Composite products of functional textile materials and methods for using them

Abstract

The present invention provides functionalization of textile surfaces, as well as aggregates of such layers, to offer functional benefits compared to individual or non-functionalized layers. [Solution] A composite material comprising stacked layers of materials is described. The composite material comprises a functional layer and a structural layer. The functional layer comprises a binderless ceramic material on a woven or non-woven substrate of natural, synthetic, or metallic material. The layers of functional and structural materials may be configured to transport moisture or heat from the inner surface to the outer surface exposed to the ambient environment.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to PCT application number PCT / US2019 / 065978 filed on 12 December 2019, and claims the benefit of U.S. Provisional Patent Applications No. 62 / 989,092, 62 / 989,150, 63 / 038,642, 63 / 038,693, and 63 / 039,965 filed on 13 March 2020, all of which are incorporated herein by reference in their entirety.

[0002] Technical field The present invention relates to the functionalization of textile surfaces using ceramic surface modifiers, particularly binderless ceramics such as metal oxides and / or metal hydroxide ceramics, or chemical conversion coatings, on textile surfaces to provide functional benefits compared to individual or non-functionalized layers, as well as aggregates of such layers. [Background technology]

[0003] Functionalizing textile surfaces provides desired benefits in terms of textile performance compared to non-functionalized textile layers. A composite of layers capable of providing multiple benefit properties to a single system or product is desirable, as these may offer additional benefits when compared to composites of individual functional or non-functionalized layers. Furthermore, desirable operating characteristics can be enhanced by forming a composite through the aggregation of individual functional layers. [Overview of the project]

[0004] The present invention provides an aggregate of functional and structural layers of a material, and / or layers having other beneficial properties. The functional layer may contain a ceramic material on a substrate such as a textile substrate.

[0005] In one aspect, an assembly of materials including a top surface and a bottom surface, comprising: (a) x layers of A of a material including one or more functional properties t layers (wherein said A t layers include the topmost layer including the top surface); (b) y layers of A of a material including one or more functional properties b layers (wherein said A b layers include the bottommost layer including the bottom surface); and (c) a B layer of z layers of an insulating material, a structural material, or another functionally beneficial material between the x layers of A t layers and the y layers of A b layers, wherein x, y, and z are the same or different numbers of layers, and said A t layers and / or said A b layers may each include a ceramic material, such as a binderless ceramic, for example, a binderless porous ceramic material, on a substrate, and the ceramic material on each A t layer and / or each A b layer is the same or different, providing said assembly. In one embodiment, at least one layer of A t layers includes a ceramic material, such as a binderless ceramic, for example, a binderless porous ceramic material, on a substrate. In another embodiment, at least one layer of A b layers includes a ceramic material, such as a binderless ceramic, for example, a binderless porous ceramic material, on a substrate. In yet another embodiment, at least one layer of A t layers and at least one layer of A b layers each include a ceramic material, such as a binderless ceramic, for example, a binderless porous ceramic material, on a substrate. In some embodiments, said top surface and / or said bottom surface include a ceramic material, such as a binderless ceramic, for example, a binderless porous ceramic material. In some embodiments, the A b layers and / or the A t layers include a plurality of functional (e.g., aesthetic and / or performance-related) properties.

[0006] In another aspect, an assembly of materials including a top surface and a bottom surface, comprising: (a) one or more func The present invention provides an assembled product comprising (b) an x ​​layer A of a material containing functional properties (wherein the A layer includes the uppermost layer including the top surface, and each of the A layers includes a binderless ceramic, such as a binderless porous ceramic material, on a substrate); and (b) an z layer B of an insulating material, structural material, or other functionally beneficial material (wherein the B layer includes the bottommost layer including the bottom surface), wherein x and z have the same or different number of layers. In some embodiments, the assembled product is A b Does not include layers.

[0007] In another embodiment, an aggregate of materials including an upper and lower surface, wherein (a) the x layer of the material having one or more functional properties A t Layer (where A t (b) The layer includes the uppermost layer including the top surface; and (b) the A layer of the material having one or more functional properties. b Layer (where A b The layer includes the bottom layer including the bottom surface, and in this case, A t Layer and A b Each layer contains a binderless ceramic, such as a binderless porous ceramic material, on a substrate, and A t The ceramic material on the layer is A b Unlike layered ceramic materials, the laminated product is provided in which x and y are the same or different. In some embodiments, the laminated product does not include a B layer. In one embodiment, at least one A layer is provided. t The layer includes a ceramic material on the substrate, such as a binderless ceramic, for example, a binderless porous ceramic material. In another embodiment, at least one layer A b The layer includes a ceramic material on the substrate, such as a binderless ceramic, for example, a binderless porous ceramic material. In a further embodiment, at least one layer A t A layer and at least one layer bEach layer contains a ceramic material on the substrate, such as a binderless ceramic, for example, a binderless porous ceramic material. In some embodiments, the upper and / or lower surfaces contain a ceramic material, such as a binderless ceramic, for example, a binderless porous ceramic material. In some embodiments, A b Layer and / or A t A layer includes multiple functional (e.g., aesthetic and / or performance-related) characteristics.

[0008] In some embodiments, the ceramic material is primarily crystalline. In some embodiments, the ceramic material comprises a metal oxide, a hydrate of a metal oxide, a metal hydroxide, and / or a hydrate of a metal hydroxide. In some embodiments, the ceramic material comprises a metal hydroxide, and at least a portion of the metal hydroxide comprises a layered double hydroxide. In some embodiments, the ceramic is a structured ceramic, such as a nanostructured ceramic.

[0009] In some embodiments, the ceramic material comprises a mixed metal oxide, a hydrate of a mixed metal oxide, a mixed metal hydroxide, and / or a hydrate of a mixed metal hydroxide. In some embodiments, the ceramic material comprises a mixed metal hydroxide, and at least a portion of the metal hydroxide comprises a layered double hydroxide.

[0010] In some embodiments, the ceramic material comprises a mixed metal oxide, a hydrate of a mixed metal oxide, a mixed metal hydroxide, and / or a chemical conversion of a hydrate of a mixed metal hydroxide. In some embodiments, the ceramic material comprises a mixed metal hydroxide, and at least a portion of the metal hydroxide comprises a layered double hydroxide in which inserted ions are exchanged (for example, the inserted metal ions originally generated in the layered double hydroxide are exchanged with different inserted ions).

[0011] In some embodiments, at least one layer of A t and / or at least one layer of A bThe substrate for the layer includes synthetic or natural textiles that are woven, non-woven, or knitted, or metal mesh, metal screen, or metal cloth. In some embodiments, at least one layer A t and / or at least one layer of A b The substrate for the layer includes synthetic or natural material films or polymers.

[0012] In some embodiments, each A t and / or A b The layers include ice or condensate management, de-icing, and anti-icing. The functional properties include one or more selected from frost resistance, superhydrophobicity, superhydrophilicity, inhibition or resistance to microbial growth, corrosion resistance, electromagnetic modulation, thermal modulation, flame retardancy, breathability, dynamic wind resistance, color, absorption, barrier, maintenance properties (e.g., color fastness, e.g., resistance to disintegration during washing, ease of cleaning, wrinkle resistance, odor resistance), aesthetic properties (e.g., color reflectivity, finish (e.g., matte, opaque), color depth (e.g., color change as a function of the viewing angle)), odor control, abrasion resistance, mechanical properties (e.g., stiffness, tensile strength (e.g., tear resistance), impact resistance), surface friction, handfeel, durability, or a combination thereof).

[0013] In some embodiments, x and / or y are greater than 1, and each A t and / or A b The layer is other A t and / or A b It includes at least one functional characteristic distinct from the layer. In some embodiments, each A t The layer is other A t It includes at least one functional characteristic distinct from the layer. In other embodiments, each A b The layer is other A b It includes at least one functional characteristic distinct from the layer. In other embodiments, A t The layer is A b It contains functional characteristics different from those of a layer.

[0014] In some embodiments, the uppermost layer (uppermost A) including the upper surface t The bottom layer (bottom A) including the bottom surfaceb The layers have the same functional characteristics. In some embodiments, the uppermost layer (uppermost A) including the upper surface is present. t The bottom layer (bottom A) including the bottom surface b The layers have different functional characteristics.

[0015] In some embodiments, each B layer includes one or more structural properties selected from thermal resistance, electrical resistance, structural support, mechanical padding, aesthetics, comfort, protection, durability, maintenance properties (e.g., rapid drying, ease of folding, color fastness, e.g., resistance to collapse during washing, easy cleaning, wrinkle resistance), fluid transport properties, or a combination thereof. In some embodiments, one or more B layers include a ceramic material selected from, for example, glass fiber, loose ceramics, and other inorganic materials.

[0016] In some embodiments of the composite products described herein, at least one A layer (for example, at least one A t and / or A b A layer includes a functional material (e.g., a surface functional topcoat material) applied to or deposited on the ceramic material to impart or enhance one or more functional properties. In some embodiments, at least one functional property imparted by these functional materials is more advanced than the same functional property imparted by the same surface functional topcoat material deposited directly on the same substrate without the ceramic material. In some embodiments of the composite described herein, at least one A layer (e.g., at least one A t and / or A b The layer comprises a functional material (e.g., a surface functional topcoat material), wherein the ceramic material and the functional material synergistically impart one or more functional properties that are more advanced than the same functional properties imparted by either the ceramic material or the topcoat material independently deposited on the same textile surface.

