WO2017100447A1 - Ajout de plastifiants pour améliorer l'adhérence entre couches dans des processus de fabrication additive - Google Patents

Ajout de plastifiants pour améliorer l'adhérence entre couches dans des processus de fabrication additive Download PDF

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Publication number
WO2017100447A1
WO2017100447A1 PCT/US2016/065615 US2016065615W WO2017100447A1 WO 2017100447 A1 WO2017100447 A1 WO 2017100447A1 US 2016065615 W US2016065615 W US 2016065615W WO 2017100447 A1 WO2017100447 A1 WO 2017100447A1
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Prior art keywords
styrene
polymer
layers
poly
additive
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Inventor
Satish Kumar Gaggar
Malvika BIHARI
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SABIC Global Technologies BV
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SABIC Global Technologies BV
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    • 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
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • 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
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • 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

Definitions

  • Additive manufacturing is a process for the manufacture of three-dimensional objects by formation of multiple fused layers. Interlayer adhesion between two adjacent fused layers is a critical parameter in some applications, because it can affect a variety of properties such as mechanical strength. If a three-dimensional object does not have the desired mechanical strength, it can limit, for example, the load-bearing ability of such objects. Thus, there remains a need in the art for additive manufacturing processes that produce objects with improved interlayer adhesion.
  • One embodiment is a method of making an article, the method comprising forming a plurality of layers of a material in a preset pattern at a build temperature from IS degrees C to 2S0 degrees C, wherein at least one of the formed layers comprises a polymer composition comprising a polymer and an additive that lowers the glass transition temperature (Tg) of the polymer composition by 5 to 100 degrees C; and fusing the plurality of formed layers to provide the article.
  • Tg glass transition temperature
  • Another embodiment is an article, comprising a plurality of layers of a material in a preset pattern of at least twenty fused, melt-extruded layers comprises a polymer composition comprising a polymer and an additive that lowers the glass transition temperature (Tg) of the polymer composition by 5 to 100 degrees C.
  • Tg glass transition temperature
  • At least one layer formed during the additive manufacturing process comprises a polymer composition.
  • This polymer composition comprises a polymer and an additive that lowers the glass transition temperature (Tg) of the polymer composition 5 to 100 degrees C.
  • the layer including the polymer and the Tg-lowering additive increases in volume before or during formation of the next layer.
  • multiple layers of different polymer compositions are extruded in a preset sequence.
  • “multiple layers” is used in reference to the number of layers in a sequence of polymer compositions, whereas “plurality of layers” is used to refer to the total number of layers used to form the printed object.
  • the number of layers in a sequence of polymer compositions is at least two, and can be up to the total number of layers used to form the article.
  • the number of layers in a sequence depends on the particular sequence of polymer compositions selected, based on the desired properties of the printed object.
  • the number of layers per sequence can be 2 to 200, or 2 to 100, or 2 to SO, or 2 to 20, or 2 to 10.
  • the number of layers per sequence includes 2, 3, 4, 5, or 6 layers.
  • layer is a term of convenience that includes any shape, regular or irregular, having at least a predetermined thickness.
  • the size and configuration two dimensions are predetermined, and on some embodiments, the size and shape of all three dimensions of the layer is predetermined.
  • the thickness of each layer can vary widely depending on the additive manufacturing method. In some embodiments the thickness of each layer as formed differs from a previous or subsequent layer. In some embodiments, the thickness of each layer is the same. In some embodiments the thickness of each layer as formed is 0.S millimeters (mm) to S mm.
  • a three dimensional article is manufactured by extruding a plurality of layers in a preset pattern by an additive manufacturing.
  • the material extrusion techniques include techniques such as fused deposition modeling and fused filament fabrication as well as others as described in ASTM F2792-12a. Any additive manufacturing process can be used, provided that the process allows formation of at least two adjacent layers comprising different polymer compositions. In some embodiments, more than two adjacent layers are extruded comprising different polymer compositions.
  • the methods herein can be used for fused deposition modelling (FDM), Big Area Additive Manufacturing (BAAM), ARBURG plastic free forming technology, and other additive manufacturing methods.
  • large format additive manufacturing systems are employed. These systems utilize pellets of polymeric material in hoppers or bins to form parts. A large extruder converts these pellets to a molten form that are then deposited on a table.
  • Large format additive manufacturing system generally comprise a frame or gantry that may include a print head that is moveable in x,y and/or z direction. Alternately, the print head may be stationary and the part is moveable in x, y and/or z axis. The print head has a supply of feed material in the form of pellets or filament and a deposition nozzle.
  • the polymeric material is stored in a hopper (for pellets) or similar storage vessel near the deposition arm or supplied from a filament spool.
  • the apparatus can include a nozzle for extruding a material.
  • the polymeric material from the barrel is extruded through the nozzle and directly deposited on the build.
  • a heat source may be positioned on or in connection with the nozzle to heat the material to a desired temperature and/or flow rate.
  • the bed may be heated or at room temperature.
