WO2020041291A1 - Additive printing filament material - Google Patents

Additive printing filament material Download PDF

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Publication number
WO2020041291A1
WO2020041291A1 PCT/US2019/047237 US2019047237W WO2020041291A1 WO 2020041291 A1 WO2020041291 A1 WO 2020041291A1 US 2019047237 W US2019047237 W US 2019047237W WO 2020041291 A1 WO2020041291 A1 WO 2020041291A1
Authority
WO
WIPO (PCT)
Prior art keywords
filament strand
core
thermoplastic
additive printing
filament
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2019/047237
Other languages
French (fr)
Inventor
Vincent P. HUIN
Martin VIEILLE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Owens Corning Intellectual Capital LLC
Original Assignee
Owens Corning Intellectual Capital LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Owens Corning Intellectual Capital LLC filed Critical Owens Corning Intellectual Capital LLC
Priority to CN201980051952.7A priority Critical patent/CN112639010A/en
Priority to EP19852910.9A priority patent/EP3841158A4/en
Priority to US17/270,077 priority patent/US12122089B2/en
Priority to JP2021510125A priority patent/JP7383694B2/en
Priority to KR1020217007777A priority patent/KR20210035310A/en
Publication of WO2020041291A1 publication Critical patent/WO2020041291A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive 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
    • B29C64/10Processes of additive manufacturing
    • B29C64/141Processes of additive manufacturing using only solid materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y70/00Materials specially adapted for additive manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y70/00Materials specially adapted for additive manufacturing
    • B33Y70/10Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/201Pre-melted polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/047Reinforcing macromolecular compounds with loose or coherent fibrous material with mixed fibrous material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/08Ingredients agglomerated by treatment with a binding agent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive 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
    • B29C64/10Processes of additive manufacturing
    • B29C64/106Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118Processes 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]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y10/00Processes of additive manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y80/00Products made by additive manufacturing
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10Homopolymers or copolymers of propene
    • C08J2323/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/06Elements
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/14Glass
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene

Definitions

  • the description relates to a filament strand for additive printing comprising a first core comprising glass fiber, a second core comprising carbon fiber, a thermoplastic matrix, and a thermoplastic sizing coating at least one of the first and second cores.
  • Additive manufacturing systems are used to print, or build, 3D parts from digital models, which can be beneficial for rapid prototyping and manufacturing.
  • One of the most common additive manufacturing techniques is the process known as fused filament fabrication, involves laying down a print material in layers.
  • the print material is in the form of a filament wound on a spool.
  • the filament is unwound, and in the case of thermoplastic print material, melted and extruded to print and produce a part.
  • Thermoplastic materials such as polylactic acid (PLA), acrylonitrile butadiene styrene (ABS), polyphenylsulfone (PPSF), polycarbonate (PC), and polyethylene terephthalate glycol (PETG) are used in additive manufacturing for their heat resistance properties.
  • PLA polylactic acid
  • ABS acrylonitrile butadiene styrene
  • PPSF polyphenylsulfone
  • PC polycarbonate
  • PETG polyethylene terephthalate glycol
  • polypropylene (PP) is not a desirable material for additive manufacturing as PP can be difficult to print with, due to heavy warping and poor layer adhesion.
  • PP has a lower tensile modulus, lower impact strength, and poorer melt strength compared to ABS and PLA. Improvement of the mechanical properties for additive manufacturing print materials is advantageous as it is desirable for an additively manufactured part to have similar mechanical properties of an injection molded part.
  • the present disclosure relates to a filament for additive printing including a first core including glass fiber, the first core comprising between about l0%-50% by weight of the filament, a second core including carbon fiber, the second core comprising between about 5%- 30% by weight of the filament, a polypropylene matrix including between about 50%-80% by weight of the filament, and a thermoplastic sizing coating at least one of the first and second cores.
  • the present disclosure relates to method of producing a filament for additive printing including applying a first thermoplastic sizing to a first core comprising glass fiber, applying a second thermoplastic sizing to a second core comprising carbon fiber heating a polypropylene matrix to a molten state, and mixing the first core and second core with the polypropylene matrix to form a mixture, wherein the first core comprises between about l0%-50% by weight of the filament; the second core comprises between about 5%-30% by weight of the filament, and the polypropylene matrix comprises between about 50%-80% by weight of the filament.
  • FIG. 1 is a schematic illustrating an additive printing process according to various aspects described herein.
  • FIG. 2 is a schematic illustrating a process for forming an additive printing filament strand according to various aspects described herein.
  • FIG. 3 is a flow chart illustrating a process for forming a filament strand according to aspects of the present disclosure.
  • FIG. 4 is a schematic bar graph illustrating the flexural modulus of materials used for additive printing and injection molding according to various aspects described herein.
  • FIG. 5 is a schematic bar graph illustrating the tensile modulus of materials used for additive printing according to various aspects described herein.
  • FIG. 6 is a schematic bar graph illustrating the flexural strength of materials used for additive printing and injection molding according to various aspects described herein.
  • FIG. 7 is a schematic bar graph illustrating the heat resistance of materials used for additive printing according to various aspects described herein.
  • Beneficial and advantageous features of the additive printing filament material according to various aspects described herein include increased mechanical performance due to a combination of glass fiber and carbon fiber reinforcements having a thermoplastic sizing within a thermoplastic matrix. Specifically, tensile modulus, flexural modulus, and thermal properties show a significant increase compared with an additive printing filament material having only glass fiber reinforcements.
  • FIG. 1 illustrates an additive printing process according to various aspects described herein.
  • An additive printing process can include a build platform 10, an extrusion head 20 having nozzles 22, 24.
  • Spools 30, 32 of a build material also known as an additive printing filament strand 40 and a support material 42 can be coupled with the nozzles 22, 24, respectively, where the additive printing filament strand 40 and the support material 42 can be heated and extruded, or dispensed, for printing.
  • the extrusion head 20 can be moved in x, y, and z directions relative to the build platform 10 in a pre-determined sequence to create a part 50 by depositing the additive printing filament strand 40 and support material 42 in layers on the build platform 10.
  • the additive printing filament strand 40 and support material 42 layers can solidify to form the part 50.
  • the support material 42 can be used to form portions 52 of the part 50 that are removable in order to provide structure for the part 50 during the printing process. While FIG. 1 illustrates the part 50 having portions 52 for support, it is also possible that the part 50 is printed without the support material 42.
  • an additive printing filament strand 40 can be formed from a hybrid material such as a composition 72 that includes a first reinforcing fiber 68, a second reinforcing fiber 70, and a thermoplastic matrix 60.
  • the printing filament strand 40 can further include additives including but not limited to pigments, such as anti-UV dyes, coupling agents, flame retardancy additives, viscosity modifiers, fillers, stabilizers, toughness modifiers, heat stabilizers, compatibilizers, processing aids, dispersing aids, and surfaces additives as well as other additives.
  • the thermoplastic matrix 60 can be polypropylene (PP), polyamide (PA6, PA8, PA11, PA12), polycarbonate (PC), polybutylene terephthalate (PBT), polyamide-imide (PAI), polyethylene (PE), polyetheretherketone (PEEK), polytherimidie (PEI), polyetherketone (PEK), polyaryletherketone (PAEK), polyethersulfone (PES), polyethylene terephthalate (PET), polyimide (PI), polyoxymethylene (POM), polyphenylether (PPE), polyphenylene sulfide (PPS), polyurethane (PETR), or any other suitable thermoplastic material.
  • PP polypropylene
  • PA6, PA8, PA11, PA12 polycarbonate
  • PC polybutylene terephthalate
  • PAI polyamide-imide
  • PE polyethylene
  • PEEK polyetheretherketone
  • PES polytherimidie
  • PES polyetherketone
  • PET polyethylene tere
  • the thermoplastic matrix 60 is a polypropylene homopolymer.
  • the thermoplastic matrix 60 can be in the range of 50% to 85% by weight of the filament strand 40, and preferably in the range of 65% to 75% by weight of the filament strand 40.
  • the first reinforcing fibers 68 can be comprised of a first core 63 coated with a thermoplastic-compatible sizing 66.
  • the first core 63 can comprise glass fibers 62, such as chopped strands that can have an initial diameter of approximately 10 0p and a length of approximately 4.0-4.5 mm.
  • the glass fibers 62 can be in the range of 10% to 50% by weight of the filament strand 40, and preferably in the range of 15% to 25%.
  • the thermoplastic-compatible sizing 66 is a polypropylene thermoplastic-compatible sizing 66 suitable for the glass fibers 62.
  • the second reinforcing fiber 70 can be comprised of a second core 65 coated with a thermoplastic-compatible sizing 67.
  • the second core 65 can comprise carbon fibers 64, such as chopped fibers.
  • the carbon fibers 64 have an initial diameter of approximately 7.0pm and a length of approximately 6.0 mm.
  • the carbon fibers 64 can be in the range of 5% to 30% by weight of the filament strand 40, and preferably in the range of 8% to 12% by weight of the filament strand 40.
  • the thermoplastic-compatible sizing 67 is a polypropylene thermoplastic-compatible sizing 67 suitable for the carbon fibers 64.
  • thermoplastic-compatible sizings 66, 67 can improve the processability of the glass fibers 62 and carbon fibers 64 by functioning as a protective coating on the surface of the fibers. Furthermore, the thermoplastic-compatible sizings 66, 67 can provide a coupling agent to enhance the bond of the glass fibers 62 and carbon fibers 64 with the thermoplastic matrix 60.
  • the thermoplastic-compatible sizings 66, 67 can be any sizing that is compatible with the thermoplastic material in the thermoplastic matrix 60 that is also suitable for coating the glass fibers 62 and/or the carbon fibers 64.
  • thermoplastic- compatible sizing 66 can be a polypropylene thermoplastic-compatible sizing 66 suitable for the glass fibers 62
  • thermoplastic-compatible sizing 67 can be a polypropylene thermoplastic-compatible sizing 67 suitable for the carbon fibers 64
  • thermoplastic-compatible sizings 66, 67, respectively, for coating the glass fibers 62 and the carbon fibers 64 can include the same thermoplastic-compatible sizing 66, 67.
  • the amount of thermoplastic-compatible sizings 66, 67 used to form reinforcing fibers 68, 70 is the percentage of material on the surface of the fibers 62, 64 and is defined by the weight percentage of the total weight of each of the reinforcing fibers 68, 70.
  • the weight percentage is measured by a loss on ignition value.
  • the loss on ignition (LOI) can be measured by strongly heating, or igniting, a sample of material at a specific temperature such that volatile substances are allowed to escape, until the mass of the sample ceases to change using ISO 1887:2014“Textile glass— Determination of Combustible-Matter Content”.
  • the LOI of the first reinforcing fiber 68 including the glass fiber 62 and the thermoplastic-compatible sizing 66 can be in the range of 0.55% and 0.75% by weight of the first reinforcing fiber 68.
  • the LOI of the second reinforcing fiber 70 including the carbon fiber 64 and the thermoplastic- compatible sizing 67 can be in the range of 2.50% and 3.00% by weight of the second reinforcing fiber 70.
  • FIG. 3 a process, or method 500 for forming a filament strand for additive printing according to an aspect of the present disclosure is illustrated. While the method 500 is described in the context of the additive printing filament strand 40, the processes described herein may be used to form other filament strands not explicitly described herein and may proceed in a different logical order or additional or intervening steps may be included.
