US20190039309A1 - Methods of 3d printing articles with particles - Google Patents

Methods of 3d printing articles with particles Download PDF

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Publication number
US20190039309A1
US20190039309A1 US15/907,085 US201815907085A US2019039309A1 US 20190039309 A1 US20190039309 A1 US 20190039309A1 US 201815907085 A US201815907085 A US 201815907085A US 2019039309 A1 US2019039309 A1 US 2019039309A1
Authority
US
United States
Prior art keywords
nozzle
article
particles
substrate
equal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US15/907,085
Other languages
English (en)
Inventor
Travis Alexander Busbee
Avin Dhoble
Noah Tremblay
Clara H. Rhee
Sean Christopher Troiano
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kornit Digital Technologies Ltd
Voxei8 inc
Original Assignee
Voxei8 inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Voxei8 inc filed Critical Voxei8 inc
Priority to US15/907,085 priority Critical patent/US20190039309A1/en
Publication of US20190039309A1 publication Critical patent/US20190039309A1/en
Assigned to Voxel8, Inc. reassignment Voxel8, Inc. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TREMBLAY, NOAH, Troiano, Sean Christopher, DHOBLE, AVIN, Rhee, Clara H., BUSBEE, TRAVIS ALEXANDER
Assigned to KORNIT DIGITAL TECHNOLOGIES LTD. reassignment KORNIT DIGITAL TECHNOLOGIES LTD. CONFIRMATORY ASSIGNMENT Assignors: Voxel8, Inc.
Abandoned legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/02—Uppers; Boot legs
    • A43B23/0245—Uppers; Boot legs characterised by the constructive form
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/16—Processes for the non-uniform application of treating agents, e.g. one-sided treatment; Differential treatment
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B1/00—Footwear characterised by the material
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B1/00—Footwear characterised by the material
    • A43B1/14—Footwear characterised by the material made of plastics
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/02—Uppers; Boot legs
    • A43B23/0205—Uppers; Boot legs characterised by the material
    • A43B23/0215—Plastics or artificial leather
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43D—MACHINES, TOOLS, EQUIPMENT OR METHODS FOR MANUFACTURING OR REPAIRING FOOTWEAR
    • A43D8/00—Machines for cutting, ornamenting, marking or otherwise working up shoe part blanks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05—Stirrers
    • B01F27/09—Stirrers characterised by the mounting of the stirrers with respect to the receptacle
    • B01F27/092—Stirrers characterised by the mounting of the stirrers with respect to the receptacle occupying substantially the whole interior space of the receptacle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05—Stirrers
    • B01F27/11—Stirrers characterised by the configuration of the stirrers
    • B01F27/117—Stirrers provided with conical-shaped elements, e.g. funnel-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/50—Pipe mixers, i.e. mixers wherein the materials to be mixed flow continuously through pipes, e.g. column mixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B13/00—Machines or plants for applying liquids or other fluent materials to surfaces of objects or other work by spraying, not covered by groups B05B1/00 - B05B11/00
    • B05B13/02—Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work
    • B05B13/04—Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work the spray heads being moved during spraying operation
    • B05B13/0405—Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work the spray heads being moved during spraying operation with reciprocating or oscillating spray heads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • 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
    • B29C64/00—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
    • B29C64/10—Processes of additive manufacturing
    • B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • 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
    • B29C64/00—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
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/307—Handling of material to be used in additive manufacturing
    • B29C64/321—Feeding
    • B29C64/336—Feeding of two or more materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D35/00—Producing footwear
    • B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
    • B29D35/122—Soles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D35/00—Producing footwear
    • B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
    • B29D35/126—Uppers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/17—Ink jet characterised by ink handling
    • B41J2/175—Ink supply systems ; Circuit parts therefor
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/141—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes mixture of two or more polyurethanes in the same layer
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/14—Soles; Sole-and-heel integral units characterised by the constructive form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B12/00—Arrangements for controlling delivery; Arrangements for controlling the spray area
    • B05B12/14—Arrangements for controlling delivery; Arrangements for controlling the spray area for supplying a selected one of a plurality of liquids or other fluent materials or several in selected proportions to a spray apparatus, e.g. to a single spray outlet
    • B05B12/1418—Arrangements for controlling delivery; Arrangements for controlling the spray area for supplying a selected one of a plurality of liquids or other fluent materials or several in selected proportions to a spray apparatus, e.g. to a single spray outlet for supplying several liquids or other fluent materials in selected proportions to a single spray outlet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B15/00—Details of spraying plant or spraying apparatus not otherwise provided for; Accessories
    • B05B15/20—Arrangements for agitating the material to be sprayed, e.g. for stirring, mixing or homogenising
    • B05B15/25—Arrangements for agitating the material to be sprayed, e.g. for stirring, mixing or homogenising using moving elements, e.g. rotating blades
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B15/00—Details of spraying plant or spraying apparatus not otherwise provided for; Accessories
    • B05B15/50—Arrangements for cleaning; Arrangements for preventing deposits, drying-out or blockage; Arrangements for detecting improper discharge caused by the presence of foreign matter
    • B05B15/55—Arrangements for cleaning; Arrangements for preventing deposits, drying-out or blockage; Arrangements for detecting improper discharge caused by the presence of foreign matter using cleaning fluids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/02—Spray pistols; Apparatus for discharge
    • B05B7/04—Spray pistols; Apparatus for discharge with arrangements for mixing liquids or other fluent materials before discharge
    • B05B7/0408—Spray pistols; Apparatus for discharge with arrangements for mixing liquids or other fluent materials before discharge with arrangements for mixing two or more liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
    • B05B7/02—Spray pistols; Apparatus for discharge
    • B05B7/06—Spray pistols; Apparatus for discharge with at least one outlet orifice surrounding another approximately in the same plane
    • B05B7/062—Spray pistols; Apparatus for discharge with at least one outlet orifice surrounding another approximately in the same plane with only one liquid outlet and at least one gas outlet
    • B05B7/066—Spray pistols; Apparatus for discharge with at least one outlet orifice surrounding another approximately in the same plane with only one liquid outlet and at least one gas outlet with an inner liquid outlet surrounded by at least one annular gas outlet
    • B05B7/068—Spray pistols; Apparatus for discharge with at least one outlet orifice surrounding another approximately in the same plane with only one liquid outlet and at least one gas outlet with an inner liquid outlet surrounded by at least one annular gas outlet the annular gas outlet being supplied by a gas conduit having an axially concave curved internal surface just upstream said outlet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • 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
    • B29C64/00—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
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/48—Wearing apparel
    • B29L2031/50—Footwear, e.g. shoes or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/068—Polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2207/00—Treatments by energy or chemical effects
    • D06N2207/12—Treatments by energy or chemical effects by wave energy or particle radiation
    • D06N2207/123—Treatments by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation, e.g. IR, UV, actinic light, laser, X-ray, gamma-ray, microwave, radio frequency
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1635—Elasticity
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/10—Clothing
    • D06N2211/106—Footwear

Definitions

  • the present invention generally relates to methods of printing articles using three-dimensional printing and other printing techniques, and to articles formed from such techniques, including the printing of articles containing particles.
  • the manufacture of composites may involve the expensive and environmentally hazardous synthesis and incorporation of new materials.
  • the properties of composites may be difficult to control. Improved methods of manufacture of composites are thus needed.
  • the present invention generally relates to methods of printing articles using three-dimensional printing and other printing techniques, and to articles formed from such techniques, including the printing of articles containing particles.
  • the subject matter of the present invention involves, in some cases, interrelated products, alternative solutions to a particular problem, and/or a plurality of different uses of one or more systems and/or articles.
  • the present invention is generally directed to a method.
  • the method includes a method for printing an article, e.g., 3D-printing an article, e.g., for use in footwear.
  • the method includes receiving object information associated with the article; identifying a target material to be printed using the object information; identifying two or more input materials to create the target material, at least one of the two or more input materials comprising particles (e.g., reinforcing particles); identifying a set of printer settings for printing the target material; generating print instructions using the set of printer parameters; and printing the article using the print instructions.
  • the method in another set of embodiments, includes flowing a first fluid through a first inlet into a nozzle; flowing a second fluid through a second inlet into the nozzle; flowing particles (e.g., reinforcing particles) into the nozzle; mixing the first fluid, the second fluid, and the particles (e.g., reinforcing particles) to form a mixture within the nozzle; and printing the mixture onto a substrate from the nozzle.
  • flowing a first fluid through a first inlet into a nozzle
  • flowing a second fluid through a second inlet into the nozzle
  • flowing particles e.g., reinforcing particles
  • the method includes flowing a fluid into a microfluidic printing nozzle, flowing particles (e.g., reinforcing particles) into the nozzle, mixing the fluid and the particles (e.g., reinforcing particles) within the microfluidic printing nozzle using an impeller to form a mixture, and printing the mixture onto a substrate.
  • flowing particles e.g., reinforcing particles
  • mixing the fluid and the particles e.g., reinforcing particles
  • the method includes flowing a first fluid through a first inlet and a second fluid through a second inlet into a microfluidic printing nozzle, where the first fluid comprises a foam precursor and the second fluid comprises a cell-forming agent, homogenously mixing the first fluid and the second fluid to form a mixture, and printing the mixture onto a substrate.
  • the method in another set of embodiments, includes flowing a fluid into a microfluidic printing nozzle, mixing the fluid with a gas within the microfluidic printing nozzle using an impeller to form a froth comprising bubbles of the gas dispersed within the fluid, and printing the froth onto a substrate.
  • the method comprises acts of mixing a first fluid and a second fluid in a mixing chamber to form a foam precursor, flowing the foam precursor and a cell-forming agent into a microfluidic printing nozzle, rotating an impeller within the microfluidic printing nozzle to form a mixture of the foam precursor and the cell-forming agent, and printing the mixture onto a substrate.
  • the method in still another set of embodiments comprises flowing at least two inputs into a mixing nozzle to form a first mixture comprising a blowing agent.
  • the method may further comprise flowing at least two inputs into a mixing nozzle to form a second mixture.
  • a first region comprising the first mixture may be deposited to form a first elastomer.
  • a second region comprising the second mixture may be deposited to form a second elastomer.
  • At least the first region of the article may be heated to a temperature greater than or equal to the activation temperature of the blowing agent. In some embodiments, heating at least the first region of the article causes differential expansion between the first region and the second region of the article and physical deformation of the article.
  • the present invention is generally directed to an article.
  • the article is an article for use in footwear.
  • the article includes a 3D-printed composite comprising a plurality of particles (e.g., reinforcing particles) having a largest numerical average dimension of greater than or equal to 10 microns and less than or equal to 400 microns.
  • the article is a 3D-printed article for use in footwear.
  • the article includes a 3D-printed article having a gradient in a property between a first portion and a second portion, wherein the 3D-printed article is a single integrated material, and wherein the property is selected from the group consisting of average largest dimension of particles (e.g., reinforcing particles), weight percent of particles (e.g., reinforcing particles), volume percent of particles (e.g., reinforcing particles), compression strength, slip resistance, abrasion resistance, density, stiffness, heat deflection temperature, pore concentration, pore size, and coefficient of thermal expansion.
  • the article comprises a polymeric structure.
  • the article may comprise particles (e.g., reinforcing particles) distributed in the polymeric structure to form a gradient of the weight percent of particles (e.g., reinforcing particles) in the polymeric structure.
  • a textile is adhered to the polymeric structure.
  • the article comprises a polymeric structure and an unexpanded chemical blowing agent in at least a portion of the polymeric structure.
  • a textile is adhered to at least a portion of the polymeric structure.
  • the present invention is generally directed to a device.
  • the device is a device for printing, e.g., 3D-printing.
  • the device comprises a first microfluidic printing nozzle comprising a first mixing chamber and a first impeller disposed therein, a second microfluidic printing nozzle comprising a second mixing chamber and a second impeller disposed therein, the second nozzle further comprising an input in fluid communication with an outlet of the first nozzle, and a controller configured and arranged to independently control rotation of the first impeller and the second impeller.
  • the device comprises a microfluidic printing nozzle comprising a mixing chamber and an impeller disposed therein, a heat source or a cooling source in thermal communication with the nozzle, and a controller constructed and arranged to control rotation of the impeller.
  • the device in yet another set of embodiments, includes a microfluidic printing nozzle comprising a mixing chamber and an impeller disposed therein, and a controller constructed and arranged to laterally move the impeller within the microfluidic printing nozzle.
  • the nozzle may be controlled, for example, using a computer or other controller, in order to control the deposition of the product onto the substrate.
  • gases or other materials may be incorporated into the product within the nozzle, e.g., to form a foam.
  • FIG. 1 illustrates a system comprising a nozzle for printing materials, in accordance with one embodiment of the invention
  • FIG. 2 illustrates a system comprising a nozzle and a mixing chamber, in another embodiment of the invention
  • FIG. 3 illustrates a system comprising multiple mixing chambers, in yet another embodiment of the invention
  • FIG. 4 illustrates a variety of inputs that can be mixed, in accordance with certain embodiments of the invention
  • FIG. 5 illustrates a system comprising a single input, in accordance with another embodiment of the invention.
  • FIG. 6 illustrates an input comprising a purge system, in still another embodiment of the invention.
  • FIG. 7 illustrates a water-blown polyurethane foam in the form of a shoe sole, in one embodiment of the invention
  • FIG. 8 illustrates a light microscopy image of a cross-section of a 3D-printed filament, in accordance with another embodiment of the invention.
  • FIG. 9 illustrates an article with a gradient in properties, in yet another embodiment of the invention.
  • FIG. 11 illustrates an example nozzle architecture, in still another embodiment of the invention.
  • FIG. 12 illustrates an example material mixing unit architecture, in another embodiment of the invention.
  • FIGS. 13A-13B illustrate examples of architectures for various subsystems in certain embodiments of the invention.
  • FIGS. 14A-14C illustrate 3D-printed articles according to certain embodiments of the invention.
  • FIG. 15 illustrates an article of footwear according to certain embodiments of the invention.
  • FIG. 17 illustrates a non-limiting schematic diagram of a printed article comprising a blowing agent in the surface layer, according to certain embodiments of the invention.
  • FIG. 18 illustrates a non-limiting schematic diagram of a printed article comprising a blowing agent dispersed throughout the printed article with local blowing agent activation, according to other embodiments of the invention.
  • FIG. 19 illustrates a non-limiting schematic diagram of a printed article comprising a blowing agent dispersed throughout the printed article with global blowing agent activation and volumetric expansion of the printed article, in certain embodiments of the invention
  • FIG. 20 is a schematic depiction of a print head and a substrate, according to certain embodiments of the invention.
  • FIGS. 21-23 are schematic depictions of a multi-axis deposition system, according to certain embodiments of the invention.
  • FIG. 24 is a non-limiting flow diagram of a method for generating print instructions from object information, in accordance with some embodiments of the invention.
  • the present invention generally relates to the printing of materials using three-dimensional printing and other printing techniques, and to articles formed from such techniques.
  • the articles may be articles for use in footwear.
  • Certain embodiments are generally directed to composites comprising particles (e.g., reinforcing particles), for example, rubber particles.
  • the particles may be used, for example, to increase slip or abrasion resistance.
  • the composites may also contain polyurethanes or other compounds, e.g., to facilitate fabrication, e.g., using three-dimensional printing and other printing techniques.
  • Other embodiments are directed to methods of making or using such articles.
  • a composite may be prepared by mixing particles (e.g., reinforcing particles) with at least a first fluid and a second fluid within a nozzle, such as a microfluidic printing nozzle, which may be used to direct the resulting product onto a substrate.
  • particles e.g., reinforcing particles
  • a nozzle such as a microfluidic printing nozzle
  • an article that is printed may comprise a composite.
  • a composite may comprise a matrix and a plurality of particles (e.g., reinforcing particles).
  • the matrix may include materials such as polyurethane or other suitable polymers, which may be used to facilitate manufacturing of articles. Examples of polyurethanes and other suitable polymers include those described in greater detail below.
  • the composite may comprise a foam, although this is not a requirement in every embodiment.
  • the particles (e.g., reinforcing particles), in some cases, may provide for increased slip resistance, e.g., due to increased friction.
  • the particles may provide increased toughness or resistance to abrasion, for example, of a surface.
  • the particles may be used for texture, for example, to produce a coarser or more bumpy surface texture to an article, to produce a certain appearance or “sheen” to the surface of an article, or the like.
  • the particles e.g., reinforcing particles
  • the rubber may arise from any suitable source, and may include virgin and/or recycled rubber.
  • the rubber may be natural rubber and/or synthetically produced rubber. Examples of rubber include, but are not limited to, ground tire rubber, recycled tire rubber, or the like.
  • the rubber forming the particles may comprise a variety of polymers, including but not limited to, natural rubber (e.g., latex rubber), styrene butadiene (SBR), polyacrylics, polyvinyl acetate (PVA), polyvinyl chloride (PVC), polychloroprene (neoprene), polyurethanes, butyl rubbers, or the like. Combinations of these and/or other rubbers may also be used in some cases. It should be noted that in some cases, the exact composition of polymers in rubber particles is unknown.
  • natural rubber e.g., latex rubber
  • SBR styrene butadiene
  • PVA polyvinyl acetate
  • PVC polyvinyl chloride
  • neoprene polychloroprene
  • polyurethanes butyl rubbers, or the like. Combinations of these and/or other rubbers may also be used in some cases. It should be noted that in some cases, the exact composition
  • the rubber may arise from a variety of natural sources (and thus comprise a variety of different polymers), the rubber may have been recycled from different sources (e.g., tires, pencil erasers, balloons, footwear, or the like), etc.
  • recycled rubber from sources such as discarded tires may be formed into particles using techniques such as mechanical grinding, cryogenic grinding, milling, cutting, shredding, screening, etc.
  • other materials may be used for reinforcing particles, e.g., in addition to and/or instead of rubber particles.
  • Non-limiting examples include silica, fumed silica, silicon carbide, titanium dioxide, fibers, carbon, carbon fiber, gypsum, glass fiber, calcium carbonates, nanorods, microrods, carbon fibers, thermoplastics, or the like.
  • the particles may comprise silicone particles, wax particles, or polytetrafluoroethylene particles, or combinations thereof.
  • the particles (e.g., reinforcing particles) may comprise a thermoplastic polyurethane that has a blowing agent inside that has yet to be expanded, or an expanded thermoplastic polyurethane.
  • the particles comprise a blowing agent that decomposes to gas above an activation temperature.
  • the particles comprise azodicarbonamide particles, sodium bicarbonate particles, hydrazine particles, toluenesulfonylhydrazine particles, or oxybisbenzenesulfonylhydrazine particles, or combinations thereof.
  • reinforcing particles may comprise hollow or solid spheres. Such spheres may comprise, as non-limiting examples, glass or polyurethane.
  • the spheres may be hollow elastomer spheres (e.g., hollow polyurethane spheres), and the density of a composite including these spheres may be reduced relative to the density of a substantially similar composite not including these spheres.
  • hollow elastomer spheres e.g., hollow polyurethane spheres
  • Particles may, in some embodiments, have a largest numerical average dimension of at least 10 microns, at least 20 microns, at least 30 microns, at least 40 microns, at least 50 microns, at least 60 microns, at least 70 microns, at least 80 microns, at least 90 microns, at least 100 microns, at least 150 microns, at least 200 microns, at least 250 microns, at least 300 microns, at least 350 microns, at least 400 microns, at least 500 microns, at least 700 microns, or at least 900 microns.
  • the particles may have a largest numerical average dimension of at most 1000 microns, at most 900 microns, at most 700 microns, at most 500 microns, at most 400 microns, at most 350 microns, at most 300 microns, at most 250 microns, at most 200 microns, at most 150 microns, at most 100 microns, at most 90 microns, at most 80 microns, at most 70 microns, at most 60 microns, at most 50 microns, at most 40 microns, at most 30 microns, or at most 20 microns.
  • the particles may be spherical and/or non-spherical. In some cases, the particles may be present in a range of sizes and/or shapes (e.g., as in the case of crumb rubber or ground tire rubber).
  • the surfaces of the particles may be functionalized.
  • Functionalization is given its ordinary meaning in the art and may refer to the process of changing the surface chemistry of a material (particles, e.g., reinforcing particles, e.g., comprising rubber).
  • functionalization involves covalently and/or non-covalently attaching molecules to the material.
  • functionalization of the particles is carried out prior to mixing the particles (e.g., reinforcing particles) with other material(s) (e.g., a first fluid, a first fluid and a second fluid, etc.).
  • This functionalization of particles may be carried out in order to improve, as non-limiting examples, certain aspects of the process of mixing the particles (e.g., reinforcing particles) with other materials (e.g., fluids), or properties of a three-dimensionally printed composite that results from depositing (e.g., 3D-printing) the resulting mixture onto a substrate and allowing it to solidify.
  • the process of mixing the particles (e.g., reinforcing particles) with the one or more materials (e.g., fluids) may be improved by reducing the viscosity of the composition in the mixing nozzle.
  • the composition in the mixing nozzle comprises the particles (e.g., reinforcing particles) and one or more materials (e.g., fluids).
  • functionalizing the particles (e.g., reinforcing particles) prior to introducing the particles into a mixing nozzle, into which one or more other materials (e.g., fluids) are also introduced may improve the mechanical properties (e.g., decrease the maximum local stiffness, increase the overall toughness) of a three-dimensionally printed composite that results from depositing (e.g., 3D-printing) the resulting mixture onto a substrate and allowing it to solidify.
  • These mechanical property improvements may be compared to a substantially similar composite comprising non-functionalized particles (e.g., reinforcing particles).
  • functionalization of the particles may improve the properties of the composition in the mixing nozzle and/or of the deposited (e.g., 3D-printed) solidified composite by means of, as a non-limiting example, improving the dispersion (e.g., minimizing aggregation) of the particles (e.g., reinforcing particles) in the matrix (e.g., comprising polyurethane) of the composite.
  • This may be useful, for example, in embodiments in which the particles (e.g., reinforcing particles) are introduced into a mixing nozzle at a high loading relative to the total volume of the composition (e.g., greater than or equal to 50 volume percent of the composition in the mixing nozzle).
  • the surfaces of the particles may be functionalized with a silane.
  • silanes include (3-aminopropyl)triethoxysilane, 3-glycidyloxy propyltriethoxysilane, 3-glycidyloxy propyltrimethoxysilane, polyether-functional trimethoxysilane, and vinylsilane.
  • Non-limiting examples of chemical groups with which to functionalize the surfaces of the particles include alkyl groups, hydroxyl groups, isocyanate groups, amine groups, amide groups, aromatic groups, glycidyl groups, epoxide groups, vinyl groups, acrylate groups, and methacrylate groups.
  • the surfaces of the particles (e.g., reinforcing particles) may be functionalized, as another non-limiting example, to facilitate bonding (e.g., covalently bonding) of the particles to the matrix material, e.g., chemically.
  • the particles e.g., reinforcing particles
  • at least 50%, at least 75%, or at least 90% of the surfaces of the particles may be functionalized, e.g., with silanes and/or other functional moieties as discussed herein.
  • the incorporation of particles (e.g., reinforcing particles) into a composite may result in a change (e.g., an improvement) in the performance of the composite with respect to one or more properties (e.g., abrasion resistance, slip resistance, or the like).
  • a composite having particles (e.g., reinforcing particles) may have greater abrasion resistance and/or greater slip resistance than a substantially similar composite lacking such particles.
  • a composite may have a lower overall density than a substantially similar composite lacking particles (e.g., reinforcing particles).
  • the incorporation of a certain type of particles (e.g., reinforcing particles) into the matrix of the composite may result in a change (e.g., an improvement) in the performance of the composite with respect to one or more properties (e.g., physical properties, environmental sustainability, cost, or the like).
  • a filler e.g., ground tire rubber
  • less waste may be produced in producing a composite comprising recycled materials, such as ground tire rubber particles.
  • certain aspects of the invention are generally directed to methods for printing an article, for example, an article comprising a composite (e.g., a composite comprising particles, e.g., reinforcing particles).
  • a composite e.g., a composite comprising particles, e.g., reinforcing particles.
  • printing an article may include flowing particles (e.g., reinforcing particles, e.g., comprising recycled tire rubber) into a nozzle (see, e.g., FIG. 16 ).
