Ceramic composite materials

Abstract

Porous, binderless ceramic surface modifiers and their uses are described. The ceramic surface material is in the form of an interconnected network of porous ceramic material on a substrate. The ceramic material may include metal oxides, metal hydroxides, and / or their hydrates, or metal carbonates or metal phosphates on the substrate surface. The substrate may be in the form of metal or polymer particles, powders, extrudates, or flakes.

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 a porous ceramic material comprising an interconnected network of ceramics, such as metal oxide ceramics, metal hydroxide ceramics, metal carbonate ceramics, metal titanate ceramics, or metal phosphate ceramics, which are immobilized on the surface of a substrate. [Background technology]

[0003] Chemical conversion coatings are a common method for adding functional layers to many metals and alloys, providing functional properties such as adhesion and corrosion resistance. These coatings work by converting the native oxide and / or native hydroxide layers on the metal surface into another substance. Common chemical conversion coatings include chromate and phosphate conversion treatments, blueing, and anodizing. All of these processes add a protective coating to the underlying metal. Other types of coatings, such as paints, drying oils, or other polymers, may be laminated onto the surface. These coatings generally require primers, have adhesion problems, have limited operating temperatures, and lack UV resistance. Novel materials that offer the advantages of both these existing technologies are desired. [Overview of the project]

[0004] This specification provides substrates with ceramic-based surface modifications and their applications.

[0005] In one embodiment, a composition is provided comprising a porous ceramic material including an interconnected network of ceramic material in contact with a substrate. In some embodiments, at least about 20% by mass, 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, 75% by mass, 80% by mass, 85% by mass, 90% by mass, or 95% by mass of the ceramic material is interconnected. In some embodiments, the porous ceramic material is binder-free. In some embodiments, at least a portion, most, or substantially all of the interconnected network of the ceramic material is in direct contact with the substrate. In other embodiments, the interconnected network of the ceramic network material may be indirectly in contact with the substrate, for example, in contact with a surface modifier or surface treatment agent on the surface of the substrate.

[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.

[0007] In some embodiments, the thickness of the ceramic material on the substrate is about 1 micrometer to about 100 micrometers.

[0008] In various embodiments, the ceramic material comprises rare earth elements, transition metal elements, alkaline earth metal elements, or aluminum. In specific embodiments, the ceramic material comprises oxides, hydroxides, or layered double hydroxides. For example, the oxides, hydroxides, or layered double hydroxides may comprise one or more of iron, aluminum, magnesium, cerium, zinc, manganese, titanium, chromium, vanadium, zirconium, nickel, cobalt, copper, silver, tantalum, tungsten, silicon, phosphorus, calcium, barium, tin, and europium. In specific embodiments, the ceramic material comprises phosphates, carbonates, titanates, aluminates, zirconates, fluoroaluminates, silicates, sulfides, vanadates, tungstates, stanates, or sulfates.

[0009] The above-mentioned substrate may include aluminum alloys, magnesium alloys, steel alloys, nickel alloys, titanium alloys, polymers, cellulosic materials (such as wood, rayon, or cotton, but not limited to these), polysaccharides, such as starch (e.g., thermoplastic starch, amylose, or amylopectin), hemicellulose, carrageenan, polysaccharides, or glass. For example, the above-mentioned substrate may be in the form of particles, powders, extruded materials, flakes, or lobed structures. In some embodiments, the above-mentioned substrate includes a maximum dimension less than about 5 mm, 4 mm, 3 mm, 2 mm, 1 mm, 500 microns, 250 microns, or 100 microns.

[0010] In some embodiments, the porous ceramic material is primarily crystalline. In some embodiments, the porous ceramic material has a density of approximately 10 m² per square meter of the projected area of ​​the substrate. 2 ~about 1500m 2 This includes the surface area. In some embodiments, the porous ceramic material is approximately 15 m² per gram of ceramic material. 2 ~about 1500m 2This includes the surface area. In some embodiments, the porous ceramic material has an average pore diameter of about 2 nm to about 20 nm. In some embodiments, the pore diameter distribution. In some embodiments, the porous ceramic material has a maximum thickness of about 50 micrometers, for example, about 0.2 micrometers to about 25 micrometers. In some embodiments, the porous ceramic material has a porosity of more than about 10%, for example, about 30% to about 95%. In some embodiments, the porous ceramic material has a porosity of about 100 mm as measured by mercury intrusion porosimetry. 3 / g ~ approx. 7500mm 3 Includes void volume of / g

[0011] In some embodiments, the porous ceramic material includes pores partially or completely filled with a gaseous substance, a liquid substance, or a solid substance, or a combination thereof. For example, the porous ceramic material includes pores partially or completely filled with a second ceramic material, and the second ceramic material is identical or different in composition to the interconnected ceramic network in contact with the substrate. In certain embodiments, the interconnected ceramic network and the second ceramic material have different compositions, while the interconnected ceramic network includes hydroxides, oxides, or layered double hydroxides, and the second ceramic material includes phosphates, carbonates, silicates, sulfates, titanates, tungstates, zirconates, vanadates, stanates, zincates, or aluminates. In some embodiments, the interconnected ceramic network and the second ceramic material each include a primary metal, and the primary metal of the interconnected ceramic network and the primary metal of the second ceramic material are identical or different. In some embodiments, the interface between the interconnected ceramic network and the second ceramic material includes a gradient, for example, a gradient of composition, such as a gradient of phosphorus, carbon, silicon, sulfur, tungsten, titanium, vanadium, manganese, magnesium, zinc, tin, zirconium, or aluminum. In one embodiment, the interconnected ceramic network includes a metal oxide and / or metal hydroxide (e.g., magnesium oxide and / or magnesium hydroxide), the second ceramic material has a different composition (e.g., magnesium carbonate or magnesium phosphate), and there is a gradient between the two compositions at the interface, for example, a gradient of carbon or phosphorus at the interface.

[0012] In another aspect, a metal-ceramic composite material or a polymer-ceramic composite material is provided. The metal-ceramic composite material or the polymer-ceramic composite material comprises an "assembly" of the substrates modified with the ceramics described in this specification, i.e., an interconnected network of a porous ceramic material contacting the substrates, optionally comprising a substrate modified with an interconnected network of a binder-free porous ceramic material. For example, a plurality of the modified substrates may be processed (e.g., by sintering, casting, or molding) into a metal-ceramic composite material or a polymer-ceramic composite material. In certain embodiments, the plurality of substrates modified with ceramics includes, for example, particles, powders, flakes, or extrudates each having a maximum dimension less than any of about 5 mm, 4 mm, 3 mm, 2 mm, 1 mm, 500 microns, 250 microns, or 100 microns.

[0013] In another embodiment, a manufacturing method is provided. The method comprises laminating an interconnected network of binder-free porous ceramic material onto a metal or polymer substrate in the form of metal or polymer particles, powder, extruded or flakes, thereby producing a surface-modified metal substrate or a surface-modified polymer substrate. The surface-modified metal substrate or surface-modified polymer substrate is molded, cast or sintered into a monolithic or mesh-like ceramic component or a metal-ceramic composite component or a polymer-ceramic composite component. The core of the metal or polymer substrate has a lower melting point than the interconnected network of porous ceramic material, and the ceramic is sufficiently porous to cause wicking of the molten metal or polymer in the core during processing (e.g., molding, casting or sintering) and / or react with the molten metal or polymer. In some embodiments, the metal particles, powder, extruded or flakes include aluminum, aluminum alloys, magnesium, magnesium alloys, zinc, zinc alloys, calcium, or calcium alloys. In some embodiments, the polymer particles, powders, extruded materials, or flakes include polyolefins, polyesters, polystyrenes, polyamides, thermoplastic starches, acrylics, or polycarbonates. In some embodiments, the ceramic includes magnesium oxide, titanium oxide, zinc oxide, manganese oxide, zirconium oxide, silica, or calcium carbonate. [Brief explanation of the drawing]

[0014] [Figure 1]Figure A shows the ceramic surface before partial filling of the pores with an alkylphosphonic acid monolayer. Larger pores are maintained and shift slightly to smaller pore diameters due to partial filling of the pores, but pore diameters less than about 2.7 nm are filled and not measured by BJH adsorption / desorption. Note: The effect observed at about 50 Å corresponds to an experimental artifact where the liquid nitrogen probe condensed in the pores evaporates rapidly under non-equilibrium conditions. Figure B shows the ceramic surface after partial filling of the pores with an alkylphosphonic acid monolayer. Larger pores are maintained and shift slightly to smaller pore diameters due to partial filling of the pores, but pore diameters less than about 2.7 nm are filled and not measured by BJH adsorption / desorption. Note: The effect observed at about 50 Å corresponds to an experimental artifact where the liquid nitrogen probe condensed in the pores evaporates rapidly under non-equilibrium conditions.