  • the pellets can have a cross- sectional dimension in the range of 0.1 mm to SO mm, or an aspect ratio of 1 to 10, or combinations thereof.
  • BAAM Big Area Additive Manufacturing
  • One embodiment of the extruder for the BAAM system is designed for extruding thermoplastic pellets at 35 lbs/hour through a nozzle and onto a print bed 157x78x34 inches. Estimated throughput of extruder increased to 50-lOOlbs/hour with expanded capability.
  • the polymer compositions are also suitable for use in droplet-based additive manufacturing systems, e.g., the FreeformerTM system by Arburg.
  • an article in fused material extrusion techniques, can be produced by heating a polymer composition to a flowable state that can be deposited to form a layer.
  • the layer can have a predetermined shape in the x-y axis and a predetermined thickness in the z-axis.
  • the flowable material can be deposited as roads as described above, or through a die to provide a specific profile.
  • the layer cools and solidifies as it is deposited.
  • a subsequent layer of melted polymer composition fuses to the previously deposited layer, and solidifies upon a drop in temperature. Extrusion of multiple subsequent layers builds the desired shape.
  • the total number of layers in the article can vary significantly. Generally but not always, at least 20 layers are present.
  • the maximum number of layers can vary greatly, determined, for example, by considerations such as the size of the article being manufactured, the technique used, the capabilities of the equipment used, and the level of detail desired in the final article. For example, 20 to 100,000 layers can be formed, or 50 to 50,000 layers can be formed.
  • the plurality of layers in the predetermined pattern is fused to provide the article. Any method effective to fuse the plurality of layers during additive manufacturing can be used. In some embodiments, the fusing occurs during formation of each of the layers. In some embodiments the fusing occurs while subsequent layers are formed, or after all layers are formed.
  • the preset pattern can be determined from a three-dimensional digital representation of the desired article as is known in the art and described in further detail below.
  • an article can be formed from a three-dimensional digital representation of the article by depositing the flowable material as one or more roads on a substrate in an x-y plane to form the layer. The position of the dispenser (e.g., a nozzle) relative to the substrate is then incremented along a z-axis (perpendicular to the x-y plane), and the process is then repeated to form an article from the digital representation.
  • the dispensed material is thus also referred to as a "modeling material” as well as a “build material.”
  • an additive manufacturing technique known generally as material extrusion can be used.
  • material extrusion an article can be formed by dispensing a flowable material in a layer-by-layer manner and fusing the layers. "Fusing" as used herein includes the chemical or physical interlocking of the individual layers.
  • the flowable material can be rendered flowable by dissolving or suspending the material in a solvent.
  • the flowable material can be rendered flowable by melting.
  • a flowable prepolymer composition that can be crosslinked or otherwise reacted to form a solid can be used. Fusing can be by removal of the solvent, cooling of the melted material, or reaction of the prepolymer composition.
  • an additive manufacturing technique known generally as material extrusion can be used.
  • material extrusion an article can be formed by dispensing a flowable material in a layer-by-layer manner and fusing the layers. "Fusing" as used herein includes the chemical or physical interlocking of the individual layers.
  • the flowable material can be rendered flowable by dissolving or suspending the material in a solvent.
  • the flowable material can be rendered flowable by melting. In other
  • a flowable prepolymer composition that can be crosslinked or otherwise reacted to form a solid can be used. Fusing can be by removal of the solvent, cooling of the melted material, or reaction of the prepolymer composition.
  • the layers are extruded from two or more nozzles. In some embodiments the layers are extruded such that all of the layers comprising a given polymer composition are extruded from the same nozzle, and any layers comprising a different polymer composition are extruded from a different nozzle. For example, in a pattern of three compositions A, B, and C, one nozzle extrudes only polymer composition A, one nozzle different from the A nozzle extrudes only polymer composition B, and one nozzle different from the A and B nozzles extrudes only polymer composition C.
  • each nozzle extrudes only a given polymer composition (for example, A, B, or C) but there can be multiple nozzles for each composition.
  • different polymer compositions are extruded from the same nozzle. This can facilitate creation of a variety of layers comprising mixtures of polymers with different ratios. This can particularly facilitate extruding layers in which a sequence of layers form a gradient of mixtures of different polymers.
  • the method can produce the product objects faster than methods that use a single nozzle, and can allow increased facility in terms of using different polymers or blends of polymers, different colors, or textures, and the like.
  • a support material as is known in the art can optionally be used to form a support structure.
  • the build material and the support material can be selectively dispensed during manufacture of the article to provide the article and a support structure.
  • the support material can be present in the form of a support structure, for example, a scaffolding, that can be mechanically removed or washed away when the layering process is completed to the desired degree.
  • the build structure and the support structure of the article formed can be extruded using different polymer compositions or different polymer composition sequences. In other embodiments, at least one support structure layer and one adjacent build structure layer are extruded using different polymer compositions or different polymer composition sequences.
  • An exemplary material extrusion additive manufacturing system includes a build chamber and a supply source for the polymer composition.