  • the nozzle may be a microfluidic printing nozzle.
  • the particles (e.g., reinforcing particles) flowing into the nozzle are contained within a fluid entering the nozzle. If more than one fluid enters the nozzle, the reinforcing particles may be in any one or more of the fluids.
  • the particles may also enter into a nozzle in some cases through an inlet separate from fluids entering the nozzle, e.g., the particles may enter the nozzle in a dry state in some cases.
  • the particles may be moved through the inlet into the nozzle by, for example, a pumping subsystem (e.g., an auger system).
  • printing an article may include mixing the particles (e.g., reinforcing particles) in the nozzle with a fluid or a plurality of fluids within the nozzle, to form a mixture.
  • the mixture comprises a froth. Examples of nozzles that can be used include those discussed in more detail below. See also U.S. Pat. Apl. Ser. No. 62/464,363, entitled “Techniques and Systems for Three-Dimensional Printing of Foam and Other Materials,” filed Feb. 27, 2017, incorporated herein by reference in its entirety.
  • the particles may be present in an article, e.g., after formation, such that the article has a weight percent of particles (e.g., reinforcing particles) of at least 5 wt %, at least 10 wt %, at least 15 wt %, at least 20 wt %, at least 25 wt %, at least 30 wt %, at least 35 wt %, at least 40 wt %, at least 45 wt %, at least 50 wt %, at least 55 wt %, at least 60 wt %, at least 65 wt %, at least 70 wt %, at least 75 wt %, at least 80 wt %, or at least 85 wt % with respect to the total weight of the article.
  • a weight percent of particles e.g., reinforcing particles
  • the article has a weight percent of particles (e.g., reinforcing particles) of at most 90 wt %, at most 85 wt %, at most 80 wt %, at most 75 wt %, at most 70 wt %, at most 65 wt %, at most 60 wt %, at most 55 wt %, at most 50 wt %, at most 45 wt %, at most 40 wt %, at most 35 wt %, at most 30 wt %, at most 25 wt %, at most 20 wt %, at most 15 wt %, or at most 10 wt % with respect to the total weight of the article. Combinations of the above-referenced ranges are also possible (e.g., at least 5 wt % and at most 90 wt %).
  • the particles may be present in an article, e.g., after formation, such that the article has a volume percent of particles (e.g., reinforcing particles) of at least 5 vol %, at least 10 vol %, at least 15 vol %, at least 20 vol %, at least 25 vol %, at least 30 vol %, at least 35 vol %, at least 40 vol %, at least 45 vol %, at least 50 vol %, at least 55 vol %, at least 60 vol %, at least 65 vol %, or at least 70 vol % with respect to the total volume of the article.
  • a volume percent of particles e.g., reinforcing particles
  • the article has a volume percent of particles (e.g., reinforcing particles) of at most 74 vol %, at most 70 vol %, at most 65 vol %, at most 60 vol %, at most 55 vol %, at most 50 vol %, at most 45 vol %, at most 40 vol %, at most 35 vol %, at most 30 vol %, at most 25 vol %, at most 20 vol %, at most 15 vol %, or at most 10 vol % with respect to with respect to the total volume of the article. Combinations of the above-referenced ranges are also possible (e.g., at least 5 vol % and at most 74 vol %).
  • printing a mixture onto a substrate may comprise depositing the mixture onto a substrate in a layer.
  • printing the mixture onto a substrate may comprise depositing the mixture onto a substrate in a plurality of layers.
  • Printing in a plurality of layers may involve depositing the mixture onto a substrate in a first layer (e.g., along a line) and then depositing the mixture onto a substrate in a second layer (e.g., along the same line, in a perpendicular line to that of the first layer, etc.).
  • Printing e.g., 3D-printing
  • a plurality of layers may involve depositing a material in a pre-determined shape with a high degree of precision and control, using for example a robotic positioning system coupled with a controller.
  • a robotic positioning system coupled with a controller.
  • Those of ordinary skill in the art will be aware of systems and methods for 3D-printing, which typically involves the formation of 3-dimensional shapes, e.g., as opposed to 2-dimensional coatings that take the shape of the surface that they are applied to.
  • 3D-printing techniques include, but are not limited to, additive manufacturing techniques such as direct ink writing (DIW), stereolithography (SL), fused deposition modeling (FDM), laser sintering, laminated object manufacturing (LOM), doctor blading, material spraying, and material jetting.
  • additive manufacturing techniques such as direct ink writing (DIW), stereolithography (SL), fused deposition modeling (FDM), laser sintering, laminated object manufacturing (LOM), doctor blading, material spraying, and material jetting.
  • 3D-printing comprises depositing a first material in a first layer via additive manufacturing, removing at least some material in the first layer via subtractive manufacturing, and after removing the at least some material in the first layer, depositing a second material in the first layer via additive manufacturing.
  • additive manufacturing comprises at least one member selected from the group consisting of: direct ink writing (DIW), stereolithography (SL), fused deposition modeling (FDM), laser sintering, laminated object manufacturing (LOM), doctor blading, material spraying, and material jetting.
  • subtractive manufacturing comprises at least one member selected from the group consisting of: milling, drilling, cutting, etching, grinding, sanding, planing, and turning.
  • 3D-printing comprises receiving, by a processing device, a 3D model of an object to be printed; receiving, by the processing device, information including at least one material property of a material to be 3D-printed; and generating, by the processing device, a set of sensor-based printer control parameters to print the object based, at least in part, on the sensor input.
  • the processing device is further adapted to execute instructions for initiating 3D-printing of the object in the 3D-printer; receiving, during 3D-printing, the input from the sensor associated with the 3D-printing; and adjusting at least one printing property based on the sensor input.
  • the sensor is a force probe, a weight sensor, an optical camera, an imaging device, an in-line imaging device, a profilometer, a laser measurement device, a 3D scanner, or an automatic digital multimeter.
  • 3D-printing includes obtaining model data representing a 3D model of an object.
  • This implementation also includes processing the model data to generate a set of commands to direct a 3D-printer to extrude a material to form a physical model associated with the object.
  • the set of commands is executable to cause an extruder (e.g., comprising a mixing nozzle) of the 3D printer to deposit a first portion of the material corresponding to a first portion of the physical model, to clean, to purge, or to clean and purge the extruder after depositing the first portion of the material, and to deposit a second portion of the material after cleaning the extruder.
  • the second portion of the material corresponds to a second portion of the physical model.
  • a printed article (e.g., a 3D-printed article comprising a composite) may have a smallest dimension of greater than 10 mm, greater than 12 mm, greater than 14 mm, greater than 16 mm, greater than 18 mm, or greater than 20 mm.
  • a printed article may have an average largest dimension of particles (e.g., reinforcing particles) of at least 10 microns, at least 20 microns, at least 30 microns, at least 40 microns, at least 50 microns, at least 60 microns, at least 70 microns, at least 80 microns, at least 90 microns, at least 100 microns, at least 150 microns, at least 200 microns, at least 250 microns, at least 300 microns, at least 350 microns, at least 400 microns, at least 500 microns, at least 700 microns, or at least 900 microns.
  • particles e.g., reinforcing particles
  • the printed article may have an average largest dimension of particles (e.g., reinforcing particles) of at most 1000 microns, at most 900 microns, at most 700 microns, at most 500 microns, at most 400 microns, at most 350 microns, at most 300 microns, at most 250 microns, at most 200 microns, at most 150 microns, at most 100 microns, at most 90 microns, at most 80 microns, at most 70 microns, at most 60 microns, at most 50 microns, at most 40 microns, at most 30 microns, or at most 20 microns.
  • particles e.g., reinforcing particles
  • Combinations of the above-referenced ranges are also possible (e.g., at least 10 microns and at most 1000 microns, or at least 50 microns and at most 400 microns, or at least 50 microns and at most 250 microns).
  • a printed article may have a compression strength of at least 0.1 MPa, at least 0.5 MPa, at least 1 MPa, at least 5 MPa, at least 10 MPa, at least 20 MPa, at least 40 MPa, at least 80 MPa, at least 100 MPa, at least 200 MPa, at least 300 MPa, or at least 400 MPa.
  • a printed article may have a compression strength of at most 500 MPa, at most 400 MPa, at most 300 MPa, at most 200 MPa, at most 100 MPa, at most 80 MPa, at most 40 MPa, at most 20 MPa, at most 10 MPa, at most 5 MPa, at most 1 MPa, or at most 0.5 MPa. Combinations of the above-referenced ranges are also possible (e.g., at least 0.1 MPa and at most 500 MPa).
  • an article comprising a composite that is printed may comprise two or more portions, wherein one or more properties (e.g., average largest dimension of particles (e.g., reinforcing particles), average concentration of particles (e.g., reinforcing particles) e.g. weight percent of particles (e.g., reinforcing particles), surface roughness, compression strength, slip resistance, abrasion resistance, density, stiffness, heat deflection temperature, pore concentration, pore size, and coefficient of thermal expansion) of a first portion may differ from one or more properties of a second portion.
  • one or more properties e.g., average largest dimension of particles (e.g., reinforcing particles), average concentration of particles (e.g., reinforcing particles) e.g. weight percent of particles (e.g., reinforcing particles), surface roughness, compression strength, slip resistance, abrasion resistance, density, stiffness, heat deflection temperature, pore concentration, pore size, and coefficient of thermal expansion
  • the difference in properties between the first portion and the second portion may comprise a gradient of the one or more properties (e.g., the property or properties may vary relatively smoothly from a first value in the first portion to a second value in the second portion). In other embodiments, there may be a sharp change in one or more of the properties at a boundary of one or more of the first portion and the second portion.
  • the article may be adhered to a textile. In some embodiments, the article may comprise a polymer. In some embodiments, the article may be a component of a shoe upper. The article may in some cases be printed directly onto a textile to make up a component of a shoe upper or article of apparel. Examples of methods of producing such particles, e.g., having differences between a first portion and a second portion, are discussed in more detail below.
  • a method of printing an article may comprise flowing at least two inputs into a mixing nozzle to form a first mixture comprising a blowing agent.
  • one of the at least two inputs to form the first mixture comprises an isocyanate and another of the at least two inputs to form the first mixture comprises a polyol system containing the blowing agent.
  • the method further comprising flowing at least a third input comprising a polyol system into the mixing nozzle to form the first mixture.
  • the method may comprise depositing a first region comprising the first mixture to form a first elastomer.
  • the method may comprise flowing at least two inputs into a mixing nozzle to form a second mixture.
  • one of the at least two inputs to form the second mixture comprises an isocyanate and another of the at least two inputs to form the second mixture comprises a polyol system.
  • the second mixture comprises a blowing agent.
  • the method further comprises flowing at least a third input comprising a polyol system containing a blowing agent into the mixing nozzle to form the second mixture.
  • the method may comprise depositing a second region adjacent to the first region, comprising the second mixture to form a second elastomer.
  • the method may comprise heating at least the first region of the article (e.g., at least the first region and the second region of the article) to a temperature greater than or equal to the activation temperature of the blowing agent. In some embodiments, heating at least the first region of the article causes differential expansion between the first region and the second region of the article and physical deformation of the article.
  • input Part A may comprise isocyanate
  • input Part B′ may comprise a polyol system
  • input Part B′′ may comprise a polyol system with a blowing agent.
  • Part A and Part B′ are mixed, an elastomer results.
  • Part A and Part B′′ are mixed, an elastomer that will expand when activated results.
  • Part A is mixed with Part B′ and Part B′′, an elastomer that will expand to a lesser extent than pure Part A with pure Part B′′ (e.g., when in the same ratio as Part A to Part B′ and Part B′′ combined) results. If a fourth input were added, then stiffness as well as expansion on activation could be controlled.
  • a printed article that comprises at least two portions, at least one of which comprises a composite (e.g., a printed article that comprises at least a first portion comprising an elastomer and a second portion comprising a elastomer containing a blowing agent) may have a ratio of a property (e.g., average largest dimension of particles (e.g., reinforcing particles), average concentration of particles (e.g., reinforcing particles), surface roughness, compression strength, slip resistance, abrasion resistance, density, stiffness, heat deflection temperature, pore concentration, pore size, and/or coefficient of thermal expansion) of the second portion of the printed article to the same property of the first portion of the printed article of greater than or equal to 1.05, greater than or equal to 1.1, greater than or equal to 1.2, greater than or equal to 1.3, greater than or equal to 1.5, greater than or equal to 2, or greater than or equal to 5.
  • a property e.g., average largest dimension of particles (e.g.,
  • a ratio of the property of the second portion of the printed article to the same property of the first portion of the printed article may be less than or equal to 10, less than or equal to 5, less than or equal to 2, less than or equal to 1.5, less than or equal to 1.3, less than or equal to 1.2, or less than or equal to 1.1. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 1.05 and less than or equal to 10).
  • the gradient in a property (e.g., volume percent of particles, e.g., reinforcing particles) in the article may be present from the surface of the article to greater than or equal to 10 microns, greater than or equal to 20 microns, greater than or equal to 30 microns greater than or equal to 50 microns, greater than or equal to 100 microns, greater than or equal to 500 microns, greater than or equal to 1000 microns, or greater than or equal to 10000 microns below the surface of the article.
  • the gradient in the property may be present throughout the thickness of the article.
  • the portions may differ for a variety of reasons, for example, different particle compositions, different particle shapes, different particle sizes, different densities of particles, or the like. Combinations of any of these are also possible. As a non-limiting example, if two average particle sizes are present, then each of the average particle sizes may independently be those described herein.
  • a printed article that comprises at least two portions comprising particles (e.g., reinforcing particles) may have a ratio of the average largest dimension of particles (e.g., reinforcing particles) in a first portion of the printed article to the average largest dimension of particles (e.g., reinforcing particles) in a second portion of the printed article of greater than or equal to 1.05, greater than or equal to 1.1, greater than or equal to 1.2, greater than or equal to 1.3, greater than or equal to 1.5, greater than or equal to 2, or greater than or equal to 5.
  • a ratio of the average largest dimension of particles (e.g., reinforcing particles) in the second portion of the printed article to the average largest dimension of particles (e.g., reinforcing particles) in the first portion of the printed article may be less than or equal to 10, less than or equal to 5, less than or equal to 2, less than or equal to 1.5, less than or equal to 1.3, less than or equal to 1.2, or less than or equal to 1.1. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 1.05 and less than or equal to 10).
  • a printed article that comprises at least one portion comprising a composite (e.g., a printed article that comprises at least a first portion comprising a composite) may have a weight percent of particles (e.g., reinforcing particles) in the first portion of the printed article of at least 5 wt %, at least 10 wt %, at least 15 wt %, at least 20 wt %, at least 25 wt %, at least 30 wt %, at least 35 wt %, at least 40 wt %, at least 45 wt %, at least 50 wt %, at least 55 wt %, at least 60 wt %, at least 65 wt %, at least 70 wt %, at least 75 wt %, at least 80 wt %, or at least 85 wt % with respect to the total weight of the article.
  • a weight percent of particles e.g., reinforcing particles
  • the first portion of the printed article has a weight percent of particles (e.g., reinforcing particles) of at most 90 wt %, at most 85 wt %, at most 80 wt %, at most 75 wt %, at most 70 wt %, at most 65 wt %, at most 60 wt %, at most 55 wt %, at most 50 wt %, at most 45 wt %, at most 40 wt %, at most 35 wt %, at most 30 wt %, at most 25 wt %, at most 20 wt %, at most 15 wt %, or at most 10 wt % with respect to the total weight of the article. Combinations of the above-referenced ranges are also possible (e.g., at least 5 wt % and at most 90 wt %).
  • a printed article that comprises at least two portions comprising a composite (e.g., a printed article that comprises at least a first portion comprising a composite and a second portion comprising a composite) may have a weight percent of particles (e.g., reinforcing particles) in the first portion of the printed article of at least 5 wt %, at least 10 wt %, at least 15 wt %, at least 20 wt %, at least 25 wt %, at least 30 wt %, at least 35 wt %, at least 40 wt %, at least 45 wt %, at least 50 wt %, at least 55 wt %, at least 60 wt %, at least 65 wt %, at least 70 wt %, at least 75 wt %, at least 80 wt %, or at least 85 wt % with respect to the total
  • the second portion of the printed article has a weight percent of particles (e.g., reinforcing particles) of at most 90 wt %, at most 85 wt %, at most 80 wt %, at most 75 wt %, at most 70 wt %, at most 65 wt %, at most 60 wt %, at most 55 wt %, at most 50 wt %, at most 45 wt %, at most 40 wt %, at most 35 wt %, at most 30 wt %, at most 25 wt %, at most 20 wt %, at most 15 wt %, or at most 10 wt % with respect to the total weight of the article. Combinations of the above-referenced ranges are also possible (e.g., at least 5 wt % and at most 90 wt %).
  • a printed article that comprises at least two portions comprising a composite (e.g., a printed article that comprises at least a first portion comprising a composite and a second portion comprising a composite) may have a ratio of the weight percent of particles (e.g., reinforcing particles) in the second portion of the printed article to the weight percent of particles (e.g., reinforcing particles) in the first portion of the printed article of greater than or equal to 1.05, greater than or equal to 1.1, greater than or equal to 1.2, greater than or equal to 1.3, greater than or equal to 1.5, greater than or equal to 2, or greater than or equal to 5.
  • a ratio of the weight percent of particles (e.g., reinforcing particles) in the second portion of the printed article to the weight percent of particles (e.g., reinforcing particles) in the first portion of the printed article may be less than or equal to 10, less than or equal to 5, less than or equal to 2, less than or equal to 1.5, less than or equal to 1.3, less than or equal to 1.2, or less than or equal to 1.1. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 1.05 and less than or equal to 10).
  • a printed article that comprises at least one portion comprising a composite (e.g., a printed article that comprises at least a first portion comprising a composite) may have a compression strength in the first portion of the printed article of at least 0.1 MPa, at least 0.5 MPa, at least 1 MPa, at least 5 MPa, at least 10 MPa, at least 20 MPa, at least 40 MPa, at least 80 MPa, at least 100 MPa, at least 200 MPa, at least 300 MPa, or at least 400 MPa.
  • the first portion of the printed article may have a compression strength of at most 500 MPa, at most 400 MPa, at most 300 MPa, at most 200 MPa, at most 100 MPa, at most 80 MPa, at most 40 MPa, at most 20 MPa, at most 10 MPa, at most 5 MPa, at most 1 MPa, or at most 0.5 MPa. Combinations of the above-referenced ranges are also possible (e.g., at least 0.1 MPa and at most 500 MPa).
  • a printed article that comprises at least two portions comprising a composite (e.g., a printed article that comprises at least a first portion comprising a composite and a second portion comprising a composite) may have a compression strength in the second portion of the printed article of at least 0.1 MPa, at least 0.5 MPa, at least 1 MPa, at least 5 MPa, at least 10 MPa, at least 20 MPa, at least 40 MPa, at least 80 MPa, at least 100 MPa, at least 200 MPa, at least 300 MPa, or at least 400 MPa.
  • the second portion of the printed article may have a compression strength of at most 500 MPa, at most 400 MPa, at most 300 MPa, at most 200 MPa, at most 100 MPa, at most 80 MPa, at most 40 MPa, at most 20 MPa, at most 10 MPa, at most 5 MPa, at most 1 MPa, or at most 0.5 MPa. Combinations of the above-referenced ranges are also possible (e.g., at least 0.1 MPa and at most 500 MPa).
  • a printed article that comprises at least two portions comprising a composite (e.g., a printed article that comprises at least a first portion comprising a composite and a second portion comprising a composite) may have a ratio of compression strength in the second portion of the printed article to compression strength in the first portion of the printed article of greater than or equal to 1.05, greater than or equal to 1.1, greater than or equal to 1.2, greater than or equal to 1.3, greater than or equal to 1.5, greater than or equal to 2, or greater than or equal to 5.
  • a ratio of compression strength in the second portion of the printed article to compression strength in the first portion of the printed article may be less than or equal to 10, less than or equal to 5, less than or equal to 2, less than or equal to 1.5, less than or equal to 1.3, less than or equal to 1.2, or less than or equal to 1.1. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 1.05 and less than or equal to 10).
  • a printed article that comprises at least two portions comprising a composite (e.g., a printed article that comprises at least a first portion comprising a composite and a second portion comprising a composite) may have a ratio of slip resistance in the second portion of the printed article to slip resistance in the first portion of the printed article of greater than or equal to 1.05, greater than or equal to 1.1, greater than or equal to 1.2, greater than or equal to 1.3, greater than or equal to 1.5, greater than or equal to 2, or greater than or equal to 5.
  • a ratio of slip resistance in the second portion of the printed article to slip resistance in the first portion of the printed article may be less than or equal to 10, less than or equal to 5, less than or equal to 2, less than or equal to 1.5, less than or equal to 1.3, less than or equal to 1.2, or less than or equal to 1.1. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 1.05 and less than or equal to 10).
  • a printed article that comprises at least two portions comprising a composite (e.g., a printed article that comprises at least a first portion comprising a composite and a second portion comprising a composite) may have a ratio of abrasion resistance in the second portion of the printed article to abrasion resistance in the first portion of the printed article of greater than or equal to 1.05, greater than or equal to 1.1, greater than or equal to 1.2, greater than or equal to 1.3, greater than or equal to 1.5, greater than or equal to 2, or greater than or equal to 5.
  • a ratio of abrasion resistance in the second portion of the printed article to abrasion resistance in the first portion of the printed article may be less than or equal to 10, less than or equal to 5, less than or equal to 2, less than or equal to 1.5, less than or equal to 1.3, less than or equal to 1.2, or less than or equal to 1.1. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 1.05 and less than or equal to 10).
  • the particles may be incorporated in order to modify the finish of the printed article.
  • finish is given its ordinary meaning in the art and may refer to the appearance experienced by the viewer. As non-limiting examples, the finish may be characterized as shiny or matte.
  • the particles may comprise a blowing agent, e.g., solid particles that decompose, above a certain activation temperature, into a gas.
  • the activation temperature of the blowing agent may be greater than the curing temperature (e.g., the maximum temperature in the curing profile) of the matrix of the printed article by e.g. at least 2 degrees Celsius, at least 5 degrees Celsius, at least 10 degrees Celsius, at least 20 degrees Celsius, at least 30 degrees Celsius, or at least 50 degrees Celsius.
  • the activation temperature of the blowing agent may be less than the curing temperature of the matrix of the printed article by e.g.
  • activation temperature is given its ordinary meaning in the art and may refer to the temperature at or above which a blowing agent comprising solid particles decomposes into a gas.
  • curing temperature is given its ordinary meaning in the art and may refer to the temperature at or above which the matrix of the printed article (e.g., comprising polyurethane) solidifies by e.g. crosslinking.
  • the blowing agent may be incorporated into the printed article by introducing a fluid comprising a blowing agent concentrate as one of the inputs of a mixing nozzle (e.g., a microfluidic printing nozzle) system with a plurality of inputs.
  • the blowing agent concentrate may be made to flow into the mixing nozzle at a constant rate, such that the volume fraction of solid particles comprising blowing agent in the matrix of the printed article is constant throughout the printed object.
  • the blowing agent concentrate may be made to flow into the mixing nozzle at a varying rate, such that the volume fraction of solid particles comprising blowing agent in the matrix of the printed article varies throughout the printed object.
  • the blowing agent concentrate is made to flow into the mixing nozzle at a varying rate as dictated by a computer.
  • the blowing agent concentrate is digitally made to flow into the mixing nozzle at a varying rate, such that a greater volume fraction of blowing agent is incorporated into at least a first portion of the printed article where shrinkage of the matrix during curing is predicted and/or known to cause warping of the printed article, and a smaller volume fraction of blowing agent is incorporated into at least a second portion of the printed article where shrinkage of the matrix during curing is predicted and/or known not to cause warping of the printed article.
  • measurement of the extent of warping of at least a first portion of a first printed article, in which the first printed article is printed and cured without the activation of a blowing agent maybe conducted to determine the locations of warping.
