Selectively applied gradient coating composition

Abstract

Surface modifiers and coating materials are provided that can be applied to substrates, such as heat exchangers, to reduce or eliminate the adverse effects of environmental influences or enhanced operational stresses. The present invention provides a composition comprising a coating or modifier for a surface of a substrate, the coating or modifier comprising a gradient of at least one physical or chemical property across at least a portion of the substrate surface. The coating or modifier is preferably provided as a monolayer on the substrate surface, and the coating or modifier preferably comprises a ceramic, a polymeric material, or a self-assembled monolayer.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to PCT Application No. PCT / US2019 / 065978, filed December 12, 2019, and the benefit of U.S. Provisional Application No. 62 / 989,092, filed March 13, 2020, U.S. Provisional Application No. 62 / 989,150, filed March 13, 2020, U.S. Provisional Application No. 63 / 038,642, filed June 12, 2020, U.S. Provisional Application No. 63 / 038,693, filed June 12, 2020, and U.S. Provisional Application No. 63 / 039,965, filed June 16, 2020, the entire contents of which are incorporated herein by reference.

[0002] FIELD OF THE INVENTION The present invention relates to coating materials, and in particular to coating materials that provide a gradient of one or more physical or chemical properties that mitigate environmental or operational stresses, such as corrosion, of a substrate to which the coating material is applied. [Background technology]

[0003] background When placed in a localized environment, heat exchangers and other related systems are exposed to conditions that can affect their performance and, ultimately, their usefulness. Observed effects include localized corrosion, water and frost accumulation, which can lead to corrosion, debris accumulation, or abrasion from airborne debris, reducing the effectiveness of corrosion protection and promoting microbial growth, which subsequently leads to corrosion. In another example, the leading edge of a heat exchanger surface accumulates significantly more debris than the trailing edge. Condensed water buildup can accumulate on the trailing edge of the heat exchanger surface, furthering corrosion and increasing damage. Road wear occurs at the tire contact area, and oil accumulation occurs in the center of the lane, both of which alter the patterns of road wear and corrosion. To improve performance in these devices and systems, it is desirable to directly address these conditions in a targeted manner in the areas of concern. Summary of the Invention

[0004] A brief summary of the invention Coating compositions and methods for their use are provided herein.

[0005] In one embodiment, a composition is provided in the form of a coating or modifier for a substrate surface, the coating or modifier comprising a gradient of at least one physical or chemical property across at least a portion of the substrate surface, For example, the gradient of at least one physical or chemical property may include, but is not limited to, one or more of film thickness, density, pore size, pore size distribution, pore fill, chemical or physical composition, oxidation state, metal concentration, crosslink density, isoelectric point, electrical conductivity, thermal conductivity, and capacitance. In some embodiments, the gradient, e.g., the gradient of any of the properties listed above, can be from about 1% to about 99%, from about 5% to about 95%, from about 10% to about 90%, or from about 20% to about 80%, or about 1%, about 5%, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, or about 99%, or at least about 1%, about 5%, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, or about 99%, of the maximum value of the given property of the coating or modifier or the maximum value of the given property on the substrate.

[0006] In some embodiments, the coating or modifier comprising a gradient of at least one physical or chemical property is in a monolayer on the substrate surface. For example, the coating or modifier may comprise a ceramic, a polymeric material, or a self-assembled monolayer.

[0007] In some embodiments, the coating or modifier comprises multiple layers, at least one of which comprises a gradient of at least one physical or chemical property. For example, the at least one layer comprising a gradient may comprise a ceramic, a polymeric material, or a self-assembled monolayer. In some embodiments, the multiple layers comprise a first layer comprising a gradient of at least one physical or chemical property in contact with the substrate, and a second layer of functional material not comprising a gradient disposed on the first layer.

[0008] In another embodiment, the plurality of layers includes a first layer that does not include a gradient in contact with the substrate and a second layer of functional material that includes a gradient disposed over the first layer.

[0009] In some embodiments, the coating or modifier is applied to spatially separated regions of the substrate surface, and one or more regions of the substrate surface are free of the coating or modifier, e.g., the coating or modifier may be applied to a plurality of spatially separated regions of the surface of the substrate. In some embodiments, about 1% to about 99%, about 5% to about 95%, about 10% to about 90%, about 20% to about 80%, or about 1%, about 5%, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, or about 99%, or at least about 1%, about 5%, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, or about 99% of the substrate surface is covered with the coating, layer(s), or modifier.

[0010] In some embodiments, the coating or modifier is spatially continuous across all areas or covers substantially all areas of the substrate surface.

[0011] In some embodiments, a substrate is modified with a finishing coating or primer over the entire substrate surface or substantially the entire substrate surface, and a layer comprising at least one gradient of physical or chemical property is applied over the finishing coating or primer. In some embodiments, the layer comprising at least one gradient of physical or chemical property is applied to spatially separated regions of the finishing coating or primer, and one or more regions of the finishing coating or primer do not include a gradient-containing layer. In some embodiments, the layer comprising at least one gradient of physical or chemical property is applied to multiple spatially separated regions of the finishing coating or primer. In some embodiments, the layer comprising at least one gradient of physical or chemical property is spatially continuous over all or substantially all regions of the finishing coating or primer. In some embodiments, the finishing coating or primer comprises one or more of chromate, fluorozirconate, fluorotitanate, sol-gel, phosphate, zirconium, rare earth metal, and blue or black oxide. In some embodiments, the layer comprising a gradient of at least one physical or chemical property comprises a ceramic, a polymeric material, or a self-assembled monolayer.

[0012] In some embodiments, a layer comprising a gradient of at least one physical or chemical property is coated on at least a portion of a substrate surface, and a homogeneous or substantially homogeneous functional material layer is coated over the gradient-containing layer across all or substantially all of the substrate surface, hi some embodiments, the gradient-containing layer comprises a ceramic, a polymeric material, or a self-assembled monolayer.

[0013] In some embodiments, the coating or modifier or layer comprising a gradient of at least one physical or chemical property comprises or consists of a ceramic material. For example, The ceramic material may be a binderless ceramic material having a crystallinity greater than about 20%. The ceramic material may include metal oxides, metal oxide hydrates, metal hydroxides, and / or metal hydroxide hydrates. In some embodiments, the ceramic material includes metal hydroxides, and at least a portion of the metal hydroxides are in the form of layered double hydroxides. In some embodiments, the ceramic material has a crystallinity greater than about 10 m per square meter of intended substrate area. 2 ~1500m 2 surface area of ​​approximately 15 m per gram of ceramic material 2 ~1500m 2 a surface area of ​​about 100 mm; an average pore diameter of about 2 nm to about 20 nm; a membrane thickness of about 0.2 micrometers to about 25 micrometers; a porosity of greater than about 10%; and 3 / g ~ approx. 7500mm 3 / g void volume.

[0014] In some embodiments, the coating or modifier or layer comprising a gradient of at least one physical or chemical property comprises or consists of a latex, paraffin (alkane), alkene, alcohol, acrylic, alkyd, enamel, epoxy, siloxane, fluoropolymer, or urethane.

[0015] In some embodiments, the coating or modifier or layer comprising a gradient of at least one physical or chemical property comprises molecules having a head group and a tail group, e.g., the head group comprises a silane group, a sulfonate group, a sulfonic acid group, a boronate group, a boronic acid group, a phosphonate group, a phosphonic acid group, a carboxylate group, a carboxylic acid group, a vinyl group, a hydroxide group, an alcohol group, a thiolate group, a thiol group, and / or a quaternary ammonium group, and the tail group comprises a hydrocarbon group, a fluorocarbon group, a vinyl group, a phenyl group, an epoxide group, an acrylic group, an acrylate group, a hydroxyl group, a carboxylic acid group, a thiol group, and / or a quaternary ammonium group.

[0016] In some embodiments, the substrate surface is the surface of a heat exchanger, vehicle, aircraft, ship, or bridge, or any other surface that is subject to environmental wear or degradation under the conditions of the environment in which it is located or operated in. For example, the substrate surface may be the surface of a brazed aluminum heat exchanger, a copper tube-aluminum fin heat exchanger, or a steel tube-aluminum fin heat exchanger.

[0017] In another aspect, a heat exchanger or component thereof is provided, wherein a composition described herein (i.e., a coating or modifier comprising a gradient of at least one physical or chemical property across at least a portion of a substrate surface described herein) is applied to a surface of the heat exchanger or a surface of a component of the heat exchanger. For example, the heat exchanger can be a brazed aluminum heat exchanger, a copper tube-aluminum fin heat exchanger, or a steel tube-aluminum fin heat exchanger. The surface or component of the heat exchanger can exhibit minimal environmental damage compared to an identical heat exchanger or component that does not include a composition described herein.

[0018] In another aspect, a method for protecting a substrate from environmental damage is provided. The method includes applying a composition described herein (i.e., a coating or modifier comprising a gradient of at least one physical or chemical property across at least a portion of a substrate surface) to a substrate, wherein the substrate can exhibit minimal environmental impact compared to an identical substrate without the composition. For example, environmental damage can include, but is not limited to, one or more of corrosion, debris accumulation, water or ice accumulation, biofouling, and abrasion. In some embodiments, corrosion due to water or ice accumulation is reduced or prevented compared to an identical substrate without the composition described herein. [Brief explanation of the drawings]

[0019] [Figure 1] 1 shows the drying rate of the ceramic coated panels described in Example 43. DETAILED DESCRIPTION OF THE INVENTION

[0020] Detailed Description Selective application of film-forming compositions can be used for environmental protection. Additionally, over time, the conditions to be prevented or treated change. This can be addressed, for example, with layered coating structures that provide different protection as layers are changed over the life of the device.

[0021] Provided herein may be film-forming compositions and substrate modifiers for minimizing environmentally induced wear or degradation, such as corrosion, in areas of particular environmental exposure and damage, such as edges, material or composite interfaces, areas of low velocity, areas of high electrochemical corrosion, or areas subject to or susceptible to excessive moisture, salts, debris accumulation, biofouling, or abrasion.

[0022] The coating or surface modifier may be used to promote or speed the movement of fluids, such as water, that escape from a substrate that is subject to stress, such as the application of corrosion-resistant materials, or areas of high environmental exposure, or stress, or stress resulting from operation, for example, while the equipment is in operation to partially coat the composition, and to partially protect the material over time if the entire surface or device does not require a coating, for example, to vary the coating or surface modifier thickness or standard surface gradient (e.g., a gradient in one or more chemical or physical properties between the overlying coating or surface modifier and the bottom in contact with the substrate surface) across the substrate surface and / or as a branding or cost-saving measure.

[0023] Selective application of coatings or surface modifiers can also be used to achieve complementary benefits, such as corrosion resistance, while minimizing potential adverse effects, such as heat transfer losses due to the thermal resistance of the coating.

[0024] One application involves heat exchangers. Some outdoor heat exchangers corrode and fail in very specific locations due to puddles after rainfall, sprinklers, use near marine environments, or animal urine, such as cat urine. Other environmental stresses that can be reduced or eliminated using the compositions and surface modifiers described herein include exhaust pollution, urban pollution, dust / debris, fertilizer, road salt, road sand, marine aerosols, industrial emissions (e.g., refineries, water treatment plants, manufacturing plants), or microbial (e.g., bacterial, fungal) or viral exposure, and / or biofilm formation (i.e., antimicrobial, antibacterial, antifungal, or antiviral coatings or surface modifiers). The properties of spatial gradients can be used to exploit gradient effects. For example, spatial gradients of porosity, which directionally wick and "pump" fluids, such as water, from one direction to another, can be used for corrosion prevention and other purposes, such as enhanced drying and fluid movement.