[0017] In some embodiments, the functional layer imparts hydrophobic properties. For example, the functional layer that imparts hydrophobic properties to the composition may include a fluoropolymer, elastomer, plastic, or a molecule having a head group and a tail group, where the head group includes a silane group, a phosphonate group, a phosphonic acid group, a carboxylic acid group, a vinyl group, an alcohol group, a hydroxide group, a thiolate group, a thiol group, and / or an ammonium group (e.g., a quaternary ammonium group), and the tail group includes a hydrocarbon group, a fluorocarbon group, a vinyl group, a phenyl group, an epoxide group, an acrylic group, an acrylate group, a hydroxyl group, a carboxylic acid group, a thiol group, and / or a quaternary ammonium group.

[0018] In some embodiments of the composite products described herein, at least one A layer (for example, at least one A t and / or at least one layer of A b The binderless ceramic material on the layer has a partially filled porous structure. For example, the voids in the ceramic material may be filled with a second ceramic material or with molecules having head and tail groups. .

[0019] In some embodiments of the composite products described herein, at least one A layer (for example, at least one A t A layer and / or at least one layer b The layer can withstand hydrostatic pressure exceeding approximately 1 kPa.

[0020] In some embodiments of the composite products described herein, at least one A layer (for example, at least one A t A layer and / or at least one layer b The layer includes a water vapor transmission rate of more than 80% of the vapor transmission rate of the same substrate that has not been modified with ceramic material (and, in some embodiments, an optional functional layer).

[0021] In some embodiments of the composite products described herein, at least one A layer (for example, at least one A tA layer and / or at least one layer b The layers include droplet water contact angles exceeding approximately 150 degrees.

[0022] In some embodiments of the composite products described herein, at least one A layer (for example, at least one A t and / or A b Layers improve aesthetics, wearer comfort, durability, or the maintenance of desirable properties (e.g., Venkatraman, P., “Fabric See "Properties and Their Characteristics, in Materials and Technology for Sportswear and Performance Apparel," 2015, CRC Press, ISBN 9781482220513.

[0023] In some embodiments, the composite material is incorporated into performance outerwear clothing, medical bandages, medical casts, surgical gowns, filtering or separation media, packing materials, hospital flooring, absorbent textiles, protective masks, protective clothing, building textiles, or geotextiles.

[0024] In some embodiments, a pipe insulating material or pipe protective material comprising a composite as described herein, comprising one or more A t The layers include hydrophobic or superhydrophobic functional properties, one or more B layers include thermal insulation, protection (e.g., protection from corrosion and / or abrasion of the piping under operating conditions or in the usage environment, and / or protection from damage to solid objects adjacent to the piping), or structural properties, and one or more A layers include hydrophobic or superhydrophobic functional properties, one or more B layers include thermal insulation, protection (e.g., protection from corrosion and / or abrasion of the piping under operating conditions or in the usage environment, and / or protection from damage to solid objects adjacent to the piping), b The present invention provides a pipe insulating material or pipe protective material having a layer that includes hydrophilic or superhydrophilic functional properties. For example, the pipe insulating material or pipe protective material may surround a pipe, in which case the bottom A b The layer is in contact with the piping, and the uppermost A t The layer is in contact with the surrounding environment. One or more layers t and / or A bThe layers may include ceramic-coated woven material. For example, the woven material may be selected from stainless steel alloy woven material, carbon steel alloy woven material, aluminum alloy woven material, and textile. In some embodiments, at least one layer B may include a material selected from fiberglass, silicon carbide (e.g., carborundum), ceramic fiber insulator, silicone or silicone foam, mineral wool, basalt, foamed glass, polyimide, calcium silicate, or silica. We also provide piping, parts of piping, or parts of reactors (such as bioreactors, adsorption beds, catalytic reactors, or distillation columns) surrounded by insulating, protective, or performance materials as described herein.

[0025] In some embodiments, the textile material includes an assembly as described herein, comprising one or more layers A t The layer contains hydrophobic or superhydrophobic functional properties, one or more B layers contain thermal insulation, protective or structural properties, and one or more A layers b The present invention provides a textile material in which the layers include hydrophilic or superhydrophilic functional properties. In some embodiments, one or multiple layers are provided. Number A t and / or A b The base material of the layer includes a woven material. For example, the woven material may be selected from textiles, polyamides, polyesters, cellulosic materials, cotton, wool, polymer films, stainless steel alloy woven materials, and aluminum alloy woven materials. In some embodiments, one or more layers of A t and / or A b The base material of the layer includes nylon or polyethylene terephthalate (PET). In some embodiments, one or more layers B include a material selected from polyester, fleece, wool, feathers, down, and other mainly organic materials. [Brief explanation of the drawing]

[0026] [Figure 1]This figure shows an exemplary embodiment of a composite material of layers for use in medical adhesive bandages. [Figure 2] This figure shows an exemplary embodiment of a composite material layer for use in performance outerwear clothing. [Figure 3] This figure shows an exemplary embodiment of a composite material consisting of layers of material for use in pipe insulation. [Figure 4] This figure shows an exemplary embodiment of a composite material of layers for use in medical casts. [Figure 5] This figure shows an exemplary embodiment of a composite material of layers for use in medical / surgical garments. [Modes for carrying out the invention]

[0027] This specification describes composite materials consisting of stacked layers of materials, as well as methods of use and applications thereof. The composite materials described herein include one or more functional ("A") layers and optionally one or more structural or bulk property ("B") layers. The functional layers include structured ceramics on a substrate material, which may be further functionalized by the application or deposition of additional surface chemical topcoat materials to provide desired functional properties and / or properties desirable for a particular application. At least a portion of the substrate surface is subjected to chemical conversion to provide a structured (e.g., nanostructured) ceramic material, and optional subsequent treatment results in further functionalization of the ceramic. Layers may be arranged to impart functional properties by directional methods, such as the transfer of vapor or thermal energy toward the ambient exposed surface. Layers may be arranged to impart functional properties by combination methods, such as a scratch-resistant layer and an insulating layer to provide both mechanical and thermal protection.

[0028] The A layer includes a structured ceramic and, optionally, a surface functional topcoat on the substrate surface to provide the substrate with one or more functional properties. A ceramic, e.g., a porous ceramic (e.g., metal oxide and / or metal hydroxide) surface modification composition is deposited on the surface of a textile or fabric substrate. The composition is provided on the surface of the substrate as a binderless surface modifier, e.g., a surface-immobilized ceramic material. In some embodiments, the ceramic material includes a metal oxide and / or hydroxide ceramic, e.g., a single metal or mixed metal oxide and / or hydroxide ceramic. In some embodiments, the ceramic material includes a metal oxide and a metal hydroxide ceramic, where the metal oxide and the metal hydroxide include the same or different single metal or mixed metal. In some embodiments, the ceramic material includes a metal oxide and / or metal hydroxide ceramic, where the substrate is hydrated with water or other compounds, resulting in a change in surface energy and potentially a change in the ratio of the metal oxide to metal hydroxide composition of the ceramic. In some embodiments, the ceramic material contains a metal hydroxide, in which case at least a portion of the metal hydroxide is in the form of a layered double hydroxide, for example, at least about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% of the metal hydroxide is a layered double hydroxide. To provide additional benefits, the inserted ions in the layered double hydroxide may be exchanged. In some embodiments of the compositions described herein, “metal oxide” or “metal hydroxide” may be in the form of a hydrate of a metal oxide or a metal hydroxide, respectively, or a portion of the metal oxide or metal hydroxide may be in the form of a hydrate of a metal oxide or a metal hydroxide, respectively.

[0029] Mixed metal oxides or mixed metal hydroxides may each contain, for example, more than one metal oxide or hydroxide, such as, but are not limited to, iron, cobalt, nickel, copper, manganese, chromium, titanium, vanadium, zirconium, molybdenum, tantalum, zinc, lead, tin, tungsten, cerium, praseodymium, samarium, gadolinium, lanthanum, magnesium, aluminum, or calcium.

[0030] In this specification, the surface modifier (e.g., a binderless porous ceramic material) is deposited onto a substrate without using a binder (e.g., by reaction with a metal on the substrate surface). In some embodiments, the surface modifier as described herein is immobilized on the substrate.

[0031] In some embodiments, the structured ceramic material is a nanostructured ceramic material.

[0032] In some embodiments, the structured ceramic material is subjected to additional chemical conversion treatment to produce a modified structure (e.g., nanostructure) ceramic material.

[0033] Non-limiting examples of binderless ceramic surface modifiers are provided in PCT application no. PCT / US19 / 65978, which is incorporated herein by reference in its entirety.

[0034] definition Numerical ranges provided herein include the numerical values ​​that define those ranges.

[0035] "A," "an," and "the" include plural references unless otherwise specified by the context.

[0036] When used herein and in the claims, the phrase "and / or" should be understood to mean "either or both" of the combined elements, that is, elements that exist sometimes conjugated and sometimes separately. Unless otherwise explicitly stated, other elements may exist at their discretion, whether related to or unrelated to the elements specifically identified by the "and / or" clause. Thus, as a non-restrictive example, when used in conjunction with unrestrictive language such as "includes," in one embodiment, A may refer to A without B (optionally including elements other than B); in another embodiment, B may refer to B without A (optionally including elements other than A); and in yet another embodiment, both A and B (optionally including other elements), and so on.

[0037] A "binder" or binder is any material or substance that holds or attracts other materials together to form a whole by mechanical, chemical, adhesive, or agglomeration.

[0038] "Binderless" specifically refers to the absence of a binder, particularly in the case of organic binders or resins (e.g., polymers, adhesives, tacks, asphalt) or inorganic binders (e.g., lime, cement glass, plaster, etc.).

[0039] A "capping agent" refers to a compound or active substance that slows crystal growth and allows for the modification of the morphology of nano-surfaces.

[0040] "Ceramics" refers to solid materials containing metals, nonmetals, or inorganic compounds with ionic and covalent bonds.

[0041] A "chemical conversion coating" refers to a surface layer in which reactants chemically react with the surface to be treated, transforming the substrate into a different compound. This treatment is typically not additive or depositional.