  • These determined locations of warping can be used to design the incorporation of varying volume fractions of blowing agent in at least a first portion and a second portion of a second printed article, in which a greater volume fraction of blowing agent is incorporated in at least the first portion of the second printed article to reduce warping (e.g., resulting from shrinkage during curing of the matrix) by means of volumetrically expanding at least the first portion of the second printed article by heating at least the first portion of the second printed article above the activation temperature of the blowing agent.
  • warping e.g., resulting from shrinkage during curing of the matrix
  • the measurement of the extent of warping of the first printed article at locations throughout the first printed article may in some embodiments, as a non-limiting example, be accomplished by the inclusion of markings in the first printed article and then video-tracking of the change in position of these markings with curing.
  • the matrix may shrink during curing by at least about 0.5% by volume, at least about 1% by volume, at least about 2% by volume, at least about 3% by volume, at least about 4% by volume, at least about 5% by volume, at least about 10% by volume, at least about 15% by volume, at least about 20% by volume, at least about 30% by volume, or at least about 40% by volume.
  • the matrix may shrink during curing by at most about 50% by volume, at most about 40% by volume, at most about 30% by volume, at most about 20% by volume, at most about 15% by volume, at most about 10% by volume, at most about 5% by volume, most about 4% by volume, at most about 3% by volume, or at most about 2% by volume.
  • heating at least a first portion of a printed article, comprising the blowing agent, at or above the activation temperature of the blowing agent causes a volumetric expansion of the printed article.
  • the at least a first portion of the printed article may volumetrically expand (e.g., upon heating at or above the blowing agent activation temperature) by at least about 1% by volume, at least about 2% by volume, at least about 3% by volume, at least about 4% by volume, at least about 5% by volume, at least about 10% by volume, at least about 15% by volume, at least about 20% by volume, at least about 30% by volume, or at least about 40% by volume.
  • the at least a first portion of the printed article may volumetrically expand (e.g., upon heating at or above the blowing agent activation temperature) by at most about 50% by volume, at most about 40% by volume, at most about 30% by volume, at most about 20% by volume, at most about 15% by volume, at most about 10% by volume, at most about 5% by volume, most about 4% by volume, at most about 3% by volume, or at most about 2% by volume.
  • the blowing agent incorporated into at least a first portion of a printed article may be present in a volume fraction such that the volumetric expansion provided by the blowing agent is within about 50%, within about 40%, within about 30%, within about 20%, within about 10%, within about 5%, within about 2%, within about 1%, or within about 0.5% of the volumetric shrinkage provided by the curing of the matrix.
  • the printed article ( FIG. 19 , initial printed article 1900 ) may initially comprise unexpanded blowing agent ( FIG. 19, 1910 ) prior to heating the printed article, in which unexpanded blowing agent is homogeneously distributed throughout the matrix ( FIG. 19, 1920 ) of the printed article.
  • heat is applied throughout the printed article such that the resulting printed article ( FIG. 19, 1901 ) comprises expanded blowing agent ( FIG. 19, 1930 ), resulting in a volumetrically expanded printed article.
  • a non-limiting set of methods of making article 1900 may comprise depositing (e.g., by extrusion through a nozzle) at least a first layer comprising both matrix and blowing agent in a volume percentage as described herein.
  • a non-limiting set of methods of making article 1901 may comprise at least one method of the non-limiting set of methods of making article 1900 followed by applying heat to the entirety of the printed article at or above the activation temperature of the blowing agent and the curing temperature of the matrix for a duration such that the matrix solidifies and the blowing agent expands to form article 1901 .
  • the volume fraction of solid blowing agent in the printed article may be at least about 0.01 volume percent, at least about 0.1 volume percent, at least about 1 volume percent, at least about 5 volume percent, at least about 10 volume percent, at least about 20 volume percent, at least about 30 volume percent, or at least about 40 volume percent. In some embodiments, the volume fraction of solid blowing agent in the printed article may be at most about 50 volume percent, at most about 40 volume percent, at most about 30 volume percent, at most about 20 volume percent, at most about 10 volume present, at most about 5 volume percent, at most about 1 volume percent, or at most about 0.1 volume percent.
  • solid particles of blowing agent may be incorporated into the entire printed article such that the solid particles are homogeneously dispersed in the matrix at a constant volume fraction.
  • the surface of the printed article may be exposed to a temperature at or above both the curing temperature of the matrix and the activation temperature of the blowing agent for a brief period of time, such that only the blowing agent at the surface of the printed article is activated.
  • such treatment of the printed article results in a surface with a matte finish.
  • the surface of the printed article may be exposed to a temperature above both the curing temperature of the matrix and the activation temperature of the blowing agent by at least about 0 degrees Celsius, at least about 1 degree Celsius, at least about 2 degrees Celsius, at least about 5 degrees Celsius, at least about 10 degrees Celsius, at least about 15 degrees Celsius, at least about 20 degrees Celsius, at least about 25 degrees Celsius, at least about 30 degrees Celsius, at least about 40 degrees Celsius, or at least about 50 degrees Celsius.
  • the surface of the printed article may be exposed to a temperature above both the curing temperature of the matrix and the activation temperature of the blowing agent by at most about 60 degrees Celsius, at most about 50 degrees Celsius, at most about 40 degrees Celsius, at most about 30 degrees Celsius, and most about 25 degrees Celsius, at most about 20 degrees Celsius, at most about 15 degrees Celsius, at most about 10 degrees Celsius, at most about 5 degrees Celsius, at most about 2 degrees Celsius, or at most about 1 degree Celsius.
  • the surface of the printed article may be exposed to a temperature at or above both the curing temperature of the matrix and the activation temperature of the blowing agent for less than or equal to about 300 seconds, less than or equal to about 240 seconds, less than or equal to about 180 seconds, less than or equal to about 120 seconds, less than or equal to about 60 seconds, less than or equal to about 30 seconds, less than or equal to about 20 seconds, less than or equal to about 10 seconds, less than or equal to about 5 seconds, less than or equal to about 2 seconds, or less than or equal to about 1 second.
  • a concentrated hot air nozzle maybe used to locally expose the surface of at least a first portion of a printed article to a temperature at or above both the curing temperature of the matrix and the activation temperature of the blowing agent.
  • the at least a first portion that was locally exposed with a concentrated hot air nozzle has a matte finish.
  • the particles may comprise solid particles comprising a blowing agent that may be incorporated into at least a first portion of the printed article.
  • the solid particles comprising a blowing agent may be incorporated into the printed article in a gradient.
  • at least a second portion of the printed article is free of solid particles comprising a blowing agent.
  • the surface layer of the printed article ( FIG. 17 , initial printed article 1700 ) may initially comprise unexpanded blowing agent ( FIG. 17, 1710 ) prior to heating the printed article, and the remainder of the printed article that is not the surface layer may be free of unexpanded blowing agent and comprise the matrix ( FIG.
  • heat is applied to the surface of the printed article or to the entire printed article such that the resulting printed article ( FIG. 17, 1701 ) has a surface layer comprising expanded blowing agent ( FIG. 17, 1730 ), resulting in a textured surface that may have a matte finish.
  • a non-limiting set of methods of making article 1700 may comprise depositing (e.g., by extrusion through a nozzle) at least a first layer comprising matrix and free of blowing agent, followed by depositing at least a first surface layer comprising both matrix and blowing agent in a volume percentage as described herein.
  • a non-limiting set of methods of making article 1701 may comprise at least one method of the non-limiting set of methods of making article 1700 followed by applying heat to the surface layer or the entirety of the printed article at or above both the curing temperature of the matrix and the activation temperature of the blowing agent for a duration such that the matrix solidifies and the blowing agent expands to form article 1701 .
  • local activation of the blowing agent may be accomplished by local application of heat to at least a first portion of the printed article in which the blowing agent has been incorporated (e.g., by flowing through a mixing nozzle).
  • a printed article that has been cured may comprise bubbles (e.g., that have been formed from the activation of the blowing agent) and may additionally comprise solid particles comprising a blowing agent that were intentionally left not activated.
  • the entire printed article was heated at or above the curing temperature of the matrix, and at least a first portion of the printed article was heated at or above the activation temperature of the blowing agent.
  • At least a second portion of the printed article was heated at or above the activation temperature of the blowing agent, in which case, e.g., the solid particles comprising a blowing agent remaining as solid particles had an activation temperature above the curing temperature of the matrix.
  • the printed article ( FIG. 18 , initial printed article 1800 ) may initially comprise unexpanded blowing agent ( FIG. 18, 1810 ) prior to heating the printed article, in which unexpanded blowing agent is homogeneously distributed throughout the matrix ( FIG. 18, 1820 ) of the printed article.
  • heat is applied locally to at least a first portion of the surface of the printed article such that the resulting printed article ( FIG. 18, 1801 ) has at least the first portion of the surface layer comprising expanded blowing agent ( FIG. 18, 1830 ), resulting in a partially textured surface that may have a matte finish in the at least one portion of the surface layer comprising expanded blowing agent.
  • a non-limiting set of methods of making article 1800 may comprise depositing (e.g., by extrusion through a nozzle) at least a first layer comprising both matrix and blowing agent in a volume percentage as described herein, followed by depositing at least a first surface layer comprising both matrix and blowing agent in a volume percentage as described herein.
  • a non-limiting set of methods of making article 1801 FIG. 18
  • article 18 may comprise at least one method of the non-limiting set of methods of making article 1800 followed by applying heat to at least a first portion of the surface layer at or above the activation temperature of the blowing agent and applying heat to the entirety of the printed article at or above the curing temperature of the matrix for a duration such that the matrix solidifies and the blowing agent expands in at least the first portion of the surface layer to form article 1801 .
  • Unexpanded blowing agent in article 1801 results from the blowing agent having an activation temperature above that of the curing temperature of the matrix.
  • a blowing agent concentrate may be one of the inputs (e.g., a first fluid) to a mixing nozzle system with a plurality of inputs.
  • the volume percent of blowing agent incorporated into a given portion of the printed article is digitally controlled.
  • the entire printed article is heated at or above the activation temperature of the blowing agent and at or above the curing temperature of the matrix, and only at least a first portion of the printed article comprising the blowing agent volumetrically expand and/or achieve a different surface texture from the at least a second portion of the printed article that is free of the blowing agent prior to heating.
  • a hybrid approach may be taken, in which a plurality of blowing agents, each with a different activation temperature and/or a different solid particle size, may be incorporated into the printed article.
  • a low-temperature activating blowing agent may be incorporated that has an activation temperature at or below the curing temperature of the matrix and therefore that is activated during curing of the printed article.
  • a blowing agent with an activation temperature above the curing temperature of the matrix may be incorporated into the printed article and may be activated by the local application of heat during or after curing the printed article.
  • an article that changes shape may be printed by controlling the ratios of two or more inputs into a mixing nozzle to deposit at least two regions each of which comprises a respective matrix (e.g., an elastomer) adjacent to one another where at least one of the regions contains a blowing agent (e.g., chemical blowing agent) that can be activated at high temperature.
  • the first region may have the same or different components from the second region.
  • the blowing agent may be activated by heating at least one portion of the article comprising the blowing agent to a temperature greater than or equal to the activation temperature of the blowing agent (and, when applicable, the curing temperature of the matrix), resulting in a differential expansion between the at least two regions that causes physical deformation of the article.
  • the differential expansion is programmed to cause the article to better conform to a shoe last.
  • the blowing agent concentration is varied between the at least two regions by controlling the ratio between two or more input materials to a mixing nozzle, one or more of which input materials comprises the blowing agent.
  • the stiffness of the matrix (e.g., elastomer) in the first region may differ from the stiffness of the matrix (e.g., elastomer) in the second region (e.g., by varying the concentration of crosslinking agent between the first region and the second region).
  • the differential expansion of the two or more regions is controlled by the stiffness difference between the two regions with respect to the matrix (e.g., elastomer) that encapsulates the blowing agent.
  • the differential expansion is controlled by both a difference in stiffness of the matrix and a difference in blowing agent concentration between the two or more regions. In some embodiments, the differential expansion is controlled by a difference between the first region and the second region of the density, blowing agent concentration, pore concentration, pore size, stiffness, heat deflection temperature, coefficient of thermal expansion, and/or filler concentration.
  • the printed article may have a ratio of the concentration of blowing agent in the first region prior to heating, to the concentration of blowing agent in the second region prior to heating, of greater than or equal to 1.05, greater than or equal to 1.1, greater than or equal to 1.2, greater than or equal to 1.3, greater than or equal to 1.5, greater than or equal to 2, or greater than or equal to 5.
  • a ratio of the concentration of blowing agent in the first region prior to heating, to the concentration of blowing agent in the second region prior to heating may be less than or equal to 10, less than or equal to 5, less than or equal to 2, less than or equal to 1.5, less than or equal to 1.3, less than or equal to 1.2, or less than or equal to 1.1. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 1.05 and less than or equal to 10).
  • the printed article may have a ratio of the concentration of crosslinking agent in the first region prior to heating, to the concentration of crosslinking agent in the second region prior to heating, of greater than or equal to 1.05, greater than or equal to 1.1, greater than or equal to 1.2, greater than or equal to 1.3, greater than or equal to 1.5, greater than or equal to 2, or greater than or equal to 5.
  • a ratio of the concentration of crosslinking agent in the first region prior to heating, to the concentration of crosslinking agent in the second region prior to heating may be less than or equal to 10, less than or equal to 5, less than or equal to 2, less than or equal to 1.5, less than or equal to 1.3, less than or equal to 1.2, or less than or equal to 1.1.
  • the activation temperature of the blowing agent may be greater than or equal to 200 degrees Celsius, greater than or equal to 250 degrees Celsius, greater than or equal to 300 degrees Celsius, greater than or equal to 350 degrees Celsius greater than or equal to 400 degrees Celsius, greater than or equal to 450 degrees Celsius, greater than or equal to 500 degrees Celsius, greater than or equal to 550 degrees Celsius, greater than or equal to 600 degrees Celsius, greater than or equal to 650 degrees Celsius, or greater than or equal to 700 degrees Celsius.
  • the activation temperature of the blowing agent may be less than or equal to 750 degrees Celsius, less than or equal to 700 degrees Celsius, less than or equal to 650 degrees Celsius, less than or equal to 600 degrees Celsius, less than or equal to 550 degrees Celsius, less than or equal to 500 degrees Celsius, less than or equal to 450 degrees Celsius, less than or equal to 400 degrees Celsius, less than or equal to 350 degrees Celsius, less than or equal to 300 degrees Celsius, or less than or equal to 250 degrees Celsius. Combinations of these activation temperatures are also possible (e.g., greater than or equal to 200 degrees Celsius and less than or equal to 750 degrees Celsius).
  • the at least one portion of the article may be heated to a temperature greater than or equal to the activation temperature of the blowing agent (and, when applicable, the curing temperature of the matrix) for greater than or equal to 1 minute, greater than or equal to 2 minutes, greater than or equal to 5 minutes, greater than or equal to 30 minutes, or greater than or equal to 60 minutes.
  • the at least one portion of the article may be heated to a temperature greater than or equal to the activation temperature of the blowing agent for less than or equal to 120 minutes, less than or equal to 60 minutes, less than or equal to 30 minutes, less than or equal to 5 minutes, or less than or equal to 2 minutes. Combinations of these heating durations are also possible (e.g., greater than or equal to 1 minute and less than or equal to 120 minutes).
  • an article may comprise a polymeric structure.
  • the polymeric structure may comprise a polymer.
  • the polymeric structure may comprise particles (e.g., reinforcing particles) (e.g., comprising a chemical blowing agent).
  • the polymeric structure has a gradient in volume percent of particles (e.g., reinforcing particles).
  • At least one portion of the polymeric structure in some embodiments may be adhered to a textile.
  • the polymeric structure may contain in at least one portion a chemical blowing agent that has not been expanded.
  • the polymeric structure may contain in at least one portion pores from chemical blowing agent that has been expanded.
  • the surface roughness of the polymeric structure may be increased by heating the polymeric structure at a portion containing chemical blowing agent to a temperature greater than or equal to the activation temperature of the blowing agent.
  • one or more materials deposited onto a substrate may comprise reactive functional groups for a period of time after deposition.
  • the reactive functional groups may be configured to react with other articles to which the deposited material is adjacent (e.g., articles of footwear, components of articles of footwear), such as an article onto which the material was deposited, an article added to the deposited material, an article positioned beside the deposited material, an article disposed on the same article onto which the material was deposited, and/or an article that is positioned partially above or below the deposited material and partially beside the deposited material.
  • Reaction between the reactive functional groups in the deposited material and one or more articles to which it is adjacent may result in bond formation between the deposited material and the articles(s), and/or may increase the adhesive strength between the deposited material and the article(s).
  • articles include textiles, molded parts, layers, further deposited materials with the same or different chemistry, and the like.
  • the deposited material may bond with two or more articles to which it is adjacent, and may adhere these articles together through bonds formed by reaction of the reactive functional groups in the deposited material with the articles.
  • Each article adhered together may comprise a deposited material (e.g., a 3D-printed article may be built up by successively depositing layers of materials comprising reactive functional groups on top of each other), some of the articles adhered together may comprise a deposited material (e.g., a deposited material may adhere another deposited material to which it is adjacent to a textile on which they are both disposed), or none of the articles adhered together may comprise a deposited material. In some cases, the articles adhered together may have different physical or chemical properties (e.g., different values of toughness, different values of Young's modulus).
  • reactive functional groups that are configured to react with an article to which a deposited material is adjacent may also be configured to react with other reactive functional groups in the deposited material.
  • Reaction between two complementary sets of functional groups within the deposited material may comprise curing of the material. As the deposited material cures, the number of reactive functional groups within the deposited material may be reduced and the deposited material may become less reactive with any articles to which it is adjacent.
  • tuning the curing time of the deposited material by varying one or more parameters may be advantageous because it may allow for tuning of the reactivity of the deposited material as a function of time.
  • the curing time may be tuned so that the deposited material is adhesive upon deposition and upon further addition of a second article to the deposited material, but is no longer adhesive during further manufacturing steps and/or when an article of which the deposited material is a part of is in use.
  • a deposited material may comprise reactive functional groups that are alcohol groups and reactive functional groups that are isocyanate groups, and the alcohol groups and isocyanate groups may react to form a polyurethane.
  • a deposited material may comprise reactive functional groups that are amine groups and reactive functional groups that are isocyanate groups, and the alcohol groups and isocyanate groups may react to form a polyureas.
  • Non-limiting examples of suitable molecules comprising alcohol groups include difunctional hydroxyl compounds such as 1,4-butanediol, hydroquinone bis(2-hydroxylethyl) ether, neopentyl glycol, diethanolamine, and methyldiethanolamine; trifunctional hydroxyl compounds such as trimethylolpropane, 1,2,6-hexanetriol, and triethanolamine; tetrafunctional hydroxyl compounds such as pentaerythritol; and polyols such as polyether polyols, polyester polyols, polytetrahydrofuran, polycaprolactone polyols, polycarbonate polyols, and polytetramethylene ether glycol-based polyols.
  • difunctional hydroxyl compounds such as 1,4-butanediol, hydroquinone bis(2-hydroxylethyl) ether, neopentyl glycol, diethanolamine, and methyldiethanolamine
  • trifunctional hydroxyl compounds such as
  • Non-limiting examples of suitable molecules comprising amine groups include difunctional amine compounds such as diethyltoluenediamine and dimethylthiotoluenediamine.
  • suitable molecules comprising isocyanate groups include methylenebis(phenyl isocyanate), toluene diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, methylene bis-cyclohexylisocyanate, and isophorone diisocyanate.
  • Other types of reactive functional groups, and other types of molecules comprising reactive functional groups are also possible.
  • a deposited material may be cured (and/or configured to be cured) at room temperature. In some embodiments, the deposited material may be cured (and/or configured to be cured) at a temperature above room temperature. The deposited material may be configured (and/or configured to be cured) to be cured at a temperature of greater than or equal to 70° C., greater than or equal to 80° C., greater than or equal to 90° C., or greater than or equal to 100° C. The deposited material may be cured (and/or configured to be cured) at a temperature of less than or equal to 110° C., less than or equal to 100° C., less than or equal to 90° C., or less than or equal to 80° C. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 70° C. and less than or equal to 110° C.). Other ranges are also possible.
  • a deposited material may be cured (and/or configured to be fully cured) over any suitable period of time.
  • the deposited material is fully cured (and/or configured to be cured) over a period of time of greater than or equal to two hours, greater than or equal to four hours, greater than or equal to eight hours, greater than or equal to 12 hours, greater than or equal to 20 hours, greater than or equal to 24 hours, greater than or equal to 36 hours, greater than or equal to 48 hours, greater than or equal to three days, greater than or equal to four days, greater than or equal to five days, or greater than or equal to six days.
  • the deposited material is fully cured (and/or configured to be fully cured) over a period of time of less than or equal to one week, less than or equal to six days, less than or equal to five days, less than or equal to four days, less than or equal to three days, less than or equal to 48 hours, less than or equal to 36 hours, less than or equal to 24 hours, less than or equal to 20 hours, less than or equal to 12 hours, less than or equal to eight hours, or less than or equal to four hours. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to two hours and less than or equal to 20 hours, or greater than or equal to 24 hours and less than or equal to one week). Other ranges are also possible.
  • a material may be fully cured over a period of time of greater than or equal to a few days and less than or equal to one week when cured at room temperature but may be fully cured over a period of time of greater than or equal to two hours and less than or equal to 20 hours at a temperature of greater than or equal to 70° C. and less than or equal to 110° C.
  • a deposited material may be deposited at any degree of curing.
  • the deposited material is at least 25% uncured upon deposition, at least 30% uncured upon deposition, at least 40% uncured upon deposition, at least 50% uncured upon deposition, at least 60% uncured upon deposition, at least 70% uncured upon deposition, at least 80% uncured upon deposition, or at least 90% uncured upon deposition.
  • the deposited material is at most 95% uncured upon deposition, at most 90% uncured upon deposition, at most 80% uncured upon deposition, at most 70% uncured upon deposition, at most 60% uncured upon deposition, at most 50% uncured upon deposition, or at most 40% uncured upon deposition. Combinations of the above-referenced ranges are also possible (e.g., at least 30% uncured upon deposition and at most 95% uncured upon deposition). Other ranges are also possible.
  • an article e.g., an article of footwear, a component of an article of footwear
  • a deposited material e.g., deposited on the deposited material, deposited adjacent the deposited material, laminated to the deposited material, etc.
  • the article may be positioned adjacent to the deposited material before at least 25% of the deposited material has cured, before at least 30% of the deposited material has cured, before at least 40% of the deposited material has cured, before at least 50% of the deposited material has cured, or before at least 60% of the deposited material has cured.
  • the article may be positioned adjacent to the deposited material before at most 70% of the deposited material has cured, before at most 60% of the deposited material has cured, before at most 50% of the deposited material has cured, before at most 40% of the deposited material has cured, or before at most 30% of the deposited material has cured. Combinations of the above-referenced ranges are also possible (e.g., before at least 25% of the deposited material has cured and before at most 70% of the deposited material has cured). Other ranges are also possible.
  • an article e.g., an article of footwear, a component of an article of footwear, an article of apparel such as a sports bra, a component of an article of apparel such as a sports bra
  • a method as described herein may include at least one step that is performed on a multi-axis deposition system.
  • multi-axis deposition systems include a print head and a substrate.
  • the print head may be any suitable print head configured to deposit a material onto the substrate.
  • the substrate may be any suitable substrate onto which a material may be deposited; in some embodiments, one or more articles (e.g., a component of an article of footwear, an upper, a sock liner) may be disposed on the substrate.
  • one or both of the print head and substrate may be translated along one or more axes and/or rotated around one or more axes. Translation and/or rotation of the print head and/or substrate may enable the position of the print head with respect to the substrate to be changed prior to, during, and/or after a printing process.
  • translation and/or rotation of the print head and/or the substrate may allow the print head to deposit material onto a wide variety of substrate surfaces and/or allow the print head to deposit material onto the substrate at a wide variety of angles.
  • the print head may be configured to be rotated and/or translated such that it can deposit material onto each surface of the substrate.
  • FIG. 20 shows one non-limiting embodiment of a multi-axis deposition system 1000 comprising print head 1010 and substrate 1020 .
  • the print head, substrate, and multi-axis deposition system will be described in further detail below.
