Assemblies of functionalized textile materials and methods of use thereof

Abstract

A collection of stacked material layers is described. The collection includes a functional layer and a structural layer. The functional layer includes binderless ceramic material on a woven or nonwoven substrate of natural, synthetic, or metallic material. The functional material layer and the structural material layer can be configured to transport moisture or heat from an interior surface to an exterior surface that is exposed to the surrounding environment.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to PCT application No. PCT / US2019 / 065978, filed December 12, 2019, and claims the benefits of U.S. Provisional Application Nos. 62 / 989,092, 62 / 989,150, 63 / 038,642, 63 / 038,693, and 63 / 038,693, all filed June 12, 2020, and June 16, 2020, all of which are incorporated herein by reference in their entirety. Technical Field

[0003] The present invention relates to the functionalization of textile surfaces by ceramic surface-modifying materials (in particular, binderless ceramics, such as metal oxide and / or metal hydroxide ceramics, or conversion coatings) used on textile surfaces; and to collections of such material layers that provide functional benefits relative to individual or unfunctionalized layers. Background Technology

[0004] Functionalization of textile surfaces offers desired benefits in terms of textile performance compared to unfunctionalized textile layers. An assembly of layers that can provide multiple beneficial properties for a single system or article is desirable and can offer additional benefits compared to an assembly of individual functional or unfunctionalized layers. Furthermore, desired performance characteristics can be enhanced by integrating individual functional layers to form an assembly. Summary of the Invention

[0005] It provides an assembly of functional material layers, structural material layers, and / or layers with other beneficial properties. The functional layers may include ceramic materials on a substrate (such as a textile substrate).

[0006] In one aspect, a material assembly including a top surface and a bottom surface is provided, said assembly comprising: (a) x A t A material layer comprising one or more functional properties, wherein A t The layer includes a topmost layer including the top surface; (b)y A b A material layer comprising one or more functional properties, wherein A b The layer includes a bottom layer including the bottom surface; and (c) in x A t Layer and y A b Between layers are z layers of B insulating, structural, or other functionally beneficial material, where x, y, and z are the same or different numbers of layers, wherein At Layer and / or the A b Each layer may comprise a ceramic material on a substrate, such as binderless ceramic, for example, a binderless porous ceramic material, and each A t Layers and / or each A b The ceramic materials on the layers may be the same or different. In one embodiment, at least one A t The layer comprises a ceramic material, such as binderless ceramic, or binderless porous ceramic material, on a substrate. In another embodiment, at least one A b The layer comprises a ceramic material, such as binderless ceramic, or binderless porous ceramic material, on a substrate. In another embodiment, at least one A t Layer and at least one A b Each layer comprises a ceramic material, such as binderless ceramic, e.g., binderless porous ceramic material, on a substrate. In some embodiments, the top surface and / or bottom surface comprises a ceramic material, such as binderless ceramic, e.g., binderless porous ceramic material. In some embodiments, A b Layer and / or A t Layers include a variety of functional (e.g., aesthetic and / or performance-related) features.

[0007] On the other hand, a material assembly including a top surface and a bottom surface is provided, wherein the assembly comprises: (a) x layers of material A, each comprising one or more functional properties, wherein each layer A comprises a top layer including the top surface, and each layer A comprises a ceramic material, such as binderless ceramic, for example, binderless porous ceramic material, on a substrate; and (b) z layers of material B, which are insulating, structural, or otherwise functionally beneficial, wherein each layer B comprises a bottom layer including the bottom surface, and wherein x and z are the same or different numbers of layers. In some embodiments, the assembly does not include layers A. b layer.

[0008] On the other hand, a material assembly including a top surface and a bottom surface is provided, wherein the assembly comprises: (a) x A t A material layer comprising one or more functional properties, wherein A t The layer includes a topmost layer including the top surface; and (b)y A b A material layer comprising one or more functional properties, wherein A b The layer includes a bottom layer including the bottom surface, wherein A t Layer and the A b Each layer comprises a ceramic material, such as binderless ceramic, for example, a binderless porous ceramic material, on a substrate, wherein A tThe ceramic material on the layer and A b The ceramic materials on the layers are different, and x and y are the same or different. In some embodiments, the assembly does not include layer B. In one embodiment, at least one A t The layer comprises a ceramic material, such as binderless ceramic, or binderless porous ceramic material, on a substrate. In another embodiment, at least one A b The layer comprises a ceramic material, such as binderless ceramic, or binderless porous ceramic material, on a substrate. In another embodiment, at least one A t Layer and at least one A b Each layer comprises a ceramic material, such as binderless ceramic, e.g., binderless porous ceramic material, on a substrate. In some embodiments, the top surface and / or bottom surface comprises a ceramic material, such as binderless ceramic, e.g., binderless porous ceramic material. In some embodiments, A b Layer and / or A t Layers include a variety of functional (e.g., aesthetic and / or performance-related) features.

[0009] In some embodiments, the ceramic material is primarily crystalline. In some embodiments, the ceramic material comprises metal oxides, hydrates of metal oxides, metal hydroxides, and / or hydrates of metal hydroxides. In some embodiments, the ceramic material comprises metal hydroxides, and at least a portion of the metal hydroxides comprises layered double hydroxides. In some embodiments, the ceramic is a structured ceramic, such as a nanostructured ceramic.

[0010] In some embodiments, the ceramic material comprises mixed metal oxides, hydrates of mixed metal oxides, mixed metal hydroxides, and / or hydrates of mixed metal hydroxides. In some embodiments, the ceramic material comprises mixed metal hydroxides, and at least a portion of the metal hydroxides comprises layered double hydroxides.

[0011] In some embodiments, the ceramic material comprises a chemical transformation of 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, wherein intercalated ions have been exchanged (e.g., the intercalated metal ions in the initially generated layered double hydroxide have been exchanged for different intercalated ions).

[0012] In some implementations, for at least one A t Layer and / or at least one A bThe substrate of the layer includes woven, nonwoven, or knitted synthetic or natural textiles, or metal mesh, metal sieve, or metal cloth. In some embodiments, it is used for at least one A t Layer and / or at least one A b The substrate of the layer includes synthetic or natural material films or polymers.

[0013] In some implementations, each A t Layer and / or A b The layer includes one or more functional properties selected from the following: ice or condensate management, anti-icing, anti-frost, superhydrophobicity, superhydrophilicity, inhibition or resistance to microbial growth, corrosion resistance, electromagnetic modulation, thermal modulation, flame retardancy, breathability, dynamic wind resistance, color, absorbency, barrier properties, maintenance properties (e.g., color fastness, resistance to degradation (e.g., during washing), easy cleaning, wrinkle resistance, odor resistance), aesthetic properties (e.g., color reflectance, finish (e.g., matte, opalescent), color depth (e.g., color variation with viewing angle)), odor control, abrasion resistance, mechanical properties (e.g., stiffness, tensile strength (e.g., tear resistance), impact resistance), surface friction, feel, durability, or combinations thereof.

[0014] In some implementations, x and / or y are greater than 1, and each A t Layer and / or A b The layer includes at least one other A t Layer and / or A b Different functional characteristics of each layer. In some implementations, each A t The layer includes at least one other A t Different functional characteristics of each layer. In other implementations, each A b The layer includes at least one other A b Different functional characteristics of layers. In other implementations, A t Layer includes A b Different functional characteristics of each layer.

[0015] In some implementations, the topmost layer (topmost A) of the top surface is included. t (layer) and the bottommost layer (bottommost A) including the bottom surface b The layers have the same functional characteristics. In some embodiments, the topmost layer (topmost A) includes the top surface. t (layer) and the bottommost layer (bottommost A) including the bottom surface b Each layer has different functional characteristics.

[0016] In some embodiments, each B layer includes one or more structural properties selected from: thermal resistance, electrical resistance, structural support, mechanical filling, aesthetics, comfort, protection, durability, maintenance properties (e.g., quick-drying, easy to fold, color fastness, resistance to degradation (e.g., during washing), easy to clean, wrinkle-resistant), fluid transport characteristics, or combinations thereof. In some embodiments, one or more B layers comprise a ceramic material, for example, selected from glass fiber, porous ceramics, and other inorganic materials.

[0017] In some implementations of the assembly described herein, at least one A layer (e.g., at least one A...) t Layer and / or A b A layer includes functional materials (e.g., surface functional topcoat materials) applied to or deposited on a ceramic material that imparts or enhances one or more functional properties. In some embodiments, the magnitude of at least one functional property imparted by these functional materials is greater than the magnitude of the same functional property imparted by an identical surface functional topcoat material deposited directly on the same substrate that does not include the ceramic material. In some embodiments of the assembly herein, at least one A layer (e.g., at least one A...) t Layer and / or A b The layer includes functional materials (e.g., surface functional topcoat materials), and the ceramic material and the functional material synergistically impart one or more functional properties, the magnitude of which is greater than the same functional properties imparted by ceramic materials or topcoat materials independently deposited on the same textile surface.

[0018] In some embodiments, the functional layer imparts hydrophobic properties. For example, the functional layer imparting hydrophobic properties to the composition may include fluoropolymers, elastomers, plastics, or molecules having head and tail groups, such as silyl, phosphonate, phosphonic acid, carboxylic acid, vinyl, alcohol, hydroxide group, mercapto, thiol, and / or ammonium (e.g., quaternary ammonium) groups, and tail groups including hydrocarbon, fluorocarbon, vinyl, phenyl, epoxy, acrylate, acrylate, hydroxy, carboxylic acid, thiol, and / or quaternary ammonium groups.

