Fused filament fabrication using multi-segment filament

• US 10,611,098 B2
• Filed: 01/17/2015
• Issued: 04/07/2020
• Est. Priority Date: 01/17/2014
• Status: Active Grant

• Current Assignee: G6 Materials Corp.
• Original Assignee: G6 Materials Corp.
• Inventors: Stolyarov, Daniel, Polyakova, Elena
• Primary Examiner(s): Thompson, Camie S
• Application Number:
  US15/112,098
• Publication Number:
  US 20160339633A1
• Time in Patent Office: 1,907 Days
• Field of Search: 428364, 428114, 4281951, 428212, 428297, 428375, 700 98, 1563041, 156167, 156175
• CPC Class Codes: B29C 2948/92571 Position, e.g. linear or angular
• CPC Class Codes: B29C 2948/9258 Velocity
• CPC Class Codes: B29C 48/02 Small extruding apparatus, e.g. handheld, toy or laboratory extruders
• CPC Class Codes: B29C 48/05 Filamentary, e.g. strands
• CPC Class Codes: B29C 48/2665 allowing small relative movement, e.g. adjustments for aligning the apparatus parts or for compensating for thermal expansion
• CPC Class Codes: B29C 48/865 Heating
• CPC Class Codes: B29C 48/92 Measuring, controlling or regulating
• CPC Class Codes: B29C 64/106 using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
• CPC Class Codes: B29C 64/118 using filamentary material being melted, e.g. fused deposition modelling [FDM]
• CPC Class Codes: B29C 64/20 Apparatus for additive manufacturing; Details thereof or accessories therefor
• CPC Class Codes: B29C 64/209 Heads; Nozzles
• CPC Class Codes: B29K 2023/04 Polymers of ethylene
• CPC Class Codes: B29K 2025/08 Copolymers of styrene, e.g. AS or SAN, i.e. acrylonitrile styrene B29K2055/02 takes precedence
• CPC Class Codes: B29L 2009/00 Layered products
• CPC Class Codes: B33Y 10/00 Processes of additive manufacturing
• CPC Class Codes: B33Y 30/00 Apparatus for additive manufacturing; Details thereof or accessories therefor
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing

Abstract

A thermoplastic filament adapted for use in a fused filament fabrication (FFF) printer which has a plurality of segments wherein each pair of adjacent segments is compositionally different and is arranged in a specific order. Also, a method for printing a three-dimensional (3D) article by printing such a filament in a fused filament fabrication (FFF) printer, wherein the fused filament fabrication (FFF) printer carries out a pattern of printing synchronized with the order of the segments in such a filament. Further, a method and device for fabricating such thermoplastic filaments.

Claims

1. An article comprising a thermoplastic filament adapted for a fused filament fabrication (FFF) printer, the filament comprising:

a plurality of segments, each of the segments comprising a thermoplastic polymer;

wherein for each pair of adjacent segments, one of the adjacent segments comprises a polymer matrix without functional materials being present, the other of the adjacent segments comprises a polymer with functional materials being present, the functional materials being one or more of electrically conductive materials or semiconductive materials;

wherein the plurality of segments are arranged in a specified order in the filament to provide a synchronized pattern of printing when the filament is printed with a fused filament fabrication (FFF) printer to form a three-dimensional structure comprising electronic circuitry formed from the functional materials.

2. The article of claim 1, wherein each pair of adjacent segments have differences in appearance which are one or more of differences in color, shape, opacity, transparency, translucency, or fluorescence.

3. The article of claim 2, wherein the at least one difference in appearance is as difference in color of each pair of adjacent segments.

4. The article of claim 1, wherein the adjacent segment without functional materials being present includes polymer matrix structural materials.

5. The article of claim 1, wherein the thermoplastic filament is provided with indicia which identify one or more of segment composition, segment length or segment order.

6. The article of claim 5, wherein the indicia identify the segment composition, segment length, and segment order of the thermoplastic filament.

7. The article of claim 6, wherein the indicia comprise one or more marks on the thermoplastic filament.

8. The article of claim 1, wherein the functional materials are one or more of graphene;

functionalized graphene;

graphene oxide;

partially reduced graphene oxide;

molybdenum disulfide;

molybdenum diselenide;

molybdenum ditelluride;

tungsten disulfide;

tungsten diselenide;

hexagonal boron nitride;

gallium sulfide;

gallium selenide;

lanthanum cuprate;

bismuth tritelluride;

bismuth triselenide;

antimony triselenide;

zinc oxide;

niobium disulfide;

niobium diselenide;

tantalum disulfide;

vanadium disulfide;

rhenium disulfide;

rhenium diselenide;

titanium disulfide;

titanium diselenide;

indium trisulfide;

zirconium disulfide;

zirconium diselenide;

or cadmium selenide.

