# US 11,998,977 B2 · Build material composition with metal powder and freeze-dried heteropolymer > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,998,977 B2 - Document ID: US11998977B2 - Status: Granted - Kind: B2 - Application number: 16/499,484 - Filed: 2018-03-15 - Published: 2020-12-31 - Granted: 2024-06-04 - Earliest claimed: 2018-03-15 - Assignees: Hewlett-Packard Development Company, L.P. - Applicants: Hewlett-Packard Development Company, L.P. - Inventors: Vladek Kasperchik; James McKinnell; Mohammed S. Shaarawi; Michael G. Monroe; Jason Hower - Web page: https://patentgrep.com/patent/US11998977B2 ## CPC - B22F 1/10: Metallic powder containing lubricating or binding agents; Metallic powder containing organic material - B22F 1/05: Metallic powder characterised by the size or surface area of the particles - B22F 1/102: Metallic powder coated with organic material - B22F 1/16: Metallic particles coated with a non-metal (coated with lubricating or binding agents or with organic material B22F1/10) - B22F 3/1021: {Removal of binder or filler (removal of binder from ceramics C04B35/638)} - B22F 10/10: Formation of a green body - B22F 10/14: by jetting of binder onto a bed of metal powder - B22F 10/73: of powder - B29C 64/165: using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber - B33Y 10/00: Processes of additive manufacturing - B33Y 40/10: Pre-treatment - B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials - C08F 2/22: Emulsion polymerisation - C08F 212/08: Styrene - C08F 220/14: Methyl esters {, e.g. methyl (meth)acrylate} - C08K 3/11: Compounds containing metals of Groups 4 to 10 or of Groups 14 to 16 of the Periodic Table - C09D 11/037: characterised by the pigment - C09D 11/322: Pigment inks - C09D 11/38: characterised by non-macromolecular additives other than solvents, pigments or dyes - B22F 10/28: Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM] - B22F 2304/10: Micron size particles, i.e. above 1 micrometer up to 500 micrometer - B22F 2998/10: Processes characterised by the sequence of their steps - B22F 2999/00: Aspects linked to processes or compositions used in powder metallurgy - B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites - Y02P 10/25: Process efficiency - B22F: WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER (making alloys by powder metallurgy C22C); APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER - B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00) - B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - 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) - B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract An example of a composition includes a host metal present in an amount ranging from about 95.00 weight percent to about 99.99 weight percent, based on a total weight of the composition. A flow additive is also present in an amount ranging from about 0.01 weight percent to about 5.00 weight percent, based on the total weight of the composition. The flow additive consists of an organic material that is pyrolyzable at a pyrolysis temperature that is less than a sintering temperature of the host metal. The composition is spreadable, having a Hausner Ratio less than 1.25. ## Claims ### Claim 1 A build material composition, comprising: a host metal powder present in an amount ranging from about 95.00 weight percent to about 99.99 weight percent, based on a total weight of the composition, the host metal powder including host metal particles having an average particle size of less than 20 micrometers and the host metal powder having a sintering temperature of from about 500° C. to about 1800° C.; and a flow additive present in an amount ranging from about 0.01 weight percent to about 5.00 weight percent, based on the total weight of the composition, wherein the flow additive consists of particles of a freeze-dried organic material that is pyrolyzable at a pyrolysis temperature that is less than the sintering temperature of the host metal powder, wherein the particles of the freeze-dried organic material include a heteropolymer having a hydrophobic component that makes up from about 65% by weight to about 99.9% by weight of the heteropolymer and a hydrophilic component that makes up from about 0.1% by weight to about 35% by weight of the heteropolymer with the hydrophobic component having a lower glass transition temperature compared to the hydrophilic component, wherein: the hydrophobic component is formed from a monomer selected from the group consisting of ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, hydroxyethyl acrylate, octadecyl methacrylate, tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofurfuryl acrylate, 2-phenoxyethyl methacrylate, benzyl acrylate, ethoxylated nonyl phenol methacrylate, cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, tridecyl methacrylate, isodecyl acrylate, dimethyl maleate, dioctyl maleate, acetoacetoxyethyl methacrylate, diacetone acrylamide, vinyl chloride, vinylidene chloride, N-vinyl imidazole, N-vinylcarbazole, N-vinyl-caprolactam, and combinations thereof; and the hydrophilic component is formed from an acidic monomer selected from the group consisting of ethacrylic acid, dimethylacrylic acid, maleic anhydride, maleic acid, vinylsulfonate, cyanoacrylic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonoic acid, fumaric acid, itaconic acid, sorbic acid, angelic acid, cinnamic acid, styrylacrylic acid, citraconic acid, glutaconic acid, aconitic acid, phenylacrylic acid, acryloxypropionic acid, aconitic acid, phenylacrylic acid, acryloxypropionic acid, vinylbenzoic acid, N-vinylsuccinamidic acid, mesaconic acid, methacroylalanine, acryloylhydroxyglycine, sulfoethyl methacrylic acid, sulfopropyl acrylic acid, styrene sulfonic acid, sulfoethylacrylic acid, 2-methacryloyloxymethane-1-sulfonic acid, 3-methacryoyloxypropane-1-sulfonic acid, 3-(vinyloxy)propane-1-sulfonic acid, ethylenesulfonic acid, vinyl sulfuric acid, 4-vinylphenyl sulfuric acid, ethylene phosphonic acid, vinyl phosphoric acid, vinyl benzoic acid, 2 acrylamido-2-methyl-1-propanesulfonic acid, and combinations thereof, and wherein the composition is spreadable, having a Hausner Ratio less than 1.25. ### Claim 2 (depends on 1) The build material composition as defined in claim 1 wherein the particles of the flow additive include primary particles having an average flow additive primary particle size ranging from about 1 to about 3 orders of magnitude smaller than the average particle size of the host metal particles. ### Claim 3 (depends on 2) The build material composition as defined in claim 2 wherein the average flow additive primary particle size ranges from about 5 nanometers to about 200 nanometers. ### Claim 4 (depends on 1) The build material composition as defined in claim 1 wherein the flow additive is a polymer having a glass transition temperature greater than about 5 degrees above a spread temperature of the composition, and wherein the spread temperature of the composition is from about 25° C. to about 200° C. ### Claim 5 (depends on 1) The build material composition as defined in claim 1 wherein the flow additive is hydrophobic. ### Claim 6 (depends on 1) The build material composition as defined in claim 1 wherein when the flow additive undergoes pyrolysis, the pyrolysis yields volatile decomposition products and non-volatile carbon-rich residue with the volatile decomposition products being at least about 90 percent of a pre-pyrolyzed weight of the flow additive. ### Claim 7 (depends on 1) The build material composition as defined in claim 1 wherein the particles of the freeze-dried organic material are a nano-powder produced by freeze drying an aqueous dispersion of polymer nano-particles. ### Claim 8 (depends on 7) The build material composition as defined in claim 7 wherein the aqueous dispersion of polymer nano-particles is produced by emulsion polymerization or co-polymerization of the monomer of the hydrophobic component and the acidic monomer of the hydrophilic component. ### Claim 9 (depends on 1) The build material composition as defined in claim 1 wherein the average particle size of the host metal particles is from about 11 micrometers to about 20 micrometers. ### Claim 10 (depends on 1) The build material composition as defined in claim 1 wherein the host metal particles are stainless steel particles and the average particle size is about 11 micrometers. ### Claim 11 (depends on 1) The build material composition as defined in claim 1 wherein the flow additive is not an adhesive. ### Claim 12 (depends on 1) The build material composition as defined in claim 1 wherein the hydrophobic component makes up about 65% by weight and the hydrophilic component makes up about 35% by weight of the heteropolymer of the freeze-dried organic material. ### Claim 13 (depends on 1) The build material composition as defined in claim 1 wherein the monomer of the hydrophobic component is selected from the group consisting of ethyl acrylate, propyl acrylate, propyl methacrylate, hydroxyethyl acrylate, tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofurfuryl acrylate, 2-phenoxyethyl methacrylate, benzyl acrylate, ethoxylated nonyl phenol methacrylate, trimethyl cyclohexyl methacrylate, n-octyl methacrylate, tridecyl methacrylate, isodecyl acrylate, dimethyl maleate, dioctylvinyl imidazole, maleate, acetoacetoxyethyl methacrylate, diacetone acrylamide, vinylidene chloride, N-N-vinylcarbazole, N-vinyl-caprolactam, and combinations thereof. ### Claim 14 A three-dimensional (3D) printing kit, comprising: a build material composition, including: a host metal powder present in an amount ranging from about 95.00 weight percent to about 99.99 weight percent, based on a total weight of the build material composition, the host metal powder including host metal particles having an average particle size of less than 20 micrometers and the host metal powder having a sintering temperature of from about 500° C. to about 1800° C.; and a flow additive present in an amount ranging from about 0.01 weight percent to about 5.00 weight percent, based on the total weight of the build material composition, wherein the flow additive consists of particles of a freeze-dried organic material that is pyrolyzable at a pyrolysis temperature less than the sintering temperature of the host metal powder, and wherein the particles of the freeze-dried organic material include a heteropolymer having a hydrophobic component that makes up from about 65% by weight to about 99.9% by weight of the heteropolymer and a hydrophilic component that makes up from about 0.1 by weight to