[0025] In some embodiments, the coating or surface modifier may make the heat exchanger or its components resistant to impinging contaminants (e.g., slaughterhouse particles, corrosive aerosols, etc.) and may also reduce thermal conductivity, thereby increasing surface temperatures and thereby increasing thermal resistance and reducing frost formation rates. Downstream of the fin pack, the coating may be modified to reduce corrosion resistance and improve heat transfer / frost suppression properties.

[0026] The coating or surface modifier may be applied to the entire substrate surface or selectively (such as to one or more portions of the substrate surface, e.g., one or more areas subject to adverse environmental conditions or environmental or operational stresses). In certain embodiments described herein, the coating or surface modifier constitutes a gradient (i.e., spatial variation) in one or more dimensions across the entire substrate surface or across the entire device or across a portion or component of the device. Exemplary material parameters include material This may include density gradients, pore size distributions, pore filling (i.e., the filling rate or spatial gradient of material filling the pores of a porous material), or film thickness of the material.

[0027] Provided is a method for reducing or preventing environmental or operational stresses on a substrate, or on an apparatus or component incorporating the substrate, comprising applying, either spatially continuous or spatially spaced apart, any of the coatings or surface modifiers described herein that include one or more materials comprising a gradient of at least one chemical or physical property, wherein the substrate exhibits reduced environmental impacts or operational hazards, such as corrosion, debris accumulation, water or ice accumulation, biofouling, or abrasion, compared to a substrate that does not include the coating or substrate modifier.

[0028] definition Numerical ranges provided herein are inclusive of the numbers defining the range.

[0029] "A," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0030] The phrase "and / or," as used in the specification and claims, should be understood to refer to the elements so conjugated, i.e., "either or both" of the elements so conjugated, i.e., that the elements are conjugated in some instances and not conjugated in other instances. Unless the context clearly dictates otherwise, other elements are optionally present other than the elements expressly designated by the phrase "and / or," whether or not those elements are related to those specifically defined. Thus, when used in conjunction with open-ended language such as "comprising," a reference to "A and / or B" may refer, without limitation, in some embodiments to A without B (optionally including elements other than B); in other embodiments to B without A (optionally including elements other than A); in yet other embodiments to A and B (optionally including other elements), etc.

[0031] A "binder" or binding agent is any material or substance that holds or attracts other materials together, forming a mechanically and chemically bonded whole.

[0032] "Binder-free" means that there are no exogenous binders that can be added to the primary material to improve its structural integrity, particularly with respect to organic binders or resins (polymers, glues, adhesives, asphalt, etc.) or inorganic binders (lime, cement glass, gypsum, etc.).

[0033] "Capillary climb" refers to the surface tension of a liquid that pushes a sample up due to a porous substrate when it comes into contact with the free surface of the liquid (capillary climb is parallel to and opposite to the direction of the gravitational force vector).

[0034] "Ceramic" or "ceramic material" refers to a solid material containing inorganic compounds of metals or metalloids and nonmetals with ionic or covalent bonds. "Nonmetals" can include oxygen (oxide ceramics), or carbon (carbides), or nitrogen (nitrides) (nonoxide ceramics). "Metals" include non-hydrogen elements from Group 1 of the periodic table, elements from Groups 2-12 of the periodic table, or elements in the p-block (Groups 12-17 of the periodic table), such as Al, Ga, In, Ti, Sn, Pb, Bi, or combinations thereof. "Metalloids" include B, Si, Ge, As, Sb, Se, Te, or Po, or combinations thereof. There is a reason.

[0035] "Contact angle" refers to the angle measured through the liquid between the surface and the gas-liquid interface of the contact surface.

[0036] "Contiguous" or "contiguity" refers to pores and structures that include walls and features that directly contact each other, or that share a common wall over a larger area or dimension relative to an individual pore or structure.

[0037] "Processed coating" refers to a surface layer in which a reactant chemically reacts with the surface being treated, converting the substrate into a different compound. This process is generally not additive or permanent and may result in a small mass change.

[0038] The "first quartile pore size" is the pore size where the cumulative pore surface area determined in the direction of increasing pore size is 25% of the total cumulative pore surface area determined by BJH gas adsorption / desorption measurements. This refers to the value of

[0039] "Functional material layer" refers to a layer of material that acts as a top surface layer that interacts with the surrounding environment or acts as an interface layer (between two other material layers) for a subsequent material. The functional material layer imparts one or more desirable functional properties to the underlying substrate and / or material to which it is attached.

[0040] "Gradient," as used herein, refers to a quantitative increase or decrease in one or more physical or chemical properties of a material as it passes spatially from one point to another along the surface of a substrate on which the material is disposed or immobilized, and as it is observed with changes in the Cartesian x, y, or z directions on or through the material. Examples of gradient properties include, but are not limited to, thickness, density, hardness, ductility, pore size, pore size distribution, pore fill, 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.

[0041] "Hydrophilic" refers to a surface that has a high affinity for water, with a contact angle that is very small (e.g., less than 30 degrees as measured from the surface through liquid water in the presence of air) and / or is not measurable.

[0042] "Layered double hydroxides" are those with the general sequence [AcB Z AcB] nwhere 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 No. PCT / US2017 / 052120, which is incorporated herein by reference in its entirety.

[0043] "Macrovoid" refers to a geometric space within a solid having a characteristic dimension substantially larger than the characteristic dimension of an individual pore or feature (e.g., membrane thickness), e.g., at least about 5 to about 10 times, or about 10 to about 100 times larger than the characteristic dimension.

[0044] "Mean" refers to the arithmetic mean or average.

[0045] The "average pore size" is calculated by dividing the total surface area and total volume measured by the Barrett-Joyner-Halenda (BJH) adsorption / desorption method by 4 times, assuming cylindrical pores. Calculate the total pore volume by dividing the total pore surface area (4V / A).

[0046] "Multimodal" refers to a distribution that contains multiple distinct modes that manifest as multiple distinct peaks.

[0047] In fluid mechanics, "permeability" is a measure of the ability of a porous material to allow fluid to pass through it. The permeability of a medium is related not only to its porosity, but also to the shape of the medium's pores and their level of connectivity.

[0048] "Pore size distribution" refers to the relative abundance of each pore size or range or pore size as determined by mercury intrusion porosimetry (MIP), Washburm equation.

[0049] "Porosity" is a measure of the void (or "empty") space within a material, and the percentage of void volume over the total volume, i.e., macrovoids, between 0 and 1, or between 0% and 100%. Porosity as disclosed herein was measured by mercury intrusion porosimetry.

[0050] "Porosity" refers to the spaces, holes, or voids within a solid material.

[0051] "Superhydrophobic" refers to a surface that is very difficult to wet. The contact angle of a water droplet on a superhydrophobic material on a superhydrophobic surface described herein is a liquid contact angle >150°. A highly hydrophobic contact angle is >120°. The contact angle described herein refers to the angle formed between a surface and a liquid.

[0052] "Surface area per square meter of substrate area of ​​interest" refers to the actual measured surface area, usually measured in square meters, and if atomically smooth (not rough), usually divided by the surface area of ​​the substrate in square meters.

[0053] "Synergy" or "synergistic" refers to the interaction or interplay between two or more substances, materials, or agents that produces a combined effect that is greater (positive synergy) or less (negative synergy) than the sum of their individual, separate effects.

[0054] "Film thickness" refers to the length between the surface of the substrate and the top of the surface modifier (eg, ceramic).

[0055] The "third quartile pore size" refers to the pore size value for which the cumulative pore surface area determined in the direction of increasing pore size is 75% of the total cumulative pore surface area determined by BJH gas adsorption / desorption measurements.

[0056] "Tortuosity" refers to the proportion of the shortest path that passes through the porous structure Δl and the Euclidean distance between the start and end points of that path Δx.

[0057] "Tunable" refers to the ability to change or modify the function, properties, or qualities of a material.

[0058] Selective Coatings and Surface Modifiers Selective coating of substrates, such as the surface of a heat exchanger; involves coating a portion of the surface of the substrate (selectively) to meet localized corrosion resistance needs or other needs, such as, but not limited to, the prevention of microorganisms (e.g., L This can be accomplished in several ways, such as by: the need to limit the growth of bacteria (e.g., Bacillus subtilis) or the migration of liquids, such as water, escaping from the substrate; the complete coating of the substrate with a first material A and the partial coating of a second material B on the first material (i.e., the selective coating of the second material B over a portion (one or more areas) of the surface of the first material A), where the second material can be the same as or different from the first material; and the reduction of environmental or operational stresses.

[0059] A gradient herein is spatially variable with respect to at least one chemical or physical property. For example, coating or surface modifier A can be a homogeneous material on the substrate surface or can include a spatial gradient (variability) in one or more properties, including, but not limited to, material density, pore size distribution, pore filling, and film thickness. In addition, an optional second material B can be applied on top of material A, which can be a homogeneous material or can provide spatial variability in one or more properties, including, but not limited to, material density, pore size distribution, film thickness, and / or pore filling of material A. In some embodiments, an optional third material C can also be applied selectively and can be a homogeneous material across the entire substrate or the material immediately below, or can provide spatial variability in one or more properties, including, but not limited to, material density, pore size distribution, film thickness, and / or pore filling of material B. In some embodiments, material C is applied to a deposit of material such as, but not limited to, ABA, and may impart spatial variability to one or more properties such as, but not limited to, material density, pore size distribution, film thickness, and / or pore filling of the material directly beneath material C, e.g., material A. An optional additional layer of homogeneous or gradient material may also be included. The coating or surface modifier(s) may be applied continuously to the entire substrate surface, or to one or more discrete (selective) areas, such as areas that will be subject to environmental or operational stresses when used in a device or component incorporating the substrate.

[0060] The gradient layers disclosed herein can include one or more gradient characteristics of the structural layer. For example, the gradient can include increased porosity near a joint, a change in thickness of the structural composite material of the panel, e.g., near the bottom or edge upon draining and drying of a dipping process at a particular temperature, selectively spraying areas of selected material, adding additional coats of material in selected areas, spray application resulting in more material at the leading edge, or a compositional change that affects the electrochemical potential.

[0061] Gradients can be generated during processing of the structured layer, for example, by varying the concentration levels of reactants or compositions (by dripping) during processing, thereby varying the composition through the coating thickness, and / or by varying the temperature, e.g., by changing the temperature of the processing bath, structure, or part temperature during processing, or by establishing variable temperature zones during processing, e.g., hot and cold zones on the part, to create thicker, thinner, or different materials, e.g., structured ceramic materials. Agitation of mechanical parts, fluid advection, localized application of heat or light, pressure differentials, and / or gravitational settling differentials to modify local chemical reactivity can also be used to create gradient properties. Drying and curing processes can also be used to create property gradients using selected temperature ranges, drying conditions, and / or selective light.

[0062] In some embodiments, one or more of the coatings or surface modifiers (e.g., Materials A-C) are structured ceramics, such as binderless ceramic surface modifiers having pores that can be filled, unfilled, or partially filled in a manner that fills a portion of the pores with a second material to create a gradient. In some embodiments, the ceramic material comprises a continuous network of pores that are filled with a second material, such as a polymeric material.

[0063] In some embodiments, the surface modifier may be a treatment coating or primer (e.g., trivalent phosphorus The coating may be a coating such as, but not limited to, chromium oxide, other chromates, fluorozirconates, fluorotitanates, sol-gels, phosphates, blue or black oxide paints, or anodizing.