  • the build chamber includes a build platform, a gantry, and a dispenser for dispensing the polymer composition, for example an extrusion head.
  • the build platform is a platform on which the article is built, and desirably moves along a vertical z-axis based on signals provided from a computer-operated controller.
  • the gantry is a guide rail system that can be configured to move the dispenser in a horizontal x-y plane within the build chamber, for example based on signals provided from a controller.
  • the horizontal x-y plane is a plane defined by an x-axis and a y-axis where the x-axis, the y-axis, and the z-axis are orthogonal to each other.
  • the platform can be configured to move in the horizontal x-y plane and the extrusion head can be configured to move along the z-axis.
  • Other similar arrangements can also be used such that one or both of the platform and extrusion head are moveable relative to each other.
  • the build platform can be isolated or exposed to atmospheric conditions.
  • both the build structure and the support structure of the article formed can include a fused expandable layer.
  • the build structured includes a fused expandable layer and the support material does not include an expandable layer.
  • the build structure does not include an expandable layer and the support structure does include a fused expandable layer.
  • the lower density of the expanded layer can allow for the support material to be easily or more easily broken off than the non-expanded layer, and re-used or discarded.
  • the support structure can be made purposely breakable, to facilitate breakage where desired.
  • the support material can have an inherently lower tensile or impact strength than the build material.
  • the shape of the support structure can be designed to increase the breakability of the support structure relative to the build structure.
  • the build material can be made from a round print nozzle or round extrusion head.
  • a round shape as used herein means any cross-sectional shape that is enclosed by one or more curved lines.
  • a round shape includes circles, ovals, ellipses, and the like, as well as shapes having an irregular cross-sectional shape.
  • Three dimensional articles formed from round shaped layers of build material can possess strong structural strength.
  • the support material for the articles can be made from a non-round print nozzle or non-round extrusion head.
  • a non-round shape means any cross- sectional shape enclosed by at least one straight line, optionally together with one or more curved lines.
  • a non-round shape can include squares, rectangles, ribbons, horseshoes, stars, T head shapes, X shapes, chevrons, and the like. These non-round shapes can render the support material weaker, brittle and with lower strength man round shaped build material.
  • the lower density support materials can be made from a non-round print nozzle or round extrusion head. These non-round shaped lower density support materials can be easily removed from build materials, particularly higher density round shaped build materials.
  • the above material extrusion techniques include techniques such as fused deposition modeling and fused filament fabrication as well as others as described in ASTM F2792-12a.
  • fused material extrusion techniques an article can be produced by heating a thermoplastic material to a flowable state that can be deposited to form a layer.
  • the layer can have a predetermined shape in the x-y axis and a predetermined thickness in the z-axis.
  • the flowable material can be deposited as roads as described above, or through a die to provide a specific profile.
  • the layer cools and solidifies as it is deposited.
  • a subsequent layer of melted thermoplastic material fuses to the previously deposited layer, and solidifies upon a drop in temperature. Extrusion of multiple subsequent layers builds the desired shape.
  • At least one layer of an article is formed by melt deposition, and in other embodiments, more than 10, or more than 20, or more than SO of the layers of an article are formed by melt deposition, up to and including all of the layers of an article being formed by melt deposition.
  • thermoplastic material is supplied in a melted form to the dispenser.
  • the dispenser can be configured as an extrusion head.
  • the extrusion head can deposit the thermoplastic composition as an extruded material strand to build the article.
  • the thermoplastic material can be extruded at a temperature of 200 to 450°C. In some embodiments the thermoplastic material can be extruded at a temperature of 300 to 415°C.
  • the layers can be deposited at a build temperature (the temperature of deposition of the thermoplastic extruded material) that is SO to 200°C lower than the extrusion temperature. For example, the build temperature can be IS to 2S0°C. In some embodiments the thermoplastic material is extruded at a temperature of 200 to 4S0°C, or 300 to 41S°C, and the build temperature is maintained at ambient temperature.
  • Methods are known for pre-incorporating a Tg-lowering additive into a polymer material, then forming the resulting polymer composition into a desired shape.
  • a Tg-lowering additive can be incorporated into a melt of the thermoplastic polymer material then the melt is formed into the desired shape and cooled.
  • the additive can be added directly to the melt used in the additive manufacturing process, or pre-incorporated or blended into the thermoplastic polymer material and the mixture can be melted together during the additive manufacturing process.
  • polymer composition refers to a composition that includes one or more polymers, and includes one or more additives known in the art.
  • a polymer composition can consist of a single polymer and one additive.
  • a polymer composition can be a combination of polymers and one additive.
  • a polymer composition can be two or more polymers and two or more additives.
  • two polymer compositions are "different" if they comprise different polymers, different ratios of the same polymers, different additives, or different levels of the same additives.
  • a polymer composition that is 30 wt.% polystyrene, 70 wt.% poly(phenylene ether) is different from a polymer composition that is 70 wt% polystyrene, 30 wt.% poly(phenylene ether).
