WO2017053850A2 - Impression 3d fabrication additive de céramiques perfectionnées - Google Patents

Impression 3d fabrication additive de céramiques perfectionnées Download PDF

Info

Publication number
WO2017053850A2
WO2017053850A2 PCT/US2016/053518 US2016053518W WO2017053850A2 WO 2017053850 A2 WO2017053850 A2 WO 2017053850A2 US 2016053518 W US2016053518 W US 2016053518W WO 2017053850 A2 WO2017053850 A2 WO 2017053850A2
Authority
WO
WIPO (PCT)
Prior art keywords
powder
ceramic
beads
green body
resin
Prior art date
Application number
PCT/US2016/053518
Other languages
English (en)
Other versions
WO2017053850A4 (fr
WO2017053850A3 (fr
Inventor
William Easter
Arnold Hill
Original Assignee
Dynamic Material Systems, 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 Dynamic Material Systems, LLC filed Critical Dynamic Material Systems, LLC
Publication of WO2017053850A2 publication Critical patent/WO2017053850A2/fr
Publication of WO2017053850A3 publication Critical patent/WO2017053850A3/fr
Publication of WO2017053850A4 publication Critical patent/WO2017053850A4/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/10—Formation of a green body
    • B22F10/16—Formation of a green body by embedding the binder within the powder bed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6269—Curing of mixtures
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1026—Alloys containing non-metals starting from a solution or a suspension of (a) compound(s) of at least one of the alloy constituents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/60—Treatment of workpieces or articles after build-up
    • B22F10/64—Treatment of workpieces or articles after build-up by thermal means
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3891—Silicides, e.g. molybdenum disilicide, iron silicide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/424—Carbon black
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/425—Graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5284—Hollow fibers, e.g. nanotubes
    • C04B2235/5288—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6026—Computer aided shaping, e.g. rapid prototyping
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • This invention relates to additive manufacturing, also known as, 3D printing of advanced ceramics, and in particular to methods, processes, systems, devices and apparatus for manufacturing bulk ceramic composites.
  • additive Manufacturing or 3D printing of ceramics or ceramic composites is in its infancy. Due to the high temperature requirements and the difficulties of using bulk ceramic precursors, additive manufacturing of ceramics is not as well developed as the 3D printing of metals and polymers which are easier to cast, mold or machine into various shapes and sizes.
  • Ceramics made with the robocasting technique include traditional ceramics such as alumina, zirconia, silicon nitride, and silicon carbide.
  • Another technology is one that is represented by 3DCeram where high viscosity, ultra violet (UV) light curable materials, in paste form are used.
  • These photocurable resin compounds containing ceramic powders are laid down in a manner such that a laser that is controlled by a 3D CAD file can polymerize the pastes.
  • another ceramic-UV curable paste layer is laid down on top of the previous layer followed by another laser treatment controlled by the 3D CAD file. This process is repeated until the final 3D shape is obtained.
  • the parts are then heat treated for the purpose of debinding the photocurable resin and then sintering the ceramic particles in order to eliminate the resin and densify the ceramic.
  • UV ultraviolet
  • SPPW self-propagating photopolymer wave-guide technology
  • the architecture of the structure is defined by a patterned mask that defines the areas exposed to a collimated UV light source.
  • the printed polymer structure is typically limited to fine features with less than approximately 3 mm in thickness in one dimension. The size limitations of the structure are a drawback.
  • PDCs Polymer Derived Ceramics
  • a primary objective of this invention is to provide methods, processes, systems, devices and apparatus to additively manufacture or 3D print bulk ceramic and ceramic composite components at considerably lower temperatures and shorter manufacturing intervals than the current state of the art.
  • a secondary objective of this invention is to provide methods, processes, systems, devices and apparatus to produce ceramic and ceramic composite material systems which have not been produced before by 3D printing.
  • a third objective of this invention is to provide methods, processes, systems, devices and apparatus to prepare a green body component starting with resin beads mixed with or without metallic powder, layered, deposited in a bed and photocured.
  • a fourth objective of this invention is to provide methods, processes, systems, devices and apparatus to prepare a green body component starting with resin beads wet with a photocurable or thermally curable resin, layered, and cured to form a green body.
  • a fifth objective of this invention is to provide methods, processes, systems, devices and apparatus to prepare a green body component starting with resin beads mixed into a paste or gel, with or without metal powder, carbide powder, ceramic powder, or mixtures thereof, loading the paste or gel into computer controlled syringes, depositing layers of the paste or gel, curing each layer with UV or IR radiation to form a green body.