[0019] In some implementations of the assembly described herein, at least one A layer (e.g., at least one A...) t Layer and / or at least one A b The binderless ceramic material on the layer is a partially filled porous structure. For example, the pores of the ceramic material may be filled with a second ceramic material or molecules having head and tail groups.

[0020] In some implementations of the assembly described herein, at least one A layer (e.g., at least one A...) t Layer and / or at least one A bThe layer can withstand a hydrostatic pressure greater than approximately 1 kPa.

[0021] In some implementations of the assembly described herein, at least one A layer (e.g., at least one A...) t Layer and / or at least one A b The layer includes a moisture permeability of approximately 80% greater than that of the same substrate without modification with ceramic materials (and optionally a functional layer in some embodiments).

[0022] In some implementations of the assembly described herein, at least one A layer (e.g., at least one A...) t Layer and / or at least one A b The layer includes a horizontal drip contact angle greater than approximately 150 degrees.

[0023] In some implementations of the assembly described herein, at least one A layer (e.g., at least one A...) t Layer and / or A b (Layer) improves aesthetics, wearing comfort, durability, or maintenance of desired characteristics. (See, for example, Venkatraman, P., “Fabric Properties and Their Characteristics, Materials and Technology for Sportswear and Performance Apparel,” 2015, CRC Press, ISBN 9781482220513.)

[0024] In some implementations, the assembly is incorporated into performance outerwear apparel, medical bandages, medical plaster, surgical gowns, filtering or separating media, packaging materials, hospital bedding, absorbent textiles, protective covers, protective clothing, architectural textiles, or geotextiles.

[0025] In some embodiments, a pipe insulation or pipe protection material is provided, comprising an assembly as described herein, wherein one or more A t The layers include hydrophobic or superhydrophobic functional properties, wherein one or more B layers include thermal insulation, protection (e.g., protection against pipe corrosion and / or abrasion under operating conditions or in the usage environment, and / or protection against harm to individuals near the pipe), or structural properties, and wherein one or more A layers... b The layers include hydrophilic or superhydrophilic functional properties. For example, the pipe insulation or pipe protection material can surround the pipe, wherein the bottommost layer A b The layer contacts the pipe, and the topmost A is described as follows. tThe layer is in contact with its surrounding environment. One or more A layers... t Layer and / or A b Layers may include ceramic-coated woven materials. For example, the woven material may be selected from stainless steel alloy woven materials, carbon steel alloy woven materials, aluminum alloy woven materials, and textiles. In some embodiments, at least one B layer may include materials selected from: glass fiber, silicon carbide (e.g., corundum), ceramic fiber insulation, silicone or silicone foam, mineral wool, basalt, foam glass, polyimide, calcium silicate, or silica. Pipes, pipe sections, or reactor (such as bioreactors, adsorption beds, catalytic reactors, or distillation columns) sections surrounded by the insulation, protection, or performance materials described herein are also provided.

[0026] In some implementations, textile materials comprising an assembly as described herein are provided, wherein one or more A t The layers include hydrophobic or superhydrophobic functional properties, wherein one or more B layers include thermal insulation, protective, or structural properties, and wherein one or more A layers... b The layer includes hydrophilic or superhydrophilic functional properties. In some embodiments, one or more A t Layer and / or A b The substrate of the layer includes a woven material. For example, the woven material can be selected from textiles, polyamides, polyesters, cellulose materials, cotton, wool, polymer films, stainless steel alloy woven materials, and aluminum alloy woven materials. In some embodiments, one or more A t Layer and / or A b The substrate of the layer comprises nylon or polyethylene terephthalate (PET). In some embodiments, one or more B layers comprise materials selected from polyester, fleece, wool, feathers, down, and other primary organic materials. Attached Figure Description

[0027] Figure 1 illustrates an exemplary embodiment of an assembly of material layers for a medical bandage.

[0028] Figure 2 illustrates an exemplary embodiment of an assembly of material layers for a functional outer garment.

[0029] Figure 3 shows an exemplary embodiment of an assembly of material layers for pipe insulation.

[0030] Figure 4 illustrates an exemplary embodiment of an assembly of material layers for medical plaster.

[0031] Figure 5 illustrates an exemplary embodiment of an assembly of material layers for medical / surgical garments. Detailed Implementation

[0032] An assembly of stacked material layers is described, along with its usage and applications. The assembly described herein includes one or more functional (“A”) layers and optionally one or more structural or bulk property (“B”) layers. The functional layer comprises a structured ceramic on a substrate material, which provides the desired functional properties and / or may be further functionalized by applying or depositing additional surface chemical topcoat materials to provide the desired properties for a particular application. At least a portion of the substrate surface undergoes a chemical transformation to provide a structured (e.g., nanostructured) ceramic material, and optional subsequent processes provide additional functionalization of the ceramic. Layers may be arranged to impart functional properties in a directional manner, such as the movement of vapor or thermal energy in a direction toward the environmentally exposed surface. Layers may be arranged to impart functional properties in a combined manner, such as wear-resistant layers and thermal insulation layers providing mechanical and thermal protection.

[0033] Layer A comprises a structured ceramic and optionally a surface-functional topcoat on a substrate surface to provide one or more functional properties to the substrate. A ceramic (e.g., porous ceramic, e.g., metal oxide and / or metal hydroxide) surface-modifying composition is deposited on the surface of a textile or fabric substrate. The composition is provided as a binder-free surface-modifying material (e.g., a surface-fixing ceramic material) on the substrate surface. In some embodiments, the ceramic material comprises metal oxide and / or hydroxide ceramics, e.g., single-metal or mixed-metal oxide and / or hydroxide ceramics. In some embodiments, the ceramic material comprises metal oxide and metal hydroxide ceramics, wherein the metal oxide and metal hydroxide contain the same or different single metals or mixed metals. In some embodiments, the ceramic material comprises metal oxide and / or metal hydroxide ceramics, wherein 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 comprises a metal hydroxide, wherein 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. In some embodiments, the intercalating ions of the layered double hydroxide may have been exchanged to impart additional benefits. 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 thereof may be in the form of a hydrate of a metal oxide or a metal hydroxide, respectively.

[0034] Mixed metal oxides or mixed metal hydroxides may each include, for example, oxides or hydroxides of more than one metal, such as, but 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.

[0035] The surface-modifying materials described herein (e.g., binderless porous ceramic materials) are deposited onto a substrate without a binder (e.g., produced by reacting with a metal on the substrate surface). In some embodiments, the surface-modifying materials as described herein are fixed onto the substrate.

[0036] In some implementations, the structured ceramic material is a nanostructured ceramic material.

[0037] In some implementations, the structured ceramic material undergoes an additional chemical transformation process to produce a modified structured (e.g., nanostructured) ceramic material.

[0038] Non-limiting examples of binderless ceramic surface modification materials are provided in PCT application number PCT / US19 / 65978, which are incorporated herein by reference in their entirety.

[0039] definition

[0040] The numerical ranges provided in this article include values ​​within a defined range.

[0041] Unless the context clearly indicates otherwise, “a,” “an,” and “the” include plural references.

[0042] The phrase “and / or” as used in the specification and claims should be understood to mean “one or both” of the combined elements, that is, elements that exist together in some cases and separately in others. Unless explicitly stated otherwise, elements other than those specifically defined by the “and / or” clause may optionally be present, whether related to or unrelated to those specifically identified elements. Thus, as a non-limiting example, when used in conjunction with open-ended language such as “comprising,” a reference to “A and / or B” may in one embodiment refer to A in the absence of B (optionally including elements other than B); in another embodiment it may refer to B in the absence of A (optionally including elements other than A); in yet another embodiment it may refer to both A and B (optionally including other elements); and so on.

[0043] "Adhesive" or "binding agent" is any material or substance that holds or pulls other materials together mechanically, chemically, by adhesive force or by cohesive force to form a cohesive whole.

[0044] "Adhesive-free" means that there is no adhesive present, specifically organic adhesives or resins (e.g., polymers, glues, adhesives, bitumen) or inorganic adhesives (e.g., lime, cement, glass, gypsum, etc.).

[0045] "Capping agent" refers to a compound or agent that slows down crystal growth and allows for the regulation of nanoscale surface morphology.

[0046] "Ceramics" refers to solid materials containing inorganic compounds that contain metals, non-metals, or ionic and covalent bonds.

[0047] "Conversion coating" refers to a surface layer in which reactants chemically react with the surface to be treated, thereby transforming the substrate into a different compound. This process is typically neither additive nor deposition.

[0048] "Fabric" means a nonwoven material that can be composed of fibers and bonded together by chemical, mechanical, thermal and / or solvent treatments. Fabrics can include, for example, felt and other materials that are neither woven nor knitted.

[0049] "Fiber" refers to the thread or filament that forms textiles.

[0050] "Hydrophilic" refers to a surface that has a high affinity for water. The contact angle may be very low and / or unmeasurable.

[0051] A “layer” refers to a piece of material, a certain amount of material or a certain thickness of material, usually one of several layers, covering a surface or body, or it can be freestanding, for example, supported by one or more supporting structures.

[0052] "Layered double hydroxides" refer to a class of ionic solids characterized by having a universal sequence [AcB Z AcB]. n The layered structure, wherein c represents a metal cation layer, A and B are hydroxide anion layers, and Z is a layer of other anions and / or neutral molecules (such as water). Layered double hydroxides are also described in PCT application number PCT / US2017 / 052120, which is incorporated herein by reference.