  • the amount of the component can vary by at least +1-5%.
  • a polymer composition having 1.00 weight percent (wt.%) of a flame retardant can differ from the identical composition if it contains 0.9S wt.% or less, or 1.0S wt.% or more of the same flame retardant.
  • the amount of a component varies by at least +/-10%, or at least +/-20%.
  • two polymers are "different” if they have a different chemical composition, structure, or other property. This can mean, for example, that the polymers comprise different monomers (e.g. polymethyl methacrylate and polyethylene oxide), or the same monomers arranged in a different orientation or linkage, or copolymers with different ratios of constituent monomers, or have different levels of crosslinking. Polymers can also differ if each as a different regiochemistry or configuration, molecular weight, molecular weight distribution, dispersity index, density, hydrophobicity, or other characteristic that affects a polymer property.
  • monomers e.g. polymethyl methacrylate and polyethylene oxide
  • At least one component can have a level or measurement in one polymer that is at least +1-5% different from the other polymer. In some embodiments, the difference is at least +/-10%, or at least +1-20%.
  • the first and second polymer compositions, and optionally additional polymer compositions are compatible with each other at an interface between them.
  • "compatible with each other at an interface” means that there are sufficiently strong interfacial interactions between the polymer compositions, such as adhesion at the interface, or attractive forces due to physical interactions at the interface. Preferably there is no repulsion and no delamination at the interface.
  • An interface between two polymer compositions preferably has adequate interfacial strength.
  • Interfacial strength (or inter-layer bonding) between adjacent layers of two different polymer compositions can be defined as the force required to peel off or separate the two adjacent layers of two different polymer compositions. Interfacial strength can be measured, for example, by the lap shear test or the peel test.
  • the lap shear test is a qualitative adhesion test method which can be used to predict interlayer adhesion for the printed objects of the disclosure.
  • the polymer composition is molded into flame bars with thickness of 1 mm. Two flame bars of the same or different polymer composition are clamped together and placed in an oven at a temperature 3- 5°C higher than the glass transition temperature of the polymer composition. After cooling the flame bars, the adhesion is characterized as,
  • the different polymers are fully compatible, including blendable or fully miscible, not just at the interface, but also in bulk.
  • blendable or fully miscible not just at the interface, but also in bulk.
  • poly(phenylene ether) and polystyrene are miscible with each other at all concentrations in bulk. And, such compatible or miscible polymers are always compatible at the interface when printed as alternate layers.
  • thermoplastic polymers that can be used include polyacetals (e.g., polyoxyethylene and polyoxymethylene), poly(Ci-6 alkyl)acrylates, polyacrylamides, polyamides, (e.g., aliphatic polyamides, polyphthalamides, and polyaramides), polyamideimides, polyanhydrides, polyarylates, polyarylene ethers (e.g., polyphenylene ethers), polyarylene sulfides (e.g., polyphenylene sulfides), polyarylenesulfone (e.g., polyphenylene sulfones), polybenzothiazoles, polybenzoxazoles, polycarbonates (including polycarbonate copolymers such as polycarbonate-siloxanes, polycarbonate-esters, and polycarbon
  • ABS acrylonitrile butadiene styrene
  • thermoplastic polymers examples include polyacetals, polyacrylates, polyacrylics, polyamideimides, polyamides, polyanhydrides, polyaramides, polyarylates, polyarylene ethers (e.g., polyphenylene ethers), polyarylene sulfides (e.g., polyphenylene sulfides), polyarylsulfones, polycarbonates (including polycarbonate copolymers such as polycarbonate-siloxanes, polycarbonate-esters, and polycarbonate-ester-siloxanes), polyesters (e.g., polyethylene terephthalates and polybutylene terephthalates),
  • polyetheretherketones polyetherimides (including copolymers such as polyetherimide-siloxane copolymers), polyetherketoneketones, polyetherketones, polyethersulfones, polyimides
  • copolymers such as polyimide-siloxane copolymers
  • polyolefins e.g., polyethylenes, polypropylenes, polytetrafluoroethylenes, and their copolymers
  • polyphthalides polysilazanes, polysiloxanes, polystyrenes (including copolymers such as acrylonitrile-butadiene-styrene (ABS) and methyl methacrylate-butadiene-styrene (MBS)), polysulfides, polysulfonamides, polysulfonates, polythioesters, polytriazines, polyureas, polyvinyl alcohols, polyvinyl esters, polyvinyl ethers, polyvinyl halides, polyvinyl ketones, polyvinylidene fluorides, polyvinyl aromatics, polyarylene sulfones, polyaryl ether ketones, poly(phenylene oxide), poly(methyl
  • polycarbonates polyesters, polyetherimides, polyolefins, and polystyrene copolymers such as acrylonitrile butadiene styrene, are especially useful in a wide variety of articles, have good processability, and are recyclable.