  • the method 500 for forming the additive printing filament strand 40 includes a coating step 505 to form the first and second reinforcing fibers 68, 70, a compounding step 510 to form the composition 72, followed by one or more extrusion steps 510, 515 to form the filament strand 40 at step 520. Once the filament strand 40 is formed at step 520, the filament strand 40 can be spooled and optionally further conditioned at step 530.
  • a first thermoplastic sizing 66 with an LOI between about 0.55-0.75% by weight of the first core 63 is applied to the first core 63 comprising glass fiber 62 to form a first reinforcing fiber 68 and a second thermoplastic sizing 67 with an LOI between about 2.5-3.0% by weight of the second core 65 is applied to the second core 65 comprising carbon fiber 64 to form the second reinforcing fiber 70.
  • the composition 72 is formed by blending, or compounding the thermoplastic matrix 60 with the first reinforcing fibers 68 and the second reinforcing fibers 70.
  • a co-rotative screw heats the thermoplastic matrix 60 to a molten state and blends the reinforcing fibers 68 and 70 with the thermoplastic matrix 60 to form the composition 72.
  • the composition 72 includes the first core 63 comprising between about l0%-50% by weight of the filament strand 40, the second core 65 comprising between about 5%-30% by weight of the filament strand 40, and the thermoplastic matrix 60, such as polypropylene, comprising between about 50%-80% by weight of the filament strand 40.
  • the composition 72 includes the first core 63 comprising between about l5%-25% by weight of the filament strand 40, the second core 65 comprising between about 8%-l2% by weight of the filament strand 40, and the thermoplastic matrix 60, such as polypropylene, comprising between about 65%-75% by weight of the filament strand 40.
  • the composition 72 can be extruded directly from the co-rotative screw to form the filament strand 40, or optionally, at 515, the composition 72 can be fed into a second extruder, such as a single screw extruder.
  • the composition 72 can optionally be mixed with the desired additives at step 510 and/or step 515.
  • the composition 72 can be pulled through a nozzle to form the filament strand 40.
  • the final diameter of the filament strand 40 can be controlled by the rate and pressure that the filament strand 40 is pulled from the nozzle of the extruder prior to entering the final die to give the final geometry of the filament strand.
  • the final diameter of the filament strand 40 can be about l .75mm (+/- 0.05mm) or 2.85mm (+/- 0.05mm).
  • the filament strand 40 can be fed into a warm water tank where the filament strand 40 can be cooled and a round cross-section can be formed. Then, the filament strand 40 can be fed through a cold water tank such that the filament strand 40 can be cooled to room temperature. When the filament strand 40 is cooled, the filament strand 40 can be wound onto the spool 30.
  • Table 1 illustrates the change in the initial length of the glass fiber 62 and the carbon fiber 64 after the compounding step 210 compared to the final filament strand 40 as determined according to ISO standard 22314:2006“Plastics - Glass-fibre reinforced products - Determination of fibre length”.
  • a bar graph 100 compares the flexural modulus of materials having exemplary compositions according to various aspects described herein using injection molding vs. additive printing.
  • the x-axis 110 identifies each of the various materials, while the y-axis 112 illustrates the flexural modulus, measured in gigapascals (GPa), of each material.
  • the first material 120 is a composition having approximately 30% by weight glass fiber.
  • the second material 130 is a composition having approximately 20% by weight glass fiber, 10% by weight carbon fiber, and a thermoplastic-compatible sizing.
  • the third material 140 is a composition having approximately 20% by weight glass fiber, 10% by weight carbon fiber, and a thermoset-compatible sizing
  • the fourth material 150 is a composition having approximately 10% by weight carbon fiber, and a thermoplastic-compatible sizing.
  • the second material 130 represents a composition according to an exemplary embodiment of the applicant’s disclosure.
  • the first material 120 has a flexural modulus of 7.0 GPa when 3D printed, as shown by bar 122 and has a flexural modulus of 6.0 GPa when injection molded, as shown by bar 124.
  • the second material 130 has a flexural modulus of 9.8 GPa when 3D printed, as shown by bar 132 and has a flexural modulus of 8.1 GPa when injection molded, as shown by bar 134.
  • the third material 140 has a flexural modulus of 8.4 GPa when 3D printed, as shown by bar 142 and has a flexural modulus of 6.9 GPa when injection molded, as shown by bar 144.
  • the fourth material 150 has a flexural modulus of 5.6 GPa when 3D printed, as shown by bar 152 and has a flexural modulus of 4.2 GPa when injection molded, as shown by bar 154.
  • the second material 130 has superior flexural modulus characteristics when compared to the other materials 120, 140, and 150.
  • the flexural modulus of the second material 130 is approximately 40% higher than the first material 120, 17% higher than the third material 140, and 75% higher than the fourth material 150.
  • the flexural modulus of the second material 130 is approximately 35% higher than the first material 120, 17% higher than the third material 140, and 93% higher than the fourth material 150.
  • FIG. 5 illustrates a bar graph 200 comparing the tensile modulus, measured in gigapascals (GPa), of the first material 120, the second material 130, and the fourth material 150 used for additive printing according to various aspects described herein. Comparison to the third material 140 was not completed.
  • the x-axis 210 identifies each of the various materials, while the y-axis 212 illustrates the tensile modulus, measured in gigapascals (GPa), of each material.
  • the first material 120 has a tensile modulus of 7.604 GPa when 3D printed, as shown by bar 222.
  • the second material 130 has a tensile modulus of 9.825 GPa when 3D printed, as shown by bar 232.
  • the fourth material 150 has a tensile modulus of 5.810 GPa when 3D printed, as shown by bar 252.
  • the second material 130 has superior tensile modulus characteristics when compared to the other materials 120 and 150.
  • the tensile modulus of the second material 130 is approximately 29% higher than the first material 120 and approximately 69% higher than fourth material 150.
  • the combination of glass and carbon fibers with a thermoplastic-compatible sizing as in the second material 130 demonstrates an increased tensile modulus compared to a material having only glass fiber as in the first material 120 or a material having carbon fiber with a thermoset-compatible sizing as in the fourth material 150.
  • FIG. 6 illustrates a bar graph 300 comparing the flexural strength of the materials 120, 130, 140, and 150 with various material compositions according to various aspects described herein when #3D printed vs. injection molded.
  • the x-axis 310 identifies each of the various materials 120, 130, 140, and 150, while the y-axis 312 illustrates the flexural strength, measured in megapascals (MPa), of each material.
  • MPa megapascals
  • the first material 120 has a flexural strength of 149.0 MPa, when 3D printed, as shown by bar 322 and has a flexural strength of 143.0 MPa when injection molded, as shown by bar 324.
  • the second material 130 has a flexural strength of 152.0 MPa, when 3D printed, as shown by bar 332 and has a flexural strength of 141.0 MPa when injection molded, as shown by bar 334.
  • the third material 140 has a flexural strength of 111.0 MPa when 3D printed, as shown by bar 342, and has a flexural strength of 105.0 MPa when injection molded, as shown by bar 344.
  • the fourth material 150 has a flexural strength of 102.0 MPa when 3D printed, as shown by bar 352, and has a flexural strength of 91.0 MPa when injection molded, as shown by bar 354.
  • the second material 130 has similar flexural strength characteristics when compared to the first material 120 and superior flexural strength characteristics when compared to the other materials 140, and 150.
  • the flexural strength of the second material 130 is approximately 37% higher than the third material 140, and 49% higher than the fourth material 150.
  • the flexural strength of the second material 130 is approximately 34% higher than the third material 140, and 55% higher than the fourth material 150.
  • the combination of glass and carbon fibers with a thermoplastic-compatible sizing as in the second material 130 demonstrates an increased flexural strength compared to a material having glass and carbon fibers with a thermoset-compatible sizing as in the third material 140 or a material having only carbon fibers with a thermoplastic-compatible sizing as in the fourth material 150.
  • FIG. 7 illustrates a bar graph 400 comparing the heat resistance of the first material 120 and the second material 130.
  • the x-axis 410 identifies each of the materials, while the y-axis 412 illustrates the heat deflection temperature, measured in degrees Celsius, of the materials 120, 130.
  • the heat deflection temperature of the first material 120 and the second material 130 were tested according to ISO 75 Standard Method A at a load of 1.8 MPa. Heat deflection temperature is defined as the temperature at which a standard test bar deflects a specified distance under a load. Heat deflection temperature is used to determine short-term heat resistance.
  • the first material 120 has a heat deflection temperature of l20°C, as shown by bar 422.
  • the second material 130 has a heat deflection temperature of l50°C, as shown by bar 432. Therefore, the second material 130 has a higher heat resistance than the first material 120 by approximately 25%.
  • the second material 130 comprising a combination of glass and carbon fibers with a thermoplastic-compatible sizing demonstrates an increase in thermal properties compared to the first material 120 having only glass fiber.
  • the aspects of the disclosure described herein can include an additive manufacturing print filament material that can provide a final part having comparable mechanical properties to an injection molded part. Therefore, the part, or prototype, produced with a printing filament strand according to aspects described herein can be a cost effective solution compared to injection molding as a mold is not required to make the prototype. Furthermore, a prototype produced from a filament strand according to aspects described herein can be tested in real conditions due to the increase in mechanical properties compared to a part additively manufactured with traditional printing filaments.