[0053] "Nanostructured" composition in this document refers to a composition having a feature portion of less than 100 nanometers in at least one dimension.

[0054] In fluid mechanics, "permeability" is a measure of a porous material's ability to allow fluid to pass through it. The permeability of a medium is related to its porosity, as well as the shape of the pores and their level of connectivity within the medium.

[0055] "Pore size distribution" refers to the relative abundance of each pore size or pore size range determined by mercury intrusion porosimetry (MIP) and the Washburn equation.

[0056] Porosity is a measure of the void (i.e., "empty") space in a material, and is the fraction of void volume to total volume, ranging between 0 and 1, or a percentage between 0% and 100%. Porosity can be measured by mercury porosimetry.

[0057] "Porous" refers to the space, holes, or voids within a solid material.

[0058] "Superhydrophilic" refers to a surface that is excessively hydrophilic or has an attractive effect on water. The contact angle of water on a superhydrophilic material is 0 degrees.

[0059] "Superhydrophobic" refers to a surface that is extremely difficult to wet. The contact angle of a water droplet on a superhydrophobic material (in this case, a superhydrophobic surface) is greater than 150°. A highly hydrophobic surface has a contact angle greater than 120°.

[0060] "Surface area per square meter of projected substrate area" refers to the actual measured surface area (usually measured in square meters) divided by the surface area of ​​the substrate (which is also usually measured in square meters if it is atomically smooth (without surface roughness).

[0061] "Synergy" or "synergistic" refers to the interaction or cooperation between two or more substances, materials, or agents that produces a combined effect that is greater (positive synergy) or less (negative synergy) than the sum of their individual effects.

[0062] "Textiles" refers to flexible materials composed of networks of natural or man-made fibers. For example, textile materials can be produced by knitting, weaving, felting, tufting, or bonding to connect fibers or groups of fibers, where fibers include all lengths of natural and synthetic forms, including metallic fibers. Textiles also include ropes and cords.

[0063] "Thickness" refers to the length between the surface of the substrate and the top of the surface-modified (e.g., ceramic) material.

[0064] A "topcoat" refers to a material or chemical treatment in which the surface and chemical substances interact, bond, or disperse to form a modified surface through changes in surface energy, microbial resistance, color, thermal properties, electrical properties, or reactivity. Property changes can be achieved at the atomic, molecular, feature, or overall component length scale.

[0065] "Adjustable" refers to the ability of a material's function, characteristics, or quality to be changed or modified.

[0066] "Vapor penetration rate" refers to the mass of vapor passing through the layer per unit area per unit time in a direction orthogonal to the plane of the layer.

[0067] "Water column breakthrough pressure" refers to the specific height of the vertical water column when the hydrostatic pressure at the bottom of the water column overcomes the layer's ability to support the water column.

[0068] Material assembly

[0069] This document discloses an assembly of material layers. The layers are typically configured in a stacked manner, with a top surface at the top of the stack and a bottom surface at the bottom. The top surface is typically in contact with the surrounding environment (e.g., air) where the assembly is located or used. The bottom surface may contact or be close to a device, surface, or individual used with the assembly, for example, a device or surface to be protected, or for the comfort of an individual in a particular usage environment.

[0070] The stacking of layers includes a ceramic material (e.g., binderless ceramic, such as binderless porous ceramic material) on a substrate (hereinafter referred to as layer "A"). Layer A imparts the desired functional properties to the assembly. For example, the ceramic material may impart one or more properties selected from: hydrophobicity, microbial growth inhibition, flame retardancy, hydrophilicity, corrosion resistance, ice or condensate management, anti-icing, anti-frost, superhydrophobicity, superhydrophilicity, microbial growth inhibition, corrosion resistance, electromagnetic modulation, thermal modulation, breathability, dynamic wind resistance, and / or color or combinations thereof. Some embodiments of the assembly herein include: a top A layer comprising the top surface of the assembly (facing the surrounding environment); and a bottom A layer comprising the bottom surface of the assembly (facing the equipment, surface, or individual used with the assembly). The binderless porous ceramic material as described herein is located on each of the top and bottom surfaces. The binderless porous ceramic material on each A layer may be the same as or different from each of the other A layers in the assembly.

[0071] Some stacks of layers include one or more “B” layers comprising structural material and / or insulating material, said layers being one or more A layers (“A” layers) on top of the stack. t "Layer" and one or more A layers at the bottom of the stack ("A"). b Between layers. In some embodiments, the assembly includes a B layer having a structural material and / or an insulating material. In other embodiments, the assembly includes two or more B layers having structural materials and / or insulating materials, and each B layer may be composed of the same or different materials or compositions as each other B layer in the assembly.

[0072] In some implementations, the collection includes an A t Layer and an Ab Layer, and A t Layers can be composed of A b The assembly is composed of layers made of the same or different materials or compositions (e.g., the same or different substrates and / or ceramic compositions). In some embodiments, the assembly comprises two or more A... t Layer (i.e., multiple A's) t (layer) and / or two or more A b Layer (i.e., multiple A's) b (layer), and each A t Layers and / or each A b A layer can be composed of each other A layer (i.e., each other A layer). t and / or A b The layers are composed of the same or different materials or compositions (e.g., the same or different substrates and / or ceramic compositions).

[0073] In some implementations, at least one A layer of the collection (e.g., at least one A layer) t and / or A b The layer imparts one or more functional properties to the assembly, such as those selected from the following: ice or condensate management (resistance to ice formation, or appropriate guidance or placement of materials that guide ice or condensate to form, concentrate, and move in a desired manner), anti-icing properties or frost delay properties, superhydrophobicity (e.g., preventing scale formation due to water ingress), superhydrophilicity (e.g., drawing water away from the surface to minimize time or humidity and / or prevent moisture-related damage), antimicrobial modulation (inhibition, elimination, or prevention of microbial growth), corrosion resistance or corrosion protection, electromagnetic modulation (changes in electromagnetic properties, such as diffuse or specular emission, diffuse or specular reflection, adsorption, transmission), thermal modulation, flame retardancy, breathability (allowing moisture to pass through the material), dynamic wind resistance (non-linear response of vapor permeability to applied wind speed), mechanical protection (abrasion resistance or impact resistance), and color and / or other aesthetic properties or combinations thereof.

[0074] In some implementations, A is included on the top surface of the assembly. t Layers and A including the bottom surface of the assembly b Layers impart different functional characteristics. In one implementation, layer A is included on the top surface of the assembly. t The layer is hydrophobic or superhydrophobic and includes A on the bottom surface of the aggregate. b The layer is hydrophilic or superhydrophilic. In another embodiment, A includes the top surface of the assembly. t The layer is hydrophobic or superhydrophobic and includes A on the bottom surface of the aggregate. b The layer is antimicrobial. In another embodiment, it includes A on the top surface of the assembly. t The layer is hydrophobic or superhydrophobic, including A on the bottom surface of the aggregate.b The layer is antimicrobial, and A is present on the bottom surface of the aggregate. b A above the layer b The layer is hydrophobic or superhydrophobic.

[0075] In some embodiments, a topcoat material is deposited or applied onto a ceramic material, thereby imparting and / or enhancing one or more functional properties described herein to layer A of the assembly. In some embodiments, the functionality imparted by the topcoat material applied or deposited onto the ceramic as described herein is enhanced relative to the functionality imparted by the same material applied or deposited onto the same substrate comprising the ceramic. In some embodiments, the ceramic material and the topcoat material synergistically impart one or more functional properties, the magnitude of which is greater than the same functional properties imparted by either the ceramic material or the topcoat material independently deposited on the surface of the same substrate.

[0076] In some implementations, the hydrophobic function is achieved by fatty acids such as stearic acid or Scotchgard. TM (3M) provides the antimicrobial function. In some embodiments, the antimicrobial function is provided by SmartShield Antimicrobial Protective Spray (Sylvane). In some embodiments, the flame retardant function is provided by No Burn 1005 Fabric Fire Protection (No-Burn, Inc.) or a halon-containing compound. In some embodiments, the hydrophilic function is provided by polyvinylpyrrolidone (PVP), polyurethane, polyacrylic acid (PAA), polyethylene oxide (PEO), or polysaccharide materials.

[0077] In some non-limiting embodiments, the topcoat may include paint, paint adhesive, hydrophobic material, hydrophilic material, metal or metal-containing compound, pigment and / or colorant or antimicrobial agent.

[0078] In some embodiments, the topcoat is a surface-modified topcoat that reduces the viscous resistance of external or internal fluids on the surface. In some embodiments, a coating is deposited onto the surface, the coating comprising a nanostructured coating composition and a surface-modified topcoat that reduces the viscous resistance of external or internal fluids on the surface, and also includes additional benefits such as corrosion resistance, fouling resistance, self-cleaning properties, thermal transfer characteristics, optical properties, chemical inertness, other useful properties, or combinations of properties.

[0079] In some embodiments, the top coating is or contains an antimicrobial agent. For example, the antimicrobial agent may be a charge-transfer compound or an agent that disrupts the movement of ions across the cell membrane, such as a quaternary ammonium. In some embodiments, the antimicrobial agent is a β-lactam, aminoglycoside, tetracycline, chloramphenicol, macrolide, lincosamide, sulfonamide, quinolone, polyene, azole, or griseofulvin.