  • thermoplastic polymer that can be used in both thermoplastic polymer compositions A and B is a polycarbonate (including homopolymers and copolymers that include carbonate units), elastomer-modified graft copolymer, polyester, polyolefin, polyetherimide, polyetherimide sulfone, polyphenylene sulfide, polysulfone, polyketone, polyphenylene ether, polystyrene, polyacrylate ester, polymethacrylate ester, or a combination comprising at least one of the foregoing.
  • polycarbonate including homopolymers and copolymers that include carbonate units
  • elastomer-modified graft copolymer polyester, polyolefin, polyetherimide, polyetherimide sulfone, polyphenylene sulfide, polysulfone, polyketone, polyphenylene ether, polystyrene, polyacrylate ester, polymethacrylate ester, or
  • Exemplary polycarbonates are described, for example, in WO 2013/175448 Al , US 2014/0295363, and WO 2014/072923.
  • Polycarbonates are generally manufactured from bisphenol compounds such as 2,2-bis(4-hydroxyphenyl) propane (“bisphenol-A” or "BPA"), 3,3-bis(4-hydroxyphenyl) phthalimidine, l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane, or l,l-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane, or a combination comprising at least one of the foregoing bisphenol compounds can also be used.
  • bisphenol compounds such as 2,2-bis(4-hydroxyphenyl) propane (“bisphenol-A” or "BPA"), 3,3-bis(4-hydroxyphenyl) phthalimidine, l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane, or l,l-bis(4-hydroxy
  • the polycarbonate is a homopolymer derived from BPA or a copolymer derived from BPA and another bisphenol or dihydroxy aromatic compound such as resorcinol.
  • Other polycarbonate copolymers include poly(aliphatic ester-carbonate) poly(siloxane-carbonate), and polycarbonate- ester-siloxanes).
  • the polycarbonate is a homopolymer derived from BPA, for example a linear homo-polycarbonate containing bisphenol A carbonate units, such as that available under the trade name LEXAN from the Innovative Plastics division of SABIC.
  • BPA a linear homo-polycarbonate containing bisphenol A carbonate units
  • LEXAN from the Innovative Plastics division of SABIC.
  • a branched, cyanophenol end-capped bisphenol A homo-polycarbonate produced via interfacial polymerization, containing 3 mol% l,l,l-tris(4-hydroxyphenyl)ethane (THPE) branching agent, commercially available under the trade name CFR from the innovative Plastics division of SABIC can be used.
  • the polycarbonate is a copolymer derived from BPA and another bisphenol or dihydroxy aromatic compound such as resorcinol (a "copolycarbonate").
  • a specific copolycarbonate includes bisphenol A and bulky bisphenol carbonate units, i.e., derived from bisphenols containing at least 12 carbon atoms, for example 12 to 60 carbon atoms or 20 to 40 carbon atoms.
  • copolycarbonates examples include copolycarbonates comprising bisphenol A carbonate units and 2-phenyl-3,3'-bis(4-hydroxyphenyl) phthalimidine carbonate units (a BPA-PPPBP copolymer, commercially available under the trade designation XHT from the Innovative Plastics division of SABIC); a copolymer comprising bisphenol A carbonate units and l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane carbonate units (a BPA-DMBPC copolymer) commercially available under the trade designation DMC from the innovative Plastics division of SABIC; and a copolymer comprising bisphenol A carbonate units and isophorone bisphenol carbonate units (available, for example, under the trade name APEC from Bayer.
  • BPA-PPPBP copolymer commercially available under the trade designation XHT from the innovative Plastics division of SABIC
  • a BPA-DMBPC copolymer commercially available under the trade designation DMC from the innovative
  • polycarbonate copolymers include poly(siloxane-carbonate)s, poly(ester- carbonate)s, poly(carbonate-ester-siloxane)s, and poly(aliphatic ester-carbonate)s.
  • Specific poly(carbonate-siloxane)s comprise bisphenol A carbonate units and siloxane units, for example blocks containing S to 200 dimethylsiloxane units, such as those commercially available under the trade name EXL from the innovative Plastics division of SABIC.
  • poly(ester- carbonate)s examples include poly(ester-carbonate)s comprising bisphenol A carbonate units and isophthalate-terephthalate-bisphenol A ester units, also commonly referred to as poly(carbonate- ester)s (PCE) or poly(phthalate-carbonate)s (PPC), depending on the relative ratio of carbonate units and ester units.
  • PCE carbonate- ester
  • PPC poly(phthalate-carbonate)s
  • poly(ester-carbonates include containing bisphenol A carbonate units and isophthalate/terephthalate esters of resorcinol, such as those available under the trade name SLX
  • the innovative Plastics division of SABIC is a poly(ester-carbonate-siloxane) comprising bisphenol A carbonate units, isophthalate-terephthalate-bisphenol A ester units, and siloxane units, for example blocks containing S to 200 dimethylsiloxane units, such as those commercially available under the trade name FST from the innovative Plastics division of SABIC.
  • Poly(aliphatic ester-carbonate)s can be used, such as those comprising bisphenol A carbonate units and sebacic acid-bisphenol A ester units, for example those commercially available under the trade name LEXAN HFD from the Innovative Plastics division of SABIC.
