, thermal conductivity, capacitance, etc.

[0081] "Hydraulic diameter" refers to the value of 4 times the cross-sectional area divided by the circumference of the cross-sectional area. In the case of a nominal cylindrical fiber with a circular cross-section, the hydraulic diameter is twice the radius of the circular cross-section.

[0082] "Hydrophilicity" refers to a surface that has a high affinity for water. The contact angle can be very low (i.e., less than 30°, as measured by passing liquid water through the surface in the presence of air) and / or unmeasurable.

[0083] "Interconnection" refers to a network or matrix of ceramic materials in which the ceramic materials in the network are physically in contact (connected) with other ceramic materials in the network. That is, most of the ceramic materials are adjacent to other ceramic materials, thereby creating a support structure that is independent or supported on a substrate. The interconnected ceramic network described herein is a continuous ceramic phase over an area or volume defined by a length greater than 100 average particle diameters and may contain pores (open spaces) with accessible pore volumes, which can be filled or partially filled with another material (such as, but not limited to, polymers).

[0084] "Layered double hydroxides" refers to a class of ionic solids characterized by having a universal sequence. The layered structure, wherein c represents a metal cation layer, A and B are hydroxide anion layers, and Z is a layer of other anions and / or neutral molecules (such as water). Layered double hydroxides are also described in PCT application PCT / US2017 / 052120, the entire contents of which are incorporated herein by reference.

[0085] "Leaf shape" is the deviation from the designed fiber cross-sectional shape. In this article, leaf shape refers to... It has a value between 0 and 1. As defined in Wang, Z. et al. (2012) Textile Research Journal 82(5): 454-462. Several different categories and examples of non-cylindrical fiber shapes are provided, including trefoil, multilobed, elongated, and deeply concave shapes. Fiber shape factor (perimeter) 2 ( / area) can be used to define non-standard fiber shapes.

[0086] "Laminate" refers to a structure or composite comprising one or more thin layers attached to other thin layers or structural layers or substrates.

[0087] The term "mean" refers to the arithmetic mean or average.

[0088] "Nanostructured" coatings refer to coating compositions having features of less than 100 nanometers in at least one dimension.

[0089] "Nominal" is used to refer to the approximate size or dimensions of a material; the actual size may be larger or smaller than the nominal size. When nominal size is used to describe nanomaterials, it 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 an approximate or measured value of the most general characteristic, but not necessarily an exact measurement. An example is the nominal surface area of ​​a fabric. The nominal surface area is defined by multiplying the length of the fabric by its width, without taking into account any increase in surface area provided by the fibers that make up the fabric.

[0090] The "rugosity ratio" is the ratio of the rugosity of the polymer-ceramic composite to the rugosity of the polymer substrate. Rugosity is a measure of small-scale amplitude variations in surface height, and is A... r Real (actual) surface area and A g The ratio of geometric surface areas.

[0091] Surface roughness, or roughness factor, is a measure of the relative smoothness of a surface profile, calculated by the deviation (macroscopic or microscopic) from the true or ideal form of the surface. The greater the deviation from the ideal form, the greater the surface roughness. The commonly used surface roughness factor is R. a It is defined as the arithmetic mean of the deviations of the profile height from the average line. Unless otherwise specified, this is the term used throughout this application.

[0092] "Fabric" is a term that includes a variety of fiber-based materials, including fibers, yarns, filaments, and threads that are combined or manufactured to produce flexible polymer films, garments, or fabrics. Fabrics or textile materials can be described as woven or non-woven, while fabric is a subset of textile that includes only woven fibers, yarns, filaments, or threads.

[0093] The “thickness” of a material (e.g., the first or second material as described herein) refers to the nominal distance between the top and bottom edges or surfaces of the material (such as, in the case of the second material, the surface defined by the edge of the interface layer in contact with the substrate or the first material, and the nominal top surface of the surface finishing material layer).

[0094] "Adjustable" refers to the ability to change or modify the function, characteristics, or quality of a material.

[0095] polymer substrate

[0096] In some embodiments, the polymer substrate on which the ceramic is deposited, as described herein, is hydrophilic. For example, the hydrophilic polymer may include one or more hydroxyl groups.

[0097] In some embodiments, the polymeric substrate on which ceramics are deposited, as described herein, is hydrophobic. In some embodiments, the hydrophobic polymeric substrate includes one or more acrylic, amide, imide, carbonate, diene, ester, ether, fluorocarbon, olefin, styrene, and / or vinyl groups. In some embodiments, the hydrophobic polymeric substrate includes one or more arylalkyl groups, which are present when the monomers used to form the polymeric substrate contain styrene or substituted styrene, and are exemplified by a phenylalkyl-containing polymeric substrate formed by polymerizing styrene. In some embodiments, the hydrophobic polymeric substrate includes one or more ester groups, which are present when the monomers used to form the polymeric substrate contain a carboxylic ester of vinyl alcohol or a substituted carboxylic ester of vinyl alcohol, and are exemplified by a polyacetate-containing polyol-containing polymeric substrate formed by polymerizing vinyl acetate. In some embodiments, the hydrophobic polymer substrate includes one or more ester groups, which are present when the monomer used to form the polymer substrate contains acrylates or substituted acrylates, as exemplified by a polymer substrate containing polymethyl esters of polyalkyl carboxylic acids formed by polymerizing methyl acrylate. In some embodiments, the hydrophobic polymer substrate includes one or more olefin groups, which are present when the monomer used to form the polymer substrate includes dienes or substituted dienes, as exemplified by a polymer substrate containing alkyl chains or side chains comprising olefin groups formed by polymerizing 1,3-butadiene.

[0098] In some embodiments, the polymer substrate on which ceramics are deposited, as described herein, is a copolymer. For example, the copolymer may be amphiphilic and comprise one or more polymer compounds, such as poly(ethylene glycol)-b-poly(lactic acid) (PEG-PLA). In some embodiments, the polymer substrate on which ceramics are deposited, as described herein, comprises 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.

[0099] In some embodiments, the polymer substrate on which ceramics are deposited, as described herein, is at least partially composed of an elastomer. For example, the substrate may be styrene elastomer fibers, polyester elastomer fibers, or nylon elastomer fibers.

[0100] In some embodiments, the polymeric substrate on which ceramics are deposited, as described herein, is at least partially composed of a resin. For example, the substrate may be a liquid crystal polymer, acrylic resin fibers, or other resin-based fibers. In some embodiments, the polymeric substrate on which ceramics are deposited, as described herein, is a manufactured fiber, such as fibers spun from a liquid crystal polymer (LCP). For example, in one embodiment, the substrate may be Vectran. ® It is an aromatic polyester produced by the condensation polymerization of 4-hydroxybenzoic acid and 6-hydroxynaphthalene-2-carboxylic acid.

[0101] In some embodiments, the polymer substrate on which ceramics are deposited, as described herein, is primarily composed of carbon fibers. For example, the substrate may be activated carbon fiber (ACF). In some embodiments, the polymer substrate on which ceramics are deposited, as described herein, is composed of crystalline filaments of carbon in many forms, including (but not limited to) woven fabrics, tapes, and unidirectional sheets. In some embodiments, the polymer substrate on which ceramics are deposited, as described herein, is primarily a composite of carbon fibers and resins. In some embodiments, various base materials pre-impregnated with resin systems (such as, but not limited to, carbon, glass fiber, or Kevlar) are used. ® The polymer substrate is used as a polymer substrate. In some embodiments, the polymer substrate on which ceramics are deposited, as described herein, is a composite of carbon and alternative fibers (such as glass) that may contain resin.

[0102] In some embodiments, the polymer substrate may include one or more polymers in the composite structure, such as different yarn or fiber materials. One such example is a carbon fiber-nylon ripstop fabric, in which the bulk of the fabric is primarily composed of nylon fibers, and the ripstop fibers are primarily composed of carbon fibers.

[0103] In some embodiments, the polymer substrate may absorb water or another solvent, as determined by the increase in mass after immersion in water or a solvent. In some embodiments, the polymer substrate may swell upon immersion in water or another solvent. In some embodiments, the solvent absorbed or swollen by the polymer substrate may include water, alcohol, acetone, dimethyl carbonate, methyl acetate, tert-butyl acetate, propylene carbonate, acetic acid, methyl ethyl ketone, or mixtures thereof. In some embodiments, the solvent includes alcohols such as (but not limited to) ethanol, methanol, isopropanol, butanol, isobutanol, propylene glycol, ethylene glycol ether, or 2-ethylhexanol, 2-butoxyethanol, or mixtures thereof.

[0104] In some embodiments, the polymer substrate absorbs water or a solvent containing water and one or more co-solvents. In some embodiments, the polymer substrate swells in water or a solvent containing water and one or more co-solvents. In some embodiments, the one or more co-solvents include alcohols, ketones, dialkyl carbonates, alkyl carboxylic acids, alkyl esters of alkyl carboxylic acids, alkyl glycols, ethers, or mixtures thereof. In some embodiments, alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-butoxyethanol, 2-ethylhexanol, or mixtures thereof. In some embodiments, alcohols include methanol. In some embodiments, ketones include acetone and / or methyl ethyl ketone. In some embodiments, dialkyl carbonates include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, or mixtures thereof. In some embodiments, alkyl carboxylic acids include formic acid, acetic acid, propionic acid, or mixtures thereof. In some embodiments, alkyl esters of alkyl carboxylic acids include 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)ethyl-1-ol, HO(CH2)2O(CH2)2O(CH2)3CH3, DEGBE], diethylene glycol monoalkyl ether, HO(CH2)2O(CH2)2O(CH2) n CH3 (where n = 0, 1, 2, or 4) or a mixture 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.

[0105] In some embodiments, the polymer substrate includes polyesters (such as polyethylene terephthalate (PET)), polyamides (such as nylon), polyvinyl chloride (PVC), polyolefins (such as polyethylene or polypropylene), polyurethanes, polyvinyl alcohol (PVOH), polyvinyl acetate (PVAc), polyvinylpyrrolidone, polyols, 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 a product of the condensation of hexamethylenediamine with terephthalic acid or a product of the condensation of p-phenylenediamine with terephthalic acid. In some embodiments, the polymer is a copolymer of more than one monomer, such as 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 hydrocolloids, such as polysaccharides. In some embodiments, the polymer substrate includes locust bean gum, 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.

[0106] In some embodiments, the polymer substrate includes locust bean gum, 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.

[0107] In some embodiments, the polymeric substrate containing cellulose or carboxymethyl cellulose includes paper, which is a sheet material produced by processing cellulose fibers derived from wood, rags, grass, or other plant sources such as cotton, banana, or hemp. In some embodiments, the cellulose fibers can be refined from natural materials by chemical treatment, thermal treatment, mechanical treatment, or a combination thereof. In some embodiments, the cellulose fibers can be recycled from paper, newsprint, or cardboard for reuse. In some embodiments, the cellulose fibers can be blended with other natural or synthetic materials (such as gypsum, starch, or polymer fibers) to improve the properties of the paper. In some embodiments, the cellulose-containing polymeric substrate can also be blended and otherwise bonded to other materials including resins, lignin, and starch. In some embodiments, the cellulose-containing polymeric substrate can include other cellulose-free materials, including woven glass, minerals, fabrics, or polymer fibers such as polyvinyl alcohol or polyvinyl acetate. In some embodiments, the cellulose-containing polymeric substrate can include other natural materials, including silk, carrageenan, or starch. In some embodiments, processes and materials are used to coat, treat, or finish cellulose-containing polymer substrates to promote color, adhesion, absorption, flame retardancy, weight reduction, strength increase, sound damping, or other properties. In some embodiments, the polymer substrate may contain cellulose that has reacted to form other products, such as carboxymethyl cellulose (CMC) or cellulose gum, wherein the carboxymethyl groups (-CH2-COOH) are bound to some hydroxyl groups of the pyranose monomers that form the cellulose backbone. For example, CMC can be synthesized by a base-catalyzed reaction of cellulose with chloroacetic acid. In some embodiments, a polymer substrate containing cellulose (such as cotton or viscose fiber) is converted into CMC.

[0108] In some embodiments, the polymer substrate comprises one or more copolymers. In some embodiments, the copolymers include polyether-polyurea copolymers, polyamide copolymers, polyester copolymers, acrylonitrile-butadiene-styrene (ABS) copolymers, styrene / butadiene copolymers (SBR), nitrile rubber, styrene-acrylonitrile copolymers, styrene-isoprene-styrene (SIS) copolymers, ethylene-vinyl acetate copolymers, or combinations thereof. In some embodiments, the copolymers include copolymers formed by chain growth polymerization and / or copolymers formed by stepwise growth polymerization.

[0109] In some embodiments, the polyamide copolymer is a copolymer that can be formed by the polycondensation of two or more dicarboxylic acids and diamines, the polycondensation of dicarboxylic acids and two or more diamines, or the polycondensation of two or more dicarboxylic acids and two or more diamines. In some embodiments, the polyamide copolymer is a copolymer formed by the polycondensation of two or more dicarboxylic acids and diamines, the polycondensation of dicarboxylic acids and two or more diamines, or the polycondensation of two or more dicarboxylic acids and two or more diamines, wherein the dicarboxylic acid is selected from picric acid, sebacic acid, 1,12-dodecanoic acid, terephthalic acid, and isophthalic acid, and wherein the diamine is selected from 1,4-diaminobutane, 1,5-diaminopentane, 2-methylpentamethylenediamine, hexamethylenediamine (1,6-diaminohexane), m-xylenediamine, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 4,4'-methylenebis(cyclohexyl-1-amine), and trimethylhexamethylenediamine. In some embodiments, the polyamide copolymer is a copolymer formed by the polycondensation of one or more aminocarboxylic acids or corresponding lactams, one or more dicarboxylic acids, and one or more diamines. In some embodiments, the polyamide copolymer is a copolymer that can be formed by the polycondensation of one or more aminocarboxylic acids or corresponding lactams, one or more dicarboxylic acids, and one or more diamines, wherein the aminocarboxylic acid or corresponding lactam is selected from autolactams, 11-aminoundecanoic acid, and... 1,4-Aminododecanoic acid, wherein the dicarboxylic acid is selected from autoic acid, sebacic acid, dodecanoic acid, terephthalic acid, and isophthalic acid, and wherein the diamine is selected from 1,4-diaminobutane, 1,5-diaminopentane, 2-methylpentamethylenediamine, hexamethylenediamine (1,6-diaminohexane), m-xylenediamine, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 4,4'-methylenedi(cyclohexyl-1-amine), and trimethylhexamethylenediamine. In some embodiments, the polyamide copolymer is a copolymer that can be formed by the condensation polymerization of two or more aminocarboxylic acids or corresponding lactams. In some embodiments, the polyamide copolymer is a copolymer that can be formed by the condensation polymerization of two or more aminocarboxylic acids or corresponding lactams, wherein the aminocarboxylic acid or corresponding lactam is selected from autolactam, 11-aminoundecanoic acid, and... 11-Aminododecanoic acid. In some embodiments, the polyamide copolymer is a copolymer that can be formed by the condensation polymerization of caprolactam and 11-aminododecanoic acid. In some embodiments, the polyamide copolymer is a copolymer that can be formed by the condensation polymerization of caprolactam and 11-aminododecanoic acid. A copolymer formed by the condensation polymerization of α-aminododecanoic acid. In some embodiments, the polyamide copolymer is a copolymer formed by the condensation polymerization of caprolactam, adipic acid, and hexamethylenediamine. In some embodiments, the polyamide copolymer is a copolymer formed by the condensation polymerization of α-aminododecanoic acid. A copolymer formed by the condensation polymerization of aminododecanic acid, adipic acid, and hexamethylenediamine. In some embodiments, the polyamide copolymer can be formed by the polymerization of caprolactam, ... A copolymer formed by the condensation polymerization of aminododecanic acid, adipic acid and hexamethylenediamine.

[0110] In some embodiments, the polymeric substrate comprises a blend of one or more polymers and / or copolymers. In some embodiments, the blend comprises 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 polyamides, said polyamides being derived from lactams (nylon-6), 11-aminoundecanoic acid (nylon-11), etc. -Aminodolaric acid (Nylon-12), adipic acid and hexamethylenediamine (Nylon-6,6), sebacic acid and hexamethylenediamine (Nylon-6,10), dodecanoic 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 m-xylenediamine, sebacic acid and 1,10-diaminodecane (Nylon-10,10), dodecanoic acid and 1,12-diaminododecane (Nylon-12,12), or dodecanoic acid and 4,4'-methylenedi(cyclohexyl-1-amine). In some embodiments, the blend of two or more polyamides comprises 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.

[0111] In some embodiments, the polymer substrate is a woven fabric, a non-woven fabric, leather, synthetic leather, or artificial leather. In some embodiments, the polymer substrate is manufactured by impregnating a non-woven or woven fabric made of nylon or polyester with polyurethane resin and then immersing the fabric in a mixture of water or solvent to cure it. In some embodiments, methods for wet-curing the polymer elasticity include, for example, immersion in a curing solution at 20°C-60°C for 1-60 minutes, the curing solution containing a good polyurethane solvent, such as N,N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and water. Coagulation methods include immersion in a coagulation solution at 20°C-60°C for 1-60 minutes. In some embodiments, the polymer substrate is manufactured by laminating polyurethane resin layers onto the surface of artificial leather. In some embodiments, the base yarn of the nonwoven fabric is composed of microfibers, for example, fibers with a diameter of about 0.1 micrometers (µm) to about 0.5µm, about 1µm, about 2µm, about 4µm, about 10µm, about 20µm, or about 50µm.

[0112] In some embodiments, the polymer substrate includes a combination of synthetic and natural fibers, such as cotton-polyester blends or cotton-nylon blends.

[0113] In some embodiments, the polymer substrate is in fibrous form. For example, the polymer substrate may be extruded into fibers before or after the addition of ceramics. In some embodiments, the fibers are knitted or woven into fabrics. In other embodiments, the fibers are assembled into nonwoven fabrics. In some embodiments, the fiber diameter (i.e., number-average diameter) is in the range of about 10 µm to about 100 µm, about 50 µm to about 250 µm, about 100 µm to about 300 µm, about 300 µm to about 500 µm, or about 100 µm to about 500 µm. In some embodiments, the average fiber diameter is in the range of about 5 µm to about 20 µm, or about 2 µm to about 10 µm, or about 1 µm to about 5 µm. In some embodiments, the average fiber diameter is in the range of about 0.1 µm to about 4 µm. In some embodiments, the average fiber diameter is less than about 1000µm, less than about 900µm, less than about 800µm, less than about 700µm, less than about 600µm, less than about 500µm, less than about 400µm, less than about 300µm, less than about 200µm, less than about 100µm, less than about 90µm, less than about 80µm, less than about 70µm, less than about 60µm, less than about 50µm, less than about 40µm, less than about 30µm, less than about 20µm, less than about 10µm, less than about 5µm, less than about 2µm, less than about 1µm, or less than about 0.5µm.