[0080] In some implementations, the topcoat is or contains a paint binder. For example, the paint binder may be an alkyd resin, an acrylic resin, a vinyl acrylate resin, a vinyl acetate / ethylene (VAE) resin, a polyurethane, a polyester, a melamine resin, an epoxy resin, a silane, or an oil.

[0081] In some embodiments, the ceramic surface-modifying material is a partially filled porous structure. For example, the pores may be partially filled with a second ceramic material (e.g., a ceramic material different from the ceramic material on the substrate surface) or molecules having head and tail groups, such as silyl, phosphonate, phosphonic acid, carboxylic acid, vinyl, alcohol, hydroxyl, mercapto, thiol, and / or ammonium (e.g., quaternary ammonium) groups, and tail groups including hydrocarbon, fluorocarbon, vinyl, phenyl, epoxy, acrylic, acrylate, hydroxyl, carboxylic acid, thiol, and / or quaternary ammonium groups.

[0082] In some embodiments, at least one B layer of the assembly imparts one or more structural and / or thermal insulation properties, selected from thermal resistance, electrical resistance, structural support, mechanical filling, and fluid transport, or combinations thereof. In some embodiments, at least one B layer of the assembly comprises a ceramic material, such as glass fiber, porous ceramic, or other inorganic material.

[0083] Binderless ceramics

[0084] Layer “A” in the layered assembly 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 its entirety.

[0085] The substrate of layer A used in the material layer assemblies (stacks) described herein is typically a flexible material suitable for the application of the assembly. In some embodiments, the substrate is a woven material, such as, but not limited to, woven stainless steel alloys, carbon steel alloys, or aluminum alloys. In some embodiments, the substrate is a textile, polymer (e.g., polyamide, polyester), cellulose material, natural material (e.g., cotton, wool), or synthetic material (e.g., nylon, PET). In some embodiments, the substrate comprises woven, nonwoven, or knitted synthetic or natural fiber textiles. In some embodiments, the substrate comprises a metal mesh, metal sieve, or metal cloth. In some embodiments, the substrate comprises a natural or synthetic polymer film or substrate (e.g., a thin (film) or thicker (substrate) polymer (e.g., plastic) material coating that is not necessarily woven into a textile).

[0086] In some implementations, the binder-free ceramic material includes approximately 1.5m² of projection substrate area per square meter. 2 Up to 100m 2 Approximately 10m 2 Approximately 1500m 2 or about 70m 2 Approximately 1000m 2 Surface area; approximately 15m² per gram of ceramic material 2 Approximately 1500m 2 or about 50m 2 Approximately 700m 2 Surface area; average pore size from about 5 nm to about 200 nm, from about 2 nm to about 20 nm, or from about 4 nm to about 11 nm; thickness from about 100 μm, from about 50 μm, from about 25 μm, from about 20 μm, or from about 0.2 μm to about 25 μm; porosity from about 5% to about 95%, from about 10% to about 90%, from about 30% to about 70%, from about 30% to about 95%, or greater than about 10%; porosity such as about 100 mm as determined by mercury porosimetry. 3 / g to approximately 7500mm 3 / g of void volume; or any combination thereof.

[0087] In some embodiments, the ceramic material (e.g., metal oxides, metal hydroxides, and / or their hydrates) comprises one or more of zinc, aluminum, manganese, magnesium, cerium, copper, gadolinium, tungsten, tin, lead, and cobalt. In some embodiments, the ceramic material comprises transition metals, Group II elements, rare earth elements (e.g., lanthanum, cerium, gadolinium, praseodymium, scandium, yttrium, samarium, or neodymium), aluminum, tin, zinc, or lead.

[0088] In some embodiments, the binderless ceramic surface-modified material comprises a thickness of about 0.5 or 1 to about 100 micrometers, or about 0.5 to about 20 micrometers, or at most about 50 micrometers, or at most about 25 micrometers. In some embodiments, the binderless porous ceramic material comprises a thickness of about 0.2 micrometers to about 25 micrometers. In some embodiments, the thickness is any one of at least 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 any one of 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.

[0089] In some implementations, the binderless ceramic surface modification material comprises approximately 1.1 m² of projected substrate area per square meter. 2 Approximately 100m 2 The surface area. In some embodiments, the binderless porous ceramic material comprises approximately 10 m² of projected substrate area per square meter. 2 Approximately 1500m 2 The surface area. In some embodiments, the surface area per square meter of the projected substrate 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. 2 Any one of them. In some embodiments, the surface area per square meter of projection substrate is about 10 to about 100, about 50 to about 250, about 150 to about 500, about 250 to about 750, about 500 to about 1000, about 750 to about 1200, about 1000 to about 1500, about 70 to about 1000, about 150 to about 800, about 500 to about 900, or about 500 to about 1000 m². 2 Any one of them.

[0090] In some implementations, the binderless ceramic material comprises approximately 15m³ per gram of ceramic material. 2 Approximately 1500m 2The surface area. In some embodiments, the surface area per gram of ceramic material 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. 2 Any one of them. In some embodiments, the surface area per gram of ceramic material is about 15 to about 100, about 50 to about 250, about 150 to about 500, about 250 to about 750, about 500 to about 1000, about 750 to about 1200, about 1000 to about 1500, about 50 to about 700, about 75 to about 600, about 150 to about 650, or about 250 to about 700 m². 2 Any one of them.

[0091] In some embodiments, the binderless ceramic surface-modified material is porous and includes a mesopore average pore size in the range of about 2 nm to about 50 nm. In some embodiments, the average pore size is in the range of about 50 nm to about 1000 nm. In some embodiments, the binderless porous ceramic material includes an average pore size of about 2 nm to about 20 nm. In some embodiments, the average pore size is any one of at least 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 average pore size is any 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.

[0092] In some embodiments, the binderless ceramic surface-modified material is porous, with a porosity of about 5% to about 95%. In some embodiments, the porosity can be at least about or greater than any one of about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%. 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%.

[0093] In some embodiments, the binder-free porous surface-modified material is porous and has a permeability of about 1 to 10,000 millidarcy. In some embodiments, the permeability can be any one of at least about 1, 10, 100, 500, 1000, 5000, or 10,000 millidarcy. In some embodiments, the permeability 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 1000, about 750 to about 2000, about 1000 to about 2500, about 2000 to about 5000, about 3000 to about 7500, about 5000 to about 10,000, about 1 to about 1000, about 1000 to about 5000, or about 5000 to about 10,000 millidarcy.

[0094] In some embodiments, the binderless ceramic material is porous and comprises approximately 100 mm², as determined by mercury porosimetry. 3 / g to approximately 7500mm 3 The void volume is approximately 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 Any of the following per gram. In some embodiments, the void volume is about 100 to about 500, about 200 to about 1000, about 400 to about 800, about 500 to about 1000, about 800 to about 1500, about 1000 to about 2000, about 1500 to about 3000, about 2000 to about 5000, about 3000 to about 7500, about 250 to about 5000, about 350 to about 4000, about 400 to about 3000, about 250 to about 1000, about 250 to about 2500, about 2500 to about 5000, or about 500 to about 4000 mm. 3 Any of / g.

[0095] The ceramic deposit layer is designed to impart one or more functional characteristics to the material aggregate layer as described herein and / or can be designed as a functionalized top coating to provide a bonding surface.

[0096] Preparation methods of ceramic materials

[0097] Ceramic surface modification materials, such as binderless porous ceramic surface modification materials, as described herein, can be prepared by a method comprising immersing or contacting a clean substrate (e.g., a textile substrate) with an aqueous solution containing one or more metal salts for a period of time to obtain a porous coating composition of 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., from about 5 minutes to about 300 minutes) are suitable for the desired thickness, morphology, and surface porosity of the surface modification material to be prepared. The pH of the solution can be adjusted to a range of 1 to 12 by adding acidic or basic materials to adjust the characteristics of the surface modification (e.g., the desired crystal structure and / or surface porosity). 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 salt of a metal cation with an anion such as sulfate, nitrate, chloride, or acetate. In other embodiments, a sodium cation salt is used in conjunction with a metal anion, such as sodium stannate. In some embodiments, the concentration of the metal salt in the aqueous solution is from about 1 mM to about 5 M. In some embodiments, chelating agents or complexing agents, such as citric acid, urea, diamine, triamine or tetraamine, thioglycerol, oleic acid or other fatty acids, polyols, Tween 80 or other surfactants, are included at a concentration of from about 1 mM to about 5 M. pH-controlling chemicals and buffers may optionally be included.

[0098] In some embodiments, the substrate is cleaned by washing and rinsing, as well as by various metal cleaning solutions or cleaning solutions described for a specific substrate, to remove loose and slightly adhered debris. Various process conditions are acceptable for successful removal of loose and slightly adhered debris.

[0099] In some embodiments, an alkaline-based cleaning solution is used to treat the substrate to saponify and remove grease and oil from it. One example is the use of caustic soda in an aqueous solution at a pH of approximately 11 or higher. Other embodiments may use alternative degreasing methods, such as steam- or solvent-based methods or proprietary cleaning agents. Various process conditions are acceptable for successful removal of surface grease and oil.