Mode for Carrying Out the Invention

[0015] The present invention provides an interconnected network of synthetic ceramics (e.g., metal oxides, hydroxides, carbonates, or phosphates) laminated on a substrate, which provides desirable functional properties such as improved corrosion resistance and / or modified electrical conductivity. In some embodiments, the ceramics are binder-free (e.g., immobilized on the surface). The first ceramic laminated on the substrate may contain accessible pore volumes partially or completely filled with the second ceramic (e.g., metal oxide ceramic, metal hydroxide ceramic, metal carbonate ceramic, or metal phosphate ceramic), or the first ceramic may be partially or completely converted into the second ceramic (e.g., metal oxide ceramic, metal hydroxide ceramic, metal carbonate ceramic, or metal phosphate ceramic), or any combination thereof. The resulting ceramic material is useful in many applications, including, but not limited to, as an electrical insulator, a high-temperature barrier coating, a UV-resistant coating, and / or a coating on metal surfaces such as heat exchangers and ship surfaces for handling condensates and fluids, for minimizing corrosion and fouling.

[0016] The present invention also provides a method for applying a non-oxide ceramic coating to a substrate. For example, a ceramic metal oxide (e.g., magnesium oxide) film or layer laminated on a metal substrate (e.g., aluminum) can be converted into a metal compound (e.g., metal phosphate or metal carbonate) film or layer. The added film or layer can retain the structural artifacts of the original ceramic metal oxide film or layer's basic structure.

[0017] definition The numerical ranges provided herein include the numbers that define those ranges.

[0018] "A," "an," and "the" include plural objects unless explicitly indicated by the context.

[0019] 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).

[0020] 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.

[0021] "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.).

[0022] "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).

[0023] "Cellulose-based" materials refer to materials that are composed of or contain cellulose or cellulose derivatives, such as cellulose ethers or esters.

[0024] "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.

[0025] "Contact angle" refers to the angle between the surface and the gas-liquid interface at a contact surface, as measured by the liquid.

[0026] "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.

[0027] A "processed coating" refers to a surface layer in which reactants chemically react with the surface being treated, converting the coating on the substrate or ceramic (e.g., metal oxides and / or metal hydroxides) into another compound. This process is generally additive, or rather, not lamination, and may result in only slight changes in mass.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] "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.

[0032] "Continuous ceramic network," "continuous network of ceramic materials," or "interconnected network of ceramics" refers to a network or matrix of ceramic materials in which the ceramic materials in the network are in physical contact (bonded) with other ceramic materials in the network. That is, the majority of the ceramic materials are adjacent to other ceramic materials and form a scaffold structure that is either self-supporting or supported on a substrate. The interconnected ceramic network described herein is a continuous ceramic phase over a macroscopic area or volume and may include pores (open spaces) having an accessible pore volume that may be filled, or partially filled, with another material, such as, but not limited to, another ceramic.

[0033] "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.

[0034] 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.

[0035] "Average" refers to the arithmetic mean or average.

[0036] 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).

[0037] "Multimodal" refers to a distribution that contains multiple different modes that appear as multiple different peaks.

[0038] 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.

[0039] "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.

[0040] "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.

[0041] "Porous" refers to spaces, holes, or voids within a solid material.

[0042] "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.

[0043] "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.

[0044] 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.

[0045] "Film thickness" refers to the distance between the surface of the substrate and the top of the surface modifier (e.g., ceramic).

[0046] 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.

[0047] "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.

[0048] "Adjustable" refers to the ability to change or modify the function, properties, or quality of a material.

[0049] Structured ceramic materials The continuous or spaced coatings or surface modifiers described herein (porous ceramic materials including interconnected networks of ceramics) may be structured ceramics, such as binder-free ceramics with a crystallinity of more than about 20%, or binder-free (e.g., surface-immobilized) ceramics such as interconnected networks of ceramic materials. In some embodiments, the structured ceramic is a porous, such as interconnected networks of porous ceramic materials. Examples of non-limiting ceramic materials are presented in PCT / US19 / 65978, the entire application of which is incorporated herein by reference.

[0050] The interconnected network of the above ceramic materials may include metal oxide ceramics and / or metal hydroxide ceramics, for example, oxide ceramics and / or hydroxide ceramics of a single metal or mixed metal. In some embodiments, the interconnected network of the above ceramic materials includes metal oxide ceramics and / or metal hydroxide ceramics, for example, oxide ceramics and / or hydroxide ceramics of a single metal or mixed metal. In some embodiments, the interconnected network of the above ceramic materials includes metal oxide ceramics 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 interconnected network of the above ceramic materials includes metal oxide ceramics and / or metal hydroxide ceramics, and the substrate is hydrated with water or other compounds, resulting in changes to the surface energy and potentially the ratio of metal oxides to the metal hydroxide composition of the ceramic. In some embodiments, the interconnected network of 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 being a layered double hydroxide.

[0051] 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.

[0052] The mixed metal oxide or mixed metal hydroxide may, for example, contain oxides or hydroxides of two or more metals respectively, and the metals 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.

[0053] In some embodiments, the interconnected network of the ceramic material is a binder-free ceramic material, that is, it is laminated on a substrate without using a binder. In some embodiments, the interconnected network of the ceramic material is immobilized on a substrate.

[0054] In some embodiments, the interconnected network of the ceramic material may be in the form of metal phosphates, metal carbonates, metal sulfates, metal borates, metal tungstates, metal molybdates, metal titanates, metal stannates, metal silicates, and metal vanadates, or combinations thereof. In some embodiments, the material may contain, but is 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, barium, or calcium.

[0055] In some embodiments, the interconnected network of the ceramic material has, for example: the ability to cause capillary rise to lift a liquid with low surface tension (e.g., less than about 25 mN / m in isopropanol) upward by more than about 5 mm above the surface against gravity within 1 hour in a sealed container; about 0.1 m 2 / g to about 10,000 m 2It 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.

[0056] The ceramic material described above is porous, and its porosity may be 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 exceeds any of the above. 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%.

[0057] In some embodiments, the porous ceramic 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.

[0058] In some embodiments, the porous ceramic material is measured by mercury intrusion porosimetry and has a thickness of approximately 100 mm. 3 / g ~ approx. 7500mm 3The 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

[0059] The porous ceramic 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 greater than 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.

[0060] The above-mentioned porous ceramic surface modifier (interconnected network of ceramics) 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 with 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.

[0061] The pores of the porous ceramic surface modifier (interconnected network of ceramics) 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.

[0062] In some embodiments, the accessible pore volume of the porous ceramic material is partially filled with a first material, and then partially or completely filled with a second material. 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.

[0063] 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.

[0064] Materials that can be used to partially or completely fill pores include molecules that can be bonded to the surface, such as molecules having a head group and a tail group, where the head group may be a silane, phosphonate, or phosphonic acid, carboxylic acid, vinyl, hydroxide, thiol, or ammonium compound. The tail group may be any functional group, such as hydrocarbons, fluorocarbons, vinyl groups, phenyl groups, and / or quaternary ammonium groups. Other ceramic materials (second ceramic materials) can also be laminated in the pores partially or completely. Polymers can also be laminated in the pores partially or completely. The second ceramic material may include, for example, one or more oxides of zinc, aluminum, manganese, magnesium, cerium, gadolinium, and cobalt. In addition, the ceramic material may include solid materials that can be added to surface modifiers, which are mainly held by ionic and covalent bonds, such as clay, silica, glass, or inorganic compounds of metals, nonmetals, or metalloid atoms. Other ceramics (second ceramic material) may include metal phosphates, metal carbonates, metal sulfates, metal borates, metal tungstates, metal molybdates, metal titanates, metal stanates, metal silicates, metal vanadates, or metal zincates. In some embodiments, the second ceramic material may include, but is 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, barium, or calcium. The polymer may include, for example, hemp, shellac, amber, wool, silk, natural rubber, cellulose, and other natural fibers, sugars, hemicellulose and holocellulose, polysaccharides, and biologically derived materials such as extracellular proteins, and 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.

[0065] In some embodiments, the accessible pore volume of the porous ceramic material is partially filled with a thin composite polymer layer to produce a surface modifier having the porosity and functionality imparted by the polymer. In other embodiments, the pores are completely filled with a thick polymer layer to produce a surface modifier comprising a thick polymer layer having the combined properties of the porous base material and the polymer layer. The polymers described in the compositions herein include copolymers.

[0066] In some embodiments, the accessible pore volume of the porous ceramic material is partially or completely filled with a layer of material laminated on the surface of the surface modifier. In some embodiments, but not limited to, a layer of material is laminated in which one or more functional groups, such as, but not limited to, ammonium groups (e.g., quaternary ammonium groups), alkyl groups, perfluoroalkyl groups, and fluoroalkyl groups, are added to the surface modifier material. In some embodiments, a polymer or ceramic layer is laminated. In some embodiments, a top surface layer of ceramic is laminated, which is the same or a different ceramic as the ceramic of the binder-free porous ceramic material on the substrate. 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.

[0067] In some embodiments, the accessible pore volumes of the porous ceramic material are partially or completely filled with a gas, liquid, or solid substance, or a combination thereof, and the composition further comprises a top layer of surface material on the ceramic material, which performs one or more functions, but is not limited to these, such as wetting by liquid and / or selective separation of compounds in liquid. In certain embodiments, the top layer material is a material separate from the substance that partially, substantially, or completely fills the pores and does not fill or penetrate the pores itself. In some embodiments, the top layer material interacts with the substance(s) in the pores. For example, the top layer material can interact with the substance(s) in the pores to provide one or more functions, but is not limited to, thermal management, regulation of electrochemical reactivity, and / or regulation of mechanical properties. In certain embodiments, the top layer material is the surrounding environment in contact with the binder-free porous ceramic material.

