Ceramic surface modification materials and methods of use thereof

Abstract

To provide porous binderless ceramic surface modification materials and applications thereof that are provided with electrochemical protection, corrosion protection, visual appearance, wettability, and durability to the environmental service conditions, which are desired in coatings and surface modifications.SOLUTION: The present invention provides binderless (e.g., surface immobilized) porous ceramic compositions on a substrate, which include metal oxides, metal hydroxides, hydrates of the metal oxides and / or hydrates of the metal hydroxides, or combinations thereof.SELECTED DRAWING: None

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims the benefit of U.S. Provisional Patent Application No. 62 / 778,888, filed Dec. 12, 2018, which is incorporated herein by reference in its entirety.

[0002] Field of the Invention This application relates to ceramic surface - modifying materials, specifically to binderless porous ceramics such as metal oxides and / or metal hydroxide ceramics on a substrate surface.

Background Art

[0003] Background Coatings and surface modifications are used to improve products and provide additional benefits. One such application area is to provide additional electrochemical protection or corrosion prevention for products. Other desired properties include visual appearance, or wettability, or electrical properties. To provide useful benefits, these coatings and surface modifications must be durable against environmental service conditions. Other desired attributes of surface modifications and coatings include being thin, conformal, having a wide range of operating conditions, and not protruding from the product surface. Multifunctional surface modifications and coatings are further desired.

Summary of the Invention

Problems to be Solved by the Invention

[0004] Brief Summary of the Invention Provided are binderless porous ceramic compositions comprising metal oxides, metal hydroxides, hydrates of metal oxides, and / or hydrates of metal hydroxides, or combinations thereof, methods of making such compositions, and uses thereof.

Means for Solving the Problems

[0005] In one aspect, a binderless (e.g., surface-fixed) porous ceramic surface modification material on a substrate is provided. In some embodiments, the ceramic material includes metal oxides, metal hydroxides, hydrates of metal oxides, and / or hydrates of metal hydroxides. In some embodiments, the ceramic material includes a metal hydroxide, and at least a portion (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%) is in the form of a layered double hydroxide. In some embodiments, the binderless porous ceramic surface modification material is a ceramic material of mixed metal oxides and / or hydroxides, and / or their hydrates. In some embodiments, the surface modification material is fixed on the substrate.

[0006] In some embodiments, the substrate contains a metal, and the main metal in the ceramic material is different from the main metal in the substrate. For example, more than 50%, 60%, 70%, or 80% of the total metal in the ceramic material is different from more than 50%, 60%, 70%, or 80% of the total metal in the substrate.

[0007] In some embodiments, the binderless porous ceramic material is mainly crystalline (e.g., exhibits ordered and controlled growth) as compared to amorphous or glass (e.g., exhibits freezing of the bulk composition). A crystalline composition is a regularly ordered array of components held together by intermolecular forces. Crystallinity may be determined, for example, by the presence of peaks due to enhanced interference in X-ray diffraction. The mainly crystalline binderless porous ceramic material may be, for example, at least about 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% crystalline.

[0008] In some embodiments, the binderless porous ceramic surface modification material described herein includes an open-cell porous structure. For example, the open-cell porous structure may be characterized by a capillary rise of a solvent having a surface tension of less than about 25 mN / m being greater than about 5 mm above a vertical surface against a gravity of about 1 G in an atmosphere saturated with the solvent at a temperature of about 15°C to about 25°C, such as 20 ± 5°C, for 1 hour.

[0009] In some embodiments, the binderless porous ceramic material has a projected area of the substrate per m 2 of about 1.5 m 2 ~100 m 2 ; about 10 m 2 ~ about 1500 m 2 ; or about 70 m 2 ~ about 1000 m 2 ; about 15 m 2 ~ about 1500 m 2 per g of the ceramic material; or about 50 m 2 ~ about 700 m 2 ; an average pore diameter of about 5 nm to about 200 nm, about 2 nm to about 20 nm, or about 4 nm to about 11 nm; a thickness of up to about 100 micrometers, up to about 50 micrometers, up to about 25 micrometers, up to about 20 micrometers, or about 0.2 micrometers to about 25 micrometers; a porosity of about 5% to about 95%, about 10% to about 90%, about 30% to about 70%, about 30% to about 95%, or greater than about 10%; a void volume of about 100 mm 3 / g to about 7500 mm 3 / g as determined by mercury intrusion porosimetry; or any combination thereof.

[0010] In some embodiments, the substrate includes aluminum, aluminum alloy, steel alloy, iron alloy, zinc, zinc alloy, copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, other useful engineering alloys, glass, polymer, copolymer, or plastic.

[0011] In some embodiments, the ceramic material (e.g., metal oxide, metal hydroxide, and / or their hydrates) contains one or more of zinc, aluminum, manganese, magnesium, cerium, copper, gadolinium, tungsten, tin, lead, and cobalt. In some embodiments, the ceramic material contains transition metals, group 2 elements, rare earth elements (e.g., lanthanum, cerium, gadolinium, praseodymium, scandium, yttrium, samarium, or neodymium), aluminum, tin, zinc, or lead.

[0012] In certain embodiments, the binderless porous ceramic surface modification material is a mixture of oxides and / or hydroxides of zinc and aluminum; a mixture of oxides and / or hydroxides of manganese and magnesium; manganese oxide and / or hydroxide; aluminum oxide and / or hydroxide; mixed metal manganese oxide and / or hydroxide; a mixture of oxides and / or hydroxides of magnesium and aluminum; magnesium oxide and / or hydroxide; a mixture of oxides and / or hydroxides of magnesium, cerium, and aluminum; a mixture of oxides and / or hydroxides of zinc, praseodymium, and aluminum; a mixture of oxides and / or hydroxides of cobalt and aluminum; a mixture of oxides and / or hydroxides of manganese and aluminum; a mixture of oxides and / or hydroxides of cerium and aluminum; a mixture of oxides and / or hydroxides of zinc and aluminum; a mixture of zinc aluminate; any and all phases (e.g., one or more phases) containing Zn, Al, and oxygen; or zinc oxide and / or hydroxide; or hydrate(s) of any of the previous compounds or mixtures. In some embodiments, the substrate contains aluminum, iron, nickel, titanium, or copper.

[0013] In some embodiments, the binderless porous ceramic surface modification material provides one or more enhanced functional characteristics compared to the same substrate without the ceramic material, including, but not limited to, wettability, hardness, elasticity, mechanical, electrical, piezoelectric, optical, adhesion or thermal properties, microbial affinity or resistance, modification of biofilm growth (e.g., resistance to or reduction of biofilm growth), catalytic activity, permeability, cosmetic appearance, liquid repellency, and corrosion resistance, or any combination of two or more of these functional characteristics. In some embodiments, the ceramic material provides enhanced wettability, corrosion resistance, adhesion, and / or optical properties compared to the same substrate without the ceramic material.

[0014] In some embodiments, the binderless porous ceramic surface modification material includes an open-cell porous structure. In an open cell, the pores of the interstices are connected to adjacent pores. In other embodiments, the surface modification material includes closed cells, where the pores of each interstice are discontinuous and completely surrounded by a solid material (e.g., encapsulated by the surrounding solid material). In some embodiments, the binderless porous ceramic surface modification material includes pores of both open cells and closed cells. In some embodiments, the binderless porous ceramic surface modification material includes open cells, and at least a portion of the open cells are open at the surface of the ceramic material, i.e., open to the surrounding environment and / or in contact with the surrounding environment. In embodiments of the invention described herein, the open cells may not be filled or may be partially, substantially, or completely filled with one or more gaseous, liquid, or solid substances, or combinations thereof.

[0015] In some embodiments, the binderless porous ceramic surface modification material includes pores that are partially or fully or substantially filled with a gas, liquid or solid substance, or a combination thereof. In some embodiments, the ceramic material includes pores that are less than 50% filled with a liquid and / or contains a liquid that is not stably contained or retained within the pores. In some embodiments, the ceramic material includes pores that are any of about 10% to about 25%, or about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or 45%, or pores that are filled with a liquid from about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or 45% to about 50%.

[0016] In some embodiments, the binderless porous ceramic surface modification material includes pores filled with a mixture of a first material (e.g., a first substance) and a second material (e.g., a second substance), the pores being initially partially filled with the first material and then partially or fully filled with the second material. In some embodiments, one or more functional characteristics of the ceramic material are modified by the inclusion of the first and / or second materials. In some embodiments, one or more functional characteristics of the ceramic material (e.g., thermal properties and / or conductivity) are adjustable by varying the amount or composition of the first and / or second materials. In some embodiments, adjustable characteristics include wettability, hardness, elasticity, mechanical, electrical, piezoelectric, optical, adhesive or thermal properties, microbial affinity or resistance, modification of biofilm growth (e.g., resistance to biofilm growth or reduction of growth), catalytic activity, permeability, cosmetic appearance, liquid repellency, and / or corrosion resistance. In some embodiments, the first material interacts with the second material in a synergistic manner to modify one or more functional characteristics of the surface modification material (e.g., one or more of the functional activities described above).

[0017] In some embodiments, the gas, liquid, or solid material inside the pores interacts with the substrate, thereby providing one or more functionalities such as fluid wicking, capillary rise, enhanced adhesiveness, thermal resistance, thermal conductivity, corrosion resistance, and / or liquid repellency. In some embodiments, the moisture in the environment interacts with the gas, solid, or liquid material inside the pores, thereby providing one or more functionalities such as a modulated evaporation rate, corrosion protection of the substrate, and / or enhanced wetting properties.

[0018] In some embodiments, the binderless porous ceramic surface modification material includes one or more properties such as wettability, hardness, elasticity, microbial affinity or resistance, modification of biofilm growth, catalytic activity, corrosion resistance, aesthetic appearance, light absorption, light trapping, and permeability.

[0019] In some embodiments, the binderless porous ceramic surface modification material further includes a topmost material layer on the ceramic material. In some embodiments, the topmost material provides functionalities such as, but not limited to, wettability by liquids or selective separation of compounds in liquids. In some embodiments, the topmost material interacts with the gas, liquid, or solid material inside the pores, thereby providing functionalities such as, but not limited to, thermal management, wettability, modulation of electrochemical reactivity (e.g., modulation of corrosiveness or catalysis, or energy storage), or modulation of mechanical properties. In one embodiment, the topmost material is the surrounding environment such as air.

[0020] In some embodiments, the topmost material includes one or more organic functional groups such as an ammonium group (e.g., a quaternary ammonium group), an alkyl group, a perfluoroalkyl group, a fluoroalkyl group, and / or a phenyl group. In some embodiments, the topmost material includes a polymer. In some embodiments, the topmost material includes a ceramic (e.g., a ceramic different from the binderless porous ceramic material on the substrate). In some embodiments, the topmost material includes a quaternary ammonium group that imparts an antimicrobial function, an alkyl chain (e.g., an alkyl group) that imparts water repellency and / or hydrocarbon affinity, a perfluoroalkyl group that imparts water repellency and / or oil repellency functions, a polymer that imparts improved mechanical properties functions, and / or a ceramic that imparts improved cosmetic performance or functions, piezoelectric performance or functions, and / or rust prevention performance or functions.

[0021] In some embodiments, the gas, liquid, or solid substances inside the pores of the binderless porous ceramic material interact with the ceramic material, thereby providing one or more functionalities, such as, but not limited to, enhanced wettability, hardness, elasticity, mechanical, electrical, piezoelectric, optical, adhesive, or thermal properties, microbial affinity or resistance, modification of biofilm growth (e.g., resistance to or reduction of biofilm growth), catalytic activity, permeability, cosmetic appearance, liquid repellency, and / or corrosion resistance, as compared to a material that does not include the binderless porous ceramic material or a binderless porous ceramic material that does not have gas, liquid, or solid substances inside the cells.

[0022] In some embodiments, the gas, liquid, or solid substances inside the pores interact with moisture in the environment (e.g., an environment with high air humidity), thereby providing one or more functionalities, such as, but not limited to, a modulated evaporation rate, condensation or water crystallization, substrate corrosion protection, and / or enhanced wettability, as compared to a material that does not include the binderless porous ceramic material or a binderless porous ceramic material that does not have gas, liquid, or solid substances inside the cells.