[0064] In some embodiments, one or more surface modifiers are applied to the paint primer. For example, the fixing material can be a paint such as latex, acrylic, alkane, alkene, alcohol, enamel, epoxy, siloxane, polysilazane, fluoropolymer, or urethane. For example, the fixing material can be a natural or modified fatty acid, alcohol, hydrocarbon, or oil, such as linoleic acid, palmitic acid, oleic acid, glycerol, paraffin, turpentine, tall oil, linseed oil, palm oil, tung oil, or boiled linseed oil, hydrogenated fatty acid, refined glycerol, distilled paraffin, mineral oil, or refined palm oil.

[0065] In some embodiments, the one or more surface modifiers are single layer chemicals and may provide any of a range of properties, including, but not limited to, wettability, sealability, light resistance, and the like.

[0066] Most substrates are multi-metal components such as copper-aluminum heat exchangers, steel-aluminum heat exchangers, brazed aluminum heat exchangers, screws and rivets in bridges and vehicles, and other components containing composite interfaces. Selective protection in these complex situations can provide additional protection (e.g., selective anodic protection) for metal couples susceptible to galvanic corrosion in various environments and anodic / cathodic regions. Other substrates, homogeneous or heterogeneous in composition, contain localized areas susceptible to corrosion due to localized environments such as localized abrasion, stagnant fluids, or airflow gradients.

[0067] In some embodiments, the substrate is a heat exchanger, such as a microchannel heat exchanger, or a component thereof. Other embodiments include bridges, aircraft, vehicles, and watercraft, or components thereof.

[0068] Examples of coating or surface modifier properties and compositions include, but are not limited to, layers ("n") as described herein: n1 processed paint or primer - continuous coating with no gradient n2 processed paint or primer - continuous coating with gradient n3 processed paint or primer - non-graded selective (spaced) coating n4 processed paint or primer - selective coating with gradient n5 Structured Ceramic - Non-graded Continuous Coating n6 Structured Ceramic - Continuous Coating with Gradient n7 Structured Ceramic - Non-graded Selective Coating n8 Structured ceramic - Selective coating with gradient N9 Fixative Monolayer / Paint / Oil / Resin - Continuous Coating with No Gradient n 10 Fixing monolayer / paint / oil / resin - continuous coating with gradient n 11 Fixed monolayer / paint / oil / resin - coating without selective gradient n 12 Selective coating with fixed monolayer / paint / oil / resin gradient

[0069] Non-limiting coating or surface modifier configurations (n=“A”, “B”, “C”, etc., where A, B, C, etc. refer to the order of application or proximity to the substrate, e.g., A being the material in contact with or proximal to the substrate, or the bottommost material in a layer of materials): A1-B 11 (Continuous coating film + selective coating paint) A1-B 10 (Continuous coating process paint film + continuous coating gradient paint) A1-B 12 (Continuous coating film + selective coating gradient paint) A1-B6 (continuous coating primer + continuous coating gradient structured ceramic) A1-B7 (continuous coating primer + selective coating structured ceramic) A1-B8 (continuous coating primer + selective coating gradient structured ceramic) A1-B5-C9-D 11 (Continuous coating processed paint film + Continuous coating structured ceramic + Continuous coating functional material layer + Selective coating paint) A1-B5-C10 (Continuously coated processed coating film + continuously coated structured ceramic + continuously coated gradient functional material layer) A1-B5-C 11 (Continuous coating film + continuous coating structured ceramic + selective functional material layer) A1-B5-C 12 (Continuous coating process film + Continuous coating structured ceramic + Selective coating gradient functional material layer) A3 (selective coating film) A5-B9-C 11 (Continuously coated structured ceramic + continuously coated functional material layer + selectively coated paint) A5-B 10 (Continuously coated structured ceramic + continuously coated gradient functional material layer) A5-B 11 (Continuously coated structured ceramic + selectively coated functional material layer) A5-B 12 (Continuously coated structured ceramic + selectively coated gradient functional material layer) A6 (continuously coated gradient structured ceramic) A6-B9 (continuously coated gradient structured ceramic + continuously coated functional material layer) A6-B 10 (Continuously coated gradient structured ceramic + continuously coated gradient functional material layer) A6-B 11 (Continuously coated gradient structured ceramic + selectively coated functional material layer) A6-B 12 (Continuously coated gradient structured ceramic + selectively coated gradient functional material layer) A7 (selectively coated structured ceramic) A7-B9 (selectively coated structured ceramic + continuous coated functional material layer) A7-B 11 (Selectively coated structured ceramic + selectively coated functional material layer) A8 (Selectively coated gradient structured ceramic) A9-B 11 (Continuous coating single layer paint + selective coating paint) A 10 (Continuous coating gradient paint) A 11 (Selective coating paint) A 12(Selective coating gradient paint).

[0070] Structured Ceramic Materials The continuous or spaced coatings or surface modifiers described herein can be structured ceramics, such as binderless (e.g., surface-immobilized) ceramics, such as binderless ceramics with a crystallinity greater than about 20%. In some embodiments, the structured ceramics are porous. Non-limiting examples of ceramic materials are provided in PCT / US19 / 65978, the entire contents of which are incorporated herein by reference.

[0071] The ceramic material can include a metal oxide and / or hydroxide ceramic, e.g., a single metal or mixed metal oxide and / or hydroxide ceramic. In some embodiments, the ceramic material includes a metal hydroxide and / or hydroxide ceramic, e.g., a single metal or mixed metal oxide and / or hydroxide ceramic. In some embodiments, the ceramic material includes a metal oxide and metal hydroxide ceramic, and the metal oxide and metal hydroxide are the same or different, single metal or mixed metal. In some embodiments, the ceramic material includes a metal oxide and / or metal hydroxide ceramic, and the substrate is hydrated with water or other compounds, thereby defining a change in surface energy and potentially the ratio of metal oxide to metal hydroxide composition of the ceramic. In some embodiments, the ceramic material includes a metal hydroxide, and at least a portion of the metal hydroxide is in the form of a layered double hydroxide, e.g., at least about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% of the metal hydroxide is a bilayer hydroxide.

[0072] In some embodiments, a "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.

[0073] A mixed metal oxide or mixed metal hydroxide can, for example, contain oxides or hydroxides of two or more metals, and the metals can 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.

[0074] In some embodiments, the ceramic material is fixed onto the substrate as a binderless ceramic material, i.e., without the use of a binder. In some embodiments, the ceramic material is immobilized on the substrate.

[0075] In some embodiments, the ceramic material may have a surface tension greater than about 5 mm or greater than about 0.1 mN / m, for example: the ability to cause a liquid with low surface tension (e.g., less than about 25 mN / m for isopropanol) to undergo capillary rise against gravity in a closed container in 1 hour; 2 / g ~ approx. 10,000m 2 / g; an average pore diameter of about 10 nm to about 1000 nm, or about 1 nm to about 1000 nm; a pore volume measured by mercury (Hg) intrusion porosimetry of about 0 to about 1 cc / g; and a tortuosity, defined as the "arc chord ratio," which is the length of the fluid path to the shortest distance, of about 1 to about 1000, and / or a permeability of about 1 to about 10,000 millidarcy.

[0076] In some embodiments, the ceramic material is porous, i.e., has a porosity of 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%. 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%.

[0077] 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, 1000, 5000, or 10,000 millidarcy. In some embodiments, the permeability is about 500 to about 1000, about 750 to about 2000, about 1000 to about 2500, about 2000 to about 5000, about 3000 to about 7500, about 5000 to about 10,000, about 1 to about 1000, about 1000 to about 5000, or about 5000 to about 10,000 millidarcy.

[0078] In some embodiments, the porous ceramic material has a thickness of about 100 mm as determined by mercury intrusion porosimetry. 3 / g ~ approx. 7500mm 3 In some embodiments, the pore volume comprises 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 mm 3 In some embodiments, the pore volume is about 100 to about 500, about 200 to about 1000, about 400 to about 800, about 500 to about 1000, about 800 to about 1500, about 1000 to about 2000, about 1500 to about 3000, about 2000 to about 5000, about 3000 to about 7500, about 250 to about 5000, about 350 to about 4000, or about 400 to about 300 0, about 250 to about 1000, about 250 to about 2500, about 2500 to about 5000, or about 500 to about 4000 mm 3 / g.

[0079] The porous ceramic materials disclosed herein can be characterized by their interaction with liquid materials. As previously mentioned, the ceramic materials can be characterized by their ability to raise a liquid with low surface tension (e.g., less than about 25 mN / m for isopropanol) against gravity in a closed container to a surface height of more than about 5 mm in one hour. Other solvents with a surface tension of less than about 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 of more 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, fumaric acid diethyl ester, decalin, nitroethane, carbon disulfide, cyclopentanol, 1,4-dioxane, 1,2-dichloroethane, chlorobenzene, dipropylene glycol, cyclohexanol, hexachlorobutadiene, bromobenzene, pyrrole (PY), N,N-dimethylacetamide (DMA), Nitromethane, phthalic acid diethyl ester, N,N-dimethylformamide (DMF), pyridine, methylnaphthalene, benzyl alcohol, anthranilic acid ethyl ester, iodobenzene, N-methyl-2-pyrrolidone, tricresyl phosphate (TCP), m-nitrotoluene, bromoform, o-nitrotoluene, phenyl isothiocyanate, a-chloronaphthalene, furfural (2-furaldehyde), quinoline, 1,5-pentanediol, aniline (AN), polyethylene glycol 200 (PEG), These include anthranilic acid methyl ester, 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.

[0080] Porous ceramic surface modifiers may have the ability to induce capillary rise of water at various temperatures. These materials may have the ability to separate binary azeotropes with miscible materials such as ethanol-water, ethyl acetate-ethanol, or butanol-water, break ternary azeotropes, or remove amyl alcohol from mixtures containing ethanol and water.

[0081] The pores of the porous ceramic surface modifier may include open cells filled with one or more gases, may include partially filled cells (e.g., partially filled with one or more solid material(s)), or may include completely or substantially filled cells (e.g., completely or substantially filled with one or more liquid and / or solid material(s)). In some embodiments, the pores are partially, substantially, or completely filled with gas, liquid, or solid substances, or combinations thereof.

[0082] In some embodiments, the pores are 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 gas, liquid, and / or solid(s) material. In some embodiments, the second material is a gas, solid, and / or liquid material(s), or atmosphere (e.g., air). Examples include functionality imparted by changes in porosity, wicking, water repellency, and / or wetting behavior; changes in composites (including the porous material and a second material) that alter the electrical / dielectric properties of abrasion resistance, hardness, toughness, tactility, 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, thermal expansion coefficient, thermal interface 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, catalysis, reactivity, inertness, compatibility, fouling resistance, ion pump blocking, microbial resistance, and / or microbial compatibility; and / or substrates for biocatalysis.

[0083] In some embodiments, the first material interacts with the second material in a positive or negative synergistic manner to alter wettability, hardness, elasticity, mechanical properties, electrical properties, piezoelectric properties, optical properties, adhesive properties, or thermal properties, affinity or resistance to microorganisms, altered biofilm growth, catalytic activity, permeability, aesthetic appearance, water repellency, and / or corrosion resistance.