[0100] In some embodiments, the substrate is further prepared to homogenize the surface using known methods of treating the surface with alkaline etching of the substrate material. This process generates surface oxides and hydroxides, reaction products, and intermetallic compound materials, some of which are insoluble in the etching solution and must be removed from the substrate by rinsing, mechanical means, or by a process known in industry as demutting. Demutting or deoxidizing solutions typically include acid solutions such as chromic acid, sulfuric acid, nitric acid, or phosphoric acid, or combinations thereof. Ferric sulfate solutions can be used. Demutting solutions remove reaction products, oxides, hydroxides, and intermetallic compound materials by dissolving or mechanically removing substances (e.g., silicon-containing particles). Many proprietary surface pretreatment materials are available. Other surface pretreatment options, such as acid etching, electropolishing, ultrasonic treatment, or other surface finishing methods for removing substrate oxides, hydroxides, reaction products, and intermetallic compounds, have also been successfully used. Various process conditions are acceptable for successful surface pretreatment of the substrate and removal of contaminants.

[0101] In other embodiments, alternative surface pretreatments for subsequent processing include exposure to strong oxidants (such as persulfates, hypochlorites, permanganates, oxidizing acids, UV / ozone, or oxygen plasma) to activate the substrate.

[0102] In some embodiments, one or more processing steps are used to treat the substrate, wherein the substrate reacts with a treatment bath to form a nanostructured material. The solutions described herein are water-based and comprise about 1 mM to about 5 M of a metal salt and / or a chelating agent or complexing agent, such as polyols, polyethers, urea, secondary and higher amines, diamines, triamines, or tetraamines, in aqueous solution. Process conditions (excluding hydrostatic pressure at different tank depths) range from 65 to 200 kPa, and the temperature range across the liquid phase equilibrium of these solutions ranges from -20°C to 190°C, depending on the concentration and composition.

[0103] In some embodiments, the substrate is removed from the solution and heated at a temperature of about 100°C to about 1000°C for about 0 hours to about 5 hours. In some embodiments, the substrate is removed from the solution and heated at a temperature of about 100°C to about 1000°C for about 0 hours to about 24 hours to remove substantially all water from the substrate and the metal oxide surface modifier. A controlled atmosphere furnace may be used to further modify the surface conditions.

[0104] Optionally, the substrate is immersed in a dilute solution (e.g., less than about 2%, or about 0.001% to about 2%) of functional molecules with a suitable solvent that can chemically bond with the ceramic surface, such that the pores are functionalized but remain open.

[0105] In some embodiments, the method includes partially filling the pores with one, two, or more materials. For example, the method includes (a) taking a substrate having a surface-fixed porous ceramic surface, immersing it in a dilute solution of functional molecules capable of chemically bonding with the ceramic surface, such that the pores are functionalized but remain open, and / or (b) immersing the substrate in another solution to deposit more ceramic within the pores and on the surface as described above, and heating as previously described to remove water; and optionally repeating (a) or (b) or (a) and (b) to stack multiple layers within the pores of various functional molecules and / or metal oxides. Other non-limiting methods for introducing the first or second material, such as spraying, pouring, dripping, or vapor deposition, may be employed.

[0106] In some embodiments, the method includes completely filling the pores with one or more materials. For example, the method includes taking a substrate having a surface-fixed porous ceramic surface and immersing it in a more concentrated solution (e.g., about 1% to about 20%) of functional molecules capable of chemically bonding with the ceramic surface, thereby filling the pores with the material; and / or immersing the substrate in another metal salt solution as described above and removing the water as described above to completely fill the pores. Other non-limiting methods for introducing pore-filling materials can be employed, such as spraying, pouring, dripping, atomizing, or vapor deposition.

[0107] Exemplary Implementation

[0108] The following provides exemplary embodiments of the material assemblies as described herein. The combination and application of materials are provided as examples and are not limiting.

[0109] medical bandages

[0110] The assemblies described herein can be configured for use in medical bandages. The bandages are designed to maintain cleanliness and prevent external moisture through an outer layer with superhydrophobic properties, an absorbent layer that removes moisture from the wound, a filling layer that provides protection for the wound, and a hydrophilic inner layer that helps keep the wound dry. Each layer can also be functionalized with antimicrobial properties or healing agents, ointments, or other materials.

[0111] As shown in Figure 1, examples of such assemblies include: those included in synthetic substrate materials. ( For example, superhydrophobic ceramics on nylon or PET (A) t Layer; and A including superhydrophilic ceramics on a natural substrate material (cotton). b layer. A t and A b The B layer between the layers provides absorption, structural, and filling properties.

[0112] Functional outerwear

[0113] The assemblies described herein can be configured for use in clothing, such as functional outerwear. An inner layer, which laterally absorbs moisture and allows it to reach the surrounding top layer, an insulation layer, and an outer layer with high moisture permeability while also repelling water and oil, for example, to promote cleanliness, can be provided.

[0114] As shown in Figure 2, examples of such assemblies include: A superhydrophobic ceramics comprising a synthetic substrate (e.g., nylon or PET). t Layer; and A including superhydrophobic ceramics on a synthetic substrate (e.g., nylon or PET). b layer. A t Layer and A b The B layer between the layers provides thermal insulation properties.

[0115] Pipe insulation

[0116] The assembly described herein can be configured for pipe insulation or pipe protection. The assembly is designed as a high-temperature insulation jacket with a hydrophobic “environmental side” liner surrounding and in contact with the pipe and a hydrophilic “thermal side” liner. For example, the environmental side liner can be composed of a metal mesh (e.g., stainless steel mesh) with a ceramic (e.g., nanostructured) surface and hydrophobic properties, which maintain insulation performance by preventing moisture from penetrating the insulation material. The thermal side liner can be composed of a metal mesh with a ceramic (e.g., nanostructured) surface that exhibits capillary action to wick moisture and promote evaporation. By combining the metal mesh layer with a barrier layer, this system offers the same technological and commercial advantages as existing insulation jacket materials at a fraction of the original cost. The system is also capable of operating at higher temperatures than existing PTFE-based solutions, and compared to metal foil, it is externally waterproof yet breathable.

[0117] As shown in Figure 3, examples of such assemblies include: A superhydrophobic ceramics comprising a metal mesh substrate. t Layer; and A including superhydrophilic ceramics on a metal mesh substrate. b layer. A t Layer and A b The B layer between the layers provides thermal insulation properties.

[0118] Medical plaster

[0119] As an extension of the aforementioned medical bandage applications, the assembly described herein can be configured as a medical plaster. An additional antimicrobial layer can be provided at the bottom of the layer stack to prevent infection and / or odors associated with cleaning difficulties that lead to microbial invasion. Additional layers may also be added.

[0120] As shown in Figure 4, examples of such assemblies include: A superhydrophobic ceramics comprising a synthetic substrate material (e.g., nylon or PET). t Layer; and A including the bottom surface of the assembly and comprising antimicrobial ceramics on a synthetic substrate material (e.g., nylon or PET). b Layer. Including A on the bottom surface of the assembly. b A above the layer b The layer comprises a superhydrophilic ceramic on a synthetic substrate material (e.g., nylon or PET). t and A b Layer B between the layers provides structural and filling properties.

[0121] Medical / surgical clothing

[0122] The assemblies described herein can be configured for use in medical / surgical instruments or clothing. The assemblies are designed to be breathable (high moisture permeability), antimicrobial, and splash-proof (waterproof), providing barrier properties without sacrificing comfort.

[0123] As shown in Figure 5, examples of such assemblies include: A superhydrophobic ceramics comprising a synthetic substrate material (e.g., nylon or PET). t Layer; and A including antimicrobial ceramics on synthetic (e.g., nylon or PET) or natural (e.g., cotton) substrate materials. b layer.

[0124] Other applications

[0125] Other non-limiting examples of applications that may employ the material assemblies described herein include the following, with each layer listed from the bottom surface layer to the top surface layer (environmentally exposed):

[0126] • Filtration / Separation: Size exclusion (retention) (A) - Structural integrity (B) - Antimicrobial (A)

[0127] Packaging materials: Moisture permeability (A) - Structural integrity (B) - Filling (B) - Waterproofing (A)

[0128] • Hospital bedding: Filling (B) - Moisture permeability (A) - Breathability (A) - Hygroscopicity (A) - Antimicrobial properties (A)

[0129] • Protective cover: Moisture permeability (A) - Breathability (A) - Antimicrobial (A) - Chemical resistance (A) - Waterproof (A)

[0130] • Protective clothing: Moisture permeability (A) - Breathability (A) - Chemical resistance (A) - Water resistance (A) - Thermal insulation (B) - Structure (B) - Flame retardancy

[0131] • Architectural textiles: Moisture permeability (A) - Breathability (A) - Chemical resistance (A) - Water resistance (A) - Thermal insulation (B) - Flame retardancy (A) - Color (A) - UV stability (A)

[0132] • Geotextiles: Moisture permeability (A) - Air permeability (A) - Chemical resistance (A) - Water resistance (A) - Thermal insulation (B) - Structure (B) - Environmental stability (A)

[0133] The order of the layers in the above-described articles and applications may differ from those in the examples, and in some embodiments, the multiple functions described may be combined into a single layer.

[0134] The following examples are intended to illustrate, rather than limit, the invention.

[0135] Example

[0136] Example 1. Method for testing the performance of layered stacks

[0137] The following methods are used to characterize the material assemblies described herein.

[0138] The contact angle of the layer was determined using the horizontal drop method by distributing a 10-microliter droplet onto the surface. An image of the droplet was captured 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 liquid-gas interface at the contact surface. This procedure was repeated three times, and the reported contact angle is the average of the three individual measurements.