9. The article of claim 1, wherein the functional materials are one or more of graphene nanoplatelets;

inorganic nanotubes;

molybdenum disulfide flakes;

tungsten disulfides flakes;

or boron nitride flakes.

10. The article of claim 1, wherein the polymer matrix structural materials comprise carbon fibers, and wherein the functional materials are other than carbon fibers.

11. The article of claim 1, wherein the thermoplastic polymer is one or more of acrylate polymers;

methylmethacrylate polymers;

copolymers of acrylate and methylmethacrylate;

polylactic acid polymers;

polyhydroxyalkanoate polymers;

polycaprolactone polymers;

polyglycolic acid polymers;

acrylonitrile-butadiene-styrene polymers;

polyvinylidene fluoride polymers;

polyurethane polymers;

polyolefin polymers;

polyester polymers;

polyalkylene oxide polymers;

polyvinyl alcohol polymers;

polyamide polymers;

polycarbonate polymers;

high impact polystyrene polymers;

or polyurethane polymers.

12. The article of claim 11, wherein the thermoplastic polymer is one or more of:

acrylonitrile-butadiene-styrene polymers;

or polyethylene oxide (PEO) polymers.

13. The article of claim 11, wherein the thermoplastic polymer is water-soluble.

14. An article comprising a thermoplastic filament adapted for a fused filament fabrication (FFF) printer, the filament comprising:

a plurality of segments, each of the segments comprising a thermoplastic polymer which is one or more of acrylate polymers;

methylmethacrylate polymers;

copolymers of acrylate and methylmethacrylate;

polylactic acid polymers;

polyhydroxyalkanoate polymers;

polycaprolactone polymers;

polyglycolic acid polymers;

acrylonitrile-butadiene-styrene polymers;

polyvinylidene fluoride polymers;

polyurethane polymers;

polyolefin polymers;

polyester polymers;

polyalkylene oxide polymers;

polyvinyl alcohol polymers;

polyamide polymers;

polycarbonate polymers;

high impact polystyrene polymers;

or polyurethane polymers;

wherein for each pair of adjacent segments, one of the adjacent segments comprises a polymer matrix without functional materials being present, and the other of the adjacent segments comprises a polymer matrix with functional materials being present, the functional materials being one or more electrically conductive or semiconductive graphene materials;

wherein the plurality of segments are arranged in a specified order in the filament to provide a synchronized pattern of printing when the filament is printed with a fused filament fabrication (FFF) printer to form a three-dimensional device comprising electronic circuitry formed from the electrically conductive or semiconductive materials materials.

15. The article of claim 14, wherein the electrically conductive or semiconductive materials materials are one or more of graphene;

functionalized graphene;

graphene oxide;

partially reduced graphene oxide;

graphite flakes;

molybdenum disulfide;

molybdenum diselenide;

molybdenum ditelluride;

tungsten disulfide;

tungsten diselenide;

hexagonal boron nitride;

gallium sulfide;

gallium selenide;

lanthanum cuprate;

bismuth tritelluride;

bismuth triselenide;

antimony triselenide;

zinc oxide;

niobium disulfide;

niobium diselenide;

tantalum disulfide;

vanadium disulfide;

rhenium disulfide;

rhenium diselenide;

titanium disulfide;

titanium diselenide;

indium trisulfide;

zirconium disulfide;

zirconium diselenide;

or cadmium selenide.

16. The article of claim 14, wherein the electrically conductive or semiconductive materials materials are one or more of graphene nanoplatelets;

carbon nanotubes;

inorganic nanotubes;

molybdenum disulfide flakes;

tungsten disulfides flakes;

boron nitride flakes;

carbon black;

or fullerenes.

17. The article of claim 14, wherein the electrically conductive or semiconductive materials materials are one or more of graphene nanoplatelets;

inorganic nanotubes;

molybdenum disulfide flakes;

tungsten disulfides flakes;

or boron nitride flakes.

18. The article of claim 14, wherein each pair of adjacent segments have differences in appearance which are one or more of differences in color, shape, opacity, transparency, translucency, or fluorescence.

19. The article of claim 18, wherein the at least one difference in appearance is as difference in color of each pair of adjacent segments.

20. The article of claim 14, wherein the adjacent segment without functional materials being present includes polymer matrix structural materials.

21. The article of claim 20, wherein the polymer matrix structural materials comprise carbon fibers, and wherein the functional materials are other than carbon fibers.

22. The article of claim 14, wherein the thermoplastic filament is provided with indicia which identify one or more of segment composition, segment length or segment order.

23. The article of claim 22, wherein the indicia identify the segment composition, segment length, and segment order of the thermoplastic filament.

24. The article of claim 23, wherein the indicia comprise one or more marks on the thermoplastic filament.

25. The article of claim 14, wherein the thermoplastic polymer is one or more of acrylonitrile-butadiene-styrene polymers or polyethylene oxide (PEO) polymers.

26. The article of claim 14, wherein the thermoplastic polymer is water-soluble.