WO2023141373A1 - Fabrication par extrusion coréactive ambiante de surfaces texturées - Google Patents

Fabrication par extrusion coréactive ambiante de surfaces texturées Download PDF

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Publication number
WO2023141373A1
WO2023141373A1 PCT/US2023/060349 US2023060349W WO2023141373A1 WO 2023141373 A1 WO2023141373 A1 WO 2023141373A1 US 2023060349 W US2023060349 W US 2023060349W WO 2023141373 A1 WO2023141373 A1 WO 2023141373A1
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WIPO (PCT)
Prior art keywords
coreactive composition
coreactive
textured
composition
applying
Prior art date
Application number
PCT/US2023/060349
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English (en)
Inventor
Cynthia Kutchko
Bret M. BOYLE
Bryan W. WILKINSON
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Ppg Industries Ohio, Inc.
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Publication of WO2023141373A1 publication Critical patent/WO2023141373A1/fr

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Classifications

    • 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
    • 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
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
    • 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
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/245—Platforms or substrates
    • 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
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/295—Heating elements
    • 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
    • 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
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • 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
    • 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
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
    • B29C2059/023—Microembossing
    • 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

Definitions

  • Textured surfaces manufactured using ambient coreactive extrusion are disclosed.
  • a coreactive thermosetting composition is extruded onto a textured template. After the deposited composition is partially or fully cured, the textured template can be removed to provide a part having a textured surface.
  • the disclosed methods can be used to prepare parts with a wide variety of textures.
  • Ambient reactive extrusion additive manufacturing is a method by which coreactive are combined and mixed to form a coreactive thermoset composition that can be extruded using additive manufacturing methods to fabricate two-dimensional and three-dimensional parts.
  • the surface quality can include smoothness or texture. Smooth surfaces of parts manufactured using ambient reactive extrusion can be obtained by removing print lines using mechanical abrasion and/or by applying leveling coatings. Textured surfaces can be fabricated using three-dimensional printing. Alternative ways of fabricated parts having a desired surface quality and/or features is desired.
  • methods of forming a part comprising a textured surface comprise applying a coreactive composition using ambient coreactive extrusion over a textured template; at least partially curing the applied coreactive composition; and removing the textured template from the at least partially cured applied coreactive composition to provide a part comprising a textured surface.
  • methods of forming a part having a textured surface comprise applying a coreactive composition to fabricate a part; and while the applied coreactive composition is partially cured, embossing a surface of the partially cured coreactive composition using a textured template to provide a part having a textured surface.
  • FIGS. 1A-1D show surfaces having leather textured surfaces ranging from a fine grain leather texture (FIG. 1A) to a heavy grain leather texture (FIG. ID) made using methods provided by the present disclosure.
  • FIGS. 2A-2D show surfaces having leather textures made using methods provided by the present disclosure.
  • the image on the left side of each figure is an optical image and the image on the right side of each figure is an image of the digitized surface profile.
  • FIG. 1A shows a leather textured surface having an S a value of 13.81 pm.
  • FIG. IB shows a leather textured surface having an S a value of 14.61 pm.
  • FIG. 1C shows a leather textured surface having an S a value of 19.91 pm.
  • FIG. ID shows a leather textured surface having an S a value of 37.19 pm.
  • FIGS. 3A-3C show surfaces with different textured patterns prepared using methods provided by the present disclosure.
  • the image on the left side of each figure is an optical image and the image on the right side of each figure is an image of the digitized surface profile.
  • FIG. 3A shows a surface with a synthetic texture having an S a of 21.96 pm.
  • FIG. 3B shows a surface with a grid texture having an S a of 8.62 pm.
  • FIG. 3C shows a surface with a woven texture having an S a of 26.09 pm.
  • FIG. 4A shows a surface having a natural woodgrain texture made using methods provided by the present disclosure.
  • the image on the left side is an optical image and the image on the right side shows an image of the digitized surface profile.
  • FIG. 4B shows a surface having a natural slate texture made using methods provided by the present disclosure.
  • the image on the left side is an optical image and the image on the right side shows an image of the digitized surface profile.
  • FIG. 5 shows a 10 inch x 10 inch surface having a woodgrain texture prepared using methods provided by the present disclosure.
  • any numerical range recited herein is intended to include all sub-ranges subsumed therein.
  • a range of “1 to 10” is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
  • Methods provided by the present disclosure comprise forming a part having a desired surface quality or feature using ambient reactive extrusion additive manufacturing (ARE- AM).
  • Parts having textured surfaces can be fabricated by depositing an ambient coreactive composition onto a substrate having a desired surface quality or features.
  • ARE- AM ambient reactive extrusion additive manufacturing
  • a textured surface refers to a surface having a surface topography.
  • the surface topography can be quantified by surface roughness S a .
  • Surface roughness can be measured, for example, using a Keyence VR 3200 Macroscope, or other suitable profilometer.
  • a surface roughness of a textured surface can range, for example, from 2 pm to 200 pm, such as from 2 pm to 150 pm, from 2 pm to 100 pm, from 2 pm to 50 pm, from 50 pm to 100 pm, from 50 pm to 150 pm, or from 50 pm to 200 pm.
  • a surface roughness of a textured surface can range, for example, greater than 2 pm and less than 200 pm, less than 150 pm, less than 100 m, or less than 50 pm.
  • a surface roughness of a textured surface can range, for example, greater than 2 pm, greater than 10 pm, greater than 20 pm, greater than 50 pm, greater than 100 pm, greater than 150 pm, or greater than 200 pm.
  • a smooth textured surface can have a surface roughness with an S a less than 2 pm.
  • a textured template can be positioned onto a print bed.
  • a coreactive composition can then be deposited onto the textured template using ambient reactive extrusion additive manufacturing. After the coreactive composition is deposited onto the textured template, the coreactive composition can be allowed to partially or fully cure. The textured template can then be separated from the partially or fully cured composition to provide a part having a textured surface.
  • Ambient coreactive extrusion refers to an additive manufacturing process in which a first component comprising a first compound and a second component comprising a second compound, where the first and second compounds are coreactive, are combined and mixed in a mixer to form a coreactive composition.
  • the coreactive composition can then be extruded through one or more nozzles and deposited onto a build surface using additive manufacturing to build a two-dimensional or three-dimensional part.
  • the build surface can be a textured template.
  • the coreactive composition can be extruded at a temperature less than 30 °C, such as at a temperature less than 25 °C.
  • the first and second compounds comprise coreactive functional groups.
  • each of the first compound and the second compound can independently comprise two or more coreactive functional groups.
  • a first component can comprise a first compound having a first functional group such as two or more first functional groups and the second component can comprise a second compound having a second functional group such as two or more second functional groups where the first functional group is reactive with the second functional group.
  • the coreactive functional groups can be selected to react to form a cured thermoset at a temperature, for example, less than 50 °C, less than 40 °C, less than 30 °C, less than 25 °C, or less than 20 °C.
  • a coreactive composition can cure at room temperature, where room temperature refers to a temperature from 20 °C to 25 °C, from 20 °C to 22 °C, or about 20 °C. [0026] A coreactive composition can thermally cure at temperatures less than 30 °C, and the cure rate can be accelerating by heating the coreactive composition to temperatures greater than 30 °C and/or by including catalysts.
  • Coreactive compositions are thermosetting compositions and when cured form thermosets.