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Abstract

A filament strand (40) for additive printing includes a first core (63) comprising glass fiber (62), the first core (63) comprising between about 10%-50% by weight of the filament strand (40), a second core (65) comprising carbon fiber (64), the second core (65) comprising between about 5%-30% by weight of the filament strand (40), a thermoplastic matrix (60) comprising between about 50%-80% by weight of the filament strand (40), and a thermoplastic sizing (66, 67) coating at least one of the first (63) and second (65) cores.

Description

ADDITIVE PRINTING FILAMENT MATERIAL
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to and benefit of U.S. Provisional Patent Application No. 62/720,497 filed August 21, 2018, which is incorporated herein in its entirety.
TECHNICAL FIELD
[0002] The description relates to a filament strand for additive printing comprising a first core comprising glass fiber, a second core comprising carbon fiber, a thermoplastic matrix, and a thermoplastic sizing coating at least one of the first and second cores.
BACKGROUND
[0003] Additive manufacturing systems are used to print, or build, 3D parts from digital models, which can be beneficial for rapid prototyping and manufacturing. One of the most common additive manufacturing techniques is the process known as fused filament fabrication, involves laying down a print material in layers. The print material is in the form of a filament wound on a spool. The filament is unwound, and in the case of thermoplastic print material, melted and extruded to print and produce a part.
[0004] Thermoplastic materials such as polylactic acid (PLA), acrylonitrile butadiene styrene (ABS), polyphenylsulfone (PPSF), polycarbonate (PC), and polyethylene terephthalate glycol (PETG) are used in additive manufacturing for their heat resistance properties. Typically, polypropylene (PP) is not a desirable material for additive manufacturing as PP can be difficult to print with, due to heavy warping and poor layer adhesion. Furthermore, PP has a lower tensile modulus, lower impact strength, and poorer melt strength compared to ABS and PLA. Improvement of the mechanical properties for additive manufacturing print materials is advantageous as it is desirable for an additively manufactured part to have similar mechanical properties of an injection molded part.
BRIEF DESCRIPTION OF THE INVENTION
[0005] In one aspect, the present disclosure relates to a filament for additive printing including a first core including glass fiber, the first core comprising between about l0%-50% by weight of the filament, a second core including carbon fiber, the second core comprising between about 5%- 30% by weight of the filament, a polypropylene matrix including between about 50%-80% by weight of the filament, and a thermoplastic sizing coating at least one of the first and second cores.
[0006] In another aspect, the present disclosure relates to method of producing a filament for additive printing including applying a first thermoplastic sizing to a first core comprising glass fiber, applying a second thermoplastic sizing to a second core comprising carbon fiber heating a polypropylene matrix to a molten state, and mixing the first core and second core with the polypropylene matrix to form a mixture, wherein the first core comprises between about l0%-50% by weight of the filament; the second core comprises between about 5%-30% by weight of the filament, and the polypropylene matrix comprises between about 50%-80% by weight of the filament.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] In the drawings:
[0008] FIG. 1 is a schematic illustrating an additive printing process according to various aspects described herein.
[0009] FIG. 2 is a schematic illustrating a process for forming an additive printing filament strand according to various aspects described herein.
[0010] FIG. 3 is a flow chart illustrating a process for forming a filament strand according to aspects of the present disclosure.
[0011] FIG. 4 is a schematic bar graph illustrating the flexural modulus of materials used for additive printing and injection molding according to various aspects described herein.
[0012] FIG. 5 is a schematic bar graph illustrating the tensile modulus of materials used for additive printing according to various aspects described herein.
[0013] FIG. 6 is a schematic bar graph illustrating the flexural strength of materials used for additive printing and injection molding according to various aspects described herein.
[0014] FIG. 7 is a schematic bar graph illustrating the heat resistance of materials used for additive printing according to various aspects described herein.
DETAILED DESCRIPTION
[0015] Beneficial and advantageous features of the additive printing filament material according to various aspects described herein include increased mechanical performance due to a combination of glass fiber and carbon fiber reinforcements having a thermoplastic sizing within a thermoplastic matrix. Specifically, tensile modulus, flexural modulus, and thermal properties show a significant increase compared with an additive printing filament material having only glass fiber reinforcements.
[0016] In addition, this increase in mechanical performance of the additive printing filament material due to the combination of glass fiber and carbon fiber reinforcements can also limit warping and deformation of the final printed product when the product is printed with the hybrid reinforced filament.
[0017] FIG. 1 illustrates an additive printing process according to various aspects described herein. An additive printing process can include a build platform 10, an extrusion head 20 having nozzles 22, 24. Spools 30, 32 of a build material also known as an additive printing filament strand 40 and a support material 42 can be coupled with the nozzles 22, 24, respectively, where the additive printing filament strand 40 and the support material 42 can be heated and extruded, or dispensed, for printing. The extrusion head 20 can be moved in x, y, and z directions relative to the build platform 10 in a pre-determined sequence to create a part 50 by depositing the additive printing filament strand 40 and support material 42 in layers on the build platform 10. The additive printing filament strand 40 and support material 42 layers can solidify to form the part 50. The support material 42 can be used to form portions 52 of the part 50 that are removable in order to provide structure for the part 50 during the printing process. While FIG. 1 illustrates the part 50 having portions 52 for support, it is also possible that the part 50 is printed without the support material 42.
[0018] Referring to FIG. 2, an additive printing filament strand 40 according to an aspect of the present disclosure can be formed from a hybrid material such as a composition 72 that includes a first reinforcing fiber 68, a second reinforcing fiber 70, and a thermoplastic matrix 60. Optionally, the printing filament strand 40 can further include additives including but not limited to pigments, such as anti-UV dyes, coupling agents, flame retardancy additives, viscosity modifiers, fillers, stabilizers, toughness modifiers, heat stabilizers, compatibilizers, processing aids, dispersing aids, and surfaces additives as well as other additives.
[0019] The thermoplastic matrix 60 can be polypropylene (PP), polyamide (PA6, PA8, PA11, PA12), polycarbonate (PC), polybutylene terephthalate (PBT), polyamide-imide (PAI), polyethylene (PE), polyetheretherketone (PEEK), polytherimidie (PEI), polyetherketone (PEK), polyaryletherketone (PAEK), polyethersulfone (PES), polyethylene terephthalate (PET), polyimide (PI), polyoxymethylene (POM), polyphenylether (PPE), polyphenylene sulfide (PPS), polyurethane (PETR), or any other suitable thermoplastic material. In one example, the thermoplastic matrix 60 is a polypropylene homopolymer. The thermoplastic matrix 60 can be in the range of 50% to 85% by weight of the filament strand 40, and preferably in the range of 65% to 75% by weight of the filament strand 40.