  • copolymers include those formed from styrene-butadiene-styrene (SBS), styrene-butadiene rubber (SBR), styrene-ethylene-butadiene-styrene (SEBS), ABS (acrylonitrile- butadiene-styrene), acrylonitrile-ethylene-propylene-diene-styrene (AES), styrene-isoprene- styrene (SIS), methyl methacrylate-butadiene-styrene (MBS), and styrene-acrylonitrile (SAN).
  • the elastomer-modified graft copolymers include acrylonitrile butadiene styrene (ABS) and blends of ABS with polycarbonates.
  • PC 1 polycarbonate polymer composition
  • PC 1 is a standard linear BPA polycarbonate that has an approximately 7 melt flow and a weight average molecular weight (Mw) of around 29,000.
  • any additive that will lower the glass transition temperature (Tg) of polymer composition by 5 to 100 degrees C can be added to polymer composition.
  • Aromatic phosphates include, phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'- trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, or the like.
  • a specific aromatic phosphate is one in which each G is aromatic, for example, triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, and the like.
  • Di- or polyfunctional aromatic phosphorus-containing compounds are also useful, for example, compounds of the formulas below:
  • Di- or polyfunctional aromatic phosphorus-containing compounds of this type include resorcinol tetraphenyl diphosphate (RDP), the bis (diphenyl) phosphate of hydroquinone, and the bis(diphenyl) phosphate of bisphenol A, respectively, their oligomeric and polymeric counterparts, and the like.
  • organophosphorus compounds may be suitable as a Tg-lowering additive for the compositions of the present invention.
  • Known compounds including
  • monophosphate esters such as, for example, triphenyl phosphate, tricresyl phosphate, tritolyl phosphate, diphenyl tricresylphosphate, phenyl bisdodecyl phosphate, ethyl diphenyl phosphate, as well as diphosphate esters and oligomeric phosphates such as, for example, resorcinol diphosphate, diphenyl hydrogen phosphate, 2-ethylhexyl hydrogen phosphate have been found to be useful.
  • Suitable oligomeric phosphate compounds are set forth in co-assigned U.S. Pat. No. 5,672,645.
  • Non-phosphorus additives and brominated or chlorinated phosphorus additives may also be added to polymer composition B to lower its Tg.
  • the amount of Tg-lowering additive can vary from 1% to 30 %, from 2% to 25%, or from 5% to 20% or any range within 1% to 30%, by weight, based on the weight of the polymer composition.
  • the polymer composition can include various other additives ordinarily incorporated into polymer compositions of this type, with the proviso that any additives is selected so as to not significantly adversely affect the desired properties of the polymer composition, in particular the adhesion properties.
  • additives can be mixed at a suitable time during the mixing of the components for forming the composition.
  • Additives include nucleating agents, fillers, reinforcing agents, antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) light stabilizers, lubricants, mold release agents, surfactants, antistatic agents, colorants such as titanium dioxide, carbon black, and organic dyes, surface effect additives, radiation stabilizers, flame retardants, and anti-drip agents.
  • a combination of additives can be used, for example a combination of a heat stabilizer and ultraviolet light stabilizer.
  • the additives are used in the amounts generally known to be effective.
  • the total amount of the additives can be 0.01 to 5 wt.%, based on the total weight of the thermoplastic material.
  • Sample strips of 5 x 0.5 x 0.03 inches (127 x 12.7 x 0.76 mm) length x width x thickness of the material noted below were molded. Two such strips were stacked one on top of the other with 0.5 inch overlap. The samples were then sandwiched between quarter inch thick metal bars and placed in the oven at optimum temperature for appropriate time. A clip was used to clamp the 2 metal bars to ensure good contact between sample strips. The samples were then taken out and the strips were subjected to lap shear test using an Instron mechanical tester at a temperature of 23°C and testing speed of 50 mm/min.
  • a cohesive failure is defined as any failure or break away from the bonded surface.
  • An adhesive failure is defined as failure at the bonded interface.
  • Table 1 shows the results of the lap shear test for samples prepared under 2 experimental conditions i.e., 105°C and 150°C for 10 minutes.
  • Table 2 shows the decreasing Tg and increasing Angular Momentum (MVR) of the materials with increasing plasticizer loading.
  • Embodiment 1 A method of making an article, the method comprising forming a plurality of layers of a material in a preset pattern at a build temperature from 15 degrees C to 250 degrees C, wherein at least one of the formed layers comprises a polymer composition comprising a polymer and an additive that lowers the glass transition temperature (Tg) of the polymer composition by 5 to 100 degrees C; and fusing the plurality of formed layers to provide the article.