[0023] In some embodiments, the binderless porous ceramic surface modification material has a fully or substantially filled porous structure, and the pores are fully or substantially filled with a second ceramic material (e.g., the same or a different ceramic material as the binderless porous ceramic material on the substrate) or a polymer. "Substantially" filled may mean filled to any of at least about 85%, about 87%, about 90%, about 95%, about 98%, or about 99%.

[0024] In some embodiments, the binderless porous ceramic surface modification material has a partially filled porous structure. For example, the pores may be partially filled with a second ceramic material (e.g., a ceramic material different from the binderless porous ceramic material) or a molecule having a head group and a terminal group. For example, head groups include silane groups, phosphonate groups, phosphonic acid groups, carboxylic acid groups, vinyl groups, alcohol groups, hydroxyl groups, thiolate groups, thiol groups, and / or ammonium groups (e.g., quaternary ammonium groups), and terminal groups include hydrocarbon groups, fluorocarbon groups, vinyl groups, phenyl groups, epoxide groups, acrylic groups, acrylate groups, hydroxyl groups, carboxylic acid groups, thiol groups, and / or quaternary ammonium groups.

[0025] In some embodiments, the binderless porous ceramic surface modification material provides an asymmetric pore structure with respect to the ceramic thickness from the substrate. For example, the pore size distribution may be characterized by the ratio of the first quartile pore size to the third quartile pore size determined by BJH gas adsorption and desorption, and may vary between about 0.2 and about 0.7 with respect to the thickness of the material.

[0026] In another aspect, a method for making the binderless porous ceramic surface modification material described herein is provided. In one embodiment, the method comprises (a) depositing a binderless porous material onto a substrate by, for example, dipping, spraying, roll coating, or otherwise contacting the substrate with an aqueous solution comprising one or more metal salts and a chelating or complexing agent, and controlling the pH and temperature to modulate the reaction rate to produce a ceramic material having a desired crystal structure, morphology, and / or surface porosity; (b) removing the substrate from the solution and heating the substrate to remove moisture; and (c) optionally, contacting (e.g., dipping) the substrate with a dilute solution of functional molecules in a solvent, wherein the functional molecules can chemically bond to the ceramic surface such that the pores are functionalized but remain open.

[0027] In some embodiments, the pores are partially filled with a first material (e.g., a first substance) and include (i) immersing, spraying, roll coating, or otherwise contacting a substrate having a binderless porous (e.g., surface-fixed) ceramic surface in a dilute solution of functional molecules that can chemically bond to the ceramic surface such that the pores are functionalized but remain open and / or (ii) in a solution comprising one or more metal salts and a chelating or complexing agent, and removing water, and optionally repeating (i) or (ii), and / or (i) and (ii) to build up multiple layers of various functional molecules and / or metal oxides within the pores.

[0028] In some embodiments, the pores are filled completely or substantially with a material (e.g., a substance) by: (i) immersing, spraying, roll coating, or otherwise contacting a substrate having a binderless porous (e.g., surface-fixed) ceramic surface, or a substrate having partially filled pores, in a solution of functional molecules capable of chemically bonding to the ceramic surface such that the pores are filled with the substance; and / or (ii) in a solution containing one or more metal salts (plural possible) and a chelating or complexing agent, and removing water to completely fill the pores.

[0029] In another aspect, the compositions described herein (binderless porous metal oxide surface modification materials on substrates) are suitable for use as heat transfer surfaces, fluid barriers, filters, fabrics or textiles, corrosion barriers, light absorbing surfaces, catalysts, or separation media.

Brief Description of the Drawings

[0030]

FIG. 1A

FIG. 1B

FIG. 1C

FIG. 2

FIG. 3A

FIG. 3B

FIG. 3C

FIG. 3D

FIG. 3E

FIG. 3F

FIG. 3G

FIG. 4A

FIG. 4B

FIG. 5A

FIG. 5B

Mode for Carrying Out the Invention

[0031] Detailed Description A porous metal oxide (e.g., metal oxide ceramic) composition is provided herein. The surface modification materials described herein impart desired properties such as durability, thinness, conformality, and / or the ability to be functionalized in various ways, which provide multifunctional benefits for a wide range of applications.

[0032] The porous metal oxide composition is deposited (e.g., coated) on a substrate as a surface modification material without using a binder. The binderless process for surface modification is advantageous because it results in an environmentally friendly process that does not use volatile organic compound (VOC) solvents, allows for operation at higher temperatures, and enables adjustment of the structure-property relationship from the substrate to the final surface.

[0033] A binderless surface modification material is provided, where the binder is not used in the synthesis of the material and the binder is not present in the final composition deposited on the substrate. The morphology of the surface modification materials described herein provides functional properties independent of the chemical nature of the composition. The geometric surface (e.g., pore structure) may impart a unique first property, the chemical composition may impart a second property, and the first and second properties are different and independent of each other. For example, in one non-limiting embodiment, the morphology of the composition may have the functional property of the ability to control the wetting of the surface, and the chemical composition may have different functional properties such as reduction of corrosion. The structure has measurable crystallinity and porosity and is distinguishable from other amorphous nanomaterials, which can be particularly useful and beneficial for specific affinity, catalysis, electromagnetic, and electrokinetic (pressure) applications.

[0034] The open pores may not be filled or may be partially or completely filled with one or more materials and / or substances that modify or enhance the functional properties of the surface modification material.

[0035] Additional layer(s) of material may further modify the functional properties. In some embodiments, the surface modification material is a capillary driven surface material, such as a very hydrophilic material. In other embodiments, the material is liquid repellent to some liquids (e.g., water), but capillary action with other liquids (e.g., isopropanol) is possible. In other embodiments, the material can separate multiple components via capillary action (e.g., a solvent or solute from a solution).

[0036] Definitions The numerical ranges provided herein include all of the numbers defining that range.

[0037] "A", "an", and "the" include plural references unless otherwise expressly indicated.

[0038] As used herein in the specification and claims, the phrase "and / or" shall be understood to mean "either or both" of the elements so conjoined, i.e., elements that coexist in some instances and separate in other instances. Unless otherwise expressly stated, other elements may exist, whether related or unrelated, to the specifically identified elements, whether or not specifically identified by the "and / or" clause. Thus, as a non-limiting example, a reference to "A and / or B" when used in conjunction with open-ended language such as "comprising" may refer to A without B in one embodiment (optionally including elements other than B); B without A in another embodiment (optionally including elements other than A); and both A and B in yet another embodiment (optionally including other elements).

[0039] "Bimodal" refers to a distribution that includes two different modes that appear as two distinct peaks.

[0040] "Binder" or "binding agent" is any material or substance that holds or draws other materials together, either mechanically, chemically, by adhesion or cohesion, to form a cohesive unity.

[0041] "Binderless" refers to the absence of a binder, particularly with respect to organic binders or resins (e.g., polymers, glues, adhesives, asphalt) or inorganic binders (e.g., lime, cement with glass, gypsum, etc.).

[0042] "Capillary rise" refers to the liquid flow driven by surface tension above a sample upon contact with the free surface of a liquid as a result of a porous substrate (capillary rise is parallel and in the opposite direction to the direction (vector) of the force due to gravity).

[0043] "Ceramic" refers to solid materials that include metals, non-metals, or inorganic compounds of ionic and covalent bonds.

[0044] "Contact angle" refers to the angle measured through a liquid between the surface and the gas-liquid interface at the contact surface.

[0045] "Conversion coating" refers to a surface layer where reactants chemically react with the surface being treated to convert the substrate into a different compound. This process is typically not addition or deposition.

[0046] "First quartile pore diameter" refers to the value of the pore diameter at which the cumulative pore surface area determined in the direction of increasing pore diameter corresponds to 25% of the total cumulative pore surface area determined by BJH gas adsorption / desorption measurements.

[0047] "Hydrophilic" refers to a surface that has a high affinity for water. The contact angle can be very low and / or unmeasurable.

[0048] "Layered double hydroxide" refers to the inclusive arrangement [AcB Z AcB] n(Here, c represents a layer of metal cations, A and B are layers of hydroxide anions, and Z is a layer of other anions and / or neutral molecules (such as water)), and refers to the classification of ionic solids characterized by a layered structure. Layered double hydroxides are also described in PCT Application No. PCT / US2017 / 052120, which is incorporated herein by reference.

[0049] "Average" refers to the arithmetic mean or average.

[0050] "Average pore diameter" is calculated using the measurement of the total surface area and total volume from the Barrett-Joyner-Halenda (BJH) adsorption / desorption method, assuming cylindrical pores and dividing four times the total pore volume by the total surface area (4V / A).

[0051] "Multimodal" refers to a distribution that includes more than one mode that appears as more than one distinct peak.

[0052] "Permeability" in a fluid mechanism is a measure of the ability of a porous material to allow a fluid to pass through it. The permeability of a medium is related to porosity but also to the shape of the pores in the medium and their connectivity.

[0053] "Pore size distribution" refers to the relative abundance, or range, or pore size of each pore size determined by mercury intrusion porosimetry (MIP) and the Washburn equation.

[0054] "Porosity" is a measure of the voids (i.e., "holes") in a material and is the fraction of the void volume to the total volume as a percentage between 0 and 1, or between 0% and 100%. The porosity disclosed herein was measured by mercury intrusion porosimetry.

[0055] "Porosity" refers to the spaces, holes, or voids within a solid material.

[0056] "Superhydrophobic" refers to a surface that is extremely difficult to wet. In the case of a superhydrophobic material, the contact angle of a water droplet on the superhydrophobic surface refers to a contact angle exceeding 150°. A highly hydrophobic contact angle exceeds 120°.

[0057] "Surface area per square meter of the projected substrate area" is usually measured in square meters and refers to the actual measured surface area that, if smooth at the atomic level (no surface roughness), is typically also in square meters and is divided by the surface area of the substrate.

[0058] "Synergy" or "synergistic" refers to the interaction or cooperation between two or more substances, materials, or agents that results in a combined effect that is greater (positive synergy) or smaller (negative synergy) than the sum of their individual effects.

[0059] "Thickness" refers to the length between the surface of the substrate and the topmost part of the surface modification (e.g., ceramic) material.

[0060] "Third quartile pore diameter" refers to the value of the pore diameter at which the cumulative pore surface area determined in the direction of increasing pore size corresponds to 75% of the total cumulative pore surface area determined by BJH gas adsorption / desorption measurements.

[0061] "Tortuosity" refers to the fraction of the shortest path Δl through the pore structure and the Euclidean distance Δx between the start and end points of that path.

[0062] "Adjustable" refers to the ability to change or modify the function, characteristics, or properties of a material.

[0063] Composition A porous ceramic (e.g., metal oxide and / or metal hydroxide) surface modification composition is provided herein. The composition is provided as a surface modification material on the surface of a substrate, e.g., a material fixed to the surface. In some embodiments, the porous ceramic material includes metal oxide and / or hydroxide ceramics, e.g., single metal or mixed metal oxide and / or hydroxide ceramics. In some embodiments, the porous ceramic material includes metal hydroxide and / or hydroxide ceramics, e.g., single metal or mixed metal oxide and / or hydroxide ceramics. In some embodiments, the porous ceramic material includes metal oxide and metal hydroxide ceramics, and the metal oxide and metal hydroxide include the same or different single metals or mixed metals. In some embodiments, the porous ceramic material includes metal oxide and / or metal hydroxide ceramics, and the substrate is hydrated by water or another compound, resulting in a change in surface energy and potentially a change in the ratio of the metal hydroxide composition of the ceramic to the metal oxide. In some embodiments, the porous 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%, about 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% of the metal hydroxide is a layered double hydroxide.

[0064] In some embodiments of the compositions described herein, "metal oxide" or "metal hydroxide" may each be in the form of a hydrate of the metal oxide or metal hydroxide, or a portion of the metal oxide or metal hydroxide may each be in the form of a hydrate of the metal oxide or metal hydroxide.

[0065] The mixed metal oxide or mixed metal hydroxide may include, for example, but not limited to, oxides or hydroxides of more than one metal such as iron, cobalt, nickel, copper, manganese, chromium, titanium, vanadium, zirconium, molybdenum, tantalum, zinc, lead, tin, tungsten, cerium, praseodymium, samarium, gadolinium, lanthanum, magnesium, aluminum, or calcium.

[0066] The surface modification material (binderless porous ceramic material) herein is deposited on a substrate without using a binder. In some embodiments, the surface modification material described herein is fixed on a substrate.

