Ceramic composite materials

Abstract

Composite ceramic materials are disclosed in which an interconnected network of ceramic material on a substrate includes pores having an accessible pore volume that are at least partially filled with a polymer, resin, and / or wax.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to PCT application PCT / US2019 / 065978 filed on 12 December 2019, and claims the benefits of U.S. Provisional Applications 62 / 989,092, 62 / 989,150, 63 / 038,642, 63 / 038,693, and 63 / 039,965, filed on 13 March 2020, which are incorporated herein by reference in their entirety.

[0002] Field of Invention The present invention relates to ceramic composite materials, more particularly to composite materials of porous ceramic materials in which an interconnected network of ceramics comprises at least partially accessible pore volumes filled with polymers, resins, and / or waxes. [Background technology]

[0003] Composite materials can offer synergistic advantages by combining the properties of each material that constitutes the composite. Metal substrates, particularly aluminum substrates, sometimes have problems with insufficient adhesion of bonded layers, and they can also corrode if the natural oxides are damaged. Polymers, resins, and wax materials are often used to protect the underlying substrate or to modify the way the substrate interacts with the environment. When these materials are applied directly to a smooth metal substrate, insufficient adhesion, or aesthetic problems such as sagging, running, and mottling, or other problems related to the amount of material applied, can occur. Materials with higher adhesion, uniformity, and / or aesthetic properties are desired. [Overview of the project]

[0004] Composite materials and compositions containing the above-mentioned composite materials are provided. Applications of the above-mentioned composite materials are also provided.

[0005] In one embodiment, a composition is provided comprising (i) a composite material comprising a polymer, wax, and / or resin impregnated in a porous ceramic material, wherein the porous ceramic material comprises at least partially an interconnected network of pores having an accessible pore volume filled with the polymer, resin, and / or wax, and (ii) a substrate, wherein the composite material is in contact with the substrate. In some embodiments, at least a portion or substantially all of the composite material is in direct contact with the substrate. In some embodiments, at least 20% by mass, 30% by mass, 40% by mass, 50% by mass, 60% by mass, 70% by mass, 80% by mass, or 90% by mass of the ceramic material is interconnected.

[0006] In some embodiments, the substrate and the ceramic material each contain a primary metal, and the primary metal in the ceramic material is different from the primary metal in the substrate. In other embodiments, the substrate and the ceramic material each contain a primary metal, and the primary metal in the ceramic material is the same as the primary metal in the substrate.

[0007] In some embodiments, the thickness of the composite material is approximately 1 micrometer to approximately 100 micrometers.

[0008] The ceramic material may contain rare earth elements, transition metal elements, alkaline earth metal elements, or aluminum. The ceramic material may also contain oxides, hydroxides, and / or layered double hydroxides. In some embodiments, the oxides, hydroxides, and / or layered double hydroxides include iron, aluminum, magnesium, cerium, zinc, manganese, titanium, chromium, nickel, cobalt, copper, silver, tantalum, tungsten, silicon, phosphorus, tin, vanadium, zirconium, calcium, barium, or europium.

[0009] The substrate may include an aluminum alloy, a steel alloy, a nickel alloy, a titanium alloy, a polymer, a polysaccharide, or a cellulose-based material (e.g., wood, cotton), or glass.

[0010] In various embodiments, the polymer, wax, and / or resin impart to the composite material one or more functional properties selected from improved hardness, elasticity, viscoelasticity, adhesion, thermal properties, aesthetic appearance, liquid repellency, sound damping, light scattering, and corrosion resistance as compared to the same ceramic material without the polymer, wax, and / or resin on the same substrate.

[0011] In one embodiment, the ceramic material is a binder-free ceramic material. In some embodiments, the polymer, wax, and / or resin includes natural polymers such as tung oil, linseed oil, walnut oil, natural rubber, cellulose, or polymers derived from chitin. In some embodiments, the polymer, wax, and / or resin includes synthetic polymers such as polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyesters such as polyethylene terephthalate, polyacrylates such as poly(methyl methacrylate), polyvinyl acetate, polyethers, polychloroprene, poly(vinyl chloride), polyurethanes, polyamides, polyimides, silicones, poly(dimethylsiloxane), or polyepoxide polymers. In some embodiments, the polymer, wax, and / or resin includes silanes, silicates (e.g., potassium silicate, sodium silicate), siliconates (e.g., potassium methyl silicate, sodium methyl silicate), organotriethoxysilane, or organotrimethoxysilane, polysilazanes (e.g., Durazane 1500, Durazane 1800, or Durazane 2200). In one embodiment, the polymer, wax, and / or resin includes petroleum waxes (e.g., paraffin wax), waxes produced by animals (e.g., beeswax, lanolin, shellac), waxes derived from plants (e.g., palm wax, carnauba wax, soybean wax), or waxes derived from minerals (e.g., ceresin, montan).

[0012] In some embodiments, the polymer, wax, and / or resin includes one or more additional additives such as, but not limited to, lubricants, plasticizers, flame retardants, dyes, UV stabilizers, free radical scavengers, or crosslinking agents. For example, the additives can impart one or more structural or functional properties such as, but not limited to, viscosity, flexibility, flammability, color, UV stability, chemical reactivity, and / or degree of crosslinking to the composite material.

[0013] In some embodiments, the polymer, wax, and / or resin fills at least about 1%, for example, about 1% to about 99%, of the pore volume of the ceramic material as measured by mercury porosimetry.

[0014] In some embodiments, the thickness of the polymer, resin, and / or wax is less than about 1.5 times the thickness of the ceramic material.

[0015] In some embodiments, the ceramic material interacts with the polymer, wax, and / or resin material, thereby altering one or more properties of the polymer, wax, and / or resin. In one example, the interaction may increase the crosslinking rate and / or degree of crosslinking of the polymer, wax, and / or resin, for example, the crosslinking rate and / or degree of crosslinking of carbon chains, compared to the crosslinking rate and / or degree of crosslinking when the polymer, wax, and / or resin is directly coated on the same substrate without the ceramic material. In another example, the interaction may increase the crystallinity of the polymer, wax, and / or resin material compared to the crystallinity when the polymer, wax, and / or resin material is directly coated on the same substrate without the ceramic material. In yet another example, the interaction may decrease the UV decomposition rate of the polymer, wax, and / or resin material compared to the UV decomposition rate of the polymer, wax, and / or resin material when directly coated on the same substrate without the ceramic material. In a non-limiting example, the zinc oxide in the ceramic material may act as a UV absorber.

[0016] In some embodiments, the ceramic material comprises magnesium, manganese, zinc oxide, or aluminum oxide or aluminum hydroxide, and the polymer, wax, and / or resin comprises a drying oil such as tung oil or paraffin.

[0017] In some embodiments, the ceramic material comprises magnesium, manganese, zinc oxide, or aluminum oxide or aluminum hydroxide, and the polymer, wax, and / or resin chemically reacts with the ceramic material to modify one or more properties of the polymer, wax, and / or resin. For example, the chemical reaction for modifying the above(s) properties of the polymer, wax, and / or resin may include crosslinking, curing, and / or polymerization of the polymer, wax, and / or resin.

[0018] In some embodiments, the composite materials described herein are used to provide the substrate with one or more functional properties, including, but not limited to, protection against corrosion of the substrate; a modifier of adhesion and / or durability against surface staining; a component that promotes or delays adhesion; a tactile modification of the surface; liquid-repellent applications; modification of optical properties; mechanical modifications such as hardness, elasticity, and viscoelasticity; self-healing and repair of surfaces and scratches; separation applications; modification of electrical properties or electrical properties; reduction and / or modification of ice, condensate, and frost; or aesthetic properties, wherein the functional properties are improved or more so than those of the same porous ceramic material on the same substrate without the polymer, resin, and / or wax, or compared to the polymer, resin, and / or wax directly applied to the same substrate.

[0019] In some embodiments, the composite material contains a critical pigment / ceramic volume concentration exceeding the critical pigment / ceramic volume concentration of the paint. In some embodiments, the pigment / ceramic volume concentration exceeds about 40%, about 50%, about 60%, about 70%, about 80%, or about 90% of the total volume of the composite material. [Brief explanation of the drawing]

[0020] [Figure 1] This figure shows the X-ray diffraction spectrum of the ceramic material described in Example 1. [Figure 2]This figure shows a comparison of aluminum plates coated with porous ceramic, coated with composite material, and uncoated, as described in Example 11. A: Porous ceramic surface, B: Porous ceramic surface partially filled with RTV silicone, C: Aluminum plate top-coated with RTV silicone [Figure 3] This figure shows a comparison of aluminum plates coated with porous ceramic, coated with composite material, and uncoated, as described in Example 12. A: Porous ceramic surface, B: Porous ceramic surface top-coated with PDMS, C: Aluminum plate top-coated with PDMS. [Figure 4] This figure shows a comparison of porous ceramic-coated, composite-coated, and uncoated aluminum plates subjected to spraying with corrosive salt, as described in Example 16. A: Porous ceramic surface, B: Aluminum plate coated with polyurethane surface treatment agent, C: Porous ceramic filled with polyurethane topcoat agent [Figure 5] This figure shows a comparison of porous ceramic-coated, composite-coated, and uncoated aluminum plates subjected to the grid adhesion test described in Example 17. A: Porous ceramic surface, B: Aluminum plate coated with polyacrylic sealant, C: Porous ceramic filled with polyacrylic sealant [Figure 6] This figure compares the sagging observed on an aluminum plate coated with an acrylic sealant and the visually apparent defects in the coating. A: The aluminum plate coated with acrylic sealant shows sagging; B: The porous ceramic surface coated with acrylic sealant shows no sagging defects. [Figure 7]This figure shows a comparison of the progression of the self-leveling effect over time on porous ceramic substrates with that of exposed aluminum substrates. On zinc oxide-based (B) and manganese oxide-based (C) porous ceramic substrates, a smaller contact angle with the epoxy resin was obtained after 10 minutes compared to the exposed aluminum plate (A). [Figure 8] This figure shows a comparison of the self-leveling effect observed on porous ceramic substrates. Compared to bare aluminum substrates, the zinc-based and manganese-based coated porous ceramic substrates showed smaller contact angles with the epoxy resin and, consequently, greater self-leveling. [Figure 9] This figure shows the wicking behavior of paraffin wax on an aluminum plate coated with the mixed zinc / aluminum oxide and mixed manganese / aluminum oxide ceramics described in Example 22. [Figure 10] This figure shows the wicking behavior of paraffin wax over time on substrates coated with Zn and Mn-based porous ceramics compared to bare aluminum. On substrates coated with porous ceramics, greater wicking, and consequently improved (more uniform) coating, is obtained in 5 minutes compared to a bare aluminum plate. [Modes for carrying out the invention]

[0021] This specification provides ceramic composite materials. The composite materials include porous ceramic materials comprising an interconnected ceramic network. At least a portion of the accessible pore volume is at least partially filled with a polymer, resin, and / or wax. The ceramic composite materials are laminated onto a substrate. The composite materials described herein can be used to provide beneficial properties such as good adhesion to a substrate, to apply a uniform external coating to a substrate such as a metal substrate, and to impart desirable aesthetic properties such as minimizing or eliminating sagging, running, and mottling that often accompanies polymers, resins, and / or waxes directly applied to the substrate described herein.

[0022] definition The numerical ranges provided herein include the numbers that define those ranges.

[0023] "A," "an," and "the" include plural objects unless explicitly indicated by the context.