  • a sixth objective of this invention is to provide methods, processes, systems, devices and apparatus to prepare a ceramic/metallic composite starting with resin beads that are converted to spherical ceramic beads, mixed with an active brazing alloy paste to form a spreadable slurry with or without metal powder, carbide powder, ceramic powder, or mixtures thereof, wherein the spreadable slurry is processed by Selective Laser Melting (SLM) techniques to produce ceramic/metallic composite components.
  • SLM Selective Laser Melting
  • a seventh objective of this invention is to provide methods, processes, systems, devices and apparatus to prepare a ceramic/metallic composite starting with resin beads that are converted to spherical ceramic beads, mixed with pastes made with glass powders to form a spreadable slurry with or without metal powder, carbide powder, ceramic powder, or mixtures thereof, wherein the spreadable slurry is processed by Selective Laser Melting (SLM) techniques to produce ceramic/metallic composite components.
  • SLM Selective Laser Melting
  • manufacturing system wherein the green body is converted to a bulk, monolithic ceramic composite can include the steps of selecting a precursor resin, converting the precursor resin to beads, blending the precursor resin beads with a powder selected from at least one of a metal powder, a carbide powder, a ceramic powder and a mixture thereof, depositing a plurality of layers of the polymer precursor resin and powder blend in a bed, spraying each layer with photocurable or thermally curable resins, heating the layers and the entire bead bed with ultraviolet or infrared radiation to cure the resin mixture and form a finished green body component, removing the finished green body component to a furnace to convert the green body to a ceramic composite having a thickness in a depth dimension in a range between approximately 200 microns and approximately 25 millimeters (mm).
  • the step of depositing of the plurality of layers of the polymer precursor resin and powder blend can be computer controlled.
  • the precursor resin can be selected from one of a liquid resin and a multiple of different precursor resins.
  • the precursor resin can be enhanced with a plurality of enhancement particles selected from the group consisting of a metallic powder, a ceramic powder, graphite powder, graphene powder, diamond powder, carbide powder, silicide powder, nitride powder, oxide powder, graphene, carbon nanofiber, carbon nanotubes, and mixtures thereof.
  • a process for forming a finished green body component, in an additive manufacturing system wherein the green body is converted to a ceramic composite can include the steps of selecting a precursor resin, converting the precursor resin to beads, pre- wetting the precursor resin beads with a photocurable or a thermally curable resin, spreading the pre-wet beads in a plurality of layers, curing the layers or the entire bead bed with computer directed ultraviolet or infrared radiation to cure the resin and form a finished green body component, and removing the finished green body component to a furnace to convert the green body to a ceramic composite.
  • the precursor resin can be selected from one of a liquid resin and a multiple of different precursor resins.
  • the precursor resin can be enhanced with a plurality of enhancement particles selected from the group consisting of a metallic powder, a ceramic powder, graphite powder, graphene powder, diamond powder, carbide powder, silicide powder, nitride powder, oxide powder, graphene, carbon nanofiber, carbon nanotubes, and mixtures thereof.
  • manufacturing system wherein the green body is converted to a ceramic composite can include the steps of selecting a precursor resin, converting the precursor resin to beads, making a paste or gel by mixing the precursor resin beads with a liquid pre-ceramic polymer which is selected from one of a photo curable or a thermally curable polymer, loading the paste or gel into computer controlled syringes which would deposit the paste or gel in a plurality of layers on a build surface in a selected pattern, curing each layer by flooding the build chamber with ultraviolet or infrared radiation to cure the resin paste or gel and form a finished green body component, and removing the finished green body component to a furnace to convert the green body to a ceramic composite.
  • the paste or gel can be further mixed with a powder selected from at least one of a metal powder, a carbide powder, a ceramic powder and a mixture thereof,
  • the precursor resin can be enhanced with a plurality of enhancement particles selected from the group consisting of a metallic powder, a ceramic powder, graphite powder, graphene powder, diamond powder, carbide powder, silicide powder, nitride powder, oxide powder, graphene, carbon nanofiber, carbon nanotubes, and mixtures thereof.
  • manufacturing system wherein the green body is converted to a ceramic composite can include the steps of selecting a precursor resin, converting the precursor resin to beads, processing un-bonded individual pre-ceramic polymer beads in a furnace to convert the beads to a plurality of individual spherical ceramic beads, mixing the spherical ceramic beads with a brazing alloy paste to form a spreadable slurry, processing the spreadable slurry via Selective Laser Melting (SLM) techniques to produce ceramic composite components.