[0084] Non-limiting examples of materials that can be used to partially or completely fill the pores include molecules capable of binding to surfaces, such as molecules having a head group and a tail group, where the head group can be a silane, phosphonate, or phosphonic acid, a carboxylic acid, a vinyl, a hydroxide, a thiol, or an ammonium compound. The tail group can be any functional group, such as a hydrocarbon, a fluorocarbon, a vinyl group, a phenyl group, and / or a quaternary ammonium group. Other ceramic materials can also be partially or completely anchored in the pores. Polymers can also be partially or completely anchored in the pores. Ceramic materials can include, for example, one or more oxides of zinc, aluminum, manganese, magnesium, cerium, gadolinium, and cobalt. Additionally, ceramic materials can include solid materials that can be added to the surface modifier, such as inorganic compounds of metal, nonmetal, or metalloid atoms, such as clay, silica, and glass, which are primarily held together by ionic and covalent bonds. Polymers may include, for example, natural polymeric materials such as hemp, shellac, amber, wool, silk, natural rubber, cellulose and other natural fibers, biologically derived materials such as sugars, hemicellulose and holocellulose, polysaccharides and extracellular proteins, DNA, chitin, etc. Synthetic polymers include, for example, polyethylene, polypropylene, polystyrene, polyvinyl chloride, synthetic rubber, phenol formaldehyde resin (or Bakelite), neoprene, nylon, polyacrylonitrile, PVB, silicone, polyisobutylene, PEEK, PMMA, and PTFE.

[0085] In some embodiments, the pores are partially filled with a thin composite polymer layer, creating a surface modifier with the porosity and functionality provided by the polymer. In other embodiments, the pores are completely filled with a thick polymer layer, creating a surface modifier with a thick polymer layer that has the composite properties of the porous base material and the polymer layer. The polymers described in the compositions herein include copolymers.

[0086] In some embodiments, the pores are partially or completely filled with a layer of material deposited on the surface of the surface modifier. In some embodiments, a layer of material is deposited that adds one or more functional groups to the surface modifier material, such as, but not limited to, ammonium groups (e.g., quaternary ammonium groups), alkyl groups, perfluoroalkyl groups, fluoroalkyl groups, etc. In some embodiments, a polymer or ceramic layer is deposited. In some embodiments, the ceramic may be the same or different from the ceramic of the binderless porous ceramic material on the substrate. Examples of functional group(s) and the functions they impart include quaternary ammonium groups for antibacterial functionality, alkyl chains for water repellency and hydrocarbon affinity, perfluoroalkyl groups for water and oil repellency, polymers for mechanical functionality, and other ceramics for aesthetic, photoelectric, or corrosion protection functionality.

[0087] In some embodiments, the pores are partially or completely filled with a gas, liquid, or solid material, or a combination thereof, and the composition further comprises a layer of material disposed on top of the ceramic material, the disposed material performing one or more functions, such as wettability by the liquid and / or selective separation of compounds in the liquid. In certain embodiments, the material disposed on the top is a separate material from the material that partially, substantially, or completely fills the pores and does not itself fill or penetrate the pores. In some embodiments, the material disposed on the top interacts with the material(s) within the pores. For example, the material disposed on the top can interact with the material(s) within the pores to provide one or more functions, including, but not limited to, thermal management, modulation of electrochemical reactivity, and / or modulation of mechanical properties. In certain embodiments, the material disposed on the top is the ambient environment with which the binder-free porous ceramic material is in contact.

[0088] In some embodiments, the pores are substantially or completely lined with a polymer or ceramic material.

[0089] In some embodiments, materials within the pores interact with the ceramic material. Examples of such materials and the functions they perform include oxidizing surface modifiers with surrounding liquids or vapors, condensing trace constituents (e.g., environmental pollutants), capturing or oxidizing harmful environmental materials such as CO or HS from ambient air, and / or capturing and retaining such materials in the environment.

[0090] In some embodiments, moisture in the environment or added to the pores interacts with the material within the pores to modify the material or surface modifiers 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, frosting, icing, or condensation.

[0091] In some embodiments, the material within the pores can be designed to interact with the ceramic material to "tune" the properties of the entire surface. Examples of tunable properties include, but are not limited to, wettability, hardness, microbial resistance, catalytic activity, corrosion resistance, color, and / or photochemical activity.

[0092] In some embodiments, the ceramic surface modifier and the material within the pore interact synergistically, e.g., to enhance or reduce at least one functionality of the surface modifier and / or the material within the pore compared to the functionality of the surface modifier and / or the material within the pore alone. In some embodiments, two or more materials within the pore interact synergistically, e.g., to enhance or reduce at least one functionality of at least one material within the pore compared to the functionality of that material alone.

[0093] In some embodiments, the ceramic surface modification agent has an asymmetric pore morphology, e.g., spherical, cylindrical, cubic, or otherwise ordered to have a well-defined, relatively consistent, normal distribution of surface area to volume, characterized by a ratio of first quartile pore size to third quartile pore size as a function of film thickness of the binderless ceramic surface modification. In particular, the pore morphology is asymmetric about its center compared to a spherical, cylindrical, or cubic structure. Without intending to be limiting, examples of asymmetric pores are shown in PCT Application No. PCT / US19 / 39743, the entire contents of which are incorporated herein by reference. Use.

[0094] Porous ceramic surface modifiers can be characterized by 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 characterized locally, for example, as described herein, and have different characteristics with distance. The resulting asymmetry is a combination of substrate, ion mobility, and processing conditions such as temperature, pressure, and concentration, and is determined in situ. The degree of asymmetry can be further controlled by bulk means such as mixing, stirring, electric field modulation, and tank filtration, or by surface-oriented process means such as altering and controlling shear rate, impingement flow, or surface charge. Asymmetry can be determined ex situ by various or additional means, such as etching, track etching, ion beam milling, oxidation, photocatalysis, etc. These techniques refer to materials with narrow or symmetrical pore structures with membrane thickness and / or pore depth, such as zeolites, track-etched membranes, or expanded PTFE membranes.

[0095] In some embodiments, the porous ceramic surface modifier comprises a mesoporous average pore size ranging from about 2 nm to about 50 nm. In other embodiments, the average pore size ranges from about 50 nm to about 1000 nm. In some embodiments, the binderless porous ceramic material comprises an average pore diameter of about 2 nm to about 20 nm. In some embodiments, the average pore diameter is at least about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 nm. In some embodiments, the average pore diameter is 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.

[0096] The ceramic surface modifier may include one or more metal oxides and / or metal hydroxides (and / or hydrates thereof). Non-limiting examples of metals that the ceramic compositions disclosed herein may include include zinc, aluminum, manganese, magnesium, cerium, copper, gadolinium, tungsten, tin, lead, and cobalt. In some embodiments, the ceramic material includes 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 includes two or more metal oxides (e.g., mixed metal oxides), such as, but not limited to, zinc, aluminum, manganese, magnesium, cerium, praseodymium, and cobalt.

[0097] In some embodiments, the ceramic surface modifiers include: mixtures of zinc and aluminum oxides and / or hydroxides; mixtures of ZnO, Al2O3, and Zn-aluminates; mixtures of materials containing any / all phases containing Zn, Al, and oxygen; mixtures of manganese and magnesium oxides and / or hydroxides; manganese oxides; aluminum oxides; mixed metal manganese oxides and / or hydroxides; mixtures of magnesium and aluminum oxides and / or hydroxides; mixtures of magnesium, cerium, and aluminum oxides and / or hydroxides; zinc, gadolinium, and aluminum oxides and / or mixtures of cobalt and aluminum oxide and / or hydroxide; mixtures of manganese and aluminum oxide and / or hydroxide; mixtures of cerium and aluminum oxide and / or hydroxide; mixtures of iron and aluminum oxide and / or hydroxide; mixtures of tungsten and aluminum oxide and / or hydroxide; mixtures of tin and aluminum oxide; tungsten oxide and / or hydroxide; magnesium oxide and / or hydroxide; manganese oxide and / or hydroxide; tin oxide and / or hydroxide; or zinc oxide and / or hydroxide.

[0098] In some embodiments, at least one metal in the ceramic material is + It is in an oxidized state.

[0099] In some embodiments, the ceramic surface modifier 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.

[0100] In some embodiments, the ceramic surface modifier is superhydrophobic. In some embodiments, the surface modifier material is highly hydrophobic. In some embodiments, the surface modifier comprises one or more functional properties selected from wettability, hardness, elasticity, mechanical properties, electrical properties, piezoelectric properties, electromagnetic properties, optical properties, adhesive or thermal properties, microbial affinity or resistance, alteration of biofilm growth, catalytic activity, permeability, aesthetic appearance, and corrosion resistance compared to a substrate that does not include the ceramic material.

[0101] In some embodiments, a layer of functional material (e.g., a top layer of material) is deposited on the ceramic material. Examples of such materials include, but are not limited to, quaternary ammonium groups for antimicrobial functionality, alkyl chains for water repellency and hydrocarbon affinity, perfluoroalkyl groups for water and oil repellency, polymers for mechanical properties, or other ceramics for aesthetic, photoelectric, or anticorrosion functionality. Examples of functionality imparted by such materials include, but are not limited to, porosity, wicking, water repellency, and / or wetting behavior; changes in 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 tensile strength, compressive strength, and / or elasticity; changes in electrical / dielectric properties of a composite (including the porous material and the second material); changes in thermal properties such as thermal diffusivity, conductivity, coefficient of thermal expansion, thermal interface 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, catalysis, reactivity, inertness, compatibility, fouling resistance, ion pump blocking, microbial resistance, and / or microbial compatibility; and / or substrates for biocatalysis.

[0102] In some embodiments, the ceramic surface modifier is more resistant to degradation by ultraviolet light than the substrate material, such as a polymer or any of the substrate materials disclosed herein.

[0103] In some embodiments, the ceramic surface modifier comprises a film thickness of about 0.5 micrometers to about 20 micrometers. In some embodiments, the ceramic material comprises a film thickness of about 0.2 micrometers to about 25 micrometers. In some embodiments, the film thickness is at least about any of 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 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.

[0104] In some embodiments, the ceramic surface modifier 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°.

[0105] In some embodiments, the ceramic surface modifier is present in an amount of about 1.1 m per square meter of intended substrate area. 2 ~approx. 100m 2 In some embodiments, the ceramic material comprises a surface area of ​​about 10 m per square meter of intended substrate area. 2 ~about 1500m 2 The surface area of In some embodiments, the surface area is at least about 10, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, or 1500 m per square meter of intended substrate area. 2In some embodiments, the surface area is about 10 to about 100, about 50 to about 250, about 150 to about 500, about 250 to about 750, about 500 to about 1000, about 750 to about 1200, about 1000 to about 1500, about 70 to about 1000, about 150 to about 800, about 500 to about 900, or about 500 to about 1000 m per square meter of intended substrate area. 2 Either:

[0106] In some embodiments, the ceramic material has a concentration of about 15 ml per gram of ceramic material. 2 ~about 1500m 2 In some embodiments, the surface area comprises 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 m per gram of ceramic material. 2 In some embodiments, the surface area is about 15 to about 100, about 50 to about 250, about 150 to about 500, about 250 to about 750, about 500 to about 1000, about 750 to about 1200, about 1000 to about 1500, about 50 to about 700, about 75 to about 600, about 150 to about 650, or about 250 to about 700 m per gram of ceramic material. 2 Either:

[0107] substrate The substrate onto which one or more coatings or surface modifiers described herein are applied or deposited can be composed of any material suitable for its structural or functional properties, or for its functional application, for example, for use in a device such as a heat exchanger. In some embodiments, the substrate is or includes aluminum (e.g., an aluminum alloy), iron alloy, zinc, zinc alloy, copper, copper alloy, nickel alloy, nickel, titanium alloy, titanium, cobalt-chromium containing alloy, glass, polymer, copolymer, natural material (e.g., a natural material containing cellulose), or plastic.