[0114] In some embodiments, the polymer substrate is in the form of a lightweight woven fabric. In some embodiments, the lightweight woven fabric is a tear-resistant fabric using reinforcement techniques to make it more resistant to tearing and / or ripping. In some embodiments, during weaving, stronger (and generally thicker) reinforcing yarns are interwoven at regular intervals in a cross-hatching pattern. When a lightweight woven fabric is used as the base fabric, the base fabric may have a density of approximately 20 g / m². 2 Approximately 400g / m 2 or approximately 30g / m 2 Up to 150g / m 2 The density of the base fabric. In some embodiments, plain weave is preferred for the structure of the base fabric from the perspective of self-weaving density and prevention of misalignment. The weave density of the base fabric can vary depending on whether the base fabric is resin-treated, or the fineness of the weaving yarns or other design factors. As an example, for warp density, the density of the woven fabric should be about 120 yarns / 2.54cm, or about 130 to about 300 yarns / 2.54cm, and for weft density, the density of the woven fabric should be about 80 yarns / 2.54cm, or about 90 to about 300 yarns / 2.54cm. The total fiber count of the base fabric can be about 20 dtex to about 80 dtex, or about 25 dtex to about 70 dtex. The cover factor (CF) can be about 800 to about 5500, or about 1000 to about 5000. The coverage factor is a value obtained from the total fiber count and beating density of the yarns used in the warp or weft, and it is defined by equation (1). In equation (1), D w It is the total warp fiber count (dtex), D f It is the total weft fiber count (dtex), N w It is the warp weave density (yarn / 2.54cm), N f It is the weft knitting density (yarn / 2.54cm).

[0115] (Equation 1)

[0116] In some embodiments, the polymer substrate is in the form of a film. For example, the polymer substrate may form a film before or after the addition of ceramics. In some embodiments, the film has an average thickness of less than about 5 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 about 10 µm to about 100 µm, about 10 µm to about 500 µm, about 100 µm to about 500 µm, about 500 µm to about 1000 µm, or about 1000 µm to about 5000 µm.

[0117] In some implementations, before or after adding ceramic materials to form a polymer-ceramic composite, the polymer substrate is formed into structural elements, cast into a shape, self-melting and nozzle arrangement is printed or otherwise deposited, or self-melting is photocured to form a complex structure.

[0118] In some embodiments, the polymer substrate is chemically modified, such as by crosslinking reactions with different portions of the polymer chains, or by reacting functional groups on the polymer chains with one or more chemical substances to form different polymers, such as vinylon from polyvinyl alcohol. In some embodiments, the polymer substrate is chemically modified before or after the addition of ceramic materials to form a polymer-ceramic composite.

[0119] In some embodiments, the polymer substrate is formed by spinning, such as wet-cooled gel spinning, wherein a resin is dissolved in a solvent, extruded into a second solvent to form a resin-gel, and the second solvent is removed to form fibers. In some embodiments, the resin is polyvinyl alcohol (PVOH). In some embodiments, the polymer substrate is a water-soluble fiber. In some embodiments, the water-soluble fiber has a dissolution temperature of about 20°C to about 95°C, about 20°C to about 60°C, about 30°C to about 70°C, about 40°C to about 80°C, about 50°C to about 95°C, about 20°C to about 45°C, about 30°C to about 80°C, about 20°C, about 40°C, about 60°C, about 70°C, about 80°C, or about 95°C. In some embodiments, the water-soluble fiber is a short fiber with a fineness of about 1 dtex to about 3 dtex, about 1.4 dtex, about 1.7 dtex, or about 2.2 dtex. In some embodiments, the water-soluble fiber is a woven yarn with a yarn count of about 20:1 English cotton yarn count (ECC) to about 80:1 ECC, about 20:1 ECC, about 30:1 ECC, about 40:1 ECC, about 50:1 ECC, or about 80:1 ECC, where ECC is the number of 840 yards per pound. In some embodiments, the polymer matrix is ​​a fiber that has been stretched to obtain a high-tenacity fiber. In some embodiments, the polymer matrix is ​​a high-tenacity material that forms chopped fibers, staple fibers, or woven yarns. In some embodiments, the polymer substrate is short-cut fibers with a toughness of about 5 cN / dtex to about 20 cN / dtex, about 5 cN / dtex to about 10 cN / dtex, about 10 cN / dtex to about 15 cN / dtex, about 15 cN / dtex to about 20 cN / dtex, about 5 cN / dtex to about 20 cN / dtex, about 10 cN / dtex to about 20 cN / dtex, about 9 cN / dtex, about 10 cN / dtex, about 12 cN / dtex, or about 15 cN / dtex. In some embodiments, the polymer substrate is short fibers with a toughness of about 10 cN / dtex, a modulus between about 75 cN / dtex and about 150 cN / dtex, and a density of about 1 dtex to about 3 dtex, about 1.3 dtex, about 1.7 dtex, or about 2.2 dtex. In some embodiments, the polymer substrate is a woven yarn with an elongation of less than any of about 10%, about 6%, about 7%, about 8%, or about 9% and a yarn count of about 5:1 English cotton yarn count (ECC) to about 80:1 ECC, about 5:1 ECC, about 10:1 ECC, about 20:1 ECC, about 30:1 ECC, about 60:1 ECC, or about 80:1 ECC, wherein ECC is the number of 840 yards per pound.

[0120] In some embodiments, the polymer substrate is a polymer film having an adhesive layer. In some embodiments, the polymer substrate is a matte cellulose acetate film with a thickness of about 10 µm to about 200 µm, about 20 µm to about 100 µm, about 30 µm to about 50 µm, about 40 µm to about 100 µm, or about 40 µm, having a synthetic acrylic adhesive layer. In some embodiments, the polymer substrate is a conductive polycarbonate with a thickness of about 10 µm to about 500 µm, about 50 µm to about 100 µm, about 75 µm to about 150 µm, about 100 µm to about 200 µm, about 150 µm to about 150 µm, about 50 µm, about 100 µm, or about 200 µm, having a carbon-filled acrylic adhesive layer.

[0121] In some embodiments, the 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 filaments or fibers, cast into a shape or film, or printed or otherwise deposited to form a melt and nozzle arrangement, thereby forming a polymer substrate. These steps can be performed before or after the addition of ceramic materials to form the polymer-ceramic composite.

[0122] ceramics

[0123] In some embodiments, the ceramic deposited on a polymer substrate as described herein comprises transition metal oxides, transition metal carbonates, transition metal oxalates, transition metal phosphates, transition metal sulfates, or combinations thereof. In some embodiments, the ceramic comprises alkali metal oxides, alkaline earth metal oxides, alkali metal carbonates, alkaline earth metal carbonates, alkali metal oxalates, alkaline earth metal oxalates, alkali metal phosphates, alkaline earth metal phosphates, alkali metal sulfates, alkaline earth metal sulfates, or combinations thereof. In some embodiments, the ceramic comprises metal oxides, metal hydroxides, layered double hydroxides, metal carbonates, metal oxalates, metal phosphates, metal sulfates, or mixtures thereof, wherein the metal is a transition metal, alkali metal, or alkaline earth metal. In some embodiments, the ceramic comprises metal oxides, metal hydroxides, layered double hydroxides, metal carbonates, metal oxalates, metal phosphates, metal sulfates, or mixtures thereof, wherein the metal is aluminum, silicon, or tin. In some embodiments, the ceramic comprises a transition metal, alkali metal, alkaline earth metal, aluminum, silicon, or tin. In some embodiments, the ceramic comprises magnesium, calcium, titanium, manganese, iron, zinc, zirconium, tungsten, nickel, cobalt, or mixtures thereof. In some embodiments, the ceramic comprises oxygen, phosphorus, sulfur, carbon, or mixtures thereof. In some embodiments, the ceramic comprises manganese oxide, zinc oxide, silicon oxide, aluminum oxide, titanium dioxide, iron oxide, cobalt oxide, nickel oxide, zirconium oxide, or mixtures thereof. In some embodiments, the ceramic comprises hydroxyapatite, calcium carbonate, magnesium carbonate, calcium sulfate, cerium oxide, octacalcium phosphate, calcium phosphate, or mixtures thereof or hydrates thereof. In some embodiments, the ceramic comprises a phosphate, which is present in a partially protonated, partially hydrated, hydrated, partially dehydrated, or dehydrated form. In some embodiments, the ceramic comprises calcium phosphate, which includes hydroxyapatite [Ca5(PO4)3OH], calcium phosphate [Ca(PO3OH], etc. [2H2O], triclinic calcium phosphate [Ca(PO3OH)], or mixtures thereof. In some embodiments, the ceramic comprises a sulfate, which is present in a partially protonated, partially hydrated, or partially dehydrated form.

[0124] In some embodiments, additional inorganic elements, inorganic compounds, and / or ionic compounds may also permeate into the ceramic deposited on the polymer substrate and into the internal volume of the polymer matrix. In some embodiments, inorganic elements, compounds, and / or ionic compounds are contained within an amorphous inorganic glass phase. In some embodiments, inorganic elements, compounds, and / or ionic compounds are contained within crystalline or polycrystalline domains or phases. In some embodiments, inorganic elements, compounds, and / or ionic compounds are contained in an ordered manner within crystalline domains. In some embodiments, inorganic elements, compounds, and / or ionic compounds are distributed or contained along crystalline domain boundaries, grain boundaries, defects, or pores. In some embodiments, inorganic elements, compounds, and / or ionic compounds are distributed along the outer surface of the polymer matrix. In some embodiments, inorganic elements, compounds, and / or ionic compounds are distributed into the internal volume of the polymer substrate. In some embodiments, inorganic elements, compounds, and / or ionic compounds are distributed in the ceramic deposited on the polymer substrate, distributed along the outer surface of the polymer substrate, distributed within the internal volume of the polymer substrate, or a combination thereof.

[0125] In some embodiments, complementary inorganic elements also permeate into the ceramic deposited on the polymer substrate and into the internal volume of the polymer matrix. In some embodiments, complementary inorganic elements are contained within an amorphous inorganic glass phase. In some embodiments, complementary inorganic elements are contained within crystalline or polycrystalline domains or phases. In some embodiments, complementary inorganic elements are contained in an ordered manner within crystalline domains. In some embodiments, complementary inorganic elements are distributed or contained along crystalline domain boundaries, grain boundaries, defects, or pores. In some embodiments, complementary inorganic elements are distributed along the outer surface of the polymer matrix. In some embodiments, complementary inorganic elements are distributed into the internal volume of the polymer substrate. In some embodiments, complementary inorganic elements are distributed in the ceramic deposited on the polymer substrate, distributed along the outer surface of the polymer substrate, distributed within the internal volume of the polymer substrate, or a combination thereof.

[0126] 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 combinations thereof. In some embodiments, the complementary inorganic element exists as a relative ion, exists as a relative ion, or exists as a component of a relative ion. In some embodiments, the relative ion is a cation or anion. In some embodiments, the relative ion is a cation. In some embodiments, the complementary inorganic element exists as a potassium cation, magnesium cation, manganese cation, aluminum cation, titanium cation, sodium cation, calcium cation, ammonium cation, or combinations thereof. In some embodiments, the complementary inorganic element exists as a cation containing potassium, magnesium, manganese, aluminum, titanium, sodium, calcium, nitrogen, or combinations thereof. In some embodiments, the complementary inorganic element is 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 depends on the effective pH of the immediate environment of the hydrated cation. In some embodiments, the relative ion is an anion. In some embodiments, the complementary inorganic element is nitrogen and is in the form of nitrate (NO3). -1 ), nitrite (NO2) -1 ), nitrides (N -3 ), amide (NH2) -1 It exists as an inorganic element or a combination thereof. In some embodiments, the complementary inorganic element is oxygen and is present as a hydroxide (OH-). -1 ), oxides (O) -2 ), peroxide (O2) -2 Hydrogen peroxide (HO2) -1 It exists as a combination of chlorine and chloride. In some embodiments, the complementary inorganic element is chlorine and is a chloride (Cl... -1 Perchlorate (ClO4) -1 ), chlorate (ClO3) -1 ), chlorite (ClO2) -1 hypochlorite (ClO) -1 It exists as a combination of bromine and bromide. In some embodiments, the complementary inorganic element is bromine and is present as a bromide (Br). -1 Perbromate (BrO4) -1 ), bromate (BrO3) -1 ), bromate (BrO2) -1 Hypobromate (BrO) -1 It exists as a combination of iodine and iodide. In some embodiments, the complementary inorganic element is iodine and is present as an iodide (I -1 ), periodate (IO4) -1 ), iodate (IO3) -1 ), iodite (IO2) -1 ), hypoiodide (IO -1 It exists as a combination of phosphates or other inorganic elements. In some embodiments, the complementary inorganic element is phosphorus and is in the form of phosphate (PO4). -3 ), hydrogen phosphate (HPO4) -2 ), dihydrogen phosphate (H2PO4) -1It exists as a combination of ) or ) in some embodiments. In some embodiments, the complementary inorganic element is sulfur and is in the form of sulfate (SO4) -2 ), hydrogen sulfate (HSO4) -1 ), sulfites (SO3) -2 ), bisulfite (HSO3) -1 ), sulfides (S -2 ), thiosulfate (S2O3) -2 ), thiocyanate (SCN) -1 It exists as a combination of the following. In some embodiments, the complementary inorganic element is carbon or nitrogen and is in the form of cyanate (OCN). -1 ), thiocyanate (SCN) -1 It may be present in combination with or in some embodiments. In some embodiments, the anion is permanganate (MnO4). -1 ) or hydrogen anion (H -1 In some embodiments, the anion is permanganate (MnO4). -1 In some embodiments, the complementary inorganic element is carbon and is in the form of carbonate (CO3). -2 ), bicarbonate (HCO3) -1 The complementary inorganic element exists as a carbon anion or a combination thereof. In some embodiments, the complementary inorganic element is carbon and exists as 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 and exists as a dicarboxylate anion. In some embodiments, the dicarboxylate anion is succinate, malonic acid, 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 depends on the effective pH of the immediate environment of the dicarboxylate anion. In some embodiments, the complementary inorganic element exists as anion containing chlorine, bromine, iodine, phosphorus, sulfur, nitrogen, oxygen, carbon, hydrogen, manganese, or a combination thereof.

[0127] In some embodiments, the ceramic precursor includes calcium nitrate and potassium phosphate, the relative ions include nitrate and potassium, and the complementary inorganic elements include nitrogen, oxygen and / or potassium. In some embodiments, the ceramic precursor includes calcium nitrate and potassium phosphate, the relative ions include nitrate and potassium, the complementary inorganic elements include nitrogen, oxygen and / or potassium, and nitrogen, oxygen, potassium, or combinations thereof permeate the internal volume of the ceramic and / or polymer matrix.

[0128] In some embodiments, the ceramic precursor comprises calcium nitrate and sodium oxalate dihydrate, the relative ions comprise nitrate and sodium, and the complementary inorganic elements comprise nitrogen, oxygen, and / or sodium. In some embodiments, the ceramic precursor comprises calcium nitrate and sodium oxalate dihydrate, the relative ions comprise nitrate and sodium, the complementary inorganic elements comprise nitrogen, oxygen, and / or sodium, and nitrogen, oxygen, sodium, or combinations thereof permeate the internal volume of the ceramic and / or polymer matrix.

[0129] In some embodiments, the ceramic precursor includes 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, with relative ions including nitrates and / or chlorides and ammonium, potassium and / or sodium, and complementary inorganic elements including nitrogen, chlorine, oxygen, potassium and / or sodium. In some embodiments, the ceramic precursor includes 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, with relative ions including nitrates and / or chlorides and ammonium, potassium and / or sodium, and complementary inorganic elements including nitrogen, chlorine, oxygen, potassium and / or sodium, and nitrogen, chlorine, oxygen, potassium, sodium, or combinations thereof permeate the internal volume of the ceramic and / or polymer matrix.

[0130] In some embodiments, the ceramic precursor includes manganese nitrate and sodium hydroxide, the relative ions include nitrate and sodium, and the complementary inorganic elements include nitrogen, oxygen, and / or sodium. In some embodiments, the ceramic precursor includes manganese nitrate and sodium hydroxide, the relative ions include nitrate and sodium, the complementary inorganic elements include nitrogen, oxygen, and / or sodium, and nitrogen, oxygen, sodium, or combinations thereof permeate the internal volume of the ceramic and / or polymer matrix.

[0131] In some embodiments, the ceramic precursor includes manganese sulfate and potassium persulfate and / or ammonium hydroxide, the relative ions include sulfate and ammonium and / or potassium, and the complementary inorganic elements include sulfur, oxygen, nitrogen, and / or potassium. In some embodiments, the ceramic precursor includes manganese sulfate and potassium persulfate and / or ammonium hydroxide, the relative ions include sulfate and ammonium and / or potassium, the complementary inorganic elements include sulfur, oxygen, nitrogen, and / or potassium, and nitrogen, oxygen, sodium, or combinations thereof permeate the internal volume of the ceramic and / or polymer matrix.

[0132] Ceramics deposited on a polymer substrate can be in the form of discrete particles or smaller aggregates. In some embodiments, the size of the discrete particles or smaller aggregates (i.e., the average particle size of the ceramic, such as the average diameter) is about 0.05 µm to about 5 µm, about 0.5 µm to about 10 µm, or about 0.1 µm to about 0.5 µm. In some embodiments, the average particle size is less than about 10 µm, less than about 5 µm, less than about 1 µm, less than about 0.5 µm, less than about 0.1 µm, or less than about 0.05 µm. In some embodiments, ceramics deposited on a polymer can be in the form of network particles, agglomerates, or aggregates. In some embodiments, the ceramic can be nanostructured and have geometrically similar features or structures such as plates, rods, spheres, or aggregates, having at least one dimension less than about 100 nm.

[0133] In some embodiments, the ceramic deposited on the polymer substrate has an average thickness outside the polymer layer of about 0.05 µm to about 5 µm, or about 0.05 µm to about 10 µm, or about 0.1 µm to about 0.5 µm, or less than about 10 µm, or less than about 5 µm, or less than about 1 µm, or less than about 0.5 µm, or less than about 0.25 µm, or less than about 0.2 µm, or less than about 0.15 µm, or less than about 0.1 µm, or less than about 0.075 µm, or less than about 0.05 µm, i.e., as measured from the outer surface of the polymer substrate. The average thickness of the ceramic is the distance from the outer surface of the polymer substrate to the outer surface of the ceramic.

[0134] In some embodiments, the ceramic deposited on the polymer substrate has a secondary structure in the form of a plate or plate on the outer surface of the ceramic.

[0135] In some embodiments, the ceramic is crystalline. In other embodiments, the ceramic is amorphous. In some embodiments, the ceramic contains aggregates of crystalline domains.

[0136] polymer-ceramic composites

[0137] In one aspect, a polymer-ceramic composite is provided. The polymer-ceramic composite includes: a polymer substrate comprising a polymer matrix having an outer surface and an internal volume; and a ceramic.