[0067] In some embodiments, the ceramic material has an open-cell porous structure, for example, the ability to cause capillary rise of a liquid having a low surface tension (e.g., less than about 25 mN / m, such as isopropanol) that is greater than about 5 mm above the surface relative to gravity in a closed container in 1 hour; about 0.1 m 2 / g to about 10,000 m 2 / g of surface area; an average pore diameter of about 10 nm to about 1000 nm or about 1 nm to about 1000 nm; a pore volume of about 0 to about 1 cc / g measured by mercury (Hg) intrusion porosimetry; and a tortuosity of about 1 to about 1000, defined by the length of the fluid path to the shortest distance, i.e., the "ratio of arc to chord"; and / or a permeability of about 1 to about 10,000 millidarcies.

[0068] The binderless ceramic surface modification material is porous and has a porosity of about 5% to about 95%. In some embodiments, the porosity is at least about 5%, about 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%, or any value greater than about 5%, about 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%.

[0069] The binderless porous surface modification material is porous and has a permeability of about 1 to 10,000 millidarcies. In some embodiments, the permeability can be at least about 1, 10, 100, 500, 1000, 5000, or 10,000 millidarcies. In some embodiments, the permeability is about 1 to about 100, about 50 to about 250, about 100 to about 500, about 250 to about 750, about 500 to about 1000, about 750 to about 2000, about 1000 to about 2500, about 2000 to about 5000, about 3000 to about 7500, about 5000 to about 10,000, about 1 to about 1000, about 1000 to about 5000, or about 5000 to about 10,000 millidarcies.

[0070] In some embodiments, the binderless porous ceramic material has a pore volume of about 100 mm 3 / g to about 7500 mm 3 / g as determined by mercury intrusion porosimetry. In some embodiments, the pore volume is 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 3Any of / g. In some embodiments, the void volume is about 100 to about 500, about 200 to about 1000, about 400 to about 800, about 500 to about 1000, about 800 to about 1500, about 1000 to about 2000, about 1500 to about 3000, about 2000 to about 5000, about 3000 to about 7500, about 250 to about 5000, about 350 to about 4000, about 400 to about 3000, about 250 to about 1000, about 250 to about 2500, about 2500 to about 5000, or about 500 to about 4000 mm 3 Any of / g.

[0071] The binderless porous ceramic surface modification material disclosed herein may be characterized by its interaction with liquid materials. As noted previously, the surface modification material may be characterized by the ability to cause capillary rise of liquids with low surface tension (e.g., less than about 25 mN / m, such as isopropanol) that are more than about 5 mm above the surface against gravity in a closed container in 1 hour. Non-limiting examples of other solvents having a surface tension of less than about 25 nM / m at 20 °C that may be used include 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, cyclohexane.Acetone (2-propanone), n-dodecane (DDEC), isovaleronitrile, tetrahydrofuran (THF), dichloromethane, n-tetradecane (TDEC), sym-tetrachloromethane, n-hexadecane (HDEC), chloroform, 1-octanol, butyronitrile, p-cymene, isopropylbenzene, toluene, dipropylene glycol monomethyl ether, 1-decanol, ethylene glycol monoethyl ether (ethyl cellosolve), 1,3,5-trimethylbenzene (mesitylene), benzene, m-xylene, n-propylbenzene, ethylbenzene, n-butylbenzene, 1-nitropropane, o-xylene, dodecylbenzene, diethyl fumarate, decalin, nitroethane, carbon disulfide, cyclopentanol, 1,4-dioxane, 1,2-dichloroethane, chlorobenzene, dipropylene glycol, cyclohexanol, hexachlorobutadiene, bromobenzene, pyrrole (PY), N,N-dimethylacetamide (DMA), nitromethane, diethyl phthalate, N,N-dimethylformamide (DMF), pyridine, methylnaphthalene, benzyl alcohol, ethyl anthranilate, iodobenzene, N-methyl-2-pyrrolidone, tricresyl phosphate (TCP), m-nitrotoluene, bromoform, o-nitrotoluene, phenyl isothiocyanate, a-chloronaphthalene, furfural (2-furaldehyde), quinoline, 1,5-pentanediol, aniline (AN), polyethylene glycol 200 (PEG), methyl anthranilate, nitrobenzene, a-bromonaphthalene (BN), diethylene glycol (DEG), 1,2,3-tribromopropane, benzyl benzoate (BNBZ), 1,3-diisopropane, 3-pyridylcarbinol (PYC), ethylene glycol (EG), 2-aminoethanol, sym-tetrabromoethane, diiodomethane (DI), thiodiglycol (2,2'-thiobisethanol) (TDG), formamide (FA), glycerol (GLY), water (WA), and other solvents having a surface tension of less than about 25 mN / m at 20 °C, including mercury, may be used.

[0072] The binderless porous ceramic surface modification material may have the ability to cause capillary rise of water at various temperatures. These materials may have the ability to separate miscible materials and binary azeotropic mixtures such as ethanol-water, ethyl acetate-ethanol or butanol-water, the ability to decompose ternary azeotropic mixtures, or the ability to remove amyl alcohol from mixtures containing ethanol and water.

[0073] The substrate on which the binderless porous ceramic surface modification material is deposited (e.g., fixed) may be composed of any material suitable for the structural or functional characteristics of the surface modification composition, or for the functional use. In some embodiments, the substrate is aluminum or contains aluminum (e.g., an aluminum alloy), a steel alloy, zinc, a zinc alloy, copper, a copper alloy, glass, a polymer, a copolymer or a plastic. In some embodiments, the substrate contains a metal, and the main metal in the ceramic material is different from the main metal in the substrate. The main metal is, for example, a metal that is at least about 50%, 60%, 70%, 80%, 90%, or 95% of the total metal in the substrate or ceramic material, as determined by X-ray diffraction based on atomic metal. Examples of the main metal of the substrate include, but are not limited to, aluminum, iron, copper, zinc, nickel, titanium and magnesium. Examples of the main metal of the ceramic include, but are not limited to, zinc, aluminum, manganese, magnesium, cerium, copper, gadolinium, tungsten, tin, lead, and cobalt.

[0074] In some embodiments, the substrate contains a metal that can react (e.g., dissolve) under reaction conditions that allow for local dissolution of the substrate metal, and the substrate metal is incorporated into the binderless porous ceramic material. For example, an aluminum substrate may provide aluminum (e.g., Al 2+ ) that is incorporated into the binderless porous ceramic material when the ceramic material is deposited on the substrate.

[0075] The binderless porous ceramic surface modification material contains one or more metal oxides and / or metal hydroxides (and / or their hydrates). Non-limiting examples of metals that can be included in the ceramic compositions disclosed herein 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, without limitation, two or more metal oxides (e.g., mixed metal oxides) including zinc, aluminum, manganese, magnesium, cerium, praseodymium, and cobalt.

[0076] In some embodiments, the binderless porous ceramic surface modification material is a mixture of oxides and / or hydroxides of zinc and aluminum; ZnO and Al 2 O 3and a mixture of zinc aluminate; a mixture of materials containing all phases containing Zn, Al, and oxygen; a mixture of oxides and / or hydroxides of manganese and magnesium; manganese oxide; aluminum oxide; oxides and / or hydroxides of mixed metal manganese; a mixture of oxides and / or hydroxides of magnesium and aluminum; a mixture of magnesium, cerium, and aluminum; a mixture of oxides and / or hydroxides of zinc, gadolinium, and aluminum; a mixture of oxides and / or hydroxides of cobalt and aluminum; a mixture of oxides and / or hydroxides of manganese and aluminum; a mixture of oxides and / or hydroxides of cerium and aluminum; a mixture of oxides and / or hydroxides of iron and aluminum; a mixture of oxides and / or hydroxides of tungsten and aluminum; a mixture of oxides of tin and aluminum; oxidized and / or hydroxylated tungsten; oxidized and / or hydroxylated magnesium; oxidized and / or hydroxylated manganese; oxidized and / or hydroxylated tin; or oxidized and / or hydroxylated zinc.

[0077] In some embodiments, at least one metal in the binderless porous ceramic material is in a + oxidized state.

[0078] In some embodiments, the binderless porous ceramic surface modification material contains 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.

[0079] In some embodiments, the binderless porous ceramic surface modification material is superhydrophobic. In some embodiments, the surface modification material is highly hydrophobic. In some embodiments, the surface modification material has one or more functional characteristics selected from wettability, hardness, elasticity, mechanical, electrical, piezoelectric, electromagnetic, optical, adhesion or thermal properties, microbial affinity or resistance, modification of biofilm growth, catalytic activity, permeability, cosmetic appearance, and corrosion resistance as compared to a substrate that does not include a ceramic material.

[0080] The pores of the binderless porous ceramic surface modification material may include open cells filled with one or more gases, may include cells that are partially filled (e.g., partially filled with one or more solid materials), or may include cells that are completely or substantially filled (e.g., completely or substantially filled with one or more liquid and / or solid materials). In some embodiments, the pores are partially, substantially, or completely filled with a gas, liquid, or solid substance, or a combination thereof.

[0081] In some embodiments, the binderless porous ceramic surface modification may be used to measure, characterize, modulate, or separate a solvent.

[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 over the partially filled pores. In some embodiments, the first material is a gas, solid, or liquid, or a combination of gases, liquids, and / or solid materials. In some embodiments, the second material is a gas, solid, and / or liquid material, or the environment (e.g., air). Examples include, and the functions imparted thereby include, changes in porosity, wicking, repellency, and / or wetting behavior; changes that modify electrical / insulating properties in a composite (including the porous material and the second material), changes to modify mechanical properties such as friction resistance, hardness, toughness, feel, modulus of elasticity, yield strength, yield stress, Young's modulus, surface (compressive or tensile) stress, and / or elasticity; changes to thermal properties such as thermal diffusivity, conductivity, coefficient of thermal expansion, thermal interface stress, and / or thermal anisotropy; modification of optical properties such as emissivity, color, reflectivity, and / or absorption coefficient; modification of chemical properties such as corrosion, catalysis, reactivity, inertness, compatibility, stain resistance, ion pump blocking, microbial resistance, and / or microbial compatibility; and / or substrates for biocatalysts.

[0083] In some embodiments, the first material interacts with the second material in a positive or negative synergistic manner to modify one or more functional characteristics of the ceramic material, including, but not limited to, wettability, hardness, elasticity, mechanical, electrical, piezoelectric, optical, adhesive, or thermal properties, microbial affinity or resistance, modification of biofilm growth, catalytic activity, permeability, cosmetic appearance, liquid repellency, and / or corrosion resistance.

[0084] Non-limiting materials that can be used to partially or completely fill the pores include molecules that can bind to the surface, such as molecules having a head group and a terminal group, where the head group is a silane, phosphonate, phosphonic acid, carboxylic acid, vinyl, hydroxide, thiol, or ammonium compound. The terminal group can include any functional group such as a hydrocarbon, fluorocarbon, vinyl group, phenyl group, and / or quaternary ammonium group. Other ceramic materials can also be partially or completely deposited in the pores. Polymers can also be partially or completely deposited in the pores. The ceramic material can include, for example, one or more oxides of zinc, aluminum, manganese, magnesium, cerium, gadolinium, and cobalt. Additionally, the ceramic material can include any solid material that can be added to a surface-modifying material, which includes, for example, inorganic compounds of metals, non-metals, or metalloids that are held primarily by ionic and covalent bonds, such as clay, silica, and glass. The polymers can include, for example, natural polymeric materials such as hemp, shellac, amber, wool, silk, natural rubber, cellulose, and other natural fibers, sugars, hemicelluloses- and halo-celluloses, polysaccharides, as well as bio-derived materials such as extracellular proteins, DNA, chitin. Synthetic polymers include, for example, polymers and copolymers containing polyethylene, polypropylene, polystyrene, polyvinyl chloride, synthetic rubber, phenol formaldehyde resin, (or bakelite), neoprene, nylon, polyacrylonitrile, PVB, silicone, polyisobutylene, PEEK, PMMA, and PTFE.