[0108] In some embodiments, the substrate comprises a metal, and the primary metal of the ceramic surface modifier described herein is different from the primary metal of the substrate. A primary metal is a metal that comprises at least about 50%, 60%, 70%, 80%, 90%, or 95% of the total metals in the substrate or ceramic material, as determined, for example, by atomic metallurgy-based X-ray diffraction. Examples of primary substrate metals include, but are not limited to, aluminum, iron, copper, zinc, nickel, titanium, and magnesium. Examples of primary ceramic metals include, but are not limited to, zinc, aluminum, manganese, magnesium, cerium, copper, gadolinium, tungsten, tin, lead, and cobalt.

[0109] In some embodiments, the substrate comprises a metal that can react (e.g., dissolve) under reaction conditions that allow for localized dissolution of the substrate metal, and the substrate metal is incorporated into a substrate modifier, such as a ceramic material, e.g., a binderless porous ceramic material. For example, an aluminum substrate may comprise aluminum (e.g., Al) that is incorporated into the ceramic material such that the ceramic material is anchored onto the substrate. 2+ ) may be provided.

[0110] The following examples are intended to illustrate, but not limit, the present invention. [Example]

[0111] The substrate or assembly to which the coating is applied typically begins with (a) surface preparation or cleaning, (b) a conversion treatment or primer step, (c) a structured ceramic attachment, and (d) a d) Through processes leading to the deposition of another ceramic layer, a transformation treatment of the deposited structured ceramic layer, or the deposition of a monolayer, paint, oil or resin. In some cases, some steps can be avoided to obtain different results.

[0112] (a) Surface Preparation and Cleaning Steps: In the following examples, surfaces were prepared as follows: Metal substrates or assemblies were pot cleaned or wiped with a towel soaked in isopropyl alcohol (IPA) to remove any remaining oil. The parts were then submerged in a caustic etching bath with a pH >10 at a nominal room temperature of 20°C until a dark color appeared on the surface, or for approximately 15 minutes. The substrates or assemblies were then rinsed with water to remove any hard or loosely attached residue. The parts were then immersed in a nitric acid solution with a pH <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 reveal a clean surface. Other surface preparation techniques that result in a clean surface are appropriate and applicable. Polymeric and cellulose substrates were pot cleaned or wiped with a towel soaked in isopropyl alcohol to remove residue.

[0113] (b) Modified Coatings or Primers: The modified coatings and / or primers in the following examples are considered continuous unless otherwise specified. Selective coverage was achieved by exposure to certain chemicals and / or using masking agents. Modified coatings or primers consist of films produced by chemical or electrochemical conversion of the substrate, resulting in thin films with lower porosity compared to the structured ceramic anchor layers described below. Modified coatings are typically oxide, phosphate, or chromate coatings and are applied at low pH. Application methods include application using an electrical bias, which is feasible in some cases, or spraying the chemical solution onto the substrate to be coated. Inorganic materials, such as aqueous acid chromium(III) containing other metals or anionic reactants, modify the pH of the aqueous solution. Solutions of insoluble solid materials are heated to 40°C to 100°C, and the solution / substrate contact is maintained for 1 to 90 minutes. The addition of surfactants can enhance film composition or substrate conversion reaction rates. The exposed substrate surface reacts to form a dense layer and converts the substrate surface to provide a diffusion barrier that limits further reaction. A thermal stabilization step can be used to accelerate the formation of the conversion layer.

[0114] The conversion layer or primer was allowed to dry before the introduction of the structured ceramic fixturing or fixed monolayer / paint / oil / resin layer unless otherwise stated. The processing time between application of the conversion layer and subsequent processing was less than 24 hours unless otherwise stated.

[0115] (c) Structured or Porous Ceramic Fixation: The structured ceramic fixation in the following examples is considered continuous unless otherwise noted. Selective coverage was achieved using some chemical exposure and / or masking agents. The substrate or assembly was then placed in a structured ceramic fixation bath containing 20-500 mM of metal nitrate and a similar amount of amine (e.g., ethylenediamine, hexamethylenetetramine, or urea) and allowed to react at a reaction temperature of 30-90°C before inserting the substrate. The assembly remained 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 to dry and / or calcine at about 100-800°C for several hours. The part was then allowed to cool to room temperature. Unless otherwise noted, Unless otherwise specified, the structured ceramic was allowed to dry before fixing the monolayer / paint / oil / resin layer.

[0116] (d) Settled Monolayer / Paint / Oil / Resin - Gradient / Non-Gradient Continuous / Selective Coverage: Settled monolayer / paint / oil / resin in the following examples are considered continuous unless otherwise noted. Selective coverage was achieved using partial contact and / or masking agents. The structured ceramics constructed in (c) were dried, unless otherwise specified, prior to post-processing steps such as conversion treatment of the set ceramic or setting of a second ceramic to partially or completely fill the void-interconnected ceramic network with a second material. The substrate temperature was typically maintained at room temperature, and the setting solution was typically maintained at ambient room temperature, unless otherwise specified. The set monolayer / paint / oil / resin consisted of a material applied to the top layer by painting, spraying, dipping, wicking, or vapor-phase condensation, and may be subjected to a thermal or catalytic treatment to promote drying of the material and / or enhance chemical or mechanical adhesion to the top layer. These processing steps are described in further detail in the respective examples, as appropriate.

[0117] Example 1.A1-B 11 -Processed coating + selective coating paint The heat exchanger (HX) is fully coated with a coating such as trivalent chromium process (TCP) via a dip or spray paint process. The manifold and the manifold-to-tube brazed joints are then painted via dip or spray application, with some specific areas of the part being painted. In this particular case, the entire coil is fully immersed to apply the coating. In the next step, the manifolds of the heat exchanger are immersed, one after the other, in the paint bath. The conversion areas of the coil are now corrosion protected while maintaining the heat transfer coefficient, and the painted manifold-to-manifold tube joints receive an additional layer of corrosion protection.

[0118] Example 2.A1-B 10 -Processed coating + gradient paint The HX is fully coated with a process coating such as TCP, which is applied to the entire HX via a dip step. This process step is followed by a full coat, where the paint thickness is thicker on the bottom of the HX than on the top. This is applied via dip coating and also encourages the paint to drain in a preferred direction, resulting in a thicker layer in that direction. A full spray, where the spray passes further to the desired thickness, also works. Areas with a thicker paint coating offer increased corrosion resistance. The top of the HX requires less paint because it is exposed to less accumulated liquid, thus reducing manufacturing costs for achieving a uniform coating thickness throughout the HX. Meanwhile, minimizing paint application to key areas requiring protection and / or limiting the amount of material applied to critical heat exchange surfaces provides similar corrosion protection.

[0119] Example 3.A1-B 10 -Processed coating + gradient paint The HX is first fully coated with a modified coating such as TCP, followed by a full coat of paint that is thicker on the bottom of the HX than on the top, i.e., applied in successive dip-coating steps with shallower immersion depths. As fluid accumulates toward the bottom of the coil during use, a thicker coating on the bottom improves corrosion resistance. The top of the HX requires less paint because it is exposed to the accumulated fluid for a shorter period of time, thus reducing manufacturing costs associated with a uniform coating thickness throughout the HX while providing similar corrosion protection.

[0120] Example 4.A1-B 12 -Processed coating + selective coating gradient paint An aluminum-containing hull alloy, which may comprise a ship's hull, may be fully coated with a modified coating such as TCP. The alloy is then coated with a corrosion-resistant paint using either a contact or spray application. The paint is applied in multiple layers to protect against abrasion in areas needing additional corrosion protection, such as near the waterline or under the hull. Thicker layers of paint provide additional corrosion resistance in areas most exposed to the corrosive environment.

[0121] Example 5. A1-B6 - Primer + Gradient Structured Ceramic The finned-tube HX coil is fully coated with a corrosion-resistant primer such as TCP or a similar phosphate paint. The HX is then fully modified with a ceramic surface modifier using an immersion fixing system. The fixing fluid velocity is varied across the coil, altering the composition of the structured ceramic in the region of the velocity change. This technique can be used to induce a pore size gradient across the coil. Varying the pore size allows the wire to be more easily removed. This changes the coating pattern and can draw water away from areas prone to corrosion.

[0122] Example 6. A1-B7 - Primer + Selective Coating Structured Ceramic The brazed aluminum HX is thoroughly coated with a corrosion-resistant ceramic surface-modifying primer, such as TCP or a similar phosphate paint. The manifold and the brazed joints of the manifold tubes are then coated with a multi-layered ceramic that prevents corrosive solutions from reaching the HX surface in the most vulnerable areas. The structured ceramic material also modifies the way the surface retains precipitation, condensate, and other applied liquids. As an example, the structured ceramic layer can have a low contact angle. Forming a thin liquid layer at the applied location leads to the surface drying out quickly.

[0123] Example 7. A1-B8 - Primer + Selective Coating Gradient Structured Ceramic The HX is fully coated with a corrosion-resistant primer or finish, such as TCP or ceria. The top half of the HX is then modified with a structured ceramic surface modifier while varying the shear rate to create a pore size gradient toward the top of the HX. The pore size gradient draws water away from the weakest areas of the HX and allows it to wick toward the top of the HX.

[0124] Example 8.A1-B5-C9-D 11 -Primer + structured ceramic + functional material layer + selective coating paint) The brazed aluminum HX is fully coated with a primer paint to provide a structured ceramic surface modification, followed by an optional functional material layer, such as a steric acid, which provides surface energy modification. The manifold and manifold tube joints are then spray- or dip-painted to provide additional corrosion protection or aesthetic appeal. The main coil area with the functional material layer has a high contact angle, increasing heat capacity and preventing water accumulation on the surface, while less functional areas prone to corrosion are protected with a corrosion-resistant paint.

[0125] Example 9.A1-B5-C 10 -Processed coating + structured ceramic + gradient functional material layer A marine alloy, such as one that may comprise a ship's hull, is fully coated with a coating such as TCP, followed by a full coating with a structured ceramic surface modification. The hull is then modified with a layer of functional material to create a superhydrophobic surface. The functional material layer is applied so that the bow of the hull is more hydrophobic than the stern. The superhydrophobic surface allows the hull to more effectively reduce drag and / or be more durable at the highest water shear rates in service, and the TCP and ceramic surface modifications protect the remainder of the hull from seawater corrosion.

[0126] Example 10.A1-B5-C 11 -Processed coating + structured ceramic + selectively coated functional material layer The HX is fully coated with a functional coating followed by a structured ceramic surface modification. The bottom half of the coil is then layered with a functional material to create a superhydrophobic surface. The bottom half of the coil eliminates water condensation and prevents water buildup at manufacturing joints and design features such as manifold tube joints, fin tube joints, and louvers. Water buildup in the coil's most vulnerable areas is reduced, protecting the coil's most vulnerable areas from corrosion.

[0127] Example 11.A1-B5-C 12 -Processed coating + structured ceramic + selectively coated gradient functional material layer The HX is completely coated with a coating, followed by a surface modification of the structured ceramic. The coil is then provided with a corrosion-resistant functional material layer, with the outer side of the HX being thicker than the inner side. This protects the outer side of the HX (environment, airflow, etc.) from corrosive environments (acid rain, cat urine, etc., or airflow containing pollutants). The inward-facing side (e.g., the side not exposed to environmental conditions or airflow) experiences less degradation in heat transfer performance. Overall, pressure drop is reduced compared to a homogeneous membrane thickness range.