[0138] In some embodiments, the polymer-ceramic composite includes ceramic on the outer surface of a polymer matrix, and the ceramic or inorganic element occupies at least a portion of the internal volume of the polymer matrix, i.e., occupies at least a portion of the internal volume of the polymer matrix.

[0139] In some embodiments, the polymer-ceramic composite is in the form of fibers or membranes. In some embodiments, the polymer-ceramic composite is in the form of fibers with an average diameter of less than about 5 mm or less than about 1 mm. In some embodiments, the polymer-ceramic composite is in the form of membranes with an average thickness of less than about 5 mm or less than about 3 mm.

[0140] In some embodiments, the polymer-ceramic composite has a core-shell structure, i.e., a polymer core and a shell comprising ceramic. In a core-shell structure, the polymer substrate comprising a polymer matrix having an outer surface and an internal volume is the core; and the ceramic comprising ceramic on the outer surface of the polymer matrix and ceramic or inorganic elements occupying at least partially the internal volume of the polymer matrix is ​​the shell. In some embodiments where the polymer-ceramic composite has a core-shell structure, the polymer substrate is in fibrous form. In some embodiments where the polymer-ceramic composite has a core-shell structure, the polymer substrate is in fibrous form and the fiber cross-section is circular, nearly circular, or elliptical. In some embodiments where the polymer-ceramic composite has a core-shell structure, the polymer substrate is in fibrous form and the fiber cross-section is semi-circular or nearly semi-circular. In some embodiments where the polymer-ceramic composite has a core-shell structure, the polymer substrate is in fibrous form and the fiber cross-section is triangular, Reuleaux triangular, or nearly triangular, or square, or nearly square, or polygonal. In some embodiments where the polymer-ceramic composite exists in a core-shell structure, the polymer substrate is in the form of fibers and the cross-section of the fibers is epicycloid, epicycloid, leaf-shaped, trilobed, pentlobed, octlobed, multilobed, oval, flat, dog-bone shaped, or star-shaped.

[0141] In some embodiments, the polymer-ceramic composite includes a core and a shell, wherein the core comprises a polymer and the shell comprises ceramic. In some embodiments, the core comprises a relative polymer weight percentage greater than about 50%, greater than about 60%, greater than about 70%, greater than about 80%, greater than about 90%, or greater than about 95%. In some embodiments, the shell comprises a relative ceramic weight percentage greater than about 10%, greater than about 20%, greater than about 30%, greater than about 40%, greater than about 50%, greater than about 60%, greater than about 70%, or greater than about 80%. In some embodiments, there is a discrete boundary between the core and the shell. In some embodiments, the core and the shell comprise the same or similar chemical components or materials in different ratios. In some embodiments, the core and the shell have a boundary that includes a spatial gradient of chemical component or material concentration in the core, a spatial gradient of chemical component or material concentration in the shell, or a spatial gradient of chemical component or material concentration in both the core and the shell. In some embodiments, the core and the shell comprise different chemical components or materials. In some embodiments, both the core and the shell comprise the same chemical component or material but have different properties, such as density, molecular weight, or degree of crosslinking.

[0142] In some embodiments, the polymer-ceramic composite is in the form of a film and a coating, wherein the polymer substrate having an outer surface and an internal volume of the polymer matrix is ​​a film; and the ceramic having ceramic or inorganic elements on the outer surface of the polymer matrix and occupying at least part of the internal volume of the polymer matrix is ​​a coating applied to one or more outer surfaces.

[0143] In some embodiments of the membrane, the ceramic concentration on one side of the outer surface of the membrane is higher than the ceramic concentration on the opposite side of the outer surface of the membrane.

[0144] In some embodiments, the polymer-ceramic composite is in the form of a laminate, and the ceramic concentration relative to the polymer matrix increases in the outermost layer of the laminate relative to the inner layers. In a laminate containing multiple layers fixed or adhered together, the top and bottom layers of the laminate serve as the polymer substrate for preparing the polymer-ceramic composite as described herein. Each of the top and bottom layers of the laminate structure contains an outer surface and an internal volume of the polymer matrix, a first portion of ceramic on the outer surface of each of the top and bottom layers, and a second portion of ceramic in the internal volume of the polymer matrix of each of the top and bottom layers of the laminate.

[0145] In some embodiments, the polymer-ceramic composite is a textile material comprising polyamide, polyester, polyolefin, substituted polyolefin, polyurethane, polyol, vinyl, polyether, cotton, wool, cellulose material, or combinations thereof.

[0146] In some embodiments, the polymer-ceramic composite includes a thermoplastic core material. Non-limiting examples of thermoplastic core materials include polyesters, polyamides, polyurethanes, acrylics (polyacrylates), polyolefins, polyols, acrylonitrile butadiene styrene (ABS), polyvinyl alcohol, or combinations thereof.

[0147] In some embodiments, the polymer-ceramic composite has a core material comprising a blend or combination of cotton, wool or cellulose materials, natural fibers and synthetic fibers.

[0148] In some embodiments, the polymer-ceramic composite as described herein includes a ceramic gradient starting from the center of the polymer substrate (i.e., from the centerline of the polymer fiber) (as in the case of woven or nonwoven fabrics), a ceramic gradient starting from the centerline of the polymer substrate (in the case of films or sheets), and a ceramic gradient starting from a distance of 2 mm from the surface of a thicker casting or molded part. In some embodiments, the relative proportion of ceramics increases from the center of the polymer substrate (e.g., polymer fiber or film) to the surface of the polymer substrate. In some embodiments, the highest proportion of ceramics is on the outside of the polymer substrate. In some embodiments, ceramic particles are embedded in the internal volume of the polymer substrate and simultaneously protrude through the surface of the polymer substrate (e.g., polymer fiber or film).

[0149] In some embodiments, 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 the total ceramic in the polymer-ceramic composite protrudes through the surface of the polymer substrate.

[0150] In some embodiments, the ceramic in the polymer-ceramic composite is nanostructured and includes structures or features such as plates, rods, spheres or aggregates that are geometrically similar and have at least one dimension less than 100 nanometers.

[0151] In some embodiments, the polymer-ceramic composite is coated with one or more functional molecules to impart one or more desired properties. In some embodiments, the polymer-ceramic composite is functionalized with a thin film with a thickness of less than about 1 µm, or 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, or less than about 20 nm, or less than about 10 nm. In some embodiments, the polymer-ceramic composite is coated with a monolayer chemical, wherein the film conformally coats the polymer-ceramic with a characteristic thickness of less than about 5 nm. In some embodiments, the polymer-ceramic composite is coated with a functional layer. In some embodiments, the functional layer comprises a monolayer chemical, i.e., the functional layer is essentially a monolayer of functional molecules. The monolayer may have a thickness of less than about 5 nm. In some embodiments, the polymer-ceramic composite is coated with silane, siloxane, urethane, acrylate, or molecules having head and tail groups, for example, wherein the head group includes silyl, phosphonate, phosphonic acid, carboxylic acid, vinyl, alcohol, hydroxyl, thiol ester, thiol and / or ammonium (e.g., quaternary ammonium), and wherein the tail group includes hydrocarbon, fluorocarbon, vinyl, phenyl, epoxy, acrylic (acrylic group), acrylate, hydroxyl, carboxylic acid, thiol and / or quaternary ammonium.

[0152] In some embodiments, the polymer-ceramic composite comprises a polymer core and a ceramic shell. In some embodiments, the thickness of the ceramic shell of the polymer-ceramic composite is less than 20% of the hydraulic diameter of the polymer core. In some embodiments, the thickness of the ceramic shell of the polymer-ceramic composite is less than about 1 micrometer. In some embodiments, the diameter or thickness of the polymer core is greater than about 1 micrometer. In some embodiments, the polymer core comprises a thermoplastic, such as polyester, polyamide, polyurethane, acrylic (polyacrylate), polyolefin, polyol, ABS, polyvinyl alcohol, or combinations thereof. In some embodiments, the polymer core comprises cotton, wool, or cellulose material. In some embodiments, the polymer-ceramic composite has a cylindrical polymer core and a ceramic shell. In some embodiments, the ceramic shell comprises a transition metal, alkali metal, or alkaline earth metal. In some embodiments, the transition metal or alkaline earth metal is iron, magnesium, zinc, manganese, calcium, or nickel. In some embodiments, the transition metal, alkali metal, or alkaline earth metal is in the form of oxides, hydroxides, phosphates, carbonates, sulfates, or combinations thereof. In some embodiments, the phosphate, carbonate, sulfate, or combinations thereof are present with varying degrees of protonation or deprotonation. In some embodiments, the carbonate is present as a carbonate or bicarbonate, or a combination thereof. In some embodiments, the phosphate is present as a hydrogen phosphate (HPO4). 2- ), dihydrogen phosphate (H2PO4) 1- ), phosphate (PO4) 3-The shell contains, or combinations thereof. In some embodiments, the sulfate is present as a sulfate, a bisulfate, or a combination thereof. In some embodiments, the ceramic weight fraction in the shell is less than about 0.9. In some embodiments, the ceramic in the shell has a morphology with at least one dimension less than 100 nanometers. In some embodiments, the ceramic in the shell has a morphology of 0-dimensional, 1-dimensional, or 2-dimensional material. In some embodiments, the ceramic shell comprises siloxanes, acrylates, phosphonates, sulfonates, urethanes, or combinations thereof. In some embodiments, the shell comprises an organosilicon polymer or an alkyl-terminated silane or siloxane. In some embodiments, the shell comprises an alkyl-terminated functional group. In some embodiments, the alkyl-terminated functional group comprises a saturated chain length longer than three carbons. In some embodiments, the shell comprises an isocyanate or an isocyanate-terminated polymer. In some embodiments, the shell adheres to the core. In some embodiments, the adhesion between the shell and the core is rated from 0 to 5 according to standard methods (such as ASTM D3359), and the adhesion rating in the core-shell structure increases compared to the initial fabric. In some embodiments, fabric testing methods (such as the single-fiber pull-out test or the fiber matrix adhesion tester (FIMATEST)) are used to measure changes in fiber adhesion to the fabric as an indicator of core-shell adhesion. In some embodiments, fabric tear strength methods (such as ASTM D1424 or ASTM D5034) are used to measure changes in tear strength as an indicator of core-shell adhesion.

[0153] In some embodiments, the surface roughness of the polymer-ceramic composite is greater than 1.1. In some embodiments, at least a portion of the ceramic in the shell is interconnected. In some embodiments, the polymer-ceramic composite comprises a laminated polymer film or polymer film layer and a deposit containing ceramic on at least one side of the film. In some embodiments, the thickness of the deposited ceramic is less than 20% of the average thickness of the polymer film. In some embodiments, the thickness of the deposited ceramic is less than about 1 micrometer. In some embodiments, the thickness of the polymer film substrate is greater than about 1 micrometer. In some embodiments, the polymer film substrate contains a thermoplastic. In non-limiting examples, the thermoplastic is polyester, polyamide, polyurethane, acrylic (acrylate polymer), polyolefin, polyol, ABS, polyvinyl alcohol, or a combination thereof. In some embodiments, the polymer film substrate contains cellulose material or cellulose-derived material. In some embodiments, the deposited ceramic comprises a transition metal or alkaline earth metal. In some embodiments, the transition metal or alkaline earth metal is iron, magnesium, zinc, manganese, calcium, or nickel. In some embodiments, the transition metal or alkaline earth metal is in the form of oxides, hydroxides, phosphates, carbonates, sulfates, 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 comprises at least one morphology with a dimension less than 100 nanometers. In some embodiments, the deposited ceramic comprises a 0-dimensional or 2-dimensional morphology. In some embodiments, the deposited ceramic comprises siloxanes, acrylates, phosphonates, sulfonates, carbamates, or combinations thereof. In some embodiments, the deposited ceramic comprises an organosilicon polymer or an alkyl-terminated silane or siloxane. In some embodiments, the deposited ceramic comprises alkyl-terminated functional groups. In some embodiments, the alkyl-terminated functional groups comprise saturated chain lengths longer than three carbons. In some embodiments, the deposited ceramic comprises an isocyanate or an isocyanate-terminated polymer. In some embodiments, the deposited ceramic is chemically bonded to a polymer film material. In some embodiments, the surface roughness of the polymer-ceramic composite is greater than 1.1. In some embodiments, at least a portion of the deposited ceramic is interconnected. In some embodiments, based on particles, more than about 50% of the ceramic is interconnected. In some implementations, based on particles, more than 20%, or more than 30%, or more than 40%, or more than 60%, or more than 70%, or more than 80%, or more than 90% of the ceramics are interconnected.

[0154] 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 contained in the crystalline particles or crystalline domains. In some embodiments, the amorphous matrix includes two or more elements common to the crystalline particles or crystalline domains. In some embodiments, the size of the crystalline domains is in the range of a nominal size of about 2 nm to a nominal size of about 200 nm. In some embodiments, the substrate is sequentially contacted with a liquid solution by spraying, pressure dyeing, or impregnation. In these cases, the first solution contacting the substrate is considered the first contact solution, and the second solution contacting the substrate after the first solution is considered the second contact solution, etc. In some embodiments, the crystalline domains or crystalline particles include metals from metal salts in the first and / or second contact solutions. In some embodiments, the crystalline domains or crystalline particles include rare earth metals, transition metals, alkaline earth metals, or combinations thereof. In some embodiments, the ceramic contains crystalline domains including Ca, Zn, Ni, Li, Mg, Ti, Mn, or combinations thereof. In some embodiments, the ceramic contains crystalline domains comprising phosphate, carbonate, or sulfate groups. In some embodiments, the phosphate is a 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 containing octacalcium phosphate, hydroxyapatite, triclinic calcium phosphate, calcium phosphate, calcium triphosphate, calcium pyrophosphate, and / or their hydrates.

[0155] In some embodiments, the polymer-ceramic composite is a component of a variety of polymer-ceramic composites, such as multiple fibers forming the component. In some embodiments, the polymer-ceramic composite fibers are assembled into yarns, woven fabrics, knitted fabrics, or non-woven fabric materials.

[0156] In some embodiments, the polymer-ceramic composite is functionalized, i.e., the ceramic, the polymer substrate, or both are functionalized, i.e., modified with one or more functional groups or molecules to impart one or more desired properties. In some embodiments, the functionalized polymer-ceramic composite increases the hydrophobicity of the substrate compared to an unfunctionalized polymer-ceramic composite. In some embodiments, the functionalized ceramic provides improved properties such as microbial resistance, UV resistance, improved chemical resistance, improved tear strength, improved moisture transmittance (MVTR), light transmittance, improved oil or stain resistance, improved abrasion resistance, or improved washability. In some embodiments, the polymer-ceramic composite improves these properties compared to a polymer substrate and functional layer or a ceramic and functional layer.

[0157] In some embodiments, the roughness value Ra of the polymer-ceramic composite is greater than about 0.025 µm, corresponding to a roughness grade number (N) of about N1 or greater, or about N1 to about N8, or about N5 or lower, or about or at least about N1 (0.025 µm), N2 (0.5 µm), N3 (0.1 µm), N4 (0.2 µm), N5 (0.4 µm), N6 (0.8 µm), N7 (1.6 µm) or N8 (3.2 µm) in DIN ISO 1302 or DIN 4768.

[0158] In some embodiments, the polymer-ceramic composites described herein exhibit improved tear strength, tensile strength, air permeability, vapor permeability, and / or abrasion resistance compared to the same polymer substrate without ceramics and / or the same polymer-ceramic composite without the functional coatings described herein. In some embodiments, the polymer-ceramic composite is measured according to ASTM D1424, wherein the tear strength is approximately 5000 gF or more, or approximately 2000 gF or more, or approximately 1000 gF or more, or approximately 500 gF or more, or approximately 100 gF greater than that of the uncoated material. In some embodiments, the polymer-ceramic composite is measured according to ASTM D5034, wherein the breaking strength (expressed in grams per square meter (gF) or gF / fabric width, i.e., elongation) is measured and is approximately 1%, approximately 2%, approximately 5%, approximately 10%, approximately 25%, approximately 50%, approximately 100%, and approximately 250% or greater. Tensile strength can be determined and is typically reported in MPa. In some embodiments, the air permeability of the polymer-ceramic composite is measured according to test standard ASTM D1434. In some embodiments, the polymer-ceramic composite is measured according to test standard ASTM E96, wherein the moisture transport rate (MVTR) is measured and reported in grams per area per time. In some embodiments, the MVTR is less than about 500 g / day / m². 2 Approximately 500g / day / m 2 Approximately 1000g / day / m 2 Approximately 1000g / day / m 2 Approximately 2500g / day / m 2 Approximately 2500g / day / m 2 Approximately 5000g / day / m 2 Approximately 5000g / day / m 2 Approximately 10,000 g / day / m 2 Or greater than approximately 10,000 g / day / m 2In some implementations, the polymer-ceramic composite is measured according to the test standard ASTM D4966, wherein the abrasion resistance is measured and reported according to the grades outlined in the standard for approximately 500 cycles, approximately 1000 cycles, approximately 5000 cycles, approximately 10000 cycles, approximately 30000 cycles, approximately 50000 cycles, or more.

[0159] In some embodiments, the polymer-ceramic composite as described herein includes a polymer substrate and a ceramic, wherein the polymer substrate has an outer surface and an internal volume of the polymer matrix, a first portion of the ceramic is on the outer surface, and a second portion of the ceramic occupies at least a portion of the internal volume of the polymer matrix, and wherein, at a temperature less than about 160°C and over a time period of less than about 90 minutes, the diffusion length of the second portion of the ceramic from the outer surface to the internal volume of the polymer matrix exceeds about 10 nm, about 50 nm, or about 100 nm.

[0160] In some embodiments, the polymer-ceramic composite as described herein includes a polymer substrate and a ceramic, wherein the polymer substrate has an outer surface and an internal volume of the polymer matrix, a first portion of the ceramic is on the outer surface, and a second portion of the ceramic occupies at least a portion of the internal volume of the polymer matrix, and wherein the second portion of the ceramic permeates from the outer surface into the internal volume of the polymer matrix in an amount 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.

[0161] In some embodiments, the polymer-ceramic composite as described herein includes a polymer substrate and a ceramic, wherein the polymer substrate has an outer surface and an internal volume of the polymer matrix, a first portion of the ceramic is on the outer surface, and a second portion of the ceramic occupies at least a portion of the internal volume of the polymer matrix, and wherein the ceramic concentration decreases when measured from the outer surface of the polymer substrate to the internal volume of the polymer matrix, or wherein the ceramic concentration decreases from the outer surface of the polymer substrate to the internal volume of the polymer matrix at a certain rate of decrease, or wherein the ceramic concentration decreases from the outer surface of the polymer substrate to the internal volume of the polymer matrix in an exponential decay manner, wherein the exponential decay constant is greater than about 0.01. The exponential decay is defined by Equation 2, where [C] is an atomic molar percentage. It is the exponential decay constant, and x is the distance into the substrate.