  • the first and second compounds can be reactive in the absence of a catalyst or a cure initiator.
  • the first and second compounds can be reactive in the presence of a catalyst capable of catalyzing the reaction between the first and second compounds.
  • the first and second compounds can be reactive upon activation of a cure initiator.
  • a coreactive composition can include coreactive compounds capable of reacting by a free radical photopolymerization mechanism and the coreactive composition can cure when a photoinitiator is activated upon exposure to actinic radiation.
  • a coreactive composition can cure upon exposure to actinic radiation such as by exposure to ultraviolet light. Certain coreactive composition cannot cure by exposure to actinic radiation such as by exposure to ultraviolet light.
  • a coreactive composition can have any suitable curing chemistry.
  • curing chemistries include isocyanate/hydroxyl, isocyanate/amine, thiol/thiol, thiol/epoxy, thiol/isocyanate, thiol/Michael acceptor, thiol/ene. thiol/yne thiol/alkenyl ether, Michael acceptor/Michael donor, epoxy/amine, acetoacetate/amine, amine/Michael acceptor, and multicure chemistries.
  • Examples of useful fast curing chemistries include hydroxyl/isocyanate, amine/isocyanate, epoxy/epoxy, and Michael acceptor/Michael acceptor reactions.
  • a first functional group can comprise an epoxy group and a second functional group can comprise an epoxy group.
  • a first functional group can comprise a Michael acceptor group and a second functional group can comprise a Michael acceptor group.
  • a first functional group can be a saturated functional group and the second functional group can be an unsaturated group.
  • Each of the first functional group and the second functional can comprise a saturated functional group.
  • Each of the first functional group and the second functional can comprise an unsaturated functional group.
  • a saturated functional group refers to a functional group not having a reactive double bond. Examples of saturated functional groups include thiol, hydroxyl, primary amine, secondary amine, and epoxy groups.
  • An unsaturated functional group refers to a group having a reactive double bond.
  • unsaturated functional groups include alkenyl groups, Michael acceptor groups, isocyanate groups, acyclic carbonate groups, acetoacetate groups, carboxylic acid groups, vinyl ether groups, (meth) acrylate groups, and malonate groups.
  • a first functional group can be a carboxylic acid group and a second functional group can be an epoxy group.
  • a first functional group can be a Michael acceptor group such as a (meth) acrylate group, a maleic group, or a fumaric group
  • a second functional group can be a primary amine group or a secondary amine group.
  • a first functional group can be an isocyanate group and a second functional group can be a primary amine group, a secondary amine group, a hydroxyl group, or a thiol group.
  • a first functional group can be a cyclic carbonate group, an acetoacetate group, or an epoxy group; and a second functional group can be a primary amine group, or a secondary amine group.
  • a first functional group can be a thiol group
  • a second functional group can be an alkenyl group, a vinyl ether group, or a (meth) acrylate group.
  • a first functional group can be a Michael acceptor group such as (meth) acrylate group, a cyanoacrylate, a vinylether a vinylpyridine, or an a,P-unsaturated carbonyl group and a second functional group can be a malonate group, an acetylacetonate, a nitroalkane, or other active alkenyl group.
  • Michael acceptor group such as (meth) acrylate group, a cyanoacrylate, a vinylether a vinylpyridine, or an a,P-unsaturated carbonyl group
  • a second functional group can be a malonate group, an acetylacetonate, a nitroalkane, or other active alkenyl group.
  • a first functional group can be a thiol group
  • the second functional group can be an alkenyl group, an epoxy group, an isocyanate group, an alkynyl group, or a Michael acceptor group.
  • a first functional group can be a Michael donor group
  • the second functional group can be a Michael acceptor group
  • Both a first functional group and a second functional group can be thiol groups.
  • Both a first functional group and a second functional group can be alkenyl groups.
  • Both a first functional group and a second functional group can be Michael acceptor groups such as (meth)acrylate groups.
  • a first functional group can be an amine and a second functional group can be selected from an epoxy group, an isocyanate group, an acrylonitrile, a carboxylic acid including esters and anhydrides, an aldehyde, or a ketone.
  • Suitable coreactive functional groups are described, for example, in Noomen, Proceedings of the Xlllth International Conference in Organic Coatings Science and Technology, Athens, 1987, page 251; and in Tillet et al., Progress in Polymer Science, 36 (2011), 191-217.
  • Functional groups can be selected to coreact, for example, at temperatures less than 60 °C, less than 50 °C, less than 40 °C, less than 30 °C, or less than 20 °C.
  • Functional groups can be selected to coreact, for example, at temperatures greater than 20 °C, greater than 30 °C, greater than 40 °C, or greater than 50 °C.
  • Functional groups can be selected to coreact, for example, at temperatures from 20 °C to 25 °C, from 20 °C to 30 °C, from 20 °C, to 40 °C, or from 20 °C to 50 °C.
  • the cure rate for any of these coreactive chemistries can be modified by including an appropriate catalyst or combination of catalysts in a coreactive composition.
  • the first and second compounds can independently be selected from prepolymers, monomers, and combinations thereof.
  • a coreactive composition can comprise a prepolymer or combination of prepolymers.
  • Prepolymers can determine properties of the cured composition such as, for example, the tensile strength, %elongation, impact strength, thermal resistance, hydrolytic stability, and chemical resistance of the cured polymer.
  • a prepolymer can include any suitable backbone suitable for an intended use.
  • a prepolymer can have a number average molecular weight, for example, less than 10,000 Da, less than 8,000 Da, less than 6,000 Da, less than 4,000 Da, less than 2,000 Da, or less than 1,000 Da.
  • a prepolymer can have a number average molecular weight, for example, greater than 1,000 Da, greater than 2,000 Da, greater than 4,000 Da, greater than 6,000 Da, or greater than 8,000 Da.
  • a prepolymer can have a number average molecular weight, for example, from 1,000 Da to 10,000 Da, from 2,000 Da to 10,000 Da, from 3,000 Da to 9,000 Da, from 4,000 Da to 8,000 Da, or from 5,000 Da to 7,000 Da.
  • a prepolymer can be liquid at 25 °C and can have a glass transition temperature T g , for example, less than -20 °C, less than -30 °C, or less than -40 °C, where the glass transition temperature T g is determined by Dynamic Mass Analysis (DMA) using a TA Instruments Q800 apparatus with a frequency of 1 Hz, an amplitude of 20 microns, and a temperature ramp of -80 °C to 25 °C, with the T g identified as the peak of the tan 6 curve.
  • DMA Dynamic Mass Analysis
  • a prepolymer can exhibit a viscosity, for example, within a range from 20 poise to 500 poise (2 Pa-sec to 50 Pa-sec), from 20 poise to 200 poise (2 Pa-sec to 20 Pa-sec) or from 40 poise to 120 poise (4 Pa-sec to 12 Pa-sec), measured using a Brookfield CAP 2000 viscometer, with a No. 6 spindle, at speed of 300 rpm, and a temperature of 25 °C.
  • a prepolymer can have a reactive functionality, for example, less than 12, less than 10, less than 8, less than 6, or less than 4.
  • a prepolymer can have a reactive functionality, for example, from 2 to 12, from 2 to 8, from 2 to 6, from 2 to 4, or from 2 to 3.
  • a prepolymer can have a reactive functionality, for example, of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.
  • a prepolymer can comprises any suitable backbone.