[0068] In some embodiments, the accessible pore volumes of the porous ceramic material are substantially or completely filled with the polymer or ceramic material.

[0069] 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.

[0070] 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.

[0071] 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, color, and / or photochemical activity.

[0072] In some embodiments, the ceramic surface modifier (an interconnected network of ceramics) 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.

[0073] In some embodiments, the ceramic surface modifier (an interconnected network of ceramics) has an asymmetric pore morphology, e.g., ordered to have a relatively constant, normal distribution of surface area to volume, clearly defined in a spherical, cylindrical, cubic, or otherwise distinct shape, characterized by a ratio of the first quartile pore diameter to the third quartile pore diameter, 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. Examples of non-limiting asymmetric pores are shown in PCT application number PCT / US19 / 39743, which is incorporated herein by reference in its entirety.

[0074] Porous ceramic surface modifiers (interconnected networks of ceramics) 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, as described herein, for example, 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.

[0075] In some embodiments, the porous ceramic surface modifier (interconnected network of ceramics) 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.

[0076] Ceramic surface modifiers (interconnected networks of ceramics) 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.

[0077] In some embodiments, as ceramic surface modifiers (interconnected networks of ceramics): mixtures of zinc and aluminum oxide and / or hydroxide; mixtures of ZnO and Al2O3 and Zn-aluminates; mixtures of materials containing any / all phases including Zn, Al, and oxygen; mixtures of manganese and magnesium oxide and / or hydroxide; manganese oxide; aluminum oxide; mixed metal manganese oxide and / or hydroxide; mixtures of magnesium and aluminum oxide and / or hydroxide; mixtures of magnesium, cerium, and aluminum oxide and / or hydroxide; zinc, gadolinium, and aluminum Mixtures of nium oxides and / or hydroxides; mixtures of cobalt and aluminum oxides and / or hydroxides; mixtures of manganese and aluminum oxides and / or hydroxides; mixtures of cerium and aluminum oxides and / or hydroxides; mixtures of iron and aluminum oxides and / or hydroxides; mixtures of tungsten and aluminum oxides and / or hydroxides; mixtures of tin and aluminum oxides; tungsten oxides and / or hydroxides; magnesium oxides and / or hydroxides; manganese oxides and / or hydroxides; tin oxides and / or hydroxides; or zinc oxides and / or hydroxides.

[0078] In some embodiments, at least one metal in the interconnected network of ceramic materials is 2 + It is in an oxidized state.

[0079] In some embodiments, the ceramic surface modifier (interconnected network of ceramics) 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.

[0080] In some embodiments, the ceramic surface modifier (an interconnected network of ceramics) 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.

[0081] In some embodiments, a functional material layer (e.g., the top layer of the material) is laminated on top of an interconnected network of ceramic materials. Examples of such materials include, but are not limited to, quaternary ammonium groups for antimicrobial properties, alkyl chains for hydrophobicity and hydrocarbon affinity, perfluoroalkyl groups for hydrophobicity and oleophobicity, 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.

[0082] In some embodiments, the ceramic surface modifier (an interconnected network of ceramics) is more resistant to ultraviolet degradation than the substrate material, such as a polymer or any substrate material disclosed herein.

[0083] In some embodiments, the ceramic surface modifier (interconnected network of ceramics) includes a film thickness of about 0.5 micrometers to about 20 micrometers. In some embodiments, the ceramic material includes a film thickness of about 0.2 micrometers to about 25 micrometers. In some embodiments, the film thickness is at least one of about 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 micrometers. In some embodiments, the film thickness is one of the following: about 0.2 to about 0.5, about 0.5 to about 1, about 1 to about 5, about 3 to about 7, about 5 to about 10, about 7 to about 15, about 10 to about 15, about 12 to about 18, about 15 to about 20, about 18 to about 25, about 0.5 to about 15, about 2 to about 10, about 1 to about 10, about 3 to about 13, about 0.5 to about 15, about 0.5 to about 5, about 0.5 to about 10, or about 5 to about 15 micrometers.

[0084] In some embodiments, the ceramic surface modifier (an interconnected network of ceramics) is characterized by a water contact angle of about 0° to about 180°. In other embodiments, the water contact angle is less than about 30°. In other embodiments, the water contact angle is greater than about 150°.

[0085] In some embodiments, the ceramic surface modifier (interconnected network of ceramics) is approximately 1.1 m² per square meter of the target substrate area. 2 ~approximately 100m 2 This includes the surface area. In some embodiments, the ceramic material has about 10 m² per square meter of the substrate area in question. 2 ~about 1500m 2The surface area includes the surface area of ​​the substrate in question, per square meter. In some embodiments, the surface area is at least about 10, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, or 1500 m². 2 In some embodiments, the surface area is approximately 10 to 100, 50 to 250, 150 to 500, 250 to 750, 500 to 1000, 750 to 1200, 1000 to 1500, 70 to 1000, 150 to 800, 500 to 900, or 500 to 1000 m² per square meter of the substrate area. 2 It is one of the following:

[0086] In some embodiments, the ceramic material (an interconnected network of ceramics) 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:

[0087] Base material The substrate on which the porous ceramic material, including the interconnected network of ceramics described herein, is coated or laminated 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.

[0088] In some embodiments, the substrate includes a metal, and the primary metal of the ceramic surface modifier described herein is different from the primary metal of 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 of the substrate include, but are not limited to, aluminum, iron, copper, zinc, nickel, titanium, and magnesium. Examples of primary metals of ceramics include, but are not limited to, zinc, aluminum, manganese, magnesium, cerium, copper, gadolinium, tungsten, tin, lead, and cobalt.

[0089] 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, an aluminum substrate is a ceramic material on which aluminum (e.g., Al) is incorporated into a ceramic material laminated on the substrate. 2+ ) may be able to provide.

[0090] In some embodiments, the substrate is a particle, powder, extruded, pellet, flake, or lobed leaf structure (e.g., a bilobe, a trilobe, a quadrilobe, etc.). In some embodiments, the substrate is a metallic particle, powder, extruded, pellet, flake, or lobed leaf structure in which an interconnected network of laminated binder-free ceramics is laminated on the surface of the substrate.

[0091] In some embodiments, the substrate is a ceramic material. In some embodiments, the substrate includes a ceramic material. In some embodiments, the ceramic material is an oxide ceramic, a non-oxide ceramic, or a combination thereof. In some embodiments, the ceramic material includes an oxide ceramic, a non-oxide ceramic, or a combination thereof. In some embodiments, the ceramic material consists of one or more oxide ceramics, one or more non-oxide ceramics, or a combination thereof. In some embodiments, the ceramic material consists of one or more oxide ceramics. In some embodiments, the ceramic material consists of one or more non-oxide ceramics. In some embodiments, the ceramic material includes an oxide ceramic. In some embodiments, the oxide ceramic is an oxide, a hydroxide, a mixed oxide / hydroxide, an aluminate, a silicate, a titanate, a zirconate, a tungstate, or a mixture thereof. In some embodiments where the oxide ceramic is a mixed oxide / hydroxide, the oxide:hydroxide ratio is a function of the degree of hydration of the mixed oxide / hydroxide. In some embodiments, the oxide ceramic is aluminum oxide (alumina), silicon oxide (silica), silica-alumina, cerium oxide (ceria), yttrium oxide (yttria), titanium oxide (titania), zirconium oxide (zirconia), hafnium oxide (hafnia), molybdenum oxide, tungsten oxide, tin oxide, or a combination thereof. In some embodiments, the oxide ceramic is alumina, silica, or silica-alumina. In some embodiments, the oxide ceramic is alumina. In some embodiments, the oxide ceramic is silica. In some embodiments, the oxide ceramic is silica-alumina. In some embodiments, the oxide ceramic is titania, zirconia, hafnia, or a combination thereof. In some embodiments, the oxide ceramic is titania. In some embodiments, the oxide ceramic is zirconia.In some embodiments, the oxide ceramic includes alkali metal oxide / hydroxide, alkaline earth metal oxide / hydroxide, or a combination thereof. In some embodiments, the oxide ceramic includes sodium oxide / sodium hydroxide or potassium oxide / potassium hydroxide. In some embodiments, the oxide ceramic includes dipotassium oxide. In some embodiments, the oxide ceramic includes disodium oxide. In some embodiments, the oxide ceramic is magnesium oxide (magnesia) or calcium oxide. In some embodiments, the oxide ceramic is magnesium oxide. In some embodiments, the oxide ceramic is magnesium aluminate or calcium aluminate. In some embodiments, the oxide ceramic is alkali metal silicate, magnesium silicate, calcium silicate, aluminum silicate, zirconium silicate, or a combination thereof. In some embodiments, the oxide ceramic is magnesium titanate or aluminum titanate. In some embodiments, the oxide ceramic is aluminum zirconate, magnesium zirconate, or calcium zirconate. In some embodiments, the oxide ceramic is zeolite. In some embodiments, the ceramic material includes non-oxide ceramics. In some embodiments, the non-oxide ceramic is a carbide, nitride, or oxynitride. In some embodiments, the non-oxide ceramic is a nitride ceramic or a carbide ceramic. In some embodiments, the non-oxide ceramic is boron nitride, aluminum nitride, silicon nitride, boron carbide, silicon carbide, titanium carbide, tungsten carbide, molybdenum carbide, or a combination thereof. In some embodiments, the non-oxide ceramic is aluminum silicon oxynitride.