[0085] In some embodiments, the pores are partially filled with a thin composite polymer layer to produce a surface-modifying material having the porosity and functionality provided by the polymer. In other embodiments, the pores are completely filled with a thick polymer layer to produce a surface-modifying material having a thick polymer layer with 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-modifying material. In some embodiments, without limitation, a layer of material that adds one or more functional groups (plural possible) to the surface-modifying material, such as an ammonium group (e.g., a quaternary ammonium group), an alkyl group, a perfluoroalkyl group, a fluoroalkyl group, etc., is deposited. In some embodiments, a polymer or ceramic layer is deposited. In one embodiment, a ceramic topmost layer that is the same or different from the ceramic of the binderless porous ceramic material on the substrate is deposited. Examples of functional groups (plural possible) and the functions thereby imparted include a quaternary ammonium group for an antimicrobial function, an alkyl group for water repellency and hydrocarbon affinity, a perfluoroalkyl group for water and oil repellency functions, a polymer for mechanical property functions, other ceramics for aesthetic, optoelectronic, or anticorrosion functions.

[0087] In some embodiments, the pores are partially or completely filled with a gas, liquid, or solid substance, or a combination thereof, and the composition further includes a layer of topmost material on the ceramic material, and the topmost material imparts one or more functionalities, such as wettability by a liquid and / or selective separation of a compound in a liquid, without limitation. In certain embodiments, the topmost material is a material different from the substance by which the pores are partially, substantially, or completely filled, and it does not itself fill and penetrate the pores. In some embodiments, the topmost material interacts with the substance(s) in the pores. For example, the topmost material may interact with the substance(s) in the pores to provide one or more functionalities, such as heat management, modulation of electrochemical reactivity, and / or modulation of mechanical properties, without limitation. In certain embodiments, the topmost material is the surrounding environment in which it is in contact with the binderless porous ceramic material.

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

[0089] In some embodiments, the material in the pores interacts with the surface-modifying material. Examples of such materials and the functions imparted thereby include oxidation of the surface-modifying material by ambient liquid or vapor, condensation of trace components (e.g., environmental contaminants), capture or oxidation of harmful environmental materials such as CO or H 2 S from the ambient air, and / or recovery and retention of materials from an added sample (i.e., HPLC column coating). For example, this can be used to fabricate a reusable chemical sensor, e.g., the sample is cooled, condensation occurs, and the electrical properties are changed (in this case, the environmental condensate can be a second (or third) material in the pores, and then exposure to UV can be used to purify the material).

[0090] In some embodiments, moisture in the environment or added to the pores interacts with the material in the pores to modify the material in the pores or the surface-modifying material. Examples of such materials and the functions imparted thereby include changes in wetting behavior in optical properties, changes in oxidation state or reactivity, evaporation, matting, icing, or changes in the rate of condensation.

[0091] In some embodiments, the material in the pores may be designed to interact with the surface-modifying 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 top layer of the material is deposited on the surface-modifying material. Examples of such top layer materials include, but are not limited to, quaternary ammonium groups for antimicrobial function, alkyl chains for water repellency and hydrocarbon affinity, perfluoroalkyl groups for water and oil repellency, polymers for mechanical property functions, other ceramics for cosmetic, optoelectronic, or rust prevention functions. Examples of the functionality imparted by such top layer materials include changes in porosity, wicking, repellency, and / or wetting behavior; changes in electrical / insulating properties in composites (including porous materials and a second material), changes for modifying mechanical properties such as friction resistance, hardness, toughness, feel, modulus of elasticity, yield strength, yield stress, Young's modulus, surface (compressive or tensile) stress, tensile strength, compressive strength, and / or elasticity; changes in thermal properties such as thermal diffusivity, conductivity, coefficient of thermal expansion, thermal interface stress, and / or thermal anisotropy; changes for modifying optical properties such as emissivity, color, reflectivity, and / or absorption coefficient; modifications of chemical properties such as corrosion, catalysis, reactivity, inertness, compatibility, stain resistance, ion pump blocking, microbial resistance, and / or microbial compatibility; and / or substrates for biocatalysts, but are not limited thereto.

[0093] In some embodiments, the binderless porous ceramic surface-modifying material and the material within the pores interact in a synergistic manner, enhancing or reducing the functionality of at least one of the surface-modifying material and / or the material within the pores as compared to the functionality of only the surface-modifying material and / or the material within the pores. In some embodiments, two or more materials within the pores interact in a synergistic manner, enhancing or reducing the functionality of at least one of the materials as compared to the functionality of only at least one of the materials within the pores.

[0094] In some embodiments, the binderless porous ceramic surface-modifying material is resistant to degradation by ultraviolet light as compared to either a substrate material such as a polymer or a substrate material disclosed herein.

[0095] In some embodiments, the binderless porous ceramic surface modification material includes a thickness of from about 0.5 micrometers to about 20 micrometers. In some embodiments, the binderless porous ceramic material includes a thickness of from about 0.2 micrometers to about 25 micrometers. In some embodiments, the thickness is any of at least about 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 micrometers. In some embodiments, the thickness is any of from about 0.2 to about 0.5, from about 0.5 to about 1, from about 1 to about 5, from about 3 to about 7, from about 5 to about 10, from about 7 to about 15, from about 10 to about 15, from about 12 to about 18, from about 15 to about 20, from about 18 to about 25, from about 0.5 to about 15, from about 2 to about 10, from about 1 to about 10, from about 3 to about 13, from about 0.5 to about 15, from about 0.5 to about 5, from about 0.5 to about 10, or from about 5 to about 15 micrometers.

[0096] In some embodiments, the binderless porous ceramic surface modification material is characterized by a water contact angle of from about 0° to about 180°. In other embodiments, the water contact angle is less than about 30°. In other embodiments, the water contact angle is greater than about 150°.

[0097] In some embodiments, the binderless porous ceramic surface modification material is asymmetric, e.g., not spherical, cylindrical, cubic, or having a pore morphology that is not clearly defined relative to volume and has a relatively uniform surface area distribution that is not otherwise ordered, and is characterized by the ratio of the pore diameter at the first quartile to the pore diameter at the third quartile as a function of the thickness of the binderless porous ceramic surface modification. Specifically, the pore morphology is asymmetric with respect to the center as compared to spherical, cylindrical, or cubic structures. Non-limiting examples of asymmetric pores are presented in PCT Application No. PCT / US19 / 39743, which is hereby incorporated by reference in its entirety.

[0098] The asymmetric binderless porous ceramic surface modification material may be characterized by a broad pore size distribution that varies with distance from the substrate. Specifically, the pore structure at a given distance from the substrate can be locally characterized, for example, as described herein, and have different characterizations at different distances. The resulting asymmetry is determined in situ by a combination of processing conditions such as the substrate, ion mobility, temperature, pressure, and concentration. The degree of asymmetry can be further modified through bulk means such as mixing, stirring, modulation of the electric field, and tank filtration, or through surface directed processing means such as shear rate, flow impingement, or modification and modulation of surface charge. The asymmetry can be determined ex situ through various means such as etching, track etching, ion beam milling, oxidation, photocatalysis, or additional means. These approaches refer to materials having a narrower, or symmetric, pore structure with thickness and / or pore depth, such as zeolites, track-etched membranes, or expanded PTFE membranes.

[0099] In some embodiments, the binderless porous ceramic surface modification material is fluorine-free. In some of these embodiments, the non-fluorinated materials are surprisingly superior to their fluorinated equivalents when measured by wettability parameters, contact angle, and capillary rise.

[0100] In some embodiments, the binderless porous ceramic surface modification material has a surface area of about 1.1 m 2 ~ about 100 m 2 / m 2 including the surface area of the substrate projected area. In some embodiments, the binderless porous ceramic material has a surface area of about 10 m 2 ~ about 1500 m 2 / m 2It includes the surface area of the substrate projected area. In some embodiments, the surface area is at least about 10, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, or 1500 m 2 / m 2 of the substrate projected area. In some embodiments, the surface area is from about 10 to about 100, from about 50 to about 250, from about 150 to about 500, from about 250 to about 750, from about 500 to about 1000, from about 750 to about 1200, from about 1000 to about 1500, from about 70 to about 1000, from about 150 to about 800, from about 500 to about 900, or from about 500 to about 1000 m 2 / m 2 of the substrate projected area.

[0101] In some embodiments, the binderless porous ceramic material includes a surface area of about 15 m 2 to about 1500 m 2 / g of the ceramic material. In some embodiments, the surface area is at least about 15, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, or 1500 m 2 / g of the ceramic material. In some embodiments, the surface area is from about 15 to about 100, from about 50 to about 250, from about 150 to about 500, from about 250 to about 750, from about 500 to about 1000, from about 750 to about 1200, from about 1000 to about 1500, from about 50 to about 700, from about 75 to about 600, from about 150 to about 650, or from about 250 to about 700 m 2 / g of the ceramic material.

[0102] In some embodiments, the binderless porous ceramic surface modification material includes a mesoporous average pore diameter in the range of about 2 nm to about 50 nm. In other embodiments, the average pore diameter is in the range of about 50 nm to about 1000 nm. In some embodiments, the binderless porous ceramic material includes an average pore diameter of about 2 nm to about 20 nm. In some embodiments, the average pore diameter is at least any one of about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 nm. In some embodiments, the average pore diameter is any one of about 2 to about 5, about 4 to about 9, about 5 to about 10, about 7 to about 12, about 9 to about 15, about 12 to about 18, about 15 to about 20, about 4 to about 11, about 5 to about 9, about 4 to about 8, or about 7 to about 11 nm.

[0103] Method for producing a binderless porous metal oxide material The binderless ceramic porous surface modification material described in this specification may be produced by a method that includes immersing a clean substrate in an aqueous solution containing one or more metal salts (multiple possible) for a certain period of time to achieve a porous coating composition of a desired thickness on the substrate. The solution may also contain a chelating or complexing agent. The pH, temperature, and deposition time (e.g., about 5 minutes to about 300 minutes) are suitable for the desired thickness, morphology, and surface porosity of the produced surface modification material. The pH of the solution may be adjusted in the range of 1 to 12 to adjust the characteristics of the surface modification (e.g., the desired crystal structure and / or surface porosity) by adding acidic or basic materials. The metal salt(s) may include salts of, for example, magnesium, aluminum, cerium, iron, cobalt, gadolinium, manganese, tungsten, zinc, and / or tin. The salt may be, for example, a metal cation salt with anions of sulfuric acid, nitric acid, chloride, or acetic acid. The anion in the metal cation salt may be, for example, nitric acid, perchloric acid, tetrafluoroboric acid, or hexafluorophosphoric acid. The anion in the metal cation salt may be a halide. The anion in the metal cation salt may be, for example, chloride, bromide, or iodide. The anion in the metal cation salt may be a carboxylic acid. The anion in the metal cation salt may be, for example, acetic acid, propionic acid, butyric acid, or isobutyric acid. The anion in the metal cation salt may be a halogenated carboxylic acid. The anion in the metal cation salt may be, for example, trichloroacetic acid or trifluoroacetic acid. In other embodiments, a sodium cation salt is used together with a metal anion such as sodium stannate. In some embodiments, the concentration of the metal salt is about 1 mM to about 5 M in the aqueous solution. In some embodiments, chelating or complexing agents such as, for example, citric acid, urea, higher amines, diamines, triamines or tetraamines, thioglycerol, oleic acid, other fatty acids, polyols, Tween 80, other surfactants, or combinations thereof are included at a concentration of about 1 mM to about 5 M.In some embodiments, for example, reducing agents such as amines (e.g., diamines such as urea or ethylenediamine, triamines, tetraamines such as hexamethylenetetraamine) or alkali metal salts (e.g., bases), or metal hydroxides such as calcium hydroxide, are included. For example, the reducing agent may change the oxidation state of the metal from a higher oxidation state to a lower oxidation state (e.g., from Fe 3+ to Fe 2+ ). In some embodiments, the ratio of metal salt to reducing agent is from about 2:1 to about 0.5:1.

[0104] In some embodiments, the reaction conditions promote the local dissolution of the metal of the substrate and its incorporation into the binderless porous ceramic material. For example, the local dissolution of aluminum from an aluminum-containing substrate may contribute aluminum (e.g., Al 2+ ) to the binderless porous ceramic material deposited on the substrate.

[0105] In some embodiments, the substrate may be cleaned to remove loosely and lightly adhered deposited flakes by washing and rinsing, and to remove various metal purification solutions or purification solutions outlined for the particular substrate. Various processing conditions are acceptable for the good removal of loosely and lightly adhered deposited flakes.