  • a prepolymer backbone can be selected, for example, based on the end use requirements of a vehicle part.
  • a prepolymer backbone can be selected based considerations of tensile strength, %elongation, thermal resistance, chemical resistance, low temperature flexibility, hardness, and a combination of any of the foregoing.
  • the selection of a prepolymer for use in a particular prepolymer can also be based on cost considerations.
  • Prepolymers can include copolymers such as alternating copolymers, random copolymers, and/or block copolymers.
  • prepolymers can comprise segments that impart desired properties to a prepolymer backbone such as flexibility.
  • a prepolymer can comprise segments having different chemical structure and properties within the prepolymer backbone.
  • the segments can be distributed randomly, in a regular distribution, or in blocks.
  • the segments can be used to impart certain properties to the prepolymer backbone.
  • the segments can comprise flexible linkages such as thioether linkages into the polymer backbone.
  • Segments having pendent groups can be incorporated into the prepolymer backbone to disrupt the symmetry of the prepolymer backbone.
  • the segments can be introduced via the reactants used to prepare a sulfur- containing prepolymer and/or the lower molecular weight sulfur-containing prepolymers can be reacted with compounds containing the segments.
  • a prepolymer can comprise a prepolymer backbone that can be terminated in suitable functional groups as appropriate for a particular curing chemistry.
  • a prepolymer can have any suitable backbone as appropriate for desired cured properties.
  • a prepolymer backbone can comprise, for example, a polythioether, a polysulfide, a polyformal, a polyisocyanate, a polyurea, polycarbonate, polyphenylene sulfide, polyethylene oxide, polystyrene, acrylonitrile-butadiene-styrene, polycarbonate, styrene acrylonitrile, poly(methyl methacrylate), polyvinylchloride, polybutadiene, polybutylene terephthalate, poly(p-phenylene oxide), polysulfone, poly ethersulf one, polyethyleneimine, polyphenylsulfone, acrylonitrile styrene acrylate, polyethylene, syndiotactic or isotactic polypropylene, polylactic acid, polyamide, ethylene-vinyl acetate homopolymer or copolymer, polyurethane, copolymers of
  • Examples of other suitable prepolymer backbones include polyolefins (such as polyethylene, linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene, polypropylene, and olefin copolymers), styrene/butadiene rubbers (SBR), styrene/ethylene/butadiene/styrene copolymers (SEBS), butyl rubbers, ethylene/propylene copolymers (EPR), ethylene/propylene/diene monomer copolymers (EPDM), polystyrene (including high impact polystyrene), poly (vinyl acetates), ethylene/vinyl acetate copolymers (EVA), poly(vinyl alcohols), ethylene/vinyl alcohol copolymers (EVOH), poly(vinyl butyral), poly(methyl methacrylate) and other acrylate polymers and copolymers (including such as methyl methacrylate) and
  • a prepolymer having an elastomeric backbone can also be used.
  • suitable prepolymers having n elastomeric backbone include polyethers, polybutadienes, fluoroelastomers, perfluoroelastomers, ethylene/acrylic copolymers, ethylene propylene diene terpolymers, nitriles, poly thiolamines, poly siloxanes, and combinations of any of the foregoing.
  • An elastomeric prepolymer can comprise any suitable elastomeric prepolymer.
  • suitable prepolymers having an elastomeric backbone include polyethers, poly butadienes, fluoroelastomers, perfluoroelastomers, ethylene/acrylic copolymers, ethylene propylene diene terpolymers, nitriles, polythiolamines, poly siloxanes, chlorosulfonated polyethylene rubbers, isoprenes, neoprenes, polysulfides, polythioethers, silicones, styrene butadienes, and combinations of any of the foregoing.
  • the elastomeric prepolymer can comprise a polysiloxane, such as, for example, a polymethylhydrosiloxane, polydimethylsiloxane, polyethylhydrosiloxane, polydiethylsiloxane, or a combination of any of the foregoing.
  • the elastomeric prepolymer can comprise terminal functional groups that have a low reactivity with amine and isocyanate groups such as silanol groups.
  • the elastomeric prepolymer can comprise, for example, a polydimethylsiloxane prepolymer, such as a silanol-terminal polysiloxane prepolymer, such as a silanol-terminated polydimethylsiloxane prepolymer.
  • a polydimethylsiloxane prepolymer such as a silanol-terminal polysiloxane prepolymer, such as a silanol-terminated polydimethylsiloxane prepolymer.
  • prepolymers having a chemically resistant backbone include polytetrafluorethylene, polyvinylidene difluoride, polyethylenetetrafluoroethylene, fluorinated ethylene propylene, perfluoroalkoxy, ethylene chlorotrifluorethylene, polychlorotrifluoroethylene, fluorinated ethylene propylene polymers polyamide, polyethylene, polypropylene, ethylene-propylene, fluorinated ethylene-propylene, polysulfone, polyarylether sulfone, polyether sulfone, polyimide, polyethylene terephthalate, polyetherketone, polyetherether ketone, polyetherimide, polyphenylene sulfide, polyarylsulfone, polybenzimidazole, polyamideimide, liquid crystal polymers, and combinations of any of the foregoing.
  • prepolymers having a sulfur- containing backbone can be used.
  • the chemical resistance can be with respect to cleaning solvents, fuels, hydraulic fluids, lubricants, oils, and/or salt spray.
  • Chemical resistance refers to the ability of a part to maintain acceptable physical and mechanical properties following exposure to atmospheric conditions such as moisture and temperature and following exposure to chemicals such as cleaning solvents, fuels, hydraulic fluid, lubricants, and/or oils.
  • a chemically resistant part has exhibits a % swell less than 25%, less than 20%, less than 15%, or less than 10%, following immersion in a chemical for 7 days at 70°C, where % swell is determined according to EN ISO 10563.
  • prepolymers having a sulfur-containing backbone include poly thioethers, polysulfides, sulfur-containing polyformals, monosulfides, or a combination of any of the foregoing.
  • Prepolymer backbones that exhibit chemical resistance can have a high sulfur content.
  • a sulfur-containing prepolymer backbone can have a sulfur content greater than 10 wt%, greater than 12 wt%, greater than 15 wt%, greater than 18 wt%, greater than 20 wt%, or greater than 25 wt%, where wt% is based on the total weight of the prepolymer backbone.
  • a chemically resistant prepolymer backbone can have a sulfur content, for example, from 10 wt % to 25 wt %, from 12 wt % to 23 wt %, from 13 wt % to 20 wt %, or from 14 wt % to 18 wt %, where wt% is based on the total weight of the prepolymer backbone.
  • a coreactive composition can comprise a monomer or a combination of monomers.
  • a monomer can comprise functional groups reactive with a prepolymer and/or another monomer.
  • a monomer can have a molecular weight, for example, less than 1,000 Da, less than 800 Da less than 600 Da, less than 500 Da, less than 400 Da, or less than 300 Da.
  • a monomer can have a molecular weight, for example, from 100 Da to 1,000 Da, from 100 Da to 800 Da, from 100 Da to 600 Da, from 150 Da, to 550 Da, or from 200 Da to 500 Da.
  • a monomer can have a molecular weight greater than 100 Da, greater than 200 Da, greater than 300 Da, greater than 400 Da, greater than 500 Da, greater than 600 Da, or greater than 800 Da.
  • a monomer can have a reactive functionality of two or more, for example, from 2 to 6, from 2 to 5, or from 2 to 4.