  • a print head in a multi-axis deposition system may be any suitable print head configured to deposit a material of interest onto the substrate.
  • a multi-axis deposition system may comprise two or more print heads.
  • suitable print heads include a direct write head, a mixing nozzle, an ink jet head, a spray valve, an aerosol jet print head, a laser cutting head, a hot air gun, a hot knife, an ultrasonic knife, a sanding head, a polishing head, a UV curing device, an engraver, an embosser, and the like.
  • the multi-axis deposition system may comprise a first print head that is comprises a mixing nozzle and a second print head that does not comprise a mixing nozzle.
  • the print head may be configured to accept one or more material inputs (e.g., one material input, two material inputs, etc.). When two or more material inputs are present, the inputs may be substantially the same or they may differ.
  • the print head may be configured to mix two or more reactive material inputs to form a reactive mixture that may be deposited onto a substrate while the first and second material inputs are reacting and/or after the first and second material inputs have reacted.
  • the print head may be configured to mix a polyol and an isocyanate to form a reactive polyurethane mixture.
  • suitable reactive mixtures include reactive polyurea mixtures, reactive mixtures comprising reactive polyurethane and reactive polyurea blends, reactive mixtures comprising epoxy groups and amine groups, and reactive silicone mixtures.
  • a substrate in a multi-axis deposition system may be any suitable substrate capable of receiving the material deposited by the print head.
  • the substrate may have a shape that enables facile deposition of the material of interest in a morphology of interest by the print head.
  • the substrate may have a shape that substantially corresponds to the morphology of interest, such as a footwear last for footwear applications (e.g., as shown in FIG.
  • the substrate may be a mold or a portion of a mold.
  • the substrate may comprise a portion that is curved, and/or the substrate as a whole be curved.
  • the substrate may have a spherical shape, or a hemispherical shape.
  • the substrate may comprise two or more surfaces that are joined at facets.
  • the substrate may be a platonic solid or may comprise a portion that is a platonic solid.
  • the substrate may be substantially flat. Other types of substrates are also possible.
  • a multi-axis deposition system may comprise a substrate that is removable.
  • the substrate may be configured to be positioned in the multi-axis deposition system during material deposition and removed after material deposition.
  • a multi-axis deposition system may comprise multiple substrates that may be added to the multi-axis deposition system prior to material deposition and/or removed from the multi-axis deposition system after material deposition.
  • Each substrate may have a different shape (e.g., a different shoe size, a different cup size, a mold for a different type of apparel), or two or more substrates may have substantially the same shape.
  • one or more articles may be disposed on the substrate prior to material deposition and/or during material deposition using a multi-axis deposition system.
  • the article(s) disposed on the substrate may be configured to be positioned on the substrate during material deposition and, optionally, removed from the substrate after material deposition.
  • a multi-axis deposition system may be configured to deposit material onto a multiple articles successively, each of which may be added to the multi-axis deposition system prior to material deposition and/or removed from the multi-axis deposition system after material deposition.
  • a textile e.g., a non-flat textile, an upper, a woven textile, a knit textile
  • a multi-axis deposition system may be employed to deposit a reactive mixture as described above onto a textile to form a 3D-printed material on the textile and/or on a succession of textiles sequentially added to the substrate.
  • the print head(s) and the substrate in a multi-axis deposition system comprising both a print head and a substrate may be oriented with respect to each other in other ways than that shown in FIG. 20 .
  • a print head may be disposed over the center of the substrate in some embodiments and over the edge of the substrate in other embodiments.
  • a print head may be oriented so that it deposits material on the substrate at a 90° angle to the substrate in some embodiments and so that it deposits material on the substrate at another angle to the substrate (e.g., 45°, 30°, or other angles) in other embodiments.
  • the substrate may present a bottom surface (e.g., a portion of a last on which a sole would be disposed) to a print head in some embodiments and may present a side or top surface (e.g., a portion of a last on which an upper would be disposed) in other embodiments.
  • the print head(s) and/or the substrate may be configured to be translated and/or rotated around one or more axes, as described further below. In such cases, the absolute positions of the print head(s) and the substrate may be varied during operation of the multi-axis system, and/or the relative position of the print head(s) with respect to the substrate may be varied during operation of the multi-axis system.
  • a multi-axis deposition system may comprise one or more print heads that may be configured to be translated along one or more axes.
  • one or more print heads may be configured to be translated along one axis, along two axes, or along three axes.
  • the axes may be perpendicular to each other. In other cases two or more of the axes are not perpendicular to each other (e.g., they may intersect at an angle between 45° and 90°).
  • the print head may be configured to be translated vertically, and/or translated in one or more directions perpendicular to the vertical direction.
  • one or more print heads may be configured to be translated in a direction perpendicular to the substrate, and/or in one or more directions parallel to the substrate.
  • one or more print heads may be configured to be translated at a 45° angle with respect to the substrate. In some cases, each axis of translation may independently be controlled by separate motors. In some embodiments, one or more print heads may not be configured to be translated.
  • one or more print heads in a multi-axis system may be configured to be rotated around one axis, around two axes, or around three axes. In some embodiments, one or more print heads may be configured to be rotated around more than three axes (e.g., around more than four axes, around more than six axes, around more than eight axes, around more than 10 axes, or around more than 12 axes). In certain cases, the axes may be perpendicular to each other. For example, in some embodiments the print head may be configured to be rotated around a vertical axis, and/or rotated around one or more axes perpendicular to the vertical axis.
  • one or more print heads may be configured to be rotated around an axis perpendicular to the substrate, and/or around one or more axes parallel to the substrate. In some cases, each axis of rotation may independently be controlled by separate motors. In some embodiments, one or more print heads may not be configured to be rotated. In some embodiments, the print head may be configured to be stationary.
  • a substrate in a multi-axis system may be configured to be translated along one axis, along two axes, or along three axes.
  • the axes may be perpendicular to each other. In other cases two or more of the axes are perpendicular to each other (e.g., they may intersect at an angle between 45° and 90°).
  • the substrate may be configured to be translated vertically, and/or translated in one or more directions perpendicular to the vertical direction.
  • the substrate may be configured to be translated in a direction perpendicular to the print head, and/or in one or more directions parallel to the print head.
  • the print head may be configured to be translated at a 45° angle with respect to the substrate.
  • each axis of translation may independently be controlled by separate motors.
  • the substrate may not be configured to be translated.
  • a substrate in a multi-axis system may be configured to be rotated around one axis, around two axes, or around three axes. In certain cases, the axes may be perpendicular to each other. In some embodiments, the substrate may be configured to be rotated around more than three axes (e.g., around more than four axes, around more than six axes, around more than eight axes, around more than 10 axes, or around more than 12 axes). For example, in some embodiments the substrate may be configured to be rotated around a vertical axis, and/or rotated around one or more axes perpendicular to the vertical axis.
  • the substrate may be configured to be rotated around an axis perpendicular to the print head, and/or around one or more axes parallel to the print head. In some cases, each axis of rotation may independently be controlled by separate motors. In some embodiments, the substrate may not be configured to be rotated. In some embodiments, the substrate may be configured to be stationary.
  • a multi-axis deposition system may comprise one or more features that aid rotation and/or translation of a print head and/or a substrate.
  • the print head may be attached to a print head arm that facilitates motion.
  • each print head may be positioned separate print head arms or two or more print heads may be positioned on the same print head arm.
  • two or more print head arms may be attached to a single gantry. The print head arms may be capable of facilitating translation and/or rotation of the print head.
  • the print head(s) may be attached to single print head arms; in other embodiments, the print head(s) may be attached to multiple print head arms that are attached at joints that allow for rotation and/or translation.
  • one or more motors may facilitate motion of one or more components of the print head arm(s).
  • the substrate may be attached to a substrate arm that facilitates motion.
  • the substrate arm may be capable of facilitating translation and/or rotation of the substrate.
  • the substrate may be attached to a single substrate arm; in other embodiments, the substrate may be attached to multiple substrate arms that are attached at joints that allow for rotation and/or translation.
  • the substrate may be attached to a robot arm.
  • one or more motors may facilitate motion of one or more components of the substrate arm(s).
  • the print head may be attached to a print head arm and the substrate may be attached to a substrate arm.
  • FIGS. 21-23 show various views of a non-limiting embodiment of a multi-axis deposition system showing various combinations of axes around which a print head and substrate therein may be configured to be rotated and/or translated.
  • FIG. 21 shows a perspective view of the system as a whole
  • FIG. 22 shows a cross-sectional view of the system as a whole
  • FIG. 23 shows a close up perspective view of the print head and the substrate. It should be understood that these figures do not show all possible combinations of print head and substrate motion, and that all combinations of print head motion and substrate motion described above are contemplated.
  • the multi-axis deposition system includes print head 1010 and substrate 1020 .
  • Print head 1010 in FIGS. 21-23 is attached to first print head arm 1031 , which is attached to second print head arm 1032 by a first print head joint configured to allow translation of first print head arm 1031 along a first print head translation axis and along a second print head translation axis.
  • Second print head arm 1032 is also attached to gantry 1050 , which supports the second print head arm.
  • the second print head arm is attached to the gantry by screws and held in a stationary position (as is shown in FIGS. 21-23 ).
  • the second print head arm is configured to be translated along one or more axes and/or rotated around one or more axes.
  • the print head may be translated along the first print head translation axis by translating the first print head arm along the first print head translation axis, and the print head may be translated along the second print head translation axis by translating the first print head arm along the second print head translation axis.
  • the second print head arm may be a track along which the first print head arm may be translated and/or the first print head joint may comprise a track along which the first print head arm may be translated.
  • other types of joints and print head arms may be employed.
  • Substrate 1010 in FIGS. 21-23 is attached to first substrate arm 1041 , which is attached to second substrate arm 1042 by a first substrate joint configured to allow rotation of first substrate arm 1041 around a first substrate rotation axis.
  • Second substrate arm 1042 is attached to third substrate arm 1043 by a second substrate joint configured to allow rotation of second substrate arm 1042 around a second substrate rotation axis.
  • the substrate may be rotated around the first substrate rotation axis by rotating the first substrate arm around the first substrate rotation axis, and around the second substrate rotation axis by rotating the second substrate arm around the second substrate rotation axis.
  • one or more of the substrate arms may curved (e.g., second substrate arm as shown in FIGS. 21-23 ).
  • Third substrate arm 1043 is attached to support 1044 by a third substrate joint configured to allow translation of the third arm along a first substrate translation axis.
  • the substrate may be translated along the first substrate translation axis by translating the third arm along the first substrate translation axis.
  • the third substrate arm may be a track along which the second substrate arm may be translated. In other embodiments, other types substrate arms may be employed.
  • a multi-axis system may comprise further features in addition to some or all of those described above.
  • the multi-axis system may be encased in a frame or enclosure.
  • FIG. 22 includes frame 1060 with feet 1070 and wheels 1080 .
  • the feet may aid stable positioning of the frame on a surface (e.g., a floor, a desktop, a lab bench).
  • the wheels may promote facile repositioning of the frame in different locations.
  • one or more components e.g., the frame, one or more arms
  • a print head may be configured to be translated vertically and in a first horizontal direction, and the substrate may be configured to be translated along a second horizontal direction perpendicular to the first horizontal direction and rotated around two distinct axes.
  • a print head may be configured to be translated in three perpendicular directions and the substrate may be configured to be rotated around two distinct axes.
  • a print head may be configured to be stationary and the substrate may be configured to be translated in three perpendicular directions and rotated around two distinct axes.
  • a print head may be configured to be translated around three distinct rotation axes and along three distinct translation axes, and the substrate may be configured to be stationary.
  • Other combinations of print head motion and substrate motion are also possible.
  • a multi-axis system may have one or more features that make it suitable for 3D-printing materials of interest.
  • the multi-axis system may be configured to deposit a material onto a substrate as a continuous stream or as a continuous filament.
  • the substrate may be in fluid communication with the print head via the material during deposition.
  • the multi-axis system may be employed to deposit a continuous stream or filament that extends from a first side of a last or a material disposed on the last (e.g., an upper, a 3D-printed material disposed on an upper) across the bottom of the last or material disposed on the last to the opposing side of the last or material disposed on the last.
  • the multi-axis system may be employed to print each portion of an article of footwear except for the upper.
  • a multi-axis system may be configured to 3D-print materials with one or more advantageous properties.
  • the multi-axis system may be configured to 3D-print materials with a feature size of greater than or equal to 100 microns, greater than or equal to 200 microns, greater than or equal to 500 microns, greater than or equal to 1 mm, greater than or equal to 2 mm, greater than or equal to 5 mm, greater than or equal to 10 mm, greater than or equal to 20 mm, greater than or equal to 50 mm, greater than or equal to 1 cm, or greater than or equal to 2 cm.
  • the multi-axis system may be configured to 3D-print materials with a feature size of less than or equal to 5 cm, less than or equal to 2 cm, less than or equal to 1 cm, less than or equal to 5 mm, less than or equal to 2 mm, less than or equal to 1 mm, less than or equal to 500 microns, or less than or equal to 200 microns. Combinations of the above-referenced ranges are also possible (e.g., greater than or equal to 100 microns and less than or equal to 5 cm). Other ranges are also possible.
  • a 3D printer may be provided that is capable of printing a material (e.g., a composite) that is formed by combing two or more other materials (e.g., a polymer and particles, e.g., reinforcing particles) to create a 3D object, such as an article of a shoe.
  • a material e.g., a composite
  • other materials e.g., a polymer and particles, e.g., reinforcing particles
  • 3D objects may comprise a gradient structure with at least one non-uniform property (e.g., color, average stiffness, average Shore A hardness, average pore size, and average density).
  • printer instructions for a 3D printer may be unable to accurately determine appropriate printer settings (e.g., a ratio of two or more inputs to a mixing chamber and/or nozzle, a spin speed of an impeller in the mixing nozzle, sequencing of material into a mixing chamber and/or nozzle, valving to change material inputs into the mixing chamber and/or nozzle, total cumulative flowrate of all inputs to a mixing chamber, vertical position of a print head relative to the substrate, speed of movement of the print head, amount of reverse pumping following a movement command, temperature of the print head, temperature of a substrate onto which the article is printed, and the calibration setting for a material inlet pump) to properly print such materials.
  • printer settings e.g., a ratio of two or more inputs to a mixing chamber and/or nozzle, a spin speed of an impeller in the mixing nozzle, sequencing of material into a mixing chamber and/or nozzle, valving to change material inputs into the mixing chamber and/or nozzle, total cumulative flowrate of all input
  • the computer program may be configured to receive object information, such as a design file for a 3D object (e.g., from a computer-aided design (CAD) program) and/or a print path for printing a 3D object (e.g., from a slicer application) with information indicative of target material properties at various points along the print path, and output print instructions that may be provided to a 3D printer to accurately create the 3D object.
  • the computer program may generate the print instructions by, for example, identifying a target material that is to be deposited, identifying the input materials required to create the target material, and identifying the printer settings to print the target material using the input materials.
  • print instructions may be generated using the identified set of printer settings. For example, print instructions may be generated that comprise a print path for the print head to follow and printer settings information indicative of the appropriate printer settings at a plurality of points along the print path.
  • the computer program may comprise a set of instructions that may be executed by a computer system comprising a processor (e.g., a hardware processor or a virtual processor) and a memory (e.g., a non-transitory computer readable medium).
  • a computer system comprising a processor (e.g., a hardware processor or a virtual processor) and a memory (e.g., a non-transitory computer readable medium).
  • the computer program may comprise a set of instructions stored in a non-transitory computer readable medium that programs at least one processor coupled to the non-transitory computer readable medium.
  • the computer system may be communicatively coupled to a 3D printer and/or integrated with the 3D printer.
  • the computer program may comprise a plurality of instructions that program at least one processor to perform a method 1000 in FIG. 24 .
  • the method 1000 comprises an act 1002 of receiving object information, an act 1004 of identifying target material to be printed, an act 1006 of identifying input materials to form the target material, an act 1008 of identifying printer settings to print the target material, and an act 1012 of generating print instructions.
  • the system may receive object information associated with a 3D object.
  • the object information may be, for example, a design file for a 3D object to be printed.
  • the design file may comprise information indicative of one or more properties of the 3D object such as shape, material composition, and/or color.
  • the design file may be in any of a variety of formats. Example formats include: Drawing Interchange Format (DXF), COLLAborative Design Activity (COLLADA), STereoLithography (STL), Initial Graphics Exchange Specification (IGES), and Virtual Reality Modeling Language (VRML).
  • DXF Drawing Interchange Format
  • COLLADA COLLAborative Design Activity
  • STL STereoLithography
  • IGES Initial Graphics Exchange Specification
  • VRML Virtual Reality Modeling Language
  • the object information may comprise a print path for a print head to follow to print the 3D object (e.g., generated by a slicer application) and information indicative of the desired material properties at various points along the print path.
  • the object information may comprise a print path comprising a plurality of points and metadata associated with one or more (or all of) the plurality of points indicative of a desired material property at the point (e.g., color, average stiffness, average Shore A hardness, average pore size, average density, etc.).
  • the metadata may be directly associated with one or more points in the plurality of points.
  • the metadata may be stored in another format and overlaid onto the print path to determine the material properties at a given point.
  • the metadata may be desired color information stored in an image comprising a plurality of pixel values that may be overlaid onto the print path.
  • the pixel value that aligns with a given point in the print path may be the metadata associated with the respective point.
  • the system may identify a target material to be printed based on the object information.
  • the object information may comprise information regarding the target material (e.g., in metadata) and the system may directly identify the target material from the received object information.
  • the system may identify input material(s) to create the target material.
  • the 3D printer may print the target material in the object by mixing a first material with a second material.
  • the system may identify the first and second materials.
  • the system may identify this information by, for example, retrieving information stored in a memory of the computer system regarding the input materials required to create the target material in the object.
  • the system identifies one or more printer settings for printing the target material using the identified input materials.
  • the system may identify one or more printer settings required to print the target material at a plurality of discrete points in the object (e.g., along the print path).
  • the system may employ interpolation techniques (e.g., linear interpolation and cubic interpolation) to smooth shifts in printer settings between the discrete points.
  • interpolation techniques e.g., linear interpolation and cubic interpolation
  • the system may fit a linear curve between the first and second points to create a smooth ramp between a 40/60 ratio and a 50/50 ratio. Thereby, the system may create a set of printer settings to employ along the print path as the print head moves from the first point to the second point.
  • the system may generate the print instructions using the identified printer settings in act 1008 .
  • the print instructions may comprise, for example, a print path for a print head to follow to print the 3D object along with printer settings at a plurality of points along the print path (e.g., generated in act 1008 ).
  • the print instructions may be, for example, G-code instructions.
  • a foam may be prepared by mixing materials within a nozzle, such as a microfluidic printing nozzle, which may be used to direct the resulting product onto a substrate.
  • the nozzle may be controlled, for example, using a computer or other controller, in order to control the deposition of material onto the substrate.
  • gases or other materials may be incorporated into the material within the nozzle, e.g., to form a foam.
  • the present invention is not limited to only foams; for example, other materials, including composites that comprise particles (e.g., reinforcing particles), are also included in other embodiments of the invention.
  • certain aspects of the invention are generally directed to devices for 3D-printing.
  • material is controllably deposited, e.g., on a substrate, to create a product.
  • the material may be deposited in a pattern defining the product, or that can be manipulated to create the product, e.g., by removing portions of the pattern.
  • a printing nozzle such as a microfluidic printing nozzle, may be used to direct material onto a substrate.
  • the nozzle may be controlled, for example, using a computer or other controller, in order to control the deposition of material onto the substrate.
  • a device 10 for printing an article is shown, using techniques such as 3D printing.
  • the device may include a nozzle 15 , through which material is directed at a substrate through outlet 18 , e.g., through a valve.
  • the substrate may be planar, or in some cases, the substrate may have a different shape.
  • the substrate may thus be any suitable target for a material exiting the nozzle.
  • the substrate may include a mold to which the material is applied.
  • Nozzle 15 in FIG. 1 is generally depicted as being conical or funnel-shaped, although it should be understood that this is by way of example only, and the nozzle may have any suitable shape able to direct a material at a substrate.
  • One or more fluids may flow into the nozzle, and in some embodiments, mixed within the nozzle, e.g., within a mixing chamber within the nozzle to form the material to be deposited on the substrate.
  • active mixing may be used to mix fluids within the nozzle.
  • an impeller 20 may be spun to cause mixing within the nozzle.
  • the impeller may have any size or shape, as discussed below.
  • the impeller when spun, may substantially conform to the mixing chamber, or at least a part of the mixing chamber.
  • material flowing through the nozzle may be disrupted through spinning of the impeller (depicted in FIG. 1 as arrow 25 ), thereby causing mixing of the material to occur.
  • the speed of the impeller may be controlled, e.g., by a computer or other electronic controller, to control the mixing and/or direction of material exiting the nozzle.
  • the controller may control a valve or other apparatus to control the exiting of material from the nozzle, for example, as the nozzle moves relative to a substrate (or equivalently, as the substrate moves relative to the nozzle). Control of nozzle mixing and the position of the nozzle relative to the substrate may thus be used to control 3D-printing of a material onto the substrate.
  • the material within the nozzle may be subjected to heating or cooling.
  • This may, for example, be used to control mixing and/or reaction within the material, to keep the temperature at substantially the temperature of the surrounding environment (e.g., at room temperature), to prevent the surrounding environmental conditions and/or the heat generated by friction of the impeller and exotherm of the material curing from affecting the reaction or the printing parameters, or the like.
  • Any method may be used to heat or cool the material within the nozzle.
  • heating or cooling may be applied to the nozzle itself, and/or to material within the nozzle. Non-limiting examples include electrical heating, Peltier cooling, application of infrared light, or other techniques such as those discussed herein.
  • one or more fluids may enter the nozzle to be mixed together.
  • the fluids may enter via a common inlet, and/or via separate inlets, for example, as is illustrated in FIG. 1 with inlets 31 , 32 , and 33 .
  • 3 inlets are illustrated in this figure, this is by way of example only, and in other embodiments, more or fewer inlets are also possible.
  • the inlets may independently be at the same or different distances away from an outlet of the nozzle.
  • the fluids may react upon contact with each other; thus, the fluids are kept separate prior to entrance into the nozzle, for example, using one or more inputs and/or valves to control contact of the fluids with each other.
  • valves may be present on one or more of the inlets to control the flow of fluid through the inlets, e.g., into the nozzle.
  • valves that can be used include needle valves, ball valves, gate valves, butterfly valves, or other suitable types of valves.
  • other types of apparatuses to control fluid flow may also be used, in addition to and/or instead of valves.
  • two or more fluids may be mixed together to form product on a substrate, for example, a foam or other article, such as a composite.
  • a material e.g., a precursor to the foam
  • the material may be deposited on a substrate in a partially fluid state, where the material is able to harden to form the product on the substrate.
  • the material may have a viscosity of less than 1,000,000 cP, less than 500,000 cP, less than 300,000 cP, less than 100,000 cP, less than 50,000 cP, less than 30,000 cP, less than 10,000 cP, less than 5,000 cP, less than 3,000 cP, less than 1,000 cP, less than 500 cP, less than 300 cP, less than 100 cP, less than 50 cP, less than 30 cP, or less than 10 cP.
  • the material may have a viscosity of at least 10 cP, at least 30 cP, at least 50 cP, at least 100 cP, at least 300 cP, at least 500 cP, at least 1,000 cP, at least 3,000 cP, at least 5,000 cP, at least 10,000 cP, at least 30,000 cP, at least 50,000 cP, at least 100,000 cP, at least 300,000 cP, at least 500,000 cP, or at least 1,000,000 cP. Combinations of any of these viscosities are also possible; for example, the viscosity of a material may be between 100 cP and 500 cP.
  • the material may form a product passively (e.g., upon drying of the material, completion of a reaction forming the product, etc.), and/or additional steps may be taken to encourage formation of the product.
  • heat may be applied to the material and/or to the substrate, light (e.g., ultraviolet light) may be applied to the material to cause a chemical reaction, etc.