  • the precursor resin can be selected from one of a liquid resin and a multiple of different precursor resins.
  • the precursor resin can be enhanced with a plurality of enhancement particles selected from the group consisting of a metallic powder, a ceramic powder, graphite powder, graphene powder, diamond powder, carbide powder, silicide powder, nitride powder, oxide powder, graphene, carbon nanofiber, carbon nanotubes, and mixtures thereof.
  • the spreadable slurry of brazing alloy and spherical ceramic beads can be further mixed with a powder selected from at least one of a metal powder, a carbide powder, a ceramic powder and a mixture thereof.
  • the processing of the spreadable slurry with Selective Laser Melting (SLM) can produce ceramic-metallic composite components.
  • manufacturing system wherein the green body is converted to a ceramic composite can comprise the steps of selecting a precursor resin, converting the precursor resin to beads, processing un-bonded individual pre-ceramic polymer beads in a furnace to convert the beads to a plurality of individual spherical ceramic beads, mixing the spherical ceramic beads with a glass powder paste to form a spreadable slurry, and processing the spreadable slurry via Selective Laser Melting (SLM) techniques to melt the glass paste, which, on cooling, produces ceramic composite components.
  • SLM Selective Laser Melting
  • the precursor resin can be selected from one of a liquid resin and a multiple of different precursor resins.
  • the precursor resin can be enhanced with a plurality of enhancement particles selected from the group consisting of a metallic powder, a ceramic powder, graphite powder, graphene powder, diamond powder, carbide powder, silicide powder, nitride powder, oxide powder, graphene, carbon nanofiber, carbon nanotubes, and mixtures thereof.
  • the spreadable slurry of glass powder paste and spherical ceramic beads can be further mixed with a powder selected from at least one of a metal powder, a carbide powder, a ceramic powder and a mixture thereof.
  • the processing of the spreadable slurry with Selective Laser Melting (SLM) can produce ceramic-glass composite components.
  • FIG. 1 is a flow chart of the process for preparing a green body component starting with resin beads mixed with or without metallic powder, carbide powder or ceramic powder, layered, deposited in a bed, sprayed with photocurable or thermally curable PDC resins and photocured to form a finished green body component.
  • FIG. 2 is a flow chart of a simplified process of Fig. 1 starting with resin beads, wet with a photocurable or thermally curable PDC resin, layered and cured to form a green body.
  • FIG. 3 is a flow chart of a process that requires mixing resin beads with liquid pre- ceramic polymers to make a paste or gel with or without metal powder, carbide powder, ceramic powder, or mixtures thereof, loading the paste or gel into computer controlled syringes, depositing layers of the paste or gel, curing each layer with UV or IR radiation to form a green body.
  • FIG. 3 is a flow chart of a process that requires mixing resin beads with liquid pre- ceramic polymers to make a paste or gel with or without metal powder, carbide powder, ceramic powder, or mixtures thereof, loading the paste or gel into computer controlled syringes, depositing layers of the paste or gel, curing each layer with UV or IR radiation to form a green body.
  • SLM Selective Laser Melting
  • FIG. 5 is a flow chart of a process for preparing a ceramic/metallic composite starting with resin beads that are converted to spherical ceramic beads, mixed with a paste made from glass powders to form a spreadable slurry with or without metal powder, carbide powder, ceramic powder, or mixtures thereof, wherein the spreadable slurry is processed by Selective Laser Melting (SLM) techniques to produce ceramic/metallic composite components.
  • SLM Selective Laser Melting
  • the term “enhancement particles” is used herein to refer to functional materials that are on the inside or outside of the polymer resin beads used herein.
  • the functional materials include, but are not limited to, at least one of a metallic powder, a ceramic powder, graphite powder, graphene powder, diamond powder, carbide powder, silicide powder, nitride powder, oxide powder, graphene, carbon nanofibers, carbon nanotubes, and mixtures thereof.
  • polymer resin beads are used interchangeably herein to mean polymeric ceramic precursor resin formed in a spherical shape by processes such as, an emulsion process or a spraying process that forms spherical droplets as disclosed in commonly owned U. S. Patent 8,961,840 to Hill et al. and commonly owned U.S. Patent Application Serial No. 14/858,096 filed September 24, 2015 to Hill et al. which claims the benefit of priority to U.S. Provisional Patent Application Serial No. 62/053,479 filed September 22, 2014. The entire disclosure of each of the applications listed in this paragraph are incorporated herein by specific reference thereto.
  • 3D printing is three-dimensional printing and is also known as additive
  • AM additive manufacturing