[0128] Example 12.A3 - Selective Coating Brazed aluminum HX is partially coated with a process coating on the manifold, and the manifold and tube braze joints are applied by selective immersion in a process bath. The coated areas protect the most vulnerable areas from corrosion.

[0129] Example 13.A5-B9-C 11 -Structured ceramic + functional material layer + selective coating paint The HX is fully coated with a structured ceramic surface modifier, followed by a layer of functional material that enhances hydrophobicity to create a superhydrophobic surface. The manifold and the brazed joints between the manifold and the tubes are painted to create corrosion-resistant areas of the coil. The superhydrophobic areas of the coil eliminate water buildup during use, and the painted manifold and manifold-tube joints further protect vulnerable areas from corrosion.

[0130] Example 14.A5-B 10 -Structured ceramic + functionally gradient material layer The HX is fully coated with a ceramic surface modifier in a binderless structure. The coil is then coated with a corrosion-resistant functional material layer, with a thickness greater on the outer side of the HX than on the inner side. This protects the outer side of the HX from corrosive environments (acid rain, cat urine, etc.) while limiting the degradation of heat transfer performance on the inner side. Overall, the pressure drop is reduced compared to a homogeneous film thickness range.

[0131] Example 15.A5-B 11 -Structured ceramic + selectively coated functional material layer A brazed aluminum heat exchanger was fully coated with a binderless magnesium oxide ceramic surface modifier and then cured in a 25-100 mM aqueous solution of magnesium nitrate and an equivalent amount of hexamethylenetetramine at a temperature of about 50-80°C for about 15-90 minutes. The coil was then calcined at about 400°C for about 1 hour. After cooling, the coil was immersed in a 25-100 mM aqueous solution of magnesium nitrate and an equivalent amount of hexamethylenetetramine at a temperature of about 50-80°C for about 15-90 minutes. The coil was then calcined again at about 400°C for about 1 hour. The coil was then cooled and partially immersed in a solution of room temperature vulcanizing (RTV) silicone in tert-butyl acetate at a concentration of 0.5% to 10% by weight, preferably about 2% by weight. The heat exchanger was immersed so that approximately half of the heat exchanger was in the solution and approximately half of the heat exchanger was in the vapor space above the solution surface. The heat exchanger was immersed for approximately 10 to 300 minutes, preferably approximately 30 minutes. The heat exchanger was then placed in air for 24 to 72 hours, after which the RTV silicone formed a superhydrophobic functional layer on the heat exchanger surface with a contact angle of greater than 120°. The unfunctionalized portion of the heat exchanger was then placed in an aqueous solution containing aminoethylaminopropylsilsesquioxane at a concentration of 0.1% by weight to 10% by weight, preferably approximately 5% by weight. The heat exchanger was immersed for 10 to 240 minutes, preferably approximately 30 minutes. The heat exchanger was then thoroughly rinsed with deionized water to remove any remaining solution from the surface, and then annealed in an oven at 90°C and 140°C, preferably approximately 110°C, for 30 to 300 minutes, preferably approximately 60 minutes. The silsequioxane functional structured ceramic was hydrophilic, and the water contact angle was <60°.

[0132] In the completed heat exchanger, an interface was observed between the RTV-functionalized ceramic surface and the silsequioxane-functionalized ceramic surface. On the RTV side of this interface, a water droplet was repelled and rolled off the surface. On the silsequioxane-functionalized ceramic surface, the water droplet wetted the surface and spread along it.

[0133] Example 16.A5-B 11 -Structured ceramic + selectively coated functional material layer The HX was fully coated with a binderless ceramic surface modification containing magnesium and aluminum oxide / hydroxide, as described above. The HX was immersed in a 25-75 mM aqueous solution of magnesium nitrate containing a similar amount of hexamethylenetetramine at a temperature of approximately 60-80°C for approximately 30-120 minutes. The coil was then calcined at a temperature of approximately 400-600°C for approximately 1 hour. Subsequent processing was performed by immersing half of the coil in a bath containing the chemicals for the functional material layer. A layer of the functional material, hexadecylphosphonic acid, was applied to the lower half of the coil. The functional material layer created a superhydrophobic surface on the lower half of the coil.

[0134] A controlled airflow was then trained through the heat exchanger and cooled using chilled glycol to below the dew point of the airflow. In the upper half of the heat exchanger, which contained only the structured ceramic layer, condensation formed during testing and remained within the body of the heat exchanger. In the lower part of the heat exchanger, which was treated with a functional material layer that resulted in a superhydrophobic surface (contact angle >150°) condition, condensation was observed, indicating heat transfer, but the condensate did not remain within the body of the exchanger because it had thermally condensed during the wind tunnel test.

[0135] Example 17.A5-B 12 -Structured ceramic + functionally gradient material layer A brazed aluminum heat exchanger was fully coated with a binderless magnesium oxide ceramic surface modification and then set in a 25-75 mM aqueous solution of magnesium nitrate and an equivalent amount of hexamethylenetetramine at a temperature of about 60-80°C for about 30-90 minutes. The coil was then calcined at a temperature of about 400-600°C for about 1 hour. The coil was cooled and then immersed twice in a 25-100 mM aqueous solution of magnesium nitrate and an equivalent amount of hexamethylenetetramine at a temperature of about 50-80°C for about 15-90 minutes. The coil was then calcined again at a temperature of about 400°C for about 1 hour. Two different solutions were used: one containing 0.5 wt% to 10 wt%, preferably 2 wt%, room temperature vulcanizing (RTV) silicone in tert-butyl acetate at room temperature. The other solution was an aqueous solution containing aminoethylaminopropylsilsesquioxane at a concentration of 0.1% to 10% by weight, preferably about 5% by weight. The heat exchanger was placed in a spray chamber, and the RTV solution was sprayed onto one side of the heat exchanger and the aminoethylaminopropylsilsesquioxane solution onto the other side over a period of 1 to 30 minutes, preferably about 5 minutes. The heat exchanger was annealed in an oven at a temperature of 90°C to 140°C, preferably about 110°C, for a period of 30 to 300 minutes, preferably about 60 minutes. The silsequioxane-functionalized structured ceramic was hydrophilic, with a water contact angle of <60°, and the RTV-functionalized structured ceramic was hydrophobic, with a contact angle of >120°.

[0136] The completed heat exchanger exhibited a gradient interface between the RTV-functionalized ceramic surface and the silsequioxane-functionalized ceramic surface as a result of the spray pattern. When water was sprayed onto the heat exchanger, the water droplets were repelled by the hydrophobic functionalized surface and wicked up into the fin pack with the hydrophilic functionalized surface. When water condensed or placed on the surface, it flowed from the hydrophobic regions to the hydrophilic regions, improving heat transfer across the surface.

[0137] Example 18.A5-B 12-Structured ceramic + selectively coated gradient functional material layer Aluminum panels were modified with a structured manganese-aluminum oxide ceramic material by setting them in a 50-150 mM aqueous solution of manganese nitrate and an equivalent amount of hexamethylenetetramine at approximately 70-80°C for approximately 30-120 minutes. The panels were then dried at approximately 400°C for approximately 1 hour. The panels were then selectively coated with oil or wax, such as drying oils like tung oil or linseed oil, or sealants like paraffin wax or beeswax, leaving approximately 10% of the top surface uncovered. This allowed electrical contact with the sample, allowing it to be used as an electrode in a battery or capacitor.

[0138] Example 19.A6 - Gradient Structured Ceramic The HX coil was fully coated with a magnesium-based structured ceramic surface modifier containing magnesium and aluminum oxide / hydroxide. The surface was fused in a 25-75 mM aqueous solution of magnesium nitrate and an equivalent amount of hexamethylenetetramine at a temperature of approximately 60-80°C for approximately 30-90 minutes. The coil was then calcined at a temperature of approximately 400-600°C for approximately 1 hour. The shear rate of the reacting chemical mixture was varied adjacent to the coil and at various regions along the coil, creating a gradient in the surface-modified film thickness. The heat exchanger was treated as described above to apply the structured ceramic. A recirculation system moved the treatment liquid from the main body of the dip tank through pumps and filters, removing suspended solids along the flow. The liquid was returned to the dip tank with the heat exchanger via a liquid ejector, which focused and amplified the liquid movement adjacent to the ejector. The recirculated fluid traveled along the length of the heat exchanger toward the midpoint of one manifold. In areas of higher shear rate, the amount of ceramic modifier increased in response to the change in pore size. The increased level of deposition was demonstrated through the aesthetic appearance of the material's color along the manifold and heat exchanger surfaces. The areas with increased deposition appeared whiter than the remainder of the heat exchanger, which was gray in appearance. X-ray fluorescence (XRF) measurements confirmed that the areas that appeared white had a higher amount of magnesium oxide and aluminum oxide surface modification compared to adjacent areas that appeared dark. These areas with a thicker structural layer may provide increased protection against corrosive elements from the surrounding environment.

[0139] Example 20.A6 - Gradient Structured Ceramic The HX coil is completely coated with a structured ceramic surface modification. The coil is placed in a 25-75 mM aqueous solution of magnesium nitrate and an equivalent amount of hexamethylenetetramine at a temperature of approximately 60-80°C for approximately 30-90 minutes. The coil is then calcined at a temperature of approximately 400-600°C for approximately 1 hour. Varying the temperature, concentration, and shear rate during processing results in the formation of a denser structure with smaller pore sizes near the fins and a less dense structure with larger pore sizes in the ceramic deposits further away from the fins. The gradient in the ceramic structure with the surface modification film thickness enhances the water absorption characteristics of the outer regions of the ceramic deposits, shortening drying time, and the increased density and reduced porosity of the HX fin surface minimizes the amount of water that comes into contact with the substrate. This improves drying time and frost formation while preventing surface corrosion.

[0140] Example 21. A6-B9 - Gradient structured ceramic + functional material layer The HX is fully coated with a magnesium oxide-based structured ceramic surface modifier. The coil is placed in a 25-75 mM aqueous solution of magnesium nitrate and an equivalent amount of hexamethylenetetramine at a temperature of approximately 60-80°C for approximately 30-90 minutes. The coil is then calcined at a temperature of approximately 400-600°C for approximately 1 hour. The shear rate is varied in various regions along the coil to create a pore size gradient and modify the ceramic surface topography. The HX is then homogeneously treated with a layer of functional material, such as perfluoroalkylsilane, fatty acid, or alkylphosphonic acid, to create a superhydrophobic surface. This gradient ceramic modification creates regions that provide droplet exclusion properties that control the wettability of specific regions of the coil. These droplet exclusion regions can be mapped to areas known to be vulnerable to corrosion-related damage.

[0141] Example 22.A6-B 10 -Gradient structured ceramic + gradient functional material layer The brazed aluminum heat exchanger is immersed in an immersion tank and, while in operation, is vibrated in a direction perpendicular to the primary air flow direction to agitate the element. The element movement results in a greater deposition of the structured ceramic layer on the leading and trailing edges, taking into account the primary operating air flow direction, than on the central portion of the heat exchanger body. This greater deposition rate results in a greater deposition rate on the leading and trailing edges, which are protected. Then a functional material layer is applied to the leading edge and this area is treated (taking into account the airflow direction) to improve the chafing and wear protection of the leading edge.