  • Tg glass transition temperature
  • Embodiment 2 The method of Embodiment 1, wherein polymer comprises a polyacetal, polyacrylate, polyacrylic, polyamide, polyamideimide, polyanhydride, polyarylate, polyarylene ether, polyarylene sulfide, polybenzoxazole, polycarbonate, polyester,
  • polyetheretherketone polyetherimide, polyetherketoneketone, polyetherketone,
  • polyethersulfone polyimide, polymethacrylate, polyolefin, polyphthalide, polysilazane, polysiloxane, polystyrene, polysulfide, polysulfonamide, polysulfonate, polythioester, polytriazine, polyurea, polyurethane, polyvinyl alcohol, polyvinyl ester, polyvinyl ether, polyvinyl halide, polyvinyl ketone, polyvinylidene fluoride polyvinyl aromatic, polysulfone, polyarylenesulfone, polyaryl ether ketone, polylactic acid, polyglycolic acid, poly-3- hydroxybutyrate, polyhydroxyalkanoate, starch, cellulose ester, or a combination comprising at least one of the foregoing polymers; or the polymer composition comprises a polystyrene, poly(phenylene ether), poly(methyl methacrylate), styrene-acrylon
  • Embodiment 3 The method of Embodiment 2, wherein the polymer comprises a polystyrene, poly(phenylene oxide), poly(methyl methacrylate), styrene-acrylonitrile, poly(ethylene oxide), epichlorohydrin polymer, polycarbonate homopolymer or copolymer, acrylonitrile-butadiene-styrene, polyimide, polyimide-polycarbonate copolymer or a
  • Embodiment 4 The method of Embodiment 1, wherein the polymer is a polycarbonate homopolymer or copolymer.
  • Embodiment 5 The method of Embodiment 2, wherein the polymer is a polyamide.
  • Embodiment 6 The method of Embodiment 2, wherein the thermoplastic polymer is elastomer-modified graft copolymer formed from styrene-butadiene-styrene (SBS), styrene-butadiene rubber (SBR), styrene-ethylene-butadiene-styrene (SEBS), ABS (acrylonitrile- butadiene-styrene), acrylonitrile-ethylene-propylene-diene-styrene (AES), styrene-isoprene- styrene (SIS), methyl methacrylate-butadiene-styrene (MBS), styrene-acrylonitrile (SAN) and acrylonitrile-butadiene-styrene blends, or a combination comprising at least one of the foregoing polymers.
  • SBS styrene-butadiene-styren
  • Embodiment 7 The method of any one or more of Embodiments 1 to 6, wherein the additive is a phosphorous containing compound.
  • Embodiment 8 The method of any one or more of Embodiments 1 to 6, wherein the additive is a non-brominated and non-chlorinated organic phosphorus-containing additive.
  • Embodiment 9 The method of any one or more of Embodiments 1 to 6, wherein the additive is an aryl phosphate.
  • Embodiment 11 The method of any one or more of Embodiments 1 to 6, wherein the non-brominated and non-chlorinated organic phosphorus-containing additive resorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl) phosphate of bisphenol A, their oligomeric and polymeric counterparts, or a combination comprising at least one of the foregoing non-brominated and non-chlorinated organic phosphorus-containing additives.
  • RDP resorcinol tetraphenyl diphosphate
  • Embodiment 12 The method of any of the preceding Embodiments, wherein the amount of Tg-lowering additive is from 1% to 30 %, from 2% to 25%, or from 5% to 20% or any range within 1% to 30%, by weight, based on the weight of the thermoplastic polymer.
  • Embodiment 13 The method of any of the preceding Embodiments, wherein the forming a plurality of layers comprises melt-extruding layers a thermoplastic material.
  • Embodiment 14 The method of any of the preceding Embodiments, wherein the wherein the plurality of layers comprises at least twenty layers.
  • Embodiment 15 The method of any of Embodiments 1 to 12, wherein forming a plurality of layers comprises forming a plurality of layers comprising a build material and forming a plurality of layers comprising a support material.
  • Embodiment 16 An article made by any of the methods of any one or more of Embodiments 1 to 15.
  • Embodiment 17 An article, comprising a plurality of layers of a material in a preset pattern of at least twenty fused, melt-extruded layers comprises a polymer composition comprising a polymer and an additive that lowers the glass transition temperature (Tg) of the polymer composition by 5 to 100 degrees C.
  • Tg glass transition temperature
  • Embodiment 18 The method of any of claims 1 to 15, wherein the method is a fused filament fabrication additive manufacturing process or a large format additive manufacturing process and the polymer composition is in the form of filaments or pellets.
  • compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate components or steps herein disclosed.
  • the compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any steps, components, materials, ingredients, adjuvants, or species that are otherwise not necessary to the achievement of the function and/or objectives of the
  • compositions, methods, and articles are compositions, methods, and articles.

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Abstract

L'invention concerne un procédé de fabrication d'un article, le procédé comprenant la formation d'une pluralité de couches d'un matériau selon un motif prédéfini à une température de construction de 15 °C à 250 °C, au moins l'une des couches formées comprenant une composition polymère comprenant un polymère et un additif qui abaisse la température de transition vitreuse (Tg) de la composition polymère de 5 à 100 degrés C ; et la fusion de la pluralité de couches formées pour obtenir l'article.