  • a foam may be prepared by mixing a polymer, a cross-linking reagent, and a cell-forming agent, e.g., within a printing nozzle such as is shown in FIG. 1 . These may be added sequentially or simultaneously in various embodiments, e.g., as discussed herein. For instance, in FIG. 1 , a cross-linking agent may be added to the nozzle via inlet 31 , a cell-forming agent may be added via inlet 32 , and a polymer may be added via inlet 33 . In some cases, these may be flowable at the temperatures in which they enter the nozzle.
  • control of these may be controlled using one or more valves or other apparatuses on any of these inlets, optionally controlled by a computer or other controller.
  • one or more of the fluids flowing into the nozzle may contain particles (e.g., reinforcing particles).
  • a suitable polymer is polyurethane; one example of a cross-linking reagent is isocyanate; and one example of a cell-forming agent is water (which can react with the isocyanate to produce carbon dioxide as the foam forms).
  • a cell-forming agent is water (which can react with the isocyanate to produce carbon dioxide as the foam forms).
  • other fluids or reactants may be combined to form a foam, and the invention is not limited to only embodiments that include a polymer, a cross-linking reagent, and a cell-forming agent; see below for additional non-limiting examples.
  • a foam may be prepared using a polymer and a cell-forming agent, but not necessarily a cross-linking agent.
  • a composite is formed that comprises particles (e.g., reinforcing particles); for example, the composite may include polyurethane or other polymers described herein, as well as particles (e.g., reinforcing particles) such as rubber particles. In some cases, the composite is a foam, although it need not be in other cases.
  • system 10 includes a nozzle 15 and a mixing chamber 19 .
  • First nozzle 15 may be a nozzle such as discussed above with respect to FIG. 1 .
  • first nozzle 15 may contain an impeller 20 , an outlet 18 , and have one, two, or more inputs, e.g., inputs 31 and 35 as shown in this figure.
  • one or more of the inputs to first nozzle 15 may be a mixing chamber, such as mixing chamber 19 , having an output 38 which fluidly communicates to inlet 35 of nozzle 15 in this figure.
  • mixing chamber may have a similar shape to nozzle 15 (e.g., mixing chamber 19 may be a nozzle), although this is not a requirement.
  • Mixing chamber may have, in some embodiments, one or more inputs (e.g., inputs 41 and 42 ).
  • mixing nozzle 19 may include an impeller 29 , or another suitable mixing apparatus. In this example, impeller 29 causes mixing via spinning (depicted in FIG. 1 as arrow 26 ).
  • the mixing may be active or passive, and may be the same or different as in nozzle 15 .
  • stages may be used, in series and/or parallel, to provide material for input into a nozzle.
  • a non-limiting example of a 3-stage serial process can be seen in FIG. 3 .
  • partial or no mixing of fluids may occur within mixing chamber 19 , e.g., the fluids may be brought into contact, and some partial or incidental mixing may occur, while more vigorous mixing may occur within first nozzle 15 .
  • FIG. 4 A more specific example is provided in FIG. 4 .
  • three inputs are provided to a nozzle, e.g., to a mixing chamber of a nozzle. These inputs are provided by way of illustration only, and may vary in different embodiments of the invention.
  • a first input may be one or more of a variety of isocyanates
  • a second input may include any one or more of a variety of inputs, including stabilizers, filler concentrate, surfactants, diols, triols, multifunctional polyols, colorants, catalysts, etc. These may be provided as inputs to a nozzle, in which mixing occurs, as shown in this figure.
  • a cell-forming agent such as a gas or a blowing agent
  • these may be substantially homogenously mixed together.
  • these may form a foam or froth, e.g., comprising a plurality of relatively small bubbles of gas dispersed within a material, e.g., substantially uniformly distributed. This may then be deposited through the outlet onto a substrate, e.g., controlled by a controller, which may control deposition using a valve or other suitable apparatus.
  • a controller which may control deposition using a valve or other suitable apparatus.
  • composites or other articles may also be formed.
  • foams are generally directed to foams.
  • foams and other articles described herein may be used in a variety of applications, such as footwear.
  • the foam if present, may be a material comprising a matrix and pores disposed within the matrix. Pores may be randomly distributed throughout the foam, or may be positioned at regular and/or pre-determined intervals.
  • the material present within the pores of a foam is typically of a different phase than the material forming the matrix of the foam (e.g., a foam may comprise pores that comprise gas within a matrix that comprises a liquid and/or a solid).
  • a closed-cell foam the cells of the foam are typically isolated or separated from each other.
  • the cells of the foam are interconnected with each other; for example, they may be formed in an interconnected fashion, or the cells may be ruptured or become interconnected during or after formation of the foam.
  • These conditions are typically more violent foaming conditions than those resulting in a closed-cell foam.
  • the foam may be formed from a variety of polymers and gases.
  • the gases may be introduced into materials to form the foam in a number of ways, including into the foam components prior to entrance into the mixing nozzle (e.g. frothed components), during the mixing of components (e.g., active frothing), upon exiting the print nozzle (e.g. release of pressure or spike in temperature to generate gas), generated during printing (e.g. water-blown polyurethanes), generated in a post process after printing is complete by thermally, or otherwise, activating a chemical additive within the material (e.g. blowing agent), etc.
  • a gas may be introduced by providing a liquid that forms a gas, e.g., upon a decrease in pressure or an increase in temperature.
  • closed cell foams and open cell foams may have different properties (e.g., closed cell foams may have different values of density, stiffness, hardness, and the like than otherwise equivalent open cell foams) and may be suitable for different applications.
  • closed cell foams may have properties that are better suited to footwear applications than open cell foams.
  • the foams may be prepared to be lightweight, tough, elastic, and/or soft, e.g., using techniques such as those discussed herein.
  • polyurethane foams can be made into a variety of different applications such as shoe soles, cushions, pads, insulation, etc.
  • the properties of the foam can be varied widely, as discussed herein.
  • similar raw materials can be used to create a piece of rigid insulation, a memory foam pillow, a low density elastic foam pad for a seat cushion, or a high density foam outsole of a shoe.
  • 3D printed shoes may be seen in a U.S. provisional patent application filed on Feb. 27, 2017, entitled “Systems and Methods for Three-Dimensional Printing of Footwear and Other Articles,” incorporated herein by reference in its entirety.
  • foams may be prepared as discussed herein using various inputs and mixing the inputs using an active mixing nozzle, as described herein.
  • the foam density may be varied by varying the amount of added gas, the amount of added water (e.g., in water-blown foam applications), the amount of added blowing agent, etc.
  • the foam density constant may be held constant, but the cross-link density or isocyanate content may be varied to change properties such as the elasticity, elongation, or stiffness of the foam.
  • a foam precursor prior to curing, may have different rheological properties than the starting raw materials without gas content.
  • a mixture of low viscosity fluids, gases, and/or surfactants, etc. having Newtonian flow behavior before foaming can be used to produce a precursor having non-Newtonian flow characteristics, e.g., with a yield stress, or shear-thickening or shear-thinning behavior. This may be used herein to produce a precursor having a rheological profile suitable for printing, e.g., on a substrate.
  • Fluids such as incompressible Newtonian fluids or gases can be introduced into a nozzle (e.g., prior to mixing) in a controlled fashion and precisely metered onto a substrate during deposition.
  • the foaming process may start within the nozzle, and this process may affect the final mechanical properties of the foam.
  • a foam may include a plurality of cells (which may include open and/or closed cells) within a polymer or other suitable matrix.
  • certain embodiments described herein are directed to systems and methods able to 3D-print a material on a substrate that is able to form a foam.
  • the material at 3D-printing, may have properties that allow it to flow, e.g., from a nozzle, onto a substrate.
  • the material may also contain a gas therein (and/or a gas precursor) that can form the cells of the foam, e.g., upon solidification of the material to form the foam.
  • a material is formed via mixing of two, three, or more fluids to form a precursor, which is 3D-printed onto a substrate and allowed to solidify to form a foam or other product, such as a thermoplastic, an elastomer, a rigid thermoset, or the like.
  • a foam or other product such as a thermoplastic, an elastomer, a rigid thermoset, or the like.
  • a variety of fluids may be reacted to form a precursor to the foam, as is discussed in further detail herein.
  • a microfluidic printing nozzle is used to prepare the material prior to deposition onto a substrate.
  • more than one fluid may be introduced into the nozzle, and the fluids can be mixed within the nozzle to produce the material to be deposited onto the substrate.
  • a nozzle is used to direct a material (e.g., a precursor) onto a substrate.
  • the nozzle can have any suitable shape.
  • the nozzle may have any suitable shape having an outlet able to direct material at a substrate.
  • the nozzle may be conical, pyramid-shaped, funnel-shaped, cylindrical, or the like.
  • the nozzle may also have any suitable size.
  • the nozzle may include one or more mixing chambers or other regions in which two fluids come into contact with each other, and can be mixed together, e.g., actively or passively.
  • the nozzle or the mixing chamber may have a volume that is less than 20 ml, less than 18 ml, less than 16 ml, less than 14 ml, less than 12 ml, less than 10 ml, less than 8 ml, less than 6 ml, less than 5 ml, less than 4 ml, less than 3 ml, less than 2 ml, less than 1 ml, less than 0.5 ml, less than 0.3 ml, less than 0.1 ml, etc., and/or a volume that is at least 0.1 ml, at least 0.3 ml, at least 0.5 ml, at least 1 ml, at least 2 ml, at least 3 ml, at least 4 ml, at least 5 ml, at least 6 ml, at least 8 ml, at least 10 ml, at least 12 ml, at least 14 ml, at least 16 ml, at least 18 ml, at least 20 ml
  • the rate of printing of product may be at least 0.1 mL/min, at least 0.3 mL/min, at least 0.5 mL/min, at least 1 mL/min, at least 3 mL/min, at least 5 mL/min, at least 10 mL/min, at least 30 mL/min, at least 50 mL/min, at least 100 mL/min, at least 300 mL/min, at least 500 mL/min, at least 1 L/min, at least 3 L/min, at least 5 L/min, at least 10 L/min, or at least 20 L/min.
  • the rate of printing may be no more than 25 L/min, no more than 20 L/min, no more than 15 L/min, no more than 10 L/min, no more than 5 L/min, no more than 3 L/min, no more than 1 L/min, no more than 500 mL/min, no more than 300 mL/min, no more than 100 mL/min, no more than 50 mL/min, no more than 30 mL/min, no more than 10 mL/min, no more than 5 mL/min, no more than 3 mL/min, no more than 1 mL/min, no more than 0.5 mL/min, no more than 0.3 mL/min, or no more than 0.1 mL/min.
  • a fluid may contain particles (e.g., reinforcing particles) in some cases.
  • particles such as reinforcing particles can be introduced into the nozzle, e.g., without the presence of a fluid.
  • the particles e.g., reinforcing particles
  • Relatively small volumes such as these may be useful in certain embodiments to promote more complete mixing, e.g., such that the fluids and/or solids are substantially mixed together, and/or to promote smaller residence times within the mixer, for example, less than 30 s, less than 25 s, less than 20 s, less than 15 s, less than 10 s, or less than 5 s.
  • relatively small volumes may be useful to more rapidly stop and/or alter the reactants (and/or additives, if present) within the nozzle or mixing chamber.
  • a smaller volume may be easier to control and/or alter the degree of mixing, e.g., to compensate for variable flowrates and system reactivities, or the like.
  • the nozzle may include a valve, such as a needle valve.
  • a valving system may be used to control fluid input into the nozzle and/or material exiting the nozzle.
  • various components of the mixing system that come in contact with the material may be set up with a valving system.
  • the fluids and/or particles (if present) may be mixed until they are substantially mixed together in certain embodiments, e.g., having a relatively uniform appearance, or are substantially homogenous mixed.
  • the fluids and/or particles (if present) may be mixed such that the individual fluids are evenly distributed relative to each other (e.g., upon exiting the nozzle).
  • portions of the exiting mixture do not exhibit large or changing variations in relative distributions or ratios of one fluid relative to other fluids.
  • the fluids and/or particles (if present) may only be partially mixed together.
  • mixing within the nozzle may be passive, e.g., where the flow of fluids and/or particles (if present) into the nozzle causes the mixing of the fluids and/or particles within the nozzle.
  • the nozzle may also contain, in some embodiments, baffles or other impediments to disrupt the flow of fluid and/or particles, e.g., to promote mixing.
  • the geometry of the nozzle can be determined in certain embodiments for a given material set and flow rate such that the material exits the nozzle with a viscosity higher than the viscosities of any of the individual inputs but has not yet solidified.
  • various polyols and the isocyanates can be selected to tune the material reactivity to suit the flow rate into the nozzle and the mixing volume, such that the materials begin to react as they are mixed and also remain fluid enough to be able to leave the nozzle at the outlet continuously.
  • Other parameters such as a catalyst or the temperature, may also be used to tune material reactivity.
  • Non-limiting examples of methods of heating or cooling a nozzle are discussed in more detail below.
  • material exiting the nozzle may pass through an opening which structures the printed line (e.g. continuously printing) or dose (e.g. dosing mode).
  • the opening can be one of a variety of geometries including, but not limited to, circular, rectangular, star-shaped, any closed two-dimensional shape, multiple separate shapes (e.g., being fed from the same nozzle), or the like.
  • the nozzle, mixing chamber, and/or the impeller may be at least partially coated with a non-stick surface to prevent material from building up on such surfaces.
  • suitable coatings include, but are not limited to, polymeric coatings such as polyurethane or epoxy coatings, or ceramic coatings.
  • FIG. 11 One non-limiting example of an architecture for a nozzle can be seen in FIG. 11 .
  • a plurality of mixing units may be used to mix various fluids, and such mixtures, and/or a purge fluid, may be combined within a mixing chamber (e.g., within a nozzle), along with gas (for example, from a suitable source, such as a pressurized gas tank, controlled using a flow regulator, a valve, or another suitable system.
  • gas for example, from a suitable source, such as a pressurized gas tank, controlled using a flow regulator, a valve, or another suitable system.
  • the product, after mixing may be controllably released through a valve to an outlet, and/or purged (for example, when different materials are mixed, as discussed herein).
  • An example of a material mixing unit can be seen in FIG. 12 .
  • a plurality of different pumping systems may be used to combine two or more fluids together within a mixing unit.
  • FIG. 13 Examples of architectures for various subsystems in certain embodiments of the invention can be seen in FIG. 13 .
  • FIG. 13A an example architecture for a pumping subsystem is shown. Material may be controlled by a pump and/or a valve, and optionally monitored by a flowmeter or other suitable sensor, e.g., as discussed herein.
  • FIG. 13B illustrates the architecture for a mixing chamber. This may include, for example, one or more inputs (e.g., a gas input or a fluid input), various sensors to for example, inspect or measure mixing, a controller to control the impeller, e.g., the speed and/or position, etc., which may lead to one or more outputs, e.g., a material output and a purge output.
  • inputs e.g., a gas input or a fluid input
  • various sensors to for example, inspect or measure mixing
  • a controller to control the impeller, e.g., the speed and/or position, etc., which may
  • architectures are by way of example only, and in other embodiments, other architectures may be used, for example, for nozzles, mixing chambers, pumping subsystems, or the like.
  • the composition or one or more of the fluids and/or particles (if present) may be changed during the mixing process, e.g., to produce a change or a gradient in properties in the product.
  • the ratio of two reactants may be changed during mixing, or one reactant may be replaced with another reactant during mixing, etc.
  • a first fluid may be changed to a different fluid in a continuous manner, e.g., without interruption.
  • particles e.g., reinforcing particles
  • Non-limiting examples of properties that may change within a product include pore or cell size, density, stiffness, hardness, degree of cross-linking, chemical composition, or the like.
  • the change may be a step change, or a more gradual change, e.g., producing a gradient in a property.
  • a foam or other product may exhibit a first portion having a first property (e.g., average pore size) and a second portion having a second property.
  • the product may have a first average pore size and a second portion that solidifies into a foam having a second average pore size, wherein the first average pore size is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, etc. greater than the second average pore size.
  • Other examples of properties that may change within a product include, but are not limited to, average largest dimension of particles (e.g., reinforcing particles), average concentration of particles (e.g., reinforcing particles), surface roughness, compression strength, slip resistance, and abrasion resistance.
  • a portion of an article may refer to any collection of points within the article (i.e., points that are within the portion of space bounded by the external surfaces of the article). Portions of the article are typically, but not always, volumes of space within the article (in some embodiments, a portion may be a surface within an article, a line within an article, or a point within an article). Portions of the article may be continuous (i.e., each point within the portion may be connected by a pathway that does not pass through any points external to the portion) or may be discontinuous (i.e., the portion may comprise at least one point that cannot be connected to at least one other point within the article by a pathway that does not pass through any points external to the portion).
  • Portions of an article may be substantially homogeneous with respect to one or more properties (e.g., one or more properties of the portion may vary with a standard deviation of less than or equal to 1%, 2%, 5%, or 10% throughout the portion), and/or may be heterogeneous with respect to one or more properties (e.g., one or more properties of the portion may vary with a standard deviation of greater than or equal to 1%, 2%, 5%, or 10% throughout the portion).
  • one or more properties of a mixture that is 3D-printed from a nozzle may change as a function of time and/or nozzle position with respect to the substrate.
  • the composition of one or more components and/or the wt % of one or more components within the mixture may change as a function of time.
  • one or more physical parameters of the nozzle and/or the substrate may change as a function of time.
  • the temperature of the nozzle and/or the substrate may change as a function of time.
  • the temperature of the nozzle and the temperature of the substrate may affect the types of reactions that occur between various components (e.g., cross-linking reactions, foaming reactions, reactions within the nozzle, reactions on the substrate) and/or the rates at which these reactions occur.
  • This may in turn affect the chemical structure of the mixture (e.g., the composition of the mixture, the degree of cross-linking of the resultant foam) during and/or after printing, and/or affect one or more physical properties of the mixture (e.g., the viscosity of the mixture, the average pore size of the resultant foam, the density of the resultant foam, the stiffness of the resultant foam, the hardness of the resultant foam) during and/or after printing.
  • the chemical structure of the mixture e.g., the composition of the mixture, the degree of cross-linking of the resultant foam
  • one or more physical properties of the mixture e.g., the viscosity of the mixture, the average pore size of the resultant foam, the density of the resultant foam, the
  • changes in substrate or nozzle temperature during printing may allow for different portions of the 3D-printed article (e.g., those printed at different times and/or in different positions on the substrate) to have different chemical or physical properties.
  • the portions with different chemical and/or physical properties may be printed in a single continuous process, and/or may together form a single integrated material.
  • active mixing processes may be used to mix the fluids.
  • an impeller or other mixing apparatus may be used to mix fluids within the nozzle, e.g., in a mixing chamber within the nozzle.
  • the impeller if present, may have any shape or size able to cause the mixing of fluids.
  • the impeller may include one or more vanes, blades, propellers, paddles, holes, and/or cavities, or the like, which may be used to cause movement (e.g., spinning) of fluids within the nozzle.
  • an impeller may include internal channels that allow a gas or fluid to enter through the impeller into the mixing chamber or nozzle.
  • the nozzle may include a spindle having one or more openings that allow gas or other fluids to be released.
  • the impeller may be fabricated out of any suitable material, e.g., metal, ceramic, a polymer, or the like. In some cases, the impeller itself may be 3D-printed.
  • the impeller may be controlled using any suitable technique, e.g., by mechanically, electrically, and/or magnetically the impeller. In some cases, more than one impeller or other mixing apparatus may be used. Non-limiting examples of other mixing apparatuses and techniques include turbines or the application of ultrasound or additional fluids into the nozzle.
  • no impeller or other mixing apparatus is used; for example, passive mixing techniques, such as controlling channel geometries or input flows, may also be used. For instance, ratios and/or compositions of incoming fluids may be controlled to control mixing, e.g., within a nozzle or mixing chamber. Combinations of mixing systems may also be used in certain embodiments, including combinations of active systems, or combinations of active and passive systems, for example, including any of the active or passive systems described herein.
  • an impeller may sweep through the nozzle or the mixing chamber such that the closest distance between the impeller as it travels and the wall of the nozzle or mixing chamber is less than 10 mm, less than 5 mm, less than 3 mm, less than 1 mm, less than 0.5 mm, less than 0.3 mm, less than 0.1 mm, less than 0.05 mm, less than 0.0.3 mm, less than 0.01 mm, less than 0.005 mm, etc.
  • the impeller may come into contact with the wall, although in other cases, the impeller may be at least 1 mm, at least 3 mm, at least 5 mm, or at least 10 mm away from the wall as it travels.
  • the impeller or other mixing apparatus may be one that substantially conforms to the shape of the nozzle or the mixing chamber in which the impeller or other mixing apparatus is located.
  • the impeller may, upon rotation, sweep through a volume that is at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95% of the volume of the nozzle or the mixing chamber.
  • the impeller may be rotated at any suitable speed.
  • the impeller may be rotated at a speed of at least 5 rpm, at least 10 rpm, at least 20 rpm, at least 30 rpm, at least 40 rpm, at least 50 rpm, etc.
  • much higher rotation speeds may be used, e.g., at least 100 rpm, at least 200 rpm, at least 300 rpm, at least 500 rpm, at least 750 rpm, at least 1000 rpm, at least 2000 rpm, at least 3000 rpm, at least 5000 rpm, at least 7500 rpm, or at least 10,000 rpm.
  • the impeller may be rotated at an rpm speed that is at least 16 times the residency time of the material in the mixing chamber or the impeller (for example, if the residency time is 10 seconds, then the rpm speed may be at least 160 rpm).
  • the impeller may be rotated at variable speeds. For instance, the impeller may be rotated at different speeds to control the formation or various properties of the foam or other product, and/or the impeller may be rotated to control the rate at which a material is deposited onto a substrate from the nozzle.
  • the impeller may be rotated at a speed that increases or decreases with respect to time.
  • changing the rotation speed of the impeller with respect to time may be used to alter a property of the foam or other product, e.g., from a first portion to a second portion.
  • An example of a system that can be used to control the speed of the impeller can be seen in Int. Pat. Apl. Pub. No. WO 2016/164562, incorporated herein by reference.
  • the impeller may be at least partially coated with a non-stick surface to prevent material build-up, as discussed herein.
  • the impeller shape has a shape that allows it to fill the majority of the volume of the mixing chamber, such that the mixing volume is relatively small.
  • the material may have a relatively short residency time in the mixer, and the material properties or gradient structures can be varied quickly.
  • the free volume of the mixing chamber or nozzle (i.e., the volume therein not occupied by the impeller) may be less than 20 ml, less than 18 ml, less than 16 ml, less than 14 ml, less than 12 ml, less than 10 ml, less than 8 ml, less than 6 ml, less than 5 ml, less than 4 ml, less than 3 ml, less than 2 ml, less than 1 ml, less than 0.5 ml, less than 0.3 ml, less than 0.1 ml, etc.
  • the impeller has a conical shape, e.g., if the mixing chamber or nozzle has a conical shape.
  • the impeller may be positioned such that the impeller as it travels has a distance from the wall of the nozzle or mixing chamber as discussed herein.
  • the position of the impeller can be controlled or altered, for example, before or during mixing.
  • the impeller may be actuatable with respect to the position of the mixing chamber, e.g., such that the mixing volume can be changed at any point to account for variable flowrate, thus keeping the residency time in the mixing chamber constant.
  • an actuator or servo may be able to move the impeller laterally within the mixing chamber, or towards an outlet, for example, during mixing or rotation of the impeller.
  • the impeller speed can be varied, such that the material experiences a fixed number of impeller rotations per residency time in the mix chamber.
  • the impeller can be used as a valve.
  • the end of the impeller may be directed into the outlet of the nozzle to block and close the nozzle, thereby preventing or controlling flow out of the chamber.
  • the impeller may be directed forward (into the outlet) to prevent flow, and/or moved various distances relative to the outlet to allow different flows of fluid out of the nozzle.
  • the nozzle and/or the mixing chamber may be heated or cooled.
  • the temperature of mixing may be controlled, for instance, to allow for uniform mixing, to facilitate reaction of fluids therein (e.g., to an optimum or desired temperature), to remove excess heat (e.g., contributed by a chemical reaction, the spinning of an impeller, etc.), or the like.
  • Various methods can be used to add heat or remove heat from the nozzle or the mixing chamber.