  • 3D CAD stands for three-dimensional Computer- Aided Design and refers to software to manipulate data as a digital information source to create three-dimensional objects.
  • IR infrared light which is a form of electromagnetic radiation that is invisible to the eye and in the wave length range between 100 and 400 nanometers (nm).
  • UV stands for ultraviolet light which is electromagnetic radiation that is invisible to the eye and in the wave length range between 800 nm to 1mm.
  • bulk ceramic is used to describe solid, monolithic, fully continuous, thick ceramic structures or objects that are defined by height, width and depth dimensions.
  • PDC Polymer derived ceramics wherein polymers are converted into ceramics upon heat treatment.
  • SLM Selected Laser Melting which is an additive manufacturing process that uses 3D CAD data as a digital information source and energy in the form of a high-power laser beam, to create three-dimensional objects.
  • Selective laser melting fully melts the metal into a solid homogeneous mass, unlike selective laser sintering (SLS) which involves binding and fusing parts to create a structure.
  • the techniques disclosed reduce manufacturing intervals, reduce manufacturing costs and produce ceramic and ceramic composite material systems which have not been produced before by 3D printing.
  • One of the inventive steps of the present invention is the use of the polymer beads in manufacturing techniques to form a network of porosity that eliminates the destructive effect of out-gassing when processing the layered build-up of the 3D structure.
  • the network of porosity formed by the spherical polymer beads allows non-destructive, non-disruptive gas release during the curing of the ceramic green body by heating, laser, UV or IR radiation.
  • the resulting ceramic composite is a commercially desirable solid, monolithic, bulk ceramic composite structure.
  • the precursor polymer beads are pyrolyzed to form spherical ceramic beads before mixing with a brazing alloy paste or a glass paste. Therefore, no outgassing occurs after the beads have been pyrolyzed.
  • the mixtures of beads and paste are arranged in layers and each layer is fused by selectively melting the metallic paste or glass paste in the mixture. The laser energy is intense enough to permit full melting of the particles to form solid metal or glass. The melting process is repeated layer after layer until the part is complete. Commercially desirable solid, monolithic bulk ceramic composite structures are produced.
  • Provisional Patent Application Serial No. 62/053,479 provides for the manufacture of a fully dense polymer derived ceramic particle with enhancement particles attached to or incorporated within the structure of the particle to provide unique sizes, compositions, mechanical and chemical properties of the preceramic polymer beads.
  • the enhancement particles that may be inside or outside the beads include, but are not limited to, functional materials selected from at least one of a metallic powder, a ceramic powder, graphite powder, graphene powder, diamond powder, carbide powder, silicide powder, nitride powder, oxide powder, carbon nanotubes, and mixtures thereof.
  • Objects can be of almost any shape or geometry that can be accommodated by the 3D printing process.
  • the three-dimensional ceramic structure provided by the present invention wherein the finished green body component is put in a furnace to convert it to a ceramic piece, the resulting ceramic structure is a solid, monolithic piece having a minimum thickness of approximately 200 microns. If the object has a cube shape, the dimensions are approximately 200 microns in height, approximately 200 microns in width and
  • the maximum thickness is approximately 25 millimeters (mm)
  • the maximum height is approximately 1000 millimeters (mm)
  • the maximum width is approximately 1000 millimeters (mm).
  • the size of the monolithic, solid structure produced is only limited by the size of the 3D printer.
  • a solid cube could have the dimensions of approximately 1000 mm x 1000 mm x 1000 mm. This is possible because there is no need for a furnace.
  • the bulk ceramic structures of the present invention can have a three- dimensional size wherein the height is between approximately 200 microns and
  • each monolithic piece is limited by the size of the inkjet printer head and when pyrolysis in a furnace is required, the size of the furnace limits the size of the bulk ceramic piece.
  • Polymer beads in layers with binder material applied to each layer Polymer beads in layers with binder material applied to each layer.
  • one or multiple different precursor resins 100 are processed to form beads 110, then individual versions of or blends of various beads 120 are mixed with or without enhancement particles, such as, metal powder, carbide powder, ceramic powder and mixtures thereof 130.
  • the beads with or without the powder are spread in alternating layers of or laterally spaced zones of different versions 140 of these polymer resin beads.
  • beads with or without the powder can be spread in non-alternating layers or non-laterally spaced zones 145 of different versions of the beads.
  • the polymer beads are deposited in a bed 150 one layer at a time.
  • metal powders, carbide powders or ceramic powders are blended into the bead layers.