PCT/US2016/065615 2015-12-11 2016-12-08 Ajout de plastifiants pour améliorer l'adhérence entre couches dans des processus de fabrication additive Ceased WO2017100447A1 (fr)

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KR20200049868A (ko) * 2017-09-15 2020-05-08 알케마 인코포레이티드 폴리에테르케톤케톤(pekk)의 압출 적층 제조방법 및 제품
CN111270346A (zh) * 2018-12-05 2020-06-12 沙特基础工业全球技术有限公司 核-壳长丝和其形成方法以及由其形成的制品
CN111757802A (zh) * 2017-12-26 2020-10-09 布拉斯科美国有限责任公司 使用高性能聚烯烃的增材制造方法
CN112566981A (zh) * 2018-08-13 2021-03-26 株式会社三养社 用于3d打印的聚碳酸酯树脂组合物和包含该聚碳酸酯树脂组合物的用于3d打印的细丝
EP3960917A2 (fr) 2020-08-27 2022-03-02 Xerox Corporation Filaments polymères comprenant un composé formant un gaz et fabrication additive les comprenant
EP3960426A2 (fr) 2020-08-27 2022-03-02 Xerox Corporation Filaments polymères comprenant un polymère d'imide soluble dans l'eau et leur utilisation comme matériau d'impression sacrificiel dans une fabrication additive
US20220212398A1 (en) * 2019-05-22 2022-07-07 Solvay Specialty Polymers Usa, Llc Additive manufacturing method for making a three-dimensional object
US11661521B2 (en) 2019-12-17 2023-05-30 Ticona Llc Three-dimensional printing system employing a thermotropic liquid crystalline polymer
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US12071539B2 (en) 2021-04-19 2024-08-27 Jabil Inc. Elastomeric additive manufacturing composition
US12076913B2 (en) 2019-12-17 2024-09-03 Ticona Llc Feed material for three-dimensional printing containing a polyoxymethylene polymer
US12234364B2 (en) 2019-12-17 2025-02-25 Ticona Llc Three-dimensional printing system employing a thermally conductive polymer composition

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KR20200049868A (ko) * 2017-09-15 2020-05-08 알케마 인코포레이티드 폴리에테르케톤케톤(pekk)의 압출 적층 제조방법 및 제품
KR102566070B1 (ko) 2017-09-15 2023-08-14 알케마 인코포레이티드 폴리에테르케톤케톤(pekk)의 압출 적층 제조방법 및 제품
CN111757802A (zh) * 2017-12-26 2020-10-09 布拉斯科美国有限责任公司 使用高性能聚烯烃的增材制造方法
CN111757802B (zh) * 2017-12-26 2023-07-18 布拉斯科美国有限责任公司 使用高性能聚烯烃的增材制造方法
CN112566981B (zh) * 2018-08-13 2023-10-10 株式会社三养社 用于3d打印的聚碳酸酯树脂组合物和包含该聚碳酸酯树脂组合物的用于3d打印的细丝
CN112566981A (zh) * 2018-08-13 2021-03-26 株式会社三养社 用于3d打印的聚碳酸酯树脂组合物和包含该聚碳酸酯树脂组合物的用于3d打印的细丝
US11834577B2 (en) 2018-09-26 2023-12-05 Sabic Global Technologies B.V. Polycarbonate composition and associated article and method of additive manufacturing
CN111270346A (zh) * 2018-12-05 2020-06-12 沙特基础工业全球技术有限公司 核-壳长丝和其形成方法以及由其形成的制品
US12172365B2 (en) * 2019-05-22 2024-12-24 Solvay Specialty Polymers Usa, Llc Additive manufacturing method for making a three-dimensional object
US20220212398A1 (en) * 2019-05-22 2022-07-07 Solvay Specialty Polymers Usa, Llc Additive manufacturing method for making a three-dimensional object
CN115943075A (zh) * 2019-05-22 2023-04-07 索尔维特殊聚合物美国有限责任公司 用于制造三维物体的增材制造方法
US11661521B2 (en) 2019-12-17 2023-05-30 Ticona Llc Three-dimensional printing system employing a thermotropic liquid crystalline polymer
US12076913B2 (en) 2019-12-17 2024-09-03 Ticona Llc Feed material for three-dimensional printing containing a polyoxymethylene polymer
US12234364B2 (en) 2019-12-17 2025-02-25 Ticona Llc Three-dimensional printing system employing a thermally conductive polymer composition
EP3960426A2 (fr) 2020-08-27 2022-03-02 Xerox Corporation Filaments polymères comprenant un polymère d'imide soluble dans l'eau et leur utilisation comme matériau d'impression sacrificiel dans une fabrication additive
EP3960917A2 (fr) 2020-08-27 2022-03-02 Xerox Corporation Filaments polymères comprenant un composé formant un gaz et fabrication additive les comprenant
US12071539B2 (en) 2021-04-19 2024-08-27 Jabil Inc. Elastomeric additive manufacturing composition

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