[0106] In some embodiments, the substrate is treated with an alkali-based purification solution to saponify and remove grease from the substrate. One example is the use of caustic soda in an aqueous solution having a pH of approximately 11 or higher. In other embodiments, an alkaline purification solution having a pH higher than about 9 is used. Other embodiments may use alternative degreasing cleaning means such as steam or solvent-based methods. Various processing conditions are acceptable for the good removal of surface grease.

[0107] In some embodiments, the substrate is further prepared to homogenize the surface using known methods for surface treatment by alkaline etching of the substrate material. This process generates surface oxides and surface hydroxides, reaction products, and intermetallic compound materials, some of which are insoluble in the etching solution and must be removed from the substrate by rinsing, mechanical means, or processes known in the art as smut removal. Smut removal or deoxidizing solutions typically include acid solutions such as chromic acid, sulfuric acid, nitric acid, or phosphoric acid, or combinations thereof. Ferric sulfate solution may be used. The smut removal solution removes reaction products, oxides, hydroxides, and intermetallic compound materials by dissolution or mechanical removal (e.g., silicon-containing particles). Many proprietary surface preparation materials are available. Other surface preparation options such as acid etching, electropolishing, ultrasonic treatment, or preliminary methods of other surface finishing treatments that remove substrate oxides, hydroxides, reaction products, and intermetallic compounds can be used successfully. Various processing conditions are acceptable for good substrate surface preparation and smut removal.

[0108] In some embodiments, the substrate is processed using one or more processing steps in which the substrate reacts with a processing bath to form nanostructured material. The solutions described herein are water-based and contain metal salts in an aqueous solution at a concentration of about 1 mM to about 5 M and / or a chelating or complexing agent such as a polyol, polyether, urea, secondary and higher amines, diamines, triamines, or tetraamines at a concentration of about 1 mM to about 5 M. Processing conditions, excluding hydrostatic pressure for different tank depths, range from 65 to 200 kPa, and the temperature ranges from -20 °C to 190 °C depending on the concentration and composition over the liquid phase equilibrium for these solutions.

[0109] In some embodiments, the substrate is removed from the solution and heated at a temperature of about 100°C to about 1000°C for about 0 hours to about 5 hours. In some embodiments, the substrate is removed from the solution and heated at a temperature of about 100°C to about 1000°C for about 0 hours to about 5 hours to remove substantially all of the water from the substrate and the metal oxide surface modifier.

[0110] Optionally, the substrate is immersed in a dilute solution of functional molecules (e.g., less than about 2%, or about 0.001% to about 2%) by a suitable solvent that can chemically bond to the ceramic surface, and such pores are functionalized but remain open.

[0111] In some embodiments, the method includes partially filling the pores with one, two, or more materials (plural available). For example, the method includes (a) obtaining a substrate having a porous ceramic surface fixed to the surface, immersing the substrate in a dilute solution of functional molecules that can chemically bond to the ceramic surface such that the pores are functionalized but remain open, and / or (b) immersing the substrate in another solution to deposit additional ceramic in the pores and on the surface as described above, heating to remove water as before, and optionally repeating (a), or (b), or (a) and (b) to stack multiple layers of various functional molecules and / or metal oxides in the pores. Other non-limiting methods for introducing the first or second material, such as spraying, injection, dropwise addition, or vapor phase deposition, may be developed.

[0112] In some embodiments, the method includes completely filling the pores with one or more materials (plural available). For example, the method includes obtaining a substrate having a porous ceramic surface fixed to the surface, and immersing the substrate in a more concentrated solution (e.g., about 1% to about 2%) of a functional molecule that can chemically bond to the ceramic surface so that the pores are filled with the substance; and / or immersing the substrate in another metal salt solution as described above, and removing water as described above to completely fill the pores. Other non-limiting methods for introducing the pore filling material, such as spraying, injection, dropping, or vapor deposition, may be developed.

[0113] Use In various embodiments, the binderless porous ceramic surface modification materials described herein may be used in various applications, such as, but not limited to, heat transfer surfaces, fluid barriers, filters, fabrics or textiles, and use as separation media.

[0114] In some embodiments, the binderless porous ceramic surface modification material is a rust-preventive material.

[0115] In some embodiments, the binderless porous ceramic surface modification material is an antimicrobial material.

[0116] In some embodiments, the binderless porous ceramic surface modification material is a self-cleaning material. For example, the surface modification material provides a surface substantially free of water and lint, i.e., does not accumulate deposition flakes due to water accumulation and / or evaporation.

[0117] In some embodiments, the binderless porous ceramic surface modification material is "tunable" for a particular use. The material(s) used to fill the pores and / or layers on the surface material enhance the functionality of the surface modification material and / or provide additional functionality. Color, as well as other properties such as red, green, white, black, brown, etc., may also be tunable thanks to the material filling the pores and / or the layered material on the surface.

[0118] In other embodiments, the material can separate multiple components via capillary action (i.e., solvent or solute from a solution). The wicking action can rapidly draw the solvent from the surface while leaving the solute in the solution. The surface is adjustable to optimize the separation effect.

[0119] The following examples illustrate the invention and are not intended to be limiting.

[0120] Examples Example 1 A composition comprising a binderless porous ceramic material on a substrate was prepared according to the following general procedure. The substrate assembly was spot cleaned with isopropanol to remove any residual oil. Next, the parts were deposited in an etching bath of caustic alkali with a pH above 11 at a temperature of about 20 °C to about 60 °C for about 5 minutes to about 20 minutes. The assembly was then rinsed with distilled water or deionized water to remove any residual caustic material or loosely adhered material. Next, the parts were deposited in a non-coordinating oxidizing acid (such as nitric acid) solution with a pH below 2 and a temperature of about 20 °C to about 60 °C to remove smut and / or deoxygenate the substrate. Thereafter, the assembly was placed in a production bath heated to a reaction temperature of about 50 °C to 85 °C and containing 20 to 250 mM of metal nitrate (such as manganese(II) nitrate), sulfate (such as manganese(II) sulfate), or mixed metal nitrate (such as manganese(II) nitrate and zinc nitrate, typically in a ratio of about 50:1 to about 1:50), or sulfate, and a similar molar amount of diamine (such as urea or ethylenediamine), triamine, or tetraamine (such as hexamethylenetetraamine), typically in a ratio of about 2:1 to about 0.5:1. The assembly was held in the bath for a time in the range of about 5 minutes to about 3 hours. The assembly was removed, rinsed with distilled water or deionized water, placed in an oven, and dried and / or calcined at 50 to 600 °C for several minutes to several hours. This deposition step can be repeated, if desired, before or after another optional drying step following the drying step (with the same or different metal salts). In some embodiments, the metal in the deposited coating can be obtained from the substrate (such as aluminum in a deposit containing hydroxides / oxides of zinc and aluminum). After cooling, the parts were further processed and / or tested as described in the following examples.

[0121] Example 2 A clean 316 stainless steel tube was coated with a porous ceramic surface based on zinc oxide. The water contact angle was measured to be less than 5° by the droplet method. The tube was then placed in a cup containing about 1 centimeter of deionized water. After 30 seconds, the capillary rise was measured to be higher than 1 centimeter above the liquid level. A schematic diagram representing this method is shown in FIGS. 1A - 1C.

[0122] Example 3 A clean 3003 aluminum plate was coated with a porous ceramic surface based on a mixture of zinc oxide and aluminum oxide. The water contact angle was measured to be less than 5° by the droplet method. The plate was then placed in a cup containing about 1 centimeter of deionized water. After 30 seconds, the capillary rise was determined to be about 0.5 centimeter above the liquid level, and after 3 minutes it rose higher than 1 cm. The substrate was then dried and placed in a vial containing Vertrel SDG, a low surface tension cleaner containing a mixture of hydrofluorocarbon and 1,2 - dichloroethylene. After 300 seconds, the capillary rise of the Vertrel SDG liquid was determined to be about 1 centimeter.

[0123] Example 4 A clean 3003 aluminum plate was coated with a porous ceramic surface based on a mixture of zinc oxide and aluminum oxide. The water contact angle was measured to be less than 5°. The plate was then placed in a cup containing deionized water with a liquid height of about 1 centimeter. After 30 seconds, the capillary rise was determined to be higher than about 2.5 centimeters above the liquid level, after 3 minutes higher than 5 cm, and after 10 minutes higher than 8 cm. The substrate was then dried and placed in a vial containing about 1 cm of Vertrel SDG, a low surface tension cleaner containing a mixture of hydrofluorocarbon and 1,2 - dichloroethylene. After 600 seconds, the Vertrel SDG liquid rose higher than 1.4 centimeters from the liquid height.

[0124] Example 5 A clean aluminum substrate was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. The weight of the substrate was measured before and after coating application. The specific mass of the coating was determined to be approximately 3 g / m2 of substrate area. The cross-sectional scanning electron microscope image of the coating showed a film thickness of approximately 2.5 microns. Based on the known theoretical density of the solid material, the surface is only about 40% dense (60% porosity) of the solid material.

[0125] Example 6 A clean 4006 aluminum foil substrate was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. Nitrogen BET surface area measurements showed that the surface area was 1000 m 2 / m 2 of the substrate projected surface area, and the mass specific surface area of the ceramic material was shown to be approximately 250 m 2 / g. BJH measurements showed that the minimum pore size was approximately 0.6 nm in diameter. The minimum pore diameter is shown in Figure 5. Mercury porosimetry showed a bimodal pore size distribution concentrated at pore diameters of approximately 33 nm and approximately 4.6 nm. Mercury porosimetry showed that this material is 75% porous compared to the bulk oxide material.

[0126] Example 7 A clean 3003 aluminum plate was coated with a porous ceramic surface based on a mixture of magnesium oxide, cerium oxide and aluminum oxide. The water contact angle was measured to be less than 5°. The plate was then placed in a cup containing deionized water with a liquid height of approximately 1 centimeter. After 30 seconds, the capillary rise was determined to be 1 centimeter above the liquid level, and after 2 minutes, the water had risen more than 2 cm above the liquid level.

[0127] Example 8 A clean aluminum substrate was coated with a porous ceramic surface based on a mixture of zinc oxide, gadolinium oxide, and aluminum oxide. The water contact angle was measured to be less than 5°. The plate was then placed in a cup containing deionized water with a liquid height of about 1 centimeter. After 120 seconds, the water rose about 1 centimeter above the liquid level, and after 10 minutes, the water rose about 1.3 centimeters above the liquid level.

[0128] Example 9 A clean 3003 aluminum plate was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. The water contact angle was measured to be less than 5°. The plate was then placed in a cup containing 0.2% by volume of Water-Glo® 802-p fluorescent dye in deionized water with a liquid height of about 1 centimeter. After about 15 minutes, the water rose about 6 centimeters above the liquid level, but the dye only rose about 1 cm above the liquid level.

[0129] Example 10 A clean 3003 aluminum plate was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. The water contact angle was measured to be less than 5°. The plate was then placed in a cup containing 1 drop of green gel food coloring in 100 ml of deionized water. After 30 minutes, the water rose about 8 centimeters above the liquid level, but the green food coloring only rose less than 0.5 cm above the liquid level. A non-porous alumina plate was purchased as a control. It was purified by heating it to 500°C for 1 hour to remove any organic contaminants. Despite having a water contact angle of less than 5°, neither the water nor the food coloring rose higher than the liquid meniscus (about 2 mm above the liquid level) on the plate.

[0130] Example 11 The vapor degreased 5000 series alloy aluminum mesh was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. The water contact angle was measured to be less than 5°. The mesh was then placed in a cup containing deionized water with a liquid height of about 1 centimeter. After about 30 seconds, the capillary rise of water was measured to be 6 centimeters above the liquid level. After 90 seconds, the water rose 9 centimeters above the liquid level. The uncoated vapor degreased 5000 series alloy aluminum mesh was also immersed in the same deionized water bath as a control. There was no measurable liquid rise from the liquid level after 30 seconds, 2 minutes, and 80 minutes.

[0131] Example 12 A clean 3003 aluminum plate was coated with a porous ceramic surface based on a mixture of cobalt oxide and aluminum oxide. The water contact angle by the droplet method was measured to be less than 5°. The plate was then placed in a cup containing about 1 centimeter of deionized water. After 15 seconds, the capillary rise was measured to be about 0.6 centimeters above the liquid level. After 300 seconds, the capillary rise was measured to be higher than 1.5 cm.