  • the layers are then sprayed 160 with a photocurable or thermally curable liquid ceramic precursor resin made from one or multiple different ceramic precursor resins. That is to say multiple spray heads are used to spray multiple different ceramic precursor resins in different areas of the bead bed.
  • the patterns sprayed onto the bead bed are controlled by the 3D CAD files of the parts to be produced.
  • the liquid resin is cured with computer directed UV or IR radiation or alternately the entire bead bed is heated 170 and if the sprayed resins are made thermally curable they will solidify on contact or soon after contact with the hot beads.
  • the result of curing the resin is to bond the individual beads together and to bond each new layer to the previous layer.
  • Polymer beads pre-wet with photocurable or thermally curable resins.
  • FIG. 2 is a simpler iteration of the process in FIG. 1.
  • One or multiple different precursor resins 200 are processed to form beads 210. If all of the beads with or without enhancement particles are of the same type or same homogenous blend of types 220, all of the beads could be pre-wetted with photocurable or thermally curable resins 230 and spread out in layers 240 and cured by computer directed ultraviolet (UV) light or infrared (IR) light radiation to create the appropriate pattern of cured green body 250.
  • UV ultraviolet
  • IR infrared
  • Polymer beads in a paste or gel deposited layer by layer to build a structure Polymer beads in a paste or gel deposited layer by layer to build a structure.
  • one or multiple different precursor resins 300 are processed to form preceramic polymer beads 310 as described in FIG. 1.
  • Individual versions or blend versions of beads 320 are made into a gel or paste 330 by mixing the beads with liquid preceramic polymers which are either photocurable or thermally curable.
  • enhancement particles such as, metal powders, carbide powders or ceramic powders can be blended into the paste or gel 340.
  • the paste or gel is then loaded into computer controlled syringes 350 which would deposit the paste or gel in layer fashion on a build surface in the desired patterns.
  • Each gel layer is photocured or thermally cured by flooding the build chamber with UV light or IR light radiation or heating the build chamber 360.
  • Polymer beads converted to spherical ceramic beads mixed with brazing alloy pastes The flow chart in FIG. 4 shows that one or multiple different precursor resins 400 are formed into beads 410, then the individual versions or blend versions of beads 420 are processed to form spherical ceramic beads 430 by firing in a furnace a quantity of un- bonded individual preceramic polymer beads that are described in FIG. 1 and U. S. Patent 8,961,840. Then individual spherical ceramic beads are mixed with enhancement particles and commercially available "active" brazing alloy pastes 440 to form a spreadable slurry. The slurries can also be mixed with metal powders, carbide powders or ceramic powders 450. The slurry with spherical ceramic beads is then processed via Selective Laser Melting (SLM) techniques to produce ceramic/metallic composite components 460.
  • SLM Selective Laser Melting
  • the brazing alloy pastes can be blended with a thermally or photocurable agent then mixed with the ceramic beads to produce a slurry that is processed to form a finished green body ceramic component that is pyrolyzed in a furnace to convert the green body to a monolithic ceramic via heat treatment.
  • the size of the ceramic structure will be limited by the size of the furnace available for pyrolysis; the furnace will melt the brazing alloy producing the ceramic-metallic composite.
  • Polymer beads converted to spherical ceramic beads mixed with glass powder pastes The process shown in FIG. 5 is similar to the process in FIG. 4 in that one or multiple different precursor resins 500 are formed into beads 510, then the individual versions or blend versions of beads 520 are processed to form spherical ceramic beads 530 by firing a quantity of un-bonded ceramic beads in a furnace.
  • pastes made with glass powders 540 are mixed enhancement particles and with the spherical ceramic beads 530 to make the slurries.
  • the slurries may also contain metal powders, carbide powders or ceramic powders 550.
  • the laser melts the glass paste which upon cooling, bonds the ceramic beads and, if present, the metal, carbide, and ceramic powders together forming a ceramic/metallic composite component 560.
  • SLM Selective Laser Melting
  • the glass pastes can be blended with a thermally or photocurable agent then mixed with the ceramic beads to produce a slurry that is processed to form a finished green body ceramic component that is pyrolyzed in a furnace to convert to ceramic.
  • the size of the ceramic structure will be limited by the size of the furnace available for pyrolysis, the furnace will melt the glass paste to produce the ceramic-glass composite.
  • the present invention solves the problem of making strong, durable quality, monolithic, bulk ceramic structures.
  • ceramic 3D structures Prior to this invention, ceramic 3D structures were considered too brittle and prone to breaking.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Producing Shaped Articles From Materials (AREA)