[0162] (Equation 2)

[0163] In some embodiments, the polymer-ceramic composite as described herein includes a polymer substrate and a ceramic, wherein the polymer substrate has an outer surface and an internal volume of the polymer matrix, a first portion of the ceramic is on the outer surface, and a second portion of the ceramic occupies at least a portion of the internal volume of the polymer matrix, wherein the second portion of the ceramic accounts for at least about 1% of the mass of the ceramic and / or the first portion of the ceramic accounts for less than about 99% of the mass of the ceramic.

[0164] In some embodiments, the polymer-ceramic composite as described herein includes a polymer substrate and a ceramic, wherein the polymer substrate has an outer surface and an internal volume of the polymer matrix, a first portion of the ceramic is on the outer surface, and wherein at least a portion of the polymer-ceramic composite has a wrinkle ratio greater than about 1.1, greater than about 1.2, greater than about 1.3, greater than about 1.5, greater than about 1.75, greater than about 2, greater than about 2.5, greater than about 3, greater than about 5, greater than about 10, greater than about 20, greater than about 50, or greater than about 100.

[0165] In some embodiments, the polymer-ceramic composite as described herein includes a polymer substrate and a ceramic, wherein the polymer substrate has an outer surface and an internal volume of the polymer matrix, a first portion of the ceramic is on the outer surface, and a second portion of the ceramic occupies at least a portion of the internal volume of the polymer matrix, wherein the second portion of the ceramic includes a metal, and wherein the atomic molar percentage of the metal in the internal volume of the polymer matrix is ​​greater than about 0.1%, greater than about 0.2%, greater than about 0.3%, greater than about 0.5%, greater than about 1%, or greater than about 5% from about 10 nm from the outer surface of the polymer substrate to the internal volume of the polymer matrix.

[0166] In some embodiments, the polymer-ceramic composite as described herein includes a polymer substrate and a ceramic, wherein the polymer substrate has an outer surface and an internal volume of the polymer matrix, a first portion of the ceramic is on the outer surface, and a second portion of the ceramic occupies at least a portion of the internal volume of the polymer matrix, wherein the second portion of the ceramic includes a metal, and wherein the atomic molar percentage of the metal includes discontinuity, wherein when measured from the outer surface to the internal volume of the polymer matrix, the atomic molar percentage of the outer surface of the polymer substrate changes significantly over a shorter relative length, as expected by two well-defined adjacent non-interacting materials.

[0167] In some embodiments, the polymer-ceramic composite as described herein includes a polymer substrate and a ceramic, wherein the polymer substrate has an outer surface and an internal volume of the polymer matrix, a first portion of the ceramic is on the outer surface, and a second portion of the ceramic occupies at least a portion of the internal volume of the polymer matrix, wherein the polymer matrix includes both convex Gaussian geometric features and concave Gaussian geometric features, wherein the ceramic includes a metal, and wherein the molar percentage of ceramic atoms of the metal in the convex feature is equal to or greater than the molar percentage of ceramic atoms of the metal in the concave feature. In some embodiments, both the convex and concave Gaussian geometric features are essentially hemispherical, parabolic, elliptical, logarithmic, linear, polynomial, or exponential.

[0168] In some embodiments, the polymer-ceramic composite as described herein includes a polymer substrate and a ceramic, wherein the polymer substrate has an outer surface and an internal volume of the polymer matrix, a first portion of the ceramic is on the outer surface, and a second portion of the ceramic occupies at least a portion of the internal volume of the polymer matrix, and wherein the ceramic includes a metal, and the diffusion length of the metal in the polymer matrix volume is greater than about 1 µm at temperatures up to about 160°C and for a time period of about 90 minutes, or wherein the ceramic includes a metal, and the diffusion coefficient of the metal in the internal volume of the polymer matrix is ​​less than about 10 under standard laboratory conditions. -8 m 2 / second, less than approximately 10 -9 m 2 / second, less than approximately 10 -10 m 2 / second or less than approximately 10 -12 m 2 / second. In some implementations, a polymer matrix swelling agent is used to increase mass transfer via diffusion.

[0169] In some embodiments, the polymer-ceramic composite as described herein includes a polymer substrate and a ceramic, wherein the polymer substrate has an outer surface and an internal volume of the polymer matrix, a first portion of the ceramic is on the outer surface, and a second portion of the ceramic occupies at least a portion of the internal volume of the polymer matrix, and wherein the mass of the ceramic accounts for less than about 10% of the mass of the polymer-ceramic composite.

[0170] In some embodiments, the polymer-ceramic composite as described herein includes a polymer substrate and a ceramic, wherein the polymer substrate has an outer surface and an internal volume of the polymer matrix, a first portion of the ceramic is on the outer surface, and a second portion of the ceramic occupies at least a portion of the internal volume of the polymer matrix, and wherein, for the nominal geometric surface area of ​​the polymer-ceramic composite, the ceramic includes less than about 2 g / m², less than about 5 g / m², less than about 10 g / m², less than about 20 g / m², less than about 50 g / m², or less than about 100 g / m².

[0171] In some embodiments, the polymer-ceramic composite as described herein includes a polymer substrate and a ceramic, wherein the polymer substrate has an outer surface and an internal volume of the polymer matrix, a first portion of the ceramic is on the outer surface, and a second portion of the ceramic occupies at least a portion of the internal volume of the polymer matrix, and wherein at least a portion of the outer surface of the polymer substrate does not include the first portion of the ceramic.

[0172] In some embodiments, the polymer-ceramic composite includes a polymer substrate, which is a polymer film having an adhesive layer; and a ceramic composite material, which is an interconnected nanostructured layer.

[0173] In some embodiments, the polymer-ceramic composite as described herein includes a polymer substrate and a ceramic, wherein the polymer substrate has an outer surface and an internal volume of the polymer matrix, a first portion of the ceramic is on the outer surface, and a second portion of the ceramic occupies at least a portion of the internal volume of the polymer matrix, and wherein the polymer-ceramic composite also contains functional molecules. In some embodiments, at least a portion of the functional molecules occupies the internal volume of the polymer matrix. In some embodiments, at least a portion of the functional molecules occupy the internal volume of the polymer matrix extending into the internal volume of the polymer matrix by more than about 10 nm. In some embodiments, the concentration of functional molecules decreases when measured from the outer surface of the polymer matrix to the internal volume of the polymer matrix. In some embodiments, at least a portion of the functional molecules occupy the internal volume of the polymer matrix, wherein the concentration of functional molecules decreases from the outer surface of the polymer substrate to the internal volume of the polymer matrix at a certain rate of decrease. In some embodiments, at least a portion of the functional molecules occupy the internal volume of the polymer matrix, wherein the distance the functional molecules travel into the internal volume of the polymer matrix of the polymer-ceramic composite is shorter compared to the same polymer substrate without ceramic. In some embodiments, at least a portion of the functional molecules occupy the internal volume of the polymer matrix, wherein the diffusion coefficient of the functional molecules in the internal volume of the polymer matrix is ​​less than about 5% compared to the same polymer substrate without ceramic.

[0174] In some embodiments, the polymer-ceramic composite as described herein also contains the functional molecules as described herein, and at least a portion of the composite has a seat-drop water contact angle greater than about 90°, greater than about 100°, greater than about 110°, greater than about 115°, greater than about 120°, greater than about 125°, greater than about 128°, greater than about 130°, greater than about 131°, greater than about 132°, greater than about 134°, greater than about 136°, greater than about 138°, greater than about 140°, greater than about 142°, greater than about 144°, greater than about 146°, greater than about 148°, greater than about 150°, greater than about 155°, greater than about 160°, greater than about 165°, greater than about 170°, greater than about 175°, greater than about 178°, or about 179°.

[0175] method

[0176] A method is provided for producing polymer-ceramic composite compositions as described herein.

[0177] In some embodiments, the polymer substrate material absorbs a metal salt or precursor, and the ceramic is formed in situ on the polymer substrate. In some embodiments, the ceramic precursor or salt is dissolved in a solvent or solvent mixture absorbed into the polymer substrate. In some embodiments, the metal salt or precursor includes metal nitrates, metal acetates, metal sulfates, metal chlorides, or mixtures thereof. In other embodiments, the metal salt or precursor includes phosphates, carbonates, oxalates, hydroxides, sulfates, or mixtures thereof. In some embodiments, the metal-containing salt or precursor comprises a component of the ceramic. In some embodiments, the metal salt or precursor includes organometallic 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 precursor includes an oxidizing agent, such as permanganate, persulfate, hydrogen peroxide, chlorate, perchlorate, or hypochlorite, which accelerates the formation of the ceramic on the polymer substrate. In other embodiments, the precursor includes an amine, amide, or ammonia, which accelerates the formation of the ceramic on the polymer substrate. In some embodiments, the precursor includes a catalyst that accelerates the deposition of ceramics on a substrate. In some embodiments, the precursor provides multiple benefits. In some embodiments, the ceramic precursor includes one or more of a metal salt, a ceramic component, a metal-organic complex, an oxidant, an amine, an amide, or ammonia.

[0178] Other non-limiting examples of materials that can be added to reactive solutions or rinsing fluids to provide process or operational benefits are penetrants and solvents, wetting agents, surfactants and dispersants, pH adjusters, scale inhibitors, colorants and defoamers.

[0179] In some embodiments, the metal salt or precursor is dissolved or dispersed in a solvent. In some embodiments, the polymer substrate is contacted with a solution comprising the metal salt or ceramic precursor and a solvent. In some embodiments, the solution is absorbed into the polymer substrate.

[0180] In some embodiments, a polymer substrate is contacted with or absorbed by multiple solutions (i.e., two or more solutions) containing different metal salts or precursor compositions. For example, the multiple solutions may contain the same or different solvents. In some embodiments, the multiple solutions react upon mixing to form a precipitate, such as a ceramic. In some embodiments, the reaction between the multiple solutions results in a double displacement reaction to form a product comprising at least one precipitate.

[0181] In some embodiments, the polymer substrate is contacted with or absorbed by a solution containing one or more metal salts and / or one or more ceramic precursors.

[0182] In some embodiments, multiple solutions are used, which, upon exposure to a pH change, will react under the new pH conditions to form a precipitate, such as a ceramic. In some embodiments, the reaction between the solutions results in a double displacement reaction. In some embodiments, the product includes at least one precipitate. In some embodiments, a single solution containing a metal salt and / or a ceramic precursor is used.

[0183] In some embodiments, a polymer substrate having an absorbent solution containing a metal salt or ceramic precursor and a solvent is heated. Heating may cause solvent evaporation and / or ceramic precipitation. In some embodiments, chemical reactions occur during heating, such as ceramic precipitation due to supersaturation, and / or the ceramic precipitate migrates to the outer surface of the polymer substrate. In some embodiments, at least a portion of the ceramic precipitate remains within the internal volume of the polymer matrix.

[0184] In some embodiments, the polymer substrate is immersed or submerged in a solution comprising a first salt, and then immersed or submerged in a solution comprising a second salt, wherein the solution is absorbed into the polymer or causes the polymer to swell. In some embodiments, the polymer comprises salt within the internal volume of the polymer substrate and / or on its outer surface. In some embodiments, the polymer substrate is then heated to evaporate the solvent, react the salt, or a combination thereof. In some embodiments, the solution migrates to the outer surface of the polymer substrate during heating. In some embodiments, ceramic is deposited within the internal volume of the polymer matrix, on the outer surface of the polymer substrate, or a combination thereof. In some embodiments, the ceramic protrudes outward from the outer surface of the polymer substrate.

[0185] In some embodiments, the polymer substrate is contacted with a solution comprising a first salt, and then with a solution comprising a second salt, wherein the polymer substrate absorbs at least a portion of one or both solutions, or swells upon contact with one or both solutions, and the solutions independently comprise water or water and one or more co-solvents, such as EGBE or DEGBE. In some embodiments, the polymer substrate is contacted with a combination of a first salt and a second salt, wherein the polymer substrate is first contacted with the first salt, and then with the second salt, the first salt comprising one or more first ionic compounds, non-limiting examples of which are calcium nitrate tetrahydrate or magnesium nitrate hexahydrate, and the second salt comprising one or more second ionic compounds, non-limiting examples of which are dipotassium hydrogen phosphate or sodium oxalate dihydrate. In some embodiments, contact includes immersing the polymer substrate in one or more solutions, submerging the polymer substrate in one or more solutions, spraying the polymer substrate with one or more solutions, or a combination thereof.

[0186] In some embodiments, the polymer substrate is pretreated before contact with a solution comprising one or more first ionic compounds. In some embodiments, the pretreatment includes one or more of the following: contacting the polymer substrate with a sodium hydroxide solution of 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 comprising water and a co-solvent; mechanically dehydrating the polymer substrate; drying the polymer substrate in an ambient atmosphere at a temperature of about ambient temperature (e.g., about 20°C) to about 140°C; and / or equilibrating the polymer substrate for environmental conditions.

[0187] In some embodiments, the polymer substrate is further treated after contact with a solution comprising one or more first ionic compounds and before contact with a solution comprising one or more second ionic compounds. In some embodiments, the temperature of the first or second solution is about 20°C, about 20°C to about 90°C, about 20°C to about 50°C, about 30°C to about 60°C, about 40°C to about 80°C, about 50°C to about 90°C, about 30°C, about 40°C, about 50°C, about 60°C, about 70°C, about 80°C, or about 90°C. In some embodiments, prior to the drying step, the first or second solution is contacted with the substrate for about 1 second, about 2 seconds, about 5 seconds, about 1 second to about 120 seconds, about 5 seconds to about 20 seconds, about 10 seconds to about 30 seconds, about 20 seconds to about 60 seconds, about 30 seconds to about 80 seconds, about 40 seconds to about 90 seconds, about 50 seconds to about 100 seconds, about 60 seconds to about 120 seconds, about 70 seconds to about 110 seconds, about 80 seconds to about 120 seconds, about 10 seconds, about 15 seconds, about 20 seconds, about 30 seconds, about 60 seconds, about 90 seconds, or about 120 seconds. In some embodiments, further processing includes mechanical dehydration of the polymer substrate and / or drying of the polymer substrate in an ambient atmosphere at a temperature from about ambient temperature (e.g., about 20°C) to about 140°C, or more of these processes.

[0188] In some embodiments, solutions comprising one or more first ionic compounds and solutions comprising one or more second ionic compounds independently comprise water or solvents comprising water and one or more co-solvents. In some embodiments where the solvent comprises water and one or more co-solvents, the ratio of water to the total amount of the one or more co-solvents is from about 1:99 (v / v) to about 999:1 (v / v). In some embodiments where the solvent comprises water and one or more co-solvents, the ratio of water to the total amount of the one or more co-solvents 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 about 0.25% (w / w) to about 50% EGBE in water (w / w). In some embodiments, the solvent is about 0.5% (w / w) to about 5% EGBE in water (w / w). In some embodiments, the solvent is about 1% (w / w) to about 2% EGBE in water (w / w). In some embodiments, the solvent is about 0.25% (w / w) to about 50% DEGBE in water (w / w). In some embodiments, the solvent is about 0.5% (w / w) to about 5% DEGBE in water (w / w). In some embodiments, the solvent is about 1% (w / w) to about 2% DEGBE in water (w / w).

[0189] In some embodiments, the polymer substrate is immersed or submerged in a solution comprising a metal-organic complex. In some embodiments, the polymer substrate comprises a metal-organic complex within the internal volume of the polymer matrix and / or on the outer surface of the polymer substrate. In some embodiments, the polymer substrate is then heated to evaporate the solvent, decompose the metal-organic complex, or react with the metal-organic complex, or a combination thereof. In some embodiments, heating decomposes the metal-organic complex into ceramic. In some embodiments, the solution migrates to the outer surface of the polymer substrate during heating. In some embodiments, ceramic is deposited within the internal volume of the polymer matrix, on the outer surface of the polymer substrate, or a combination thereof. In some embodiments, the ceramic protrudes outward from the outer surface of the polymer substrate.

[0190] In some embodiments, the polymer substrate is immersed or submerged in a solution comprising a metal-organic complex. In some embodiments, the polymer substrate comprises a metal-organic complex within the internal volume of the polymer matrix and / or on the outer surface of the polymer substrate. In some embodiments, the polymer substrate is then contacted with a pH-adjusting solution and / or a solution containing a catalyst to form a ceramic precipitate. In some embodiments, the solution migrates into the polymer substrate. In some embodiments, the ceramic precipitates within the internal volume of the polymer matrix, on the outer surface of the polymer substrate, or a combination thereof. In some embodiments, the ceramic protrudes outward from the outer surface of the polymer substrate.

[0191] In some embodiments, the polymer substrate is immersed or submerged in a solution containing a metal salt and an oxidizing agent. In some embodiments, the polymer substrate comprises a metal salt and / or an oxidizing agent within the internal volume of the polymer matrix and / or on the outer surface of the polymer substrate. In some embodiments, the polymer substrate is sequentially immersed in a solution containing a metal salt, and then immersed in a solution containing an oxidizing agent. In some embodiments, the polymer substrate is first immersed in a solution containing an oxidizing agent, and then immersed in a solution containing a metal salt. In some embodiments, the oxidizing agent oxidizes metal ions in the solution and forms a ceramic precipitate within the internal volume of the polymer matrix and / or on the outer surface of the polymer substrate. In some embodiments, the ceramic protrudes outward from the outer surface of the polymer substrate.

[0192] In some embodiments, the polymer substrate is contacted with a solution containing a metal salt and an oxidizing agent by spraying, flooding, dyeing, or gravure coating. In some embodiments, the polymer substrate includes the metal salt and / or oxidizing agent within the internal volume of the polymer matrix and / or on the outer surface of the polymer substrate. In some embodiments, the polymer substrate is sequentially contacted with a solution containing a metal salt by spraying, flooding, dyeing, or gravure coating, followed by contact with a solution containing an oxidizing agent. In some embodiments, the polymer substrate is first sprayed, flooded, dyed, or gravure coated into a solution containing an oxidizing agent, and then sprayed, flooded, dyed, or gravure coated into a solution containing a metal salt. In some embodiments, the oxidizing agent oxidizes metal ions in the solution and forms a ceramic precipitate within the internal volume of the polymer matrix and / or on the outer surface of the polymer substrate. In some embodiments, the ceramic precipitate protrudes outward from the outer surface of the polymer substrate.

[0193] In some embodiments, the polymer-ceramic composite is functionalized via spraying, impregnation, immersion, vapor deposition, spin coating, gravure coating, doctor blade coating, or roll coating. In some embodiments, the functionalizing molecule used in the functionalization step is one or more of silanes, siloxanes, urethanes, acrylates, or molecules having head and tail groups. For example, the head group includes silyl, phosphonate, phosphonic acid, carboxylic acid, vinyl, alcohol, hydroxyl, thiol ester, thiol, and / or ammonium (e.g., quaternary ammonium) groups, and the tail group includes hydrocarbon, fluorocarbon, vinyl, phenyl, epoxy, acrylic (acrylic group), acrylate, hydroxyl, carboxylic acid, thiol, and / or quaternary ammonium. 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 hexane or heptane; or an aromatic hydrocarbon such as (but not limited to) xylene or toluene. In some implementations, the functionalized polymer ceramic is cured at elevated temperatures to stabilize the functional molecules.