[0020] The first reinforcing fibers 68 can be comprised of a first core 63 coated with a thermoplastic-compatible sizing 66. The first core 63 can comprise glass fibers 62, such as chopped strands that can have an initial diameter of approximately 10 0p and a length of approximately 4.0-4.5 mm. The glass fibers 62 can be in the range of 10% to 50% by weight of the filament strand 40, and preferably in the range of 15% to 25%. In one example, the thermoplastic-compatible sizing 66 is a polypropylene thermoplastic-compatible sizing 66 suitable for the glass fibers 62.
[0021] The second reinforcing fiber 70 can be comprised of a second core 65 coated with a thermoplastic-compatible sizing 67. The second core 65 can comprise carbon fibers 64, such as chopped fibers. In one example, the carbon fibers 64 have an initial diameter of approximately 7.0pm and a length of approximately 6.0 mm. The carbon fibers 64 can be in the range of 5% to 30% by weight of the filament strand 40, and preferably in the range of 8% to 12% by weight of the filament strand 40. In one example, the thermoplastic-compatible sizing 67 is a polypropylene thermoplastic-compatible sizing 67 suitable for the carbon fibers 64.
[0022] The thermoplastic-compatible sizings 66, 67, or thermoplastic sizings, can improve the processability of the glass fibers 62 and carbon fibers 64 by functioning as a protective coating on the surface of the fibers. Furthermore, the thermoplastic-compatible sizings 66, 67 can provide a coupling agent to enhance the bond of the glass fibers 62 and carbon fibers 64 with the thermoplastic matrix 60. The thermoplastic-compatible sizings 66, 67 can be any sizing that is compatible with the thermoplastic material in the thermoplastic matrix 60 that is also suitable for coating the glass fibers 62 and/or the carbon fibers 64. In one example, the thermoplastic- compatible sizing 66 can be a polypropylene thermoplastic-compatible sizing 66 suitable for the glass fibers 62, while the thermoplastic-compatible sizing 67 can be a polypropylene thermoplastic-compatible sizing 67 suitable for the carbon fibers 64. Alternatively, in another aspect of the present disclosure, the thermoplastic-compatible sizings 66, 67, respectively, for coating the glass fibers 62 and the carbon fibers 64, can include the same thermoplastic-compatible sizing 66, 67.
[0023] The amount of thermoplastic-compatible sizings 66, 67 used to form reinforcing fibers 68, 70 is the percentage of material on the surface of the fibers 62, 64 and is defined by the weight percentage of the total weight of each of the reinforcing fibers 68, 70. The weight percentage is measured by a loss on ignition value. The loss on ignition (LOI) can be measured by strongly heating, or igniting, a sample of material at a specific temperature such that volatile substances are allowed to escape, until the mass of the sample ceases to change using ISO 1887:2014“Textile glass— Determination of Combustible-Matter Content”. In one example, the LOI of the first reinforcing fiber 68 including the glass fiber 62 and the thermoplastic-compatible sizing 66 can be in the range of 0.55% and 0.75% by weight of the first reinforcing fiber 68. In another example, the LOI of the second reinforcing fiber 70 including the carbon fiber 64 and the thermoplastic- compatible sizing 67 can be in the range of 2.50% and 3.00% by weight of the second reinforcing fiber 70.
[0024] Referring now to FIG. 3, a process, or method 500 for forming a filament strand for additive printing according to an aspect of the present disclosure is illustrated. While the method 500 is described in the context of the additive printing filament strand 40, the processes described herein may be used to form other filament strands not explicitly described herein and may proceed in a different logical order or additional or intervening steps may be included.
[0025] The method 500 for forming the additive printing filament strand 40 includes a coating step 505 to form the first and second reinforcing fibers 68, 70, a compounding step 510 to form the composition 72, followed by one or more extrusion steps 510, 515 to form the filament strand 40 at step 520. Once the filament strand 40 is formed at step 520, the filament strand 40 can be spooled and optionally further conditioned at step 530.
[0026] At 505, a first thermoplastic sizing 66 with an LOI between about 0.55-0.75% by weight of the first core 63 is applied to the first core 63 comprising glass fiber 62 to form a first reinforcing fiber 68 and a second thermoplastic sizing 67 with an LOI between about 2.5-3.0% by weight of the second core 65 is applied to the second core 65 comprising carbon fiber 64 to form the second reinforcing fiber 70.
[0027] At compounding step 510, the composition 72 is formed by blending, or compounding the thermoplastic matrix 60 with the first reinforcing fibers 68 and the second reinforcing fibers 70. In one example, a co-rotative screw heats the thermoplastic matrix 60 to a molten state and blends the reinforcing fibers 68 and 70 with the thermoplastic matrix 60 to form the composition 72. In one aspect of the present disclosure, the composition 72 includes the first core 63 comprising between about l0%-50% by weight of the filament strand 40, the second core 65 comprising between about 5%-30% by weight of the filament strand 40, and the thermoplastic matrix 60, such as polypropylene, comprising between about 50%-80% by weight of the filament strand 40. In another aspect, the composition 72 includes the first core 63 comprising between about l5%-25% by weight of the filament strand 40, the second core 65 comprising between about 8%-l2% by weight of the filament strand 40, and the thermoplastic matrix 60, such as polypropylene, comprising between about 65%-75% by weight of the filament strand 40.
[0028] At 510, the composition 72 can be extruded directly from the co-rotative screw to form the filament strand 40, or optionally, at 515, the composition 72 can be fed into a second extruder, such as a single screw extruder. The composition 72 can optionally be mixed with the desired additives at step 510 and/or step 515. At 520, the composition 72 can be pulled through a nozzle to form the filament strand 40. The final diameter of the filament strand 40 can be controlled by the rate and pressure that the filament strand 40 is pulled from the nozzle of the extruder prior to entering the final die to give the final geometry of the filament strand. The final diameter of the filament strand 40 can be about l .75mm (+/- 0.05mm) or 2.85mm (+/- 0.05mm). At 530, the filament strand 40 can be fed into a warm water tank where the filament strand 40 can be cooled and a round cross-section can be formed. Then, the filament strand 40 can be fed through a cold water tank such that the filament strand 40 can be cooled to room temperature. When the filament strand 40 is cooled, the filament strand 40 can be wound onto the spool 30.
[0029] Table 1 illustrates the change in the initial length of the glass fiber 62 and the carbon fiber 64 after the compounding step 210 compared to the final filament strand 40 as determined according to ISO standard 22314:2006“Plastics - Glass-fibre reinforced products - Determination of fibre length”.
Table 1 : Length of glass fiber and carbon fiber during 3D strand manufacturing
Figure imgf000008_0001
[0030] Turning to FIG. 4, a bar graph 100 compares the flexural modulus of materials having exemplary compositions according to various aspects described herein using injection molding vs. additive printing. The x-axis 110 identifies each of the various materials, while the y-axis 112 illustrates the flexural modulus, measured in gigapascals (GPa), of each material. The first material 120 is a composition having approximately 30% by weight glass fiber. The second material 130 is a composition having approximately 20% by weight glass fiber, 10% by weight carbon fiber, and a thermoplastic-compatible sizing. The third material 140 is a composition having approximately 20% by weight glass fiber, 10% by weight carbon fiber, and a thermoset-compatible sizing, and the fourth material 150 is a composition having approximately 10% by weight carbon fiber, and a thermoplastic-compatible sizing. The second material 130 represents a composition according to an exemplary embodiment of the applicant’s disclosure.