  • a monomer can have a functionality of 2, 3, 4, 5, or 6.
  • a monomer can have an average reactive functionality, for example, from 2 to 6, from 2 to 5, from 2 to 4, from 2 to 3, from 2.1 to 2.8, or from 2.2 to 2.6.
  • a monomer can comprise any suitable functional group such as, for example, a thiol, alkenyl, alkynyl, epoxy, isocyanate, Michael acceptor, Michael donor, hydroxyl, amine, silanol, polyalkoxysilyl, or other suitable reactive functional group.
  • a suitable functional group such as, for example, a thiol, alkenyl, alkynyl, epoxy, isocyanate, Michael acceptor, Michael donor, hydroxyl, amine, silanol, polyalkoxysilyl, or other suitable reactive functional group.
  • a monomer can comprise, for example, a polythiol, a polyalkenyl, a polyalkynyl, a poly epoxide, a polyfunctional Michael acceptor, a polyfunctional Michael donor, a polyisocyanate, a polyol, a polyamine, a polyfunctional silanol, a polyfunctional polyalkoxysilyl, or a combination of any of the foregoing.
  • a monomer can comprise a polyfunctionalizing agent or a combination of poly functionalizing agents.
  • Polyfunctionalizing agents can have a functionality of three or more functional groups that can be included in a composition to increase the cross-linking density of a cured polymer matrix.
  • a polyfunctionalizing agent can comprise functional groups reactive with prepolymers and/or monomers.
  • a polyfunctionalizing agent can comprise an average functionality, for example, from 3 to 6, such as from 3 to 5, or from 3 to 4.
  • a polyfunctionalizing agent can have a functionality of 3, 4, 5, 6, or a combination of any of the foregoing.
  • a polyfunctionalizing agent can comprise, for example, a polythiol, a polyalkenyl, a polyalkynyl, a polyepoxide, a polyfunctional Michael acceptor, a polyfunctional Michael donor, a polyisocyanate, a polyol, a polyamine, a polyfunctional silanol, a polyfunctional polyalkoxysilyl, or a combination of any of the foregoing.
  • a coreactive composition can comprise one or more additives such as, for example, catalysts, polymerization initiators, adhesion promoters, reactive diluents, plasticizers, filler, colorants, photochromic agents, rheology modifiers, cure activators and accelerators, corrosion inhibitors, fire retardants, UV stabilizers, thermal stabilizers, rain erosion inhibitors, or a combination of any of the foregoing.
  • additives such as, for example, catalysts, polymerization initiators, adhesion promoters, reactive diluents, plasticizers, filler, colorants, photochromic agents, rheology modifiers, cure activators and accelerators, corrosion inhibitors, fire retardants, UV stabilizers, thermal stabilizers, rain erosion inhibitors, or a combination of any of the foregoing.
  • a coreactive composition can have a viscosity, for example, from 200 cP to 500,000,000 cP, from 200 cP to 250,000,000 cP, from 200 cP to 100,000,000 cP, from 200 cP to 50,000,000 cP, or from 200 cP to 10,000,000 cP measured using an Anton Paar MCR 302 rheometer with a 25 mm-diameter parallel plate spindle, an oscillation frequency of 1 Hz and amplitude of 0.3%, and with a rheometer plate temperature of 25 °C.
  • a coreactive composition can have an as-extruded viscosity, for example, greater than 200 cP, greater than 1,000 cP, greater than 10,000 cP, greater than 100,000 cP, greater than 1,000,000 cP, greater than 10,000,000 cP, or greater than 100,000,000 cP, measured using an Anton Paar MCR 302 rheometer with a 25 mm-diameter parallel plate spindle, an oscillation frequency of 1 Hz and amplitude of 0.3%, and with a rheometer plate temperature of 25 °C.
  • a coreactive composition can have an as- extruded viscosity, for example, less than 500,000,000 less than 250,000,000 cP, less than 100,000,000 cP, less than 10,000,000 cP, less than 1,000,000 cP, less than 100,000 cP, less than 10,000 cP, or less than 1,000 cP, measured using an Anton Paar MCR 302 rheometer with a 25 mm-diameter parallel plate spindle, an oscillation frequency of 1 Hz and amplitude of 0.3%, and with a rheometer plate temperature of 25 °C.
  • a suitable viscosity can be determined, for example, by the topography of the textured template, the cure profile of the coreactive composition, the print speed of the extruder, and/or the extruder pressure.
  • Initial viscosity refers to the viscosity of the coreactive composition at the time the coreactive composition is deposited on the surface template.
  • a coreactive composition can have an initial viscosity and an as-deposited a gel time sufficient to allow the deposited coreactive composition to conform to the surface of a textured template.
  • coreactive compositions having a low viscosity can rapidly conform to the surface of a textured template and can have a fast or slow gel time.
  • a coreactive composition having a higher viscosity will take a longer time to conform to the surface of the textured template and longer gel times can be more appropriate.
  • a suitable coreactive composition for a particular application can depend on the surface topography of the textured template.
  • a coreactive composition can have a fast gel time, for example, less than 5 minutes, less than 4 minutes, less than 3 minutes, less than 2 minutes, less than 1 minute, less than 45 seconds, less than 30 seconds, less than 15 seconds, or less than 5 seconds.
  • a coreactive composition can have a fast gel time, for example, from 0.1 seconds to 5 minutes, from 0.2 seconds to 3 minutes, from 0.5 seconds to 2 minutes, from 1 second to 1 minute, or from 2 seconds to 40 seconds.
  • Gel time refers to the time following mixing of the coreactive components to when the coreactive composition is no longer stirrable by hand.
  • a coreactive composition can have an intermediate gel time, for example, form 5 minutes to 60 minutes, such as from 10 minutes to 40 minutes, or from 20 minutes to 30 minutes.
  • a coreactive composition can have a long gel time, for example, of greater than 60 minutes, greater than 2 hours, greater than 4 hours, greater than 6 hours, or greater than 12 hours.
  • a coreactive composition can have a tack free time, for example, of less than 2 minutes, less than 4 minutes, less than 6 minutes, less than 8 minutes, less than 10 minutes, less than 20 minutes, or less than 30 minutes.
  • a coreactive composition can have a time to a hardness of Shore 10A, for example, of less than 2 minutes, less than 4 minutes, less than 6 minutes, less than 8 minutes, less than 10 minutes, less than 20 minutes, less than 30 minutes, less than 1 hour, less than 5 hours, or less than 10 hours.
  • a coreactive composition can have a time to a hardness of Shore 10A, for example, of greater than 2 minutes, greater than 30 minutes, greater than 1 hour, or greater than 5 hours.
  • a coreactive composition can have a time to a hardness of Shore 10A, for example, of from 2 minutes to 10 hours, from 5 minutes to 5 hours, or from 30 minutes to 3 hours.
  • the properties of a coreactive composition can be selected such that a deposited coreactive composition maintains an intended shape when deposited.
  • a coreactive composition can having a high viscosity and/or a slow cure rate and maintain an intended deposited shape, and a low viscosity coreactive composition can have a fast cure rate and/or fast gel time and maintain an intended deposited shape.
  • a coreactive composition can have a time to full cure, for example, of less than 10 seconds, less than 1 minute, less than 10 minutes, less than 1 hour, less than 6 hours, less than 12 hours, less than 1 day, or less than 7 days.