[0139] The vapor transmission rate of a stacked layer is determined as follows. Each layer is cut to the same size and stacked. A container filled with a known mass of dry desiccant is sealed to the bottom side of the stack. For stacks consisting of multiple layers, these layers are sealed together along their edges, so that the only path for vapor to enter the stack is through the top layer. The stack and desiccant are placed in a temperature and humidity controlled chamber. Samples are collected every 30 minutes to determine the amount of water vapor that passes through the layers and adsorbs onto the desiccant from the chamber. Once the mass of the desiccant is increased by 10%, the test is stopped, and the vapor transmission rate per unit area per unit time through each stack is measured.

[0140] The water column breakthrough pressure was determined as follows. A vertical tube with an inner diameter of 12.7 mm was sealed to the top layer of a stack. For stacks consisting of multiple layers, these layers were sealed together along their edges, allowing water to enter or leave the stack only by flowing through the top and bottom layers. The tube was filled by distributing water downwards along its side to prevent direct impact on the top layer of the stack. Water was incrementally distributed, increasing the water column height by 1 cm at a time, followed by a 5-second interval of no water distribution. The column was filled in this manner until the water column height began to decrease, indicating that water in the column had broken through the material stack. The maximum filling height for each sample was recorded.

[0141] Example 2

[0142] The functionalized mesh material as described in the following examples was prepared as follows. First, the mesh substrate was immersed in an acetone bath, and then immersed in an IPA bath to remove any residual oil. These components were then air-dried for 15 minutes. Next, the mesh substrate was placed in a preparative bath containing 20-250 mM of a metal nitrate or sulfate, or a mixture of metal nitrates or sulfates, and similar molar amounts of a diamine, triamine, or tetraamine, and allowed to react and settle at a reaction temperature of 50-85°C. The aggregate was held in the bath for approximately 5 minutes to approximately 3 hours. The aggregate was removed, the liquid drained, and placed in an oven to dry and / or calcined at 50-600°C for several minutes to several hours. Optionally, this deposition and calcination step could be repeated if desired. After cooling, this portion was further processed and / or tested as described in the following examples.

[0143] Example 3

[0144] The stainless steel mesh layer is coated with a ceramic material composed of manganese oxide, thus achieving hydrophilic surface properties. The water contact angle, measured by the horizontal drop method, is less than 5 degrees. The layer is placed in a cup containing approximately 1 cm of deionized water, with a portion of the layered sample in contact with the deionized water. After 2 minutes, the capillary rise, as observed through the visible wet line, is measured to be approximately 3 cm above the liquid level on the sample. The capillary rise is measured as described in PCT application number PCT / US19 / 65978 (see, for example, Figures 1A to 1C). The vapor transmission rate is measured to be 130 g / h / m. 2 The test water column broke through the pressure, and the layer could not support any measurable water column height.

[0145] Example 4

[0146] A stainless steel mesh layer is coated with a ceramic material composed of manganese oxide. The surface is then functionalized using a dilute solution of hexadecylphosphonic acid in isopropanol to achieve hydrophobic properties. The water contact angle was measured to be 151 degrees using the horizontal drop method. The layer was placed in a cup containing approximately 1 cm of deionized water. After 2 minutes, no significant rise in water level was observed above the liquid level. The vapor transmission rate was measured to be 145 g / h / m. 2 The breakthrough pressure of the water column was measured to be a water level difference of 25 cm.

[0147] Example 5

[0148] The test was conducted on a stainless steel mesh layer without any surface pre-processing. The water contact angle was measured to be 20 degrees using the horizontal drop method. The layer was placed in a cup containing approximately 1 cm of deionized water. After 2 minutes, there was no significant rise in water level above the surface. The vapor transmission rate was determined to be 152 g / h / m. 2 The test water column broke through the pressure, and the layer could not support any measurable water column height.

[0149] Example 6

[0150] A glass fiber insulation layer with a thickness of 5.08 cm and an insulation value of R-6.7 was tested. The vapor transmission rate was measured to be 48 g / h / m. 2 The test water column broke through the pressure, and the layer could not support any measurable water column height.

[0151] Example 7

[0152] The stack of two layers was tested. The top layer was a hydrophobic stainless steel mesh as described in Example 3. The bottom layer was a glass fiber insulation material as described in Example 5. The two layers were joined together by sealing the edges with Kapton tape to prevent compression of the insulation layer. The vapor transmission rate of the entire stack was measured to be 43 g / h / m. 2 The breakthrough pressure of the water column in the entire stack was measured to be 23 cm water level difference.

[0153] Example 8

[0154] The stack of two layers was tested. The top layer was a stainless steel mesh without any surface pre-processing as described in Example 4. The bottom layer was a glass fiber insulation material as described in Example 5. The two layers were joined together by sealing the edges with Kapton tape to prevent compression of the insulation layer. The vapor transmission rate of the entire stack was measured to be 49 g / h / m. 2 The test water column broke through the pressure, and the layer could not support any measurable water column height.

[0155] Example 9

[0156] The three-layer stack was tested. The top layer was a hydrophobic stainless steel mesh as described in Example 3. The middle layer was a glass fiber insulation material 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 insulation layer. The vapor transmission rate of the entire stack was measured to be 53 g / h / m. 2 The breakthrough pressure of the water column in the entire stack was measured to be 22 cm water level difference.

[0157] Example 10

[0158] The three-layer stack was tested. The top layer was a stainless steel mesh without any surface alteration as described in Example 4. The middle layer was a glass fiber insulation material as described in Example 5. The bottom layer was a stainless steel mesh without any surface alteration as described in Example 4. The vapor transmission rate of the entire stack was measured to be 55 g / h / m. 2 The test water column broke through the pressure, and the layer could not support any measurable water column height.

[0159] Example 11

[0160] The aluminum mesh layer is coated with a ceramic material composed of magnesium oxide, thus achieving hydrophilic surface properties. The water contact angle, measured by the horizontal drop method, is less than 5 degrees. The layer is placed in a cup containing approximately 1 cm of deionized water. After 2 minutes, the capillary rise is measured to be approximately 5 cm above the liquid level. The vapor transmission rate is measured to be 150 g / h / m. 2 The test water column broke through the pressure, and the layer could not support any measurable water column height.

[0161] Example 12

[0162] An aluminum mesh layer is coated with a ceramic material composed of magnesium oxide. The surface is then functionalized using a dilute solution of hexadecylphosphonic acid in isopropanol to achieve hydrophobic properties. The water contact angle was measured to be 160 degrees using the horizontal drop method. The layer was placed in a cup containing approximately 1 cm of deionized water. After 2 minutes, no significant rise in water level was observed above the liquid level. The vapor transmission rate was measured to be 150 g / h / m. 2 The breakthrough pressure of the water column was measured to be a water level difference of 100 cm.

[0163] Example 13

[0164] The test was conducted on an aluminum mesh layer without any surface pre-processing. The water contact angle was measured to be 20 degrees using the horizontal drop method. The layer was placed in a cup containing approximately 1 cm of deionized water. After 2 minutes, there was no significant rise in water level above the surface. The vapor transmission rate was determined to be 153 g / h / m. 2 The test water column broke through the pressure, and the layer could not support any measurable water column height.

[0165] Example 14

[0166] The stack of two layers was tested. The top layer was a hydrophobic aluminum mesh as described in Example 11. The middle layer was a glass fiber insulation material as described in Example 5. The two layers were joined together by sealing the edges with Kapton tape to prevent compression of the insulation layer. The vapor transmission rate of the entire stack was measured to be 48 g / h / m. 2The breakthrough pressure of the water column in the entire stack was measured to be 62 cm water level difference.

[0167] Example 15

[0168] The stack of two layers was tested. The top layer was an aluminum mesh without any surface pre-processing as described in Example 12. The middle layer was a glass fiber insulation material as described in Example 5. The two layers were joined together by sealing the edges with Kapton tape to prevent compression of the insulation layer. The vapor transmission rate of the entire stack was measured to be 48 g / h / m. 2 The test water column broke through the pressure, and the layer could not support any measurable water column height.

[0169] Example 16

[0170] The three-layer stack was tested. The top layer was a hydrophobic aluminum mesh as described in Example 11. The middle layer was a glass fiber insulation material as described in Example 5. The bottom layer was a hydrophilic aluminum mesh as described in Example 10. The three layers were joined together by sealing the edges with Kapton tape to prevent compression of the insulation layer. The vapor transmission rate of the entire stack was measured to be 48 g / h / m. 2 The breakthrough pressure of the water column in the entire stack was measured to be 62 cm water level difference.

[0171] Example 17

[0172] The three-layer stack was tested. The top layer was an aluminum mesh without any surface alteration as described in Example 12. The middle layer was a glass fiber insulation material as described in Example 5. The bottom layer was an aluminum mesh without any surface alteration as described in Example 12. The three layers were joined together by sealing the edges with Kapton tape to prevent compression of the insulation layer. The vapor transmission rate of the entire stack was measured to be 47 g / h / m. 2 The test water column broke through the pressure, and the layer could not support any measurable water column height.

[0173] Example 18

[0174] A polyester film moisture barrier with a thickness of 0.005 cm was tested. The vapor transmission rate was determined to be 1 g / h / m. 2 The breakthrough pressure of the water column was measured to be greater than a water level difference of 200 cm.