[0024] The phrase "and / or" as used herein and in the claims should be understood to mean that the elements thus combined, i.e., "either or both," that is, that these elements are conjugated in some cases and not in other cases. Unless explicitly indicated in the context, other elements may be present, whether related to or unrelated to those specifically defined, other than those explicitly indicated by the phrase "and / or." Therefore, the statement "A and / or B," when used in combination with open-ended language such as "comprising," may, in some embodiments, refer to A without B (optionally including elements other than B); in another embodiment, to B without A (optionally including elements other than A); and in yet another embodiment, to refer to A and B (optionally including other elements).

[0025] A "binder" or "binding agent" is any material or substance that holds or attracts other materials together to form a whole by mechanical or chemical bonding.

[0026] "Binder-free" means, in particular, that there are no binders that can be exogenously added to the primary material to improve structural integrity, whether organic binders or resins (polymers, adhesives, asphalt, etc.) or inorganic binders (lime, cement glass, gypsum, etc.).

[0027] "Capillary climb" refers to the surface tension of a liquid that pushes up a sample when it comes into contact with the free surface of a porous substrate (the capillary climb is parallel to and opposite to the direction of the force (vector) due to gravity).

[0028] "Cellulose-based" materials refer to materials composed of or containing cellulose or cellulose derivatives, such as cellulose ethers or esters.

[0029] "Ceramics" or "ceramic materials" refer to solid materials containing inorganic compounds of metals or metalloids, and nonmetals having ionic or covalent bonds. "Nonmetals" may include oxygen (oxide ceramics), or carbon (carbides), or nitrogen (nitrides) (non-oxide ceramics). "Metals" include non-hydrogen elements of Group 1 of the periodic table, elements of Groups 2-12 of the periodic table, or elements of the p block (Groups 12-17 of the periodic table), such as Al, Ga, In, Ti, Sn, Pb, Bi, or combinations thereof. "Metaroids" include B, Si, Ge, As, Sb, Se, Te, or Po, or combinations thereof.

[0030] "Contact angle" refers to the angle between the surface and the gas-liquid interface at a contact surface, as measured by the liquid.

[0031] "Contiguous" or "contiguity" refers to pores and structures that include walls and features that are in direct contact with each other, or that share common walls over a large area or dimension relative to individual pores or structures.

[0032] A "processed coating" refers to a surface layer in which reactants chemically react with the surface being treated, converting the substrate into a different compound. This process is generally additive, or rather, not lamination, and can result in only slight changes in mass.

[0033] The "first quartile pore diameter" refers to the pore diameter value in which the cumulative pore surface area determined in the direction of increasing pore diameter corresponds to 25% of the total cumulative pore surface area determined by the adsorption / desorption measurement of BJH gas.

[0034] A "functional material layer" refers to a layer of material that functions as the uppermost surface layer interacting with the surrounding environment, or as an interface layer with subsequent materials (an intermediate layer between the other two material layers). The functional material layer imparts one or more desirable functional properties to the substrate below, and / or the material on which the functional material layer is laminated.

[0035] In this specification, "gradient" refers to a quantitative increase or decrease in one or more physical or chemical properties of a material observed by spatially passing through one point to another along the surface of a substrate on which the material is placed or fixed, and by changing the x, y, or z direction of Cartesian coordinates on or through the material. Non-limiting examples of gradient properties include thickness, density, hardness, ductility, pore size, pore size distribution, pore fill rate, or chemical or physical composition, such as oxidation state, metal concentration, or crosslink density, resulting in variations in isoelectric point, electrical conductivity, thermal conductivity, capacitance, etc.

[0036] "Hydrophilic" refers to a surface that has a high affinity for water. The contact angle is very small (for example, less than 30 degrees from the surface through liquid water in the presence of air) and / or impossible to measure.

[0037] "Impregnated" polymers, resins, and / or waxes refer to polymers, resins, and / or waxes dispersed within the pores of the porous ceramic material described herein.

[0038] "Interconnected ceramic network" or "interconnected ceramic network" refers to a network or matrix of ceramic materials in which the ceramic materials in the network are in physical contact (connected) with other ceramic materials in the network. This is in contrast to suspensions containing ceramic particles, such as paints, in which individual ceramic particles are suspended in a medium such as a binder, resin, oil, or wax, and the ceramic particles are not in fixed contact with each other. The interconnected ceramic network described herein is a continuous ceramic phase over a macroscopic area or volume, and may include pores (open spaces) within the ceramic having an accessible pore volume that can be filled or partially filled with another material.

[0039] "Layered double hydroxides" are typically arranged in the sequence [AcB Z AcB]. n This refers to a class of ionic solids characterized by a layered structure, where c is a layer of metal cations, A and B are layers of hydroxide anions, and Z is a layer of other anions and / or neutral molecules (such as water). Layered double hydroxides are also described in PCT application PCT / US2017 / 052120, which is incorporated herein by reference in its entirety.

[0040] A "macrovoid" refers to a geometric space within a solid that has a characteristic dimension substantially larger than the characteristic dimension of an individual pore or feature (e.g., film thickness), for example, at least about 5 to 10 times, or about 10 to 100 times, the characteristic dimension.

[0041] "Average" refers to the arithmetic mean or average.

[0042] The "average pore diameter" is calculated by using the total surface area and total volume measurements obtained by the Barrett-Joyner-Halenda (BJH) adsorption / desorption method, assuming cylindrical pores, and dividing the total pore volume (4 times the total pore volume) by the total pore surface area (4V / A).

[0043] "Multimodal" refers to a distribution that contains multiple different modes that appear as multiple different peaks.

[0044] In fluid dynamics, "permeability" is a measure of a porous material's ability to allow a fluid to pass through. The permeability of a medium depends not only on its porosity but also on the shape of its pores and the level of their connectivity.

[0045] "Pore size distribution" refers to the relative abundance of each pore size, range, or pore size, as determined by mercury intrusion porosimetry (MIP) and the Washburn equation.

[0046] "Porrosion" is a measure of the amount of empty space (i.e., "empty") within a material, and the proportion of void volume is between 0 and 1, or exceeds the total volume between 0% and 100%, i.e., macrovoids. The porosity disclosed herein was measured by mercury intrusion porosimetry.

[0047] "Porous" refers to spaces, holes, or voids within a solid material.

[0048] In this specification, “resin” means a solid or highly viscous substance comprising a mixture of compounds of plant or synthetic origin that are partially or completely converted into polymers or that can be converted into polymers.

[0049] "Superhydrophobic" refers to a surface that is very difficult to wet. In this specification, the contact angle of a water droplet on a superhydrophobic surface refers to a droplet contact angle >150°. A large hydrophobic contact angle is >120°. The contact angle as described herein is the angle formed between surfaces via a liquid.

[0050] "Surface area per square meter of the target substrate area" refers to the actually measured surface area, which is usually measured in square meters. If the surface is atomically smooth (not rough), it is usually calculated by dividing the surface area of ​​the substrate by the area in square meters.

[0051] A "synergy" or "synergistic" refers to the interaction or synergistic relationship between two or more substances, materials, or active ingredients that produces a combined effect that is greater (positive synergy) or less (negative synergy) than the sum of their individual effects.

[0052] "Film thickness" refers to the distance between the surface of the substrate and the top of the surface modifier (e.g., ceramic).

[0053] The "third quartile pore diameter" refers to the pore diameter value in which the cumulative pore surface area determined in the direction of increasing pore diameter corresponds to 75% of the total cumulative pore surface area determined by the adsorption / desorption measurement of BJH gas.

[0054] "Flexibility" refers to the ratio of the shortest paths passing through a porous structure Δl, and the Euclidean distance between the start and end points of those paths Δx.

[0055] "Adjustable" refers to the ability to change or modify the function, properties, or quality of a material.

[0056] In this specification, “wax” generally refers to naturally occurring or synthetic organic compounds containing hydrocarbons that are lipophilic and malleable solids at moderate temperatures and liquids of lower viscosity at high temperatures. Waxes typically contain long aliphatic alkyl chains and may also contain a variety of functional groups, including fatty acids, lipids, alkanes, primary and secondary alcohols, ketones, aldehydes, and fatty acid esters. Synthetic waxes often contain long-chain aliphatic hydrocarbons (alkanes or paraffins) of the same group that do not contain functional groups.

[0057] Ceramic composite materials Ceramic composite materials are provided herein. These composite materials comprise polymers, waxes, and / or resins impregnated within the pores of an interconnected ceramic network. The polymers, waxes, and / or resins at least partially fill at least a portion of the accessible pore volume of the ceramic network. The ceramic network comprises an aggregate of pores within a ceramic base material network. The pores may be interconnected (typically open cells), independent (typically closed cells), or a combination of interconnected and independent (mixed cells). The pores may be fluidly separated by a ceramic layer, but may be linked or connected by ceramics between the pores. For example, at least about 20% by mass, 30% by mass, 40% by mass, 50% by mass, 60% by mass, 70% by mass, 75% by mass, 80% by mass, 85% by mass, 90% by mass, 95% by mass, 98% by mass, 99% by mass, or 99.5% by mass of the above ceramic is interconnected (ceramic material between pores is in contact with other ceramic material), in contrast to unconnected ceramic particles surrounded by another material such as polymer, resin, and / or wax.

[0058] The ceramic composite materials described herein differ from paints in that, in paints, the pigment or ceramic particles are suspended, and when the paint is applied to a surface, the pigment or ceramic particles are generally surrounded by and in physical contact with resins, polymers, waxes, or oils rather than with other ceramic particles or pigments in the paint. In contrast to the ceramic composition materials described herein which include interconnected ceramic networks, the pigment or ceramic particles in paints are suspended in the paint formulation and are not in fixed contact with each other. Paints are typically formulated below the critical pigment volume concentration to prevent the formation of interconnected pigment or ceramic networks and to prevent voids, so that the binder can reliably coat all the pigments. The ceramic composite materials described herein include ceramic materials in which the ceramic or pigment is interconnected without resins, polymers, waxes, or oils that separate the ceramic or pigment from other ceramic particles or pigments. In some embodiments, the majority of the interconnected ceramic networks in the composite material are interconnected into a single network. In other embodiments, the interconnected ceramic networks are applied to spaced portions of a substrate. In some embodiments, the continuity of the interconnected ceramic network may be interrupted by cracks within the interconnected ceramic network, forming islands of the interconnected ceramic network.In some embodiments, the islands of the interconnected ceramic network within the composite material have an arithmetic mean area or median area projected onto the nominal mean plane of the interconnected substrates, where this area is approximately 10 square micrometers to approximately 1 square centimeter, approximately 1,000 square micrometers to approximately 10,000 square millimeters, approximately 5,000 square micrometers to approximately 50,000 square millimeters, approximately 20,000 square millimeters to approximately 100,000 square millimeters, and approximately 250,000 square millimeters to approximately 1 square centimeter. It is either a cubic meter or greater than any of the following: about 10 square micrometers, about 50 square micrometers, about 100 square micrometers, about 200 square micrometers, about 500 square micrometers, about 1000 square micrometers, about 2000 square micrometers, about 5000 square micrometers, about 10,000 square millimeters, about 20,000 square millimeters, about 50,000 square millimeters, about 100,000 square millimeters, about 500,000 square millimeters, or about 1 square centimeter. In some embodiments, substantially all ceramics in the composite material are interconnected.

[0059] The ceramic material may contain rare earth elements, transition metals, alkaline earth metal elements, and / or aluminum. The ceramic material may also be in the form of metal oxides, metal hydroxides, or layered double hydroxides, or combinations thereof. For example, the ceramic may contain, but is not limited to, one or more elements selected from iron, aluminum, magnesium, cerium, zinc, manganese, titanium, chromium, nickel, cobalt, copper, silver, tantalum, tungsten, silicon, phosphorus, tin, and europium.