[0042] "Fabric" refers to a non-woven material that is constructed from fibers and may be bonded together by chemical, mechanical, thermal, and / or solvent treatments. Fabrics may include, for example, felt and other materials that are neither woven nor knitted.

[0043] "Fiber" refers to the threads or filaments from which textiles are formed.

[0044] "Hydrophilic" refers to a surface that has a high affinity for water. The contact angle may be very low and / or immeasurable.

[0045] "Layer" refers to a sheet, quantity, or thickness of material, typically one of several covering a surface or body supported by one or more supporting structures, or a self-supporting body.

[0046] "Layered double hydroxides" have a general sequence [AcB Z AcB] n This refers to a group of ionic solids characterized by a layered structure having, where c represents a layer of metal cations, A and B are layers of hydroxide anions, and Z is a layer of other anions and / or neutral molecules (such as water). Layered double hydroxides are also described in PCT application number PCT / US2017 / 052120, which is incorporated herein by reference.

[0047] In this specification, a "nanostructure" composition refers to a composition having at least one dimension less than 100 nanometers.

[0048] In fluid dynamics, "permeability" is a measure of a porous material's ability to allow a fluid to pass through it. While the permeability of a medium is related to its porosity, it is also related to the shape of the pores in the medium and the level of their connectivity.

[0049] "Pore size distribution" refers to the relative abundance or range or pore diameter of each pore size as measured by mercury intrusion porosimetry (MIP) and the Washburn equation.

[0050] Porosity is a measure of the amount of empty (i.e., "empty") space in a material, and is either a fraction of the volume of empty space relative to the total volume, between 0 and 1, or a percentage between 0% and 100%. Porosity can be measured by mercury intrusion porosimetry.

[0051] "Porous" refers to spaces, holes, or voids within a solid material.

[0052] "Superhydrophilic" refers to a surface that exhibits excessive hydrophilicity or an attractive force towards water. The contact angle of water with a superhydrophilic material is equal to zero degrees.

[0053] "Superhydrophobic" refers to a surface that is extremely difficult to wet. Superhydrophobic materials, in this case, On a superhydrophobic surface, the contact angle of a water droplet is greater than 150°. A highly hydrophobic contact angle is greater than 120°.

[0054] "Surface area per square meter of projected substrate area" refers to the actual measured surface area (usually measured in square meters) obtained by dividing it by the surface area of ​​the substrate if it were atomically smooth (no surface roughness) (also typically in square meters).

[0055] "Synergistic" or "combined" refers to the interaction or cooperation between two or more substances, materials, or agents that result in a combined effect that is higher (positive synergy) or lower (negative synergy) than the sum of their individual separate effects.

[0056] "Textiles" refer to flexible materials consisting of networks of natural or synthetic fibers. For example, textile materials can be made by combining fibers or groups of fibers through knitting, weaving, felting, tufting, or bonding, in which case the fibers include both natural and synthetic forms of all lengths, including metallic fibers. Textiles also include ropes and cords.

[0057] "Thickness" refers to the distance between the surface of the substrate and the top layer of the surface-modified material (e.g., ceramic).

[0058] "Topcoat" refers to a material or chemical treatment in which a surface and chemicals interact, bond, or disperse to form a modified surface through changes in surface energy, microbial resistance, color, thermal properties, conductivity, or reactivity. These property changes can be achieved on an atomic, molecular, feature, or overall length scale.

[0059] "Adjustable" refers to the ability to change or modify the function, characteristics, or quantity of a material.

[0060] "Vapor permeability" refers to the amount of vapor per unit time per unit area passing through a layer in a direction perpendicular to the layer's surface.

[0061] "Water column breakthrough pressure" refers to the relative height of a vertical water column at which the hydrostatic pressure acting on a layer at the bottom of the water column exceeds the capacity of the layer supporting the water column, resulting in water flow through the layer.

[0062] Composite material This specification discloses an assembly of layers of material. The layers are generally stacked and consist of an upper surface at the top of the stack and a lower surface at the bottom of the stack. The upper surface generally contacts the surrounding environment (e.g., air) in which the assembly is placed or used. The lower surface may contact or be in close proximity to a device, surface, or solid in which the assembly is used, for example, a device or surface that needs to be protected or for the comfort of a solid in a particular environment of use.

[0063] The layer stacking includes a material containing ceramics (e.g., binderless ceramics such as binderless porous ceramic materials) on a substrate (referred to herein as layer "A"). Layer A imparts desired functional properties to the composite. For example, the ceramic material can impart one or more properties selected from those selected from hydrophobicity, inhibition of microbial growth, flame retardancy, hydrophilicity, corrosion resistance, ice or condensate management, anti-icing, anti-frost, superhydrophobicity, superhydrophilicity, inhibition of microbial growth, corrosion resistance, electromagnetic regulation, thermal modulation, permeability, dynamic wind resistance, and / or color, or a combination thereof. Some embodiments of the composite described herein have the top surface of the composite It includes an upper A layer (facing the surrounding environment) and a lower A layer (facing the device, surface, or solid in which the assembled product is used). The binderless porous ceramic material as described herein is present on both the upper and lower surfaces. The binderless porous ceramic material on each A layer may be the same as or different from the other A layers in the assembled product.

[0064] Some stacking of layers involves one or more A layers on top of the stacking ("A t The "A" layer) and one or more A layers ("A" layer) located at the bottom of the stack. b The assembly includes one or more "B" layers between the "B" layer and the "B" layer, each "B" layer comprising structural and / or insulating material. In some embodiments, the assembly includes one B layer comprising structural and / or insulating material. In other embodiments, the assembly includes two or more B layers comprising structural and / or insulating material, each B layer may be composed of the same or different material or composition as the other B layers in the assembly.

[0065] In some embodiments, the laminated product is made of one layer A t Layer and Layer A b Includes layer, A t The layer is A b The layers may be made of the same or different materials or compositions (e.g., the same or different substrates and / or ceramic compositions). In some embodiments, the composite consists of two or more layers of A t Layers (i.e., multiple At layer(s) and / or two or more A b layers (i.e., a plurality of A b layers), and each A t layer and / or each A b layer may be composed of the same or different materials or compositions (e.g., the same or different substrates and / or ceramic compositions) from other A layers (i.e., other A t and / or A b layers).

[0066] In some embodiments, at least one A layer of the integrated product (e.g., at least one A t and / or A b layer) imparts to the integrated product one or more functional properties selected from, for example, ice or condensate management (managing the material to form, collect, and move ice or condensate in a desired manner, such as anti-icing resistance, or installing such materials), anti-icing performance or frost delay characteristics, superhydrophobicity (e.g., preventing fouling by water ingress), superhydrophilicity (e.g., sucking up water from the surface to minimize wetting time and / or prevent moisture-related damage), antimicrobial regulation (inhibiting, removing, or preventing microbial growth), corrosion resistance or prevention, electromagnetic regulation (changing electromagnetic properties, such as diffusion or specular radiation, diffusion or specular reflection, adsorption, transmission), thermal modulation, flame retardancy, breathability (enabling water vapor to be transported through the material), dynamic wind resistance (non-linear response of vapor transmission to the applied wind speed), mechanical protection (scratch or impact resistance), and color and / or other aesthetic properties, or combinations thereof.

[0067] In some embodiments, the A t layer including the upper surface of the integrated product and the A b layer including the lower surface of the integrated product impart different functional properties. In one embodiment, the A t layer including the upper surface of the integrated product is hydrophobic or superhydrophobic, and the A b layer including the lower surface of the integrated product is hydrophilic or superhydrophilic. In another embodiment, the A tThe layer is hydrophobic or superhydrophobic and includes the lower surface of the composite product A b The layer is antimicrobial. In another embodiment, A includes the upper surface of the composite. t The layer is hydrophobic or superhydrophobic and includes the lower surface of the composite product A b The layer is antimicrobial and includes the bottom surface of the composite product. b A on the layer b The layers are hydrophobic or superhydrophobic.

[0068] In certain embodiments, a topcoat material is deposited or applied on the ceramic material to impart and / or enhance one or more functional properties to layer A of the composite as described herein. In some embodiments, the functionality imparted by the topcoat material applied or deposited on the ceramic as described herein is enhanced compared to the functionality of the same material applied or deposited on the same substrate without the ceramic. In some embodiments, the ceramic material and the topcoat The topcoat material synergistically imparts one or more functional properties that are superior to the same functional properties imparted by either a ceramic material or a topcoat material independently deposited on the same substrate surface.

[0069] In some embodiments, hydrophobic functionality is provided by fatty acids such as stearic acid or Scotchgard® (3M). In some embodiments, antimicrobial functionality is provided by SmartShield Antimicrobial Protective Spray (Sylvane). In some embodiments, flame retardant functionality is provided by No Burn. 1005 Fabric Fire Protection (No-Burn, Inc.) or halon-containing compounds are provided. In some embodiments, hydrophilic functionality is provided by polyvinylpyrrolidone (PVP), polyurethane, polyacrylic acid (PAA), polyethylene oxide (PEO), or polysaccharide materials.

[0070] In certain non-limiting embodiments, the topcoat may comprise a paint, a paint binder, a hydrophobic material, a hydrophilic material, a metal or metal-containing compound, a pigment and / or colorant, or an antimicrobial agent.

[0071] In some embodiments, the topcoat is a surface-modifying topcoat that reduces the viscous drag of external or internal fluids on the surface. In some embodiments, the nanostructured coating composition and the surface-modifying topcoat that reduces the viscous drag of external or internal liquids on the surface are deposited on the surface, further providing additional benefits such as corrosion resistance, fouling resistance, self-cleaning, heat transfer properties, optical properties, chemical inertness, and other useful properties or combinations of properties.