[0194] In some embodiments, the polymer-ceramic composite includes a polymer substrate, which is a polymer film having an adhesive layer; and a ceramic composite material, which is an interconnected nanostructured layer transferred to the adhesive layer by direct or contact transfer. In some embodiments, direct or contact transfer is achieved by cold or hot pressing, rolling, peeling, or lamination. In some embodiments, the adhesive layer is used to facilitate transfer. In some embodiments, the interconnected nanostructured layer is transferred directly to the substrate. In some embodiments, the interconnected nanostructured layer is removed from the substrate and transferred using a liquid carrier.

[0195] Example

[0196] The following examples are intended to illustrate but not limit the invention.

[0197] Example 1

[0198] Lightweight (approximately 2 oz / yd), 50D (denier) rip-stop nylon was used as the polymer substrate for the deposited ceramics. The polymer substrate material was cleaned by immersion in a solution for approximately 10 minutes, followed by scouring with 2% NaOH, rinsing with water, mechanical dehydration, air drying at approximately 105°C, and conditioning to laboratory conditions.

[0199] The cleaned substrates were then treated by batch solution contact at approximately 20°C, alternating between immersion in a 25 mM solution of a calcium source (i.e., calcium nitrate tetrahydrate) and a similar concentration of a phosphate source (i.e., diammonium hydrogen phosphate dibasic) for approximately 30 seconds per stage. Continuous solution contact through immersion was used to process the samples to produce a more uniform deposition structure and particle size. The samples were dehydrated using mechanical rollers to increase uniformity and reduce particle formation in the immersion bath. After solution contact via immersion cycles, the samples were air-dried at room temperature until dry, and then annealed at approximately 140°C for approximately 10 minutes. The result was the deposition of structured ceramics on a nylon substrate. The deposition structure was imaged to evaluate uniformity and characterize the material.

[0200] The results are shown in Figures 1a and 1b. Representative fiber cross-sections were captured and imaged using scanning electron microscopy (SEM), and elemental concentrations were measured along the fiber radius using energy-dispersive X-ray spectroscopy (EDS). The roundness of the fiber in Figure 1a was estimated to be approximately 0.95 based on SEM analysis. Line scans were performed starting from the fiber exterior and moving towards the fiber center. Calcium and phosphate concentrations were highest outside the fiber exterior and decreased to their lowest values ​​at approximately 1.5 µm from the outer surface of the fiber. EDS line scans showed a calcium concentration ([Ca]) of approximately 2.5 wt% on the outer surface of the polymer substrate, approximately 1 wt% at a depth of approximately 0.7 µm (below the outer surface of the polymer substrate), and approximately 0.1 wt% at a depth of 1.5 µm. The diffusion profile was reasonably modeled using an error function for a fixed surface concentration and a semi-infinite solid approximation. Approximately 80% of the ceramic protrudes outward from the polymer layer, and approximately 20% of the ceramic partially occupies the internal volume of the polymer matrix. Excessive solution contact due to immersion time or concentration results in excess material, which leads to an uneven appearance that can be described by the naked eye as spots, streaks, color changes or other defects on the fabric surface.

[0201] The treated deposit structure was further functionalized to impart hydrophobicity by immersing it in an ethanol solution containing about 20 mM hexadecyltriethoxysilane (HDTES), about 3 wt% water and a catalytic amount of acetic acid for about 10 minutes for batch solution contact, and then annealed at a temperature of about 140°C for about 10 minutes.

[0202] The spray rating of the sample was tested and evaluated according to AATCC 22 standard, and it was observed to have a spray rating greater than 90. Contact angle measurements indicated that the contact angle increased with repeated cycles, as shown in Figure 2a. Wash resistance was measured by washing the material for three wash / dry cycles in a household washing machine. The sample was retested and rated according to AATCC 22 standard, and a spray rating greater than 80 was observed under most conditions, as shown in Figure 2b. Air permeability was measured according to ASTM D737 after treatment, and it remained within 25% of the condition of the untreated fabric after treatment and washing.

[0203] SEM analysis before and after washing showed good adhesion between the ceramic and polymer substrates, as no loosely adhered material or areas that appeared to have been previously present were observed.

[0204] Example 2

[0205] By impregnating the material with batch solution contact using several formulations as outlined in Table 1 below, the material processed according to the steps outlined in Example 1 to form a treated deposit structure is further functionalized to impart hydrophobicity.

[0206] The spray rating of the sample was tested and evaluated according to AATCC 22 standard, and water resistance with a spray rating greater than 90 was observed. Contact angle measurements indicated that the contact angle increased with repeated solution contact via immersion cycles. Wash resistance was measured by washing the material in a household washing machine for three wash / dry cycles. The sample was retested and rated according to AATCC 22 standard, and a spray rating greater than 70 was observed. Air permeability was measured after treatment, and it remained within 30% of the condition of the untreated fabric after treatment and washing. These results demonstrate both the improved contact angle of the treated deposit structure and the compatibility of the treated deposit structure with certain functional formulations.

[0207] SEM analysis of the samples before and after washing showed good adhesion between the ceramic and the polymer substrate, as no loosely adhered material or areas that appeared to have been previously present were observed.

[0208] Table 1

[0209]

[0210] Example 3

[0211] Lightweight (approximately 2 oz / yd), 50D (denier) tear-resistant nylon was used as the substrate for the deposited ceramics. The polymer substrate material was cleaned by immersion in a solution for approximately 10 minutes followed by rinsing with 2% NaOH, rinsing with water, mechanically dehydrating, air-drying at approximately 105°C, and adjusting to laboratory conditions.

[0212] The cleaned substrates were then treated with batch solution contact, alternating between immersion in approximately 25 mM solutions of calcium source (calcium nitrate tetrahydrate) and oxalate source (sodium oxalate dihydrate) for approximately 30 seconds each, at similar concentrations and temperatures of approximately 20°C. Continuous cyclic processing of the samples was performed to produce a more uniform deposition structure and microparticles. The samples were dehydrated using mechanical rollers to increase uniformity and reduce microparticle formation in the immersion bath. After immersion cycles, the samples were air-dried at room temperature until dry, and then annealed at approximately 140°C for approximately 20 minutes. The result was the deposition of structured ceramics on a nylon substrate. The deposition structure was imaged to evaluate uniformity and characterize the material.

[0213] The treated deposit structure is further functionalized to impart hydrophobicity by batch impregnation in a mixture of commercially available PFC-free products. In one case, the top coating mixture contains a nonionic polymer and a surfactant compound, a glycol-based solvent, water, a weakly cationic water repellent containing organosilicon, and a blocked isocyanate crosslinking compound. The treated deposit structure is impregnated in a gently agitated solution at laboratory temperature (approximately 20°C) for less than 5 minutes, and then annealed in two stages: less than 2 minutes at approximately 130°C and less than 2 minutes at approximately 170°C. In a top coating mixture comprising a high-solids silicone emulsion concentrate diluted with water and a blocked isocyanate crosslinking compound, the treated deposit structure is immersed in a slightly agitated solution for less than 5 minutes at laboratory temperature (approximately 20°C), mechanically squeezed by nip rolling to remove excess liquid, and then annealed in two stages at approximately 160°C for less than 5 minutes.

[0214] In both scenarios, the spray rating of the samples was tested and evaluated according to AATCC 22 standard, and it was observed that they exhibited water resistance with a spray rating greater than 90. Contact angle measurements indicated that the contact angle increased with repeated cycles and increasing concentration.

[0215] Excessive contact with the first and second solutions due to immersion time exceeding 5 minutes or concentrations of approximately 250 mM or higher will result in an excess of material, which will cause visual non-uniformity to become apparent when observed with the naked eye.

[0216] A cleaned substrate is produced by alternating solution contact at a temperature of about 20°C in a first solution of about 25 mM calcium source (calcium nitrate tetrahydrate) and a second solution of phosphate source and oxalate source (sodium oxalate dihydrate) for about 30 seconds per stage. This produces a ceramic structure similar to that produced by alternating calcium and oxalate sources or calcium and phosphate sources alone.

[0217] Example 4

[0218] Lightweight (approximately 2 oz / yd), 50D (denier) tear-resistant nylon was used as the substrate for the deposited ceramics. The polymer substrate material was cleaned by immersion in a solution for approximately 15 minutes, followed by rinsing with 2% NaOH, rinsing with water, mechanically dehydrating, air-drying at approximately 105°C, and conditioning to laboratory conditions.

[0219] The cleaned substrates are then treated by batch immersion in at least one first solution, including a metal salt, a metal-organic complex, or other reactive precursor, wherein the solution is absorbed into the polymer. The polymer substrates are then heated to a temperature sufficient to remove the solvent from the polymer and sufficient to drive a ceramic formation reaction with the metal salt, or sufficient to decompose or react the metal-organic complex, to form an insoluble ceramic.

[0220] In this manufacturing method, the metal salt includes transition metal nitrates, transition metal chlorides, transition metal sulfates, transition metal acetates, alkaline earth metal nitrates, alkaline earth metal chlorides, alkaline earth metal sulfates, alkaline earth metal acetates, or combinations thereof, or the metal-organic complex includes metal-amine complexes, wherein the amine includes free amines.

[0221] In this manufacturing method, absorption diffusion includes solution contact by immersion in a solution containing a soluble precursor at a temperature of about 20°C to about 160°C for about 10 seconds to about 72 hours, with solvent removal and reaction temperature ranging from about 30°C to about 200°C for about 10 seconds to about 10 minutes. The absorption step is performed in both batch and continuous processes. The sample is treated in continuous solution contact via immersion cycles to produce a more uniformly deposited structure and particles. The sample is dehydrated using mechanical rollers to increase uniformity and reduce particle formation in the immersion bath. The result is the deposition of structured ceramics on a nylon polymer substrate. The deposit structure is imaged to evaluate uniformity and characterize the material. The ceramic is formed under these conditions. Excessive solution contact due to immersion time or concentration results in excess material, leading to an uneven appearance when observed with the naked eye.

[0222] The samples were batch-impregnated with an ethanol solution containing approximately 20 mM hexadecyltriethoxysilane (HDTES), approximately 3 wt% water, and a catalytic amount of acetic acid for approximately 10 minutes, or with an organosilicon-containing solution containing approximately 2 wt% to 6 wt% for approximately 2 minutes. The treated deposit structure was optionally further functionalized to impart hydrophobicity. The samples were annealed at approximately 120°C to approximately 180°C for approximately 0.5 minutes to approximately 15 minutes. The spray rating of the samples was tested and evaluated according to AATCC 22 standards, and water resistance with a spray rating greater than 90 was observed. Contact angle measurements indicated that the contact angle increased with increasing concentration of the ceramic forming reactant.

[0223] SEM analysis before and after washing showed good adhesion between the ceramic and polymer substrates, as no loosely adhered material or areas that appeared to have been previously present were observed.

[0224] Example 5

[0225] Lightweight (approximately 1.5 oz / yd), 20D (denier) tear-resistant PET polyester was used as the substrate for the deposited ceramics. The substrate material was cleaned by immersion in a solution for approximately 1 minute followed by rinsing with 2% NaOH, rinsing with water, mechanically dehydrating, air-drying at approximately 105°C, and adjusting to laboratory conditions.

[0226] The cleaned substrates were then treated with batch solution contact by alternating immersion in a first solution of 25 mM to 500 mM calcium source and a second solution of 15 mM to 500 mM phosphate source. The temperature of the first and second solutions was approximately 20 °C, and the cycle time was as low as approximately 10 seconds. Samples were treated in continuous immersion cycles to produce a more uniform deposited structure and microparticles. The samples were dehydrated using mechanical rollers to increase uniformity and reduce microparticle formation in the immersion bath. After solution contact via immersion cycles, the samples were air-dried at room temperature until dry, and then annealed at a temperature of approximately 80 °C to approximately 160 °C for several minutes. The result was the deposition of structured ceramics on a nylon substrate, as measured by XRF. The deposit structure was imaged to evaluate uniformity and characterize the material. Lower concentrations of contact solution produced discrete microparticles. Higher concentrations produced agglomerated structures. Solution concentrations greater than 500 mM or excessive cycling produced excess material, resulting in an uneven appearance when observed with the naked eye. SEM studies estimated the fiber roundness to be greater than approximately 0.7.

[0227] The samples were batch-impregnated to further functionalize the deposit structure to impart hydrophobicity by immersion in an ethanol solution containing approximately 20 mM hexadecyltriethoxysilane (HDTES), approximately 3 wt% water, and a catalytic amount of acetic acid for approximately 10 minutes, or in an organosilicon-containing solution with a concentration of approximately 2 wt% to approximately 6 wt% for approximately 2 minutes. The samples were then annealed at approximately 120°C to approximately 180°C for several minutes. The spray rating of the samples was tested and evaluated according to AATCC 22 standards, and a spray rating greater than 90 was observed. Contact angle measurements indicated that the contact angle increased with increasing concentration of the ceramic reactant or through repeated contact via immersion cycles. Washability was measured by washing the material in a household washing machine for three wash / dry cycles. The samples were retested and rated according to AATCC 22 standards, and a spray rating greater than 80 was observed. Samples with an uneven appearance performed worse than more uniform samples. The air permeability was measured after treatment, and it remained within 25% of the condition of the untreated fabric after treatment and washing.

[0228] Example 6

[0229] The alternative polymer substrate, or a blend of nylon or polyester, is treated according to the steps outlined in Example 1, with a density up to 5 oz / yd and 300D (denier) and a polyester or nylon blend (including up to 100% recycled polymer content). One such fabric is a plain weave fabric of 95% recycled nylon and 5% spandex with a density of 150D (denier). This polymer substrate has a density of approximately 150 g / m². 2 It has a density of approximately 3 cfm and a breathability of approximately 3 cfm.

[0230] The treated polymer substrate was then further functionalized to impart hydrophobicity through batch contact impregnation with several topcoat formulations. The spray rating of the samples was tested and evaluated according to AATCC 22 standards, and water resistance with a spray rating greater than 90 was observed. Contact angle measurements indicated an increase in contact angle compared to the bare polymer substrate.

[0231] Example 7

[0232] Use approximately 64g / m 2Lightweight nylon tear-resistant fabric was used as the polymer substrate for deposited ceramics. The study included solutions of several metal precursors, including Ni, Zn, Cu, and Mn. Approximately 40 mL of approximately 1 M X(II)SO4 and approximately 30 mL of approximately 0.25 M potassium persulfate (KPS) were mixed in a container, where X is Ni, Zn, Cu, or Mn. Approximately 10 mL of ammonia was slowly added as approximately 28% NH3. The mixture was stirred for approximately 30 seconds and diluted with deionized water to approximately 100 mL. Within approximately 10 minutes of adding the ammonia solution, the polymer substrate sample was rapidly added to the mixture. The polymer substrate was immersed in the solution for approximately 30 minutes, approximately 60 minutes, approximately 90 minutes, and approximately 18 hours, and the resulting coated substrates were imaged.

[0233] Copper solutions are unstable and do not produce consistent observations. Structures observed on Ni, Zn, and Mn substrate fibers exhibit a series of interconnected plates and pores of coated fibers, with lateral dimensions less than about 1 µm and thicknesses less than about 0.2 µm. Solution contacts with longer immersion times produce larger and more porous structures compared to shorter immersion times, resulting in denser film structures. Excessive solution contact due to immersion time or concentration produces excess material, leading to an uneven appearance when observed with the naked eye.

[0234] The treated substrate was observed to wet much faster than the untreated nylon fabric. The ceramic structure of Ni on the nylon substrate was very uniform around the fibers and was not easily removed by friction.

[0235] The treated substrate sample was further treated with an ethanol mixture containing silane and annealed in a manner similar to that described in Example 1 above. Ni treatment was unsuccessful and did not reduce the hydrophilicity of the treated nylon. The functionalization of the structure treated with Zn and Mn increased the contact angle of the coated substrate compared to a similarly functionalized standard substrate.

[0236] Example 8

[0237] Lightweight (approximately 2 oz / yd), 50D (denier) tear-resistant nylon and lightweight (approximately 1.5 oz / yd), 20D (denier) tear-resistant polyethylene terephthalate (PET) polyester are used as polymer substrates for deposited ceramics.

[0238] A first solution containing manganese sulfate at concentrations of approximately 400 mM, 100 mM, 25 mM, 5 mM, and 1 mM, and up to approximately 2 wt% ethylene glycol butyl ether or diethylene glycol monobutyl ether (DEGBE) was prepared in a reaction vessel. The polymer substrate was added to a 50 ml polypropylene tube containing this solution and allowed to equilibrate on an orbital oscillator at 25°C for approximately 72 hours. The sample was then removed and dried in an oven at approximately 105°C for approximately 10 minutes.

[0239] A second reaction solution containing approximately 75 mM potassium persulfate and approximately 1.5 M ammonia was prepared and maintained at approximately 25 °C. The sample exposed to the first solution was then added to these second reaction solutions and maintained for approximately 90 minutes. The sample was then removed and thoroughly rinsed with DI water to remove any loosely adhering material. After rinsing, the sample was dried in an oven at approximately 140 °C for approximately 10 minutes. The prepared sample was imaged using a scanning electron microscope to examine the resulting ceramic structure formed on the polymer substrate. The resulting structures were similar, comprising a series of interconnected plates and pores coated on the polymer substrate fibers, with lateral dimensions less than 1 µm and thicknesses less than approximately 0.2 µm. The wall thickness of the nanostructured plates was approximately 20 nm. An excess concentration of 100 mM or higher in the first solution resulted in excess material, leading to an uneven appearance when observed with the naked eye.

[0240] The treated substrate was then further treated with an ethanol mixture containing silane and annealed in an oven in a manner similar to that described in Example 1. The functionalization resulted in a higher water contact angle for the coated substrate compared to a standard nylon substrate with similar functionalization.

[0241] Example 9

[0242] Lightweight (approximately 2 oz / yd), 50D (denier) tear-resistant nylon and lightweight (approximately 1.5 oz / yd), 20D (denier) tear-resistant PET polyester are used as the substrates for deposited ceramics.

[0243] Cut the fabric sample into strips and place them in a 2wt% NaOH aqueous solution bath for about 2 minutes, then rinse thoroughly to clean the fabric surface. Next, immerse the sample in an aqueous solution bath maintained at about 70°C for about 60 minutes, containing about 25 mM, about 50 mM, or about 100 mM KMnO4, each containing 200 mM NH3. Rinse the sample and dry it at about 105°C for about 60 minutes. Then immerse it in a second bath containing an equimolar concentration of Mn(NO3)2 and hexamethylenetetramine at concentrations of about 25 mM, about 50 mM, about 75 mM, or about 100 mM. Immerse the sample at about 80°C for about 60 minutes, rinse thoroughly, and dry it at about 105°C for about 60 minutes.