[0132] Example 13 A clean 3003 aluminum plate was coated with a porous ceramic surface based on a mixture of manganese oxide and aluminum oxide. The water contact angle by the droplet method was measured to be less than 5°. The plate was then placed in a cup containing about 1 centimeter of deionized water. After 30 minutes, the capillary rise of water was measured to be 3 centimeters above the liquid level.

[0133] Example 14 A clean 3003 aluminum plate was coated with a porous ceramic surface based on cerium oxide. The water contact angle by the droplet method was measured to be less than 5°. The plate was then placed in a cup containing deionized water with a liquid height of about 1.5 cm. After 30 seconds, the water rose 3 cm above the liquid surface. As a control, a cerium-based conversion coating was applied to the 3003 aluminum plate by immersing the plate in a dilute solution of about 1% cerium nitrate at about 55 °C for 1 hour. This plate was then placed in a cup containing about 1 cm of deionized water. After 2 minutes, there was no measurable capillary rise from the liquid surface.

[0134] Example 15 An alumina plate with 99%+ theoretical density (porosity less than 1%) was heated to 400 °C for 1 hour to remove any surface organic contaminants. The water contact angle by the droplet method was measured to be less than 5°. The plate was then placed in a cup containing deionized water with a liquid height of about 1 cm. After 20 minutes, the water did not rise from the meniscus (less than 3 mm) above the liquid surface.

[0135] Example 16 A clean 3003 aluminum plate was coated with a porous ceramic surface based on magnesium oxide and aluminum oxide. The surface was then functionalized using a dilute solution (less than 0.5%) of hexadecylphosphonic acid in isopropanol at room temperature for 2 - 5 hours. The substrate was then removed and dried at 105 °C for about 1 hour. The water contact angle by the droplet method was measured to exceed 165°. The plate was then placed in a cup containing about 5 centimeters of deionized water. After 30 seconds, the substrate was completely encapsulated in bubbles and had no contact with the water at all. The substrate was taken out and dried completely, and placed in a vial containing about 1 cm of Vertrel SDG, a low surface tension cleaner containing a mixture of hydrofluorocarbon and 1,2 - dichloroethylene. After 30 seconds, the capillary rise of the Vertrel SDG liquid was measured to be 1 centimeter above the liquid height, and after 15 minutes, it was about 1.5 cm above the liquid height. The substrate was then dried and placed in a vial containing isopropanol with a liquid height of about 1 cm. After 30 seconds, the isopropanol rose about 0.8 centimeters from the liquid height, and after 20 minutes, it rose about 2 cm. The substrate was then dried and placed in a vial containing about 1 cm of mineral spirit. After 30 seconds, the mineral spirit rose 1 centimeter from the liquid surface, 3 cm after 10 minutes, and 7 cm after 90 minutes. The water contact angle by the droplet method was measured after deposition into the solvent, and it still exceeded 165°.

[0136] Example 17 A clean 4006 aluminum foil substrate was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. The surface was then functionalized using a dilute solution of hexadecylphosphonic acid in isopropanol in the same procedure as in Example 16. Nitrogen BET surface area measurements showed that the surface area was 300 - 500 m 2 / m 2 per substrate projected surface area, and the mass specific surface area of the ceramic material was 150 - 200 m 2It was shown to be / g. Mercury porosimetry showed a bimodal pore size distribution concentrated at pore diameters of approximately 5 nm and approximately 30 nm. BJH measurements indicate that the volume of pores smaller than 2.7 nm in diameter is virtually zero. This indicates that the minimum pore diameter is 2.7 nm in diameter. The pore size distributions determined by BJH adsorption measurements before and after partial filling surface functionalization are shown in FIGS. 5A - 5B. Additionally, mercury porosimetry shows that this material is 52% - 69% porous compared to bulk oxide materials.

[0137] Example 18 A clean 4006 aluminum foil substrate was coated with a porous ceramic surface based on a mixture of magnesium oxide, cerium oxide, and aluminum oxide. Krypton BET surface area measurements indicate that the surface area is approximately 200 m 2 / m 2 of the substrate projected surface area.

[0138] Example 19 The vapor degreasing 5000 series alloy aluminum mesh was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. The surface was then functionalized using a dilute solution of hexadecylphosphonic acid in isopropanol in the same procedure as in Example 16. The plate was then placed in a cup containing approximately 5 centimeters of deionized water. After 30 seconds, the substrate was completely encapsulated in bubbles and was not in contact with the water at all. The substrate was removed and dried completely, and placed in a vial containing approximately 1 cm of Vertrel SDG, a low surface tension cleaner containing a mixture of hydrofluorocarbon and 1,2-dichloroethylene. After 30 seconds, the capillary rise of the Vertrel SDG liquid was measured to be approximately 2.5 centimeters above the liquid height, and after 15 minutes, it was 8 cm above the liquid height. The substrate was then dried and then placed in a vial containing approximately 1 cm of isopropanol. After 30 seconds, the isopropanol rose 2 centimeters above the liquid height, and after 15 minutes, it rose 6.5 cm. The substrate was then dried and placed in a vial containing approximately 1 cm of mineral spirits. After 30 seconds, the mineral spirits rose 2.5 centimeters above the liquid level, and after 15 minutes, it rose 7 cm.

[0139] Example 20 A clean 3003 aluminum plate was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. The surface was then functionalized using a solution of 1 - 5% perfluorodecyltriethoxysilane, 1 - 3% acetic acid, and 2 - 5% water balanced with ethanol. The surface was then removed from the functionalizing solution, rinsed with ethanol, and dried at 105 °C for 1 hour. The water contact angle by the drop method was measured to exceed 160°. The plate was then placed in a cup containing approximately 5 centimeters of deionized water. After 30 seconds, the substrate was completely encapsulated in bubbles. The substrate was then placed in a vial containing approximately 1 cm of isopropanol. After 300 seconds, the isopropanol rose approximately 1 centimeter above the liquid height.

[0140] Example 21 A clean 304 stainless steel plate was coated with a zinc oxide porous ceramic surface. The surface was then functionalized by immersing the surface in a dilute solution of stearic acid in mineral spirits (from about 0.1% to about 1%) at room temperature for about 15 minutes to about 2 hours. The surface was then removed and dried at room temperature. The contact angle was measured to exceed 150°. The plate was then placed in a cup containing about 5 centimeters of deionized water. After 15 seconds, the substrate was completely encapsulated in bubbles. The substrate was removed and then placed in a vial containing isopropanol with a liquid height of about 1 cm. After 30 seconds, the isopropanol rose more than 1 centimeter above the liquid height.

[0141] Example 22 A clean slide glass was coated with a porous zinc oxide ceramic surface. In this particular example, any steps involving caustic etching baths and nitric acid baths were omitted. The surface was then functionalized using a dilute solution of hexadecylphosphonic acid in the same procedure as in Example 16. The water contact angle by the droplet method was measured to exceed 160°. The slide was then placed in a cup containing about 1 centimeter of deionized water. After 30 seconds, the substrate was completely encapsulated in bubbles. The substrate was removed and placed in a vial containing about 1 cm of isopropanol. After 30 seconds, the isopropanol liquid rose 1 centimeter above the liquid height.

[0142] Example 23 A clean slide glass was coated with a porous zinc oxide ceramic surface. In this particular example, any steps involving caustic substance etching baths and nitric acid baths were omitted. The water contact angle by the droplet method was measured to be less than 5°. The plate was then placed in a cup containing about 0.5 centimeters of deionized water. After about 10 seconds, the capillary rise of water was measured to be 2 centimeters above the liquid height, which is the full length of the substrate.

[0143] Example 24 A polypropylene sheet was coated on the surface of a porous magnesium hydroxide ceramic. In this particular example, the steps involving etching baths and nitric acid baths of caustic substances were omitted. The water contact angle by the droplet method was measured to be less than 5°. The plate was then placed in a cup containing about 1 centimeter of deionized water. After about 30 seconds, the water rose more than 1 centimeter above the liquid height.

[0144] Example 25 A clean 3003 aluminum plate was coated on the surface of a porous ceramic based on a mixture of magnesium oxide and aluminum oxide. The water contact angle by the droplet method was measured to be less than 5°. The plate was then deposited in a dilute solution (about 0.1%) of polychloroprene in t-butyl acetate at room temperature for about 1 - 2 hours, taken out, and dried overnight at room temperature. The water contact angle by the droplet method was then measured to exceed 150°. The plate was then placed in a cup containing about 1 centimeter of deionized water. After 30 seconds, the substrate was completely encapsulated in bubbles. The substrate was then placed in a vial containing about 1 cm of isopropanol. After about 300 seconds, the isopropanol rose more than 1.2 centimeters above the liquid height.

[0145] Example 26 A clean 3003 aluminum plate was coated on the surface of a porous ceramic based on a mixture of magnesium oxide and aluminum oxide. The water contact angle by the droplet method was measured to be less than 5°. The plate was then deposited in a concentrated solution (about 2%) of polychloroprene in t-butyl acetate at room temperature for about 1 - 2 hours, taken out, and dried overnight at room temperature. The water contact angle by the droplet method was then measured to be about 85°. The plate was then placed in a cup containing about 1 centimeter of deionized water. After 30 seconds, there was no capillary rise. The substrate was then placed in a vial containing about 1 cm of isopropanol. After about 300 seconds, there was no capillary rise.

[0146] Example 27 Similar to the procedure of Example 20, a rough superhydrophobic surface made of zinc oxide on a 3003 aluminum substrate and functionalized with a monolayer of perfluorodecyltriethoxysilane was measured to have a contact angle exceeding 168°. When this substrate was immersed in water, it was encapsulated in bubbles. The substrate was then immersed in a solution having Vertrel SDG, isopropanol, and mineral spirits with a liquid height of about 1 cm. None of these solutions had a measurable capillary rise from the liquid height on this substrate after 10 minutes. This indicates that roughness or contact angle alone is not sufficient to enable capillary rise.

[0147] Example 28 A clean 3003 aluminum plate was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. The water contact angle by the droplet method was measured to be less than 5°. Then, one-fourth from the bottom of the plate was deposited in a dilute solution (about 0.1%) of polychloroprene in t-butyl acetate and sealed in a vial. After 1 minute, the liquid was sucked up over the entire length of the surface (about 3 cm). The substrate was left in the solution for about 30 minutes, taken out from the vial, and then air-dried. The water contact angle by the droplet method was then measured to exceed 150° in the part deposited in the liquid and less than 5° in the part where the solution was sucked up.

[0148] Example 29 A clean 3003 aluminum plate was coated with a porous ceramic surface based on a mixture of cerium oxide and aluminum oxide. The contact angle was measured to be less than 5°. The plate was then placed in a cup containing deionized water with a liquid height of about 1.5 centimeters. After 30 seconds, the water rose 3 centimeters above the liquid level. A clean 3003 aluminum plate and this sample coated with a mixture of cerium oxide and aluminum oxide were characterized for corrosion resistance using electrochemical impedance spectroscopy. The ceramic-modified sample was shown to have a corrosion resistance 500 times higher than the exposed 3003 aluminum plate.

[0149] Example 30 A clean 3003 aluminum plate was coated with a porous ceramic surface based on a mixture of tungsten oxide and aluminum oxide. The water contact angle by the droplet method was measured to be less than 5°. The plate was then placed in a cup containing deionized water with a liquid height of about 1 centimeter. After 30 seconds, the capillary rise of water was measured to be 3 centimeters above the liquid surface.

[0150] Example 31 A clean 3003 aluminum plate was coated with a porous ceramic surface based on a mixture of tin oxide and aluminum oxide. The water contact angle by the droplet method was measured to be less than 5°. The plate was then placed in a cup containing about 1 centimeter of deionized water. After 30 minutes, the water rose 3 centimeters from the liquid surface.

[0151] Example 32 A clean 4006 aluminum foil substrate was coated with a porous ceramic surface based on a mixture of magnesium hydroxide and aluminum hydroxide. Krypton BET surface area measurements indicate that the surface area is about 180 m 2 / m 2 of the substrate projected surface area, and that the mass specific surface area of the ceramic material is 67 m 2 / g. Mercury porosimetry indicates that the ceramic material contains a pore volume of 293 mm 3 / g. Mercury porosimetry indicates that this material is 51% porous compared to the bulk oxide material.