[0092] In some embodiments, the substrate includes a ceramic material. In some embodiments, the ceramic material includes an oxide ceramic. In some embodiments, the oxide ceramic includes a sulfated oxide. In some embodiments, the sulfated oxide is sulfated titania, sulfated zirconia, or sulfated tin oxide.

[0093] In some embodiments, the substrate includes a ceramic material. In some embodiments, the ceramic material includes an oxide ceramic. In some embodiments, the oxide ceramic includes an alkali metal halide, an alkaline earth metal halide, or a combination thereof. In some embodiments, the oxide ceramic includes sodium chloride, potassium chloride, potassium bromide, calcium chloride, magnesium chloride, or a combination thereof. In some embodiments, the oxide ceramic includes magnesium chloride.

[0094] In some embodiments, the base material is formed. In some embodiments, the base material is a formed ceramic material. In some embodiments, the formed ceramic material is in the form of a pellet, a sphere, a ring, a cylinder, a honeycomb, a leaf-like structure with three lobes, or a leaf-like structure with four lobes. In some embodiments, the formed ceramic material is in the form of a pellet. In some embodiments, the formed ceramic material is in the form of a sphere. In some embodiments, the formed ceramic material is in the form of a ring. In some embodiments, the formed ceramic material is in the form of a cylinder. In some embodiments, the formed ceramic material is in the form of a honeycomb. In some embodiments, the formed ceramic material is in the form of a leaf-like structure with three lobes. In some embodiments, the formed ceramic material is in the form of a leaf-like structure with four lobes. In some embodiments, the formed ceramic material is an extrusion. In some embodiments, the extruded material has a diameter of approximately 0.5 mm to 5 mm, 0.5 mm to 4 mm, 0.5 mm to 3 mm, 0.5 mm to 2 mm, 0.5 mm to 1 mm, 1 mm to 5 mm, 1 mm to 4 mm, 1 mm to 3 mm, or 1 mm to 2 mm. In some embodiments, the formed ceramic material is in a random or loosely filled shape such as a saddle, helipac, or rasch ring. In some embodiments, the formed ceramic material is in a mesh shape. In some embodiments, the formed ceramic material is in a structured filled shape.

[0095] Conversion of metal oxides This specification provides products formed as a result of the chemical conversion of ceramic surface modifiers (e.g., porous metal oxide and / or hydroxide ceramic surface modifiers, e.g., interconnected networks of porous metal oxide and / or hydroxide ceramics). The conversion products described herein impart one or more properties to the substrate, which may be identical or different from the properties(s) imparted by the original ceramic surface modifier. The advantages provided by the conversion products have broad applicability. The products formed are modifications of the original metal oxide and / or hydroxide ceramic material, including, but not limited to, metal oxides / hydroxides, metal phosphates, metal carbonates, metal sulfates, metal borates, metal tungstates, metal molybdates, metal titanates, metal stanates, metal silicates, or metal vanadates.

[0096] In some embodiments, the conversion can impart further corrosion resistance compared to the same ceramic material without the conversion; shift the isoelectric point or zero charge point of the surface; protect against acids or bases; modify optical properties to absorb, reflect, or emit light at different frequencies; inhibit plasma membrane ATPases; impart ferroelectric properties; increase capacitance or improve dielectric properties; adjust the temperature coefficient of resistance; improve thermal stability; impart piezoelectric properties; increase surface area; promote adsorption; alter color tone through specific chemical reactions; improve ultraviolet (UV) resistance; and / or impart pseudocapacitive properties.

[0097] In one embodiment, the above conversion reduces the substrate's susceptibility to corrosion. In non-limiting examples, the substrate is protected from corrosive environments and / or chemicals by an inert metal phosphate or metal carbonate barrier. This protective layer may act through two main pathways to prevent corrosion and / or deconductivity of the substrate. The primary protection is physical, where the inert barrier prevents corrosive species from attacking the substrate and deconducting its conductivity. The secondary function of the metal phosphate layer is to act as a sacrificial element that reacts with corrosive species on behalf of the substrate.

[0098] Purpose In some embodiments, the modified substrate is a coated article used either in its as-coated state or after being installed in a system such as a heat exchanger, reactor, or distillation column. In other embodiments, the coated substrate can also be used as an additive, such as modified particles, powder, extruded material, or flakes, in thermal grease or polymer-ceramic composite materials. In other embodiments, the modified substrate can also be processed into sized parts by sintering (e.g., laser sintering), molten casting, injection molding, or 3D printing (e.g., fused deposition modeling (FDM) 3D printing) of the coated substrate or composite material of the coated substrate. In some embodiments, the coated substrate is a surface-modified ceramic particle, powder, extruded material, pellet, flake, or notched leaf-like structure which, when sintered together (e.g., using laser sintering), produces a metal-ceramic composite material. In some embodiments, such as packing for reactors or distillations, the modified substrate may be formed into structural steel shapes, such as saddles, but not limited to, and then joined (e.g., sintered) to larger components used in the system. In some embodiments, the modified substrate may be formed into structural steel shapes used as molds for filling larger components used in the system. In some embodiments, the metal-ceramic composite material contains magnesium oxide and aluminum oxide. In other embodiments, a ceramic monolith is obtained by sintering (e.g., laser sintering, uniaxial hot pressing, hot isostatic pressing), molten casting, or injection molding of modified particles, powders, extruded materials, pellets, or flakes. In some embodiments, the ceramic monolith has a density of about 80%, about 90%, or about 95% of the theoretical density. In some embodiments, the ceramic monolith contains magnesium-aluminum spinel, aluminum titanate, zinc-aluminum spinel, or silicon, aluminum, magnesium, zirconium, titanium, or calcium.

[0099] In some embodiments, optically transparent monoliths are produced by post-processing ceramic-modified metal particles, powders, extrudes, pellets, or flakes. In some embodiments, these monoliths can be used as screens or windows. In some embodiments, post-processing ceramic-modified metal particles, powders, extrudes, pellets, or flakes produces metal-ceramic composite materials with increased yield strength, toughness, and / or hardness compared to solid metal without the ceramic.

[0100] In some embodiments, within the post-processed ceramic-metal composite material, the ceramic forms an interconnected network throughout the monolithic solid. In some embodiments, during sintering (e.g., laser sintering), casting (e.g., molten casting), or molding (e.g., injection molding), particles, powders, extrudes, or flakes of the metal substrate melt and flow within or through the porous, interconnected ceramic coating to produce a fidelity object. In some embodiments, this post-processing can produce a mesh-shaped component. In other embodiments, the coated particles, powders, or extrudes can be molten-cast into a film. In some embodiments, the film is optically transparent.

[0101] In some embodiments, the particle size of the substrate can be selected to determine the ratio of metal to ceramic in the post-processed portion. In some embodiments, this can be used to obtain a metal-ceramic composite material. In other embodiments, this can be used to obtain ceramic. In other embodiments, in the post-processed portion, the ceramic content is approximately 10%, approximately 20%, approximately 30%, approximately 40%, approximately 50%, approximately 60%, approximately 70%, approximately 80%, approximately 90%, approximately 95%, and approximately 99%.

[0102] In some embodiments, parts containing the ceramic surface modifier can be processed at lower temperatures than other manufacturing techniques. In some processing techniques, the substrate melts and reacts with the porous ceramic coating. In some embodiments, this reaction forms a refractory material. In some embodiments, the ceramic coating modifies the optical properties of the substrate, resulting in improved post-processing.

[0103] The following examples are intended to illustrate the present invention and are not intended to limit it. [Examples]

[0104] The substrates or assemblies to which the porous ceramic material described in the following examples is coated typically undergo the following processes: (a) surface preparation or cleaning, followed by (b) lamination of the structured ceramic, and (c) lamination of another ceramic layer or conversion of the laminated structured ceramic layer.

[0105] (a) Surface preparation and cleaning steps: In the following example, the surface was prepared as follows: Metal substrates or assemblies were washed in a container or wiped with isopropyl alcohol (IPA) and a towel to remove all residual oil. The parts were then immersed in a caustic etching bath with pH > 10 at nominal room temperature of 20°C until the surface darkened or for about 15 minutes. The substrates or assemblies were then rinsed with water to remove all remaining caustic solution or lightly adhering material. The parts were then immersed in a nitric acid solution with pH less than 3 and a temperature of 20°C to remove dirt, etching reaction products, intermetallic compounds, and surface oxides, or the substrates were acid-washed to expose a clean surface. Other surface preparation techniques that yield a clean surface are preferred and available. Polymer substrates and cellulosic substrates were washed in a container or wiped with a towel soaked in isopropyl alcohol to remove all residue.