[0060] The ceramic material may be conductive, insulating, or semiconducting. In some embodiments, the ceramic material is more electrically resistant than the substrate. In other embodiments, the ceramic material is more conductive than the substrate. In some embodiments, the ceramic material is a semiconductor with a band gap of about 0.1 eV to about 4 eV. In some embodiments, the ceramic material is photoactive, piezoelectric, or has the ability to generate electricity when a pressure gradient or thermal gradient is applied. In some embodiments, the ceramic material is an insulating material. In other embodiments, the ceramic material is a thermal conductor.

[0061] The interconnected ceramic network material described above is laminated on a substrate. In some embodiments, the interconnected ceramic network material is fixed to the substrate. In some embodiments, the interconnected ceramic network material is a binder-free porous ceramic material on the substrate. In some embodiments, the interconnected ceramic network material may be in direct contact with the substrate. In other embodiments, the interconnected ceramic network material may be in indirect contact with the substrate, for example, in contact with a surface modifier or surface treatment agent on the surface of the substrate. The substrate may include metals or alloys (such as, but not limited to, aluminum, steel, titanium, or alloys thereof), polymers, polysaccharides, cellulosic materials, wood, cotton, or glass. In some embodiments, the substrate includes one or more metals, and the primary metal in the substrate is different from the primary metal in the ceramic material.

[0062] The thickness of the composite material on the above substrate may be approximately 1 micrometer to approximately 100 micrometers. For example, the thickness of the composite material may be approximately 1 μm to approximately 10 μm, approximately 5 μm to approximately 25 μm, approximately 10 μm to approximately 50 μm, approximately 25 μm to approximately 75 μm, approximately 50 μm to approximately 100 μm, approximately 1 μm to approximately 25 μm, approximately 10 μm to approximately 100 μm, or at least approximately 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 90 μm, 95 μm, or 100 μm.

[0063] In some embodiments, the polymer, resin, and / or wax fills about 1% to about 99% of the accessible pore volume of the ceramic material, as measured, for example, by mercury porosimetry testing. For example, about 1% to about 5%, about 5% to about 20%, about 10% to about 30%, about 20% to about 40%, about 30% to about 50%, about 40% to about 60%, about 50% to about 70%, about 60% to about 80%, about 70% to about 90%, about 80% to about 99%, about 1% to about 20%, about 10% to about 50%, about 25% to about 75%, about 50% to about 99%, Approximately 10% to 90%, 1% to 99.9%, or at least 1%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% to approximately 99% of the polymer, resin, and / or wax is filled.

[0064] In one example, the polymer, resin, and / or wax not only fills a portion of the accessible pore volume of the ceramic, but their thickness is greater than the thickness of the porous ceramic structure (an interconnected ceramic network) (e.g., protruding from the pores of the porous ceramic structure). In another example, the polymer, resin, and / or wax fills a portion of the accessible pore volume, but their thickness is not greater than the thickness of the porous ceramic structure (e.g., housed within the pores of an interconnected ceramic network of porous ceramic structures).

[0065] In some embodiments, the polymer, resin, and / or wax is in the form of a layer less than about 1.5 times the thickness of the ceramic material. In some embodiments, the polymer, resin, and / or wax is in the form of a layer up to about 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 times the thickness of the ceramic material.

[0066] Non-limiting examples of natural polymers in the composite materials described herein include tung oil, linseed oil, walnut oil, natural rubber, cellulose, and chitin. Non-limiting examples of synthetic polymers in the composite materials described herein include polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyethylene terephthalate, poly(methyl methacrylate), polyvinyl acetate, polychloroprene, poly(vinyl chloride), polyurethane, polyamide, polyimide, poly(dimethyl)siloxane), polysilazane, and polyepoxides, as well as copolymers thereof.

[0067] Non-limiting examples of polymers or resins in the composite materials described herein include silanes, silicates (such as sodium silicate or potassium silicate), siliconates (such as sodium methyl silicate or potassium methyl silicate), polysilazanes, organotriethoxysilanes and oragnotrimethoxysilanes, and shellac.

[0068] Non-limiting examples of waxes in composite materials described herein include petroleum waxes, animal-derived waxes, plant-derived waxes, or mineral-derived waxes, such as paraffin wax, beeswax, lanolin, palm wax, carnauba wax, soy wax, ceresin, and montan.

[0069] The polymers, resins, and / or waxes described above may contain one or more additives that impart functional or chemical / physical properties, such as, but not limited to, lubricants (e.g., for providing viscosity), plasticizers (e.g., for providing flexibility), flame retardants (for providing flame retardancy), dyes or pigments (for providing color), ultraviolet (UV) stabilizers (for providing UV stability), free radical scavengers (e.g., for providing resistance to chemical reactivity), or crosslinking agents (for providing degree of crosslinking).

[0070] In some embodiments of the composite materials described herein, the polymer, resin, and / or wax may interact chemically or physically with the ceramic material to provide desirable functional or structural properties. For example, such interaction may increase the crosslinking rate and / or degree of crosslinking of the polymer, resin, and / or wax compared to when the polymer, resin, and / or wax are directly coated or laminated onto the same substrate without the ceramic material. In another example, such interaction may increase the crystallinity of the polymer, resin, and / or wax compared to when the polymer, resin, and / or wax are directly coated or laminated onto the same substrate without the ceramic material. In yet another example, such interaction may decrease the UV decomposition rate of the polymer, resin, and / or wax compared to when the polymer, resin, and / or wax are directly coated or laminated onto the same substrate without the ceramic material. In some embodiments, the ceramic material and the polymer, wax, and / or resin interact synergistically to provide one or more improved or enhanced functional properties compared to any of the materials laminated individually on the same substrate.

[0071] In some embodiments, the porous or structured ceramic material is used to improve the transport or wicking of the polymer, wax, or resin, thereby promoting flow around the edges and / or creating a layer of more uniform thickness. In some embodiments, the structured ceramic layer enables uniform spraying of the polymer, wax, or resin onto substrates with complex shapes or narrow spacing, such as heat exchangers. In some embodiments, the composite material provides performance equivalent to that of a substrate coated with paint or polymer, wax, or resin, without including the structured ceramic layer, despite using less material. In some embodiments, the composite material reduces or eliminates defects such as, but are not limited to, alligator cracking, bleeding, blistering, blooming, brushing, bridging, bubbling, chalking, checking, repulsion, spiderweb-like wrinkles, craters, crazing, crow's feet, flaking, tortoise shell cracking, orange peel, pinholes, ripples, flow, sagging, solvent lifting, and / or stress cracking.

[0072] In some embodiments, multiple polymers, waxes, and / or resins are used to produce a composite material. In some embodiments, a first polymer layer is used to partially fill the pores of the structured ceramic material layer. In some embodiments, a second polymer layer is used to further fill the pores of the ceramic material. In some embodiments, the interlayer polishing step is eliminated or the degree of polishing is reduced compared to laminating multiple polymer, resin, and / or wax layers on a substrate without interconnected structured ceramic layers.

[0073] Purpose The composite materials described herein can be used in a variety of applications, including protection against corrosion of substrates; modification of adhesion and durability against surface staining; configuration for promoting or delaying adhesion; tactile modification of surfaces; hydrophilicity; modification of properties against microorganisms, viruses, and fungi; modification of optical properties; mechanical modifications such as hardness, elasticity, and viscoelasticity; self-healing and repair of surfaces and scratches; separation; modification of electrical properties; reduction and modification of ice, condensate, and frost; or aesthetic properties. These composite materials can improve any one or any combination of the above functional properties compared to the same porous ceramic material on the same substrate that does not contain the above polymers, waxes, and / or resins, or compared to the same polymers, waxes, and / or resins directly applied to the same substrate.

[0074] Structured ceramic materials The continuous or spaced coatings or surface modifiers described herein may be structured ceramics, such as binder-free (e.g., surface-immobilized) ceramics, including binder-free ceramics with a crystallinity of more than about 20%. The structured ceramics are porous, i.e., the interconnected ceramic network material contains voids or pores. Examples of ceramic materials not intended to be limiting are presented in PCT / US19 / 65978, the entire application of which is incorporated herein by reference.

[0075] The ceramic material may include metal oxides and / or hydroxide ceramics, e.g., single metal or mixed metal oxides and / or hydroxide ceramics. In some embodiments, the ceramic material includes metal hydroxides and / or hydroxide ceramics, e.g., single metal or mixed metal oxides and / or hydroxide ceramics. In some embodiments, the ceramic material includes metal oxides and metal hydroxide ceramics, and the metal oxides and metal hydroxides include the same or different single metals or mixed metals. In some embodiments, the ceramic material includes metal oxides and / or metal hydroxide ceramics, and the substrate is hydrated with water or other compounds, which in turn determines the change in surface energy and potentially the ratio of metal oxides to the metal hydroxide composition of the ceramic. In some embodiments, the ceramic material comprises a metal hydroxide, and 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 double hydroxide.

[0076] In some embodiments, the "metal oxide" or "metal hydroxide" may be in the form of a hydrate of the metal oxide or metal hydroxide, respectively, or a portion of the metal oxide or metal hydroxide may be in the form of a hydrate of the metal oxide or metal hydroxide, respectively.

[0077] A mixed metal oxide or mixed metal hydroxide may, for example, contain oxides or hydroxides of two or more metals, and such metals may include, but are not limited to, iron, cobalt, nickel, copper, manganese, chromium, titanium, vanadium, zirconium, molybdenum, tantalum, zinc, lead, tin, tungsten, cerium, praseodymium, samarium, gadolinium, lanthanum, magnesium, aluminum, or calcium.

[0078] In some embodiments, the ceramic material is a binder-free ceramic material, i.e., it is laminated on a substrate without using a binder. In some embodiments, the ceramic material is fixed on a substrate.

[0079] In some embodiments, the interconnected ceramic network material has the ability to cause capillary rise in which a liquid with low surface tension (e.g., less than about 25 mN / m for isopropanol) is lifted against gravity in a sealed container to a surface of about 5 mm or more in 1 hour; about 0.1 m 2 / g~approx. 10,000m 2 It has a continuous porous structure characterized by one or more of the following: surface area per g; average pore size of approximately 10 nm to approximately 1000 nm, or approximately 1 nm to approximately 1000 nm; pore volume measured by mercury (Hg) penetration porosimetry of approximately 0 to approximately 1 cc / g; and a degree of curvature of approximately 1 to approximately 1000, defined by the "arc code ratio," which is the length of the fluid path to the shortest distance, and / or a permeability of approximately 1 to approximately 10,000 millidarcy.

[0080] In some embodiments, the porosity of the interconnected ceramic network is about 5% to about 95%. In some embodiments, the porosity is at least about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% or more. In some embodiments, the porosity is about 10% to about 90%, about 30% to about 90%, about 40% to about 80%, or about 50% to about 70%.

[0081] In some embodiments, the interconnected ceramic network material has a permeability of about 1 to 10,000 millidarcy. In some embodiments, the permeability can be at least about 1, 10, 100, 500, 1,000, 5,000, 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 1,000, about 750 to about 2,000, about 1,000 to about 2,500, about 2,000 to about 5,000, about 3,000 to about 7,500, about 5,000 to about 10,000, about 1 to about 1,000, about 1,000 to about 5,000, or about 5,000 to about 10,000 millidarcy.