[0031] As shown in the graph 100, the first material 120 has a flexural modulus of 7.0 GPa when 3D printed, as shown by bar 122 and has a flexural modulus of 6.0 GPa when injection molded, as shown by bar 124. The second material 130 has a flexural modulus of 9.8 GPa when 3D printed, as shown by bar 132 and has a flexural modulus of 8.1 GPa when injection molded, as shown by bar 134. The third material 140 has a flexural modulus of 8.4 GPa when 3D printed, as shown by bar 142 and has a flexural modulus of 6.9 GPa when injection molded, as shown by bar 144. The fourth material 150 has a flexural modulus of 5.6 GPa when 3D printed, as shown by bar 152 and has a flexural modulus of 4.2 GPa when injection molded, as shown by bar 154.
[0032] As evident from the graph 100, the second material 130 has superior flexural modulus characteristics when compared to the other materials 120, 140, and 150. When used as an additive printing filament strand 40, the flexural modulus of the second material 130 is approximately 40% higher than the first material 120, 17% higher than the third material 140, and 75% higher than the fourth material 150. When used as an injection molding filament, the flexural modulus of the second material 130 is approximately 35% higher than the first material 120, 17% higher than the third material 140, and 93% higher than the fourth material 150. Thus, the combination of glass and carbon fibers with a thermoplastic-compatible sizing as in the second material 130 demonstrates an increased flexural modulus compared to a material having only glass fiber as in the first material 120 or a material having glass and carbon fibers with a thermoset-compatible sizing as in the third material 140 or a material having only carbon fibers with a thermoplastic- compatible sizing as in the fourth material 150. [0033] FIG. 5 illustrates a bar graph 200 comparing the tensile modulus, measured in gigapascals (GPa), of the first material 120, the second material 130, and the fourth material 150 used for additive printing according to various aspects described herein. Comparison to the third material 140 was not completed. The x-axis 210 identifies each of the various materials, while the y-axis 212 illustrates the tensile modulus, measured in gigapascals (GPa), of each material.
[0034] As shown in the graph 200, the first material 120 has a tensile modulus of 7.604 GPa when 3D printed, as shown by bar 222. The second material 130 has a tensile modulus of 9.825 GPa when 3D printed, as shown by bar 232. The fourth material 150 has a tensile modulus of 5.810 GPa when 3D printed, as shown by bar 252.
[0035] As evident from the graph 200, the second material 130 has superior tensile modulus characteristics when compared to the other materials 120 and 150. When used as an additive printing filament strand 40, the tensile modulus of the second material 130 is approximately 29% higher than the first material 120 and approximately 69% higher than fourth material 150. Thus, the combination of glass and carbon fibers with a thermoplastic-compatible sizing as in the second material 130 demonstrates an increased tensile modulus compared to a material having only glass fiber as in the first material 120 or a material having carbon fiber with a thermoset-compatible sizing as in the fourth material 150.
[0036] FIG. 6 illustrates a bar graph 300 comparing the flexural strength of the materials 120, 130, 140, and 150 with various material compositions according to various aspects described herein when #3D printed vs. injection molded. The x-axis 310 identifies each of the various materials 120, 130, 140, and 150, while the y-axis 312 illustrates the flexural strength, measured in megapascals (MPa), of each material.
[0037] As shown in the graph 300, the first material 120 has a flexural strength of 149.0 MPa, when 3D printed, as shown by bar 322 and has a flexural strength of 143.0 MPa when injection molded, as shown by bar 324. The second material 130 has a flexural strength of 152.0 MPa, when 3D printed, as shown by bar 332 and has a flexural strength of 141.0 MPa when injection molded, as shown by bar 334. The third material 140 has a flexural strength of 111.0 MPa when 3D printed, as shown by bar 342, and has a flexural strength of 105.0 MPa when injection molded, as shown by bar 344. The fourth material 150 has a flexural strength of 102.0 MPa when 3D printed, as shown by bar 352, and has a flexural strength of 91.0 MPa when injection molded, as shown by bar 354. [0038] As evident from the graph 300, the second material 130 has similar flexural strength characteristics when compared to the first material 120 and superior flexural strength characteristics when compared to the other materials 140, and 150. When used as an additive printing filament strand 40, the flexural strength of the second material 130 is approximately 37% higher than the third material 140, and 49% higher than the fourth material 150. When used as an injection molding filament, the flexural strength of the second material 130 is approximately 34% higher than the third material 140, and 55% higher than the fourth material 150. Thus, the combination of glass and carbon fibers with a thermoplastic-compatible sizing as in the second material 130 demonstrates an increased flexural strength compared to a material having glass and carbon fibers with a thermoset-compatible sizing as in the third material 140 or a material having only carbon fibers with a thermoplastic-compatible sizing as in the fourth material 150.
[0039] FIG. 7 illustrates a bar graph 400 comparing the heat resistance of the first material 120 and the second material 130. The x-axis 410 identifies each of the materials, while the y-axis 412 illustrates the heat deflection temperature, measured in degrees Celsius, of the materials 120, 130. The heat deflection temperature of the first material 120 and the second material 130 were tested according to ISO 75 Standard Method A at a load of 1.8 MPa. Heat deflection temperature is defined as the temperature at which a standard test bar deflects a specified distance under a load. Heat deflection temperature is used to determine short-term heat resistance.
[0040] As shown in the graph 400, the first material 120 has a heat deflection temperature of l20°C, as shown by bar 422. The second material 130 has a heat deflection temperature of l50°C, as shown by bar 432. Therefore, the second material 130 has a higher heat resistance than the first material 120 by approximately 25%. Thus, the second material 130 comprising a combination of glass and carbon fibers with a thermoplastic-compatible sizing demonstrates an increase in thermal properties compared to the first material 120 having only glass fiber.
[0041] The aspects of the disclosure described herein can include an additive manufacturing print filament material that can provide a final part having comparable mechanical properties to an injection molded part. Therefore, the part, or prototype, produced with a printing filament strand according to aspects described herein can be a cost effective solution compared to injection molding as a mold is not required to make the prototype. Furthermore, a prototype produced from a filament strand according to aspects described herein can be tested in real conditions due to the increase in mechanical properties compared to a part additively manufactured with traditional printing filaments.
[0042] To the extent not already described, the different features and structures of the various embodiments can be used in combination with each other as desired. That one feature cannot be illustrated in all of the embodiments is not meant to be construed that it cannot be, but is done for brevity of description. Thus, the various features of the different embodiments can be mixed and matched as desired to form new embodiments, whether or not the new embodiments are expressly described.
[0043] While the invention has been specifically described in connection with certain specific embodiments thereof, it is to be understood that this is by way of illustration and not of limitation. Reasonable variation and modification are possible within the scope of the forgoing disclosure and drawings without departing from the spirit of the invention which is defined in the appended claims.