[0106] (b) Lamination of structured ceramics: Lamination of structured ceramics in the following examples is considered continuous unless otherwise stated. Selective coating was carried out by exposure to a partial chemical and / or the use of a masking agent. The substrate or assembly was then placed in a bath for laminating structured ceramics containing 20-500 mM metal nitrate and an amount of amine (such as ethylenediamine, hexamethylenetetramine, or urea), and reacted at a reaction temperature of 30°C-90°C before inserting the substrate. The assembly was kept in the bath until the turbidity was below 100 NTU, or for about 5 minutes to about 90 minutes. The substrate or assembly was removed, drained, rinsed, and placed in an oven and dried and / or fired at about 100°C-800°C for several hours. The parts were then cooled to room temperature.

[0107] (c) Lamination of a second ceramic or conversion of a laminated structured ceramic: Unless otherwise specified, the structured ceramic prepared in (b) was dried before any post-processing steps such as conversion of a laminated ceramic or lamination of a second ceramic in which the second material partially or completely fills the porous interconnected ceramic network described above. Unless otherwise specified, the processing time from coating to subsequent processing was less than 24 hours.

[0108] Example 1 A phosphate-based corrosion-preventive layer was fabricated by converting a ceramic surface modifier consisting of interconnected metal (magnesium) oxides, prepared on a substrate plate as described above. A 3003 aluminum alloy substrate, pre-modified with a magnesium oxide structured ceramic surface agent (using magnesium nitrate and hexamethylenetetramine), was immersed in a phosphate aqueous solution conversion bath. The phosphate conversion occurred in an aqueous solution heated to 50°C to 90°C. This solution requires three main components: A = phosphate source, B = buffer species, and C = catalyst. Component A may be phosphoric acid or alkaline phosphate at a concentration of 0.250 M or less. Component B may be a suitable buffer at a concentration of 0.150 M or less, such as acetic acid and its conjugate base salt, or citric acid and its conjugate base salt. Component C is a stanate such as hexahydrostanate at a concentration of 0.1 M or less. It is necessary to select an appropriate combination of components A, B, and C so that the pH is between 6 and 8.5.

[0109] The electrochemical impedance of these plates was tested in a neutral 3.5% NaCl solution, and it was found that the impedance was, on average, an order of magnitude higher than that of the unconverted surface modifier. The samples were evaluated for 94 hours in an acidic salt spray test according to ASTM G85 A3, along with the unconverted samples. The amount of pitting corrosion observed on the phosphate samples was reduced compared to the unconverted surface modifier samples. The chemical composition after conversion, observed by X-ray fluorescence (XRF), showed an increase in phosphorus content from 0% to 30±7% and an increase in tin content from 0% to 0.5±0.2%. Fourier transform infrared (FTIR) spectroscopy suggested the presence of PO bonds.

[0110] Example 2 A carbonate-based corrosion-preventive layer was fabricated by converting a ceramic surface modifier, consisting of interconnected metal oxides, prepared on a substrate plate as described above. An aluminum alloy substrate, pre-modified with magnesium oxide structured ceramic, was immersed in a carbonate aqueous solution conversion bath. Carbonate conversion occurred in an aqueous solution heated to 50°C to 90°C. This solution requires one component that constitutes the carbonate source. This component may be a carbonate such as potassium carbonate, sodium bicarbonate, or ammonium bicarbonate, or a source for generating carbon dioxide in the solution, such as bubbling carbon dioxide. The carbonate concentration was 0.01M to 1M, and the optimal immersion time was 600 to 1500 minutes.

[0111] In one specific case, a 125 mM NaHCO3 deionized (DI) aqueous solution was prepared and heated to 80°C for 1 hour to equilibrate. A substrate having a structured magnesium oxide laminate was immersed in the carbonation solution for 16 hours, and water was added to maintain the liquid level. The sample was removed and dried.

[0112] Using SEM, we observed changes in surface structure due to carbonate-based conversion. The presence of carbonate compounds on the surface was confirmed at 1408 cm². -1 This was confirmed by a strong IR absorbance peak.

[0113] The samples were evaluated for 94 hours using an acidic salt spray test in accordance with ASTM G85 A3, along with samples that had not been converted. The amount of pitting corrosion observed was reduced compared to the substrate material of the exposed board.

[0114] Analysis of the above sample using X-ray diffraction (XRD) revealed that the compounds in the sample included magnesium hydroxide, aluminum hydroxide, and the carbonate-containing mineral hydrotalcite.

[0115] Example 3 A structured ceramic of interconnected metal oxide ceramics, prepared on the substrate as described above, is converted into calcium phosphate to create a corrosion-resistant layer of hydroxyapatite, octacalcium phosphate, and tricalcium phosphate. The surface-modified substrate is immersed in an aqueous bath containing calcium salts such as calcium chloride or calcium nitrate, phosphates such as potassium hydrogen phosphate, and chelating / complexing agents such as urea, hexamethylenetetramine, or ethylenediaminetetraacetic acid. The concentrations of all components are in the range of 0.01 M to 1 M. The conversion is carried out in a heated aqueous solution at 50°C to 90°C, and the immersion time is 60 to 1500 minutes. Following the immersion, hot annealing is performed at a temperature of 200°C to 600°C for 60 to 1500 minutes.

[0116] Example 4 A corrosion-resistant layer of hydroxyapatite, octacalcium phosphate, and tricalcium phosphate is prepared by directly laminating interconnected ceramics containing calcium phosphate onto a substrate. This substrate is then immersed in an aqueous bath containing calcium salts such as calcium chloride or calcium nitrate, phosphates such as potassium hydrogen phosphate, and chelating / complexing agents such as urea, hexamethylenetetramine, or ethylenediaminetetraacetic acid. The concentrations of all components are in the range of 0.025 M to 1 M. Conversion is carried out in a heated aqueous solution at 50°C to 90°C for 60 to 1500 minutes. Following immersion, hot annealing is performed at a temperature of 200°C to 600°C for 60 to 1500 minutes.

[0117] Example 5 A mixed metal-ceramic surface modifier is prepared by converting the interconnected metal oxide structured ceramic prepared on the substrate as described above. The surface-modified substrate is immersed in an aqueous conversion bath to introduce another metal in the form of anions. These anions function as a source of corrosion inhibitors. The anion sources are salts of specific oxyanions such as sodium stannate, sodium tungstate, or sodium molybdate, or phosphoryl oxyanion salts such as sodium phosphotungstate or sodium phosphomolybdate. The aqueous solution may contain a buffer to stabilize the ions and surface modifier in the solution. Examples of buffers include citrate-based, phosphoric acid-based, carbonate-based, acetic acid-based, or common biological buffers such as tris(hydroxymethyl)aminomethane (Tris) or 3-(N-morpholino)propanesulfonic acid (MOPS). The concentration of the components in the solution is 0.01M to 1M. Immersion is performed at a temperature of 50°C to 90°C for 5 to 1500 minutes. After immersion, hot annealing is performed at a temperature of 200°C to 600°C for 60 to 1500 minutes.

[0118] Example 6 A mixed metal ceramic surface modifier was prepared by converting the interconnected magnesium oxide ceramic surface modifier prepared on the substrate as described above. The surface-modified substrate was immersed in an aqueous conversion bath containing sodium molybdate to introduce anionic molybdenum. Sodium molybdate functions as a corrosion inhibitor when injected into the ceramic matrix. Sodium molybdate was present in the solution at a concentration of 0.01 M to 500 mM, usually about 100 mM, and this solution was maintained at a temperature in the range of 20°C to 90°C, usually about 20°C. The immersion time was 60 to 1500 minutes, usually about 120 minutes. After the conversion step, the sample was thoroughly rinsed with deionized water to remove all solution from the surface. The sample was then dried at a temperature of 20°C to 105°C. EDS and XRF measurements performed after conversion at both conversion bath temperatures of 20°C and 80°C revealed the presence of molybdenum on the surface of this material. The structures of the interconnected magnesium oxide surface modifier and the magnesium oxide surface modifier converted with interconnected molybdenum were found to be similar when examined using a scanning electron microscope (SEM).

[0119] Example 7 A mixed metal ceramic surface modifier was prepared by converting the interconnected magnesium oxide ceramic surface modifier prepared on the substrate as described above. The surface-modified substrate was immersed in an aqueous conversion bath containing sodium molybdate to introduce anionic molybdenum. Sodium molybdate functions as a corrosion inhibitor when injected into the ceramic matrix. Sodium molybdate was present in the solution at a concentration of 0.01 M to 500 mM, usually about 100 mM, and this solution was maintained at a temperature in the range of 20°C to 90°C, usually about 20°C. The immersion time was 60 to 1500 minutes, usually about 120 minutes. After the conversion step, the sample was thoroughly rinsed with deionized water to remove all solution from the surface. The sample was then hot annealed at a temperature of 400°C to 600°C for 60 to 1500 minutes, usually about 120 minutes. EDS and XRF measurements performed after conversion at both 20°C and 80°C revealed the presence of molybdenum on the surface of this material. The interconnected structures of the magnesium oxide surface modifier and the magnesium oxide surface modifier converted with the interconnected molybdenum were found to be similar when examined by SEM.