[0082] In some embodiments, the interconnected ceramic network material is measured by mercury intrusion porosimetry to be approximately 100 mm 3 / g ~ approx. 7500mm 3 The void volume includes a void volume of at least about 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, or 7500 mm². 3 The void volume is one of the following: 100-500, 200-1000, 400-800, 500-1000, 800-1500, 1000-2000, 1500-3000, 2000-5000, 3000-7500, 250-5000, 350-4000, 400-3000, 250-1000, 250-2500, 250-5000, or 500-4000 mm 3 It is either / g or

[0083] The interconnected ceramic network materials disclosed herein may be characterized by their interaction with liquid materials. As previously stated, such ceramic materials may be characterized by the ability to capillarily elevate liquids with low surface tension (e.g., less than about 25 mN / m for isopropanol) to a surface above about 5 mm against gravity in a sealed container in one hour. Other solvents with a surface tension of less than 25 mN / m at 20°C include, but are not limited to, perfluorohexane, perfluoroheptane, perfluorooctane, n-hexane (HEX), polydimethylsiloxane (Baysilone M5), tert-butyl chloride, n-heptane, n-octane (OCT), isobutyl chloride, ethanol, methanol, isopropanol, 1-chlorobutane, isoamyl chloride, propanol, n-decane (DEC), ethyl bromide, methyl ethyl ketone (MEK), n-undecane, and cyclohexane.Other solvents with a surface tension greater than 25 mN / m at 20°C include: acetone (2-propane), n-dodecane (DDEC), isovaleronitrile, tetrahydrofuran (THF), dichloromethane, n-tetradecane (TDEC), sym-tetrachloromethane, n-hexadecane (HDEC), chloroform, 1-octanol, butyronitrile, p-cymene, isopropylbenzene, toluene, dipropylene glycol monomethyl ether, 1-decanol, ethylene glycol monoethyl ether (ethyl cellosolve) ), 1,3,5-trimethylbenzene (mesitylene), benzene, m-xylene, n-propylbenzene, ethylbenzene, n-butylbenzene, 1-nitropropane, o-xylene, dodecylbenzene, diethyl fumarate, decalin, nitroethane, carbon disulfide, cyclopentanol, 1,4-dioxane, 1,2-dichloroethane, chlorobenzene, dipropylene glycol, cyclohexanol, hexachlorobutadiene, bromobenzene, pyrrole (PY), N,N-dimethylacetamide (DMA), Nitromethane, diethyl phthalate, N,N-dimethylformamide (DMF), pyridine, methylnaphthalene, benzyl alcohol, ethyl anthranilate, iodobenzene, N-methyl-2-pyrrolidone, tricresyl phosphate (TCP), m-nitrotoluene, bromoform, o-nitrotoluene, phenylisothiocyanate, α-chloronaphthalene, furfural (2-fluoraldehyde), quinoline, 1,5-pentanediol, aniline (AN), polyethylene glycol 200 (PEG), These include methyl anthranilate, nitrobenzene, α-bromonaphthalene (BN), diethylene glycol (DEG), 1,2,3-tribromopropane, benzyl benzoate (BNBZ), 1,3-diiodopropane, 3-pyridylcarbinol (PYC), ethylene glycol (EG), 2-aminoethanol, sym-tetrabromoethane, diiodomethane (DI), thiodiglycol (2,2'-thiobisethanol) (TDG), formamide (FA), glycerol (GLY), water (WA), and mercury.

[0084] The interconnected ceramic network material described above may have the ability to induce capillary rise of water at various temperatures. These materials may have the ability to separate two-component azeotropic mixtures from miscible materials such as ethanol-water, ethyl acetate-ethanol, or butanol-water, to break up three-component azeotropic mixtures, or to remove amyl alcohol from mixtures containing ethanol and water.

[0085] The pores of the interconnected ceramic network material described above may include open cells filled with one or more gases, partially filled cells (e.g., partially filled with one or more solid materials), or completely or substantially filled cells (e.g., completely or substantially filled with one or more liquids and / or solid materials). In some embodiments, the pores are partially, substantially, or completely filled with gases, liquids, or solids, or a combination thereof.

[0086] In some embodiments, the pores are partially filled with a first material, and then partially or completely filled with a second material. In one non-limiting embodiment, the first material is a resin and the second material is a wax. In another non-limiting embodiment, the first material is a resin and the second material is a sealant, protective topcoat, protective finish, or paint. In some embodiments, the second material is added as a layer of material covering the partially filled pores. In some embodiments, the first material is a gas, solid, or liquid, or a combination of gaseous, liquid, and / or solid substances. In some embodiments, the second material is a gaseous, solid, and / or liquid substance, or an atmosphere (e.g., air). Examples include: functions imparted by changes in porosity, wicking, water repellency, and / or wetting behavior; changes in electrical / dielectric properties that alter mechanical properties such as abrasion resistance, hardness, toughness, tactile feel, modulus of elasticity, yield strength, yield stress, Young's modulus, surface (compressive or tensile) stress, and / or elasticity; changes in thermal properties such as thermal diffusivity, conductivity, coefficient of thermal expansion, thermal interfacial stress, and / or thermal anisotropy; changes in optical properties such as emissivity, color, reflectance, and / or absorption coefficient; changes in chemical properties such as corrosion, catalytic activity, reactivity, inertness, compatibility, fouling resistance, ion pump blocking, microbial resistance, and / or microbial compatibility; and / or biocatalytic substrates.

[0087] In some embodiments, the first material interacts with the second material in a positive or negative synergistic manner to alter one or more functional properties of the ceramic material, including, but not limited to, wettability, hardness, elasticity, mechanical properties, electrical properties, piezoelectric properties, optical properties, adhesion, or thermal properties, affinity or resistance to microorganisms, changes in biofilm growth, catalytic activity, permeability, aesthetic appearance, water repellency, and / or corrosion resistance.

[0088] In some embodiments, the ratio of ceramic or pigment to resin in the composite material described herein exceeds the critical pigment volume concentration of the coating. In some embodiments, the concentration of the ceramic or pigment exceeds about 40%, about 50%, about 60%, about 70%, about 80%, or about 90% of the total volume of the composite material.

[0089] Furthermore, the polymers, resins, and / or wax materials described herein may be deposited into the pores to partially or substantially completely fill them. Ceramic materials may include, for example, one or more oxides of zinc, aluminum, manganese, magnesium, cerium, gadolinium, and cobalt. In addition, ceramic materials may include solid materials that can be added to surface modifiers, such as clay, silica, glass, and inorganic compounds of metals, nonmetals, or metalloid atoms, which are mainly held together by ionic and covalent bonds. Polymers may include, for example, hemp, shellac, amber, wool, silk, natural rubber, cellulose, and other natural fibers, saccharides, hemicellulose and holocellulose, polysaccharides, and biologically derived materials such as extracellular proteins, as well as natural polymer materials such as DNA and chitin. Examples of synthetic polymers include polymers and copolymers containing polyethylene, polypropylene, polystyrene, polyvinyl chloride, synthetic rubber, phenol-formaldehyde resin (or Bakelite), neoprene, nylon, polyacrylonitrile, PVB, silicone, polyisobutylene, PEEK, PMMA, and PTFE.

[0090] In some embodiments, the pores are partially filled with a thin composite polymer layer, producing a surface modifier having the porosity and functionality provided by the polymer. In other embodiments, the pores are completely filled with a thick polymer layer, producing a surface modifier with a thick polymer layer having the combined properties of a porous-based material and a polymer layer. The polymers described in the compositions herein include copolymers.

[0091] In some embodiments, but not limited thereto, layers of material are laminated in which one or more functional groups, such as ammonium groups (e.g., quaternary ammonium groups), alkyl groups, perfluoroalkyl groups, and fluoroalkyl groups, are added to a surface modifier material. In some embodiments, polymer or ceramic layers are laminated. Examples of functional groups and the functions they impart include quaternary ammonium groups exhibiting antimicrobial properties, alkyl chains exhibiting water repellency and hydrocarbon affinity, perfluoroalkyl groups exhibiting water repellency and oil repellency, polymers exhibiting mechanical properties, and other ceramics exhibiting aesthetic, photoelectronic, or corrosion-resistant properties.

[0092] In some embodiments, the pores are substantially or completely filled with a polymer or ceramic material.

[0093] In some embodiments, the material within the pores interacts with the ceramic material. Examples of such materials and the functions they perform include oxidation of surface modifiers by ambient liquid or vapor, condensation of trace components (e.g., environmental pollutants), capture or oxidation of harmful environmental materials such as CO or H2S from ambient air, and / or recovery and retention of those materials in the environment.

[0094] In some embodiments, moisture in the environment or moisture added to pores interacts with the material within the pores to modify the material or surface modifier within the pores. Examples of such substances and the functions they perform include changes in wetting behavior, changes in optical properties, changes in oxidation state or reactivity, changes in evaporation rate, frost formation, ice formation, or condensation.

[0095] In some embodiments, the material within the pores may be designed to interact with the ceramic material to "tune" the overall surface properties. Examples of tunable properties include, but are not limited to, wettability, hardness, microbial resistance, catalytic activity, corrosion resistance, acoustic properties, light reflectivity, color, and / or photochemical activity.

[0096] In some embodiments, the ceramic surface modifier and the material within the pores interact synergistically to enhance or reduce at least one functionality of the surface modifier and / or the material within the pores compared to the functionality of the surface modifier and / or the material within the pores alone. In some embodiments, two or more materials within the pores interact synergistically to enhance or reduce at least one functionality of at least one of the materials within the pores compared to the functionality of the material alone.

[0097] In some embodiments, the ceramic surface modifier is ordered to have an asymmetric pore morphology, e.g., spherical, cylindrical, cubic, or otherwise clearly defined, relatively constant, normal distribution of surface area to volume, and the ratio of the first quartile pore diameter to the third quartile pore diameter is characterized depending on the function of the film thickness of the binder-free ceramic surface modifier. In particular, the pore morphology is asymmetric with respect to its center compared to a spherical, cylindrical, or cubic structure. Without limitation, an example of asymmetric pores is shown in PCT application PCT / US19 / 39743, which is incorporated herein by reference in its entirety.

[0098] Porous ceramic materials (interconnected ceramic networks) may feature a broad pore size distribution that varies with distance from the substrate. In particular, the pore structure at a given distance from the substrate can be locally characterized, for example, as described herein, and also has different characteristics with distance. The resulting asymmetry is a combination of the substrate, ion mobility, and processing conditions such as temperature, pressure, and concentration, and is determined in situ. The degree of asymmetry can be further regulated by bulk means such as mixing, stirring, electric field adjustment, and tank filtration, or by surface orientation process means such as shear rate, impingement flow, or modification and adjustment of surface charge. Asymmetry can be determined in excitually by various means such as etching, track etching, ion beam milling, oxidation, photocatalysis, or further means. These methods refer to materials having narrow or symmetrical pore structures with film thickness and / or pore depth, such as zeolites, track-etched films, or expanded PTFE films.

[0099] In some embodiments, the interconnected ceramic network material includes a mesoporous average pore size in the range of about 2 nm to about 50 nm. In other embodiments, the average pore size is in the range of about 50 nm to about 1000 nm. In some embodiments, the binder-free porous ceramic material includes an average pore diameter of about 2 nm to about 20 nm. In some embodiments, the average pore diameter is at least one of about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 nm. In some embodiments, the average pore diameter is one of about 2 to about 5, about 4 to about 9, about 5 to about 10, about 7 to about 12, about 9 to about 15, about 12 to about 18, about 15 to about 20, about 4 to about 11, about 5 to about 9, about 4 to about 8, or about 7 to about 11 nm.