  • a heat source may be positioned to deliver heat to the nozzle or mixing chamber, or to one or more fluids entering therein.
  • heat sources include electrically resistive heaters, infrared light sources, or heating fluids (e.g., which can transmit heat using a heat exchanger or the like). In some cases, more than one heat source may be used.
  • cooling sources can be used in some embodiments to remove heat from the nozzle or mixing chamber. Non-limiting examples include Peltier coolers or cooling fluids (e.g., which can remove heat using a heat exchanger or the like).
  • Heating and/or cooling may, for example, be used to control mixing and/or reaction within the material, to keep the temperature at substantially the temperature of the surrounding environment (e.g., at room temperature), to prevent the surrounding environmental conditions and/or the heat generated by friction of the impeller and exotherm of the material curing from affecting the reaction or the printing parameters, or the like.
  • the temperature may be altered by at least 5° C., at least 10° C., at least 15° C., at least 20° C., or by other ranges such as those discussed herein. In other embodiments, however, the temperature may be controlled or altered by no more than 20° C., no more than 15° C., no more than 10° C., no more than 5° C., etc. relative to the incoming fluids or the surrounding environmental conditions.
  • one or more sensors may be present, e.g., within the nozzle or mixing chamber, within an outlet, within the substrate, or within sensing communication of the nozzle, mixing chamber, outlet, and/or substrate.
  • Such sensors may be used to determine a property of the incoming fluids, the mixing process, and/or the exiting material (for example, the flowrate), e.g., qualitatively and/or quantitatively.
  • such information may be used to control the process, e.g., by controlling the flow of fluid into the nozzle or mixing chamber, the mixing speed (e.g., of an impeller), the flow exiting an outlet, the opening and closing of a valve at the outlet, or the like.
  • Non-limiting examples include temperature sensors (e.g., thermocouples, infrared cameras, or the like), pressure transducers, photodiodes, colorimetric sensors, etc.
  • more than one sensor can be used in some cases.
  • Fluid, or solid particles, or a semi-solid paste may be introduced into the nozzle or mixing chamber from one, two, three, or more inputs, in one set of embodiments.
  • the inputs may independently have the same or different distances from the outlet of the nozzle or mixing chamber.
  • two inputs may be near the top of a nozzle or mixing chamber, e.g., to allow two fluids to mix, and additional inputs may be lower, e.g., to introduce additional components (for instance, additives) as the fluids flow down the mixing chamber.
  • additional components for instance, additives
  • this may be useful to allow reactions to occur in a certain order, to build viscosity first before starting to foam, to mix surfactants before adding filler, to mix ingredients prior to adding a catalyst, or the like.
  • one or more of the inlets may be controlled using one or more valves or other apparatuses.
  • the valves may be controlled using a computer or other controller, e.g., as discussed herein.
  • valves may be used to control flow into (and/or out of) the nozzle.
  • valves may be used to control the flow of fluids through channel intersections, e.g., to keep fluids from reacting or curing too early (e.g., by creating a cured skin at the interface of an inactive channel).
  • valves that can be used include, but are not limited to, needle valves, ball valves, gate valves, butterfly valves, and the like.
  • valves can independently be controlled, e.g., by electrical actuation, pneumatic actuation, or the like.
  • an impeller if present may be used as a needle valve, e.g., in conjunction with an outlet, as discussed herein.
  • the entering fluid may be gas, a liquid, a viscoelastic material, and/or any other flowable or deformable material.
  • the fluid may also contain particles such as particles (e.g., reinforcing particles), including those discussed above.
  • the entering fluid may include combinations of any of these in certain embodiments.
  • two or more fluids may be mixed prior to delivery, e.g., as discussed in detail herein. However, in some cases, two or more fluids may not be mixed prior to delivery. For instance, two or more inlets into the nozzle or mixing chamber may be used to introduce two or more separate fluids. These fluids can then be mixed in the nozzle or mixing chamber.
  • the fluids may be delivered using any suitable technique, and the same or different techniques may be used to delivery different fluids.
  • fluids may be delivered passively (i.e., by gravitational flow), or actively (for example, by using pumps such as progressive cavity pumps, auger pumps, gear pumps, or the like).
  • the fluids may delivered using input channels that may have features to create turbulent flow and/or to cause passive mixing, e.g., as fluid flows through the channels. This may be useful, for example, in causing some mixing (for example, of a fluid with an additive) in order to occur prior to entry into a nozzle or mixing chamber such as described herein.
  • the nozzle may also include particles such as reinforcing particles, which may be incorporated into the final product, e.g., as a composite material.
  • active mixing may be used to control the delivery of different fluids and/or particles (if present). This may be useful, for example, for mixing fluids entering in at different flowrates (e.g., as in a 4:1 or 10:1 ratio), different viscosities, or the like.
  • fluids that may be used include fluids that have relatively high viscosities, or viscoelastic solids that exhibit a yield stress, etc.
  • a gas and a liquid may be mixed within the nozzle, e.g., as discussed above, to produce a froth.
  • the gas may be added to the nozzle, and/or generated within the nozzle.
  • the froth may comprise bubbles or pockets of gas dispersed within the fluid. The bubbles within the froth may be dispersed relatively uniformly or homogenously, or may have a relatively small average size.
  • the average bubble size within the froth may be less than 10 mm, less than 5 mm, less than 3 mm, less than 1 mm, less than 500 micrometers, less than 400 micrometers, less than 300 micrometers, less than 200 micrometers, less than 100 micrometers, less than 50 micrometers, less than 30 micrometers, less than 10 micrometers, less than 5 micrometers, etc.
  • the average bubble size in average or characteristic diameter and/or the average bubble size may be at least 1 micrometer, at least 2 micrometers, at least 3 micrometers, at least 4 micrometers, at least 5 micrometers, at least 10 micrometers, at least 30 micrometers, at least 50 micrometers, at least 100 micrometers, at least 300 micrometers, at least 500 micrometers, at least 1 mm, at least 3 mm, at least 5 mm, etc.
  • the bubbles may also exhibit a relatively uniform distribution of sizes, for example, such that at least 80%, at least 90%, or at least 95% of the bubbles within a sample of froth have an average diameter that is between 80% and 120%, or between 90% and 110% of the average bubble diameter.
  • the gas may be introduced as one of the fluids entering the nozzle, and/or generated through chemical reaction of fluids within the nozzle.
  • gases that may be used include air, carbon dioxide, nitrogen, argon, or the like.
  • the froth may be deposited onto a substrate, e.g., as discussed herein.
  • the froth may, in some embodiments, comprise at least 20%, at least 30%, at least 40%, or at least 50% by volume of gas.
  • the froth may also contain particles (e.g., reinforcing particles).
  • the nozzle may include more than one fluid that can be mixed with the gas.
  • reactive fluids or fluids that contain surfactants that facilitate the introduction of the gas as bubbles in the fluids may be used. Examples of surfactants are discussed in more detail below.
  • mixing may occur relatively rapidly (for example, by spinning the mixing impeller at high velocity), and the froth would be in its near final form upon exiting the mixing nozzle. The froth may then be deposited or hardened to form a foam. The density of the froth (or the subsequent foam) can be varied by varying the ratio of the gas to the liquid.
  • the mean bubble size in the froth (or the foam) can be varied, for example, by changing the impeller rotational velocity and/or the residence time in the nozzle or mixing chamber.
  • the mechanical properties of the foam can also be changed, for example, by varying fluid compositions entering the nozzle during the formation process (for example, the ratio of isocyanate to polyol).
  • producing froths or other materials containing gas within the nozzle may allow control over the froth or subsequent product that is formed.
  • rheological properties may be controlled or altered by controlling mixing and/or the introduction of fluids within the nozzle.
  • Froth development also may be at least somewhat independent of reaction rates, as it can be partially controlled by controlling external factors such as the mixing rate, e.g., at least in embodiments where no gas is produced by reaction (although in other embodiments, gases that contribute to the froth may desirably be produced by reaction).
  • a material when deposited onto a substrate, may have a variety of rheological properties.
  • the material may be substantially fluid and able to flow, e.g., to conform a mold or other substrate to which it is deposited.
  • the material may have a viscosity of less than less than 1,000 cP, less than 500 cP, less than 300 cP, less than 100 cP, less than 50 cP, less than 30 cP, or less than 10 cP.
  • the material may also be Newtonian or non-Newtonian.
  • the material may exhibit some degree of solidity or elasticity, e.g., having a non-zero yield stress, and/or by exhibiting at least some resistance to a distorting influence or deforming force that is applied to the material.
  • the material may be sufficiently solid as to be able to define or hold a shape.
  • the material may be sufficiently solid such that it deforms from its original shape by less than 10% (by volume) after deposition on a substrate, e.g., within 30 seconds after printing onto the substrate.
  • the substrate may be any suitable target for a material exiting a nozzle.
  • the substrate is planar, although in other cases, the substrate is non-planar.
  • the substrate may be a mold (e.g., the mold of a shoe), to which a material may be introduced.
  • the material may be relatively fluid and able to conform to contours within the substrate (e.g., if the substrate is a mold).
  • the material may be relatively solid, e.g., having a defined shape, upon deposition onto the substrate, such as is discussed herein.
  • the substrate may also be heated or cooled, e.g., to promote or inhibit a reaction, to cause solidification to occur, or the like.
  • the temperature may be altered by at least 5° C., at least 10° C., or by other ranges such as those discussed herein.
  • Any method may be used to heat or cool the substrate.
  • heat or cooling sources may be used to apply heat or cooling to the substrate, the substrate may be contained within a heated or cooled environment, or a source of a heated or cooled fluid may be used to heat or cool the substrate, e.g., via a heat exchanger).
  • radiant light or infrared radiation may be applied to the substrate for heating.
  • a two-stage foaming system that implements two foaming types may be used.
  • using mechanical frothing in the nozzle may be used to mix a Newtonian liquid with a blowing agent into a printable viscoelastic foam formulation.
  • the polymer in the foam may be completely or partly cured.
  • the temperature of the polymer can be raised to drive the decomposition of the blowing agent, and the subsequent expansion of the foam.
  • a nozzle involving mechanical frothing may be used to create a foam having a yield stress that behaves viscoelastically. After deposition, the foam may be heated to achieve further expansion of the foam. This secondary expansion can be carried out, for example, using an agent, such as azodicarbonamide.
  • an agent such as azodicarbonamide.
  • one or more inputs can be used to deliver a polyol loaded with surfactant and a blowing agent into a nozzle, which are then mixed together, e.g., such that a froth is formed.
  • two or more fluids may be mixed prior to introduction into a nozzle.
  • the fluids may be mixed in a second nozzle or mixing chamber (e.g., separate from the first nozzle), and in some cases, a series of mixing chambers may be used, in any arrangement, e.g., in series and/or parallel.
  • a series of mixing chambers may be used, in any arrangement, e.g., in series and/or parallel.
  • more than one stage of mixing or combining fluids may be used.
  • FIG. 2 shows a mixing chamber that outputs into an input of a printing nozzle
  • FIG. 3 shows two mixing chambers in series with a printing nozzle.
  • Mixing within a mixing chamber may be relatively complete, or may be partial in some cases.
  • no mixing may occur in a mixing chamber, other than incidental mixing or diffusion (for example, as two fluids come into contact with each other).
  • more vigorous mixing can occur within the printing nozzle, which may lessen the need for complete mixing to occur upstream.
  • more complete mixing may occur within one or more mixing chambers upstream of the printing nozzle.
  • one or more purge fluids may be used to purge one or more of the inlets, outlets, nozzles, and/or mixing chambers, etc.
  • a purge fluid may be passed through one or more of these when they are not actively being used to mix or print, and/or to clear fluids so that different fluids can be used.
  • a purge fluid may flow through an inlet when switching the inlet from a first fluid source to a second fluid source, e.g., to purge residual fluid from the first fluid source that may be present.
  • the purge fluid may flow through the nozzle in some cases, and/or be removed prior to the nozzle.
  • Non-limiting examples of purge fluids include gases such as air, carbon dioxide, nitrogen, argon, or the like, and/or liquids such as water (which may be pure, contain one or more additives such as surfactants in some cases, etc.).
  • Purge fluids could also be a non-reactive paste such as petroleum jelly or a viscous silicone oil or paraffin wax, or an aqueous or alcohol based gel such as pluronic or carbopol. Combinations of purge fluids may also be used in some embodiments.
  • a nozzle may have a first inlet and a second inlet, in which two fluids (A and B) are reacted together to produce a first product.
  • the nozzle may also be used to produce a second product also formed from two fluids (A′ and B′), where one or both of A′ and B′ are different than A and B. Both A and A′ may be introduced using the first inlet, while B and B′ may be introduced using the second inlet.
  • one or more purge fluids may be introduced between introducing A and A′ to the nozzle and/or B and B′ to the nozzle.
  • sufficient purge fluid may be introduced to clear the entire nozzle or mixing chamber between different fluids, although in other cases, some degree of contamination may be deemed to be acceptable, e.g., the purge fluid may be used to reduce but not completely eliminate contamination.
  • the introduction of more than one fluid into an inlet may be controlled using any suitable technique; e.g., one or more fluid sources may be able to be placed in fluid communication with an inlet, where control of such fluid communication may be controlled using one or more valves (e.g., needle valves or other valves such as those discussed herein), which in some cases may be controlled using a computer or other controller.
  • FIG. 5 illustrates the use of a nozzle or mixing chamber with only one input.
  • nozzle 15 includes an outlet 18 and a single input 39 .
  • sources of fluid 51 , 52 , 53 , 54 , and 55 are provided here by way of example only, but more or fewer sources may be used in other embodiments.
  • source 51 may be, for example, a purge fluid
  • sources 52 , 53 , 54 , and 55 may be sources of various fluids or reactants to be introduced into nozzle 15 .
  • different combinations of reactants may be introduced into the nozzle from the different sources of fluid, while purge fluid from source 51 may be used to purge inlet 39 between different fluids, e.g., to reduce contamination.
  • FIG. 6 illustrates a system in which a purge fluid may be withdrawn at various locations.
  • nozzle 15 includes an inlet 31 in fluid communication with a source of purge fluid 51 and a sources of other fluids 52 and 53 . (Two are shown here for explanatory purposes, but more or fewer sources may be used in other embodiments.) Also shown in this figure are outlets 63 and 65 , in addition to outlet 18 of the nozzle.
  • the flow of fluid may be controlled by one or more valves or other apparatuses, e.g., controlled by a computer or other controller.
  • a purge fluid may be introduced from fluid source 51 and controllably withdrawn using outlet 63 (i.e., without entering nozzle 15 ), outlet 65 (i.e., passing through nozzle 15 but not outlet 18 ), or outlet 18 .
  • outlet 63 i.e., without entering nozzle 15
  • outlet 65 i.e., passing through nozzle 15 but not outlet 18
  • outlet 18 i.e., passing through nozzle 15 but not outlet 18
  • a foam may be created from a foam precursor comprising a polymer and a cross-linking agent.
  • the polymer can comprise polyol such as a low number average molecular weight diol, high number-average molecular weight diol, a low number-average molecular weight triol, a high number-average molecular weight triol, or a high number-average molecular weight monol.
  • a high molecular weight monol, diol, or triol may have a number-average molecular weight of greater than 300, 400, or 500, while a low molecular weight monol, diol, or triol may have a number-average molecular weight less than 300, 400, or 500.
  • Other examples of polymers include, but are not limited to, epoxies, acrylates, cyanate esters, silicones, polyesters, phenolics, hydrogels, or the like.
  • the polymer includes a polyurethane, e.g., formed by reacting the polyol with an isocyanate.
  • the polyol may be any suitable polyhydroxy compound.
  • the polyol may be a hydroxy-terminated ester, ether or carbonate diol, or a hydroxyl-terminated polybutadiene polymer.
  • Non-limiting examples of polyalkylene ether glycols include polyethylene ether glycols, poly-1,2-propylene ether glycols, polytetramethylene ether glycols, poly-1,2-dimethylethylene ether glycols, poly-1,2-butylene ether glycol, and polydecamethylene ether glycols.
  • polyester polyols include polybutylene adipate and polyethylene terephthalate.
  • polycarbonate diols include polytetramethylene carbonate diol, polypentamethylene carbonate diol, polyhexamethylene carbonate diol, polyhexane-1,6-carbonate diol and poly(1,6-hexyl-1,2-ethyl carbonate)diol.
  • polyhydroxy compounds can also be used depending upon the desired application.
  • Any suitable polyol, polythiol or polyamine or mixture thereof that is suitable for this purpose may be used, such as, for example, mixed diols comprising a 2,4-dialkyl-1,5-pentanediol and a 2,2-dialkyl-1,3-propanediol.
  • 2,4-dialkyl-1,5-pentanediols include 2,4-dimethyl-1,5-pentanediol, 2-ethyl-4-methyl-1,5-pentanediol, 2-methyl-4-propyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-4-propyl-1,5-pentanediol, 2,4-dipropyl-1,5-pentanediol, 2-isoptopyl-4-methyl-1,5-pentanediol, 2-ethyl-4-isoptopyl-1,5-pentanediol, 2,4-diisopropyl-1,5-pentanediol, 2-isopropyl-4-propyl-1,5-pentanediol, 2,4-dibutyl-1,5-
  • longer-chain or higher molecular weight polyols may be used to produce relatively softer materials because they have more polyol relative to isocyanate.
  • the isocyanate can also be underindexed compared to the number of reactive sites on the polyol to make a softer foam that behaves less elastically.
  • the cross-linking agent can comprise an isocyanate in some cases, and/or an isocyanate prepolymer.
  • An isocyanate may have more than one functional isocyanate group per molecule and may be any suitable aromatic, aliphatic or cycloaliphatic polyisocyanate.
  • the isocyanate is a diisocyanate.
  • One non-limiting example is an organic diisocyanate, such as methylene diphenyl diisocyanate.
  • organic diisocyanates include 4,4′-diisocyanatodiphenylmethane, 2,4′-diisocyanatodiphenylmethane, isophorone diisocyanate, p-phenylene diisocyanate, 2,6-toluene diisocyanate, polyphenyl polymethylene polyisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-diisocyanatocyclohexane, 1,6-hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, 3,3′-dimethyl-4,4′-biphenyl diisocyanate, 4,4′-diisocyanatodicyclohexylmethane, 2,4′-diisocyanatodicyclohexylmethane, and 2,4-toluene diisocyanate, or combinations thereof.
  • an isocyanate prepolymer may be used, e.g., in addition to and/or instead of an isocyanate.
  • an isocyanate prepolymer may be used, e.g., in addition to and/or instead of an isocyanate.
  • two isocyanates are added to the ends of a polyol, so it still has functionality of two, but with a higher molecular weight.
  • a cross-linking agent is not required.
  • a polymer such as a thermoplastic polyurethane
  • a polymer can be mixed with fillers and frothed in a nozzle or a mixing chamber, then cooled upon exiting to form a foam.
  • a high number-average molecular weight diol may be mixed with an isocyanate (e.g., a diisocyanate, or other isocyanates described herein) and deposited onto a substrate, e.g., to produce a thermoplastic elastomer.
  • an isocyanate e.g., a diisocyanate, or other isocyanates described herein
  • a low number-average molecular weight diol can be mixed with an isocyanate and deposited onto a substrate, e.g., to produce a rigid thermoplastic.
  • a high number-average molecular weight diol and a high number-average molecular weight triol can be mixed, and then the polyol mixture mixed with an isocyanate and deposited onto a substrate, e.g., to produce a flexible thermosetting elastomer with high resiliency.
  • the foam precursor comprises a polyurethane, an epoxy, a silicone, a cyanoacrylate, an adhesive, a cyanate ester, a polyester, a polyimide, a phenolic, or another suitable material.
  • the foam precursor could comprise a decomposeable binder and particles which stabilize the bubble interface.
  • the particles may be sintered at the bubble interface to form a non-polymeric foam, e.g., a metal foam or a ceramic foam.
  • a high number-average molecular weight diol and a high number-average molecular weight triol are mixed with a surfactant, and then the polyol-surfactant mixture is mixed with an isocyanate.
  • the foam precursor that results may be mixed with nitrogen, or another gas, and deposited onto a substrate. Mixing techniques such as those discussed herein, e.g., involving more than one stage of mixing or combining fluids, may be used.
  • a high number-average molecular weight diol and a high number-average molecular weight monol are mixed with a surfactant, and then the polyol-surfactant mixture is mixed with an isocyanate.
  • Mixing techniques such as those discussed herein, e.g., involving more than one stage of mixing or combining fluids, may be used.
  • the foam precursor that results is then mixed with nitrogen, or another gas, and deposited onto a substrate. This may be used to produce memory foam, or other types of foam.
  • a surfactant may be used to produce a foam or other product as discussed herein.
  • a surfactant may be used to facilitate the introduction of gas into a fluid, the subsequent stability of the bubbles that are formed, and/or the rheology of the foam can be altered or tuned using various surfactants, or altering their concentration, etc.
  • a surfactant may be used that comprises a first moiety with affinity for an air-liquid interface, e.g., to facilitate the introduction of gas into a fluid.
  • Non-limiting examples of such surfactants include sodium stearate, sodium dodecyl sulfate, or silicone-based surfactants such as silicone polyethers. Many such surfactants are widely available commercially.
  • a surfactant molecule may be used that allows production of a high yield stress foam, e.g., a foam able to maintain its shape after deposition on a substrate.
  • a high-yield stress inducing surfactant is one where the end of the surfactant is more soluble in the continuous phase of the foam precursor.
  • the surfactant may have a relatively high molecular weight, and may be non-ionic.
  • Non-limiting examples of such surfactants include surfactants with a molecular weight of greater than or equal to 1500 Daltons.
  • a surfactant molecule may be used that allows production of a low yield stress foam, e.g., a foam unable to maintain its shape after deposition on a substrate, and the foam may conform to the material around it after deposition.
  • a low-yield stress inducing surfactant is one where the soluble end may be either charged or have a relatively low molecular weight, e.g., such that no entanglement between the surfactants is able to occur.
  • Non-limiting examples of such surfactants include surfactants with a low molecular weight (e.g., silicone surfactants with a low molecular weight).
  • different types of surfactants may be used, e.g., a high yield and a low yield surfactant.
  • the resultant foam may vary from high yield stress to low or no yield stress, depending upon the application.
  • the first surfactant molecule may comprise a first moiety having an affinity for an air-liquid interface, and a second moiety that comprises a long chain that is soluble in the foam precursor and prone to entanglement.
  • the second surfactant molecule may, in some instances, comprise the same first moiety with affinity for the air-liquid interface, and a second moiety that comprises a short chain with an electrostatic charge.
  • the electrostatic charge may in some cases be such that the cells of the closed-cell foam repel one another and can move freely past one another.
  • the cell-forming agent forms cells within a material such as a foam or froth, as discussed herein.
  • the cell-forming agent may comprise water, and/or a gaseous material such as air, carbon dioxide, nitrogen, butane, or the like.
  • the cell-forming agent comprises a blowing agent that is added that can generate a gas, e.g., chemically.
  • the microfluidic printing nozzle may disperse the blowing agent in a material, for example a polymer, to form a two-phase mixture of blowing agent cells within the polymer.
  • the blowing agent can comprise a material that decomposes into a gas, e.g., at an elevated temperature.
  • the blowing agent can comprise a gaseous material that maintains its liquid state by cooling or pressurization, and reverts to its native gas state when the pressure is released or the blowing agent is heated, which may cause the blowing agent to form a gas, e.g., to cause cells in the polymer to grow.
  • the resultant gas may become trapped in cells within the material, e.g., forming a foam.
  • the microfluidic printing nozzle may mix a blowing agent with a material, for example a polymer, which may undergo a chemical reaction to cause the formation of a gas.
  • Chemical blowing agents may include generally low molecular weight organic compounds that decompose to release a gas such as nitrogen, carbon dioxide, or carbon monoxide.
  • Non-limiting examples of chemical blowing agents include azo compounds such as azodicarbonamide.
  • the blowing agent can be used to create foams that form cells by induction by heat, removal of pressure, or the like.
  • a foam precursor can be mixed with the blowing agent and deposited onto a substrate or part without forming cells until after deposition, or with only partially formed cells.