  • a coreactive composition can have a time to full cure, for example, of less than 7 days, less than 1 day, less than 12 hours, less than 6 hours, less than 1 hour, less than 10 minutes, or less than 1 minute.
  • the time to full cure refers to the duration from when the coreactive composition is first prepared to the time when the hardness is within 10% of the maximum hardness of the cured coreactive composition.
  • the time to cure can depend on the temperature of the coreactive composition during mixing, during extrusion, and following deposition onto a textured template.
  • a coreactive composition can be substantially free of solvent.
  • a coreactive composition can comprise less than 5 wt% solvent, less than 2 wt%, less than 1 wt%, or less than 0.1 wt% solvent, where wt% is based on the total weight of the coreactive composition.
  • a coreactive composition can be deposited onto a textured template using ambient reactive extrusion.
  • a template can comprise a surface having a quality and/or features that are intended to be transferred to a finished part using the methods provided by the present disclosure.
  • a textured template includes surfaces having a surface topography such as surfaces having a surface roughness S a greater than 2 pm.
  • a smooth-textured template refers to a textured template having a surface roughness Sa less than 2 pm.
  • Surface quality includes attributes such as smoothness, roughness, and can include surface attributes such as optical reflection and/or absorption, tactile properties, and large surface areas.Surface features include features that are functional and features that are aesthetic.
  • Examples of functional features include features such as rivulets or dimples to enhance aerodynamics, ridges for gripping, and features to enhance or diminish optical reflection.
  • Examples of aesthetic surface features include wood grain textures, leather textures, matte surfaces, regular patterns, irregular patterns, synthetic textures and patterns, and natural textures and patterns.
  • a textured surface can have a pattern of substantially the same height, a pattern having more than one height, or a pattern having an irregular height.
  • the height of a surface feature refers to the height above a nominal surface plane.
  • a smooth surface refers to a surface having a surface roughness S a of less than 2 pm, such as less than 1 pm, less than 0.5 pm or less than 0.1 pm.
  • a textured surface can have a surface roughness, for example, greater than 2 pm, greater than 5 pm, greater than 10 pm, greater than 20 pm, greater than 40 pm, greater than 60 pm, greater than 80 pm, or greater than 100 pm.
  • a textured template can be made of any suitable material that can maintain structural integrity at temperatures of the curing temperature of the coreactive composition.
  • the textured template can comprise a material capable of maintaining structural integrity at a temperature, for example, of greater than 20 °C, greater than 30 °C, greater than 40 °C, or greater than 50 °C.
  • curing of the deposited coreactive composition can be accelerated by exposing the deposited coreactive composition as well as the textured template to an elevated temperature such as a temperature greater than 40 °C, greater than 50 °C, greater than 60 °C, or greater than 70 °C for a period of time.
  • a textured template can be selected to maintain structural integrity at a temperature at which the deposited coreactive composition at least partially cures and can retain the surface texture when the textured template is removed from the surface of the at least partially cured coreactive composition.
  • a coreactive composition can partially cure and the viscosity increase such that the coreactive composition retains the intended surface features.
  • the textured template can be removed from the at least partially cured coreactive composition, and the at least partially cured coreactive composition can then be fully cured.
  • Suitable textured template materials include metals, metal alloys, thermoplastics, thermosets, papers, leathers, wood, ceramics, glass, composites, laminates, stone, and foam
  • a textured template can be a textured casting paper and release paper.
  • suitable textured release paper are available from Sappi and Surteco GmbH.
  • a textured template can be in the form of a substantially flat sheet having a textured surface.
  • a textured template can be in the form of a sheet having a topography and a textured surface.
  • the long-range topography of the sheet can be wavy, corrugated, or patterned.
  • the sheet topography can be on a larger dimension than the dimensions of the surface texture.
  • the sheet topography can have dimensions that are greater than 10 times, greater than 100 times, greater than 1,000 times, or greater than 10,000 times the dimensions of the surface texture.
  • a textured template can have a three dimensional shape.
  • a textured template can have a single surface texture or can have multiple surface textures. For example, some portions of a textured template can be smooth and other portions can have a texture or pattern.
  • a textured template can have a variety of surface textures and/or patterns across the surface of the template.
  • a textured template can comprise a rigid material or a flexible material.
  • a textured template can comprise a flexible or bendable material.
  • a sheet comprising a flexible template and one or more overlying layers of an at least partially cured coreactive composition can be formed into a desired shape.
  • the flexible template can be removed.
  • An example of a flexible textured template is textured release paper.
  • a partially cured coreactive composition can be removed from a textured template, and the partially cured, flexible coreactive composition can be formed into a desired shape, and subsequently cured to form a completed part.
  • a textured template can be at a temperature, for example, from 20 °C to 30 °C.
  • a textured template can have a temperature, for example, greater than 30 °C, greater than 40 °C, greater than 50 °C, greater than 60 °C, or greater than 70 °C.
  • a heated textured template can accelerate the cure of a thermally cured coreactive composition or at least the portion of the coreactive composition that is proximate to the heated textured template.
  • a textured template can be unheated at the time a coreactive composition is deposited onto the textured surface of the textured template and then heated after the coreactive composition is deposited.
  • a low viscosity coreactive composition can be initially allowed to flow and conform to the textured surface and subsequent heating can accelerate the cure of the coreactive composition.
  • a textured template can be heated at the time a coreactive composition is deposited onto the textured surface and then cooled after the coreactive composition is deposited.
  • a heated textured template can facilitate the ability of a higher viscosity coreactive composition to flow and conform to the textured surface and subsequently cooled to allow the coreactive composition to cure.
  • a textured template can comprise a release layer.
  • the release layer can be bonded to the surface of the textured template or can comprise a film or coating of a release material applied to the surface of the textured template before depositing a coreactive composition onto the textured surface.
  • a release layer can facilitate the ability of an at least partially cured coreactive composition to release from the textured template.
  • a textured template can comprise a release layer bonded to the surface.
  • a release layer can comprise, for example, a fluoropolymer or as silicone based polymer.
  • a release coating can comprise a silicone-based release coating, a fluorocarbon- based release coating, or a combination thereof.
  • a release coating may be dissolvable in a solvent, such as in water.
  • a layer of dissolvable release coating can be applied to the surface of the textured template, and, upon application of a solvent, such as water, the release layer can dissolve nearly completely or entirely, leaving only the textured coreactive layer. In this case, the resulting textured coreactive composition may be nearlyee, or completely free from the dissolvable release layer.
  • a silicone-based release coating can comprise, for example, (tris(n- methylamino)methylsilane, silanol-terminated polydimethyl siloxane, or a combination thereof.
  • Suitable fluorocarbon-based release coatings can comprise, for example, a fluoropolymer selected from, but are not limited to, polytetrafluoroethylene (PTFE), poly vinylidene fluoride (PVDF), polyvinylfluoride (PVF), fluorinated ethylene-propylene (FEP), poly chlorotrifluoroethylene, (PCTFE), perfluoroalkoxy polymer (PF A), polyethylenetetrafluoroethylene (ETFE), polyethylene-chlorotrifluoro- ethylene (ECTFE), perfluoropoly ether (PFPE), and a combination of any of the foregoing.