[0100] The interconnected ceramic network material described above may contain one or more metal oxides and / or metal hydroxides (and / or hydrates thereof). Examples of metals that may be included in the ceramic compositions disclosed herein, but are not intended to be limiting, include: zinc, aluminum, manganese, magnesium, cerium, copper, gadolinium, tungsten, tin, lead, and cobalt. In some embodiments, the ceramic material may be a transition metal, a group II element, a rare earth element (e.g., lanthanum, cerium-gadolinium, praseodymium, scandium, yttrium, samarium, or neodymium), aluminum, tin, or lead. In some embodiments, the ceramic material may, but are not intended to be limiting, include two or more metal oxides (e.g., mixed metal oxides) such as zinc, aluminum, manganese, magnesium, cerium, praseodymium, and cobalt.

[0101] In some embodiments, the interconnected ceramic network material may include: a mixture of zinc and aluminum oxide and / or hydroxide; a mixture of ZnO, Al2O3, and Zn-aluminate; a mixture of materials containing any / all phases including Zn, Al, and oxygen; a mixture of manganese and magnesium oxide and / or hydroxide; manganese oxide; aluminum oxide; mixed metal manganese oxide and / or hydroxide; a mixture of magnesium and aluminum oxide and / or hydroxide; a mixture of magnesium, cerium, and aluminum oxide and / or hydroxide; and zinc, gadolinium, and aluminum oxide. Examples include mixtures of and / or hydroxides; mixtures of cobalt with aluminum oxide and / or hydroxide; mixtures of manganese with aluminum oxide and / or hydroxide; mixtures of cerium with aluminum oxide and / or hydroxide; mixtures of iron with aluminum oxide and / or hydroxide; mixtures of tungsten with aluminum oxide and / or hydroxide; mixtures of tin with aluminum oxide; tungsten oxide and / or hydroxide; magnesium oxide and / or hydroxide; manganese oxide and / or hydroxide; tin oxide and / or hydroxide; or zinc oxide and / or hydroxide.

[0102] In some embodiments, at least one metal in the ceramic material is 2 + It is in an oxidized state.

[0103] In some embodiments, the interconnected ceramic network material comprises one or more oxides and / or hydroxides of zinc, aluminum, manganese, magnesium, cerium, gadolinium, and cobalt, and the substrate is aluminum or an aluminum alloy.

[0104] In some embodiments, the interconnected ceramic network material is superhydrophobic. In some embodiments, the surface modifier material is highly hydrophobic. In some embodiments, the surface modifier includes one or more functional properties, selected from wettability, hardness, elasticity, mechanical properties, electrical properties, piezoelectric properties, electromagnetic properties, optical properties, adhesion, or thermal properties, microbial affinity or resistance, changes in biofilm growth, catalytic activity, permeability, aesthetic appearance, and corrosion resistance, compared to a substrate without ceramic material.

[0105] In some embodiments, a functional material layer (e.g., the top layer of the material) is laminated on top of a ceramic material. Examples of such materials include, but are not limited to, quaternary ammonium groups for antimicrobial properties, alkyl chains for water repellency and hydrocarbon affinity, perfluoroalkyl groups for water repellency and oil repellency, polymers for mechanical properties, and other ceramics for aesthetic, photoelectronic, or corrosion-resistant properties. Examples of functions that such materials can impart, but are not limited to, include: porosity, wicking, water repellency, and / or wetting behavior; changes in electrical / dielectric properties that alter mechanical properties such as abrasion resistance, hardness, toughness, tactile feel, elastic modulus, yield strength, yield stress, Young's modulus, surface (compressive or tensile) stress, tensile strength, compressive strength, and / or elasticity; changes in thermal properties such as thermal diffusivity, conductivity, coefficient of thermal expansion, thermal interfacial stress, and thermal anisotropy; changes in optical properties such as emissivity, color, reflectance, and / or absorption coefficient; changes in chemical properties such as corrosion resistance, catalytic activity, reactivity, inertness, compatibility, fouling resistance, ion pump blocking, microbial resistance, and / or microbial compatibility; and substrates that enhance adhesion to subsequent material layers and / or biocatalyze.

[0106] In some embodiments, the interconnected ceramic network material is more resistant to ultraviolet degradation than substrate materials such as polymers or any substrate material disclosed herein.

[0107] In some embodiments, the interconnected ceramic network material includes a film thickness of from about 0.5 micrometers to about 20 micrometers. In some embodiments, the ceramic material includes a film thickness of from about 0.2 micrometers to about 25 micrometers. In some embodiments, the film 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 film thickness is any one of from about 0.2 to about 0.5, from about 0.5 to about 1, from about 1 to about 5, from about 3 to about 7, from about 5 to about 10, from about 7 to about 15, from about 10 to about 15, from about 12 to about 18, from about 15 to about 20, from about 18 to about 25, from about 0.5 to about 15, from about 2 to about 10, from about 1 to about 10, from about 3 to about 13, from about 0.5 to about 15, from about 0.5 to about 5, from about 0.5 to about 10, or from about 5 to about 15 micrometers.

[0108] In some embodiments, the interconnected ceramic network material is characterized by a water contact angle of from about 0° to about 180°. In other embodiments, the water contact angle is less than about 30 degrees. In other embodiments, the water contact angle is greater than about 150 degrees.

[0109] In some embodiments, the interconnected ceramic network material has a surface area of from about 1.1 m 2 to about 100 m 2 per square meter of the substrate area of interest. In some embodiments, the ceramic material has a surface area of from about 10 m 2 to about 1500 m 2 per square meter of the substrate area of interest. In some embodiments, the surface area is at least about 10, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, or 1500 m 2In some embodiments, the surface area is approximately 10 to 100, 50 to 250, 150 to 500, 250 to 750, 500 to 1000, 750 to 1200, 1000 to 1500, 70 to 1000, 150 to 800, 500 to 900, or 500 to 1000 m² per square meter of the substrate area. 2 It is one of the following:

[0110] In some embodiments, the interconnected ceramic network material is approximately 15 m per gram of ceramic material. 2 ~about 1500m 2 This includes the surface area. In some embodiments, the surface area is at least about 15, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, or 1500 m² per gram of ceramic material. 2 In some embodiments, the surface area is approximately 15 to 100, 50 to 250, 150 to 500, 250 to 750, 500 to 1000, 750 to 1200, 1000 to 1500, 50 to 700, 75 to 600, 150 to 650, or 250 to 700 m² per gram of ceramic material. 2 It is one of the following:

[0111] Base material A substrate coated or laminated with the porous ceramic material (interconnected ceramic network) described herein may consist of any material suitable for structural or functional properties, or any material suitable for functional applications such as use in devices such as heat exchangers. In some embodiments, the substrate is aluminum or contains aluminum (e.g., aluminum alloys), iron alloys, zinc, zinc alloys, copper, copper alloys, nickel alloys, nickel, titanium alloys, titanium, cobalt-chromium alloys, glass, polymers, copolymers, natural materials (e.g., natural materials containing cellulose), or plastics.

[0112] In some embodiments, the substrate includes a metal, and the primary metal in the interconnected ceramic network material described herein is different from the primary metal in the substrate. The primary metal is determined, for example, by atomic metal-based X-ray diffraction, to be a metal that accounts for at least about 50%, 60%, 70%, 80%, 90%, or 95% of the total metal in the substrate or ceramic material. Examples of primary metals in the substrate include, but are not limited to, aluminum, iron, copper, zinc, nickel, titanium, and magnesium. Examples of primary metals in ceramics include, but are not limited to, zinc, aluminum, manganese, magnesium, cerium, copper, gadolinium, tungsten, tin, lead, and cobalt.

[0113] In some embodiments, the substrate comprises a metal that can react (e.g., dissolve) under reaction conditions that allow for local dissolution of the substrate metal, and the substrate metal is incorporated into a substrate modifier such as a ceramic material, e.g., a porous ceramic material without a binder. For example, in an aluminum substrate, since the ceramic material is laminated on the substrate, aluminum (e.g., Al) is incorporated into the ceramic material. 3+ ) can be provided.

[0114] The following examples are illustrative of the present invention and are not intended to limit it. [Examples]

[0115] The surface modifiers described in the following examples were prepared as follows: Parts, substrates, or assemblies were cleaned with isopropyl alcohol (IPA) and a towel to remove all residual oil. Polymer substrates or pH-sensitive substrates were typically cleaned only with IPA and not subjected to subsequent caustic and acid treatment steps. Next, metal parts or substrates were immersed in a caustic etching bath with pH > 11 at a temperature of about 20°C to about 60°C for about 5 to about 20 minutes. The assemblies were then rinsed with water to remove all residual caustic or loosely adhering substances. Next, the parts were immersed in a nitric acid solution with pH less than 1 and a temperature of about 20°C to about 40°C to remove dirt and / or deoxidize the substrate. The assemblies were then placed in a reactive manufacturing bath containing 20 to 250 mM of metal nitrates or sulfates, or mixed metal nitrates or sulfates, and similar molar amounts of diamine, triamine, or tetramine, and allowed to stand at a reaction temperature of 50 to 85°C. The parts, substrates, or assemblies were kept in the bath for a period ranging from approximately 5 minutes to approximately 3 hours. The substrates were removed, drained, and placed in an oven for drying and / or firing for several minutes to several hours at a temperature sufficient to convert the ceramic material to oxide to a high degree, such as approximately 65% ​​or more (e.g., retaining some hydroxide while changing the hydroxide / oxide ratio), for example, approximately 50°C to approximately 600°C. This lamination step may be optionally repeated before or after the drying step, and any additional drying step may be performed thereafter as needed. After cooling, the parts were further processed and / or tested as described in the following example.

[0116] Example 1 A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface agent based on a mixture of magnesium oxide and aluminum oxide. The interconnected porous ceramic surface agent was laminated with a 25-100 mM aqueous solution of magnesium nitrate and an equivalent amount of hexamethylenetetramine at a temperature of approximately 50°C-80°C for approximately 15-90 minutes. The coil was then fired at a temperature of approximately 300°C-500°C for approximately 1 hour. First, the ceramic surface was covered with epoxy resin, and then a focused ion beam was irradiated onto the top surface of the sample until enough material was removed to expose the sides of the interconnected porous ceramic layer, thereby preparing a cross-section for scanning electron microscopy (SEM). The thickness of the interconnected porous ceramic layer was measured perpendicular to the aluminum substrate surface and was found to be approximately 5 microns. The sample was analyzed using mercury porosimetry, X-ray diffraction (XRD), differential scanning calorimetry, nanoindentation, and polarization resistance. Mercury porosimetry revealed that the pore volume of the above sample was 1400 mm². 3 The concentration was found to be / g, and the total porosity was revealed to be 84%. The XRD spectrum in Figure 1 shows clear peaks at 35.6°, 43.4°, and 62.7°, indicating a layered structure of crystalline MgO.

[0117] Example 2 A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface agent based on a mixture of magnesium oxide and aluminum oxide, using a procedure similar to that described in Example 1. A toluene solution of polystyrene was cast onto the surface of the laminate, which was maintained at 20°C to 35°C. The solvent was evaporated until the sample was completely dry.

[0118] Example 3 A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface agent based on a mixture of magnesium oxide and aluminum oxide, using a procedure similar to that described in Example 1. The plate was then immersed in a toluene solution of polystyrene maintained at 20°C to 35°C. After several hours, the sample was removed from the solution, and the solvent retained on the surface was evaporated until the sample was completely dry.

[0119] Example 4 A clean 3003 aluminum plate is coated with an interconnected porous ceramic surface agent based on zinc oxide. Separately, a clean 3003 aluminum plate is coated with an interconnected porous ceramic surface agent consisting of approximately 66% by mass of zinc oxide and 34% by mass of magnesium oxide. Separately, a clean 3003 aluminum plate is coated with an interconnected porous ceramic surface agent based on magnesium oxide. All three samples are immersed in a tert-butyl acetate solution of polychloroprene for 90 minutes. The samples are then removed from the solution and cured at 160°C for 40 minutes under a nitrogen atmosphere.