[0072] In some embodiments, the topcoat is or contains an antimicrobial agent. For example, the antimicrobial agent may be a charge-transfer compound or active substance that disrupts the movement of ions across the cell membrane, such as a quaternary amine. In some embodiments, the antimicrobial agent is a beta-lactam, aminoglycoside, tetracycline, chloramphenicol, macrolide, lincosamide, sulfonamide, quinolone, polyene, azole, or griseofulvin.

[0073] In some embodiments, the topcoat is or contains a paint binder. For example, the paint binder may be alkyd, acrylic, vinyl acrylic, vinyl acetate / ethylene (VAE), polyurethane, polyester, melamine resin, epoxy, silane, or oil.

[0074] In some embodiments, the ceramic surface modifier has a partially filled porous structure. For example, the voids may be partially filled with a second ceramic material (e.g., a ceramic material different from the ceramic material on the substrate surface) or with a head group and a tail group, for example, the head group may include a silane group, a phosphonate group, a phosphonic acid group, a carboxylic acid group, a vinyl group, an alcohol group, a hydroxide group, a thiolate group, a thiol group, and / or an ammonium group (e.g., a quaternary ammonium group), and the tail group may include a hydrocarbon group, a fluorocarbon group, a vinyl group, a phenyl group, an epoxide group, an acrylic group, an acrylate group, a hydroxyl group, a carboxylic acid group, a thiol group, and / or a quaternary ammonium group.

[0075] In some embodiments, at least one layer B of the composite imparts one or more structural and / or insulating properties selected from thermal resistance, electrical resistance, structural support, mechanical padding, and fluid transport, or a combination thereof. In some embodiments, at least one layer B of the composite imparts glass fiber, loose ceramic, or other inorganic material such as Includes ceramic materials.

[0076] Binderless ceramic The "A" layer in the layered composite as described herein comprises a binderless porous ceramic material on a substrate. Non-limiting examples of such ceramic materials are described in PCT / US19 / 65978, which is incorporated herein by reference in whole.

[0077] The substrate for layer A of a laminate (stack) of the materials described herein is typically a flexible material suitable for the intended use of the laminate. In some embodiments, the substrate is a woven material such as stainless steel alloy, carbon steel alloy, or aluminum alloy woven material, but is not limited to these. In some embodiments, the substrate is a textile, polymer (e.g., polyamide, polyester), cellulosic material, natural material (e.g., cotton, wool), or synthetic material (e.g., nylon, PET). In some embodiments, the substrate includes synthetic or natural fiber textiles that are woven, non-woven, or knitted. In some embodiments, the substrate includes a metal mesh, metal screen, or metal cloth. In some embodiments, the substrate includes a natural or synthetic polymer film or substrate (e.g., a coating of a thin (film) or thick (substrate) polymer (e.g., plastic) material that is not necessarily woven into a textile).

[0078] In some embodiments, the binderless ceramic material is approximately 1.5 m² per square meter of projected substrate area. 2 ~100m 2 , about 10m 2 ~about 1500m 2 , or approximately 70m 2 ~about 1000m 2 Surface area; approximately 15 m² per gram of ceramic material 2 ~about 1500m 2 , or approximately 50m 2 ~about 700m 2 Surface area; average pore diameter of approximately 5 nm to 200 nm, 2 nm to 20 nm, or 4 nm to 11 nm; thickness of up to approximately 100 micrometers, up to approximately 50 micrometers, up to approximately 25 micrometers, up to approximately 20 micrometers, or 0.2 micrometers to approximately 25 micrometers; porosity of approximately 5% to 95%, 10% to 90%, 30% to 70%, 30% to 95%, or greater than approximately 10%; approximately 100 mm when determined by mercury intrusion porosimetry. 3 / g ~ approx. 7500mm 3 The void volume per g; including any combination of these.

[0079] In some embodiments, the ceramic material (e.g., metal oxides, metal hydroxides, and / or hydrates thereof) includes one or more of zinc, aluminum, manganese, magnesium, cerium, copper, gadolinium, tungsten, tin, lead, and cobalt. In some embodiments, the ceramic material includes transition metals, Group II elements, rare earth elements (e.g., lanthanum, cerium, gadolinium, praseodymium, scandium, yttrium, samarium, or neodymium), aluminum, tin, zinc, or lead.

[0080] In some embodiments, the binderless ceramic surface modifier includes thicknesses of about 0.5 or 1 to about 100 micrometers, or about 0.5 micrometers to about 20 micrometers, or up to about 50 micrometers, or up to about 25 micrometers. In some embodiments, the binderless porous ceramic material includes thicknesses of about 0.2 micrometers to about 25 micrometers. In some embodiments, the thickness is at least one of about 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 micrometers. In some embodiments, the thickness is one of the following: about 0.2 to about 0.5, about 0.5 to about 1, about 1 to about 5, about 3 to about 7, about 5 to about 10, about 7 to about 15, about 10 to about 15, about 12 to about 18, about 15 to about 20, about 18 to about 25, about 0.5 to about 15, about 2 to about 10, about 1 to about 10, about 3 to about 13, about 0.5 to about 15, about 0.5 to about 5, about 0.5 to about 10, or about 5 to about 15 micrometers.

[0081] In some embodiments, the binderless ceramic surface modifier is approximately 1.1 m² per square meter of projected substrate area. 2 ~approximately 100m 2 This includes the surface area. In some embodiments, the binderless porous ceramic material has a surface area of ​​approximately 10 m² per square meter of projected substrate area. 2 ~about 1500m 2This includes the surface area. In some embodiments, the surface area is at least about 10, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, or 1500 m² per square meter of projected substrate area. 2 In some embodiments, the surface area is approximately 10 to 100, 50 to 250, 150 to 500, 250 to 750, 500 to 1000, 750 to 1200, 1000 to 1500, 70 to 1000, 150 to 800, 500 to 900, or 500 to 1000 m² per square meter of projected substrate area. 2 It is one of the following:

[0082] In some embodiments, the binderless ceramic material is approximately 15 m³ per gram of ceramic material. 2 ~about 1500m 2 This includes the surface area. In some embodiments, the surface area is at least about 15, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, or 1500 m² per gram of ceramic material. 2 In some embodiments, the surface area is approximately 15 to 100, 50 to 250, 150 to 500, 250 to 750, 500 to 1000, 750 to 1200, 1000 to 1500, 50 to 700, 75 to 600, 150 to 650, or 250 to 700 m² per gram of ceramic material. 2 It is one of the following:

[0083] In some embodiments, the binderless ceramic surface modifier is porous and includes a mesoporous mean pore size in the range of about 2 nm to about 50 nm. In other embodiments, the mean pore size is in the range of about 50 nm to about 1000 nm. In some embodiments, the binderless porous ceramic material includes a mean pore diameter of about 2 nm to about 20 nm. In some embodiments, the mean pore diameter is at least one of about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 nm. In some embodiments, the mean pore diameter is one of about 2 to about 5, about 4 to about 9, about 5 to about 10, about 7 to about 12, about 9 to about 15, about 12 to about 18, about 15 to about 20, about 4 to about 11, about 5 to about 9, about 4 to about 8, or about 7 to about 11 nm.

[0084] In some embodiments, the binderless ceramic surface modifier is porous and has a porosity of about 5% to about 95%. In some embodiments, the porosity may be at least about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% or more. In some embodiments, the porosity is about 10% to about 90%, about 30% to about 90%, about 40% to about 80%, or about 50% to about 70%.

[0085] In some embodiments, the binderless porous surface modifier is porous and has a transmittance of about 1 to 10,000 millidarcy. In some embodiments, the transmittance may be at least about 1, 10, 100, 500, 1,000, 5,000, or 10,000 millidarcy. In some embodiments, the transmittance is about 1 to about 100, about 50 to about 250, about 100 to about 500, about 250 to about 750, about 500 to about 1,000, about 750 to about 2,000, about 1,000 to about 2,500, about 2,000 to about 5,000, about 3,000 to about 7,500, about 5,000 to about 10,000, about 1 to about 1,000, about 1,000 to about 5,000, or about 5,000 to about 10,000 millidarcy.

[0086] In some embodiments, the binderless ceramic material is porous and, when determined by mercury intrusion porosimetry, has a density of approximately 100 mm. 3 / g ~ approx. 7500mm 3 The void volume includes a void volume of at least about 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, or 7500 mm². 3 The void volume is one of the following: / g. In some embodiments, the void volume is approximately 100-500, approximately 200-1000, approximately 400-800, approximately 500-1000, approximately 800-1500, approximately 1000-2000, approximately 1500-3000, approximately 2000-5000, approximately 3000-7500, approximately 250-5000, approximately 350-4000, approximately 400-3000, approximately 250-1000, approximately 250-2500, approximately 250-5000, or approximately 500-4000 mm 3 It is either / g or

[0087] A ceramic deposit layer can be designed to impart one or more functional features to a layer of materials as described herein, and / or to provide a bonding surface for a functionalized topcoat.