  • PTFE polytetrafluoroethylene
  • PVDF poly vinylidene fluoride
  • PVF polyvinylfluoride
  • FEP fluorinated ethylene-propylene
  • PCTFE poly chlorotrifluoroethylene
  • PF A perfluoroalkoxy polymer
  • ETFE polyethylenetetrafluoro
  • a release coating can have a thickness, for example, from 20 pm to 100 pm, such as from 20 pm to 60 pm.
  • a release coating can have a thickness, for example, less than 100 pm, less than 80 pm, less than 60 pm, or less than 40 pm.
  • a release coating can have a thickness, for example, greater than 20 pm, greater than 40 pm, greater than 60 pm, or greater than 80 pm.
  • a release coating can be applied over the surface of the textured template using any suitable method such as spraying, wiping, brushing, or roller coating.
  • a release coating can be applied to a surface of a textured template using an electrostatic air spray gun or a high-volume low pressure (HVEP) spray gun. Spraying can be done manually or using robotics.
  • HVEP high-volume low pressure
  • Methods provided by the present disclosure include providing a textured template, depositing a coreactive composition onto the textured template, at least partially curing the deposited coreactive composition, and removing the textured template to provide a part comprising the at least partially cured coreactive composition.
  • the textured template can comprise a release layer bonded to the surface, or a release layer can be applied to the textured template before depositing the coreactive composition.
  • a coreactive composition can be applied to the textured template in adjacent beads of material or in any other suitable deposition pattern.
  • Adjacent beads of a coreactive composition can comprise the same coreactive composition or a different coreactive composition.
  • Different coreactive compositions can be deposited such that different lateral portions of a textured part have different properties.
  • some lateral portions of a part can be rigid, and other portions of the part can be flexible or elastic.
  • the coreactive composition can be partially cured or fully cured.
  • the textured template can be removed from the partially or fully cured coreactive composition.
  • the partially cured coreactive composition can be flexible.
  • a partially cured coreactive composition can be flexible and the flexible coreactive composition can be formed into a desired shape and fully cured.
  • the textured template can be removed from the flexible coreactive composition while the coreactive composition is partially cured or fully cured.
  • Applying a coreactive composition over a textured template can comprise apply a single layer of a coreactive composition or two or more layers of a coreactive composition.
  • Each of the two or more layers can comprise the same coreactive composition or at least one of the layers can comprise a different coreactive composition than another layer.
  • Each of the two or more layers can independently comprise a coreactive composition that is the same or different coreactive composition than another layer.
  • the coreactive compositions can be the same or different, for example, in terms of curing chemistries, polymers, monomers, additives, and/or concentrations of constituents.
  • Adjacent coreactive compositions can have the same curing chemistry or can comprise compounds with functional groups that are reactive with functional groups of compounds in the adjacent coreactive composition such that adjacent layers can chemically bond.
  • a cured layer can be rigid, flexible, or can comprise a foam.
  • Each cured layer of a multilayer structure can have a desired property such as hardness, elasticity, chemical resistance, electrical properties, magnetic properties, modulus, durability, density, and/or color.
  • a first deposited coreactive composition can have a low viscosity to facilitate the ability of the deposited coreactive composition to conform to the textured surface.
  • the first deposited coreactive composition can have a fast curing rate to facilitate the ability of the first deposited layer to retain structural integrity during the deposition of subsequent layers.
  • a second or subsequent layer can have a higher viscosity and/or slower cure rate, which provides greater design flexibility and facilitates the ability to use layers optimized to have different properties.
  • a first coreactive composition that cures rapidly at a temperature less than 30 °C can be deposited on the textured template.
  • a second coreactive composition can be deposited over the at least partially cured first coreactive composition.
  • the textured template can be removed from the at least partially cured first coreactive composition and the multilayer part including the first and second coreactive compositions can be exposed to elevated temperature if desired to fully cure the part.
  • a multilayer structure can be fabricated by depositing overlying layers of coreactive compositions.
  • a coreactive composition can be applied to an existing structure that has been formed from either the same, or a different, coreactive material, whereas the surface of the coreactive material may be textured by any of the methods described herein.
  • the textured coreactive composition can be applied in a way that the existing structure is either partially or fully enveloped by the textured coreactive composition.
  • a first coreactive composition may be additively manufactured to form an internal structure of a component, such as the internal structure of an armrest of a vehicle.
  • the internal structure may comprise a foam, or other suitable rigid/ semi-rigid structures.
  • the internal structure may then be partially or fully enveloped by a textured coreactive composition by either applying a previously additively manufactured and textured coreactive layer to the exterior surface of the existing structure, or by printing the coreactive composition directly onto the existing structure and texturing the surface thereafter.
  • a previously additively manufactured and textured coreactive composition can be wrapped either partially, or fully around the internal structure, nearly completely or completely enveloping the structural component, therefore providing a textured surface to the internal structure.
  • the base of the aforementioned internal structure may be formed of a first coreactive composition.
  • a foam portion may be 3D printed on top of the base structure, or an existing foam portion may be added to the base structure.
  • the components may be combined to form a two layer component comprising the internal structure of the armrest.
  • the textured layer may thereafter be applied, fully or partially enveloping the multi-layer existing structure.
  • more layers and additional materials could also be utilized.
  • the existing structure may comprise any number of materials, such as non-coreactive thermosets/thermoplastics, woods, metals, etc., and may be manufactured by other means such as non-three-dimensionally printing (e.g., cast, injection molded, etc.), subtractively manufactured, etc. Therefore, the textured surface comprising coreactive compositions may be added to a wide variety of existing structures, resulting in partially or fully enveloped components with textured surfaces.
  • a multilayer structure can also include multiple coreactive compositions deposited in a single layer.
  • a surface coating can be applied to the textured template before one or more layers of a coreactive composition is applied to the textured template using ambient reactive extrusion.
  • a surface coating can be applied over a release coating on a textured template by spraying or roller/film coating.
  • a surface coating can comprise, for example, a primer coating, a base coat, and/or a topcoat.
  • a surface coating can provide chemical resistance, facilitate cleaning, aesthetics, color, scratch resistance, tactile properties, UV resistance, and/or erosion resistance to the finished part.
  • suitable surfacer coating compositions such as paints
  • the coating composition imparting any number of effects, such as imparting additional texture (e.g., surface roughening/smoo thing effects), color/pigmentation, and/or visual effects such as metallic flake and/or reflective properties to the textured layer.
  • a surface coating can be applied over the release layer, and the coreactive composition can be deposited onto the surface coating.
  • a surface coating can be allowed to dry to evaporate solvents before a coreactive composition is applied.
  • a surface coating can be fully cured or partially cured at the time the coreactive composition is applied.
  • a surface coating can be applied over the release layer by spraying using any suitable method.
  • a surface coating can be applied using an electrostatic air spray gun or a high-volume low pressure (HVLP) spray gun. Spraying can be done manually or using robotics.
  • HVLP high-volume low pressure
  • a surface coating can be applied to provide a coating having an average wet thickness, for example, from 1 mils (25.4 pm) to 5 mils (127 pm), or from 2 mils (50.8 pm) to 4 mils (101.6 pm).
  • a surface coating can be applied to have an average wet thickness, for example, less than 5 mils (127 pm), less than 4 mils (101.6 pm), less than 3 mils (76.2 pm), less than 2 mils (50.8 pm), or less than 1 mil (25.4 pm).
  • a surface coating can be applied to provide a coating having an average wet thickness, for example, greater than 1 mil (25.4 pm), greater than 2 mils (50.8 pm), greater than 3 mils (76.2 pm), or greater than 4 mils (101.6 pm).