[0244] The surface microstructure was analyzed by SEM, revealing a dense nanostructure shell containing manganese oxide and manganese hydroxide outside the textile fibers. Excessive solution contact caused by immersion time or a concentration of approximately 50 mM Mn(NO3)2 resulted in excess material, leading to an uneven appearance when observed with the naked eye.

[0245] Example 10

[0246] Lightweight (approximately 2 oz / yd), 50D (denier) tear-resistant nylon and lightweight (approximately 1.5 oz / yd), 20D (denier) tear-resistant PET polyester are used as the substrates for deposited ceramics.

[0247] Fabric samples were cut into strips and placed in a 2 wt% NaOH aqueous solution bath for approximately 2 minutes, followed by thorough rinsing to clean the fabric surface. The cleaned fabric strips were then immersed in an aqueous solution bath maintained at approximately 20°C for approximately 30 seconds, containing 50 mM each of manganese nitrate and hexamethylenetetramine. The fabric samples were then transferred to an approximately 100 mM NaOH aqueous solution with a pH greater than approximately 12 and immersed for 30 seconds. A brown precipitate was observed immediately upon introduction of the fabric into the NaOH bath, indicating a surface reaction. The samples were then removed from the solution and dried at approximately 140°C for approximately 10 minutes before imaging via SEM.

[0248] When imaged using SEM, dense nanostructured shells of manganese hydroxide were observed on the surfaces of nylon and polyester fabrics. Energy-dispersive X-ray spectroscopy (EDS) confirmed the composition of the coating, revealing a mixture of manganese and oxygen on top of the predominantly carbon-containing polymer surface. Excessive solution contact due to immersion time or concentration resulted in excess material, leading to an uneven appearance when observed with the naked eye.

[0249] The structure is then functionalized with a hydrophobic treatment similar to that described in Example 1, which results in an increased contact angle compared to the untreated fabric.

[0250] Example 11

[0251] Lightweight (approximately 2 oz / yd), 50D (denier) tear-resistant nylon and lightweight (approximately 1.5 oz / yd), 20D (denier) tear-resistant PET polyester are used as the substrates for deposited ceramics.

[0252] Fabric samples were cut into strips and placed in a 2 wt% NaOH aqueous solution bath for 2 minutes, followed by thorough rinsing to clean the fabric surface. The cleaned fabric strips were then immersed in an aqueous solution bath containing approximately 50 mM manganese nitrate, maintained at approximately 20°C, for about 30 seconds. The fabric samples were then transferred to a 100 mM NaOH aqueous solution with a pH greater than 12 and immersed for 30 seconds. A light brown precipitate was observed immediately upon introduction of the fabric into the NaOH bath, indicating a surface reaction. The samples were then removed from the solution and dried at approximately 140°C for 10 minutes before being imaged via SEM.

[0253] Fine agglomerations of manganese hydroxide nanoparticles were observed on the surfaces of nylon and polyester fabrics during SEM imaging. Energy dispersive X-ray spectroscopy (EDS) confirmed the composition of the coating, revealing a mixture of manganese and oxygen on top of the predominantly carbon-containing polymer surface. Excessive solution contact due to immersion time or concentration resulted in excess material, leading to an uneven appearance when observed with the naked eye.

[0254] The structure is then functionalized with a hydrophobic treatment similar to that described in Example 1, which results in an increased contact angle compared to the untreated fabric.

[0255] Example 12

[0256] Lightweight (approximately 2 oz / yd), 50D (denier) crack-resistant nylon was used as the polymer substrate for the deposited ceramics. The sample was immersed in the first solution, removed, and dried at approximately 140°C for 10 minutes. It was then immersed in the second solution, removed, rinsed twice in DI water, and dried at approximately 140°C for approximately 10 minutes.

[0257] The first solution contains approximately 1 mM, 5 mM, 25 mM, 100 mM, 400 mM, or 1000 mM of Mn(SO4) and approximately 170 mM of ethylene glycol butyl ether (EGBE). The sample is immersed in the first solution at approximately 60°C for approximately 2 hours, approximately 60°C for approximately 18 hours, or approximately 40°C for approximately 72 hours. Each solution contact is performed by immersion in 50 mL vials on a shaker set to 75 rpm. The sample is then removed and dried at approximately 140°C for approximately 10 minutes.

[0258] Each sample was then contacted with the second solution at approximately 25°C for approximately 1.5 hours. The second solution contained approximately 75 mM K₂S₂O₈ and approximately 1453 mM NH₃. The samples were then removed, rinsed twice with deionized (DI) (Class II) water, and dried at approximately 140°C for approximately 10 minutes.

[0259] The sample was then contacted by impregnation with a silane-containing solution similar to that described in Example 1, and cured in an oven to evaluate the effect on the contact angle of the seat drop method.

[0260] SEM imaging of the samples revealed minimal differences between the initial solution contacts under immersion solution exposure conditions. Samples with an initial solution concentration greater than approximately 400 mM exhibited a continuously interconnected plate-like nanostructured layer and some larger discrete particles; some breaks in the continuous structure were observed. The thickness of the nanostructured layer was less than approximately 0.2 µm. The remaining samples showed discrete structures with dimensions less than 1 µm.

[0261] The prepared substrate was then functionalized using a hydrophobic treatment, which resulted in an increased contact angle compared to an unprepared substrate treated with the same method. Samples with a first solution concentration greater than about 25 mM produced a seated drop contact angle ranging from about 140° to about 165°. Samples with a first solution concentration less than about 25 mM produced a seated drop contact angle less than about 130°.

[0262] Example 13

[0263] A lightweight (approximately 2 oz / yd), 50D (denier) tear-resistant nylon substrate was impregnated in a weakly acidic solution containing approximately 5 mM to approximately 200 mM of calcium. The exposure time and conditions ranged from approximately 20°C to approximately 140°C for approximately 30 seconds to approximately 24 hours. Temperatures above approximately 100°C were assessed by heating the solution in an autoclave reactor.

[0264] The samples were fixed and polished with epoxy resin and then subjected to cross-sectional SEM-EDS to quantify composition and gradient. When exposed to a 25 mM Ca solution at approximately 25°C for approximately 24 hours, no significant Ca composition was observed in the fiber cross-section. When exposed to a 25 mM Ca solution at approximately 130°C for 3 hours, the samples showed a detectable Ca composition of approximately 0.02 at% in a large number of fibers.

[0265] These results indicate a concentration ratio (defined as the concentration at a certain depth in the polymer substrate divided by the concentration at the surface of the polymer substrate) of approximately 1, assuming a diffusion coefficient of approximately 1e at 25°C. -11 m 2 / second. After approximately 1 hour, 5 minutes, or 30 seconds of exposure, the concentration at a depth of approximately 20 µm was approximately 95%, 80%, and 40% of the expected levels, respectively.

[0266] Example 14

[0267] A lightweight (approximately 2 oz / yd), 50D (denier) tear-resistant nylon substrate is immersed in weakly acidic calcium solutions of concentrations of approximately 25 mM, 100 mM, 250 mM, and 500 mM for approximately 30 seconds. Upon removal, the immersed substrate is dehydrated using mechanical rollers. The substrate is then immersed in a second solution containing phosphate concentrations of approximately 15 mM, 60 mM, 150 mM, or 300 mM for approximately 30 seconds. Upon removal, the immersed substrate is dehydrated using mechanical rollers. The substrate is then subjected to a heat drying step at up to approximately 140°C for approximately 10 minutes. Excessive solution contact due to immersion time or concentration results in excess material, leading to an uneven appearance when observed with the naked eye.

[0268] The treated substrate was further functionalized to impart hydrophobicity by batch solution contact in a mixture comprising solutions containing silanes and siloxanes, and cured in a manner similar to that described in Example 1. The seat-drop contact angle of water on the treated and functionalized substrates was investigated and compared with that of functionalized substrates untreated with the first and second solutions. The substrates functionalized with the first and second solutions, as well as the functionalized substrate alone, were then washed in a typical household washing machine to evaluate the stability and durability of the hydrophobicity. The functionalized substrate initially had a contact angle of approximately 130°, which decreased by approximately 5° during washing. The functionalized substrates treated with the first and second solutions had contact angles greater than approximately 132° to greater than approximately 140°, depending on the concentration. The decrease in contact angle indicates wash resistance and ranges from a decrease of less than approximately 1% to a decrease of more than approximately 10%, depending on the concentration, as shown in Table 2. At medium concentrations within the tested range, a decrease in contact angle of less than approximately 5% indicates an optimal treatment range.

[0269] Table 2

[0270]

[0271] Example 15

[0272] A sample of lightweight (approximately 2 oz / yd), 50D (denier) crack-resistant nylon was used as the substrate for the deposited ceramic.

[0273] The sample was placed in a reaction vessel in an orbital oscillator operating at approximately 75 rpm, with a temperature setpoint of approximately 40°C, for a period of approximately 72 hours. A first solution was prepared in the reaction vessel containing approximately 1 mM, approximately 5 mM, approximately 25 mM, approximately 100 mM, and approximately 0.4 M manganese sulfate and approximately 2 wt% ethylene glycol butyl ether. After the diffusion period, the sample was removed and dried at a temperature up to approximately 105°C for approximately 10 minutes. The sample was then placed in a second solution containing approximately 75 mM potassium persulfate and approximately 1.5 M ammonia and immersed for approximately 90 minutes or approximately 18 hours. After this testing period, the sample was thoroughly rinsed in deionized water and removed to dry at a temperature up to approximately 140°C for approximately 10 minutes.

[0274] At the 90-minute time point of solution contact via immersion, a continuous structure was observed on the substrate when the initial solution contained metal sulfates at a concentration greater than approximately 25 mM, and a discontinuous structure was observed when the initial solution contained metal sulfates at a concentration greater than approximately 5 mM. No significant differences were observed between samples immersed for approximately 90 minutes or approximately 18 hours. Inductively coupled plasma-optical emission spectrometry (ICP-OES) measurements of the samples indicated a linear relationship between the initial solution concentration and the measured metal content of the sample.

[0275] Example 16

[0276] Alternative polymer substrates (including polyethylene terephthalate (PET), polyamide or nylon, polyvinyl chloride (PVC), polyolefins (such as polyethylene or polypropylene), polyurethane, polyols, polyvinyl alcohol (PVOH), polyethylene glycol (PEG), vinyl acetate, polyvinylpyrrolidone, mixtures thereof, or copolymers thereof) are treated according to the steps outlined in Example 1 or Example 9 to form a treated deposit structure, and further functionalized to impart hydrophobicity by batch solution contact with several top coat formulations.

[0277] In one case, a density of approximately 230 g / m³ was used. 2 Polyvinyl alcohol synthetic canvas material is used as the polymer base material. A water-washing-based treatment is used, which includes immersion in water at a temperature of approximately 25°C for approximately 5 minutes, followed by water removal via pinch rollers. This process removes material that negatively impacts water repellency by approximately 10-25 points in AATCC 22 testing.

[0278] Wax coating patterns on the same polymer substrate were measured, exhibiting an AATCC spray rating of 95, a permeability of 0 cfm, a seat-drop contact angle of approximately 130°, and a surface energy rating of 6.5 (according to AATCC 193).

[0279] Following the pretreatment process, the polymer substrate was treated according to the conditions of Example 1, resulting in an AATCC spray rating of 80, an air permeability of 4.2 cfm, a seat-drop contact angle of approximately 141°, and a surface energy rating of 7 (according to AATCC 193).

[0280] Following the pretreatment process, the polymer substrate was treated according to the conditions of Example 9, resulting in an AATCC spray rating of 95, an air permeability of approximately 4.5 cfm to approximately 6 cfm, a seat-drop contact angle of approximately 151°, and a surface energy rating of 7 (according to AATCC 193). The fabric density was reduced to approximately 200 g / m². 2 .

[0281] Example 17

[0282] The alternative polymer substrate (including hydrocolloids or locust bean gum, starch, carrageenan, pectin, chitosan, xanthan gum, cellulose, or carboxymethyl cellulose) is treated according to the steps outlined in Example 1 to form a treated deposit structure, and further functionalized to impart hydrophobicity by batch solution contact with several topcoat formulations.

[0283] Two different samples were processed on a polymer matrix substrate containing cellulose, and the deposition of ceramics was evaluated. An initial weight of approximately 85 g / m³ was used. 2 and approximately 125g / m 2 8” An 8” kraft paper sample was used as the substrate.

[0284] These substrates were treated by batch solution contact at a temperature of approximately 20°C, alternating between immersion in a 25 mM solution of a calcium source (i.e., calcium nitrate tetrahydrate) and a similar concentration of a phosphate source (i.e., diammonium hydrogen phosphate) for approximately 30 seconds per stage. Continuous solution contact through immersion was used to treat the samples to produce a more uniformly deposited structure and microparticles. After solution contact via immersion cycles, the samples were air-dried at room temperature until dry, and then annealed at approximately 140°C for approximately 10 minutes. The substrates were then immersed in an alkylsilane solution containing approximately 1% silane for approximately 10 minutes, and then annealed at approximately 140°C for approximately 10 minutes. The result was the deposition of structured ceramics on a cellulose substrate.

[0285] Structured deposits of calcium phosphate were observed on the surface of the cellulose matrix during SEM imaging. The composition of the coating was confirmed by dispersive X-ray spectroscopy (EDS), revealing a mixture of calcium, phosphorus, and oxygen on top of the predominantly carbon-containing polymer surface. Moisture vapor transmission (MVTR) of the substrate was analyzed using the desiccant method as described in ASTM-E96. No significant change in MVTR was observed in the substrate compared to the untreated substrate. The water contact angle of the substrate was then analyzed using the seat drop method after laboratory conditioning and tape adhesion. A value of 125 g / m² was found. 2 The substrate has a water contact angle of approximately 145° and is unaffected by tape adhesion and removal. 85 g / m³ was found. 2 The substrate has a water contact angle of approximately 150° and is unaffected by tape adhesion and removal. The surface energy of the substrate was then analyzed using AATCC TM-193, revealing a value of 125 g / m². 2 The substrate has a surface energy level of approximately 5 and was found to have 85 g / m². 2 The substrate has a surface energy level of approximately 4.

[0286] Example 18 (Prophetic)

[0287] The alternative polymer substrate (including wool, cotton, hemp, animal hair, collagen, keratin, silk, chitin, flax, jute, hydroxyapatite, enamel, or mixtures thereof) is treated according to the steps outlined in Example 1 to form a treated deposit structure, and further functionalized to impart hydrophobicity by batch solution contact with several topcoat formulations.

[0288] Example 19 (Predictive)

[0289] Lightweight (approximately 2 oz / yd), 50D (denier) polyester fabrics (such as PET polyester), or medium-weight nylon fabrics (such as 75-200D nylon 6,6), or heavier copolymer fabrics (such as cotton-polyester (approximately 200-400D)), or stretch fabrics (such as nylon-elastomeric fibers) are used as the polymer substrate for deposited ceramics. The polymer substrate is optionally cleaned by immersion in a 1% NaOH solution for approximately 15 minutes followed by a 1% NaOH rinsing process, rinsed with water, optionally mechanically dehydrated, air-dried at approximately 105°C, and adjusted to laboratory conditions.

[0290] The substrate is then treated by alternating immersion in a first contact solution and a second contact solution in batches. The first solution contains about 25 mM to about 500 mM of a calcium source, such as calcium nitrate tetrahydrate, calcium nitrate hydrate, or calcium chloride, and the second solution contains about 15 mM to about 300 mM of a phosphate source, such as diammonium phosphate, ammonium dihydrogen phosphate, potassium phosphate (mono-, dibasic), or sodium phosphate (mono-, dibasic), at a temperature ranging from about 20°C to about 80°C, with each stage lasting about 10 seconds to about 10 minutes. The sample is then optionally dehydrated, for example using a mechanical roller, to increase uniformity and reduce particle formation in the immersion bath.

[0291] After solution contact via immersion cycling, the sample is air-dried at room temperature and then annealed at 80°C to 160°C for approximately 1 minute to approximately 20 minutes. This results in the deposition of ceramics on the substrate, comprising at least one calcium phosphate phase.

[0292] The polymer-ceramic composite was then immersed in a titanium-containing solution of a titanium source (such as titanium chloride or titanium isopropoxide) at a concentration of approximately 25 mM to approximately 500 mM. The substrate was then removed, rinsed, and dried. The polymer-ceramic composite contained titanium apatite or titanium dioxide.

[0293] This sample of titanium apatite or titanium dioxide-containing polymer-ceramic composite is UV-absorbing (as determined by UV-Vis spectroscopy) and catalytic (as determined by monitoring reaction and / or decomposition by FTIR or other means).

[0294] Example 20

[0295] Lightweight (approximately 2 oz / yd), 50D (denier) tear-resistant nylon and medium-weight (approximately 4 oz / yd), 75 / 100D (denier) polyester (PET) twill fabrics were used as polymer substrates for the deposited ceramics. The substrates were cleaned by immersing them in a solution for 5 minutes, rinsing them with 2% NaOH, rinsing them with water, and air-drying them.

[0296] The substrates were then treated with batch solution contact by immersion in a first solution of approximately 100 mM calcium source (calcium nitrate tetrahydrate) for approximately 30 seconds, followed by mechanical dehydration. These substrates were then immersed in a second solution of approximately 60 mM phosphate source (potassium phosphate (dibasic)) at approximately 30°C for approximately 30 seconds. The samples were then dehydrated, for example using mechanical rollers, to increase uniformity and reduce particle formation in the immersion bath.

[0297] After solution contact via immersion cycling, the samples were air-dried at room temperature until dry, and then annealed at approximately 120°C for about 10 minutes. This resulted in the deposition of ceramics on the nylon substrate, comprising at least one calcium phosphate phase. The samples were then coated with two different commercially available silicone-based fabric repellent solutions as recommended by the manufacturer, and tear strength was tested according to ASTM D1424. For each sample, the tear strength of each substrate was measured and determined to be more than 200% of that of the commercially available C6-containing PFAS formulation (Table 3) and more than 200% of that of the untreated substrate (Table 4). The samples also exhibited excellent tear strength relative to the uncoated nylon polymer substrate.

[0298] Table 3

[0299]

[0300] Table 4

[0301]

[0302] Example 21

[0303] Lightweight (approximately 2 oz / yd), 50D (denier) nylon fabric was used as the polymer substrate for the deposited ceramics. The nylon substrate was cleaned by immersion in a solution for approximately 10 minutes, followed by rinsing with 2% NaOH, rinsing with water, mechanically dehydrating, and air-drying at approximately 105°C, and then conditioning to laboratory conditions.

[0304] The polymer substrate was then contacted with a room temperature solution containing approximately 75 mM calcium nitrate for about 30 seconds. The sample was then removed and mechanically dehydrated. The sample was then contacted with a room temperature solution containing approximately 45 mM dipotassium hydrogen phosphate for about 30 seconds. The sample was then removed and mechanically dehydrated. The sample was air-dried and annealed in an oven set to approximately 140°C for about 20 minutes.