[0088] Methods for producing ceramic materials Ceramic surface modifiers, such as binderless ceramic porous surface modifiers as described herein, can be prepared by a method comprising immersing or otherwise contacting a clean substrate (e.g., a textile substrate) with an aqueous solution containing one or more metal salts for a duration sufficient to achieve a porous coating composition of a desired thickness on the substrate. The solution may also contain a chelating agent or a complexing agent. The pH, temperature, and deposition time (e.g., about 5 minutes to about 300 minutes) are appropriate for the desired thickness, morphology, and surface porosity of the surface modifier to be prepared. The pH of the solution can be adjusted over a range of 1 to 12 to adjust the surface modification characteristics (e.g., desired crystal structure and / or surface porosity) by adding acidic or basic materials. The metal salts may include, for example, salts of magnesium, aluminum, cerium, iron, cobalt, gadolinium, manganese, tungsten, zinc, vanadium, titanium, and / or tin. The salt may be a metal cation salt containing, for example, an anion of a sulfate, nitrate, chloride, or acetate. In other embodiments, a sodium cation salt is used with a metal anion such as sodium tannate. In some embodiments, the metal salt concentration is about 1 mM to about 5 M in aqueous solution. In some embodiments, a chelating agent or complexing agent such as citric acid, urea, diamine, triamine, or tetramine, thioglycerol, oleic acid or other fatty acids, polyol, Tween 80 or other surfactants is included at a concentration of about 1 mM to about 5 M. pH adjusters and buffers may be optionally included.

[0089] In some embodiments, the substrate is cleaned by washing and rinsing, as well as by various metal cleaning solutions or cleaning solutions outlined for specific substrates, to remove loosely adhering, unattached debris. Various treatment conditions are permissible to successfully remove loosely adhering, unattached debris.

[0090] In some embodiments, the substrate is treated with an alkali-based cleaning solution to saponify and remove oils and greases from the substrate. One example is the use of caustic soda in an aqueous solution having a pH of approximately 11 or higher. Other embodiments may use steam or solvent-based methods or alternative degreasing means such as patented cleaning agents. A variety of treatment conditions are permissible for successful removal of surface oils and greases.

[0091] In some embodiments, the substrate is further prepared and its surface homogenized by using a known method for treating the surface of the substrate material by alkaline etching. This process yields oxides and surface hydroxides, reaction products, and intermetallic materials, some of which are insoluble in the etching solution and must be removed from the substrate by rinsing, mechanical means, or by treatments known in the art as smut removal. Smut removal or deoxidation solutions typically contain acidic solutions such as chromic acid, sulfuric acid, nitric acid, or phosphoric acid, or combinations thereof. Ferric sulfate solutions may also be used. Smut removal solutions remove reaction products, oxides, hydroxides, and intermetallic materials by solubilization or mechanical removal (e.g., silicon-containing particles). Many patented surface conditioning materials are available. Other surface conditioning alternatives, such as acidic etching, electropolishing, sonication, or other surface finishing conditioning methods, can also be successfully used to remove substrate oxides, hydroxides, reaction products, and intermetallic compounds. A variety of treatment conditions are permissible for successful surface conditioning of the substrate and removal of smut.

[0092] In other embodiments, alternative surface preparations for subsequent processing include activating the substrate by exposure to a strong oxidizing agent such as persulfates, hypochlorites, permanganates, or oxidizing acids, UV / ozone, or oxygen plasma.

[0093] In some embodiments, the substrate is treated using one or more processing steps, in which the substrate is reacted with a processing bath to form a nanostructured material. The solutions described herein are aqueous solution-based and contain in aqueous solution about 1 mM to about 5 M of a metal salt and / or a chelating agent or complexing agent such as a polyol, polyether, urea, secondary or higher amine, diamine, triamine, or tetraamine at a concentration of about 1 mM to about 5 M. The processing conditions are in the range of 65 to 200 kPa, excluding hydrostatic pressure at various tank depths, and the temperature over the liquid phase equilibrium for these solutions is in the range of -20°C to 190°C, depending on the concentration and composition.

[0094] In some embodiments, the substrate is removed from the solution and heated at a temperature of approximately 100°C to approximately 1000°C for a period of approximately 0 to approximately 5 hours. In some embodiments, the substrate is removed from the solution and heated at a temperature of approximately 100°C to approximately 1000°C for a period of approximately 0 to approximately 24 hours to remove substantially all water from the substrate and the metal oxide surface modification. The surface condition may be further modified using controlled atmospheric furnace treatment.

[0095] Optionally, the substrate is immersed in a diluted solution of functional molecules (e.g., less than about 2%, or about 0.001% to about 2%) containing a suitable solvent that can chemically bond to the ceramic surface so that the pores are functionalized but remain open.

[0096] In some embodiments, the method includes partially filling the voids with one, two, or more materials. For example, the method includes (a) taking a substrate having a surface-immobilized porous ceramic surface and immersing it in a diluted solution of functional molecules that can chemically bond to the ceramic surface such that the voids are functionalized but remain open, and / or (b) immersing the substrate in another solution for depositing further ceramic in the voids and on the surface as described above, and heating to expel the water as described above; and optionally repeating (a) or (b) or (a) and (b) to deposit multiple layers of various functional molecules and / or metal oxides in the voids. Other non-limiting methods for introducing the first or second material may be used, such as spraying, pouring, dropping, or vapor deposition.

[0097] In some embodiments, the method includes completely filling the voids with one or more materials. For example, the method involves taking a substrate having a surface-immobilized porous ceramic surface and immersing it in a more concentrated solution (e.g., about 1% to about 20%) of functional molecules that can chemically bond to the ceramic surface so that the voids are filled with the material; and / or immersing the substrate in another metal salt solution as described above and removing the water as described above. This includes dispensing and completely filling the voids. Other non-limiting methods for introducing the void-filling material may be used, such as spraying, pouring, dripping, fogging, or gas-phase deposition.

[0098] Exemplary Embodiments Exemplary embodiments of composite materials as described herein are provided below. Combinations of materials and uses are provided as examples, but are not intended to be limiting.

[0099] Medical bandages The composite materials described herein can be configured for use in medical adhesive bandages. The bandage is designed to avoid external moisture through an outer layer that maintains cleanliness and has superhydrophobic properties, an adsorbent layer for removing moisture from the wound, a padding layer for providing protection to the wound, and a hydrophilic inner layer that helps maintain the dryness of the wound. Each of the layers can be further functionalized with antimicrobial properties, or with therapeutic agents, topical agents, or other materials.

[0100] As shown in Figure 1, an example of such an composite material is one in which a superhydrophobic ceramic is included on a synthetic substrate material (e.g., nylon or PET). t A layer containing superhydrophilic ceramic on a natural base material (cotton) b Includes layers. A t and A b The B layer between the layers provides absorption, structure, and padding properties.

[0101] Performance outerwear clothing The composite material described herein can be constructed for use in clothing such as performance outerwear. It can provide an inner layer that absorbs moisture that has passed through the outer, surrounding upper layer, an insulating layer, and an outer layer that has high water vapor permeability and repels water and oil, for example, to promote cleanliness.

[0102] As shown in Figure 2, an example of such an composite is A, which includes a superhydrophobic ceramic on a synthetic substrate (e.g., nylon or PET). t A layer and A containing a superhydrophobic ceramic on a synthetic substrate (e.g., nylon or PET) b Includes layers. A t and A b The B layer between the layers provides thermal insulation properties.

[0103] Pipe insulation The composite materials described herein can be configured for use as pipe insulation or pipe protection. The composite materials are designed as a high-temperature insulation jacket comprising a hydrophobic "peripheral" liner and a hydrophilic "high-temperature" liner surrounding and in contact with the pipe. For example, the peripheral liner can be constructed from a metal mesh (e.g., stainless steel mesh) with a ceramic (e.g., nanostructured) surface and hydrophobic properties that maintain insulation performance by preventing moisture from penetrating the insulation. The high-temperature liner can be constructed from a metal mesh with a ceramic (e.g., nanostructured) surface that exhibits capillary action, absorbing moisture and promoting evaporation. The technical and commercial advantages of this system are that, by combining a metal mesh layer and a barrier layer, it provides the same advantages as existing insulation jacket materials at a fraction of the cost. The system can also operate at higher temperatures than existing Teflon®-based solutions, and unlike metal foil, the system is vapor permeable while being externally waterproof.

[0104] As shown in Figure 3, an example of such an composite material is A, which contains superhydrophobic ceramic on a metal mesh substrate. t A layer containing a superhydrophilic ceramic on a metal mesh substrate b Includes layers. A t and A b The B layer between the layers provides thermal insulation properties.

[0105] Medical cast As an extension of the medical adhesive bandage applications described above, the composite material described herein can be configured for use as a medical cast. An additional antimicrobial layer can be provided at the bottom of the layer stacking to prevent infection and / or odor associated with microbial entry, which can be difficult to clean. Additional layers can also be added.

[0106] As shown in Figure 4, an example of such an composite material is A, which contains a superhydrophobic ceramic on a synthetic substrate material (e.g., nylon or PET). tA includes a layer and the bottom surface of the composite, and contains an antimicrobial ceramic on a synthetic substrate material (e.g., nylon or PET). b Includes layers. Includes the bottom surface of the laminated product. b A on the layer b The layer comprises a superhydrophilic ceramic on a synthetic substrate material (e.g., nylon or PET). t and A b The B layer between the layers provides structural and padding properties.

[0107] Medical / surgical clothing The composites described herein can be constructed for use in clothing / surgical equipment or clothing. The composites are designed to be breathable (high moisture transport rate), antimicrobial and splash-proof (water-repellent), and to provide barrier properties without sacrificing comfort.

[0108] As shown in Figure 5, an example of such an composite material is A, which contains a superhydrophobic ceramic on a synthetic substrate material (e.g., nylon or PET). t A layer comprising an antimicrobial ceramic on a synthetic (e.g., nylon or PET) or natural (e.g., cotton) substrate material. b Includes layers.