[0175] Example 19

[0176] The stacking of two layers was tested. The top layer was a polyester film as described in Example 16. The bottom layer was a glass fiber insulation material as described in Example 4. The vapor transmission rate was measured to be 1 g / h / m. 2The breakthrough pressure of the water column was measured to be greater than a water level difference of 200 cm.

[0177] Example 20

[0178] A 40d (40 denier) woven polyamide textile layer is coated with a ceramic material composed of magnesium oxide, resulting in a hydrophilic surface. The water contact angle, measured by the horizontal drop method, is less than 5 degrees. The vapor transmission rate is determined to be 175 g / h / m². 2 The test water column broke through the pressure, and the layer could not support any measurable water column height.

[0179] Example 21

[0180] A 40-day woven polyamide textile layer was coated with a ceramic material composed of magnesium oxide. The surface was then functionalized using a dilute solution of hexadecylphosphonic acid in isopropanol to achieve hydrophobic properties. The vapor transmission rate was measured to be 170 g / h / m. 2 The breakthrough pressure of the water column was measured to be 55 cm of water level difference.

[0181] Example 22

[0182] The test was conducted on a 40-day woven polyamide textile layer without any surface pre-treatment. The vapor transmission rate was determined to be 170 g / h / m. 2 The test water column broke through the pressure, and the layer could not support any measurable water column height.

[0183] Example 23

[0184] The test was conducted on a 1.1 cm thick Thinsulate G80 layer with an insulation value of R-1.6. The vapor transmission rate was measured to be 100 g / h / m. 2 The test water column broke through the pressure, and the layer could not support any measurable water column height.

[0185] Example 24

[0186] The stack of two layers was tested. The top layer was a hydrophobic 40d woven polyamide textile as described in Example 19. The bottom layer was Thinsulate G80 as described in Example 21. The vapor transmission rate of the entire stack was measured to be 100 g / h / m. 2 The breakthrough pressure of the water column in the entire stack was measured to be 55 cm water level difference.

[0187] Example 25

[0188] The stack of two layers was tested. The top layer was a 40-day woven polyamide textile without any surface pretreatment as described in Example 20. The bottom layer was Thinsulate G80 as described in Example 21. The vapor transmission rate of the entire stack was measured to be 100 g / h / m. 2 The test water column broke through the pressure, and the layer could not support any measurable water column height.

[0189] Example 26

[0190] The three-layer stack was tested. The top layer was a hydrophobic 40-day 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 40-day woven polyamide textile as described in Example 18. The vapor transmission rate of the entire stack was measured to be 90 g / h / m. 2 The breakthrough pressure of the water column in the entire stack was measured to be 50 cm water level difference.

[0191] Example 27

[0192] The three-layer stack was tested. The top layer was a 40-day woven polyamide textile with no surface alteration as described in Example 20. The middle layer was Thinsulate G80 as described in Example 21. The bottom layer was a 40-day woven polyamide textile with no surface alteration as described in Example 20. The vapor transmission rate of the entire stack was measured to be 90 g / h / m. 2 The test water column broke through the pressure, and the layer could not support any measurable water column height.

[0193] Example 28

[0194] A stainless steel mesh layer was pitted during acid etching, then coated with a binder-free structured manganese oxide ceramic surface modifier. The stainless steel mesh layer was deposited in a 25-75 mM aqueous manganese nitrate solution and a similar amount of hexamethylenetetramine or urea at a temperature of approximately 60°C to 80°C for approximately 60 to 240 minutes. The mesh was then calcined at approximately 400°C to 600°C for approximately 1 hour to obtain a hydrophilic surface. The water contact angle was measured to be less than 5 degrees using the horizontal drop method. The mesh was placed in a cup containing approximately 1 cm of deionized water. After 2 minutes, the capillary rise was measured to be approximately 3 cm above the liquid level. The capillary rise was measured as described in PCT application number PCT / US19 / 65978 (see, for example, Figures 1A to 1C). The vapor transmission rate was measured to be 130 g / h / m. 2 The test water column broke through the pressure, and the layer could not support any measurable water column height.

[0195] Example 29

[0196] An aluminum mesh layer coated with a ceramic material composed of magnesium oxide was deposited in a 25-75 mM magnesium nitrate aqueous solution and a similar amount of hexamethylenetetramine at a temperature of approximately 60°C to 80°C for approximately 30-90 minutes. The mesh was then calcined at approximately 300°C to 600°C for approximately 1 hour to obtain hydrophilic surface properties. The water contact angle was measured to be less than 5 degrees using the horizontal drop method. The layer was placed in a cup containing approximately 1 cm of deionized water. After 2 minutes, the capillary rise was measured to be approximately 5 cm above the liquid level. The vapor transmission rate was measured to be approximately 150 g / h / m. 2 The water column was tested for pressure; the layer could not support any measurable water column height.

[0197] Example 30

[0198] Woven polyester and woven nylon textiles were sputtered with aluminum to approximately 250 nm. The textiles were cut into small pieces and coated with three different ceramic materials: a) a magnesium oxide / magnesium hydroxide-based ceramic, b) and a manganese oxide / manganese hydroxide-based ceramic, and c) and a zinc oxide / hydroxide-based ceramic. All three ceramics contained a significant amount of alumina / aluminum hydroxide. The ceramics were deposited using a method similar to that described in Example 1 (using a 2+ metal nitrate or metal sulfate of each corresponding cation found in the ceramic). The contact angle of the samples was tested, and the samples showed a contact angle of less than 15 degrees. The ceramic-modified textiles were then dipped into a diluted bath (0.1% to 1%) of hexadecylphosphonic acid in isopropanol or hexadecyltriethoxysilane in ethanol. In the case of silanes, a small amount of acetic acid catalyst was sometimes used. The contact angle of the samples was then measured again, and the samples showed a contact angle of approximately 150 to 160 degrees. Moisture transmittance was within the measurement error of the unmodified fabric.

[0199] Example 31

[0200] Polyester, polyamide, and Tencel textiles coated with zinc oxide-based ceramics were woven by immersing textiles in approximately 200-500 mM zinc sulfate, approximately 50-150 mM potassium persulfate, and approximately 1.2 to 1.7 mol ammonium hydroxide for approximately 5 to 60 minutes at room temperature. Nickel oxide deposits were also formed on the polyester by replacing zinc sulfate with nickel sulfate. Similarly, manganese oxide deposits were formed on the polyester by replacing zinc sulfate with manganese sulfate and permanganate with persulfate. These samples were then dried at approximately 105°C to approximately 140°C for approximately 1 to 2 hours. The contact angle of the samples was tested, and the samples showed a contact angle of less than 15 degrees. The ceramic-modified textiles were then dipped into a diluted bath (0.1% to 1%) of hexadecylphosphonic acid in isopropanol or hexadecyltriethoxysilane in ethanol. In the case of silanes, a small amount of acetic acid catalyst was sometimes used. The contact angle of the samples was then measured again, and the samples showed a contact angle of approximately 150 to 160 degrees.

[0201] Example 32

[0202] At a temperature of approximately room temperature to approximately 80°C, woven polyamide and polyester textiles are immersed in a water bath containing approximately 5 to 200 mM potassium permanganate and approximately 10 to 400 mM ammonium hydroxide for approximately 5 minutes to approximately 1 hour. A typical ratio of permanganate to ammonium hydroxide is approximately 1:2. The substrate is then dried, and a structured ceramic layer comprising manganese oxide / manganese hydroxide, zinc oxide / zinc hydroxide, or magnesium oxide / magnesium hydroxide is deposited on the substrate by immersing it in an aqueous solution of 25 to 150 mM metal (Mn, Zn, or Mg) nitrate and a similar amount of hexamethylenetetramine for approximately 5 to 90 minutes. The web is then dried at a temperature of approximately 100 to 250°C for approximately 1 hour. The contact angle of the sample is measured and found to be less than approximately 15 degrees. The ceramic-modified textile is then dipped into a diluted bath (0.1% to 1%) of hexadecylphosphonic acid in isopropanol or hexadecyltriethoxysilane in ethanol. In the case of silanes, a small amount of acetic acid catalyst is sometimes used. The contact angle of the sample was then measured again, and the sample showed a contact angle of approximately 150 to 160 degrees.

[0203] While the invention has been described in detail with reference to illustrations and embodiments for clarity, it will be apparent to those skilled in the art that certain changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. Therefore, the description should not be construed as limiting the scope of the invention.

[0204] All publications, patents and patent applications cited herein are incorporated herein in their entirety by reference for all purposes, and to the extent that each individual publication, patent or patent application is expressly and individually indicated as being incorporated herein by reference.