[0120] Example 8 A mixed metal ceramic surface modifier was prepared by converting the interconnected magnesium oxide structured ceramic surface modifier, which had been prepared on the substrate as described above. The surface-modified substrate was immersed in an aqueous solution conversion bath to introduce anionic tin. The anions function as a source of corrosion inhibitors. Sodium stannate was added to the aqueous solution bath. The pH of the solution was controlled to 7-13, usually about 8-9, by adding 1M nitric acid. A buffer was added as needed to maintain the pH of the solution and to help stabilize the ions in the solution. The concentration of the components in the solution was 0.01M-1M, usually about 100mM. Immersion was carried out at a temperature of 20°C-90°C, usually 20°C, for 5-1500 minutes, usually about 900 minutes. After immersion, these samples were thoroughly rinsed with deionized water to remove all aqueous solution from the surface. The samples were dried at a temperature of 15°C-105°C. After the samples were dried, they were analyzed by EDS and XRF, which identified tin in the ceramic structure in relation to exposure to conversion baths at 20°C and 80°C. Furthermore, imaging using SEM before and after immersion in a sodium stannate bath showed that the interconnected structure of the ceramic surface modifier was similar.

[0121] Example 9 A mixed metal ceramic surface modifier was prepared by converting an interconnected magnesium oxide structured ceramic surface modifier on an aluminum substrate to a surface modifier consisting of a mixture of tin oxide and magnesium oxide on an aluminum substrate. The substrate surface-modified with interconnected structured magnesium oxide was prepared as described above. At the end of this step, the surface of the aluminum substrate surface-modified with interconnected magnesium oxide appeared white. Next, the substrate surface-modified with interconnected magnesium was immersed in a 0.005-1 M, usually about 100 mM sodium stannate solution. The pH of this solution was controlled to 7-13, usually about pH 12, by adding 1 M nitric acid. Buffering agents were added as needed to maintain the pH of the solution and to help stabilize the ions in the solution. The temperature of the solution was controlled to 15°C-90°C, usually about 20°C, and the immersion time was 60-1500 minutes, usually about 120 minutes. After removing the sample, the surface of the solution was cleaned by gently rinsing with deionized water. An optional hot annealing step was performed at a temperature of 200°C to 600°C, typically around 400°C, for 60 to 1500 minutes, typically around 120 minutes. At the end of both conversion steps at 20°C and 80°C, the appearance of the mixed metal ceramic surface modifier was silvery and metallic. At the end of the hot annealing step, the surface color became dark gray. After the conversion step, the atomic composition of the surface of the sample treated at 20°C, as determined by energy-dispersive X-ray spectroscopy (EDS), was 1.31% Mg, 17.65% Sn, 3.17% Al, 77.53% O, and trace amounts of sodium. The atomic composition of the surface of the sample treated at 80°C, as determined by EDS, was 14.1% Sn, 85.0% O, and trace amounts of Al, Mg, and Na. The surfaces of both samples were interconnected and showed nanoscale roughness as measured by SEM imaging.

[0122] Example 10 A low-temperature (<100°C) thermochromic active surface modifier was prepared by converting the interconnected magnesium oxide structured ceramic surface modifier prepared on the substrate as described above. The magnesium oxide structured surface modifier was white after the hot annealing step. This surface-modified substrate was immersed in an aqueous solution conversion bath to convert the original ceramic metal oxide into a mixed metal oxide containing thermochromic active metal oxides. The immersion bath contained an aqueous solution of sodium metavanadate at a concentration of 10-200 mM, usually about 100 mM. The pH of the aqueous solution was maintained at 3-7 by adding 1 M nitric acid, and the aqueous solution contained buffers such as citrate-based, phosphoric acid-based, carbonate-based, acetic acid-based, or common biological buffers such as tris or MOPS, as needed. After pH adjustment, the color of the solution changed to bright orange, indicating the presence of decapanadate ions. The concentrations of all components were in the range of 0.01 M to 200 mM. The conversion was carried out in an aqueous solution maintained at 20°C to 90°C, usually around 20°C, with an immersion time of 60 to 1500 minutes, usually around 120 minutes. After immersion, the sample was thoroughly rinsed with deionized water and dried. After removing the substrate from the 20°C and 80°C immersion baths, the surface color was yellow-orange, indicating the presence of vanadium compounds on the surface. EDS revealed that the atomic composition of the surface treated at 20°C was 23.7% Al, 9.6% Mg, 12.1% V, and 54.6% O. Furthermore, FTIR analysis of the surface revealed decavanadate ions (V 10 O 28 6- ) and V6O 16 2- Polymeric anions such as [V3O8] n n- The existence of the decapanadate anion was shown to be 812 cm². -1 Observed at 957 cm, the decapanadate ion or terminal VO3 unit exhibits a symmetric stretching vibration of 957 cm. -1 , 1025cm -1These were observed. These FTIR peaks were not present in samples analyzed before treatment in a bath containing vanadium salts. SEM examination revealed that the surface was similar in structure to unconverted, interconnected magnesium oxide structured ceramics.

[0123] Example 11 A low-temperature (<100°C) thermochromic active surface modifier was prepared by converting the interconnected magnesium oxide structured ceramic surface modifier, prepared on the substrate as described above. The color of the magnesium oxide surface modifier after the hot annealing step was white. The surface-modified substrate was immersed in an aqueous conversion bath to convert the original ceramic metal oxide into a mixed metal oxide containing thermochromic active metal oxides. The immersion bath contained a salt of the desired metal, such as vanadium chloride or sodium orthovanadate. The pH of the aqueous solution was maintained at 3-7 by adding 1M nitric acid, and the aqueous solution contained, if necessary, buffers such as citrate-based, phosphoric acid-based, carbonate-based, acetic acid-based, or common biological buffers such as tris or MOPS. After pH adjustment, the color of the solution changed to bright orange, indicating the presence of decapanadate ions. The concentrations of all components were in the range of 0.01M-1M, usually about 100mM. The conversion was carried out in an aqueous solution maintained at 20°C to 90°C, usually at 20°C, with an immersion time of 60 to 1500 minutes, usually about 120 minutes. After immersion, the sample was thoroughly rinsed with deionized water and calcined at 400°C for 60 minutes. After removing the substrate from the 20°C and 60°C immersion baths, the surface color was yellow-orange, indicating the presence of vanadium compounds on the surface. After the calcination step, the sample still retained some orange color on the surface of the material, indicating the presence of vanadium compounds on the surface. XRF analysis revealed the presence of vanadium in this sample. Furthermore, SEM analysis revealed that the surface structure of vanadium-converted magnesium oxide was similar to that of unconverted magnesium oxide—that the surfaces of both were interconnected.

[0124] Example 12 A luminescent ceramic surface modifier is prepared by converting the metal oxide structured ceramic surface modifier prepared on the substrate as described above. The surface-modified substrate is immersed in an aqueous solution conversion bath to introduce light emission, or the metal oxide is converted into a luminescent compound. The aqueous solution may contain a light source such as europium nitrate or quinine. The concentration of all components is in the range of 0.01 M to 1 M. The conversion is carried out in a heated aqueous solution at 50°C to 90°C, with an immersion time of 60 to 1500 minutes. After immersion, hot annealing is performed at a temperature of 100°C to 600°C for 60 to 1500 minutes.

[0125] Example 13 A carbonate-based corrosion-preventive layer was fabricated by converting the interconnected metal oxide structured ceramic surface modifier prepared on the substrate as described above. An aluminum alloy substrate, previously modified with interconnected magnesium oxide structured surface modifier, was subjected to light at 70°C, 295-340 nm, and 1-2 W / m². 2 The sample was immersed and held in a chamber containing a UV light source with an irradiance of 1 / nm. The chamber contained water in equilibrium with the surrounding CO2. The sample was held in the chamber for 500 hours.

[0126] The samples were evaluated for 94 hours using an acidic salt spray test in accordance with ASTM G85 A3, along with samples that had not been converted. The number of corrosion-induced defects observed was reduced compared to the surface-modified samples that had not been converted.

[0127] Example 14 A surface modifier of interconnected magnesium oxide porous ceramic is applied to aluminum particles, powders, flakes, or extruded materials with a maximum dimension of less than 1 cm, as described above. The thickness of the coating and the particle size are selected so that the aluminum-to-magnesium ratio is greater than 2:1. These particles, powders, flakes, or extruded materials are then post-processed into monolithic or mesh-shaped objects by sintering, casting, or molding, by melting an aluminum substrate and flowing it through the porous ceramic coating, thereby obtaining a ceramic-metal composite material with improved strength compared to aluminum.

[0128] Example 15 A structured ceramic surface modifier of interconnected magnesium oxide is applied to aluminum particles, powders, flakes, or extruded materials with a maximum dimension of less than 1 cm, as described above. The thickness of the coating and the particle size are selected so that the aluminum-to-magnesium ratio is approximately 2:1. These particles, powders, flakes, or extruded materials are then post-processed into monolithic or mesh-like objects by sintering, casting, or molding, by melting an aluminum substrate and flowing it through the porous ceramic coating, thereby obtaining spinel monoliths by the reaction of molten aluminum with a stoichiometric amount of magnesium oxide. This process is repeated using a titania coating on aluminum particles to produce aluminum titanate.