[0109] Other uses Additional non-limiting examples of applications in which laminates of the materials described herein may be used include those having layers listed from the bottom layer to the top layer (exposed to the surroundings): • Filtration / Separation: Size exclusion (retention) layer (A) - Structural preservation layer (B) - Antimicrobial layer (A) • Packing material: Moisture transport layer (A) - Structural preservation layer (B) - Padding layer (B) - Water repellent layer (A) • Hospital floor covering: Padding layer (B) - Moisture transport layer (A) - Ventilation layer (A) - Moisture absorption layer (A) - Antimicrobial layer (A) • Protective mask: Moisture transport layer (A) - Breathable layer (A) - Antimicrobial layer (A) - Chemical resistant layer (A) - Water repellent layer (A) • Protective clothing: Moisture transport layer (A) - Breathable layer (A) - Chemical resistant layer (A) - Water repellent layer (A) - Insulation layer (B) - Structural layer (B) - Flame retardant layer • Architectural textiles: Moisture transport layer (A) - Ventilation layer (A) - Chemical-resistant layer (A) - Water-repellent layer (A) - Heat insulation layer (B) - Flame-retardant layer (A) - Color layer (A) - UV-stabilizing layer (A) Geotextile: Moisture transport layer (A) - breathable layer (A) - chemical resistant layer (A) - water repellent layer (A) - heat insulating layer (B) - structural layer (B) - environmentally stable layer (A).

[0110] The order of layers in the products and uses described above may differ from those illustrated, and in some embodiments, the multiple functions described may be combined into a single layer.

[0111] The following examples are illustrative and not intended to limit the invention. [Examples]

[0112] Example 1. Method for testing the performance of layered stacking. The following method was used to determine the properties of the composite materials as described herein.

[0113] The contact angle of the layer was determined using the droplet method, which involves metering and distributing 10 microliters of droplets onto the surface. Images of the droplets were taken from the front using a camera positioned at the same height as the surface. The contact angle was determined by measuring the angle between the surface and the surface-to-liquid-vapor interface at the contact surface. This process was repeated three times, and the reported contact angle is the average of the three individual measurements.

[0114] The vapor permeability of the stacked layers was determined as follows: Each layer was cut to the same size and collected. A container filled with a known amount of dry desiccant was sealed to the underside of the lower layer of the stack. In stacks consisting of multiple layers, the layers were sealed together along their edges so that the only way vapor could penetrate the stack was by passing through the upper layer. The stacks and desiccant were placed in a chamber with controlled temperature and humidity. Samples were collected every 30 minutes to determine the amount of water vapor from the chamber that passed through the layers and was adsorbed onto the desiccant. When the mass of the desiccant increased by 10%, the test was stopped and the rate of vapor permeation through each stack per unit area per unit time was determined.

[0115] The water column break pressure was determined as follows: A vertical tube with an inner diameter of 12.7 mm was sealed against the upper layer of the stack. In stacks consisting of multiple layers, the layers were sealed together along their edges so that water could only enter or exit the stack by flowing through the upper and lower layers, respectively. The tube was filled by injecting water downwards from the side of the tube so that the water would not directly affect the upper layer of the stack. Water was injected in increments, raising the height of the water column by 1 cm at a time, followed by a 5-second period during which no water was injected. The water column was filled using this method until the height of the water column began to decrease, indicating breakthrough of water in the water column through the material stack. The maximum filling height for each sample was recorded.

[0116] Example 2 The functionalized mesh material, as described in the examples below, was prepared as follows: The mesh substrate was first immersed in an acetone bath, then in an IPA bath, to remove any residual oil. The parts were then air-dried for 15 minutes. Next, the mesh substrate was placed in a production bath containing 20-250 mM nitric acid or sulfuric acid metal salt or a mixture of nitric acid or sulfuric acid metal salts, and similar molar amounts of diamine, triamine, or tetramine, which can react and precipitate at a reaction temperature of 50-85°C. The assembled product was kept in the bath for a period ranging from about 5 minutes to about 3 hours. The assembled product was removed, drained, and placed in a furnace for drying and / or calcination at a heat treatment of 50-600°C for several minutes to several hours. This deposition and calcination step is optional and can be repeated if desired. After cooling, the parts were further processed and / or tested as described in the examples below.

[0117] Example 3 A stainless steel mesh layer was coated with a ceramic material composed of manganese oxide to provide surface hydrophilic properties. The water contact angle was measured to be less than 5 degrees by the droplet method. The layer was placed in a cup containing approximately 1 cm of deionized water, and a portion of the layered sample was brought into contact with the deionized water. After 2 minutes, the capillary rise, as observed by the visible wet line, was determined to be approximately 3 cm above the sample above the liquid surface. The capillary rise was determined as described in PCT application number PCT / US19 / 65978 (see, for example, Figures 1A-1C). The vapor transmission rate was 130 g / hour / m³. 2 It was determined that the layer could not support any measurable height of water column overpressure.

[0118] Example 4 A stainless steel mesh layer was coated with a ceramic material composed of manganese oxide. The surface was then functionalized using a diluted solution of hexadecylphosphonic acid in isopropanol, thereby imparting hydrophobic properties. The water contact angle was measured at 151 degrees by the droplet method. The layer was placed in a cup containing approximately 1 cm of deionized water. After 2 minutes, no significant water rise was observed above the liquid level. The vapor transmission rate was 145 g / hour / m². 2 It was determined that the water column break pressure was 25 cm in water head.

[0119] Example 5 A stainless steel mesh layer without any surface treatment was tested. The water contact angle was measured at 20 degrees by the droplet method. The layer was placed in a cup containing approximately 1 cm of deionized water. After 2 minutes, no significant rise of water was observed above the liquid level. The vapor transmission rate was 152 g / hour / m². 2 It was determined that the layer could not support any measurable height of water column overpressure.

[0120] Example 6 A fiberglass insulation layer with a thickness of 5.08 cm and a thermal insulation value of R-6.7 was tested. The vapor transmission rate was 48 g / hour / m². 2 It was determined that the layer could not support any measurable height of water column overpressure.

[0121] Example 7 A two-layer stack was tested. The upper layer was a hydrophobic stainless steel mesh as described in Example 3. The lower layer was a fiberglass insulator as described in Example 5. The two layers were joined together by sealing the edges with Kapton tape to prevent compression of the insulating layer. The vapor transmission rate of the entire stack was 43 g / hour / m². 2 It was determined that the water column break pressure for the entire stack was determined to be 23 cm in water head.

[0122] Example 8 A two-layer stack was tested. The upper layer was a stainless steel mesh without any surface treatment as described in Example 4. The lower layer was a fiberglass insulator as described in Example 5. The two layers were joined together by sealing the edges with Kapton tape to prevent compression of the insulating layer. The vapor transmission rate of the entire stack was 49 g / hour / m². 2 It was determined that the layer could not support any measurable height of water column overpressure.

[0123] Example 9 A three-layer stack was tested. The top layer was a hydrophobic stainless steel mesh as described in Example 3. The middle layer was a fiberglass insulator as described in Example 5. The bottom layer was a hydrophilic stainless steel mesh as described in Example 2. The three layers were joined together by sealing the edges with Kapton tape to prevent compression of the insulating layer. The vapor transmission rate of the entire stack was 53 g / hour / m². 2 It was determined that the water column break pressure for the entire stack was determined to be 22 cm in water head.

[0124] Example 10 A three-layer stack was tested. The top layer was a stainless steel mesh without any surface modification, as described in Example 4. The middle layer was a fiberglass insulator, as described in Example 5. The bottom layer was a stainless steel mesh without any surface modification, as described in Example 4. The vapor transmission rate of the entire stack was 55 g / hour / m². 2 It was determined that the layer could not support any measurable height of water column overpressure.

[0125] Example 11 An aluminum mesh layer is coated with a ceramic material composed of magnesium oxide, thereby providing surface hydrophilic properties. The water contact angle is measured to be less than 5 degrees by the droplet method. The layer is placed in a cup containing approximately 1 cm of deionized water. After 2 minutes, the capillary rise is determined to be approximately 5 cm above the liquid surface. The vapor transmission rate is 150 g / hour / m³. 2 It is determined that, when the water column break pressure is tested, the layer cannot support a water column of any measurable height.

[0126] Example 12 An aluminum mesh layer is coated with a ceramic material composed of magnesium oxide. The surface is then functionalized using a diluted solution of hexadecylphosphonic acid in isopropanol, thereby providing surface hydrophobic properties. The water contact angle is measured to be 160 degrees by the droplet method. The layer is placed in a cup containing approximately 1 cm of deionized water. After 2 minutes, no significant water rise is observed above the liquid level. The vapor transmission rate is 150 g / hour / m². 2 It is determined that the water column break pressure is 100 cm of water head.

[0127] Example 13 An aluminum mesh layer without any surface preparation was tested. The water contact angle was measured to be 20 degrees by the droplet method. The layer was placed in a cup containing approximately 1 cm of deionized water. After 2 minutes, no significant rise of water was observed above the liquid level. The vapor transmission rate was 153 g / hour / m². 2 It is determined that the layer could not support any measurable height of water column overpressure when tested for water column burst pressure.

[0128] Example 14 A two-layer stacking test is conducted. The upper layer is a hydrophobic aluminum mesh as described in Example 11. The intermediate layer is a fiberglass insulator as described in Example 5. The two layers are joined together by sealing the edges with Kapton tape to prevent compression of the insulating layer. The vapor transmission rate of the entire stack is 48 g / hour / m². 2It is determined that the water column break pressure for the entire stack is determined to be a water head of 62 cm.

[0129] Example 15 The two-layer stacking is tested. The upper layer is an aluminum mesh without any surface treatment, as described in Example 12. The intermediate layer is a fiberglass insulator, as described in Example 5. The two layers are joined together by sealing the edges with Kapton tape to prevent compression of the insulating layer. The vapor transmission rate of the entire stack is 48 g / hour / m². 2 It is determined that, when the water column break pressure is tested, the layer cannot support a water column of any measurable height.