Claims

1. A material assembly including a top surface and a bottom surface, comprising: (a) x A's t A material layer comprising one or more functional properties, wherein A t The material layer includes a top layer including the top surface, wherein one or more functional properties include anti-icing, anti-frost, superhydrophobicity, superhydrophilicity, microbial growth inhibition, corrosion resistance, flame retardancy, dynamic wind resistance, abrasion resistance, durability, or a combination thereof. (b) y A's b A material layer comprising one or more functional properties, wherein A b The material layer includes a bottom layer comprising the bottom surface, wherein the one or more functional properties include anti-icing, anti-frost, superhydrophobicity, superhydrophilicity, microbial growth inhibition, corrosion resistance, flame retardancy, dynamic wind resistance, abrasion resistance, durability, or combinations thereof; and (c) In the x A t Material layer and the y A b Z B-layers of insulating or structural material between material layers. Where x, y, and z are the same or different layer numbers. Wherein A t Material layer and the A b Each material layer comprises a nanostructured binderless ceramic material directly deposited on the substrate. Where direct deposition is in each A t Material layers and / or each A b The nanostructured binderless ceramic materials on the substrate of the material layer may be the same or different, and The deposition in each A t Material layers and / or each A b The nanostructured binderless ceramic material on the material layer is a partially filled porous structure. The pores of the nanostructured binderless ceramic material are partially filled with a second ceramic material or molecules having head and tail groups. The material assembly described herein includes breathability through which the material assembly passes. Wherein is used for A t Material layer and the A b The substrate of the material layer includes materials selected from: woven, nonwoven, or knitted synthetic or natural textiles, or synthetic or natural polymer materials. At least one of A t Material layer and / or at least one A b The material layer includes a topcoat material, and wherein the nanostructured binderless ceramic material and the topcoat material synergistically impart one or more functional properties, the magnitude of which is greater than the same functional properties imparted by the nanostructured binderless ceramic material or the topcoat material independently deposited on the same substrate surface.

2. The material assembly according to claim 1, wherein the polymer material is a film.

3. The material assembly according to claim 1, wherein the nanostructured binderless ceramic material is primarily crystalline.

4. The material assembly according to claim 1, wherein the nanostructured binderless ceramic material comprises metal oxides, hydrates of metal oxides, metal hydroxides and / or hydrates of metal hydroxides.

5. The material assembly of claim 4, wherein the nanostructured binderless ceramic material comprises a metal hydroxide, and wherein at least a portion of the metal hydroxide comprises a layered double hydroxide.

6. The material assembly according to claim 1, wherein at least one A t The substrate of the material layer and for at least one A b The substrate of the material layer, or for at least two A t The substrate of the material layer, or for at least two A b The substrate of the material layer includes different materials.

7. The material assembly according to claim 6, wherein x and / or y are greater than 1, and wherein each A t Material layers and / or each A b The material layer includes other A t Material layer and / or A b Different functional properties of material layers.

8. The material assembly of claim 6, wherein the topmost layer including the top surface and the bottommost layer including the bottom surface have the same functional characteristics.

9. The material assembly of claim 6, wherein the topmost layer including the top surface and the bottommost layer including the bottom surface have different functional characteristics.

10. The material assembly of claim 1, wherein each B insulating or structural material layer comprises one or more structural properties selected from: thermal resistance, electrical resistance, structural support, mechanical filling and fluid transport features or combinations thereof.

11. The material assembly of claim 1, wherein one or more B insulating or structural material layers comprise a second ceramic material selected from glass fiber, porous ceramics and other inorganic materials.

12. The material assembly according to any one of claims 1 to 11, wherein the material assembly is incorporated into functional outerwear, medical bandages, medical plaster, surgical gowns, filtering or separating media, packaging materials, hospital bedding, absorbent textiles, protective covers, protective clothing, architectural textiles or geotextiles.

13. A pipe insulation or protection material comprising the material assembly as described in claim 1, One or more of A t The material layers include hydrophobic or superhydrophobic functional properties, wherein one or more B-layer insulating or structural material layers include thermal insulation, protective, or structural properties, and One or more of A b The material layer includes hydrophilic or superhydrophilic functional properties.

14. The pipe insulation or protection material according to claim 13, The material assembly described above surrounds the pipe. The bottommost A b The material layer is in contact with the pipe, and The topmost A t The material layer is in contact with the surrounding environment.

15. The pipe insulation or protection material according to claim 13, wherein one or more A t Material layer and / or one or more A b The textile or polymer material substrate of the material layer includes ceramic-coated woven materials.

16. The pipe insulation or protection material according to claim 13, wherein at least one B insulation or structural material layer comprises a material selected from: glass fiber, silicon carbide, ceramic fiber insulation material, silicone, mineral wool, basalt, foam glass, polyimide, calcium silicate, and silicon dioxide.

17. The pipe insulation or protection material according to claim 16, wherein the silicone is silicone foam.

18. A conduit surrounded by a conduit insulation or protective material according to any one of claims 13 to 17.

19. A textile material comprising the material assembly as described in claim 1, One or more of A t The material layer includes hydrophobic or superhydrophobic functional properties. One or more of the B-layers of insulating or structural material include thermal, protective, or structural properties, and One or more of A b The material layer includes hydrophilic or superhydrophilic functional properties.

20. The textile material according to claim 19, wherein one or more A t Material layer and / or one or more A b The substrate of the material layer includes woven materials.

21. The textile material according to claim 19, wherein one or more A t Material layer and / or one or more A b The substrate of the material layer includes textiles.

22. The textile material of claim 20, wherein the weaving material is selected from: polymer substrates, cellulose materials, cotton, and wool.

23. The textile material according to claim 22, wherein the polymer substrate is polyamide or polyester.

24. The textile material according to claim 22, wherein the polymer substrate is a film.

25. The textile material according to claim 19, wherein one or more A t Material layer and / or one or more A b The substrate of the material layer includes nylon or polyethylene terephthalate (PET).

26. The textile material according to any one of claims 19 to 25, wherein one or more B insulating or structural material layers comprise materials selected from: polyester, fleece, wool, and feathers.

27. A material assembly including a top surface and a bottom surface, comprising: (a) x layers of material A, each comprising one or more functional properties, wherein the material A layers include a top layer comprising the top surface, wherein the one or more functional properties include anti-icing, anti-frost, superhydrophobicity, superhydrophilicity, microbial growth inhibition, corrosion resistance, flame retardancy, dynamic wind resistance, abrasion resistance, durability, or a combination thereof. Each of the A material layers comprises a nanostructured binderless ceramic material directly deposited on a substrate; and (b) z layers of B-type insulating or structural material. The B insulating or structural material layer includes a bottom layer comprising the bottom surface, and Where x and z are the same or different layer numbers. The nanostructured binderless ceramic material on at least one A material layer is a partially filled porous structure. The pores of the nanostructured binderless ceramic material are partially filled with a second ceramic material or molecules having head and tail groups. The material assembly described herein includes breathability through which the material assembly passes. The substrate used for the A material layer comprises materials selected from: woven, nonwoven, or knitted synthetic or natural textiles, or synthetic or natural polymer materials. At least one of the A material layers includes a topcoat material, and the nanostructured binderless ceramic material and the topcoat material synergistically impart one or more functional properties, the magnitude of which is greater than the same functional properties imparted by the nanostructured binderless ceramic material or the topcoat material independently deposited on the same substrate surface.

28. The material assembly according to claim 27, wherein the polymer material is a film.

29. A material assembly including a top surface and a bottom surface, comprising: (a) x A's t A material layer comprising one or more functional properties, wherein A t The material layer includes a top layer comprising the top surface, wherein the one or more functional properties include anti-icing, anti-frost, superhydrophobicity, superhydrophilicity, microbial growth inhibition, corrosion resistance, flame retardancy, dynamic wind resistance, abrasion resistance, durability, or a combination thereof; and (b) y A's b A material layer comprising one or more functional properties, wherein A b The material layer includes a bottom layer comprising the bottom surface, wherein the one or more functional properties include anti-icing, anti-frost, superhydrophobicity, superhydrophilicity, microbial growth inhibition, corrosion resistance, flame retardancy, dynamic wind resistance, abrasion resistance, durability, or a combination thereof. Wherein A t Material layer and the A b Each material layer comprises a nanostructured binderless ceramic material directly deposited on the substrate. Direct deposition in A t The ceramic material on the substrate of the material layer and directly deposited on A b The ceramic material on the substrate of the material layer is different. Where x and y are the same or different The deposition is in at least A t Material layer and / or at least one A b The nanostructured binderless ceramic material on the material layer is a partially filled porous structure. The pores of the nanostructured binderless ceramic material are partially filled with a second ceramic material or molecules having head and tail groups. The material assembly described herein includes breathability through which the material assembly passes. Wherein is used for A t Material layer and the A b The substrate of the material layer includes materials selected from: woven, nonwoven, or knitted synthetic or natural textiles, or synthetic or natural polymer materials. At least one of A t Material layer and / or at least one A b The material layer includes a topcoat material, and wherein the nanostructured binderless ceramic material and the topcoat material synergistically impart one or more functional properties, the magnitude of which is greater than the same functional properties imparted by the nanostructured binderless ceramic material or the topcoat material independently deposited on the same substrate surface.

30. The material assembly according to claim 29, wherein the polymer material is a film.

31. The material assembly according to any one of claims 27-30, wherein the nanostructured binderless ceramic material is primarily crystalline.

32. The material assembly according to any one of claims 27-30, wherein the nanostructured binderless ceramic material comprises metal oxides, hydrates of metal oxides, metal hydroxides and / or hydrates of metal hydroxides.

33. The material assembly of claim 32, wherein the nanostructured binderless ceramic material comprises a metal hydroxide, and wherein at least a portion of the metal hydroxide comprises a layered double hydroxide.

34. The material assembly according to any one of claims 1, 2, 27, 28, 29, or 30, wherein the material assembly is externally waterproof but permeable to vapor.

35. The material assembly of claim 34, wherein the material assembly is waterproof as measured by contact angle and vapor-permeable as measured by vapor transmission rate.

36. The material assembly according to claim 35, wherein the contact angle is greater than 120°.

37. The material assembly according to claim 36, wherein the contact angle is greater than 150°.

Images