[0129] Example 16 A porous ceramic surface modifier of interconnected magnesium oxide is applied to aluminum particles, powders, flakes, or extruded materials with a maximum dimension of less than 1 cm, as described above. The magnesium oxide layer imparts electrical insulation properties compared to uncoated aluminum. This modified powder, flake, particle, or extruded material is then added to a resin or binder to produce a thermally conductive paste with electrical insulation properties.

[0130] Example 17 A porous ceramic surface modifier of interconnected magnesium oxide was applied to a brazed aluminum heat exchanger. The heat exchanger was then placed in a bath, and the surface modifier was partially converted into a carbonate-based corrosion protection layer. This corrosion protection layer was formed by converting the structured metal oxide ceramic surface modifier prepared on the heat exchanger as described above. The brazed aluminum heat exchanger, previously modified with the structured magnesium oxide surface modifier, was immersed in a carbonate aqueous solution conversion bath. The carbonate conversion was carried out in an aqueous solution heated to 50°C to 90°C. This solution requires one component that constitutes a carbonate source. This component may be a carbonate such as potassium carbonate, sodium bicarbonate, or ammonium bicarbonate, or a source for generating carbon dioxide in the solution, such as bubbling carbon dioxide. The carbonate concentration is 0.01M to 1M, usually about 100mM, and the optimal immersion time is 600 to 1500 minutes. The heat exchanger was removed before the conversion to carbonate was complete, creating a surface containing both carbonate-containing ceramic and metal hydroxide. This heat exchanger was then subjected to an ASTM G85-A3 salt spray test, resulting in less salt deposition and corrosion products on average over 1000 hours compared to an uncoated heat exchanger.

[0131] Example 18 Interconnected zinc oxide porous ceramic surface modifications were laminated onto a 3003 Al substrate as described above. Next, the 3003 aluminum alloy substrate modified with the interconnected zinc oxide was placed in a second lamination bath containing manganese nitrate and a complexing agent (such as hexamethylenetetramine) at a temperature of approximately 50°C to 80°C for approximately 10 to 90 minutes, as described above. This generated a porous ceramic network of zinc oxide filled with manganese oxide. The presence of both zinc and manganese was shown by EDS analysis, indicating that both zinc oxide and manganese oxide were present on the surface of the interconnected material.

[0132] Example 19 An aluminum plate modified with the interconnected structured manganese oxide described above is prepared. Next, another ceramic material is filled into this modified plate by sputtering, ALD, or by casting a solution of a metal salt or a suspension of metal particles into the pores. This yields an interconnected ceramic network filled with ceramic. The first and second ceramics may be the same or different ceramic materials.

[0133] Example 20 A clean 4006 aluminum foil substrate was coated with an interconnected, structured ceramic surface agent based on a mixture of magnesium oxide, cerium oxide, and aluminum oxide. Krypton BET surface area measurement showed that the surface area was approximately 200 square meters per square meter of the substrate's projected surface area.

[0134] Example 21 A clean 4006 aluminum foil substrate was coated with an interconnected structured ceramic surface agent based on a mixture of magnesium oxide and aluminum oxide. ,table The surface was functionalized using a dilute isopropanol solution of hexadecylphosphonic acid. Nitrogen BET surface area measurement revealed that the surface area was 300-500 square meters per square meter of the projected surface area of ​​the substrate, and the specific surface area of ​​the ceramic material relative to its mass was 150-200 m². 2 It was shown to be / g. Mercury porosimetry revealed a bimodal pore size distribution with pore sizes concentrated at approximately 5 nm and 30 nm. BJH measurement showed that the volume of pores with a diameter of less than 2.7 nm was virtually zero. This indicates that the smallest pore diameter was 2.7 nm. The pore size distribution measured by BJH adsorption measurements before and after the partial filling surface functionalization described above is shown in Figures 1A and 1B. Furthermore, mercury porosimetry showed that this material is 52% to 69% more porous than bulk oxide materials.

[0135] Example 22 - Ceramic-Ceramic Composite Materials As described above, a structured magnesium oxide ceramic surface modifier was prepared on a 1 mm thick 3003 aluminum alloy substrate and converted to create a ceramic surface modifier with interconnected mixed metals. Next, this substrate was placed on a wire mesh stand and subjected to heat treatment conditions of 650°C to 1800°C. Under these conditions, the substrate melted, but the ceramic surface modifier did not. The molten substrate flowed through the pores of the ceramic surface modifier into a drain receiver below the wire mesh stand. Upon cooling the sample, two regimes were present: one regime contained only the surface modifier, and because this ceramic surface modifier was interconnected, this regime was connected as one. The other regime contained the surface modifier and solidified substrate held in place by surface tension. When the substrate reached its melting point, it filled the pores of the ceramic surface modifier. Upon further heating, the substrate was oxidized to aluminum oxide, creating a structured ceramic material of interconnected magnesium oxide and aluminum oxide. This resulted in the creation of an interconnected aluminum oxide-magnesium oxide composite material.

[0136] Example 23 As described above, a mixed metal ceramic surface modifier is prepared by converting an interconnected structured metal oxide ceramic surface modifier prepared on a cellulose substrate such as cellulose acetate. The surface-modified substrate is immersed in an aqueous conversion bath to introduce another metal in anionic form. The surface-modified substrate is immersed in an aqueous conversion bath to convert the original ceramic metal oxide into a mixed metal oxide containing a metal oxide with thermochromic activity. The immersion bath contains a salt of the desired metal, such as vanadium chloride or sodium orthovanadate. The pH of the aqueous solution is maintained at 3-7 by the addition of 1M nitric acid, and the aqueous solution may contain buffers such as citrate-based, phosphoric acid-based, carbonate-based, acetic acid-based, or common biological buffers such as tris or MOPS. The concentration of all components is in the range of 0.01M-1M, usually about 100mM. The conversion was carried out in an aqueous solution maintained at 20°C to 90°C, usually around 70°C, for an immersion time of 60 to 1500 minutes, usually around 90 minutes. Following the immersion step, the solution was thoroughly rinsed with deionized water and dried.

[0137] 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.