[0130] Example 16 A three-layer stacking test is conducted. The top layer is a hydrophobic aluminum mesh as described in Example 11. The middle layer is a fiberglass insulator as described in Example 5. The bottom layer is a hydrophilic aluminum mesh as described in Example 10. The three layers are joined together by sealing the edges with Kapton tape to prevent compression of the insulating layer. The vapor transmission rate of the entire stack is 48 g / hour / m². 2 It is determined that the water column break pressure for the entire stack is determined to be a water head of 62 cm.

[0131] Example 17 A three-layer stacking test is conducted. The top layer is an aluminum mesh without any surface treatment, as described in Example 12. The middle layer is a fiberglass insulator as described in Example 5. The bottom layer is an aluminum mesh without any surface treatment, as described in Example 12. It is an aluminum mesh. The three layers are joined together by sealing the edges with Kapton tape to prevent the insulating layer from being compressed. The vapor transmission rate of the entire stack is 47 g / hour / m 2 It is determined that, when the water column break pressure is tested, the layer cannot support a water column of any measurable height.

[0132] Example 18 A moisture barrier layer of a polyester film with a thickness of 0.005 cm was tested. The vapor transmission rate was 1 g / hour / m². 2 It was determined that the water column break pressure was greater than 200 cm in water head.

[0133] Example 19 A two-layer stack was tested. The upper layer was a polyester film as described in Example 16. The lower layer was a fiberglass insulator as described in Example 4. The vapor transmission rate was 1 g / hour / m². 2 It was determined that the water column break pressure was greater than 200 cm in water head.

[0134] Example 20 A 40d (40 denier) woven polyamide textile layer was coated with a ceramic material composed of magnesium oxide, thereby obtaining surface hydrophilic properties. The water contact angle was measured to be less than 5 degrees by the droplet method. The vapor transmission rate was 175 g / hour / m². 2 It was determined that the layer could not support any measurable height of water column overpressure.

[0135] Example 21 A 40d woven polyamide textile layer was coated with a ceramic material composed of magnesium oxide. The surface was then functionalized using a diluted solution of hexadecylphosphonic acid in isopropanol, thereby obtaining surface hydrophobic properties. The vapor transmission rate was 170 g / hour / m². 2 It is determined that the water column break pressure is 55 cm at the water head.

[0136] Example 22 A 40d woven polyamide textile layer without any surface treatment was tested. The vapor transmission rate was 170 g / hour / m². 2 It was determined that the layer could not support any measurable height of water column overpressure.

[0137] Example 23 A Thinsulate G80 layer with a thickness of 1.1 cm and an insulating value of R-1.6 will be tested. The vapor transmission rate will be 100 g / hour / m². 2 It is determined that, when the water column break pressure is tested, the layer cannot support a water column of any measurable height.

[0138] Example 24 A two-layer stacking test was conducted. The upper layer was a hydrophobic 40d woven polyamide textile as described in Example 19. The lower layer was Thinsulate G80 as described in Example 21. The vapor transmission rate of the entire stacking was 100 g / hour / m². 2 It is determined that the water column break pressure for the entire stack is determined to be a water head of 55 cm.

[0139] Example 25 The two-layer stacking is tested. The upper layer is a 40d woven polyamide textile with no surface treatment, as described in Example 20. The lower layer is Thinsulate G80, as described in Example 21. Vapor permeability of the entire stacking. This is 100g / hour / m 2 It is determined that, when the water column break pressure is tested, the layer cannot support a water column of any measurable height.

[0140] Example 26 A three-layer stack was tested. The top layer was a hydrophobic 40d woven polyamide textile as described in Example 19. The middle layer was Thinsulate G80 as described in Example 21. The bottom layer was a hydrophilic 40d woven polyamide textile as described in Example 18. The vapor transmission rate of the entire stack was 90 g / hour / m². 2 It is determined that the water column burst pressure for the entire stack is determined to be a water head of 50 cm.

[0141] Example 27 A three-layer stack was tested. The top layer was a 40d woven polyamide textile without any surface treatment, as described in Example 20. The middle layer was Thinsulate G80, as described in Example 21. The bottom layer was a 40d woven polyamide textile without any surface treatment, as described in Example 20. The vapor transmission rate of the entire stack was 90 g / hour / m². 2 It is determined that, when the water column break pressure is tested, the layer cannot support a water column of any measurable height.

[0142] Example 28 A stainless steel mesh layer was pitted in an acidic etching solution and then coated with a binderless structured manganese oxide ceramic surface modifier deposited in a 25-75 mM aqueous solution of manganese nitrate and similar amounts of hexamethylenetetramine or urea at a temperature of approximately 60°C-80°C for approximately 60-240 minutes. The mesh was then calcined at a temperature of approximately 400°C-600°C for approximately 1 hour to obtain surface hydrophilic properties. The water contact angle was measured to be less than 5 degrees by the droplet method. The mesh was placed in a cup containing approximately 1 cm of deionized water. After 2 minutes, the capillary rise was determined to be approximately 3 cm above the liquid surface. The capillary rise was determined as described in PCT application number PCT / US19 / 65978 (see, for example, Figures 1A-1C). The vapor transmission rate was 130 g / hour / m³. 2 It was determined that the layer could not support any measurable height of water column overpressure.

[0143] Example 29 An aluminum mesh layer was coated with a ceramic material composed of magnesium oxide deposited in a 25-75 mM aqueous solution of manganese nitrate and an equal amount of hexamethylenetetramine at a temperature of approximately 60°C-80°C for approximately 30-90 minutes. The mesh was then calcined at a temperature of approximately 300°C-600°C for approximately 1 hour to obtain surface hydrophilic properties. The water contact angle was measured to be less than 5 degrees by the droplet method. The layer was placed in a cup containing approximately 1 cm of deionized water. After 2 minutes, the capillary rise was determined to be approximately 5 cm above the liquid surface. The vapor transmission rate was approximately 150 g / hour / m². 2 It was determined that, when the water column break pressure was tested, the layer could not support any water column of any measurable height.

[0144] Example 30 Aluminum at approximately 250 nm was sputtered onto woven polyester textiles and woven nylon textiles. The textiles were cut into small pieces and coated with three different ceramic materials: a) magnesium oxide / hydroxide-based ceramic, b) manganese oxide / hydroxide-based ceramic, and c) zinc oxide / hydroxide-based ceramic. All three ceramics contained aluminum oxide / hydroxide. The ceramics were deposited in the same manner as described in Example 1 (for each individual cation found in the ceramic, 2+ metal nitrate or metal sulfate was used). (Using [the specified method]). When the samples were tested for contact angle, they showed a contact angle of less than 15 degrees. Next, the ceramic-modified textiles were immersion-coated in a diluted bath (0.1%~1%) of hexadecylphosphonic acid in isopropanol or hexadecyltriethoxysilane in ethanol. In the case of silane, a small amount of acetic acid catalyst was sometimes used. Then, when the samples were measured again for contact angle, they showed a contact angle of approximately 150~160 degrees. Water vapor permeability was within the measurement error of the unmodified fabric.

[0145] Example 31 Woven polyester, polyamide, and Tencel textiles were coated with zinc oxide-based ceramics by immersion in batches of approximately 200–500 mM zinc sulfate, approximately 50–150 mM potassium persulfate, and approximately 1.2–1.7 mol of ammonium hydroxide at room temperature for approximately 5–60 minutes. Nickel oxide deposits were also deposited on the polyester by using nickel sulfate instead of zinc sulfate. Manganese oxide deposits were also created on the polyester by using manganese sulfate instead of zinc sulfate and permanganate instead of persulfate. These samples were then dried at a temperature of approximately 105°C–140°C for approximately 1–2 hours. When the samples were tested for contact angle, they showed a contact angle of less than 15 degrees. The ceramic-modified textiles were then coated by immersion in a diluted bath (0.1%–1%) of hexadecylphosphonic acid in isopropanol or hexadecyltriethoxysilane in ethanol. In the case of silane, a small amount of acetic acid catalyst was occasionally used. Subsequently, when the contact angle of the sample was measured again, it showed a contact angle of approximately 150-160 degrees.

[0146] Example 32 Woven polyamides and polyester textiles were immersed in aqueous baths of approximately 5–200 mM potassium permanganate and approximately 10–400 mM ammonium hydroxide at temperatures ranging from approximately room temperature to approximately 80°C for approximately 5 minutes to approximately 1 hour. The typical ratio of permanganate to ammonium hydroxide was approximately 1–2. The substrates were then dried, and structured ceramic layers containing manganese oxide / hydroxide, zinc oxide / hydroxide, or magnesium oxide / hydroxide were deposited by immersion in 25–150 mM aqueous solutions of metal (Mn, Zn, or Mg) nitrates and similar amounts of hexamethylenetetramine at temperatures ranging from approximately 60°C to 80°C for approximately 5–90 minutes. The meshes were then dried at temperatures ranging from approximately 100°C to 250°C for approximately 1 hour. The contact angles of these samples were measured and determined to be less than approximately 15 degrees. Next, the ceramic-modified textile was immersion-coated in a diluted bath (0.1% to 1%) of hexadecylphosphonic acid in isopropanol or hexadecyltriethoxysilane in ethanol. In the case of silane, a small amount of acetic acid catalyst was sometimes used. The samples were then measured again for contact angle, which showed a contact angle of approximately 150 to 160 degrees.

[0147] Although the aforementioned invention has been described in some detail as examples and embodiments for the purpose of clarifying its understanding, it will be apparent to those skilled in the art that certain changes and modifications can be made without departing from the intent and scope of the invention as described in the attached claims. Therefore, these descriptions should not be interpreted as limiting the scope of the invention.

[0148] All publications, patents, and patent applications cited herein are incorporated herein by reference in whole for all purposes, to the same extent as any individual publication, patent, or patent application is specifically and individually incorporated herein by reference.