[0142] Example 23.A6-B 11 -Gradient structured ceramic + selectively coated functional material layer An aluminum alloy, which may comprise the body of an aircraft, is coated with a structured ceramic surface modifier. Shear rates are varied to increase the variability of the topography of the forward portions of the wings, propeller blades, horizontal stabilizer, and rudder. The forward-facing portions of the wings, propeller blades, horizontal stabilizer, and rudder are then selectively treated with a functional material layer. The increased variability of the topography from the ceramic surface modifier creates a functional material layer with droplet shedding properties that help prevent ice formation in the aircraft's most vulnerable areas. The overall weight of the aircraft is moderated by the selective protection.

[0143] Example 24.A6-B 12 -Gradient structured ceramic + selectively coated gradient functional material layer The HX is completely coated with a structured ceramic surface modifier. The shear rate is varied so that the top of the HX has a thicker ceramic layer than the bottom. The bottom half of the coil is then painted with a dip or spray paint, aligned with the manifold tube braze joint. The thicker areas of paint protect the weaker areas of the coil, while the thicker ceramic layer wicks water away from the lower layers of the paint, preventing water and other corrosive solutions from destroying the paint's effectiveness.

[0144] Example 25.A7 - Selectively Coated Structured Ceramic Steel-aluminum heat exchangers were coated with a structured ceramic surface modifier that resists corrosion and preferentially adheres to the aluminum fins rather than the steel tubes. The coils were placed in a 25-75 mM aqueous solution of magnesium nitrate and an equivalent amount of hexamethylenetetramine at temperatures of approximately 60-80°C for approximately 30-90 minutes. The coils were then calcined at temperatures of approximately 400-600°C for approximately 1 hour. The structured ceramic contained zinc and aluminum oxide / hydroxide. The ceramic surface was hydrophilic, allowing good water flow from the steel tube to the aluminum fins while protecting the steel tube from corrosion, improving water management and improving heat exchanger performance.

[0145] Example 26.A7 - Selectively Coated Structured Ceramic An aluminum panel was selectively masked with a pattern. The panel was then masked with silicone tape to the desired pattern, and the masked panel was then affixed with a structured ceramic. The masked surface was placed in a 25-75 mM aqueous solution of magnesium nitrate and an equal amount of hexamethylenetetramine at a temperature of approximately 60-80°C for approximately 30-90 minutes. The mask was removed from the panel, and the panel was then calcined at a temperature of approximately 400-600°C for approximately 1 hour. Removal of the mask left behind a patterned structured ceramic, allowing for selective moisture collection (wicking) or moisture removal (exhaust) patterns. This also included bare metal areas adjacent to the structured layer, which could be used for electrical contact with the substrate.

[0146] Example 27.A7 - Selectively Coated Structured Ceramic An aluminum panel was selectively masked with a pattern. The panel was masked with a permanent marker pen containing dye pigments, resin, and an organic solvent. The masked panel was then coated with a binderless structured ceramic surface modifier containing zinc and aluminum oxide / hydroxide. The masked panel was then fixed in a 25-75 mM aqueous solution of zinc nitrate and an equivalent amount of hexamethylenetetramine at a temperature of about 60-80°C for about 30-90 minutes. The panel was then calcined at a temperature of about 400-600°C for about 1 hour. During the heat treatment, the dye pigments, resin, and organic solvent under the mask evaporated and oxidized, leaving behind a bare aluminum substrate. The remaining structured ceramic was then selectively coated. This allowed for selective moisture collection (wicking) or moisture removal (drainage) patterns, including bare metal areas adjacent to the structured layer that could be used for electrical contact with the substrate.

[0147] Example 28.A7 - Selectively Coated Structured Ceramic An aluminum panel was selectively masked with a pattern. The desired pattern was created using an oil-based marker pen containing dye pigments, resin, and organic solvent. The masked panel was then coated with a binderless structured ceramic surface modifier containing zinc and aluminum oxide / hydroxide. The masked panel was then immersed in a 25-75 mM aqueous solution of zinc nitrate and an equivalent amount of hexamethylenetetramine at a temperature of approximately 60-80°C for approximately 30-90 minutes. The panel was then calcined at a temperature of approximately 400-600°C for approximately 1 hour. During the heat treatment, the dye pigments, resin, and organic solvent underneath the mask evaporated and oxidized, leaving the bare aluminum substrate. The structured ceramic was then modified with a hexadecylphosphonic acid functional layer, which is selective to the ceramic material. This resulted in a superhydrophobic structured ceramic surface adjacent to the largely hydrophilic bare aluminum surface. The contact angle of water on the functionalized structured ceramic surface was greater than that on the bare aluminum panel.

[0148] Example 29. A7B9 - Selectively coated structured ceramic + continuous functional material An aluminum panel was selectively masked with a pattern. The panel was then masked with polyimide tape in the desired pattern and coated with a structured, binderless ceramic surface modifier containing magnesium and aluminum oxide / hydroxide. The panel was then immersed in a 25-75 mM aqueous solution of magnesium nitrate and an equivalent amount of hexamethylenetetramine at a temperature of approximately 60-80°C for approximately 30-90 minutes. The panel was then calcined at a temperature of approximately 400-600°C for approximately 1 hour. The adhesive from the polyimide tape evaporated and reattached to the metal surface, forming a superhydrophobic ceramic structure. Upon removal of the mask, the presence of the structured ceramic layer revealed a difference in contact angle between the structured ceramic surface coated with the functional layer and an aluminum surface with the same functional layer.

[0149] Example 30.A7 - Selectively Coated Structured Ceramic An aluminum panel is selectively protected (masked) with a pattern. The masked panel is then sprayed or showered to deposit a ceramic surface modifier onto the unmasked surface. When the mask is removed, a patterned, structured ceramic containing magnesium and aluminum oxide / hydroxide remains, allowing for selective moisture collection (wicking) or moisture removal (draining) patterns. Spraying or showering the ceramic material further increases deposit coverage at preferential drainage locations.

[0150] Example 31.A7-B 11 -Selective coating structured ceramic + selective coating paint An aluminum panel was selectively masked with a pattern using Kapton (polyimide) adhesive tape. The masked panel was then coated with a binderless structured ceramic surface modifier containing magnesium and aluminum oxide / hydroxide, as described in Example 29. Silicone tape was also used on the aluminum panel and HX substrate. The mask was removed, leaving the patterned structured ceramic. The patterned panel was then immersed in an anodic dye, and the patterned structured ceramic preferentially absorbed the dye pigment, changing the color of only the structured fixture area.

[0151] Example 32. A7-B9 - Selectively coated structured ceramic + functional material layer A stainless steel-aluminum heat exchanger was coated with a structured ceramic surface modifier that favored aluminum fins over stainless steel or copper tubes. The structured ceramic surface was coated by immersing the heat exchanger in a 25-75 mM aqueous solution of magnesium nitrate and an equivalent amount of hexamethylenetetramine at a temperature of approximately 60-80°C for approximately 30-90 minutes. The coil was then calcined at a temperature of approximately 400-600°C for approximately 1 hour. The heat exchanger was then functionalized with a single layer of material by immersing it in a dilute solution (0.1-1 wt%) of hexadecylphosphonic acid, perfluoroalkylsilane, fatty acid, or alkylsilane to create a superhydrophobic surface on the aluminum fins. The superhydrophobic functional material layer on the fins provided droplet removal properties, prevented water accumulation on the fins, and improved the heat exchanger's performance compared to similar uncoated heat exchangers. The surface properties also provided a protective layer against corrosion. Because the ceramic surface modifier selectively modifies the aluminum fins, less raw material is used and the process is cheaper than if both the fins and the tubes were surface modified.

[0152] Example 33. A7-B9 - Selectively coated structured ceramic + functional material layer An aluminum panel was selectively masked with a pattern. The panel was then masked with polyimide tape in the desired pattern. A structured ceramic material was then deposited on the masked panel, and the polyimide material was not removed before heating. The panel was then placed in a 25-75 mM aqueous solution of magnesium nitrate and an equivalent amount of hexamethylenetetramine at a temperature of approximately 60-80°C for approximately 30-90 minutes. The panel was then calcined at a temperature of approximately 400-600°C for approximately 1 hour. The resulting panel contained a patterned structured ceramic containing magnesium and aluminum oxide / hydroxide, and the regions containing the structured ceramic layer were significantly more hydrophobic than the patterned (covered) regions without the structured ceramic. The masked regions also exhibited a difference in contact angle compared to the untreated panel.

[0153] Example 34.A7-B 11 -Selectively coated structured ceramic + selectively coated functional material layer A stainless steel-aluminum heat exchanger is coated with a structured ceramic surface modifier that prefers aluminum fins over stainless steel or copper tubing. A functional material is then selectively layered onto the ceramic material, relying solely on the selectivity of chemical bonding between the steel and ceramic. This creates a superhydrophobic surface on the fins, preventing water retention and reducing airflow through the heat exchanger's fin pack while maintaining the inherent corrosion resistance of unmodified stainless steel.

[0154] Example 35.A8 - Selectively Coated Gradient Structured Ceramic The stainless steel-aluminum heat exchanger is coated with a structured ceramic surface modifier that favors the aluminum fins rather than the stainless steel tubes. The fins are treated so that one side is longer than the other, creating a porosity gradient across the aluminum fins.

[0155] Example 36.A8 - Selectively Coated Gradient Structured Ceramic Stainless steel-aluminum heat exchangers are coated with a structured ceramic surface modifier that preferentially targets the aluminum fins rather than the stainless steel tubes. The fins have surface roughness due to the manufacturing process and grain boundaries, but depositing a thick structured ceramic material selectively targets these areas, mitigating corrosion.

[0156] Example 37.A8 - Selectively Coated Gradient Structured Ceramic As shown in Table 1, a series of 3003 aluminum Q panel test substrates were coated with a binderless structural ceramic surface modification containing magnesium and aluminum oxide / hydroxide and subjected to various flow conditions during the fixing process. The panels were placed in a 25-75 mM aqueous solution of magnesium nitrate and a similar amount of hexamethylenetetramine at temperatures between about 60°C and 80°C for about 30-90 minutes. The panels were then heated to temperatures between about 400°C and 60°C. It was calcined at a temperature of 0° C. for about 1 hour.

[0157] As shown in Table 1, the speed, mass of deposit, and resulting concentration are based on the base case shown in the second row, where the speed setting and resulting mass and concentration are the reference. The change in flow conditions resulted in a change in the amount of deposit and the composition of the deposit. All other process parameters, temperature, composition, and materials remained unchanged. This example uses processing parameters to create a gradient in the structural properties of the binderless ceramic surface layer, which can provide useful benefits. [Table 1]

[0158] Example 38.A8 - Selectively Coated Gradient Structured Ceramic An aluminum heat exchanger is coated with a structured ceramic surface modifier and the process conditions are varied during treatment: the temperature of the treatment bath is decreased during treatment, resulting in a change in the composition of the structured layer depending on the deposit film thickness, compared to a heat exchanger treated at a uniform temperature.

[0159] Alternatively, the chemical composition of the processing bath may evolve during processing, resulting in a change in the composition of the structure layer depending on the build film thickness, compared to a heat exchanger that processes with a homogenous chemical composition.

[0160] Alternatively, when a working fluid at a different temperature than the process bath passes through the heat exchanger during processing, the temperature across the heat exchanger's surface changes. The structured ceramic material has structural properties that match the local temperature during processing. During use, the heat exchanger may have an operating temperature gradient due to temperature differences across the heat exchanger, and therefore the desired properties of the ceramic surface layer are matched to the needs of the heat exchanger during use.