  • material may be deposited onto a substrate, then induced to form cells by heating the material. After deposition, cells may form within the product, e.g., by induction by heat, removal of pressure, or the like.
  • a foam may comprise an ethylene-vinyl acetate foam, which may be utilized in footwear or other applications.
  • a blowing agent may be selected such that the agent phase-transitions into a gas at a temperature at which the polymer containing it is soft and malleable.
  • the polymer can expand (e.g., expand up to 600%) as the cells form without rupturing, and the resultant material can be cooled to form a solid foam.
  • water may be used in another embodiment as a cell-forming agent.
  • a water-blown foam may be produced where water and a surfactant are mixed into a polymer component, which is then mixed with isocyanate or another substance able to react with water, e.g., to produce a gas.
  • isocyanate chemically reacts with both water and polyol; the reaction of polyols with isocyanate may be used to increase the molecular weight of the polymer, e.g., to form a polyurethane, while the reaction of water with the isocyanate forms carbon dioxide gas. The carbon dioxide gas becomes trapped in the polymer as it solidifies, and a foam is thus created.
  • the amount of water may be controlled to control the properties of the resulting foam, such as density or cell size, e.g., during the reaction process.
  • a blowing agent that decomposes very slowly with time may be selected, such that a foam may be very slowly inflated without any heating required. In some cases, this may result in a foam with improved in rebound properties (e.g., compression strength) versus a substantially similar foam where heat was applied to activate the blowing agent, resulting in a higher performing article for use in footwear.
  • a material may be deposited onto a substrate, e.g., to fill a mold, then the mold may be sealed and the blowing agent induced to form a foam, which may then start to fill in the mold as the foam expands.
  • additives are introduced into the mixture. They may be introduced at any suitable point, for example, directly into a nozzle or mixing chamber (e.g., through one or more separate inlets), or upstream of the nozzle or mixing chamber (e.g., using a series of mixing chambers, as described herein). In some embodiments, an additive may be added directly to another fluid (e.g., without necessarily requiring a mixing chamber).
  • additives can comprise particles such as reinforcing particles (e.g., as described herein), hollow glass spheres, hollow elastomer spheres (e.g., hollow polyurethane spheres), a pigment, a metal, a filler such as a thermally conductive filler, a filler having a relative dielectric constant of at least 5, an ultraviolet stabilizer, a filler concentrate, or another suitable additive.
  • additional examples of additives include surfactants (e.g., silicone surfactants), catalysts, nucleation promotors, fillers for better abrasion resistance, chemical foaming agents, etc. Combinations of these and/or other additives are also possible.
  • a 3D printed closed-cell foam may be produced that incorporates particulate additives comprising a cellular network of cell walls separating empty cells, where the cell walls comprise a polymer composite including filler particles dispersed in a polymer matrix.
  • hollow glass spheres or hollow elastomer spheres may be incorporated into polyurethanes or other polymers as discussed herein to reduce density, increase stiffness, reduce dielectric constant, provide more nucleation sites for bubble formation, or the like.
  • hollow spheres may be used to decrease weight.
  • Hollow spheres, for example hollow glass spheres or hollow polymer spheres can be varied, e.g., spatially, in order to change the properties of the product.
  • particles e.g., reinforcing particles
  • particles that can be used, e.g., in addition to and/or instead of hollow glass spheres include, but are not limited to, rubber particles and other particles described herein.
  • a foam may be printed (e.g., via 3D-printing) into a structure defining a plurality of cells, i.e., into a foam-like structure.
  • a foam may be printed as part of a larger foam-like structure, e.g., where the walls of the foam-like structure (e.g., defining cells of the foam-like structure themselves) are foams having cells.
  • the foam-like structure may have open cells, closed cells, or any combination of open and closed cells, independently of the structure of the foam itself forming the foam-like structure.
  • one or more methods for manufacturing 3D-printed articles as described herein may be advantageous in comparison to other methods for making articles for use in footwear.
  • a footwear manufacturer employing a method as described herein may be able to use fewer processes to create the article than would be employed in other comparable processes (e.g., the manufacturer may use a three-dimensional printer (3D printer) in a single process to make a component that would otherwise be made by a combination of several processes such as injection molding, lamination, and the like). This may allow for more rapid and/or more facile manufacturing.
  • one or more of the methods described herein may not necessarily require the use equipment that is expensive to manufacture and whose cost is typically recovered only after repeated use (e.g., molds).
  • Some of the methods described herein may instead employ a 3D printer to create articles whose design can be modified as desired with little or no added cost.
  • it may be economical for methods as described herein to create small batches of 3D-printed articles (e.g., batches of less than 100, less than 50, or less than 10). It is thus possible for manufacturers may employ some of the methods described herein to respond to changing market conditions, to create articles for use in footwear that are designed for individual users or groups of users, etc.
  • Other examples may be seen in U.S. Pat. Apl. Ser. No. 62/464,364, entitled “Systems and Methods for Three-Dimensional Printing of Footwear and Other Articles,” filed Feb. 27, 2017, incorporated herein by reference in its entirety.
  • 3D-printed article 100 comprises first portion 110 and second portion 120 .
  • a portion of an article may refer to any collection of points within the article (i.e., points that are within the portion of space bounded by the external surfaces of the article). Portions of the article are typically, but not always, volumes of space within the article (in some embodiments, a portion may be a surface within an article, a line within an article, or a point within an article).
  • Portions of the article may be continuous (i.e., each point within the portion may be connected by a pathway that does not pass through any points external to the portion) or may be discontinuous (i.e., the portion may comprise at least one point that cannot be connected to at least one other point within the article by a pathway that does not pass through any points external to the portion).
  • Portions of an article may be substantially homogeneous with respect to one or more properties (e.g., one or more properties of the portion may vary with a standard deviation of less than or equal to 1%, 2%, 5%, or 10% throughout the portion), and/or may be heterogeneous with respect to one or more properties (e.g., one or more properties of the portion may vary with a standard deviation of greater than or equal to 1%, 2%, 5%, or 10% throughout the portion).
  • a 3D-printed article may comprise two or more portions, where one or more properties (e.g., average pore size, density, stiffness, stiffness of solid components of the article, Shore A hardness, degree of cross-linking, chemical composition, color, abrasion resistance, thermal conductivity, electrical conductivity, stiffness anisotropy, elastic modulus, flexural modulus, filler content, opacity, conductivity, breathability) of a first portion may differ from one or more properties of a second portion.
  • the difference in properties between the first portion and the second portion may comprise a gradient of the one or more properties (e.g., the property or properties may vary relatively smoothly from a first value in the first portion to a second value in the second portion).
  • Other examples include, but are not limited to, average largest dimension of particles (e.g., reinforcing particles), average concentration of particles (e.g., reinforcing particles), surface roughness, compression strength, slip resistance, or abrasion resistance.
  • FIG. 14A shows the second portion positioned above the first portion
  • the first portion may be positioned beside the second portion, the first portion may surround the second portion, the first portion and the second portion may interpenetrate (e.g., a first portion may comprise a foam that interpenetrates with a second portion that comprises an elastomer), etc.
  • FIG. 14A shows the second portion directly adjacent the first portion, this configuration should not be understood to be limiting.
  • the first portion may be separated from the second portion by one or more intervening portions positioned between the first portion and the second portion.
  • a portion that is positioned “between” two portions may be directly between the two portions such that no intervening portion is present, or an intervening portion may be present.
  • FIG. 14A only depicts two portions, it should also be understood that an article may comprise three portions, four portions, or more portions.
  • portions within a 3D-printed article as described herein may also further comprise sub-portions.
  • Each portion and/or sub-portion may differ from each other (sub-)portion in at least one way (e.g., any two (sub-)portions may comprise at least one property that is different), or one or more (sub-)portions may be substantially similar to other (sub-)portion(s) of the 3D-printed article.
  • a first portion and a second portion as described herein may be components of a 3D-printed article that is a single integrated material.
  • a single integrated material may not separate into discrete parts during the course of normal use, and/or may be separated into discrete parts whose morphologies would not be predictable prior to normal use and/or along interfaces that would not be predictable prior to normal use.
  • a single integrated material may lack seams, lack an adhesive that bonds two or more portions together, and/or lack an interface at which one or more properties (e.g., average pore size, density, stiffness, stiffness of solid components of the article, Shore A hardness, degree of cross-linking, chemical composition, color, abrasion resistance, thermal conductivity, electrical conductivity, stiffness anisotropy, elastic modulus, flexural modulus, filler content, opacity, conductivity, breathability) undergo step changes.
  • properties e.g., average pore size, density, stiffness, stiffness of solid components of the article, Shore A hardness, degree of cross-linking, chemical composition, color, abrasion resistance, thermal conductivity, electrical conductivity, stiffness anisotropy, elastic modulus, flexural modulus, filler content, opacity, conductivity, breathability
  • one or more portions may together form an 3D-printed article with one or more of the following features: macrovoids embedded within the article (e.g., a midsole) without an intersecting interface from overmolding, lamination, or ultrasonic welding; one or more open cell lattices; variations in density across geometries that would be challenging to form by molding; interpenetrating foams and elastomers that may, in some embodiments, not be separated by an interface due to molding or lamination; and/or one or more interfaces between different materials with extreme undercuts (e.g., materials with a negative draft angle, materials which cannot be injection molded using a single mold because they would be unable to slide out of the mold).
  • macrovoids embedded within the article e.g., a midsole
  • open cell lattices variations in density across geometries that would be challenging to form by molding
  • interpenetrating foams and elastomers that may, in some embodiments, not be separated by an interface due to molding or
  • a 3D-printed article may be a foam (e.g., a closed cell foam).
  • FIG. 14B shows one non-limiting embodiment of a 3D-printed article 100 which is a foam comprising pores 130 .
  • the foam may be a material comprising a matrix and pores disposed within the matrix. Pores may be randomly distributed throughout the foam, or may be positioned at regular and/or pre-determined intervals.
  • the material present within the pores of a foam is typically of a different phase than the material forming the matrix of the foam (e.g., a foam may comprise pores that comprise gas within a matrix that comprises a liquid and/or a solid).
  • the cells of the foam are typically isolated or separated from each other.
  • the cells of the foam are interconnected with each other; for example, they may be formed in an interconnected fashion, or the cells may be ruptured or become interconnected during or after formation of the foam.
  • the foam may be formed from a variety of polymers and gases. The gases may be introduced into the foam during formation (e.g., physically), and/or generated during formation (e.g., via chemical reaction).
  • a gas may be introduced by providing a liquid that forms a gas, e.g., upon a decrease in pressure or an increase in temperature.
  • a liquid such as butane may be kept under pressure and/or cooled prior to introduction into the nozzle or the mixing chamber; a change in temperature and/or pressure may cause the liquid to form a gas.
  • closed cell foams and open cell foams may have different properties (e.g., closed cell foams may have different values of density, stiffness, Shore A hardness, and the like than otherwise equivalent open cell foams) and may be suitable for different applications.
  • closed cell foams may have properties that are better suited to footwear applications than open cell foams.
  • a 3D-printed article or a portion thereof may comprise an enclosed open cell foam, or an open cell foam surrounded by a layer of continuous material.
  • an enclosed open cell foam may be suitable for use as an air cushion, and/or may have tactile properties that may be varied by varying infill density.
  • certain 3D-printed articles described herein may not be foams (i.e., they may not include any pores).
  • certain embodiments may relate to 3D-printed articles that are not foams and that comprise one or more elastomers.
  • an article may be printed that can then be formed into a foam, e.g., using a chemical reaction to produce a gas within the article.
  • a 3D-printed article that is a foam may comprise one or more portions having different properties.
  • FIG. 14C shows 3D-printed article 100 comprising first portion 110 , second portion 120 , and pores 130 .
  • FIG. 14C depicts a 3D-printed article comprising an average pore (or cell) size in the first portion (i.e.
  • first portion and the second portion may have the same average pore size but may comprise differences in other properties (e.g., one or more of the density, stiffness, Shore A hardness, degree of cross-linking, chemical composition may be different in the first portion than in the second portion).
  • differences in other properties e.g., one or more of the density, stiffness, Shore A hardness, degree of cross-linking, chemical composition may be different in the first portion than in the second portion.
  • the pore sizes are presented here for illustrative portions only.
  • FIG. 14C shows an average pore size in the first portion that is larger than the average pore size in the second portion, in some embodiments the average pore size of the first portion may be smaller than the average pore size of the second portion.
  • a 3D-printed article as designed herein may be suitable for use as a component of one or more articles of footwear.
  • FIG. 15 shows one non-limiting embodiment of an article of footwear 1000 .
  • the article of footwear comprises a sole, a toe box, an upper; lacing, a heel counter, and a pull tab. It should be understood that 3D-printed articles suitable for use in footwear may form any of the components or be a portion of any or all of the components shown in FIG. 15 .
  • multiple 3D-printed articles may be positioned on a single article of footwear (e.g., a single article of footwear may comprise a 3D-printed article that is disposed on a sole or is a sole and a 3D-printed article that is disposed on an upper).
  • the 3D-printed article may be a sole or a sole component, such as an outsole, a midsole, or an insole.
  • the 3D-printed article may be an article that is printed onto a sole component, such as a midsole and/or insole that is printed onto an outsole (e.g., a commercially available outsole, an outsole produced by a non-3D printing process).
  • the 3D-printed article may be an article that is printed onto an upper, such as a toe box, a heel counter, an ankle support, and/or a pull tab.
  • the upper may be one component of a fully assembled shoe which lacks the part(s) to be printed, or it may be an upper that has not been assembled with other footwear components.
  • a 3D-printed article may be a combination of two or more footwear components that are typically provided as separate articles.
  • the 3D-printed article may be able to serve as both a midsole and an insole, or may comprise a midsole and an insole that are a single integrated material.
  • the 3D-printed article may be able to serve as both an outsole and an insole, or may comprise an outsole and an insole that are a single integrated material.
  • a 3D-printed article comprising two or more footwear components e.g., a 3D-printed article comprising a midsole and an insole, a 3D-printed article comprising an outsole and an insole
  • FIG. 15 shows an athletic shoe, 3D-printed articles suitable for use in other types of footwear are also contemplated as described in further detail below.
  • the 3D-printed article may also or instead be suitable for one or more non-footwear components, such as orthotics and/or prosthetics.
  • an article as described herein may be formed by a process involving one or more 3D-printing steps.
  • an article may be formed by a process involving both one or more 3D-printing steps and one or more non-3D-printing steps.
  • an article may be formed by a first 3D-printing step followed by a first non-3D-printing step which is optionally followed by one or more further 3D-printing steps or non-3D-printing steps.
  • a sole or sole component may be 3D-printed into a mold to form a first portion and then a material may be injection molded or compression molded above the first portion to form the second portion.
  • Third, fourth, fifth, and/or higher numbered portions may then optionally be formed on the second portion (by, e.g., 3D-printing).
  • a non-3D printing step may comprise directly bonding two materials by pressing a first material (e.g., a non-3D-printed material, an upper) into a second 3D-printed material (e.g., a 3D-printed midsole) prior to full curing of the second material.
  • an inkjet finishing process may be applied to deposit one or more materials (e.g., one more pigments) on a 3D-printed article or on a material disposed on a 3D-printed article (e.g., a material injection molded or compression molded on a 3D-printed article).
  • an inkjet finishing process may enhance the surface quality of the article that is subject to it.
  • 3D-printed foams may be prepared as discussed herein using various inputs, as described herein.
  • the foam density may be varied by varying the amount of added gas, the amount of added water (e.g., in water-blown foam applications), the amount of added chemical blowing agent, etc.
  • the foam density constant may be held constant, but the cross-link density or isocyanate content may be varied to change properties such as the elasticity, elongation, or stiffness of the foam.
  • one or more properties of a mixture that is 3D-printed from a nozzle may change as a function of time and/or nozzle position with respect to the substrate.
  • the composition of one or more components and/or the wt % of one or more components within the mixture may change as a function of time.
  • one or more physical parameters of the nozzle and/or the substrate may change as a function of time.
  • the temperature of the nozzle and/or the substrate may change as a function of time.
  • the temperature of the nozzle and the temperature of the substrate may affect the types of reactions that occur between various components (e.g., cross-linking reactions, foaming reactions, reactions within the nozzle, reactions on the substrate) and/or the rates at which these reactions occur.
  • This may in turn affect the chemical structure of the mixture (e.g., the composition of the mixture, the degree of cross-linking of the resultant foam) during and/or after printing, and/or affect one or more physical properties of the mixture (e.g., the viscosity of the mixture, the average pore size of the resultant foam, the density of the resultant foam, the stiffness of the resultant foam, the Shore A hardness of the resultant foam) during and/or after printing.
  • the chemical structure of the mixture e.g., the composition of the mixture, the degree of cross-linking of the resultant foam
  • one or more physical properties of the mixture e.g., the viscosity of the mixture, the average pore size of the resultant foam, the density of the resultant foam
  • changes in substrate or nozzle temperature during printing may allow for different portions of the 3D-printed article (e.g., those printed at different times and/or in different positions on the substrate) to have different chemical or physical properties.
  • the portions with different chemical and/or physical properties may be printed in a single continuous process, and/or may together form a single integrated material.
  • a foam precursor prior to curing, may have different rheological properties than the starting raw materials without gas content.
  • a mixture of low viscosity fluids, gases, and/or surfactants, etc. having Newtonian flow behavior before foaming can be used to produce a precursor having non-Newtonian flow characteristics, e.g., with a yield stress, or shear-thickening or shear-thinning behavior. This may be used herein to produce a precursor having a rheological profile suitable for printing, e.g., on a substrate.
  • Fluids such as incompressible Newtonian fluids or gases can be controlled introduced into a nozzle (e.g., prior to mixing) and precisely metered onto a substrate during deposition.
  • the foaming process may start within the nozzle, and controlled to control deposition of the precursor and/or the final mechanical properties of the foam.
  • a mixing nozzle was configured to have two inputs: Input A for an isocyanate pre-polymer, and Input B for a mixture of polyols, surfactants, and water.
  • Input A for an isocyanate pre-polymer
  • Input B for a mixture of polyols, surfactants, and water.
  • Input A (one or more of the following components flowed into the mixing nozzle)
  • Amount Component Description (g) Polytech 20-A Isocyanate prepolymer 150 BJB enterprises f-115-a Isocyanate prepolymer 150 Polytech F-3 - A Isocyanate prepolymer 110 Polyfiber II Polyethylene fiber 40 (rheological modifier) Input B: (one or more of the following components flowed into the mixing nozzle, in addition to water)
  • Amount Component Description (g) Polytech 20-B Polyol blend for elastomer 150 BJB enterprises F-115-B Polyol blend for soft elastomer 150 Polytech F-3-B Polyol, water, surfactant blend 220 for foam promotion 3M S32 glass bubbles Foam stabilizer and bubble 42 nucleation site Polyfiber II Polyethylene fiber (rheological 40 modifier) Polytech White White Pigment 16 Poly UV UV stabilizer 3.38 Evonik Tegostab B 8952 Silicone surfactant for foam 10 stabilizing Polytek 74/75 part X Organometallic catalyst 15.2 accelerator Such a water-blown polyurethane foam (white, top portion) was co-printed with a non-foaming two-part polyurethane elastomer (blue, bottom portion) to form a shoe sole, as is shown in FIG. 7 .
  • a mean pore size of the foam was characterized by slicing through a 3D-printed filament to obtain a cross-section of the foam and then imaging the cross-section with a light microscope and using image analysis (depicted in FIG. 8 with circles and measurements in microns).
  • Silicone gradient material A coupon with a gradient in both stiffness and color was fabricated using a two-input mixing nozzle system, as shown in FIG. 9 .
  • the clear-colored silicone (left) was a soft elastomer with a Shore hardness of 10 A.
  • parts A and B were mixed together to make a precursor to the soft elastomer (Input 1), and parts A′ and B′ were mixed together to make a precursor to the hard elastomer (Input 2) prior to injecting into the mixing chamber.
  • the coupon was printed with each layer as a single meandering print path where the beginning of the print path (left-most position in FIG.
  • Input 1, A and B (two or more of the following components flowed into the mixing nozzle)
  • Amount Component Description (g) Blue star LSR 4301 A Part A soft platinum cure silicone 74 elastomer Blue star LSR 4301 B Part B soft platinum cure silicone 74 elastomer Aerosil 300 Fumed silica (rheological modifier) 8.9 Input 2, A′ and B′: (two or more of the following components flowed into the mixing nozzle)
  • a hydrogel structure is formed using the mixing system.
  • a first input to the mixing nozzle comprises a cross-linking agent for the hydrogel, and a second input to the mixing nozzle comprises an uncross-linked hydrogel precursor. Additional inputs into the mixing nozzle include concentrated cell suspensions of various types, different types of cell media, and concentrates of cell growth factors and chemical signaling agents.
  • a mixing nozzle comprises a mixing/frothing chamber and at least three inputs.
  • a first input is a gas such as nitrogen or air.
  • a second input is a bisphenol-A-based resin such as Epon® Resin 828, with an added surfactant that stabilizes bubbles.
  • a third input is a curing agent for epoxy resin such as a diamine like ethylenediamine. The second and third input are added to the mixing chamber to induce the epoxy resin to cross-link into a solid thermoset.
  • the gas input flowrate can be varied along with the impeller speed to create a rigid thermosetting foam with variable dielectric properties due to air content.
  • a multi-input system can be used for creating a therapeutic-impregnated matrix of material such as a pill.
  • Inputs include: a solution of a biodegradable polymer with a high degradation rate; a solution of a biodegradable polymer with a low degradation rate; a solution of a first active therapeutic agent; a solution of a second active therapeutic agent; a sugar or flow inducing agent; or another suitable input.
  • a pill-like architecture can then be 3D-printed, wherein the composition of the pill can be varied spatially.
  • the external part of the pill could be 3D-printed to contain a first therapeutic agent, and the material printed has a fast degradation profile for a quick release of the first therapeutic agent.
  • the internal part of the pill may be printed with a material that degrades slowly, and may contain two different types of therapeutic agents.
  • the external surface of the pill may have a printed inert sugar coating so that no therapeutic release occurs until the pill has passed through the esophagus. This allows the possibility of combining many pills into one.
  • a 3D-printed pill can have a customized therapeutic release profile that is specific to a patient.
  • 3D-print pills can be applied to 3D-printed implantable long-term therapeutic release depots.
  • this 3D-printing methodology can be applied towards fabricating a skin tissue graft, wherein drugs, growth factors, antibiotics, and cells can be printed with variable spatial concentration to promote the regrowth of a skin defect such as a severe burn.
  • Printing an implantable therapeutic depot may involve an input that induces polymerization or cross-linking.
  • a system comprising at least four inputs may be used to 3D-print a stimuli-responsive structure, the inputs comprising: an isocyanate cross-linking agent; a polyol mixture wherein the components have low stiffness; a polyol mixture wherein the components have high stiffness; and a chemical blowing agent concentrate dissolved in polyol.
  • a tri-layer architecture can be 3D-printed to accomplish the stimuli-responsive property.
  • the top layer ( 1 ) forms a low-stiffness/high-flexibility elastomer from inputs comprising a low-stiffness polyol mixture and an isocyanate.
  • the middle layer ( 2 ) in FIG. 10 forms a high-stiffness elastomer from inputs comprising a high stiffness polyol mixture and an isocyanate.
  • Layer ( 2 ) functions as a strain-limiting layer.
  • FIG. 10 illustrates a 3D-printed stimuli-responsive tri-layer polyurethane system, where heating results in curling of the tri-layer structure (Example 6)
  • Selective placement of the expandable material containing the blowing agent can be utilized to programmatically define deformations in printed parts that will not occur until after the part is printed and heated.
  • This example illustrates the formulation and printing of an outsole material.
  • a polyol concentrate was made by mixing the ingredients at the prescribed ratio (Part B Fluid) using a planetary centrifugal mixer.
  • the fillers (Outsole Formulation, Part B) were added to the polyol concentrate and mixed with a planetary centrifugal mixer under vacuum.
  • the Part B mixture was loaded into a syringe, and used to feed into one side of the active mixing head. The same protocol was done for Part A in a separate container.