Claims

1. A composite material including the top and bottom surfaces: (a) A layer of the x-layer of the material containing one or more functional properties ｔ Layer (where A ｔ The layers include the uppermost layer, which includes the top surface; (b) A of the y layer of the material containing one or more functional properties ｂ Layer (where A ｂ The layers include the bottom layer including the bottom surface; and (c) Includes an insulating material or structural material z layer B located between the x layer A layer and the y layer A layer, In that case, x, y, and z are the same or different in number of layers. A ｔ Layer and A ｂ Each layer contains a binderless ceramic material on a substrate. and each A ｔ Layers and / or each A ｂ The composite product wherein the ceramic materials on the layers are the same or different.

2. The composite article according to claim 1, wherein the binderless ceramic material is mainly crystalline.

3. The composite article according to claim 1, wherein the ceramic material comprises a metal oxide, a hydrate of a metal oxide, a metal hydroxide, and / or a hydrate of a metal hydroxide.

4. The composite article according to claim 3, wherein the ceramic material contains a metal hydroxide, and at least a portion of the metal hydroxide contains a layered double hydroxide.

5. The composite product according to any one of claims 1 to 4, wherein the ceramic is a nanostructured ceramic.

6. At least one layer of A ｔ layer and / or at least one layer of A ｂ The integrated product according to claim 1, wherein the substrate for the layer is a material selected from synthetic or natural textiles, metal meshes, metal screens, metal cloths, synthetic or natural polymer materials or films, which are woven, non-woven, or knitted.

7. At least one layer A ｔ Substrate for the layer and at least one layer A ｂ A substrate for the layer, or at least two layers A ｔ A substrate for the layer, or at least two layers A ｂ The composite article according to claim 6, wherein the base material for the layer comprises different materials selected from synthetic or natural textiles, metal mesh, metal screens, metal cloths, synthetic or natural polymer materials or films, which are woven, non-woven, or knitted.

8. Each A ｔ and / or A ｂ The composite article according to claim 1, wherein the layer includes one or more functional properties selected from ice or condensate management, de-icing, frost protection, superhydrophobicity, superhydrophilicity, inhibition of microbial growth, corrosion resistance, electromagnetic modulation, thermal modulation, flame retardancy, breathability, dynamic wind resistance, color, absorption, barrier, maintenance properties, aesthetic properties, odor control, abrasion resistance, mechanical properties, surface friction, feel, durability, or a combination thereof.

9. x and / or y are greater than 1, and each A ｔ and / or A ｂ The layer is other A ｔ and / or A ｂ The composite product according to claim 8, which includes functional characteristics different from those of the layers.

10. The composite product according to claim 8, wherein the uppermost layer including the upper surface and the lowermost layer including the lower surface have the same functional characteristics.

11. The composite product according to claim 8, wherein the uppermost layer including the upper surface and the lowermost layer including the lower surface have different functional characteristics.

12. At least one layer A ｔ and / or at least one layer A ｂ The composite article according to claim 1, wherein the layer comprises a topcoat material that imparts one or more functional properties, and at least one functional property imparted by the topcoat material is more advanced than the same functional property imparted by the same topcoat material directly deposited on the same substrate that does not contain the ceramic material.

13. At least one layer A ｔ and / or at least one layer A ｂ The composite article according to claim 1, wherein the layer includes a topcoat material, and the ceramic material and the topcoat material synergistically impart one or more functional properties that are superior to the same functional properties imparted by either the ceramic material or the topcoat material independently deposited on the same substrate surface.

14. At least one layer A ｔ and / or at least one layer A ｂ The composite article according to claim 1, wherein the layered binderless ceramic material has a partially filled porous structure.

15. The composite article according to claim 14, wherein the pores of the ceramic material are partially filled with a second ceramic material or with molecules having head groups and tail groups.

16. The composite article according to claim 1, wherein each B layer includes one or more structural properties selected from thermal resistance, electrical resistance, structural support, mechanical padding, and fluid transfer properties, or a combination thereof.

17. The composite article according to claim 1, wherein one or more B layers comprise a ceramic material selected from glass fiber, loose ceramics, and other inorganic materials.

18. An assembly according to any one of claims 1 to 17, incorporated into performance outerwear clothing, medical bandages, medical casts, surgical gowns, filtering or separating media, packing materials, hospital flooring, absorbent textiles, protective masks, protective clothing, building textiles, or geotextiles.

19. An insulating or protective material for piping, comprising the laminated product described in claim 1, One or more layers of A ｔ The layer contains hydrophobic or superhydrophobic functional properties, and one or more B layers contain thermal insulation, protective, or structural properties, One or more layers of A ｂ The insulating or protective material for piping, wherein the layer includes hydrophilic or superhydrophilic functional properties.

20. The aforementioned composite product surrounds the piping, The lowermost A mentioned above ｂ The layer is in contact with the piping, and The uppermost A ｔ The insulating or protective material for piping according to claim 19, wherein the layer is in contact with the surrounding environment.

21. One or more layers of A ｔ and / or one or more layers of A ｂ The pipe insulation or protective material according to claim 19 or 20, wherein the layer comprises a ceramic-coated woven material.

22. The woven material is selected from stainless steel alloy woven material, carbon steel alloy woven material, aluminum alloy woven material, and textile, as described in claim 21, as an insulating or protective material for piping.

23. The piping insulation or protective material according to any one of claims 19 to 22, wherein at least one layer B comprises a material selected from fiberglass, silicon carbide, ceramic fiber insulation, silicone or silicone foam, mineral wool, basalt, bubble glass, polyimide, calcium silicate, or silica.

24. A pipe surrounded by a pipe insulating material or protective material according to any one of claims 19 to 23.

25. A textile material comprising the composite product described in claim 1, One or more layers of A ｔ The layer contains hydrophobic or superhydrophobic water functional properties, and one or more B layers contain thermal insulation, protective, or structural properties, One or more layers of A ｂ The textile material wherein the layer includes hydrophilic or superhydrophilic functional properties.

26. One or more layers of A ｔ and / or one or more layers of A ｂ The textile material according to claim 25, wherein the base material of the layer includes a woven material.

27. The textile material according to claim 26, wherein the woven material may be selected from textiles, polyamides, polyesters, polymer substrates or films, cellulosic materials, cotton, wool, stainless steel alloy woven materials, and aluminum alloy woven materials.

28. One or more layers of A ｔ and / or one or more layers of A ｂ The textile material according to claim 25, wherein the base material of the layer comprises nylon or polyethylene terephthalate (PET).

29. The textile material according to any one of claims 25 to 28, wherein one or more layers B comprise a material selected from polyester, fleece, wool, feathers, down, and other primarily organic materials.

30. A composite material including the top and bottom surfaces: (a) Layer A of the x layer of the material having one or more functional properties (wherein layer A includes the uppermost layer including the upper surface, Each of the aforementioned A layers includes a binderless ceramic material on the substrate; and (b) comprising a B layer of the z layer of an insulating or structural material (wherein the B layer includes the bottom layer including the bottom surface), In this case, x and z have the same or different number of layers in the assembled product.

31. A composite material including the top and bottom surfaces: (a) A layer of the x-layer of the material containing one or more functional properties ｔ Layer (where A ｔ The layers include the uppermost layer including the top surface; and (b) A of the y layer of the material containing one or more functional properties ｂ Layer (where A ｂ The layers include the bottom layer which includes the bottom surface, At that time, A ｔ Layer and A ｂ Each layer contains a binderless ceramic material on a substrate. A ｔ The ceramic material on the layer is A ｂ Unlike layered ceramic materials, The composite product wherein x and y are the same or different.

32. The composite product according to claim 30 or 31, wherein the ceramic material is mainly crystalline.

33. The composite article according to claim 30 or 31, wherein the ceramic material comprises a metal oxide, a hydrate of a metal oxide, a metal hydroxide, and / or a hydrate of a metal hydroxide.

34. The composite article according to claim 33, wherein the ceramic material contains a metal hydroxide, and at least a portion of the metal hydroxide contains a layered double hydroxide.

35. The composite product according to any one of claims 30 to 34, wherein the ceramic is a nanostructured ceramic.

36. The composite article according to claim 30, wherein at least one layer A comprises a topcoat material that imparts one or more functional properties, and at least one functional property imparted by the topcoat material is more advanced than the same functional property imparted by the same topcoat material directly deposited on the same substrate without the ceramic material.

37. The composite article according to claim 30, wherein at least one layer A comprises a topcoat material, and the ceramic material and the topcoat material synergistically impart one or more functional properties that are superior to the same functional properties imparted by either the ceramic material or the topcoat material independently deposited on the same textile surface.

38. The composite article according to claim 30, wherein at least one layer A of the binderless ceramic material has a partially filled porous structure.

39. The composite article according to claim 38, wherein the pores of the ceramic material are partially filled with a second ceramic material or with molecules having head groups and tail groups.

40. At least one layer A ｔ and / or at least one layer A ｂ The composite article according to claim 31, wherein the layer comprises a topcoat material that imparts one or more functional properties, and at least one functional property imparted by the topcoat material is more advanced than the same functional property imparted by the same topcoat material directly deposited on the same substrate that does not contain the ceramic material.

41. At least one layer A ｔ and / or at least one layer A ｂ The composite article according to claim 31, wherein the layer includes a topcoat material, and the ceramic material and the topcoat material synergistically impart one or more functional properties that are superior to the same functional properties imparted by either the ceramic material or the topcoat material independently deposited on the same textile surface.

42. At least one layer A ｔ and / or at least one layer A ｂ The composite article according to claim 31, wherein the layered binderless ceramic material has a partially filled porous structure.

43. The composite article according to claim 42, wherein the voids in the ceramic material are partially filled with a second ceramic material or with molecules having head groups and tail groups.

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