[0120] Each sample was analyzed using solvent swelling with toluene and Fourier transform infrared spectroscopy (FTIR) to measure the degree of crosslinking of the polychloroprene. The sample based solely on zinc oxide had the highest degree of crosslinking, the sample based solely on magnesium oxide had the lowest degree of crosslinking, and the sample consisting of both zinc oxide and magnesium oxide showed a degree of crosslinking between the values ​​of the other two types of samples.

[0121] Example 5 A clean 3003 aluminum plate, oxidationThe sample was coated with a porous, interconnected ceramic surface modifier based on a mixture of zinc and aluminum oxide. This porous ceramic surface modifier was laminated with a 25-100 mM aqueous solution of zinc nitrate and an equivalent amount of hexamethylenetetramine at a temperature of approximately 50°C-80°C for approximately 15-120 minutes. The coil was then fired at a temperature of approximately 350°C-550°C for approximately 1 hour. Next, the sample was held at 100°C, and molten paraffin wax was dripped onto the surface to wick it. The sample was then allowed to cool to room temperature. 24 hours after cooling to room temperature, the sample was subjected to electrochemical testing. The polarization resistance method was performed on the sample, and the corrosion resistance was found to be 2.3 × 10⁻⁶. 6 It was determined to be ohmic. Next, this sample was subjected to 3 hours of immersion in a corrosive environment according to the ASTM G85-A3 protocol, 115 hours of UV exposure according to the ASTM D4587 protocol, and 180 hours of immersion in water according to the ASTM D870 protocol. This sample was again subjected to polarization resistance testing, and its corrosion resistance was found to be 4.2 × 10⁻⁶. 5 It was found to be ohms. For comparison, the polarization resistance method was performed on a clean 3003 aluminum plate coated with an interconnected porous ceramic surface agent based on a mixture of zinc oxide and aluminum oxide, without a paraffin layer, and the corrosion resistance was 4.3 × 10⁻⁶. 4 It has been revealed that it is an Ohm.

[0122] Example 6 A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface agent based on a mixture of magnesium oxide and aluminum oxide, using a procedure similar to that described in Example 1. Next, the sample was maintained at 100°C, and molten paraffin wax was dripped onto the surface of the sample for wicking. The sample was then allowed to cool to room temperature. 24 hours after cooling to room temperature, the sample was subjected to electrochemical testing. The polarization resistance method was performed on the sample, and the corrosion resistance was found to be 1.3 × 10⁻⁶. 6It was determined to be ohmic. Next, this sample was subjected to 3 hours of immersion in a corrosive environment according to the ASTM G85-A3 protocol, 115 hours of UV exposure according to the ASTM D4587 protocol, and 159 hours of immersion in water according to the ASTM D870 protocol. This sample was again subjected to polarization resistance testing, and its corrosion resistance was found to be 1.7 × 10⁻⁶. 5 It was found to be ohms. For comparison, the polarization resistance method was performed on a clean 3003 aluminum plate coated with an interconnected porous ceramic surface agent based on a mixture of magnesium oxide and aluminum oxide, without a paraffin layer, and the corrosion resistance was 2.2 × 10⁻⁶. 4 It has been revealed that it is an Ohm.

[0123] Example 7 A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface agent based on a mixture of manganese oxide and aluminum oxide, using a procedure similar to that described in Example 1, but with manganese nitrate or manganese sulfate instead of magnesium nitrate. Next, the sample was held at 100°C, and molten paraffin wax was dripped onto the surface of the sample for wicking. The sample was then allowed to cool to room temperature. 24 hours after cooling to room temperature, the sample was subjected to electrochemical testing. The polarization resistance method was performed on the sample, and the corrosion resistance was found to be 3.7 × 10⁻⁶. 6 It was determined to be ohmic. Next, this sample was subjected to 3 hours of immersion in a corrosive environment according to the ASTM G85-A3 protocol, 115 hours of UV exposure according to the ASTM D4587 protocol, and 159 hours of immersion in water according to the ASTM D870 protocol. This sample was again subjected to polarization resistance testing, and its corrosion resistance was found to be 1.1 × 10⁻⁶. 6 It was found to be ohms. For comparison, the polarization resistance method was performed on a clean 3003 aluminum plate coated with an interconnected porous ceramic surface agent based on a mixture of manganese oxide and aluminum oxide, without a paraffin layer, and the corrosion resistance was 4.6 × 10⁻⁶. 4 It has been revealed that it is an Ohm.

[0124] Example 8 A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface agent based on a mixture of manganese oxide and aluminum oxide, using a procedure similar to that described in Example 7. Next, this sample was coated with a layer of tung oil by dropwise spreading using a solution of 50% by volume of tung oil and 50% by volume of limonene. After the wicking of the above solution covered the entire sample, the sample was hung to dry at room temperature for 3 days.

[0125] After drying, the polarization resistance method was performed on the above sample, and the corrosion resistance was 3.4 × 10⁻⁶. 5 It was determined to be ohmic. Next, this sample was subjected to 3 hours of immersion in a corrosive environment according to the ASTM G85-A3 protocol, 115 hours of UV exposure according to the ASTM D4587 protocol, and 158 hours of immersion in water according to the ASTM D870 protocol. This sample was again subjected to polarization resistance testing, and its corrosion resistance was found to be 7.6 × 10⁻⁶. 5 It was found to be ohms. For comparison, the polarization resistance method was performed on a clean 3003 aluminum plate coated with an interconnected porous ceramic surface agent based on a mixture of manganese oxide and aluminum oxide, without a tung oil layer, and the corrosion resistance was 4.6 × 10⁻⁶. 4 It has been revealed that it is an Ohm.

[0126] Example 9 A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface agent based on a mixture of zinc oxide and aluminum oxide, using a procedure similar to that described in Example 5. This sample was then coated with a layer of tung oil by dropwise spreading using a solution of 50% by volume of tung oil and 50% by volume of limonene. After the wicking of the above solution covered the entire sample, the sample was hung to dry at room temperature for 3 days.

[0127] After drying, the polarization resistance method was performed on the above sample, and the corrosion resistance was 8.0 × 10⁻⁶. 5It was found to be ohms. For comparison, the polarization resistance method was performed on a clean 3003 aluminum plate coated with an interconnected porous ceramic surface agent based on a mixture of zinc oxide and aluminum oxide, without a tung oil layer, and the corrosion resistance was 4.3 × 10⁻⁶. 4 It has been revealed that it is an Ohm.

[0128] Example 10 A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface agent based on a mixture of magnesium oxide and aluminum oxide, using a procedure similar to that described in Example 1. This sample was then coated with a layer of tung oil by dropwise spreading using a solution of 50% by volume of tung oil and 50% by volume of limonene. After the wicking of the above solution covered the entire sample, the sample was hung to dry at room temperature for 3 days.

[0129] After drying, the polarization resistance method was performed on the above sample, and the corrosion resistance was 6.1 × 10⁻⁶. 5 It was found to be ohmic. For comparison, the polarization resistance method was performed on a clean 3003 aluminum plate coated with an interconnected porous ceramic surface agent based on a mixture of magnesium oxide and aluminum oxide, without a tung oil layer, and the corrosion resistance was 2.2 × 10⁻⁶. 4 It has been revealed that it is an Ohm.

[0130] Example 11 Two clean 3003 aluminum plates were coated with an interconnected porous ceramic surface agent based on a mixture of zinc oxide and aluminum oxide, using a procedure similar to that described in Example 5. The aluminum plates coated with the interconnected porous ceramic and the bare, uncoated 3003 aluminum plate were immersed in a solution of 1-5% room-temperature vulcanizable (RTV) fluorosilicone dispersed in tert-butyl acetate, and then removed to form a continuous film. The solvent was evaporated until both samples were completely dry. The plates were cured in the ambient environment at room temperature for 48 hours by moisture. Contact angles were measured for all three types of plates: a) interconnected porous ceramic surface agent, b) interconnected porous ceramic surface agent partially filled with RTV silicone, and c) 3003 aluminum plate top-coated with RTV silicone. Figure 1 shows SEM images of all three types of plates, with the maximum contact angle being 151° for plate (b) with the interconnected porous ceramic structure partially filled with RTV silicone. The contact angles observed for plates (c) and (b) were 114° and <15°, respectively. Plate (b) was again immersed in a solution of RTV silicone dispersed in tert-butyl acetate to completely fill the interconnected porous ceramic structure, and the measured contact angle was 117°. The results are shown in Figures 2A-C.

[0131] Example 12 Two clean 3003 aluminum plates were coated with an interconnected porous ceramic surface agent based on a mixture of manganese oxide and aluminum oxide, using a procedure similar to that described in Example 7. The aluminum plates coated with the interconnected porous ceramic and the bare, uncoated 3003 aluminum plate were immersed in a solution of 1-5% polydimethylsiloxane (PDMS) (Sylgard 182) dispersed in toluene, and then removed to form a continuous film. The solvent was evaporated until both samples were completely dry, and the plates were cured at 80°C for 2 hours. Contact angles were measured for all three types of plates: a) interconnected porous ceramic surface agent, b) interconnected porous ceramic surface agent top-coated with PDMS, and c) 3003 aluminum plate top-coated with PDMS. Figures 3A-C show SEM images of all three types of plates, with the maximum contact angle being 141° for plate (b) where the interconnected porous ceramic structure was partially filled with the top coating agent. The contact angles observed on plates (c) and (b) were 117° and <15°, respectively.

[0132] Example 13 Three clean 3003 aluminum plates were coated with three types of sealants: a) polyurethane (Varathane), b) polyether-based silane-terminated polymer (Geniosil WP1), and c) solvent-based acrylic (Krylon Crystal Clear Acrylic). Polarization resistance testing was performed in a 3.5% NaCl solution at open-circuit potentials of -0.15mV to 0.15mV for all three plates. Corrosion resistance was assessed for polyurethane, polyether-based silane-terminated polymer, and acrylic surface treatment agents, with values ​​of 5.9 × 10⁻⁶ each. 7 Ohm, 3.7 × 10 2 Ohm, and 9.7 × 10 3It was measured to be ohms. For comparison, the polarization resistance was measured on an interconnected porous ceramic surface material based on a mixture of zinc oxide and aluminum oxide, without a top coating, prepared using a procedure similar to that described in Example 6, and was 1.1 × 10⁻⁶. 3 It was revealed to be an ohm. For comparison, three clean 3003 aluminum plates were coated with an interconnected porous ceramic surface agent based on a mixture of zinc oxide and aluminum oxide. The three plates were then recoated with the same polymers as above: a) polyurethane, b) polyether-based silane-terminated polymer, and c) solvent-based acrylic. The corrosion resistance was 1.4 × 10⁻⁶ for each. 8 Ohm, 1.4 × 10 7 Ohm, and 1.0 × 10 7 It was measured in ohms.

[0133] Example 14 Three clean 3003 aluminum plates, prepared using a procedure similar to that described in Example 7, were coated with an interconnected porous ceramic surface agent based on a manganese oxide and aluminum oxide mixture. These were then further filled with various sealants based on a) polyurethane (Varathane Ultimate Spar), b) aqueous polyacrylic (Minwax Polyacrylic), and c) polyether-based silane-terminated polymer (Geniosil WP1). Corrosion resistance was measured to be 9.8 × 10⁻⁶. 7 Ohm, 5.7 × 10 7 Ohm, and 6.5 × 10 5 The resistance was ohms. For comparison, the polarization resistance method was performed on a clean 3003 aluminum plate coated with an aqueous polyacrylic sealant, yielding 9.6 × 10⁻⁶. 3 It was found to be ohm. The corrosion resistance on a clean 3003 aluminum plate with an interconnected porous ceramic surface agent based on a mixture of manganese oxide and aluminum oxide was 1.7 × 10⁻⁶. 4 It was in ohms. The resistance of sealant on a bare aluminum plate is shown in Example 13.