  • a surface coating can be applied to a surface to provide a coating having a dry thickness, for example, less than 2 mils (50.8 pm), less than 1 mils (25.4 pm), or less than 0.5 mils (12.7 pm).
  • a partially cured coating refers to an applied coating that has not fully cured.
  • a partially cured coating can have a hardness that is less than 10% of the maximum hardness of a fully cured coating.
  • a partially cured coating can have reactive functional groups capable of chemically reacting with unreacted functional groups in an overlying coreactive composition such that when the surface coating and the overlying coreactive composition are fully cured, the surface coating and the adjacent coreactive composition are chemically bonded.
  • a surface coating can have the same curing chemistry as the coreactive composition such that chemical bonds can form between the compounds in the surface coating and the coreactive composition.
  • a surface coating can include compounds having functional groups that are reactive with functional groups of compounds included in a coreactive composition such that chemical bonds can form between the compounds in the surface coating and compounds in the coreactive composition.
  • an ambient reactive extrusion three-dimensional printing apparatus can comprise an extrusion nozzle; a mixer coupled to the extrusion nozzle; a first primary pump coupled to the mixer and a second primary pump coupled to the mixer; a first primary reservoir coupled to the first primary pump and a second primary reservoir coupled to the second primary pump; and a controller interconnected to the first primary pump and the second primary pump, wherein the controller can be configured to change a volume mix ratio of a first component being pumped by the first primary pump and a second component being pumped by the second primary pump.
  • Each of the first primary pump and the secondary pump can be independently controllable, for example to change the flow rate of a component being pumped into the mixer, to change the extrusion rate of a coreactive composition being extruded from the apparatus, and/or to change the volume mix ratio of the components being combined in the mixer.
  • the controller can change these parameters continuously or discontinuously during deposition of a coreactive composition, or the parameters can be held constant during portions of the deposition process.
  • the extruder can include a section before the mixer, a section after the mixer, and an extrusion nozzle.
  • the extruder can include a shear-thinning device such a helical mixer situated by the mixer and the extrusion nozzle.
  • the extrusion nozzle can be a coextrusion nozzle.
  • the apparatus can include one or more additional primary pumps coupled to the extruder wherein each of the one or more primary pumps can be independently coupled to a respect primary reservoir.
  • the one or more additional pumps can independently be coupled to the extruder before the mixer and/or between mixer and the extrusion nozzle.
  • Each of the primary reservoirs can be couple to purges, which allow the primary reservoirs to be evacuated to remove material from the apparatus before depositing a new coreactive composition.
  • Each of the primary reservoirs can be coupled to one or more secondary reservoirs through respective secondary pumps.
  • Each of the secondary pumps can be independently controllable.
  • the secondary reservoirs can contain different compositions which can be combined in different volume mix ratios to dynamically change the constituents form a component during deposition.
  • the constituents forming a component can be changed continuously, changed discontinuously, or can remain constant at different times while a part is being fabricated.
  • Two or more of the secondary reservoirs can be coupled to a mixer such that the compositions in the secondary reservoirs are combined and mixed before being pumped into the primary reservoir.
  • mixing of the compositions can occur when an unmixed component is combined and mixed with another component in the mixer.
  • An apparatus provided by the present disclosure can be mounted on a gantry that provides for three-dimensional motion of the extrusion nozzle to fabricate a part.
  • An apparatus provided by the present disclosure can further comprise one or more devices for activating a cure initiator such as a source of actinic radiation or heat, or a device that generates a mechanical force such as a shear force.
  • a cure initiator such as a source of actinic radiation or heat
  • a device that generates a mechanical force such as a shear force
  • a nozzle can be fitted with a blade or other suitable device that trails the leading edge of the bead of coreactive composition being deposited, where the blade is configured to press the coreactive composition into the surface of the textured template.
  • a nozzle can be configured to deposit a coreactive composition such that the coreactive composition adjoins previously deposited beads or layers of a coreactive composition and does not create voids, gaps, or pockets between the coreactive composition and the textured template or the between adjacent beads or layers of a coreactive composition.
  • Methods provided by the present disclosure include embossing a texture onto the surface of a partially cured coreactive composition.
  • Embossing methods can include forming a part using ambient reaction extrusion such that at least the surface of the part is partially cured.
  • a textured template can be pressed onto the surface of the partially cured coreactive composition.
  • the textured template can be removed from the surface after the embossing step, or the textured template can remain on the surface of the part until the coreactive composition has fully cured or until the coreactive composition maintains the embossed texture.
  • Methods provided by the present disclosure can be used to fabricate any suitable part.
  • parts include vehicle parts, architectural parts, construction parts, electronic parts, furniture, medical devices, portable devices, telecommunications devices, athletic equipment, consumer products, apparel, recreational parts, and toys.
  • Any suitable vehicle part can be fabricated using the methods provided by the present disclosure.
  • a vehicle part can be a new part or a replacement part.
  • a vehicle is used in its broadest sense and includes all types of aircraft, spacecraft, watercraft, and ground vehicles.
  • a vehicle can include, aerospace vehicles such as airplanes including private aircraft, and small, medium, or large commercial passenger, freight, and military aircraft; helicopters, including private, commercial, and military helicopters; aerospace vehicles including, rockets and other spacecraft.
  • a vehicle can include a ground vehicle such as, for example, trailers, cars, trucks, buses, vans, construction vehicles, golf carts, motorcycles, bicycles, scooters, trains, and railroad cars.
  • a vehicle can also include watercraft such as, for example, ships, boats, and hovercraft.
  • a vehicle part can be, for example, part for a motor vehicle, including automobile, truck, bus, van, motorcycles, scooters, and recreational motor vehicles; railed vehicles including trains and trams; bicycles; aerospace vehicles including airplanes, rockets, spacecraft, jets, and helicopters; military vehicles including jeeps, transports, combat support vehicles, personnel carriers, infantry fighting vehicles, mine-protected vehicles, light armored vehicles, light utility vehicles, and military trucks; and watercraft including ships, boats, and recreational watercraft.
  • a vehicle can be a railed vehicle.
  • Examples of aviation vehicles include F/A-18 jet or related aircraft such as the F/A- 18E Super Hornet and F/A-18F; in the Boeing 787 Dreamliner, 737, 747, 717 passenger jet aircraft, a related aircraft (produced by Boeing Commercial Airplanes); in the V-22 Osprey; VH-92, S-92, and related aircraft (produced by NAVAIR and Sikorsky); in the G650, G600, G550, G500, G450, and related aircraft (produced by Gulfstream); and in the A350, A320, A330, and related aircraft (produced by Airbus).
  • Methods provided by the present disclosure can be used in any suitable commercial, military, or general aviation aircraft such as, for example, those produced by Bombardier Inc.
  • Bombardier Aerospace such as the Canadair Regional Jet (CRJ) and related aircraft; produced by Eockheed Martin such as the F-22 Raptor, the F-35 Lightning, and related aircraft; produced by Northrop Grumman such as the B-2 Spirit and related aircraft; produced by Pilatus Aircraft Ltd.; produced by Eclipse Aviation Corporation; or produced by Eclipse Aerospace (Kestrel Aircraft).