[0138] All publications, patents, and patent applications cited herein are, in whole, invoked by reference for all purposes, and each individual publication, patent, or patent application is invoked by reference to the same extent as each individual publication, patent, or patent application is specifically and individually indicated to be invoked by reference. Specific embodiments of the present invention are as follows. [Aspect 1] A composition comprising a porous ceramic material including an interconnected network of ceramics in contact with a substrate. [Aspect 2] The composition according to embodiment 1, wherein the porous ceramic material is a binder-free ceramic material. [Aspect 3] 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 4] The composition according to embodiment 1, wherein the thickness of the interconnected network of ceramics on the substrate is about 1 micrometer to about 100 micrometers. [Aspect 5] The composition according to embodiment 1, wherein at least about 20% by mass of the ceramic content is interconnected. [Aspect 6] The composition according to embodiment 1, wherein the interconnected network of the ceramics is larger than about 10 square micrometers. [Aspect 7] The composition according to embodiment 1, comprising an interconnected network of a plurality of ceramics in contact with the substrate. [Aspect 8] The composition according to embodiment 7, wherein the median area of ​​the interconnected network of ceramics within the interconnected network of the plurality of ceramics is greater than approximately 10 square micrometers. [Aspect 9] The composition according to any one of embodiments 1 to 8, wherein the porous ceramic material comprises a rare earth element, a transition metal element, an alkaline earth metal element, or aluminum. [Aspect 10] The composition according to any one of embodiments 1 to 8, wherein the porous ceramic material comprises an oxide, a hydroxide, or a layered double hydroxide. [Aspect 11] The composition according to embodiment 10, wherein the oxide, hydroxide, or layered double hydroxide comprises iron, aluminum, magnesium, cerium, zinc, manganese, titanium, chromium, vanadium, zirconium, nickel, cobalt, copper, silver, tantalum, tungsten, silicon, phosphorus, calcium, barium, tin, or europium. [Aspect 12] The composition according to embodiment 11, wherein the porous ceramic material comprises a phosphate, a carbonate, a titanate, an aluminate, a zirconate, a fluoroaluminate, a silicate, a sulfide, a vanadate, a tungstate, a tinate, or a sulfate. [Aspect 13] The composition according to any one of embodiments 1 to 8, wherein the substrate comprises an aluminum alloy, a magnesium alloy, a steel alloy, a nickel alloy, a titanium alloy, a polymer, a cellulosic material, a polysaccharide, or glass. [Aspect 14] The composition according to embodiment 13, wherein the substrate comprises a cellulosic material selected from wood, rayon, and cotton. [Aspect 15] The composition according to embodiment 14, wherein the substrate is a particle, powder, extruded product, flake, or leaf-like structure with incisions. [Aspect 16] The composition according to embodiment 15, wherein the substrate has a maximum dimension of less than approximately 5 mm. [Aspect 17] The composition according to any one of embodiments 1 to 8, wherein the porous ceramic material is mainly crystalline. [Aspect 18] The porous ceramic material has a density of approximately 10 m² per square meter of the projected area of ​​the substrate. 2 ~about 1500m 2 A composition according to any one of embodiments 1 to 8, including the surface area of ​​[the specified area]. [Aspect 19] The porous ceramic material is approximately 15 m³ per gram of ceramic material. 2 ~about 1500m 2 A composition according to any one of embodiments 1 to 8, including the surface area of ​​[the specified area]. [Aspect 20] The composition according to any one of embodiments 1 to 8, wherein the porous ceramic material has an average pore size of about 2 nm to about 20 nm. [Aspect 21] The composition according to any one of embodiments 1 to 8, wherein the porous ceramic material includes pores having a multi-modal pore size distribution. [Aspect 22] The composition according to any one of embodiments 1 to 8, wherein the porous ceramic material has a maximum thickness of about 50 micrometers. [Aspect 23] The composition according to embodiment 22, wherein the porous ceramic material has a thickness of about 0.2 micrometers to about 25 micrometers. [Aspect 24] The composition according to embodiment 22, wherein the porous ceramic material has a porosity of more than about 10%. [Aspect 25] The composition according to embodiment 24, wherein the porous ceramic material has a void ratio of about 30% to about 95%. [Aspect 26] The porous ceramic material was measured by mercury intrusion porosimetry and measured approximately 100 mm 3 / g ~ approx. 7500mm 3 The composition according to any one of embodiments 1 to 8, comprising a void volume of / g. [Aspect 27] The composition according to any one of embodiments 1 to 8, wherein the porous ceramic material comprises accessible pore volumes partially or completely filled with a gaseous substance, a liquid substance, or a solid substance, or a combination thereof. [Aspect 28] The composition according to embodiment 27, wherein the porous ceramic material comprises pores partially or completely filled with the second ceramic material. [Aspect 29] The composition according to embodiment 28, wherein the second ceramic material has a different composition from the ceramics in the interconnected network of ceramics. [Aspect 30] The composition according to embodiment 29, wherein the interconnected network of ceramics comprises hydroxides, oxides, or layered double hydroxides, and the second ceramic material comprises phosphates, carbonates, silicates, sulfates, titanates, tungstates, zirconates, vanadates, stanates, zincates, or aluminates. [Aspect 31] The composition according to any one of embodiments 28 to 30, wherein the interconnected network of ceramics and the second ceramic material each contain a primary metal, and the primary metal of the interconnected network of ceramics and the primary metal of the second ceramic material are the same. [Aspect 32] The composition according to any one of embodiments 28 to 30, comprising an interface between the interconnected ceramic network and a second ceramic material, wherein the interface includes a gradient. [Aspect 33] The composition according to embodiment 32, wherein the gradient includes a gradient of phosphorus, carbon, silicon, sulfur, tungsten, titanium, vanadium, manganese, magnesium, zinc, tin, zirconium, or aluminum. [Aspect 34] A metal-ceramic composite or polymer-ceramic composite comprising an assembly of multiple substrates, wherein each of the multiple substrates is modified with a porous ceramic material comprising an interconnected network of ceramics in contact with the substrate. [Aspect 35] The metal-ceramic composite or polymer-ceramic composite according to embodiment 34, wherein the assembly of the ceramic modified substrate comprises particles, powders, flakes, or extruded materials, each having a maximum dimension of less than about 5 mm. [Aspect 36] A porous ceramic material containing an interconnected network of ceramics is laminated onto a metal or polymer substrate in the form of metal or polymer particles, powder, extruded material, or flakes, thereby producing a surface-modified metal substrate or a surface-modified polymer substrate. The surface-modified metal substrate or surface-modified polymer substrate is molded, cast, or sintered into a monolithic or mesh-like ceramic component, metal-ceramic composite component, or polymer-ceramic composite component. The core of the metal or polymer substrate has a lower melting point than the interconnected network of the ceramic, and the ceramic is sufficiently porous to cause wicking of the molten metal or polymer and / or react with the molten metal or polymer. A method for manufacturing a surface-modified substrate. [Aspect 37] The manufacturing method according to embodiment 36, wherein the metal particles, powder, extruded product, or flakes include aluminum, aluminum alloy, magnesium, magnesium alloy, zinc, zinc alloy, calcium, or calcium alloy. [Aspect 38] The manufacturing method according to embodiment 36, wherein the polymer particles, powder, extruded product, or flakes include polyolefin, polyester, polystyrene, polyamide, thermoplastic starch, acrylic, or polycarbonate. [Aspect 39] The manufacturing method according to embodiment 37 or 38, wherein the ceramic comprises magnesium oxide, titanium oxide, zinc oxide, manganese oxide, zirconium oxide, silica, or calcium carbonate.

Claims

1. A composition comprising a porous ceramic material including an interconnected network of ceramics in contact with a substrate, The said substrate includes aluminum, an aluminum alloy, or a cellulose-based material. The porous ceramic material comprises a hydroxide or a layered double hydroxide, The hydroxide or layered double hydroxide comprises aluminum, magnesium, cerium, or zinc. The porous ceramic material is a binder-free ceramic material, The porous ceramic material includes pores partially or completely filled with the second ceramic material, The composition wherein the second ceramic material has a different composition from the ceramics in the interconnected network of the ceramics.

2. The composition according to claim 1, wherein the substrate is aluminum or an aluminum alloy, and each of the porous ceramic materials 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.

3. The composition according to claim 1, (i) The thickness of the interconnected network of ceramics on the substrate is 1 micrometer to 100 micrometers, (ii) At least 20% by mass of the ceramic content is interconnected, (iii) The interconnected network of the ceramics is larger than 10 square micrometers, (iv) The composition includes an interconnected network of a plurality of ceramics in contact with the substrate, The aforementioned composition.

4. The composition according to claim 1, wherein the substrate comprises a cellulosic material selected from wood, rayon, and cotton.

5. The composition according to claim 1, wherein the base material is a particle, powder, extruded product, flake, or leaf-like structure with incisions.

6. The composition according to claim 1, comprising a maximum dimension of less than 5 mm for the substrate.

7. The porous ceramic material (i) Primarily crystalline, or (ii) 10 m² per square meter of the projected area of ​​the substrate ２ ~1500m ２ Including the surface area, or (iii) 15 m per gram of ceramic material ２ ~1500m ２ Including the surface area, or (iv) containing an average pore size of 2 nm to 20 nm, (v) Includes pores with a multimodal pore size distribution, The composition according to any one of claims 1 to 3.

8. The composition according to any one of claims 1 to 3, wherein the porous ceramic material has a porosity of more than 10%.

9. The porous ceramic material was measured by mercury intrusion porosimetry and measured to be 100 mm ３ / g to 7500mm ３ A composition according to any one of claims 1 to 3, comprising a void volume of / g.

10. The composition according to claim 1, wherein the second ceramic material comprises a phosphate, a carbonate, a vanadate, or a molybdate.

11. The composition according to claim 1, Each of the interconnected network of ceramics and the second ceramic material contains a primary metal that is at least 50% of the total metal in the interconnected network of ceramics or the second ceramic material, and the primary metal of the interconnected network of ceramics and the primary metal of the second ceramic material are the same. The aforementioned composition.

12. The composition according to claim 1, comprising an interface between the interconnected ceramic network and a second ceramic material, wherein the interface includes a gradient.

13. The composition according to claim 12, wherein the gradient includes a gradient of phosphorus, carbon, vanadium, manganese, magnesium, zinc, or aluminum.

14. A metal-ceramic composite material or polymer-ceramic composite material comprising an assembly of multiple substrates, wherein each of the multiple substrates is modified with a porous ceramic material comprising an interconnected network of ceramics in contact with the substrate, The said substrate includes aluminum, an aluminum alloy, or a cellulose-based material. The porous ceramic material comprises a hydroxide or a layered double hydroxide, The hydroxide or layered double hydroxide comprises aluminum, magnesium, cerium, or zinc. The porous ceramic material is a binder-free ceramic material, The porous ceramic material includes pores partially or completely filled with the second ceramic material, The metal-ceramic composite material or polymer-ceramic composite material wherein the second ceramic material has a different composition from the ceramics in the interconnected network of ceramics.

15. The metal-ceramic composite or polymer-ceramic composite according to claim 14, wherein the assembly of the ceramic modified substrate comprises particles, powders, flakes, or extruded materials, each having a maximum dimension of less than 5 mm.

16. A porous ceramic material containing an interconnected network of ceramics is laminated onto an aluminum substrate or aluminum alloy substrate in the form of particles, powder, extruded material, or flakes, thereby producing a surface-modified aluminum substrate or surface-modified aluminum alloy substrate. The porous ceramic material comprises a hydroxide or a layered double hydroxide, The hydroxide or layered double hydroxide comprises aluminum, magnesium, cerium, or zinc. The porous ceramic material is a binder-free ceramic material, The surface-modified aluminum substrate or surface-modified aluminum alloy substrate is molded, cast, or sintered into a monolithic or mesh-shaped ceramic component, an aluminum-ceramic composite component, or an aluminum alloy-ceramic composite component, and The core of the aluminum substrate or aluminum alloy substrate has a lower melting point than the interconnected network of the ceramic, and the ceramic is sufficiently porous to cause wicking of the aluminum or aluminum alloy and / or to react with the aluminum or aluminum alloy. A method for manufacturing a surface-modified substrate.

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