[0134] Example 15 Two clean 3003 aluminum plates were coated with an interconnected porous ceramic surface agent based on a mixture of magnesium oxide and aluminum oxide, prepared using a procedure similar to that described in Example 1. One of the plates was immersion-coated with a water-based Minwax polyacrylic surface treatment agent and kept at room temperature to allow the surface treatment agent to wick onto the surface of the sample. A polarization resistance test was performed on this plate, and the corrosion resistance was found to be 2.1 × 10⁻⁶. 5 It was revealed to be an ohm. For comparison, the corrosion resistance of a water-based polyacrylic sealant coated on a clean 3003 aluminum plate using the same procedure was 1.1 × 10⁻⁶. 4 It has been revealed that it is an Ohm.

[0135] Example 16 Two clean 3003 aluminum plates were coated with an interconnected porous ceramic surface agent based on a zinc oxide and aluminum oxide mixture, prepared using a procedure similar to that described in Example 5. One of the samples was sprayed with an aerosol polyurethane sealant (Varathane), wicked onto the surface, and cured at room temperature for 48 hours. The other clean 3003 aluminum plate was coated with the aerosol polyurethane surface treatment agent using a similar procedure. All three samples were then subjected to 100 hours of salt spraying in a corrosive environment according to the ASTM G85-A3 protocol, gently washed with deionized (DI) water, sonicated in DI water for 10 minutes, dried at room temperature for 1 hour, and then imaged. Figures 4A-C show the degree of corrosion in all three samples: a) a plate modified solely with an interconnected porous ceramic surface agent based on a mixture of zinc oxide and aluminum oxide; b) a clean 3003 aluminum plate coated with an aerosol-based polyurethane top coating agent; and c) a plate coated with an interconnected porous ceramic surface agent based on a mixture of zinc oxide and aluminum oxide, and filled with an aerosol-based polyurethane surface treatment agent. Unlike sample (b), composite material (c) prevented corrosion around the edges. Pit densities are shown in Figures 4A-C.

[0136] Example 17 Two clean 3003 aluminum plates were coated with an interconnected porous ceramic surface agent based on a magnesium oxide and aluminum oxide mixture, prepared using a procedure similar to that described in Example 1. One of the samples was immersed in an aqueous polyacrylic sealant (Minwax polyacrylic), wicked onto the surface of the sample, and cured at room temperature for 24 hours. Another clean 3003 aluminum plate was coated with the aqueous polyacrylic sealant as a control. All three samples were then subjected to a grid adhesion test according to the ASTM D3359 protocol. Figures 5A-C show the degree of delamination of the coatings in all three samples: a) a plate coated with an interconnected porous ceramic surface agent based on a mixture of magnesium oxide and aluminum oxide (ASTM class: 5B), b) a 3003 aluminum plate coated with an aqueous polyacrylic sealant (ASTM class: 1B), and c) a plate coated with an interconnected porous ceramic surface agent based on a mixture of magnesium oxide and aluminum oxide and filled with an aqueous polyacrylic sealant (5B). The ceramics improved the adhesion performance of the polymers.

[0137] Example 18 A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface agent based on a mixture of zinc oxide and aluminum oxide, prepared using a procedure similar to that described in Example 5. Subsequently, an acrylic sealant was sprayed onto the sample and dried at room temperature for 24 hours. The sample was then subjected to a pencil hardness test according to the ASTM D3363 protocol, revealing scratch and gouge hardnesses of HB and 4H, respectively. For comparison, the scratch and gouge hardnesses of a clean 3003 aluminum plate sprayed with an acrylic top coating agent according to the aforementioned procedure and dried were 5B and 3B, respectively.

[0138] Example 19 A clean 3003 aluminum plate was coated with an interconnected porous ceramic surface agent based on a mixture of zinc oxide and aluminum oxide, prepared using a procedure similar to that described in Example 5. Subsequently, this sample was coated with an acrylic sealant along with a clean 3003 aluminum plate, and both samples were visually inspected for any coating defects. As shown in Figures 6A and 6B, sagging was observed in the clean 3003 aluminum plate coated with the acrylic sealant (Figure 6A), while no defects were observed in the plate coated with the interconnected porous ceramic surface agent and then filled with the acrylic sealant (Figure 6B).

[0139] Example 20 An epoxy resin was dropped onto the surface of a clean 3003 aluminum plate, and the progression of the contact angle was measured over time (Sample A). For comparison, a clean 3003 aluminum plate was coated with an interconnected porous ceramic surface agent based on a mixture of zinc oxide and aluminum oxide, prepared using a procedure similar to that described in Example 5, and the progression of the contact angle was measured over time (Sample B). Another clean 3003 aluminum plate was coated with an interconnected porous ceramic surface agent based on a mixture of manganese oxide and aluminum oxide, prepared using a procedure similar to that described in Example 7, and the self-leveling properties were investigated by measuring the progression of the contact angle with respect to the epoxy resin over time according to the same protocol as above (Sample C). Figures 7A to 7C show a comparison of the self-leveling phenomena of all three types of plates.

[0140] Example 21 Two clean 3003 aluminum plates were coated with interconnected porous ceramic surface agents based on zinc oxide / aluminum oxide and manganese oxide / aluminum oxide mixtures (prepared using procedures similar to those described in Examples 5 and 7, respectively). Contact angles using droplets of aqueous polyacrylic surface treatment were measured on both plates, revealing values ​​of approximately 57° and <15°, respectively. For comparison, to demonstrate the self-leveling phenomenon, the contact angle of the aqueous polyacrylic surface treatment on a clean 3003 aluminum plate was measured at 73°, as shown in Figure 8.

[0141] Example 22 Two clean 3003 aluminum plates (2 x 4 inches) 2 The samples were coated with interconnected porous ceramic surface agents based on zinc oxide / aluminum oxide and manganese oxide / aluminum oxide mixtures (prepared using procedures similar to those described in Examples 5 and 7, respectively). 180 mg of paraffin wax with a melting point below 70°C was dropped into the center of each sample held on a 100°C heating plate, and the wicking behavior was examined. For comparison, 180 mg of paraffin wax was also dropped into the center of a clean 3003 Al plate, similarly held on a 100°C heating plate. Figure 9 shows a comparison of all samples and the paraffin coating state obtained on the samples after 5 minutes. The paraffin coverage rate (area %) of each sample was measured using the Region of Interest function in ImageJ, and was measured to be 93.1% for the zinc / aluminum-based surface agent, 66.4% for the manganese / aluminum-based surface agent, and 23.5% for the 3003 aluminum plate. Figure 10 shows the wicking behavior of paraffin wax on all three substrates. In zinc / aluminum-based ceramic surface coatings, paraffin was able to wick from the edges to the back of the plate. The penetration of paraffin from the edges was measured on the back of the plate, and it was approximately 2 mm toward the center of the sample on the back.

[0142] Example 23 A brazed aluminum heat exchanger approximately 3 centimeters thick was coated with a binder-free structured ceramic material based on manganese oxide and aluminum oxide, prepared using a procedure similar to that described in Example 7. This sample was heated in a drying oven, and then heated paraffin wax was sprayed onto both sides. Wicking occurred inward due to the structured ceramic layer of wax, resulting in a more uniformly coated component than that of a heat exchanger without the structured ceramic material.

[0143] Example 24 Two clean 3003 aluminum plates were coated with an interconnected porous ceramic surface agent based on a manganese oxide and aluminum oxide mixture, prepared using a procedure similar to that described in Example 7. 200 μL of a 2 wt% polysilazane (Durazane 1500) solution dispersed in n-butyl acetate was dropwise cast onto the interconnected porous ceramic-coated aluminum plate (plate A) and onto an uncoated, bare 3003 aluminum plate (plate B). Similarly, 200 μL of a 20 wt% polysilazane solution was dropwise cast onto another interconnected porous ceramic-coated aluminum plate (plate C) and onto an uncoated, bare 3003 aluminum plate (plate D). The solvent was evaporated until all four samples were completely dry, and they were cured at 200°C for 8 hours. Contact angles were measured for all plates using 2 μL of DI water droplets. The measured contact angles were 141°, 97°, 150°, and 81° for plates A, B, C, and D, respectively. These samples were then subjected to pencil hardness testing according to the ASTM D3363 protocol, and the scratch and gouge hardness were measured. It was found that plate A was 4B and 3H, plate B was 2B and 2H, plate C was 4B and 4H, and plate D was 2B and 5H.

[0144] Example 25 Following a procedure similar to that described in Example 24, two interconnected porous ceramic-coated aluminum plates were coated with a 2 wt% (plate E) and 20 wt% (plate G) Durazane 1800-based formulation, respectively, and cured. Two more bare, uncoated 3003 aluminum plates were then coated with a 2 wt% (plate F) and 20 wt% (plate H) Durazane 1800-based formulation, respectively, and cured. Contact angles were measured for all plates using 2 μL droplets of DI water. The measured contact angles were 141°, 87°, 108°, and 75° for plates E, F, G, and H, respectively. These samples were then subjected to pencil hardness testing according to the ASTM D3363 protocol, and scratch and gouge hardness were measured. It was found that plate E was HB and 3H, plate F was H and 4H, plate G was 2H and 5H, and plate H was 3HB and 6H.

[0145] Example 26 A thin film of cellulose acetate was coated with a zinc oxide-based interconnected porous ceramic coating agent. This film was oxidized using a dilute aqueous solution of potassium persulfate. Next, this film was coated with a zinc oxide-based interconnected porous ceramic surface modifier using a method similar to that described in the above example. The electrical resistance of the exposed cellulose acetate film, measured by linear four-point probe measurement, was outside the range of the measuring instrument (10 10 The resistance was (exceeding ohms). The electrical resistance of the cellulose acetate film coated with zinc oxide was approximately 10 6 ~about 10 7 The resistance was measured to be ohms. The electrical resistance of the above film decreased when the above interconnected porous zinc oxide ceramic layer was coated onto the film.

[0146] Although the aforementioned invention has been described in detail at the level of examples and embodiments for the purpose of clarifying understanding, it will be obvious to those skilled in the art that certain changes and modifications can be implemented without departing from the technical spirit and scope of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the detailed description.