about 35% by weight of the heteropolymer with the hydrophobic component having a lower glass transition temperature compared to the hydrophilic component, wherein: the hydrophobic component is formed from a monomer selected from the group consisting of ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, hydroxyethyl acrylate, octadecyl methacrylate, tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofurfuryl acrylate, 2-phenoxyethyl methacrylate, benzyl acrylate, ethoxylated nonyl phenol methacrylate, cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, tridecyl methacrylate, isodecyl acrylate, dimethyl maleate, dioctyl maleate, acetoacetoxyethyl methacrylate, diacetone acrylamide, vinyl chloride, vinylidene chloride, N-vinyl imidazole, N-vinylcarbazole, N-vinyl-caprolactam, and combinations thereof; and the hydrophilic component is formed from an acidic monomer from the group consisting of ethacrylic acid, dimethylacrylic acid, maleic anhydride, maleic acid, vinylsulfonate, cyanoacrylic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonoic acid, fumaric acid, itaconic acid, sorbic acid, angelic acid, cinnamic acid, styrylacrylic acid, citraconic acid, glutaconic acid, aconitic acid, phenylacrylic acid, acryloxypropionic acid, aconitic acid, phenylacrylic acid, acryloxypropionic acid, vinylbenzoic acid, N-vinylsuccinamidic acid, mesaconic acid, methacroylalanine, acryloylhydroxyglycine, sulfoethyl methacrylic acid, sulfopropyl acrylic acid, styrene sulfonic acid, sulfoethylacrylic acid, 2-methacryloyloxymethane-1-sulfonic acid, 3-methacryoyloxypropane-1-sulfonic acid, 3-(vinyloxy)propane-1-sulfonic acid, ethylenesulfonic acid, vinyl sulfuric acid, 4-vinylphenyl sulfuric acid, ethylene phosphonic acid, vinyl phosphoric acid, vinyl benzoic acid, 2 acrylamido-2-methyl-1-propanesulfonic acid, and combinations thereof, and wherein the build material composition is spreadable, having a Hausner Ratio less than 1.25; and a binder agent to be applied to at least a portion of a layer of the build material composition via an inkjet printhead to pattern a cross-section of an intermediate part. ### Claim 15 A method for making a three-dimensional printing build material composition, comprising: combining a host metal powder and a flow additive to form a build material mixture, the host metal powder being present in an amount ranging from about 95.00 weight percent to about 99.99 weight percent based on a total weight of the build material mixture and the flow additive being present in an amount ranging from about 0.01 weight percent to about 5.00 weight percent based on the total weight of the build material mixture, wherein the host metal powder has a sintering temperature of from about 500° C. to about 1800° C. and includes host metal particles having an average particle size of less than 20 micrometers, and the flow additive consists of particles of a freeze-dried organic material that is pyrolyzable at a pyrolysis temperature that is less than the sintering temperature of the host metal powder with the particles of the freeze-dried organic material including a heteropolymer having a hydrophobic component that makes up from about 65% by weight to about 99.9% by weight of the heteropolymer and a hydrophilic component that makes up from about 0.1% by weight to about 35% by weight of the heteropolymer with the hydrophobic component having a lower glass transition temperature compared to the hydrophilic component, wherein: the hydrophobic component is formed from a monomer selected from the group consisting of ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, hydroxyethyl acrylate, octadecyl methacrylate, tetrahydrofurfuryl acrylate, alkoxylated tetrahydrofurfuryl acrylate, 2-phenoxyethyl methacrylate, benzyl acrylate, ethoxylated nonyl phenol methacrylate, cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, tridecyl methacrylate, isodecyl acrylate, dimethyl maleate, dioctyl maleate, acetoacetoxyethyl methacrylate, diacetone acrylamide, vinyl chloride, vinylidene chloride, N-vinyl imidazole, N-vinylcarbazole, N-vinyl-caprolactam, and combinations thereof; and the hydrophilic component is formed from an acidic monomer selected from the group consisting of ethacrylic acid, dimethylacrylic acid, maleic anhydride, maleic acid, vinylsulfonate, cyanoacrylic acid, vinylacetic acid, allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonoic acid, fumaric acid, itaconic acid, sorbic acid, angelic acid, cinnamic acid, styrylacrylic acid, citraconic acid, glutaconic acid, aconitic acid, phenylacrylic acid, acryloxypropionic acid, aconitic acid, phenylacrylic acid, acryloxypropionic acid, vinylbenzoic acid, N-vinylsuccinamidic acid, mesaconic acid, methacroylalanine, acryloylhydroxyglycine, sulfoethyl methacrylic acid, sulfopropyl acrylic acid, styrene sulfonic acid, sulfoethylacrylic acid, 2-methacryloyloxymethane-1-sulfonic acid, 3-methacryoyloxypropane-1-sulfonic acid, 3-(vinyloxy)propane-1-sulfonic acid, ethylenesulfonic acid, vinyl sulfuric acid, 4-vinylphenyl sulfuric acid, ethylene phosphonic acid, vinyl phosphoric acid, vinyl benzoic acid, 2 acrylamido-2-methyl-1-propanesulfonic acid, and combinations thereof; and mixing the build material mixture until a build material composition having a Hausner Ratio less than 1.25 is formed.