Claims

1. A filament strand (40) for additive printing comprising;
a first core (63) comprising glass fiber (62); the first core (63) comprising between about l0%-50% by weight of the filament strand (40);
a second core (65) comprising carbon fiber (64); the second core (65) comprising between about 5%-30% by weight of the filament strand (40);
a thermoplastic matrix (60) comprising between about 50%-80% by weight of the filament; and
a thermoplastic-compatible sizing (66, 67) coating at least one of the first (63) and second (64) cores.
2. The filament strand (40) for additive printing of claim 1, wherein the thermoplastic matrix (60) comprises at least one of polypropylene (PP), polyamide (PA6, PA8, PA11, PA12), or polycarbonate (PC), polybutylene terephthalate (PBT), polyamide-imide (PAI), polyethylene (PE), polyetheretherketone (PEEK), polyetherimide (PEI), polyetherketone (PEK), polyaryletherketone (PAEK), polyethersulfone (PES), polyethylene terephthalate (PET), polyimide (PI), polyoxymethylene (POM), polyphenylether (PPE), Polyphenylene sulfide (PPS), polyurethane (PUR).
3. The filament strand (40) for additive printing of claim 1, wherein the thermoplastic matrix (60) comprises polypropylene.
4. The filament strand (40) for additive printing of claim 1 , wherein the thermoplastic- compatible sizing (66, 67) coats the first core (63).
5. The filament strand (40) for additive printing of claim 1, wherein the glass fiber (64) is chopped strand.
6. The filament strand (40) for additive printing of claim 5, wherein the final dimensions for chopped strands in the filament strand (40) are 200pm to 500pm.
7. The filament strand (40) for additive printing of claim 1 , wherein the thermoplastic- compatible sizing (66, 67) coats the second core (65).
8. The filament strand (40) for additive printing of claim 1, wherein the thermoplastic- compatible sizing (66, 67) is a first thermoplastic-compatible sizing (66) that coats the first core (63) and a second thermoplastic-compatible sizing (67) coats the second core (65).
9. The filament strand (40) for additive printing of claim 1, wherein first core (63) comprises between about l5%-25% by weight of the filament.
10. The filament strand (40) for additive printing of claim 9, wherein the first core (63) comprises about 20% by weight of the filament strand (40).
11. The filament strand (40) for additive printing of claim 1, wherein the second core (65) comprises between about 8%-l2% by weight of the filament strand (40).
12. The filament strand (40) for additive printing of claim 11, wherein the second core (65) comprises about 10% by weight of the filament strand (40).
13. The filament strand (40) for additive printing of claim 12, wherein the thermoplastic matrix (60) comprises between about 65%-75% by weight of the filament strand (40).
14. The filament strand (40) for additive printing of claim 1, wherein first core (63) comprises between about 15%-25% by weight of the filament strand (40), wherein the second core (65) comprises between about 8%-l2% by weight of the filament strand (40), wherein the thermoplastic matrix (60) comprises between about 65%-75% by weight of the filament strand (40).
15. The filament strand (40) for additive printing of claim 14, wherein the thermoplastic-compatible sizing (66, 67) is a first thermoplastic sizing (66) that coats the first core (63) and a second thermoplastic-compatible sizing (67) coats the second core (65).
16. The filament strand (40) for additive printing of claim 1, wherein the thermoplastic matrix (60) is a homopolymer.
17. A method (500) of producing a filament strand (40) for additive printing comprising:
applying a first thermoplastic-compatible sizing (66) to a first core (63) comprising glass fiber (62);
applying a second thermoplastic-compatible sizing (67) to a second core (65) comprising carbon fiber (64);
heating a thermoplastic matrix (60) to a molten state;
mixing the first core (63) and second core (65) with the thermoplastic matrix (60) to form a composition (72); and
extruding the composition (72) to form the filament strand (40),
wherein the first core (63) comprises between about l0%-50% by weight of the filament strand (40); the second core (65) comprises between about 5%-30% by weight of the filament strand (40); and the thermoplastic matrix (60) comprises between about 50%-80% by weight of the filament strand (40).
18. The method (500) of producing a filament strand (40) for additive printing of claim 17, wherein extruding the composition (72) comprises a compounding step and an extrusion step to give one or more desired final dimensions to the filament strand (40).
19. The method (500) of producing a filament strand (40) for additive printing of claim 17, wherein the one or more desired dimensions of the filament strand (40) is a diameter of 1 5mm to l .9mm, preferably l .75mm.
20. The method (500) of producing a filament strand (40) for additive printing of claim 17, wherein the one or more desired dimensions of the filament strand (40) is a diameter of 2.5mm to 3. lmm, preferably 2.85mm.
21. The method (500) of producing a filament strand 40) for additive printing of claim 17, wherein the first core (63) comprises between about l5%-25% by weight of the filament strand (40), wherein the second core (65) comprises between about 8%-l2% by weight of the filament strand (40), and wherein the thermoplastic matrix (60) comprises between about 65%-75% by weight of the filament strand (40).
22. The method (500) of producing a filament strand (40) for additive printing of claim 17, wherein the glass fiber (62) is chopped strand.
23. The method (500) of producing a filament strand (40) for additive printing of claim 22, wherein the final dimensions for chopped strands in the filament strand (40) are lOOpm to 1500pm, preferably 200pm to 800pm, and ideally 250pm to 500pm.
PCT/US2019/047237 2018-08-21 2019-08-20 Additive printing filament material Ceased WO2020041291A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201980051952.7A CN112639010A (en) 2018-08-21 2019-08-20 Additive printing filament material
EP19852910.9A EP3841158A4 (en) 2018-08-21 2019-08-20 ADDITIVE PRINTING FILAMENT MATERIAL
US17/270,077 US12122089B2 (en) 2018-08-21 2019-08-20 Additive printing filament material
JP2021510125A JP7383694B2 (en) 2018-08-21 2019-08-20 Filament materials for additive printing
KR1020217007777A KR20210035310A (en) 2018-08-21 2019-08-20 Filament material for lamination printing