  • Part B Fluid Polyol concentrate:
  • Amount Component Description isocyanate prepolymer Part A 15 fumed silica Part A; filler 0.6 polyol concentrate Part B 15 fumed silica Part B; filler, 0.45 with PDMS coating ground tire rubber Part B; filler, with particles 10 size 180 microns chopped glass fiber Part B; filler; 1/32 inches long 3 with amino silane coating silicone oil Part B; filler; with viscosity of 0.45 60,000 cP
  • a reference to “A and/or B”, when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.
  • the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements.
  • This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified.
  • “at least one of A and B” can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.
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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110116496A (zh) * 2019-04-30 2019-08-13 西北农林科技大学 一种可掺杂复合材料颗粒的3d打印设备结构
US10532334B2 (en) * 2017-02-14 2020-01-14 Walmart Apollo, Llc Paint mixing system
US10932515B2 (en) * 2017-02-27 2021-03-02 Voxel8, Inc. 3D printed articles of footwear with sensors and methods of forming the same
US10953605B2 (en) * 2017-04-04 2021-03-23 Massachusetts Institute of Technology, Cambridge, Massachusetts and Steeicase Incorporated Additive manufacturing in gel-supported environment
CN112692303A (zh) * 2020-12-14 2021-04-23 江苏大学 一种微流控3d打印复合材料制备装置及方法
US11052597B2 (en) 2016-05-16 2021-07-06 Massachusetts Institute Of Technology Additive manufacturing of viscoelastic materials
US11155025B2 (en) 2013-12-05 2021-10-26 Massachusetts Institute Of Technology Methods for additive manufacturing of an object
WO2022047025A1 (en) * 2020-08-26 2022-03-03 Kornit Digital Technologies Ltd. Methods for three-dimensionally printing and associated multi-input print heads and systems
US11312071B2 (en) 2018-11-12 2022-04-26 Ossur Iceland Ehf Additive manufacturing system, method and corresponding components for making elastomeric structures
US20220154478A1 (en) * 2019-03-15 2022-05-19 Sika Technology Ag Method for applying a building material
US11446889B2 (en) 2018-01-12 2022-09-20 Kornit Digital Technologies Ltd. 3D printed cage structures for apparel
US11470908B2 (en) 2017-02-27 2022-10-18 Kornit Digital Technologies Ltd. Articles of footwear and apparel having a three-dimensionally printed feature
WO2022221347A1 (en) * 2021-04-16 2022-10-20 Segun Ogundipe Hockey blade protection sleeve
US11497275B2 (en) 2017-02-27 2022-11-15 Kornit Digital Technologies Ltd. 3D printed articles of footwear with particles
US11667072B2 (en) 2019-10-16 2023-06-06 Massachusetts Institute Of Technology Liquid metal printing
US11701813B2 (en) 2017-02-27 2023-07-18 Kornit Digital Technologies Ltd. Methods for three-dimensionally printing and associated multi-input print heads and systems
US11857023B2 (en) 2017-02-27 2024-01-02 Kornit Digital Technologies Ltd. Digital molding and associated articles and methods
WO2024008818A1 (fr) 2022-07-06 2024-01-11 Cockcinel Semelle intermediaire pour chaussure
US11883306B2 (en) 2019-11-12 2024-01-30 Ossur Iceland Ehf Ventilated prosthetic liner
US11904614B2 (en) 2017-02-27 2024-02-20 Kornit Digital Technologies Ltd. Multi-input print heads for three-dimensionally printing and associated systems and methods

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9925440B2 (en) 2014-05-13 2018-03-27 Bauer Hockey, Llc Sporting goods including microlattice structures
AU2015353634B2 (en) 2014-11-24 2018-06-14 Ppg Industries Ohio, Inc. Methods for reactive three-dimensional printing by extrusion
US10434704B2 (en) 2017-08-18 2019-10-08 Ppg Industries Ohio, Inc. Additive manufacturing using polyurea materials
CN111182813B (zh) * 2017-10-13 2022-05-17 株式会社爱世克私 鞋底用构件和鞋
EP3762214A4 (en) * 2018-09-18 2021-10-27 Hewlett-Packard Development Company, L.P. THREE-DIMENSIONAL PRINTING
US20220098355A1 (en) * 2019-02-11 2022-03-31 Ppg Industries Ohio, Inc. Elastomeric compositions and methods of use
EP4349601A2 (en) * 2019-02-11 2024-04-10 PPG Industries Ohio, Inc. Coreactive three-dimensional printing of parts
CN109942771B (zh) * 2019-03-12 2021-02-26 温州市显兴鞋材有限公司 一种鞋底成型方法
US20220162375A1 (en) * 2019-03-20 2022-05-26 Ppg Industries Ohio, Inc. Two component coating compositions
WO2020232550A1 (en) 2019-05-21 2020-11-26 Bauer Hockey Ltd. Helmets comprising additively-manufactured components
WO2020232555A1 (en) * 2019-05-21 2020-11-26 Bauer Hockey Ltd. Articles comprising additively-manufactured components and methods of additive manufacturing
JP2020189444A (ja) * 2019-05-22 2020-11-26 パナソニックＩｐマネジメント株式会社 印刷装置
DE102019113816A1 (de) * 2019-05-23 2020-11-26 Bayerische Motoren Werke Aktiengesellschaft Kraftfahrzeugsitz
CN113950499B (zh) * 2019-07-02 2024-01-02 Sika技术股份公司 通过3d打印制备大尺寸模型和工具的双组分聚氨酯组合物
CN110257243B (zh) * 2019-07-23 2021-06-25 清华大学深圳研究生院 微流控芯片打印喷嘴和生物3d打印系统
US20210040276A1 (en) * 2019-08-06 2021-02-11 University Of South Florida Composite materials and filaments composed of the same for printing three dimensional articles
TWI821428B (zh) * 2019-10-04 2023-11-11 豐泰企業股份有限公司 ３ｄ立體列印熱膨脹結構的製造方法
TWI729559B (zh) * 2019-11-07 2021-06-01 頡欣機械有限公司 用於鞋類大底自動列印貼合中底之方法
EP4065337A4 (en) * 2019-11-26 2024-03-20 Univ Massachusetts NOZZLES, PIPE, HOT ENDS AND METHODS OF USE THEREOF
IT201900023874A1 (it) * 2019-12-13 2021-06-13 Ama Gusberti S R L Testa nebulizzatrice
CN114829118A (zh) * 2020-01-03 2022-07-29 泰州鑫宇精工股份有限公司 一种成型装置
CN111210946B (zh) * 2020-01-08 2020-09-15 广东工业大学 一种可控的可拉伸双螺旋微导线的加工方法及其装置
WO2022077163A1 (zh) * 2020-10-12 2022-04-21 苏州美梦机器有限公司 具有可变尺寸的挤出口的3d打印装置及其控制方法
CN112477134B (zh) * 2020-11-03 2023-01-06 深圳市纵维立方科技有限公司 送料装置和3d打印机
CN112537031A (zh) * 2020-11-05 2021-03-23 北京化工大学 一种梯度聚合物复合材料3d打印方法及设备
CN113263838A (zh) * 2021-05-20 2021-08-17 北京航空航天大学 基于多级空气动力学透镜的气溶胶喷墨打印喷嘴
CN113459671B (zh) * 2021-06-28 2022-04-22 华南理工大学 基于电磁耦合作用的柔性可变尺寸微压电喷头及调节方法
US20230080827A1 (en) * 2021-09-13 2023-03-16 Triex, Llc Additive manufacturing system with flow control and additive injection device
CN114147952B (zh) * 2021-11-30 2022-08-05 浙江大学 一种大孔水凝胶3d打印装置及打印方法
CN115364709A (zh) * 2022-01-28 2022-11-22 湖南云箭集团有限公司 一种微滴喷印装备高速高压雾化混料工艺及装置
WO2023195167A1 (ja) * 2022-04-08 2023-10-12 株式会社アシックス 靴底用部材及び靴
CN115946346B (zh) * 2023-03-15 2023-05-30 杭州极筑科技有限公司 一种加减色法的彩色高分子3d打印的工艺方法

Family Cites Families (89)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3053454A (en) * 1959-04-13 1962-09-11 Buensod Stacey Corp Fluid mixer and flow regulator
US3982663A (en) * 1975-02-07 1976-09-28 The Gates Rubber Company Method and apparatus for metering thixotropic battery paste
US4078576A (en) * 1976-09-17 1978-03-14 American Air Filter Company, Inc. Gas mixer
US4708292A (en) * 1985-06-05 1987-11-24 Olin Corporation Foam dispensing gun with improved mixing chamber
JPH03201809A (ja) 1989-12-28 1991-09-03 Toshiba Corp 差動出力回路
US5385953A (en) 1991-10-02 1995-01-31 Urethane Technologies, Inc. Microcellular polyurethane composite
JP3201809B2 (ja) 1992-01-30 2001-08-27 三菱電機株式会社 パルスレーザ装置
US5335992A (en) 1993-03-15 1994-08-09 Holl Richard A Methods and apparatus for the mixing and dispersion of flowable materials
US5820354A (en) 1996-11-08 1998-10-13 Robbins & Myers, Inc. Cascaded progressing cavity pump system
US5979787A (en) 1997-12-13 1999-11-09 Usbi Co. Apparatus and method for convergently applying polymer foam to substrate
US6165406A (en) 1999-05-27 2000-12-26 Nanotek Instruments, Inc. 3-D color model making apparatus and process
US7300619B2 (en) 2000-03-13 2007-11-27 Objet Geometries Ltd. Compositions and methods for use in three dimensional model printing
US6986739B2 (en) * 2001-08-23 2006-01-17 Sciperio, Inc. Architecture tool and methods of use
GB0127252D0 (en) 2001-11-13 2002-01-02 Vantico Ag Production of composite articles composed of thin layers
US20040126254A1 (en) 2002-10-31 2004-07-01 Chen Ching Jen Surface micromachined mechanical micropumps and fluid shear mixing, lysing, and separation microsystems
US8333330B2 (en) * 2004-09-17 2012-12-18 Active Power, Inc. Systems and methods for controlling temperature and pressure of fluids
DE602005026430D1 (de) 2004-11-04 2011-03-31 Showa Denko Kk Isocyanatverbindung enthaltend eine ethylenisch ungesättigte gruppe und verfahren zu deren herstellung, sowie reaktives monomer, reaktives (meth)acrylatpolymer und anwendung davon
JP2008529663A (ja) 2005-02-09 2008-08-07 チルドレンズ メディカル センター コーポレイション 組織回復のために流体を混合および供給するデバイス
US20080026190A1 (en) 2006-07-28 2008-01-31 General Electric Company Durable membranes and methods for improving membrane durability
US8245378B2 (en) 2007-09-13 2012-08-21 Nike, Inc. Method and apparatus for manufacturing components used for the manufacture of articles
FR2939141B1 (fr) * 2008-12-03 2012-12-14 Michelin Soc Tech Objet pneumatique pourvu d'une couche etanche aux gaz a base d'un elastomere thermoplastique et de microspheres thermoplastiques expansees
US20100140852A1 (en) * 2008-12-04 2010-06-10 Objet Geometries Ltd. Preparation of building material for solid freeform fabrication
EP2311563A1 (en) 2009-08-07 2011-04-20 F. Hoffmann-La Roche AG Processing units and methods for the processing of liquid samples
US8758263B1 (en) 2009-10-31 2014-06-24 Voxel Rad, Ltd. Systems and methods for frameless image-guided biopsy and therapeutic intervention
GB2488508B (en) 2010-11-29 2015-10-07 Halliburton Energy Services Inc 3D-printed bodies for molding downhole equipment
AU2012214157A1 (en) 2011-02-11 2013-08-29 Code Footwear, Llc Reconfigurable apparel manufacture and business processes
WO2013012427A1 (en) 2011-07-21 2013-01-24 Rhino Linings Corporation Systems and methods for processing and dispensing filled multi-component materials
DE102011086742B4 (de) 2011-11-21 2019-12-19 Adidas Ag Schuh und Verfahren zur Herstellung zumindest eines Teilbereichs eines Schafts eines Schuhs
DE102012206094B4 (de) 2012-04-13 2019-12-05 Adidas Ag Sohlen für Sportschuhe, Schuhe und Verfahren zur Herstellung einer Schuhsohle
US20160374431A1 (en) 2012-07-18 2016-12-29 Adam P. Tow Systems and Methods for Manufacturing of Multi-Property Anatomically Customized Devices
US8993061B2 (en) 2012-07-19 2015-03-31 Nike, Inc. Direct printing to fabric
US9005710B2 (en) * 2012-07-19 2015-04-14 Nike, Inc. Footwear assembly method with 3D printing
US9694389B2 (en) * 2012-07-24 2017-07-04 Integrated Deposition Solutions, Inc. Methods for producing coaxial structures using a microfluidic jet
KR102137742B1 (ko) 2012-12-19 2020-07-24 뉴우바란스아스레틱스인코포레이팃드 사용자 맞춤형 신발, 및 그 설계와 제조 방법
US11612209B2 (en) 2012-12-19 2023-03-28 New Balance Athletics, Inc. Footwear with traction elements
CN103909655A (zh) 2013-01-06 2014-07-09 北京国视国电科技有限公司 3d快速成型立体三维打印装置和工艺
US9144956B2 (en) 2013-02-12 2015-09-29 Nike, Inc. Bead foam compression molding method with in situ steam generation for low density product
EP4008521B1 (en) 2013-03-22 2024-01-03 Markforged, Inc. Three dimensional printing of reinforced filament
US10119108B2 (en) 2013-08-01 2018-11-06 Sartorius Stedim Biotech Gmbh Manufacturing within a single-use container
CN105722663B (zh) * 2013-11-18 2019-05-21 张凯瑞 彩色或多材质3d打印机
BR112016011566A2 (pt) * 2013-11-21 2017-08-08 Schlumberger Technology Bv Aparelho de teste para caracterizar propriedades de um fluido, método de teste para caracterizar propriedades de um fluido, e método de teste para caracterizar propriedades que se referem à condição de formação de clatrato hidratado de um fluido que inclui um componente de fluido de reservatório
US9375051B2 (en) * 2014-01-22 2016-06-28 Nike, Inc. Article with coloring layer and control surface layer
CN105313332B (zh) 2014-06-09 2020-05-05 联合工艺公司 由两部分组成的热固性树脂增材制造系统
EP3158399B1 (en) 2014-06-23 2022-10-26 Carbon, Inc. Polyurethane resins having multiple mechanisms of hardening for use in producing three-dimensional objects
US20160021969A1 (en) 2014-07-25 2016-01-28 Vorbeck Materials Corp Performance outdoor footwear
WO2016016887A1 (en) 2014-07-28 2016-02-04 Beyon 3D Ltd Method and system for fabrication of custom-made molds and concrete-architectural components
CN104191616A (zh) 2014-08-29 2014-12-10 马驰 一种喷墨3d打印设备及打印方法
US10226103B2 (en) 2015-01-05 2019-03-12 Markforged, Inc. Footwear fabrication by composite filament 3D printing
EP3653060B1 (en) 2015-01-16 2024-05-01 Cocoterra Company Chocolate processing system and method
US9474331B2 (en) * 2015-02-03 2016-10-25 Nike, Inc. Method of making an article of footwear having printed structures
EP3253560B1 (en) 2015-02-05 2019-11-06 Stratasys Ltd. Digitally-controlled three-dimensional printing of polymerizable materials
US10244818B2 (en) * 2015-02-18 2019-04-02 Clemson University Research Foundation Variable hardness orthotic
WO2016164562A1 (en) * 2015-04-07 2016-10-13 President And Fellows Of Harvard College Microfluidic active mixing nozzle for three-dimensional printing of viscoelastic inks
EP3285989B1 (de) 2015-04-21 2022-04-13 Covestro Deutschland AG Verfahren zur herstellung von 3d objekten
CN104786506A (zh) 2015-05-11 2015-07-22 北京化工大学 一种可制备软硬复合聚氨酯制品三维成型设备
CN104875389B (zh) 2015-05-19 2017-05-17 珠海天威飞马打印耗材有限公司 三维打印机和打印方法、三维打印头
WO2016191329A1 (en) 2015-05-22 2016-12-01 Georgia-Pacific Chemicals Llc Apparatus and methods for multicomponent thermoset resin systems in additive manufacturing
WO2016209872A1 (en) 2015-06-23 2016-12-29 Sabic Global Technologies B.V. Process for additive manufacturing
DE102015212099B4 (de) 2015-06-29 2022-01-27 Adidas Ag Sohlen für Sportschuhe
US10394202B2 (en) 2015-08-21 2019-08-27 Voxel8, Inc. 3D printer calibration and control
CN205058637U (zh) * 2015-10-30 2016-03-02 兰红波 一种单喷头多材料多尺度3d打印装置
WO2017075396A1 (en) 2015-10-30 2017-05-04 Stratasys, Inc. Viscosity pump with fill and flow control and method thereof
CN205741716U (zh) * 2015-11-13 2016-11-30 创方拓展有限公司 功能织物及由其制成的服装
WO2017100207A2 (en) 2015-12-07 2017-06-15 Nike Innovate C.V. Article of footwear with tubular structures having tab portions
US20170164899A1 (en) 2015-12-14 2017-06-15 Erika Yang Devices embedded smart shoes
DE102015016464B4 (de) 2015-12-21 2024-04-25 Voxeljet Ag Verfahren und Vorrichtung zum Herstellen von 3D-Formteilen
CN117283450A (zh) 2016-01-19 2023-12-26 应用材料公司 多孔化学机械抛光垫
WO2017136405A1 (en) * 2016-02-02 2017-08-10 Hanger, Inc. Digital to definitive orthotic and prosthetic device manufacturing system and method
TWI629012B (zh) 2016-02-24 2018-07-11 國立清華大學 智慧鞋墊
US20170251713A1 (en) 2016-03-07 2017-09-07 Telamens, Inc. 3d printer and method for printing an object using a curable liquid
JP6896758B2 (ja) 2016-03-15 2021-06-30 ナイキ イノベイト シーブイ 履物のための容量性足存在センシング
CA3022913C (en) 2016-05-04 2023-08-15 Allen Selner Instrumented orthotic
WO2017223276A1 (en) 2016-06-24 2017-12-28 Polyone Corporation Coc polymer compounds for 3d printing
US10254499B1 (en) 2016-08-05 2019-04-09 Southern Methodist University Additive manufacturing of active devices using dielectric, conductive and magnetic materials
CN106331236B (zh) 2016-09-18 2019-06-04 广东劲胜智能集团股份有限公司 一种钛合金塑料复合材料手机框架及其制作方法
GB201621769D0 (en) 2016-12-20 2017-02-01 Staffordshire Univ Deformable support structure
US20190387839A1 (en) 2017-02-03 2019-12-26 Nike, Inc. Fiber-Bound Engineered Materials Formed Using Zonal Scrims
US11497275B2 (en) 2017-02-27 2022-11-15 Kornit Digital Technologies Ltd. 3D printed articles of footwear with particles
US11857023B2 (en) 2017-02-27 2024-01-02 Kornit Digital Technologies Ltd. Digital molding and associated articles and methods
US20190039311A1 (en) 2017-02-27 2019-02-07 Voxel8, Inc. Systems and methods for 3d printing articles of footwear with property gradients
US11470908B2 (en) 2017-02-27 2022-10-18 Kornit Digital Technologies Ltd. Articles of footwear and apparel having a three-dimensionally printed feature
US11904614B2 (en) 2017-02-27 2024-02-20 Kornit Digital Technologies Ltd. Multi-input print heads for three-dimensionally printing and associated systems and methods
US20190039299A1 (en) 2017-02-27 2019-02-07 Voxel8, Inc. 3d printing devices including mixing nozzles
US11701813B2 (en) 2017-02-27 2023-07-18 Kornit Digital Technologies Ltd. Methods for three-dimensionally printing and associated multi-input print heads and systems
US11446889B2 (en) 2018-01-12 2022-09-20 Kornit Digital Technologies Ltd. 3D printed cage structures for apparel
US20190246741A1 (en) 2018-01-12 2019-08-15 Voxei8, Inc. 3d printed cage structures for footwear
CN115956737A (zh) 2018-12-06 2023-04-14 耐克创新有限合伙公司 利用泡沫颗粒制造物品的方法
US11805843B2 (en) 2020-03-06 2023-11-07 Alexander Louis Gross Midsole of a shoe
WO2022047025A1 (en) 2020-08-26 2022-03-03 Kornit Digital Technologies Ltd. Methods for three-dimensionally printing and associated multi-input print heads and systems

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11155025B2 (en) 2013-12-05 2021-10-26 Massachusetts Institute Of Technology Methods for additive manufacturing of an object
US11052597B2 (en) 2016-05-16 2021-07-06 Massachusetts Institute Of Technology Additive manufacturing of viscoelastic materials
US10532334B2 (en) * 2017-02-14 2020-01-14 Walmart Apollo, Llc Paint mixing system
US11470908B2 (en) 2017-02-27 2022-10-18 Kornit Digital Technologies Ltd. Articles of footwear and apparel having a three-dimensionally printed feature
US10932515B2 (en) * 2017-02-27 2021-03-02 Voxel8, Inc. 3D printed articles of footwear with sensors and methods of forming the same
US11904614B2 (en) 2017-02-27 2024-02-20 Kornit Digital Technologies Ltd. Multi-input print heads for three-dimensionally printing and associated systems and methods
US11857023B2 (en) 2017-02-27 2024-01-02 Kornit Digital Technologies Ltd. Digital molding and associated articles and methods
US11701813B2 (en) 2017-02-27 2023-07-18 Kornit Digital Technologies Ltd. Methods for three-dimensionally printing and associated multi-input print heads and systems
US11647805B2 (en) 2017-02-27 2023-05-16 Kornit Digital Technologies Ltd. 3D printed articles of footwear with sensors and methods of forming the same
US11497275B2 (en) 2017-02-27 2022-11-15 Kornit Digital Technologies Ltd. 3D printed articles of footwear with particles
US20210178702A1 (en) * 2017-04-04 2021-06-17 Massachusetts Institute Of Technology Additive manufacturing in gel-supported environment
US20210138737A1 (en) * 2017-04-04 2021-05-13 Massachusetts Institute Of Technology Additive manufacturing in gel-supported environment
US10953605B2 (en) * 2017-04-04 2021-03-23 Massachusetts Institute of Technology, Cambridge, Massachusetts and Steeicase Incorporated Additive manufacturing in gel-supported environment
US11446889B2 (en) 2018-01-12 2022-09-20 Kornit Digital Technologies Ltd. 3D printed cage structures for apparel
US11312071B2 (en) 2018-11-12 2022-04-26 Ossur Iceland Ehf Additive manufacturing system, method and corresponding components for making elastomeric structures
US11390025B2 (en) 2018-11-12 2022-07-19 Ossur Iceland Ehf Medical device including a structure based on filaments
US20220219391A1 (en) * 2018-11-12 2022-07-14 Ossur Iceland Ehf Additive manufacturing system, method and corresponding components for making elastomeric structures
US20220154478A1 (en) * 2019-03-15 2022-05-19 Sika Technology Ag Method for applying a building material
CN110116496A (zh) * 2019-04-30 2019-08-13 西北农林科技大学 一种可掺杂复合材料颗粒的3d打印设备结构
US11667072B2 (en) 2019-10-16 2023-06-06 Massachusetts Institute Of Technology Liquid metal printing
US11883306B2 (en) 2019-11-12 2024-01-30 Ossur Iceland Ehf Ventilated prosthetic liner
WO2022047025A1 (en) * 2020-08-26 2022-03-03 Kornit Digital Technologies Ltd. Methods for three-dimensionally printing and associated multi-input print heads and systems
CN112692303A (zh) * 2020-12-14 2021-04-23 江苏大学 一种微流控3d打印复合材料制备装置及方法
WO2022221347A1 (en) * 2021-04-16 2022-10-20 Segun Ogundipe Hockey blade protection sleeve
WO2024008818A1 (fr) 2022-07-06 2024-01-11 Cockcinel Semelle intermediaire pour chaussure
FR3137543A1 (fr) * 2022-07-06 2024-01-12 Enrick BOISDUR Semelle de chaussure intermediaire

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