  • CJ Canadair Regional Jet
  • Eockheed Martin such as the F-22 Raptor, the F-35 Lightning, and related aircraft
  • Northrop Grumman such as the B-2 Spirit and related aircraft
  • Pilatus Aircraft Ltd. produced by Eclipse Aviation Corporation
  • Eclipse Aerospace Kerestrel Aircraft
  • a vehicle part can be an interior vehicle part or an exterior vehicle part.
  • a vehicle can comprise a motor vehicle and the motor vehicle part can comprise a hood, door, side panel, bumper, roof, wheel well, dashboard, seat, trunk, handle, floor, chassis, cabin, chassis, cargo bed, steering wheel, fuel tank, engine block, trim, bumper, and/or a battery casing.
  • a vehicle can comprise a railed vehicle and the railed vehicle part can comprise an engine and/or a rail car.
  • a vehicle can comprise an aerospace vehicle and the aerospace part can comprise a cockpit, fuselage, wing, aileron, tail, door, seat, interior panel, fuel tank, interior panel, flooring, and/or frame.
  • a vehicle can comprise a military vehicle and the military vehicle part can comprise a hood, door, side panel, bumper, roof, wheel well, dashboard, seat, trunk, handle, floor, chassis, cabin, chassis, cargo bed, steering wheel, fuel tank, engine block, trim, bumper, a mount, a turret, an undercarriage, and/or a battery casing.
  • a vehicle comprises a watercraft and the watercraft part can comprise a hull, an engine mount, a seat, a handle, a chassis, a battery, a battery mount, a fuel tank, an interior accessory, flooring, and/or paneling.
  • Vehicle parts fabricated using the materials and methods according to the present invention can have properties for the intended purpose.
  • an automotive part can be designed have a light weight.
  • An external part for military vehicle can be designed to have a high impact strength.
  • a part for a commercial aerospace vehicle can be designed to have a light weight and/or to be static dissipative.
  • An external part for a military aircraft can be designed to exhibit RFI/EMI shielding properties.
  • a part such as a windmill, airfoil, aerospace surface, or wind turbine can have an aerodynamic surface.
  • Coreactive three-dimensional printing methods can be adapted to fabricate custom designed vehicle parts, replacement parts, upgraded parts, specialty parts, and/or high- performance parts rapidly and cost-effectively in low volume production.
  • Embodiments provided by the present disclosure are further illustrated by reference to the following examples, which describe methods of forming a texture surface and parts having a textured surface. It will be apparent to those skilled in the art that many modifications, both to materials and methods, may be practiced without departing from the scope of the disclosure.
  • a coreactive composition for ambient coreactive extrusion was prepared by combining and mixing an isocyanate component and an amine component. Each component was prepared by combining the constituent materials in a Max 300 L DAC cup an mixed using a Flacktek Speedmixer®.
  • Example 1 The coreactive polyurea composition described in Example 1 was used to fabricate parts having textured surfaces.
  • a calibrated Viscotec® 2K extruder with the “long nozzle” (MKH-03-16S) mounted on a Lulzbot® Taz 6 three-dimensional printing gantry was used to print the coreactive polyurea composition.
  • the coreactive polyurea composition was printed at a print speed of 3 mL/min at a volume ratio of 1.5:1 (isocyanate component : amine component).
  • Textured templates were flattened and secured onto a print bed before printing.
  • the textured templates were textured release paper available, for example, from Sappi.
  • the printed samples including the release paper and the printed coreactive polyurea composition were exposed to 160 °F (71.1 °C) for 2 days to fully cure the polyurea composition. After the polyurea was fully cured the printed samples were allowed to cool to room temperature before removing the textured release paper.
  • the surface roughness (S a ) was measured using a Keyence VR 3200 Macroscope. Optical and digitized profile images were also obtained.
  • FIGS. 1A- 1D Examples of textured surface obtained using these methods are shown in FIGS. 1A- 1D.
  • the samples have dimensions of the samples is 2.5 in x 2.5 in.
  • leather textures can range from fine grain to heavy grain, with the surface area roughness increasing from FIGS. 1A-1D.
  • FIGS. 2A-2D show surfaces having four different leather textures prepared using the materials and methods described in Examples 1 and 2.
  • the image on the left is an optical image and the image on the right is a digitized profile map of the same surface obtained using a Keyence VR 3200 Macroscope.
  • the surface roughness S a for the leather textures was 13.81 pm, 14.61 pm, 19.91 pm, and 37.19 pm for the leather textures shown in FIGS. 2A-2D, respectively.
  • FIGS. 3A-3C show optical images and topography maps of patterned surfaces prepared using the material and methods described in Examples 1 and 2. The images were obtained using a Keyence VR 3200 Macroscope.
  • FIG. 3A shows a surface with a synthetic texture having an S a of 21.96 pm
  • FIG. 3B shows a surface with a grid texture having an S a of 8.62
  • FIG. 3C shows a surface with a grid texture having an S a of 26.09
  • FIGS. 4A-4B show optical images and topography maps of patterned surfaces prepared using the material and methods described in Examples 1 and 2. The images were obtained using a Keyence VR 3200 Macroscope.
  • FIG. 4A shows a surface with a natural woodgrain having an S a of 14.53 pm
  • FIG. 4B shows a surface with a natural slate texture having an S a of 6.2 pm. Note that in FIG. 4B, the parallel print lines are visible.
  • the constituent materials for the isocyanate component and the amine component are provided in Tables 3 and 4, respectively.
  • FIG. 5 An optical image of the cured polyurea surface having a wood grain texture is shown in FIG. 5.

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Abstract

La fabrication additive par extrusion coréactive ambiante est utilisée pour fabriquer des pièces ayant des surfaces texturées. Une composition thermodurcissable coréactive est extrudée sur un modèle texturé. Une fois que la composition coréactive déposée est partiellement ou complètement durcie, le modèle texturé peut être retiré et la composition coréactive complètement durcie pour former une pièce ayant une surface texturée. Les procédés de l'invention peuvent être utilisés pour préparer des pièces avec une grande variété de textures.
PCT/US2023/060349 2022-01-19 2023-01-10 Fabrication par extrusion coréactive ambiante de surfaces texturées WO2023141373A1 (fr)

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Citations (3)

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WO2020167622A1 (fr) * 2019-02-11 2020-08-20 Ppg Industries Ohio, Inc. Procédés de fabrication de composants d'étanchéité chimiquement résistants
US20210115293A1 (en) * 2018-04-09 2021-04-22 Prc-Desoto International, Inc. Coatings for Textured 3D-Printed Substrates
US20210145116A1 (en) * 2019-11-19 2021-05-20 Nike, Inc. Methods of manufacturing articles having foam particles

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Publication number Priority date Publication date Assignee Title
US20210115293A1 (en) * 2018-04-09 2021-04-22 Prc-Desoto International, Inc. Coatings for Textured 3D-Printed Substrates
WO2020167622A1 (fr) * 2019-02-11 2020-08-20 Ppg Industries Ohio, Inc. Procédés de fabrication de composants d'étanchéité chimiquement résistants
US20210145116A1 (en) * 2019-11-19 2021-05-20 Nike, Inc. Methods of manufacturing articles having foam particles

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Title
NOOMEN: "Proceedings of the XIIIth International Conference", 1987, ORGANIC COATINGS SCIENCE AND TECHNOLOGY, pages: 251
TILLET ET AL., PROGRESS IN POLYMER SCIENCE, vol. 36, 2011, pages 191 - 217

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