# US 10,370,556 B2 · Surface modification by polymer anchoring on porous substrates > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,370,556 B2 - Document ID: US10370556B2 - Status: Granted - Kind: B2 - Application number: 15/375,418 - Filed: 2016-12-12 - Published: 2018-06-14 - Granted: 2019-08-06 - Earliest claimed: 2016-12-12 - Assignees: International Business Machines Corporation - Applicants: International Business Machines Corporation - Inventors: Geraud J. M. Dubois; Krystelle Lionti; Teddie P. Magbitang; Willi Volksen - Web page: https://patentgrep.com/patent/US10370556B2 ## CPC - C09D 133/12: Homopolymers or copolymers of methyl methacrylate - B05D 1/005: {Spin coating} - B05D 3/02: by baking {(B05D3/04 takes precedence)} - B05D 3/107: {Post-treatment of applied coatings} - B05D 5/00: Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures - C09D 125/06: Polystyrene - B05D 2203/30: Other inorganic substrates, e.g. ceramics, silicon - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02) ## Abstract Disclosed is a method for mechanically anchoring polymers on the surface of a porous substrate by trapping polymer chains within the pores of the substrate under capillary forces. Surface modification of the porous substrate is achieved by anchoring one end of the polymer chains within the pores while one or more other ends of the polymer chains dangle from the surface of the porous substrate. The method provides a unique way of modifying the surface of a material without chemical reactions or precursor-substrate interactions. ## Claims ### Claim 1 A method comprising: (a) depositing a polymeric material comprising individual polymer chains over a surface of a porous substrate, wherein each individual polymer chain has a first end and at least one end opposite to the first end; (b) treating the polymeric material such that (i) the first end of each of the individual polymer chains mechanically anchors to a pore of the porous substrate and (ii) the at least one opposite end of each of the individual polymer chains extends from the surface of the porous substrate, wherein the mechanical anchoring is free of chemical bonds; and (c) removing excess polymeric material from the surface of the porous substrate, thereby removing individual polymer chains that are not mechanically anchored to a pore of the porous substrate. ### Claim 2 (depends on 1) The method of claim 1, where the at least one opposite end of the individual polymer chain comprises more than one opposite end extending from the surface of the porous substrate. ### Claim 3 (depends on 1) The method of claim 1, wherein each individual polymer chain has an end-to-end radius (Ree) that is five to ten times larger than the average pore diameter (ØD) of the porous substrate. ### Claim 4 (depends on 1) The method of claim 1, wherein pores of the porous substrate have an average pore diameter in the range of about 1 nm to about 1 μm. ### Claim 5 (depends on 1) The method of claim 1, wherein pores of the porous substrate have an average pore diameter in the range of about 1 nm to about 200 nm. ### Claim 6 (depends on 1) The method of claim 1, wherein the polymeric material comprises linear polymers. ### Claim 7 (depends on 1) The method of claim 1, wherein the polymeric material comprises branched polymers. ### Claim 8 (depends on 1) The method of claim 1, wherein the polymeric material comprises a combination of linear and branched polymers. ### Claim 9 (depends on 1) The method of claim 1, wherein the polymeric material comprises linear and/or branched polymers selected from the group consisting of polymethacrylates, polyimides, polybenzoxazoles, polybenzimidazoles, poly(aniline), poly(phenylene sulfide), phenol-formaldehyde/cresol-formaldehyde resins, polystyrenes, polylactic acid, polyesters, poly(bisbenzocyclobutene), poly(divinylsiloxanebis-benzocyclobutene), poly(aromatics), polyamides, polyamide-imides, polyetherimides, polyphenylquinoxalines, poly(perfluoroethers), soluble, fluorinated polyalkanes, poly(acrylonitrile), polyetherketones, poly(vinylalcohol), poly(styrene-co-styrene sulfonic acid), poly(acrylic acid), poly(hydroxyethylmethacrylate), poly(vinyl imidizolium sulfobetaine), poly(vinyl pyridinium sulfobetaine), poly(amido amines), poly(styrene-butadiene-styrene) block copolymers, poly(butadiene), poly(isoprene), polysilazanes, polyureasilazane, poly(perhydrosilazane), polysilazanes, poly(metal oxides), silicates, titanates, aluminosilicates, aluminates, zirconates, and combinations thereof. ### Claim 10 (depends on 1) The method of claim 1, wherein the polymeric material comprises poly(methyl methacrylate) (PMMA). ### Claim 11 (depends on 1) The method of claim 1, wherein the polymeric material comprises polystyrene. ### Claim 12 (depends on 1) The method of claim 1, wherein the polymeric material comprises a combination of poly(methylacrylate) and polystyrene. ### Claim 13 (depends on 1) The method of claim 1, wherein the porous substrate is a silica film. ### Claim 14 (depends on 1) The method of claim 1, wherein the porous substrate is a material selected from the group consisting of zeolites, zeolite-like materials, pillared materials, clathrasils, clathrates, carbon molecular sieves, ordered mesoporous materials, organic/inorganic porous hybrid materials, porous metal oxides, and combinations thereof. ### Claim 15 (depends on 14) The method of claim 14, wherein the organic/inorganic porous hybrid materials include a porous hybrid silica film. ### Claim 16 (depends on 1) The method of claim 1, wherein the polymeric material is treated by baking the porous substrate at a temperature above the glass transition temperature of the polymer. ### Claim 17 (depends on 1) The method of claim 1, wherein the excess polymeric material is removed from the porous substrate with a solvent. ### Claim 18 (depends on 17) The method of claim 17, wherein the solvent is selected from the group consisting of propylene glycol methyl ether acetate, propylene glycol monomethyl ether, toluene, and combinations thereof. ### Claim 19 A method, comprising: (a) depositing a polymeric material comprising individual polymer chains over a porous substrate, wherein each individual polymer chain has a first end and at least one end opposite to the first end; (b) promoting flow of the polymeric material into pores on a top portion of the porous substrate, wherein (i) the first end of the individual polymer chains mechanically anchors to a pore of the porous substrate, (ii) the at least one opposite end of the individual polymer chains extends from the surface of the porous substrate, and further wherein the polymeric material is not chemically bonded to pore walls of the porous substrate; and (c) removing, from the top portion of the porous substrate, a portion of the polymeric material, thereby removing individual polymer chains that are not mechanically anchored to a pore of the porous substrate. ### Claim 20 (depends on 19) The method of claim 19, wherein individual polymer chains of the polymeric material each have an end-to-end radius (Ree) that is five to ten times larger than the average pore diameter (ØD) of the porous substrate. ### Claim 21 (depends on 19) The method of claim 19, wherein pores of the porous substrate have an average pore diameter in the range of 1 nm to 1 μm. ### Claim 22 (depends on 19) The method of claim 19, wherein pores of the porous substrate have an average pore diameter in the range of 1 nm to 200 nm.