[0305] Cross-sections of polymer substrates are imaged using SEM-EDS, such as... Figure 3 As shown in Figure 4a, it is determined to have a calcium and phosphorus-containing structure, wherein the percentage of calcium atoms in the cross-section shown in Figure 4a is 15.61%. 3.53, with a phosphorus atomic percentage of 10.72%. 3.09, and the percentage of calcium to phosphorus atoms is 1.46. 0.53.

[0306] The calcium and phosphate-containing structures are distributed throughout the sample as discrete particles, aggregates, or clusters. The ceramic features appear to adhere well to the polymer substrate, as no loosely adhered material or areas of apparent prior material presence were observed. The deposited ceramics typically have an amorphous and unaggregated appearance, but are generally composed of low aspect ratio features. The estimated average feature size of the particles is between 250 nm and 1 µm, with very few particles larger than 5 µm. The overall estimated size distribution ranges from approximately 0.05 µm to approximately 5 µm. The deposited ceramics are characterized by a low aspect ratio (the ratio of the primary dimension length to the secondary dimension length). However, the deposited ceramic particles are not inherently spherical or round. The average sphericity and roundness of the deposited ceramic particles are estimated to be from approximately 0.3 to approximately 0.9 based on SEM analysis.

[0307] A portion of the sample was ground away using a gallium focused ion beam to create a small window cross-section, as shown in Figure 4b. In the cross-section, calcium and phosphate-containing microparticles and aggregates were observed on the polymer surface, with a nominal thickness of approximately 20 nm to approximately 200 nm. This region was probed using transmission electron microscopy (TEM) with selected area electron diffraction (SAED), as shown in Figures 4c and 4d. Small microcrystalline domains with a nominal size of approximately 5 nm and a nominal roundness of approximately 0.5 to approximately 0.9 were observed within the microparticle and aggregate layer. Nominally ordered lattice spacing was observed within these microcrystalline domains. Adjacent microcrystals exhibited similar lattice spacing but were oriented at different angles.

[0308] Crystalline domains were found in an amorphous matrix of similar elements. These domains are typically 0-dimensional particle-shaped features, and can be single-crystal particles. Larger domains become more 2-dimensional. The maximum nominal size of the domains ranges from about 2 nm to about 200 nm. High-resolution tunneling electron microscopy (HRTEM) images were acquired, and selected regions of the images were subjected to Fast Fourier Transform (FFT). The measured lattice spacing and SEM-EDS analysis of the composition reasonably indicate that the crystalline structure is a mixture of hydroxyapatite (HA), octacalcium phosphate (OCP), and calcium phosphate. The amorphous matrix also contains calcium and phosphorus, with a Ca:P ratio similar to that of calcium orthophosphate. EDS line scans from the outer surface to the polymer matrix indicate the calcium gradient within the fibers, as shown in Figure 4e.

[0309] Example 22

[0310] Lightweight (approximately 2 oz / yd), 50D (denier) nylon fabric was used as the polymer substrate for the deposited ceramics. The polyester substrate was cleaned by immersion in a solution for approximately 5 minutes followed by rinsing with 2% NaOH, rinsing with water, and air-drying at approximately 105°C, adjusted to laboratory conditions. The rinsed polymer substrate was then divided into three parts.

[0311] The first portion of the polymer substrate was then contacted with a room-temperature solution containing approximately 25 mM calcium nitrate for about 30 seconds. The sample was then removed and mechanically dehydrated. The sample was then contacted with a room-temperature solution of approximately 15 mM dipotassium hydrogen phosphate for about 30 seconds. The sample was then removed and mechanically dehydrated. The sample was air-dried and annealed in an oven set to approximately 140°C for about 10 minutes.

[0312] The second part of the polymer substrate is then contacted with a room temperature solution containing approximately 25 mM calcium nitrate for about 30 seconds. The sample is then removed and mechanically dehydrated. The sample is then contacted with a room temperature solution containing approximately 15 mM potassium phosphate for about 30 seconds. The sample is then removed and mechanically dehydrated. This sequence of solution contact and dehydration via immersion is repeated twice more, for a total of three cycles. The sample is then air-dried and annealed in an oven set to approximately 140°C for about 10 minutes.

[0313] The third part of the polymer substrate is then contacted with a room temperature solution containing approximately 25 mM calcium nitrate for about 30 seconds. The sample is then removed and mechanically dehydrated. The sample is then contacted with a room temperature solution containing approximately 15 mM dipotassium hydrogen phosphate for about 30 seconds. The sample is then removed and mechanically dehydrated. This sequence of solution contact and dehydration via immersion is repeated four more times, for a total of five cycles. The sample is then air-dried and annealed in an oven set to approximately 140°C for about 10 minutes.

[0314] Samples from each of the three parts were coated with a commercially available silicone-containing fabric repellent solution, which included a crosslinking agent and a penetrant.

[0315] Samples from each section were fixed in epoxy resin and studied by TEM (Figs. 5a-5c). The silicone coating thickness used for all samples was from approximately 50 nm to approximately 150 nm. In all cases, particles containing calcium and phosphate were identified. Increasing the number of impregnation cycles increased the amount and morphology of the ceramic deposit. As the number of particles increased, the particles began to transform from individual discrete microparticles into aggregates. The cross-section of the first sample section showed nominally spherical microparticles with an estimated roundness of 0.5 to 0.9 and nominal sizes ranging from approximately 10 nm to approximately 50 nm. The cross-section of the second section began to show aggregated structures and microparticles with nominal sizes ranging from approximately 10 nm to approximately 200 nm. Some regions showed crystallinity as observed by faceted, planar, and anisotropic features. These regions showed less amorphous material and showed overall alignment of major dimensions parallel to local tangents along the outer diameter of the polymer substrate fibers. Within the larger aggregates, crystalline regions with nominally spherical diameters (roundness of 0.5 to 1) appeared. The cross-section of the third section shows additional agglomerates and a more contiguous portion with fewer individual particles. The agglomerates and particles have a nominal thickness of approximately 10 nm to approximately 200 nm in the radial direction.

[0316] Example 23

[0317] Lightweight (approximately 2 oz / yd), 50D (denier) nylon fabric was used as the polymer substrate for the deposited ceramics. Samples (6 inches) were then placed... The samples (6 inches) were rapidly immersed in a 75 mM calcium nitrate solution for approximately 2 seconds and mechanically dehydrated using a padder. While still wet, the samples were placed on one of the rollers of an automatic clamping roller for dehydration. The rollers were engaged at a web speed equivalent to 10 m / min. As part of the process, the samples were immersed in a tank containing a 45 mM dipotassium hydrogen phosphate solution. The entire solution contact, achieved through the immersion process on the rollers, lasted approximately 2 seconds. The impregnated material was dehydrated using a padder, then removed from the padder and rapidly transferred to a preheated oven at approximately 140°C. This transfer process lasted approximately 2 to 5 seconds. The samples were then dried for approximately 2 minutes. X-ray fluorescence (XRF) data were also collected, indicating a calcium (Ca) level of approximately 570 ppm and a phosphorus (P) level of approximately 370 ppm. SEM images of these samples showed the formation of ceramic deposits on the fibers, containing some individual particles and some agglomerates. Figure 6 ).

[0318] Example 24

[0319] Lightweight (approximately 1.5 oz / yd), 20D (denier) tear-resistant PET polyester is used as the polymer substrate for deposited ceramics.

[0320] A solution containing approximately 500 mM ammonium acetate, approximately 50 mM ammonium persulfate, and approximately 50 mM ferric(II) sulfate or ferric(II) acetate was prepared by mixing for approximately 1 hour. The pH of the solution was measured and adjusted using acetic acid or ammonium hydroxide to form solutions with pH values ​​of approximately 3, 5, 6, 7, 8, and 9. A polyester substrate was introduced into the solution and held for approximately 10 minutes, followed by drying at approximately 140°C for approximately 30 minutes. The prepared substrate was then functionalized with a silane-based hydrophobic treatment free of perfluoroalkyl and polyfluoroalkyl substances (PFAS) in a manner similar to that described in Example 1. Iron-based deposits on the substrate were evaluated by XRF. An increase of up to 200 ppm of iron was measured on the substrate in samples exposed to solutions with pH values ​​of approximately 6 to approximately 9 compared to samples exposed to conditions ranging from approximately 3 to approximately 5.

[0321] The spray rating of the sample was tested and evaluated according to AATCC 22 standard, and it was observed to have a spray rating greater than 90. The durability of the water repellency was measured by washing the material in a household washing machine for three wash cycles. The sample was retested and rated according to AATCC 22 standard, and a spray rating as high as 70 was observed.

[0322] Example 25

[0323] Artificial suede leather substrate is used as the polymer substrate for deposited ceramics. The material is a 90% PET and 10% polyurethane composite. The 6-inch wafers are treated by solution contact, immersing them in a solution of 100mM or 25mM manganese sulfate and approximately 170mM ethylene glycol butyl ether at approximately 40°C for approximately 18 hours. 6-inch sample. Upon removal, rinse the sample and pass it through a manual chuck to remove excess liquid. Then place the sample in a solution containing approximately 75 mM potassium persulfate or sodium persulfate and approximately 1.5 M ammonia at approximately 20°C for approximately 90 minutes. Remove the sample, pass it through a manual chuck to remove excess liquid, and dry it at approximately 140°C for approximately 10 minutes. Immerse the sample in a solution containing alkylsilane at approximately 20°C for approximately 10 minutes. Upon removal, pass the sample through a chuck to remove excess liquid, and dry it in an oven at approximately 140°C for approximately 10 minutes.

[0324] Large color deviations in samples were studied using optical methods, and color value differences at five points on each sample were determined using a color detector. E. Higher concentration samples are registered at 1.5 or greater. E. Lower concentration samples were registered at approximately 1.4 or lower. E (color value difference).

[0325] The water repellency of the samples was measured using the AATCC 22 spray rating, achieving a score of 85-90. The wicking of the samples was also tested according to AATCC 197, and no significant wicking was observed at a distance of less than 1 cm after 2 hours of exposure. The samples were also weighed and placed in a beaker filled with water at room temperature. The samples showed the presence of air bubbles around the surface, thus preventing any wetting of the material for approximately 2 hours.

[0326] Example 26

[0327] The material uses a flexible, open-mesh upper as the polymer substrate for the deposited ceramics. This material has a breathability of approximately 350 cfm (ASTM D737) and a weight capacity of approximately 3000 g / day / m². 2 Moisture-transferring blue recycled blue nylon. A 6-inch [structure / type] is treated by immersion in a solution of approximately 25 mM manganese sulfate and approximately 170 mM ethylene glycol butyl ether at approximately 40°C for approximately 18 hours. 6-inch sample. Upon removal, rinse the sample and pass it through a manual chuck to remove excess liquid. Then place the sample in a solution containing approximately 75 mM potassium persulfate or sodium persulfate and approximately 1.5 M ammonia at approximately 20°C for approximately 90 minutes. Remove the sample, pass it through a manual chuck to remove excess liquid, and dry it at approximately 140°C for approximately 10 minutes. Immerse the sample in a solution containing alkylsilane at approximately 20°C for approximately 10 minutes. Upon removal, pass the sample through a chuck to remove excess liquid, and dry it in an oven at approximately 140°C for approximately 10 minutes.

[0328] Large color deviations in the samples were studied optically, and a color detector was used to determine the color at 5 points on each sample. E. Sample registration approximately 1.25 E.

[0329] The water repellency of the sample was measured using the AATCC 22 spray rating, achieving a score of 95. The wicking of the sample was also tested according to AATCC 197, and no significant wicking was observed at a distance of less than 1 cm after 2 hours of exposure. The sample was also weighed and placed in a beaker filled with water at room temperature. The sample showed the presence of air bubbles around its surface, thus preventing any wetting of the material for approximately 2 hours.

[0330] Example 27

[0331] Lightweight (approximately 2 oz / yd), 50D (denier) crack-resistant nylon was used as the polymer substrate for the deposited ceramics. The sample was immersed in the first solution, removed, and dried at 140°C for approximately 10 minutes. It was then immersed in the second solution, removed, rinsed twice in deionized (DI) water, and dried at approximately 140°C for approximately 10 minutes.

[0332] The first solution contained approximately 400 mM Mn(SO4) and approximately 170 mM ethylene glycol butyl ether (EGBE). The sample was immersed in the first solution at approximately 40°C for approximately 72 hours. Each solution contact was performed in 50 mL vials by immersion on a shaker set to approximately 75 rpm. The sample was then removed and dried at approximately 140°C for approximately 10 minutes.

[0333] Each sample was then contacted with the second solution at approximately 25°C for approximately 1.5 hours. The second solution contained approximately 75 mM K₂S₂O₈ and approximately 1453 mM, or approximately 750 mM, or approximately 150 mM, or approximately 15 mM, or NH₃-free. An additional second solution containing approximately 750 mM, approximately 150 mM, approximately 15 mM, or NH₃-free was prepared, and KOH was added to bring the solution to a pH of approximately 13.5. The samples were then removed, rinsed twice with DI (Class II) water, and dried at approximately 140°C for approximately 10 minutes.

[0334] Samples were imaged using SEM. Samples exposed to a second solution greater than 150 mM NH3 exhibited a continuously interconnected plate-like nanostructured layer and some larger discrete particles, with some breaks in the continuous structure observed. The thickness of the nanostructured layer was less than approximately 0.2 µm. Samples with 15 mM NH3 showed some discrete granular structures with a size less than 1 µm. No structure was observed in samples without NH3 exposure. Samples exposed to a second solution greater than 150 mM NH3 and KOH showed a continuously interconnected plate-like nanostructured layer and some larger discrete particles, with some breaks in the continuous structure observed. The thickness of the nanostructured layer was less than approximately 0.2 µm. Samples with 15 mM NH3 containing KOH and samples without NH3 showed discrete granular structures with a size less than 1 µm. EDS analysis indicated the presence of Mn in the structure.

[0335] Example 28

[0336] Three different materials were used as polymer substrates for the deposited ceramics: lightweight (approx. 2 oz / yd), 50D (denier) tear-resistant nylon; lightweight (approx. 1.5 oz / yd), 20D (denier) tear-resistant PET polyester; and medium-weight (approx. 4 oz / yd), 75 / 100D (denier) polyester (PET) twill. Each fabric sample was cleaned with isopropanol solution and dried at 105°C for approximately 10 minutes. The samples were then immersed in the reaction mixture, removed, and dried.

[0337] The reaction mixture was prepared by adding approximately 20 mL of approximately 10% TiCl3 to approximately 15% TiCl3 (in HCl) to approximately 90 mL of DI water while stirring. A second mixture was generated by combining approximately 10% NH3 and approximately 1% H2O2 in water. The second mixture was added dropwise to the initial solution while stirring until the desired pH was reached, resulting in four (4) reaction mixtures with pH values ​​of approximately 3, approximately 4.5, approximately 6, and approximately 7.5.

[0338] One sample of each fabric was suspended in each reaction mixture for approximately 18 hours. Upon removal, each fabric sample was rinsed by repeated immersion in DI water until no further particles or holdup were visible. The samples were then dried in a forced convection oven at approximately 140°C for approximately 2 minutes.

[0339] The samples were imaged by SEM, revealing highly textured structures on all samples. XRF was used to investigate the titanium concentration [Ti] on the samples. Each fabric showed a maximum [Ti] at a pH setpoint of 4.5. The amount of deposited material was correlated with the initial wet pickup of the fabric. Fabrics with higher wet pickup exhibited nearly continuous shell-like structures with a thickness of less than approximately 0.5 µm.

[0340] Example 29

[0341] Use approximately 64g / m 2 Lightweight nylon tear-resistant fabric was used as the polymer substrate for deposited ceramics. A first solution was prepared consisting of 50 mM calcium nitrate tetrahydrate and 50 mM titanium oxysulfate (TiO(SO4)). A second solution was prepared consisting of 60 mM dipotassium hydrogen phosphate. The first set of samples (6 inches) The sample (6 inches) was immersed in the first solution at approximately 25°C for about 30 seconds and mechanically dehydrated using a dyeing press. The sample was then immersed in the second solution at approximately 25°C for about 30 seconds and mechanically dehydrated using a dyeing press. The immersed and dehydrated sample was then removed from the dyeing press and quickly transferred to a preheated oven at approximately 140°C and dried for about 20 minutes.

[0342] The second group of samples was immersed in the first solution for dehydration, and then immersed in the second solution for dehydration. This cycle was repeated three times before the drying step.

[0343] SEM images of these samples revealed ceramic deposits with some individual particles and agglomerates formed on the fibers. The first sample showed particles and agglomerates with a nominal size of approximately 2 µm. The second group of samples showed particles and agglomerates with a nominal size of approximately 5 µm. EDS analysis of all samples detected uniformly distributed Ca and Ti signals. Figure 7 The second set of samples from three cycles of processing showed increased signal strength and a larger amount of aggregates, as defined by signal clumping.

[0344] Example 30

[0345] A cellulose-based polymer matrix was used as the substrate for the deposited ceramics. The initial weight was approximately 255 g / m³. 2 8” The 8” sample was used as the substrate.

[0346] The polymer sample was immersed in an aqueous bath containing 50 mM ammonium acetate, 500 mM manganese(II) acetate, 4350 mM acetic acid, and 50 mM ammonium persulfate for about 30 minutes, maintained at approximately 20°C. The immersed sample was then transferred to a deionized water bath and immersed for 30 seconds. The sample was then removed from the solution and dried at approximately 105°C for about 10 minutes. The sample was then immersed in an ethanol bath containing approximately 1% alkylsilane for 18 hours. The sample was then removed from the solution and annealed at 105°C for 60 minutes.

[0347] When imaged by SEM, a dense nanostructured shell of manganese hydroxide was observed on the surface of the cellulose matrix. Energy dispersive X-ray spectroscopy (EDS) confirmed the composition of the coating, revealing a mixture of manganese and oxygen on top of the predominantly carbon-containing polymer surface. The water contact angle of the sample was analyzed by the seat drop method after laboratory conditioning and tape adhesion. The substrate exhibited a water contact angle of approximately 145° before and after tape adhesion and removal.

[0348] Example 31

[0349] A cellulose-based polymer matrix was used as the substrate for the deposited ceramics. The initial weight was approximately 255 g / m³. 2 8” The 8” sample was used as the substrate.

[0350] Polymer samples were immersed in two different alternating aqueous solutions to deposit interconnected plate-like ceramic structures on a substrate. The procedure for each sample was to immerse the sample in solution (a) for approximately 30 seconds, remove it and allow it to drain in air for approximately 10 seconds, then immerse the sample in solution (b) for approximately 30 seconds, remove it and allow it to drain in air for approximately 10 seconds. This immersion and drying sequence was repeated three times for each sample. The conditions for solutions (a) and (b) are shown in Table 5.

[0351] Table 5

[0352]

[0353] The aqueous baths (a) contain calcium nitrate tetrahydrate and (b) contain dipotassium hydrogen phosphate (at the concentrations indicated in Table 5).