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022270320A1 (en) * 2021-06-24 2022-12-29
CN115803371A (en) * 2020-07-17 2023-03-14 索尔维特殊聚合物美国有限责任公司 Process for producing continuous fiber filaments, continuous fiber filaments and use thereof
WO2023126391A1 (en) * 2021-12-29 2023-07-06 Luxembourg Institute Of Science And Technology (List) Reinforced composite filament for an additive manufacturing application and method for manufacturing thereof
WO2023126395A1 (en) * 2021-12-29 2023-07-06 Luxembourg Institute Of Science And Technology (List) Reinforced composite filament for an additive manufacturing application and method for manufacturing thereof
US12359042B2 (en) 2021-03-22 2025-07-15 Braskem America, Inc. Fiber-blended heterophasic copolymer for additive-manufacture feedstock

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102022120545A1 (en) 2022-08-15 2024-02-15 Technische Universität Dresden, Körperschaft des öffentlichen Rechts METHOD FOR PRODUCING A CFC MOLDED BODY WITH HIGH STIFFNESS AND HIGH TENSILE STRENGTH USING CONTINUOUS 3D PRINTING OF A PRE-CARBON FIBER REINFORCED MATRIX
CN116423826A (en) * 2023-04-25 2023-07-14 华中科技大学 Additive manufacturing method and manufacturing device for complex structure of fiber-reinforced composite material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010033923A1 (en) * 1999-01-22 2001-10-25 Mulder Roger E. Glass fiber mats, laminates reinforced with the same and methods for making the same
US20070082199A1 (en) * 2005-10-11 2007-04-12 Schweizer Robert A Fiber size, sized reinforcements, and articles reinforced with such reinforcements
US20140050921A1 (en) * 2011-12-31 2014-02-20 The Boeing Company Method of reinforcement for additive manufacturing
US20150314531A1 (en) * 2013-03-22 2015-11-05 Markforged, Inc. Methods for composite filament threading in three dimensional printing
US20170259502A1 (en) * 2016-03-10 2017-09-14 Mantis Composites Inc. Additive manufacturing of composite materials

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2376076T3 (en) * 2007-12-21 2012-03-08 Saudi Basic Industries Corporation PROCEDURE TO PRODUCE THERMOPLED COMPOSITIONS REINFORCED STICES WITH LONG GLASS FIBER.
CA3121870A1 (en) * 2013-03-22 2014-09-25 Markforged, Inc. Three dimensional printing
BR112017007431A2 (en) * 2014-10-08 2017-12-19 Ocv Intellectual Capital Llc hybrid long fiber thermoplastic composites
CN107428061A (en) 2015-03-31 2017-12-01 京洛株式会社 Line resin molded body, method for molding three-dimensional object, and method for manufacturing line resin molded body
JP6761567B2 (en) 2015-03-31 2020-09-30 キョーラク株式会社 Manufacturing method of linear resin molded product
JP2016193801A (en) * 2015-03-31 2016-11-17 多木化学株式会社 Method for producing titanium oxide sol doped with niobium and/or tantalum
US9908978B2 (en) * 2015-04-08 2018-03-06 Arevo Inc. Method to manufacture polymer composite materials with nano-fillers for use in additive manufacturing to improve material properties
US11117311B2 (en) 2015-10-05 2021-09-14 Arevo, Inc. Amorphous polyaryletherketone and blends thereof for use in additive manufacturing
WO2017096576A1 (en) * 2015-12-10 2017-06-15 邢皓宇 Stereo
CN109952203B (en) * 2016-06-01 2022-04-01 阿科玛法国公司 Dimensionally stable acrylic alloys for 3D printing
JP6897057B2 (en) * 2016-10-21 2021-06-30 富士フイルムビジネスイノベーション株式会社 Resin composition and resin molded product
EP3775046A1 (en) * 2018-04-06 2021-02-17 Dupont Polymers, Inc. Additive manufacturing compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010033923A1 (en) * 1999-01-22 2001-10-25 Mulder Roger E. Glass fiber mats, laminates reinforced with the same and methods for making the same
US20070082199A1 (en) * 2005-10-11 2007-04-12 Schweizer Robert A Fiber size, sized reinforcements, and articles reinforced with such reinforcements
US20140050921A1 (en) * 2011-12-31 2014-02-20 The Boeing Company Method of reinforcement for additive manufacturing
US20150314531A1 (en) * 2013-03-22 2015-11-05 Markforged, Inc. Methods for composite filament threading in three dimensional printing
US20170259502A1 (en) * 2016-03-10 2017-09-14 Mantis Composites Inc. Additive manufacturing of composite materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3841158A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115803371A (en) * 2020-07-17 2023-03-14 索尔维特殊聚合物美国有限责任公司 Process for producing continuous fiber filaments, continuous fiber filaments and use thereof
US12359042B2 (en) 2021-03-22 2025-07-15 Braskem America, Inc. Fiber-blended heterophasic copolymer for additive-manufacture feedstock
JPWO2022270320A1 (en) * 2021-06-24 2022-12-29
WO2022270320A1 (en) * 2021-06-24 2022-12-29 Dic株式会社 Fiber-reinforced thermoplastic resin filament and fabricated article
JP7294547B2 (en) 2021-06-24 2023-06-20 Dic株式会社 Fiber-reinforced thermoplastic resin filaments and shaped objects
WO2023126391A1 (en) * 2021-12-29 2023-07-06 Luxembourg Institute Of Science And Technology (List) Reinforced composite filament for an additive manufacturing application and method for manufacturing thereof
WO2023126395A1 (en) * 2021-12-29 2023-07-06 Luxembourg Institute Of Science And Technology (List) Reinforced composite filament for an additive manufacturing application and method for manufacturing thereof

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US12122089B2 (en) 2024-10-22
JP2021535004A (en) 2021-12-16

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