[0152] Example 33 A clean 4006 aluminum foil substrate was coated with a porous ceramic surface based on a mixture of manganese oxide and aluminum oxide. Nitrogen BET surface area measurements indicate that the surface area is about 180 m 2 / m 2 of the substrate projected surface area, and that the mass specific surface area of the ceramic material is 110 m 2It was shown to be / g. Mercury porosimetry showed a bimodal pore size distribution concentrated at pore diameters of 5.3 nm and 28 nm. Mercury porosimetry showed that the ceramic material contains a pore volume of 670 mm 3 / g. Mercury porosimetry showed that this material is 77% porous compared to the bulk oxide material.

[0153] Example 34 A clean 4006 aluminum foil substrate was coated with a porous ceramic surface based on a mixture of zinc oxide and aluminum oxide. Nitrogen BET surface area measurements showed that the surface area is approximately 160 m 2 / m 2 of the substrate projected surface area, and that the mass specific surface area of the ceramic material is 95 m 2 / g. Mercury porosimetry showed a bimodal pore size distribution concentrated at pore diameters of approximately 29 nm and 4.8 nm. Mercury porosimetry showed that this material is 86% porous compared to the bulk oxide material.

[0154] Example 35 A clean 4006 aluminum foil substrate was coated with a porous ceramic surface based on a mixture of manganese hydroxide and aluminum hydroxide without a heat treatment step. Nitrogen BET surface area measurements showed that the surface area is approximately 110 m 2 / m 2 of the substrate projected surface area, and that the mass specific surface area of the ceramic material is 53 m 2 / g. Mercury porosimetry indicates a multimodal pore size distribution concentrated in pores of 27 nm, 9.4 nm and 5.3 nm. Mercury porosimetry showed that the ceramic material contains a pore volume of 540 mm 3 / g. Mercury porosimetry showed that the ceramic material is 72% porous compared to the bulk oxide material.

[0155] Example 36 A clean 4006 aluminum foil substrate was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. Nitrogen BET surface area measurements indicate that the surface area is 250 - 350 m 2 / m 2 of the substrate projected surface area, and that the mass specific surface area of the ceramic material is 183 m 2 / g. Mercury porosimetry indicated a bimodal pore size distribution concentrated at pore diameters of approximately 28 nm and approximately 5 nm. Mercury porosimetry indicated that the ceramic material contains a pore volume of 951 mm 3 / g. Mercury porosimetry indicated that the ceramic material is 77% porous compared to the bulk oxide material.

[0156] Example 37 A clean 4006 aluminum foil substrate was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. Nitrogen BET surface area measurements indicate that the surface area is approximately 1000 m 2 / m 2 of the substrate projected surface area, and that the mass specific surface area of the ceramic material is approximately 240 m 2 / g. Mercury porosimetry indicates that the intrusion volume of pores between 0.1 micron and 10 microns in diameter is 2.35 mL / m 2 of the substrate. Separately, a second clean 4006 aluminum foil substrate was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide using the same processing conditions as the first sample. The surface pore structure of the second sample was then substantially filled using a latex spray paint that is applied according to the manufacturer's instructions. Nitrogen BET surface area measurements indicate that the surface area of the second sample is approximately 3 m 2 / m 2 of the substrate projected surface area, and that the mass specific surface area of the ceramic material is less than 0.1 m 2 / g. The mercury porosimetry of the second sample indicates that the intrusion volume of pores between 0.1 micron and 10 microns in diameter is 0.29 mL / m 2It was shown to be a substrate. This demonstrated that 87% of the pore volume in the range of 0.1 micron to 10 microns was filled using spray paint.

[0157] Example 38 A clean 4006 aluminum foil substrate without coating material was analyzed. Krypton BET surface area measurement showed that the surface area was about 0.036 m 2 / g. Mercury porosimetry showed that this material had less than 1% porosity.

[0158] Example 39 A clean 4006 aluminum foil substrate was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. The ratio of the first quartile pore diameter to the third quartile pore diameter determined by BJH gas adsorption was found to be 0.63. Mercury porosimetry showed that the ceramic material contained a void volume of 3091 mm 3 / g. Mercury porosimetry showed that the ceramic material was 92% porous compared to the bulk oxide material. Based on the measured void volume and porosity, the thickness of the ceramic material was calculated to be 0.68 microns thick. Separately, different clean 4006 aluminum foil substrates were coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. The ratio of the first quartile pore diameter to the third quartile pore diameter determined by BJH gas adsorption was found to be 0.45. Mercury porosimetry showed that the ceramic material contained a void volume of 2264 mm 3 / g. Mercury porosimetry showed that the ceramic material was 89% porous compared to the bulk oxide material. Based on the measured void volume and porosity, the thickness of the ceramic material was calculated to be 0.94 microns thick. Separately, different clean 4006 aluminum foil substrates were coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. The ratio of the first quartile pore diameter to the third quartile pore diameter determined by BJH gas adsorption was found to be 0.41. Mercury porosimetry showed that the ceramic material was 1660 mm3 showed the inclusion of a void volume of / g. Mercury porosimetry showed that the ceramic material was 86% porous compared to the bulk oxide material. Based on the measured void volume and porosity, the thickness of the ceramic material was calculated to be 1.15 microns thick. Separately, different clean 4006 aluminum foil substrates were coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. The ratio of the first quartile pore diameter to the third quartile pore diameter, as determined by BJH gas adsorption, was found to be 0.32. Mercury porosimetry showed that the ceramic material had a void volume of 1455 mm 3 / g. Mercury porosimetry showed that the ceramic material was 84% porous compared to the bulk oxide material. Based on the measured void volume and porosity, the thickness of the ceramic material was calculated to be 2.05 microns thick. These substrates were modified with the same ceramic surface, and the only difference was the thickness. These trends are represented in FIGS. 4A - 4B.

[0159] Example 40 A clean 4006 aluminum foil substrate was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. Nitrogen BET surface area measurements showed that the surface area was approximately 70 m 2 / m 2 of the substrate projected surface area, and that the mass - specific surface area of the ceramic material was 350 m 2 / g. Mercury porosimetry showed that the ceramic material had a void volume of 3091 mm 3 / g. Mercury porosimetry showed that the ceramic material was 92% porous compared to the bulk oxide material.

[0160] Example 41 A clean 4006 aluminum foil substrate was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. Nitrogen BET surface area measurements showed that the surface area was approximately 170 m 2 / m 2 of the substrate projected surface area, and that the mass - specific surface area of the ceramic material was approximately 700 m 2It indicates being / g. Mercury porosimetry showed that the ceramic material contains a pore volume of 3067 mm 3 / g. Mercury porosimetry showed that the ceramic material is 92% porous compared to the bulk oxide material.

[0161] Example 42 A clean 4006 aluminum foil substrate was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. Nitrogen BET surface area measurements showed that the surface area is about 85 m 2 / m 2 of the substrate projected surface area, and the mass specific surface area of the ceramic material is about 370 m 2 / g. Mercury porosimetry showed that the ceramic material contains a pore volume of about 4900 mm 3 / g. Mercury porosimetry showed that the ceramic material is 95% porous compared to the bulk oxide material.

[0162] Example 43 A clean 3003 aluminum plate was coated with a porous ceramic surface based on a mixture of zinc hydroxide and aluminum hydroxide. The plate was then placed in a sealed vial containing 1 cm of isopropanol. After 30 seconds, the isopropanol rose approximately 0.5 cm from the liquidus. After 5 minutes, the isopropanol rose 1 cm from the liquidus. The plate was then removed and dried. The surface was then functionalized using a dilute solution of hexadecylphosphonic acid in isopropanol using the same procedure as in Example 16. The plate was then placed in a sealed vial containing 1 cm of isopropanol. After 30 seconds, the isopropanol rose approximately 0.6 cm from the liquidus. After 5 minutes, the isopropanol rose 1.4 cm from the liquidus. A schematic diagram representing this method is shown in FIGS. 1A - 1C.

[0163] Example 44 A clean 3003 aluminum plate was coated with a porous ceramic surface based on a mixture of magnesium hydroxide and aluminum hydroxide. The plate was then placed in a sealed vial containing 1 cm of isopropanol. After 30 seconds, the isopropanol rose approximately 1.4 cm above the liquidus. After 5 minutes, the isopropanol rose 3.5 cm above the liquidus. The plate was then removed and dried. The surface was then functionalized using a dilute solution of hexadecylphosphonic acid in isopropanol using the same procedure as in Example 16. The plate was then placed in a sealed vial containing 1 cm of isopropanol. After 30 seconds, the isopropanol rose approximately 1.5 cm above the liquidus. After 5 minutes, the isopropanol rose 3.6 cm above the liquidus. A schematic diagram representing this method is shown in FIGS. 1A-1C.

[0164] Example 45 A clean 3003 aluminum plate was coated with a porous ceramic surface based on a mixture of manganese hydroxide and aluminum hydroxide. The surface was then functionalized using a dilute solution of hexadecylphosphonic acid in isopropanol using the same procedure as in Example 16. The plate was then placed in a sealed vial containing 1 cm of isopropanol. After 30 seconds, the isopropanol rose approximately 0.6 cm above the liquidus. After 5 minutes, the isopropanol rose 1.7 cm above the liquidus. A schematic diagram representing this method is shown in FIGS. 1A-1C.

[0165] Example 46 A clean 3003 aluminum plate was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. The coating process was the same as the process used in Example 36, the only difference being the aluminum alloy. The water contact angle was measured to be less than 5° via the droplet method. The plate was then placed in a cup containing approximately 4 centimeters of deionized water. After 30 seconds, the capillary rise was determined to be approximately 0.8 cm above the liquid level, and it rose 2 cm after 5 minutes. A schematic diagram representing this method is shown in FIGS. 1A-1C.

[0166] Example 47 A clean substrate containing 99.999% aluminum was coated with a porous ceramic surface based on zinc oxide and aluminum oxide. The sample was analyzed using grazing-incidence X-rays with CuK-alpha radiation. The measurement was a 2-theta scan with a scan range of 15 to 90° and an incident angle of 1°. The obtained X-ray diffraction peaks verified that the surface material was crystalline and mainly contained zinc oxide. The obtained spectrum is shown in Fig. 3A.

[0167] Example 48 A clean substrate containing 99.999% aluminum was coated with a porous ceramic surface based on zinc hydroxide and aluminum hydroxide. The sample was analyzed using grazing-incidence X-rays with CuK-alpha radiation. The measurement was a 2-theta scan with a scan range of 15 to 90° and an incident angle of 1°. The obtained X-ray diffraction peaks verified that the surface material was crystalline and mainly contained zinc-aluminum layered double hydroxide. The obtained spectrum is shown in Fig. 3B.

[0168] Example 49 A clean substrate containing 99.999% aluminum was coated with a porous ceramic surface based on manganese oxide. The sample was analyzed using grazing-incidence X-rays with CuK-alpha radiation. The measurement was a 2-theta scan with a scan range of 15 to 90° and an incident angle of 1°. The obtained X-ray diffraction peaks verified that the surface material was crystalline and mainly contained manganese oxide. The obtained spectrum is shown in Fig. 3C.

[0169] Example 50 A clean substrate containing 99.999% aluminum was coated with a porous ceramic surface based on manganese hydroxide and aluminum hydroxide. The sample was analyzed using grazing-incidence X-rays with CuK-alpha radiation. The measurement was a 2-theta scan with a scan range of 15 to 90° and an incident angle of 1°. The obtained X-ray diffraction peaks verified that the surface material was crystalline and mainly contained mixed manganese-aluminum hydroxide. The obtained spectrum is shown in Fig. 3D.

[0170] Example 51 A clean substrate containing 99.999% aluminum was coated with a porous ceramic surface based on magnesium oxide. The sample was analyzed using grazing-incidence X-rays with CuK-alpha radiation. The measurement was a two-theta scan with a scan range of 15 - 90° and an incident angle of 1°. The obtained X-ray diffraction peaks verified that the surface material was crystalline and mainly contained magnesium oxide. The obtained spectrum is shown in Figure 3E.

[0171] Example 52 A clean substrate containing 99.999% aluminum was coated with a porous ceramic surface based on magnesium hydroxide and aluminum hydroxide. The sample was analyzed using grazing-incidence X-rays with CuK-alpha radiation. The measurement was a two-theta scan with a scan range of 15 - 90° and an incident angle of 1°. The obtained X-ray diffraction peaks verified that the surface material was composed of magnesium-aluminum layered double hydroxide. The obtained spectrum is shown in Figure 3F.