[0354] When imaged by SEM, a dense nanostructured interconnected layer of calcium phosphate was observed on the surface of the cellulose matrix. Energy-dispersive X-ray spectroscopy (EDS) confirmed the composition of the coating, revealing a mixture of calcium and phosphorus on top of the predominantly carbon-containing polymer surface. The water contact angle of the sample was analyzed by the seated drop method after laboratory conditioning and tape adhesion. The substrate exhibited a water contact angle of approximately 145° before and after tape adhesion and removal. The conditions corresponding to Figure 8e resulted in an extremely thick coating, leading to large, flake-like coatings on the paper substrate.

[0355] Example 32

[0356] A cellulose-based polymer matrix was used as the substrate for the deposited ceramics. The initial weight was approximately 255 g / m³. 2 8” An 8” sample was used as the substrate. The sample (Fig. 8e) produced under the conditions corresponding to Example 31 was placed in contact with a 200µm thick conductive polycarbonate tape, which has a 30µm thick carbon-filled acrylic adhesive on both sides.

[0357] SEM images of the tape were taken after adhesion to the polymer-ceramic composite. Adhesion was achieved by placing the coated sample in contact with the tape for approximately 20 seconds with a gloved hand under light pressure. Figure 8f shows the interconnected ceramic structure transferred to the tape. Figure 8e shows the interconnected ceramic structure retained on the polymer substrate. These images demonstrate the strong adhesion of the ceramic to both the substrate and the adhesive.

[0358] Although the foregoing invention has been described in considerable detail with reference to illustration and examples for purposes of clarity, those skilled in the art will understand that certain changes and modifications may be practiced without departing from the spirit and scope of the invention as set forth in the appended claims. Therefore, this description should not be construed as limiting the scope of the invention.

[0359] All publications, patents and patent applications cited herein are incorporated herein by reference in their entirety for all purposes, as if each individual publication, patent or patent application were specifically and individually indicated to be so incorporated by reference.

Claims

1. A polymer-ceramic composite comprising a core and a shell, wherein the core comprises a polymer and the shell comprises ceramic.

2. The polymer-ceramic composite of claim 1, wherein the core comprises a hydraulic diameter, and wherein the shell has a thickness less than 20% of the hydraulic diameter of the core.

3. The polymer-ceramic composite according to claim 1, wherein the shell has a thickness of less than about 1 micrometer.

4. The polymer-ceramic composite according to claim 1, wherein the core has a diameter or thickness greater than about 1 micrometer.

5. The polymer-ceramic composite of claim 1, wherein the polymer comprises a thermoplastic.

6. The polymer-ceramic composite of claim 1, wherein the thermoplastic comprises polyester, polyamide, polyurethane, acrylic (polyacrylate), polyolefin, polyol, acrylonitrile butadiene styrene (ABS), or a combination thereof.

7. The polymer-ceramic composite of claim 1, wherein the polymer comprises cotton, wool, paper, or cellulose material.

8. The polymer-ceramic composite according to claim 7, wherein the cross-section of the core is a circle with a roundness greater than 0.7, or a semicircle with a semicircle greater than 0.7, or a leaf shape with a leaf shape greater than 0.

7.

9. The polymer-ceramic composite according to claim 1, wherein the weight fraction of ceramic in the shell is less than about 0.

9.

10. The polymer-ceramic composite of claim 1, wherein at least one dimension of the ceramic is less than about 100 nanometers.

11. The polymer-ceramic composite of claim 1, wherein the ceramic in the shell comprises a morphology of 0-dimensional, 1-dimensional, or 2-dimensional material.

12. The polymer-ceramic composite of claim 1, wherein the shell further comprises siloxane, acrylate, phosphonate, sulfonate, carbamate or a combination thereof.

13. The polymer-ceramic composite of claim 1, wherein the shell further comprises an organosilicon polymer, an alkyl-terminated silane, or an alkyl-terminated siloxane.

14. The polymer-ceramic composite according to any one of claims 1, wherein the shell further comprises alkyl-terminated functional groups.

15. The polymer-ceramic composite of claim 14, wherein the alkyl-terminated functional group comprises an alkyl group with more than three carbon atoms.

16. The polymer-ceramic composite of claim 15, wherein the alkyl group comprises fewer than nineteen carbon atoms.

17. The polymer-ceramic composite of claim 1, wherein the shell further comprises an isocyanate or an isocyanate-terminated polymer.

18. The polymer-ceramic composite of claim 1, wherein the shell is chemically bonded to the core.

19. The polymer-ceramic composite according to claim 1, wherein the polymer-ceramic composite has a surface roughness greater than 1.

1.

20. The polymer-ceramic composite of claim 1, wherein at least a portion of the ceramic is interconnected.

21. The polymer-ceramic composite of claim 20, wherein, based on particles, more than 50% of the ceramic is interconnected.

22. The polymer-ceramic composite of claim 1, wherein the ceramic comprises crystalline domains.

23. The polymer-ceramic composite of claim 22, wherein one or more of the crystalline domains comprise crystalline particles.

24. The polymer-ceramic composite of claim 22, wherein the crystalline domain is embedded in an amorphous matrix.

25. The polymer-ceramic composite of claim 24, wherein the amorphous matrix comprises at least two elements present in the crystalline domain, excluding carbon, hydrogen, oxygen, or nitrogen.

26. The polymer-ceramic composite of claim 25, wherein the amorphous matrix comprises at least three elements common to the crystalline particles or crystalline domains.

27. The polymer-ceramic composite of claim 24, wherein the amorphous matrix comprises calcium and / or phosphorus.

28. The polymer-ceramic composite of claim 22, wherein the size of the crystalline domain is in the range of a nominal size of about 2 nm to a nominal size of about 200 nm.

29. The polymer-ceramic composite of claim 22, wherein the crystalline domain comprises octacalcium phosphate, hydroxyapatite, triclinic calcium phosphate, calcium phosphate, calcium triphosphate, calcium pyrophosphate and / or their hydrates.

30. The polymer-ceramic composite of claim 22, wherein the crystalline domain comprises phosphate groups in the form of pyrophosphate, hydrogen phosphate, dihydrogen phosphate, orthophosphate, or combinations thereof.

31. A composite component comprising the polymer-ceramic composite of claim 1, wherein at least a portion of the polymer-ceramic composite is in fibrous form.

32. The composite component of claim 31, wherein the fibers are assembled into yarns, woven fabrics, knitted fabrics, or non-woven fabrics.

33. A polymer-ceramic composite comprising: a polymer substrate and a ceramic, wherein the polymer substrate has an outer surface and an internal volume of the polymer matrix, a first portion of the ceramic is on the outer surface, and a second portion of the ceramic occupies at least a portion of the internal volume of the polymer matrix.

34. The polymer-ceramic composite of claim 33, wherein the polymer-ceramic composite is a fiber, laminate, membrane, textile material, paper, or a combination thereof.

35. The polymer-ceramic composite of claim 34, wherein the polymer-ceramic composite comprises fibers with an average diameter of less than about 5 mm or less than about 1 mm.

36. The polymer-ceramic composite of claim 34, wherein the fibers form a fabric or are incorporated into a fabric.

37. The polymer-ceramic composite of claim 36, wherein the formation or incorporation comprises knitting, weaving, bonding or entanglement of the fibers by chemical, mechanical and / or by applying heat or one or more solvents.

38. The polymer-ceramic composite of claim 34, wherein the polymer-ceramic composite is a film having an average thickness of less than about 5 mm or less than about 3 mm.

39. The polymer-ceramic composite of claim 34, wherein the polymer substrate is a textile material.

40. The polymer-ceramic composite of claim 33, wherein the polymer substrate comprises polyester, polyamide, polyolefin, substituted polyolefin, polyurethane, polyol, vinyl polymer, acrylate polymer, polycarbonate, polyether, cotton, wool, paper, cellulose material, or a combination thereof.

41. The polymer-ceramic composite of claim 40, wherein the polymer substrate comprises polyethylene terephthalate (PET), nylon, polyethylene, polypropylene, polyvinyl chloride (PVC), polyvinyl alcohol (PVOH), polyvinyl acetate (PVAc), polyvinylpyrrolidone, polyethylene glycol (PEG), polymethyl methacrylate (PMMA), cellulose, or mixtures thereof.

42. The polymer-ceramic composite of claim 33, wherein the polymer substrate comprises a hydrocolloid.

43. The polymer-ceramic composite of claim 42, wherein the hydrocolloid comprises a polysaccharide.

44. The polymer-ceramic composite of claim 33, wherein the polymer substrate comprises locust bean gum, starch, carrageenan, pectin, chitosan, xanthan gum, cellulose, carboxymethyl cellulose, or mixtures thereof.

45. The polymer-ceramic composite of claim 33, wherein the polymer substrate comprises wool, cotton, hemp, animal hair, collagen, keratin, silk, chitin, flax, jute, or mixtures thereof.

46. ​​The polymer-ceramic composite of claim 33, wherein the first portion of the ceramic comprises more than about 20% of the ceramic.

47. The polymer-ceramic composite of claim 33, wherein the thickness of the first portion of the ceramic is less than about 1 µm or less than about 100 nm.

48. The polymer-ceramic composite of claim 33, wherein the ceramic layer is nanostructured.

49. The polymer-ceramic composite of claim 33, wherein the second portion of the ceramic penetrates from the outer surface into the internal volume of the polymer matrix by more than about 10 nanometers.

50. The polymer-ceramic composite of claim 33, wherein the polymer matrix comprises a hydraulic diameter, and wherein the second portion of the ceramic penetrates from the outer surface of the polymer substrate into the interior volume of the polymer matrix in a volume less than about 90% of the hydraulic diameter.

51. The polymer-ceramic composite of claim 33, wherein the ceramic comprises a metal, and wherein the atomic molar percentage of the metal in the second portion of the ceramic decreases when measured from the outer surface of the polymer substrate into the internal volume of the polymer matrix.

52. The polymer-ceramic composite of claim 51, wherein the atomic molar percentage of the metal decreases from the outer surface of the polymer substrate into the internal volume of the polymer matrix at a certain rate.

53. The polymer-ceramic composite of claim 52, wherein the atomic molar percentage of the metal decreases exponentially from the surface into the internal volume of the polymer matrix.

54. The polymer-ceramic composite of claim 53, wherein the exponential decay constant is greater than about 0.

01.

55. The polymer-ceramic composite of claim 33, wherein the second portion of the ceramic accounts for at least about 1% of the mass of the ceramic and / or the first portion of the ceramic accounts for less than about 99% of the mass of the ceramic.

56. The polymer-ceramic composite of claim 33, wherein the ceramic comprises a metal, and wherein the atomic molar percentage of the metal in the internal volume of the polymer matrix is ​​greater than about 0.1% at a depth of about 10 nm from the outer surface to the internal volume of the polymer matrix.

57. The polymer-ceramic composite of claim 33, wherein the ceramic comprises a metal, and wherein the atomic molar percentage of the metal, when measured from the outer surface into the internal volume of the polymer matrix, comprises a discontinuity at the outer surface of the polymer substrate.

58. The polymer-ceramic composite of claim 33, wherein the internal volume of the polymer matrix comprises both convex Gaussian geometric features and concave Gaussian geometric features, wherein the ceramic comprises a metal, and wherein the atomic molar percentage of the metal in the convex feature is equal to or greater than the atomic molar percentage of the metal in the concave feature.

59. The polymer-ceramic composite of claim 33, wherein the ceramic comprises a metal, and wherein the diffusion length of the metal in the internal volume of the polymer matrix is ​​greater than about 1 µm.

60. The polymer-ceramic composite of claim 33, wherein the ceramic comprises a metal, and wherein the diffusion coefficient of the metal in the volume within the polymer matrix is ​​less than about 10. -8 m 2 / Second.

61. The polymer-ceramic composite of claim 33, wherein the mass of the ceramic is less than about 10% as a percentage of the mass of the polymer-ceramic composite.

62. The polymer-ceramic composite of claim 33, wherein the ceramic comprises less than about 10 grams per square meter of the nominal geometric surface area of ​​the polymer-ceramic composite.

63. The polymer-ceramic composite according to claim 33, further comprising functional molecules.

64. The polymer-ceramic composite of claim 63, wherein the functional molecule comprises silane, siloxane, phosphonic acid, phosphonate, sulfonate, sulfonic acid, carboxylic acid, carboxylic acid ester, carbamate, vinyl, acrylate, or a molecule having a head group and a tail group.

65. The polymer-ceramic composite of claim 64, wherein the functional molecule comprises a molecule having a head group and a tail group, wherein the head group comprises silyl, phosphonate, phosphonic acid, carboxylic acid, vinyl, alcohol, hydroxyl, thiol ester, thiol, and / or ammonium, and wherein the tail group comprises hydrocarbon, fluorocarbon, vinyl, phenyl, epoxy, acrylic, acrylate, hydroxyl, carboxylic acid, thiol, and / or quaternary ammonium.

66. The polymer-ceramic composite of claim 65, wherein the head group comprises an ammonium group, wherein the ammonium group is a quaternary ammonium group.

67. The polymer-ceramic composite of claim 63, wherein at least a portion of the functional molecule occupies the internal volume of the polymer matrix.

68. The polymer-ceramic composite of claim 67, wherein the functional molecule penetrates into the internal volume of the polymer matrix by more than about 10 nanometers.

69. The polymer-ceramic composite of claim 63, wherein the concentration of the functional molecule decreases when measured from the outer surface of the polymer substrate into the internal volume of the polymer matrix.

70. The polymer-ceramic composite of claim 69, wherein the concentration of the functional molecule decreases at a certain rate from the outer surface of the polymer substrate into the internal volume of the polymer matrix.

71. The polymer-ceramic composite of claim 63, wherein the functional molecule penetrates a shorter distance into the internal volume of the polymer matrix compared to the same polymer substrate that does not contain the ceramic.

72. The polymer-ceramic composite of claim 63, wherein the diffusion coefficient of the functional molecule in the volume within the polymer matrix is ​​more than about 5% smaller than the diffusion coefficient of the functional molecule in the same polymer substrate not containing the ceramic.

73. The polymer-ceramic composite of claim 33, wherein at least a portion of the outer surface of the polymer substrate does not include the first portion of the ceramic.

74. The polymer-ceramic composite of claim 33, wherein at least a portion of the polymer-ceramic composite has a seat-drop water contact angle greater than about 90°.

75. The polymer-ceramic composite of claim 33, wherein at least a portion of the polymer-ceramic composite has a wrinkle ratio greater than about 1.

3.

76. The polymer-ceramic composite of claim 33, wherein the tear strength, tensile strength, air permeability, vapor permeability and / or abrasion resistance are improved relative to the polymer substrate.

77. The polymer-ceramic composite of claim 76, wherein the tear strength is greater than about 1000 gF.

78. The polymer-ceramic composite of claim 63, wherein tear strength, tensile strength, air permeability, vapor permeability and / or abrasion resistance are improved compared to the same polymer-ceramic composite without the functional molecule.

79. The polymer-ceramic composite according to any one of claims 1-30 and 33-78 or the component according to claim 31 or 32, wherein the ceramic comprises rare earth metals, transition metals, alkali metals, alkaline earth metals, or combinations thereof.

80. The polymer-ceramic composite of claim 79, wherein the ceramic comprises calcium, manganese, phosphorus, iron, nickel, magnesium, titanium, lithium, copper or zinc.

81. The polymer-ceramic composite of claim 79, wherein the ceramic comprises the rare earth metal, the transition metal, the alkali metal or the oxide, hydroxide, phosphate, layered double hydroxide, sulfate, carbonate or oxalate, or a combination thereof.

82. The polymer-ceramic composite according to claim 81, wherein the ceramic comprises manganese oxide, iron oxide, calcium carbonate, hydroxyapatite, calcium phosphate, calcium oxalate, magnesium carbonate, calcium sulfate, magnesium sulfate, or a combination thereof.

83. A method for manufacturing the polymer-ceramic composite according to claim 1 or 33, comprising: (a) Contacting a polymer substrate with at least one solution comprising a metal salt or a metal-organic complex and optionally an oxidant, amine, ammonia, a penetrant, surfactant, release agent or other reactive precursor or combination thereof, wherein the solution is at least partially absorbed into the polymer substrate; (b) Heating or otherwise ensuring that the polymer substrate produced in step (a) reaches a temperature sufficient to remove the solvent from the polymer substrate, sufficient to drive a ceramic formation reaction with one or more of the metal salts, or sufficient to decompose or react the metal-organic complex, thereby forming a polymer-ceramic composite; and (c) Optionally, the polymer-ceramic composite produced in step (b) is coated with one or more functional layers or molecules.

84. The method of claim 83, wherein the reactive precursor in step (a) comprises a catalyst in a solvent.

85. The method according to claim 83, wherein the metal salt in step (a) comprises transition metal nitrates, transition metal chlorides, transition metal sulfates, alkali metal nitrates, alkaline earth metal nitrates, alkali metal chlorides, alkaline earth metal chlorides, alkali metal sulfates, alkaline earth metal sulfates, or combinations thereof.

86. The method of claim 83, wherein the metal-organic complex in step (a) comprises a metal-amine complex.

87. The method of claim 83, wherein the amine in step (a) comprises a free amine.

88. The method according to any one of claims 83-87, wherein the temperature in step (b) is in the range of about 30°C to about 200°C.

89. The method of claim 83, wherein the method comprises coating the polymer-ceramic composite produced in step (b) with one or more functional layers.

90. The method of claim 89, wherein the functional layer in step (c) comprises a single-layer chemical with a thickness of less than about 5 nm.

91. The method of claim 90, wherein the monolayer chemical comprises silane, siloxane, urethane, acrylate, or a molecule having a head group and a tail group.

92. The method of claim 90, wherein the monolayer chemical comprises a molecule having a head group and a tail group, wherein the head group comprises silyl, phosphonate, phosphonic acid, carboxylic acid, vinyl, alcohol, hydroxyl, thiol ester, thiol, and / or ammonium, and wherein the tail group comprises hydrocarbon, fluorocarbon, vinyl, phenyl, epoxy, acrylic, acrylate, hydroxyl, carboxylic acid, thiol, and / or quaternary ammonium.

93. The method of claim 91, wherein the head group comprises an ammonium group, wherein the ammonium group is a quaternary ammonium group.

94. The method of claim 83, wherein steps (a) and (b) comprise forming the polymer-ceramic composite on a first substrate, wherein the polymer-ceramic composite on the first substrate is in the form of an interconnected nanostructured layer on the first substrate. The method further includes contacting the second substrate with the polymer-ceramic composite, causing at least a portion of the interconnected nanostructured layer to transfer to the second substrate, thereby forming the second substrate-ceramic composite. Optionally, the second substrate-ceramic composite may be coated with one or more functional layers or molecules.

95. The method of claim 94, wherein the polymer-ceramic composite on the first substrate is brought into contact with the second substrate under pressure according to standard method ASTM D3359.

96. The method of claim 94, wherein the polymer-ceramic composite on the first substrate is brought into contact with the second substrate by a roll lamination process or by hot pressing at a temperature of about 40°C to about 200°C and a pressure of about 0.1 MPa to about 10 MPa.

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