Abstract

L'invention concerne des procédés, des processus, des systèmes, des dispositifs et des appareils destinés à la fabrication additive entraînant l'impression 3D de nouveaux composites céramiques. La fabrication additive ou l'impression 3D de céramique en vrac et d'éléments composites céramiques se produit à température considérablement plus basse et pendant des intervalles de fabrication plus courts que dans l'état actuel de la technique. Les procédés, les processus, les systèmes, les dispositifs et les appareils et la sélection des résines précurseurs produisent des céramiques et des systèmes de matériaux composites céramiques n'ayant jamais été produits auparavant par impression 3D.
PCT/US2016/053518 2015-09-24 2016-09-23 Impression 3d fabrication additive de céramiques perfectionnées WO2017053850A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201562232033P 2015-09-24 2015-09-24
US62/232,033 2015-09-24

Publications (3)

Publication Number Publication Date
WO2017053850A2 true WO2017053850A2 (fr) 2017-03-30
WO2017053850A3 WO2017053850A3 (fr) 2017-07-20
WO2017053850A4 WO2017053850A4 (fr) 2018-05-11

Family

ID=58387497

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2016/053518 WO2017053850A2 (fr) 2015-09-24 2016-09-23 Impression 3d fabrication additive de céramiques perfectionnées

Country Status (1)