[0161] Example 39.A9-B 11 -Coating + selective coating paint All steel surfaces used in a bridge are coated with a corrosion-resistant paint to prevent corrosion of the steel. The surface of the bridge closest to the roadway is then painted with a protective paint. This partial paint layer protects the corrosion-resistant paint from the strong chloride ions used in deicing agents. Rather than painting all structural steel elements of the bridge, only the areas where deicing agents are used require a protective paint layer, reducing overall painting costs.

[0162] Example 40.A 10 -Gradient paint The HX is painted with a corrosion-resistant paint via dipping or spraying. The paint is applied thinnest in the center of the coil and thickest at the manifold ends, reducing painting costs while maintaining corrosion protection in the most vulnerable areas.

[0163] Example 41.A 11 -Selective coating paint For brazed aluminum HX coils, the manifold and manifold tube braze joints are painted by dipping or spray painting, which creates a corrosion-resistant coating around the most vulnerable areas of the coil.

[0164] Example 42.A 12 -Selective coating gradient paint For HX coils, only the manifold and manifold tube braze joints are painted with corrosion-resistant paint via dipping or spraying. The gradient is created by applying multiple layers to selected areas of the substrate or by varying the spray time. The paint application is targeted to the manifold tube braze joints, which are most vulnerable to corrosion-related failure. This process significantly reduces painting costs while preserving the areas most in need of corrosion protection. Not painting functional areas of the coil (fin pack) prevents degradation of HX performance.

[0165] Example 43 3003 aluminum panels were tested for improved drying characteristics as outlined herein. All panels were subjected to controlled ambient conditions ranging from 68-70°F and 30-50% relative humidity (RH) by measuring the panel's mass and then monitoring its mass during subsequent drying upon application of two 100-microliter droplets. The minimum panel had a drying rate (measured by mass loss after droplet application) of approximately 3 mg of water / cm²-hour. Similarly, electrocoated panels with polyurethane UV protection were determined to have a similar drying rate of 3 mg / cm²-hour. The drying rates of panels coated with various structured ceramic layers, as described in PCT / US19 / 65978, were determined to be between 20 and 50 mg / cm²-hour. Three different structured ceramic layer formulations were applied. One panel contained magnesium and aluminum oxide / hydroxide ("structured ceramic") applied as described in PCT / US19 / 65978. Another panel contained magnesium and aluminum oxide / hydroxide ("Structured Ceramic 2") and was set for a shorter time under similar process conditions. A third panel contained manganese and aluminum oxide / hydroxide ("Structured Ceramic 3"). The results are shown in Figure 1.

[0166] A similar panel containing the structured ceramic layer was further treated with a functional material layer containing hexadecylphosphonic acid to increase the contact angle. A 100 microliter droplet of water was applied, causing it to roll off the panel's surface. The mass of the droplet was not measured because it had already been rolling off the surface before the initial time point.

[0167] Example 44 A series of 3003 aluminum q-panels were coated with a binderless structured ceramic surface modifier containing magnesium and aluminum oxide / hydroxide and subjected to immersion temperatures of either 70°C or 80°C and immersion times ranging from 1 minute to 64 minutes, similar to those described in Example 33. Previous samples constructed under these same conditions demonstrated that the porosity and pore size distribution of the structured ceramic surface varied with immersion time. The capillary rise of the samples in deionized water was measured, and the data demonstrated the ability of process parameters to influence the water-surface interaction. Longer immersion times improved the capillary rise, and high-temperature immersion also showed improved capillary rise. This indicates that specific application across the surface of the material, using varying process parameters, can optimize the surface-water interaction. Scanning electron microscope (SEM) images of the structured ceramic layer showed differences in features at both the nanometer and micrometer scales. Capillary rise measurements were performed using minimal aluminum q-panels, but the air-water interface remained unchanged.

[0168] Although the foregoing invention has been described in detail at the level of illustrations and examples for purposes of clarity of understanding, those skilled in the art will readily appreciate that certain changes and modifications can be made without departing from the spirit and scope of the invention. Therefore, the detailed description should not be construed as limiting the scope of the invention.

[0169] All publications, patents, and patent applications cited herein are hereby incorporated by reference for all purposes. Each individual publication, patent, or patent application is herein incorporated by reference in its entirety to the same extent as if specifically and individually indicated by reference.

Claims

1. A composition comprising a coating or modifier for a surface of a substrate, the coating or modifier comprising a gradient of at least one physical or chemical property across at least a portion of the substrate surface.

2. The composition of claim 1 , wherein the gradient-containing coating or modifier is applied to the substrate surface in a monolayer.

3. The composition of claim 2 , wherein the coating or modifier comprises a ceramic, a polymeric material, or a self-assembled monolayer.

4. 10. The composition of claim 1, wherein the coating or modifier comprises multiple layers, and at least one of the layers comprises a gradient of the at least one physical or chemical property.

5. The composition of claim 4 , wherein the at least one layer comprising a gradient of at least one physical or chemical property comprises a ceramic, a polymeric material, or a self-assembled monolayer.

6. 5. The composition of claim 4, wherein the plurality of layers comprises a first layer in contact with the substrate that includes a gradient of the at least one physical or chemical property, and a second functional material layer in the first layer that does not include the gradient.

7. 5. The composition of claim 4, wherein the plurality of layers comprises a first layer in contact with the substrate that does not include a gradient of the at least one physical or chemical property, and a second functional material layer that includes the gradient in the first layer.

8. 8. The composition of any one of claims 1 to 7, wherein the coating or modifier is applied to spatially separated regions of the substrate surface, and wherein one or more regions of the substrate surface are free of the coating or modifier.

9. 9. The composition of claim 8, wherein the coating or modifier is applied to a plurality of spatially separated regions of the substrate surface.

10. The composition of any one of claims 1 to 7, wherein the coating or modifier is spatially continuous over substantially all areas of the substrate surface.

11. 10. The composition of claim 1, wherein the substrate is modified with a treatment coating or primer over substantially the entire substrate surface, and the layer comprising the gradient of at least one physical or chemical property is coated over the treatment coating or primer.

12. 12. The composition of claim 11, wherein the layer containing the gradient of the at least one physical or chemical property is applied to spatially separated regions of the finishing coat or primer, and one or more of the finishing coats or primers does not contain the gradient.

13. 13. The composition of claim 12, wherein the layer containing the gradient of the at least one physical or chemical property is applied to a plurality of spatially separated regions of the working coat or primer.

14. The layer containing the gradient of at least one physical or chemical property is 12. The composition of claim 11, wherein the nucleic acid sequence is spatially contiguous over substantially all of the region of the primer.

15. 15. The composition of any one of claims 11 to 14, wherein the processing coat or primer comprises a chromate, a fluorozirconate, a fluorothionate, a sol-gel, a phosphate, zirconium, a rare earth metal, or a blue or black oxide.

16. The composition of any one of claims 11 to 15, wherein the layer comprising a gradient of at least one physical or chemical property comprises a ceramic, a polymeric material, or a self-assembled monolayer.

17. 10. The composition of claim 1, wherein a layer comprising a gradient of at least one physical or chemical property is coated on at least a portion of the substrate surface, and a substantially homogeneous functional material layer is coated on the layer comprising the gradient and across substantially all areas of the substrate surface.

18. 20. The composition of claim 17, wherein the layer comprising a gradient of at least one physical or chemical property comprises a ceramic, a polymeric material, or a self-assembled monolayer.

19. the coating or modifier or layer containing the gradient of at least one physical or chemical property comprises a ceramic material; and The composition of any one of claims 1 to 18, wherein the ceramic material is a binderless ceramic material exhibiting a crystallinity of greater than about 20%.

20. The composition of any one of claims 1 to 19, wherein the ceramic material comprises a metal oxide, a metal oxide hydrate, a metal hydroxide, and / or a metal hydroxide hydrate.

21. 21. The composition of claim 20, wherein the ceramic material comprises a metal hydroxide, and at least a portion of the metal hydroxide comprises a layered double hydroxide.

22. The ceramic material comprises: Approximately 10m ２ ~1500m ２ of surface area / square meter of predicted ceramic material; Approximately 15m ２ ~1500m ２ of surface area / gram of ceramic material; an average pore size of about 2 nm to about 20 nm; a film thickness of about 0.2 micrometers to about 25 micrometers; a porosity greater than about 10%; and Approximately 100 mm determined by mercury intrusion porosimetry ３ / g ~ approx. 7500mm ３ The composition of any one of claims 19 to 21, comprising one or more of:

23. 18. The composition of any one of claims 1 to 17, wherein the coating or modifier or layer comprising a gradient of at least one physical or chemical property comprises a latex, an alkane, an alkene, an alcohol, an acrylic, an alkyd, an enamel, an epoxy, a siloxane, a fluoropolymer, or a urethane.

24. the coating or modifier or layer containing a gradient of at least one physical or chemical property comprises molecules having a head group and a tail group; the head group comprises a silane group, a sulfonate group, a sulfonic acid group, a boronate group, a boronic acid group, a phosphonate group, a phosphonic acid group, a carboxylate group, a carboxylic acid group, a vinyl group, a hydroxide group, an alcohol group, a thiolate group, a thiol group, and / or a quaternary ammonium group; and 18. The composition of any one of claims 1 to 17, wherein the tail group comprises a hydrocarbon group, a fluorocarbon group, a vinyl group, a phenyl group, an epoxide group, an acrylic group, an acrylate group, a hydroxyl group, a carboxylic acid group, a thiol group, and / or a quaternary ammonium group.

25. 25. The composition of any one of claims 1 to 24, wherein the at least one physical or chemical property of the gradient is selected from membrane thickness, density, pore size, pore size distribution, pore filling rate, chemical or physical composition, oxidation state, metal concentration, crosslink density, isoelectric point, electrical conductivity, thermal conductivity, capacitance, or a combination thereof.

26. The composition of any one of claims 1 to 25, wherein the substrate surface is a surface of a heat exchanger, a vehicle, an aircraft, a ship, or a bridge.

27. 27. The composition of claim 26, wherein the substrate surface is a surface of a heat exchanger, or a component thereof.

28. 28. The composition of claim 27, wherein the heat exchanger is a brazed aluminum heat exchanger, a copper tube-aluminum fin heat exchanger, or a steel tube-aluminum fin heat exchanger.

29. 30. The composition of claim 27, wherein the heat exchanger or component thereof is more resistant to environmental damage compared to the same heat exchanger or component without the composition.

30. 1. A heat exchanger or component thereof comprising a coating or modifier on a surface of the heat exchanger or component thereof, wherein the coating or modifier comprises a gradient of at least one physical or chemical property across at least a portion of a surface of the heat exchanger or component.

31. 31. The heat exchanger or component thereof of claim 30, wherein the heat exchanger is a brazed aluminum heat exchanger, a copper tube-to-aluminum fin heat exchanger, or a steel tube-to-aluminum fin heat exchanger.

32. 31. The heat exchanger or component thereof of claim 30, wherein the heat exchanger or component thereof has a higher resistance to environmental damage compared to the same heat exchanger or component without the coating or modifier.

33. 26. A method of protecting a substrate from environmental damage, comprising applying to a substrate the composition of any one of claims 1 to 25, wherein the substrate has a higher resistance to environmental damage compared to the same substrate without the composition.

34. 34. The method of claim 33, wherein the environmental damage comprises one or more of corrosion, debris accumulation, water or ice accumulation, biofouling, and abrasion.

35. 35. The method of claim 34, wherein corrosion caused by water or ice accumulation is inhibited or prevented.

36. The method of any one of claims 33 to 35, wherein the substrate is a surface of a heat exchanger or a component thereof.

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