[0172] Example 53 A clean substrate containing 99.999% aluminum that was not coated with any additional material. The sample was analyzed using grazing-incidence X-rays with CuK-alpha radiation. The measurement was a two-theta scan with a scan range of 15 - 90° and an incident angle of 1°. The obtained X-ray diffraction peaks verified that the surface was composed of pure aluminum. The obtained spectrum is shown in Figure 3G.

[0173] Example 54 A clean 4006 aluminum foil substrate was coated with a porous ceramic surface based on a mixture of magnesium oxide and aluminum oxide. Nitrogen BET surface area measurements showed that the surface area was 180 m 2 / m 2 per projected surface area of the substrate, and the mass specific surface area of the ceramic material was 300 m 2It indicates being / g. Mercury porosimetry shows a bimodal pore size distribution concentrated at pore sizes of about 12.7 and about 5 nm. The pore size distribution is shown in Figure 2. Mercury porosimetry shows that the ceramic material has a void volume of 1450 mm 3 / g. Mercury porosimetry shows that the ceramic material is 84% porous compared to the bulk oxide material.

[0174] Although foreign inventions are described in some detail using illustrations and examples for clarity of understanding, it will be apparent to those skilled in the art that certain changes and improvements can be made without departing from the spirit and scope of the present invention. Therefore, this specification should not be construed as limiting the scope of the invention recited in the appended claims.

[0175] All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety for all purposes to the same extent as if each individual publication, patent, or patent application were specifically and individually indicated to be incorporated by reference.

Claims

1. A composition comprising a binderless porous ceramic material on a substrate.

2. The composition of claim 1 , wherein the porous ceramic material is predominantly crystalline.

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

4. The composition of claim 3 , wherein the ceramic material comprises a metal hydroxide, and at least a portion of the metal hydroxide comprises a layered double hydroxide.

5. The ceramic material has a projected area m ２ Approximately 10m per ２ ~1500m ２ The composition of any one of claims 1 to 4, comprising a surface area of

6. The ceramic material has a viscosity of about 15 m per gram of ceramic material. ２ ~1500m ２ The composition of any one of claims 1 to 4, comprising a surface area of

7. The composition of any of claims 1 to 4, wherein the ceramic material comprises an average pore size of about 2 nm to about 20 nm.

8. The composition of claims 1 to 4, wherein the pore size distribution is multimodal.

9. The composition of any of claims 1 to 4, wherein the ceramic material comprises a thickness of up to about 50 micrometers.

10. The composition of claim 9 , wherein the ceramic material comprises a thickness of up to about 25 micrometers.

11. The composition of any of claims 1-4 or 9-10, wherein the ceramic material comprises a thickness of about 0.2 micrometers to about 25 micrometers.

12. The composition of any of claims 1 to 4, wherein the ceramic material comprises a porosity greater than about 10%.

13. The composition of claim 12, wherein the ceramic material comprises about 30% to about 95% porosity.

14. The ceramic material has a thickness of about 100 mm as determined by mercury intrusion porosimetry. ３ / g ~ approx. 7500mm ３ The composition of any one of claims 1 to 4, comprising a void volume of about 1 / g.

15. The composition of any of claims 1 to 4, wherein the substrate comprises aluminum, an aluminum alloy, a steel alloy, an iron alloy, zinc, a zinc alloy, copper, a copper alloy, nickel, a nickel alloy, titanium, a titanium alloy, glass, a polymer, a copolymer, or a plastic.

16. The composition of any of claims 1 to 4, wherein the ceramic material comprises a transition metal, a group 2 element, a rare earth element, aluminum, tin, or lead.

17. 17. The composition of claim 16, wherein the ceramic material comprises one or more of zinc, aluminum, manganese, magnesium, cerium, copper, gadolinium, tungsten, tin, zinc, lead, and cobalt.

18. 4. The composition of any of claims 1 to 3, wherein the ceramic material comprises a mixture of oxides and / or hydroxides of zinc and aluminum; a mixture of oxides and / or hydroxides of manganese and magnesium; manganese oxide and / or hydroxide; aluminum oxide and / or hydroxide; mixed metal manganese oxide and / or hydroxide; a mixture of oxides and / or hydroxides of magnesium and aluminum; magnesium oxide and / or hydroxide; a mixture of oxides and / or hydroxides of magnesium, cerium, and aluminum; a mixture of oxides and / or hydroxides of zinc, praseodymium, and aluminum; a mixture of oxides and / or hydroxides of cobalt and aluminum; a mixture of oxides and / or hydroxides of manganese and aluminum; a mixture of oxides and / or hydroxides of cerium and aluminum; a mixture of oxides and / or hydroxides of copper and aluminum; a mixture of oxides and / or hydroxides of zinc and aluminum; a mixture of zinc aluminates; a mixture containing one or more phases containing Zn, Al and oxygen; zinc oxide and / or hydroxide; or a hydrate of any of the above compounds or mixtures.

19. 20. The composition of claim 18, wherein the substrate comprises aluminum, iron, nickel, titanium, or copper.

20. 20. The composition of any of claims 1 to 19, wherein the ceramic material provides one or more functional characteristics selected from enhanced wettability, hardness, elasticity, mechanical, electrical, piezoelectric, optical, adhesive, or thermal properties, microbial affinity or resistance, altered biofilm growth, catalytic activity, permeability, cosmetic appearance, liquid repellency, and corrosion resistance compared to a substrate not comprising the ceramic material.

21. 21. The composition of claim 20, wherein the ceramic material provides wettability, corrosion resistance, adhesion, and / or optical properties.

22. The composition of any one of claims 1 to 4, wherein the ceramic material comprises an open cell porous structure.

23. 23. The composition of claim 22, wherein the open cell porous structure is characterized by a capillary rise of greater than about 5 mm above a vertical surface against a gravitational force of about 1 G in an atmosphere saturated with a solvent comprising a surface tension of less than about 25 mN / m at a temperature of about 15° C. to about 25° C. for 1 hour.

24. The composition of any of claims 1 to 4, wherein the ceramic material comprises pores that are partially, substantially, or completely filled with a gas, liquid, or solid substance, or a combination thereof.

25. 25. The composition of claim 24, wherein the ceramic material comprises pores that are less than 50% filled with the liquid and / or pores that contain liquid that is not stably contained or retained within the pores.

26. 5. The composition of claim 1, wherein the ceramic material comprises pores filled with a mixture of a first material and a second material, the pores being first partially filled with the first material and then partially or completely filled with the second material.

27. 27. The composition of claim 26, wherein one or more functional characteristics of the ceramic material are modified by the inclusion of the first and / or second material.

28. 30. The composition of claim 27, wherein one or more functional characteristics of the ceramic material are tunable by varying the amount or composition of the first and / or second materials.

29. 30. The composition of claim 28, wherein the tunable characteristics include wettability, hardness, elasticity, mechanical, electrical, piezoelectric, optical, adhesive or thermal properties, microbial affinity or resistance, modification of biofilm growth, catalytic activity, permeability, cosmetic appearance, liquid repellency, and / or corrosion resistance.

30. 27. The composition of claim 26, wherein the first material interacts with the second material in a synergistic manner to modify one or more functional characteristics of the ceramic material.

31. 31. The composition of claim 30, wherein the one or more functional characteristics comprise wettability, hardness, elasticity, mechanical, electrical, piezoelectric, optical, adhesive or thermal properties, microbial affinity or resistance, modification of biofilm growth, catalytic activity, permeability, cosmetic appearance, liquid repellency, and / or corrosion resistance.

32. 25. The composition of claim 24, further comprising a layer of a top surface material over said ceramic material, said top surface material providing functionality comprising wettability with a liquid or selective separation of a compound in a liquid.

33. 33. The composition of claim 32, wherein the top surface material interacts with the gas, liquid or solid material inside the pores, thereby providing functionality selected from thermal management, wettability, modulation of electrochemical reactivity, or modulation of mechanical properties.

34. 34. The composition of claim 32 or 33, wherein the top surface material comprises the surrounding environment.

35. 34. The composition of claim 32 or 33, wherein the top surface material comprises air.

36. 34. The composition of claim 33, wherein the modulation of electrochemical reactivity comprises modulation of corrosivity, modulation of catalysis, or energy storage.

37. 34. The composition of claim 33, wherein the top surface material comprises an ammonium group, an alkyl group, a perfluoroalkyl group, a fluoroalkyl group, a phenyl group, a polymer, and / or a ceramic.

38. 38. The composition of claim 37, wherein the top surface material comprises a quaternary ammonium group to impart antimicrobial activity, an alkyl group to impart water repellency, an alkyl group to impart hydrocarbon affinity, a perfluoroalkyl group to impart water repellency, a perfluoroalkyl group to impart oil repellency, a polymer to impart improved mechanical properties, and / or a ceramic to impart improved cosmetic, piezoelectric, or anti-corrosive properties.

39. 25. The composition of claim 24, wherein the gas, liquid, or solid matter within the pores interacts with the ceramic material, thereby providing one or more functionalities selected from wettability, hardness, elasticity, mechanical, electrical, piezoelectric, optical, adhesive or thermal properties, microbial affinity or resistance, modification of biofilm growth, catalytic activity, permeability, cosmetic appearance, liquid repellency, and corrosion resistance.

40. 25. The composition of claim 24, wherein moisture in the environment interacts with the gas, solid, or liquid material inside the pores, thereby providing one or more functionalities selected from modulated evaporation rate, condensation, or water crystallization, corrosion protection of the substrate, and / or enhanced wettability.

41. 25. The composition of claim 24, wherein the ceramic material is a substantially filled or completely filled porous structure, the pores being filled with another ceramic material or a polymer.

42. 25. The composition of claim 24, wherein the ceramic material is a partially filled porous structure, the pores being partially filled with ceramic or with molecules having a head group and an end group, the head group comprising 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 hydroxyl group, an alcohol group, a thiolate group, a thiol group, and / or a quaternary ammonium group, and the end group comprising 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.

43. The composition of any one of claims 1 to 4, wherein the ceramic material provides an asymmetric pore structure with respect to the ceramic thickness from the substrate.

44. 44. The composition of claim 43, wherein the pore size distribution is characterized by a ratio of the first quartile pore size to the third quartile pore size as determined by BJH gas adsorption and desorption and varies between 0.2 and 0.7 depending on the thickness of the material.

45. The composition of any of claims 1 to 4, wherein the substrate comprises a metal and the predominant metal in the ceramic material is different from the predominant metal in the substrate.

46. (a) depositing the binderless ceramic porous material onto the substrate, the depositing comprising dipping, spraying, rolling or otherwise contacting the substrate with an aqueous solution comprising one or more metal salt(s) and a chelating or complexing agent, and controlling the pH and temperature to modulate the reaction rate to produce a ceramic material comprising a desired crystal structure, morphology, and / or surface porosity; and (b) removing the substrate from the solution and heating and / or calcining the substrate to remove moisture; A method for making the composition of any one of claims 1 to 4, comprising:

47. (c) immersing the substrate in a dilute solution of functional molecules in a solvent capable of chemically bonding to the ceramic surface such that the pores are functionalized but remain open; 47. The method of claim 46, further comprising:

48. the pores are partially filled with a first material; (i) dipping, spraying, rolling or otherwise contacting a substrate having a porous ceramic surface fixed thereon into a dilute solution of functional molecules capable of chemically bonding to the ceramic surface such that the pores are functionalized but remain open; and / or (ii) into a solution comprising one or more metal salt(s) and a chelating or complexing agent, and removing the water; and (i) or (ii) or (i) and (ii) are optionally repeated to deposit within said pores multiple layers of different functional molecules and / or metal oxides and / or metal hydroxides and / or layered double hydroxides, 48. The method of claim 47, comprising:

49. 49. The method of claim 47 or 48, wherein the pores are completely or substantially filled with a material, comprising: dipping, spraying, rolling or otherwise contacting the substrate having a porous ceramic surface or having partially filled pores fixed thereon in a solution of (i) functional molecules capable of chemically bonding with the ceramic surface such that the pores are filled with the substance; and / or (ii) one or more metal salt(s) and a chelating or complexing agent, and removing water to completely fill the pores.

50. 5. The composition of any of claims 1 to 4 adapted for use as a heat transfer surface, a fluid barrier, a filter, a fabric or textile, a corrosion barrier, a light absorbing surface, a catalyst, or a separation medium.

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