[0147] All publications, patents, and patent applications referenced herein are incorporated herein by reference, in the same way that each individual publication, patent, or patent application is specifically and individually presented, for all purposes. Specific embodiments of the present invention are as follows. [Aspect 1] (i) A composite material comprising a polymer, wax, and / or resin impregnated in a porous ceramic material, wherein the porous ceramic material comprises an interconnected network of ceramics and, at least partially, an accessible pore volume filled with the polymer, wax, and / or resin, (ii) Substrate and Includes, A composition in which the composite material is in contact with the substrate. [Aspect 2] The composition according to embodiment 1, wherein the substrate and the ceramic material each contain a primary metal, and the primary metal in the ceramic material is different from the primary metal in the substrate. [Aspect 3] The composition according to embodiment 1, wherein the thickness of the composite material is about 1 micrometer to about 100 micrometers. [Aspect 4] The composition according to embodiment 1, wherein at least about 20% by mass of the total ceramic content in the composite material is interconnected. [Aspect 5] The composition according to embodiment 1, wherein the interconnected network of ceramic materials is larger than about 10 square micrometers. [Aspect 6] The composition according to embodiment 1, wherein the composite material includes an interconnected network of multiple ceramic materials. [Aspect 7] The composition according to embodiment 6, wherein the median area of ​​the interconnected network of one ceramic material within the interconnected network of the plurality of ceramic materials is greater than about 10 square micrometers. [Aspect 8] The composition according to any one of embodiments 1 to 7, wherein the ceramic material comprises a rare earth element, a transition metal element, an alkaline earth metal element, or aluminum. [Aspect 9] The composition according to any one of embodiments 1 to 7, wherein the ceramic material comprises an oxide, a hydroxide, and / or a layered double hydroxide. [Aspect 10] The composition according to embodiment 9, wherein the oxide, hydroxide, and / or layered double hydroxide comprises iron, aluminum, magnesium, cerium, zinc, manganese, titanium, chromium, nickel, cobalt, copper, silver, tantalum, tungsten, silicon, phosphorus, tin, vanadium, zirconium, calcium, barium, or europium. [Aspect 11] The composition according to any one of embodiments 1 to 7, wherein the substrate comprises an aluminum alloy, a steel alloy, a nickel alloy, a titanium alloy, a polymer, a cellulosic material, a polysaccharide, wood, cotton, or glass. [Aspect 12] The composition according to any one of embodiments 1 to 7, wherein the polymer, wax, and / or resin imparts one or more functional properties selected from improved hardness, elasticity, viscoelasticity, adhesion, thermal properties, aesthetic appearance, liquid repellency, and corrosion resistance compared to the same ceramic material on the same substrate that does not contain the polymer, resin, and / or wax. [Aspect 13] The composition according to any one of embodiments 1 to 7, wherein the ceramic material is a binder-free ceramic material. [Aspect 14] The composition according to any one of embodiments 1 to 7, wherein the polymer, wax, and / or resin comprises a polymer derived from tung oil, linseed oil, walnut oil, natural rubber, cellulose, or chitin. [Aspect 15] The composition according to any one of embodiments 1 to 7, wherein the polymer, wax, and / or resin comprises polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyethylene terephthalate, polyacrylate, poly(methyl methacrylate), polyvinyl acetate, polyether, polychloroprene, poly(vinyl chloride), polyurethane, polyamide, polyimide, silicone, poly(dimethylsiloxane), or polyepoxide polymer. [Aspect 16] The composition according to any one of embodiments 1 to 7, wherein the polymer, wax, and / or resin comprises a silane, silicate, siliconate, polysilazane, organotriethoxysilane, or organotrimethoxysilane. [Aspect 17] The composition according to embodiment 16, wherein the polymer, wax, and / or resin comprises potassium methyl silicate, sodium silicate, potassium silicate, or sodium methyl silicate. [Aspect 18] The composition according to any one of embodiments 1 to 7, wherein the polymer, wax, and / or resin comprises petroleum wax, animal-derived wax, plant-derived wax, or mineral-derived wax. [Aspect 19] The composition according to embodiment 18, wherein the polymer, wax, and / or resin comprises paraffin wax, beeswax, lanolin, shellac, palm wax, carnauba wax, soy wax, ceresin, or montan. [Aspect 20] The composition according to any one of embodiments 1 to 7, wherein the polymer, wax, and / or resin comprises one or more further additives selected from lubricants, plasticizers, flame retardants, dyes, UV stabilizers, free radical scavengers, and crosslinking agents. [Aspect 21] The composition according to embodiment 20, wherein the additive imparts one or more properties selected from viscosity, flexibility, flammability, color, UV stability, chemical reactivity, and degree of crosslinking to the composite material. [Aspect 22] The composition according to any one of embodiments 1 to 7, wherein, as measured by mercury porosimetry, the polymer, wax, and / or resin fills more than about 1% of the accessible pore volume. [Aspect 23] The composition according to any one of embodiments 1 to 7, wherein the thickness of the polymer, resin, and / or wax is less than about 1.5 times the thickness of the ceramic material. [Aspect 24] The composition according to any one of embodiments 1 to 7, wherein the ceramic material interacts with the polymer, wax, and / or resin material, thereby increasing the crosslinking rate and / or degree of crosslinking of the polymer, wax, and / or resin compared to the crosslinking rate and / or degree of crosslinking when the polymer, wax, and / or resin is directly applied to the same substrate without the ceramic material. [Aspect 25] The composition according to any one of embodiments 1 to 7, wherein the ceramic material interacts with the polymer, wax, and / or resin material, thereby increasing the degree of crystallinity of the polymer, wax, and / or resin material compared to the degree of crystallinity of the polymer, wax, and / or resin material when it is directly applied to the same substrate without the ceramic material. [Aspect 26] The composition according to any one of embodiments 1 to 7, wherein the ceramic material interacts with the polymer, wax, and / or resin material, thereby reducing the UV decomposition rate of the polymer, wax, and / or resin material compared to the UV decomposition rate of the polymer, wax, and / or resin material applied directly to the same substrate without the ceramic material. [Aspect 27] The composition according to any one of embodiments 1 to 7, wherein the ceramic material comprises magnesium, manganese, zinc oxide, or aluminum oxide or aluminum hydroxide, and the polymer, wax, and / or resin comprises a drying oil such as tung oil or paraffin. [Aspect 28] The composition according to any one of embodiments 1 to 7, wherein the ceramic material comprises magnesium, manganese, zinc oxide, or aluminum oxide or aluminum hydroxide, and the polymer, wax, and / or resin chemically reacts with the ceramic material to modify the properties of the polymer, wax, and / or resin. [Aspect 29] The composition according to embodiment 28, wherein the chemical reaction for modifying the properties of the polymer, wax, and / or resin comprises crosslinking, curing, and / or polymerization. [Aspect 30] The composite material is applied to the substrate to provide one or more functional properties selected from the following: protection against corrosion of the substrate; durability modifier against adhesion and / or surface staining; configuration to promote or delay adhesion; tactile modification of the surface; liquid-repellent applications; modification of optical properties; mechanical modification such as hardness, elasticity, and viscoelasticity; self-healing and repair of surfaces and scratches; separation applications; modification of electrical properties or electrical properties; reduction and / or modification of ice, condensate, and frost; surface uniformity; defect reduction; and aesthetic properties. The composition according to any one of embodiments 1 to 7, wherein the functional properties are improved or more significantly compared to the same porous ceramic material on the same substrate, without the polymer, resin, and / or wax, or compared to the same substrate to which the polymer, resin, and / or wax is directly coated. [Aspect 31] The composition according to any one of embodiments 1 to 7, wherein the composite material contains a ceramic volume concentration exceeding approximately 40% of the total volume of the composite material.

Claims

1. A composition, (i) A composite material comprising a polymer, wax, and / or resin impregnated in a porous ceramic material, wherein the porous ceramic material comprises an interconnected network of ceramics and pores having accessible pore volumes filled at least partially with the polymer, wax, and / or resin, The porous ceramic material is a binder-free ceramic material, The porous ceramic material includes zinc oxide, a combination of aluminum oxide and magnesium oxide, a combination of aluminum oxide and zinc oxide, or a combination of aluminum oxide and manganese oxide, (a) The composite material wherein, as measured by mercury porosimetry, at least 5% of the accessible pore volume is filled with the polymer, wax, and / or resin, and (b) the thickness of the polymer, wax, and / or resin is up to 5 times the thickness of the porous ceramic material, (ii) A substrate containing aluminum, aluminum alloy, or cellulosic material Includes, The composition wherein the composite material is in contact with the substrate.

2. (i) Each of the substrate and the porous ceramic material contains a primary metal that is at least 50% of the total metal in the substrate or the porous ceramic material, and the primary metal in the porous ceramic material is different from the primary metal in the substrate, (ii) The thickness of the composite material is 1 micrometer to 100 micrometers, (iii) At least 20% by mass of the total ceramic content in the composite material is interconnected, (iv) The interconnected network of the ceramics is larger than 10 square micrometers. The composition according to claim 1.

3. The composition according to claim 1, wherein the composite material includes a network of interconnected ceramic materials.

4. The aforementioned polymer, wax, and / or resin (i) To impart one or more functional properties selected from improved hardness, elasticity, viscoelasticity, adhesion, thermal properties, aesthetic appearance, liquid repellency, and corrosion resistance compared to the same ceramic material on the same substrate that does not contain the polymer, wax, and / or resin, or (ii) containing polymers derived from tung oil, (iii) comprising polystyrene, polyacrylate, polyether, polychloroprene, polyurethane, silicone, poly(dimethylsiloxane), or polyepoxy polymer, The composition according to any one of claims 1 to 3.

5. The composition according to any one of claims 1 to 3, wherein the polymer, wax, and / or resin comprises a silane, a polysilazane, an organotriethoxysilane, or an organotrimethoxysilane.

6. The composition according to any one of claims 1 to 3, wherein the polymer, wax, and / or resin comprises petroleum wax, animal-derived wax, plant-derived wax, or mineral-derived wax.

7. The composition according to claim 6, wherein the polymer, wax, and / or resin comprises paraffin wax.

8. The composition according to any one of claims 1 to 3, wherein the polymer, wax, and / or resin comprises one or more further additives selected from lubricants, plasticizers, flame retardants, dyes, UV stabilizers, free radical scavengers, and crosslinking agents.

9. The composition according to claim 8, wherein one or more further additives impart to the composite material one or more properties selected from viscosity, flexibility, flammability, color, UV stability, chemical reactivity, and degree of crosslinking.

10. The porous ceramic material interacts with the polymer, wax, and / or resin material, thereby, (i) The crosslinking rate and / or degree of crosslinking of the polymer, wax, and / or resin is increased compared to the crosslinking rate and / or degree of crosslinking when the polymer, wax, and / or resin is applied directly to the same substrate that does not contain the porous ceramic material, or (ii) The degree of crystallinity of the polymer, wax, and / or resin material increases compared to the degree of crystallinity of the polymer, wax, and / or resin material when it is applied directly to the same substrate without the porous ceramic material, or (iii) The UV degradation rate of the polymer, wax, and / or resin material is lower than the UV degradation rate of the polymer, wax, and / or resin material applied directly to the same substrate without the porous ceramic material. The composition according to any one of claims 1 to 3.

11. The composition according to any one of claims 1 to 3, wherein the polymer, wax, and / or resin comprises a drying oil.

12. The composition according to claim 11, wherein the drying oil comprises tung oil or paraffin.

13. The composition according to any one of claims 1 to 3, wherein the polymer, wax, and / or resin chemically reacts with the porous ceramic material to modify the properties of the polymer, wax, and / or resin.

14. The composition according to claim 13, wherein the chemical reaction for modifying the properties of the polymer, wax, and / or resin comprises crosslinking, curing, and / or polymerization.

15. The composite material is applied to the substrate to provide one or more functional properties selected from the following: protection against corrosion of the substrate; durability modifier against adhesion and / or surface staining; configuration to promote or delay adhesion; tactile modification of the surface; liquid repellency; modification of optical properties; mechanical modification such as hardness, elasticity, and viscoelasticity; self-healing and repair of surfaces and scratches; separation applications; modification of electrical properties or electrical properties; reduction and / or modification of ice, condensate, and frost; surface uniformity; defect reduction; and aesthetic properties. The composition according to any one of claims 1 to 3, wherein the functional properties are improved or more significantly compared to the same porous ceramic material on the same substrate that does not contain the polymer, wax, and / or resin, or compared to the same substrate on which the polymer, wax, and / or resin is directly coated.

16. The composition according to any one of claims 1 to 3, wherein the composite material contains a ceramic volume concentration exceeding 40% of the total volume of the composite material.

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