Country Link
WO (1) WO2017053850A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021096904A1 (fr) * 2019-11-15 2021-05-20 Hasbro, Inc. Fabrication de figurine-jouet
CN115403390A (zh) * 2022-09-20 2022-11-29 吉林大学 一种利用高固含量/低透光度碳基浆料通过光固化3d打印制备多孔碳骨架的方法
CN116947524A (zh) * 2023-09-20 2023-10-27 华侨大学 陶瓷结合剂细粒度金刚石蜂窝磨块的激光固化成形方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5204124A (en) * 1990-10-09 1993-04-20 Stanley Secretan Continuous extruded bead object fabrication apparatus
US20050023710A1 (en) * 1998-07-10 2005-02-03 Dmitri Brodkin Solid free-form fabrication methods for the production of dental restorations
US7658603B2 (en) * 2005-03-31 2010-02-09 Board Of Regents, The University Of Texas System Methods and systems for integrating fluid dispensing technology with stereolithography
CN102009175B (zh) * 2010-10-08 2013-08-21 李亚东 一种多层壳芯复合结构零件的制备方法
WO2015023612A2 (fr) * 2013-08-15 2015-02-19 Oxane Materials, Inc. Fabrication d'additifs d'agent de soutènement

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021096904A1 (fr) * 2019-11-15 2021-05-20 Hasbro, Inc. Fabrication de figurine-jouet
CN115403390A (zh) * 2022-09-20 2022-11-29 吉林大学 一种利用高固含量/低透光度碳基浆料通过光固化3d打印制备多孔碳骨架的方法
CN116947524A (zh) * 2023-09-20 2023-10-27 华侨大学 陶瓷结合剂细粒度金刚石蜂窝磨块的激光固化成形方法
CN116947524B (zh) * 2023-09-20 2023-12-22 华侨大学 陶瓷结合剂细粒度金刚石蜂窝磨块的激光固化成形方法

Also Published As

Publication number Publication date
WO2017053850A4 (fr) 2018-05-11
WO2017053850A3 (fr) 2017-07-20

Similar Documents

Publication Publication Date Title
US9944021B2 (en) Additive manufacturing 3D printing of advanced ceramics
Moritz et al. Additive manufacturing of ceramic components
Wang et al. Review of additive manufacturing methods for high-performance ceramic materials
Lakhdar et al. Additive manufacturing of advanced ceramic materials
Deckers et al. Additive manufacturing of ceramics: A review
Zocca et al. Additive manufacturing of ceramics: issues, potentialities, and opportunities
Miyanaji et al. Process development for green part printing using binder jetting additive manufacturing
Colombo et al. Additive manufacturing techniques for fabricating complex ceramic components from preceramic polymers
Pelz et al. Additive manufacturing of structural ceramics: a historical perspective
Travitzky et al. Additive manufacturing of ceramic‐based materials
Liu et al. Indirect selective laser sintering of epoxy resin-Al2O3 ceramic powders combined with cold isostatic pressing
Bai et al. Stereolithography additive manufacturing and sintering approaches of SiC ceramics
US11883978B2 (en) In situ synthesis, densification and shaping of non-oxide ceramics by vacuum additive manufacturing technologies
Yeong et al. State-of-the-art review on selective laser melting of ceramics
Dadkhah et al. Additive manufacturing of ceramics: Advances, challenges, and outlook
Dong et al. Additive manufacturing of silicon nitride ceramics: A review of advances and perspectives
CN106270490B (zh) 表层为TiC-Ni-10TaC-10Mo2C金属陶瓷层的硬质合金及其制备方法
WO2017053850A2 (fr) Impression 3d fabrication additive de céramiques perfectionnées
CN109128164A (zh) 一种硬质合金零件的制造方法
CN112088148A (zh) 用于增材制造技术的陶瓷浆料
Moghadasi et al. Combining powder bed compaction and nanopowders to improve density in ceramic binder jetting additive manufacturing
Tang Direct laser fusing to form ceramic parts
Feng et al. Preparation of low residual silicon content Si-SiC ceramics by binder jetting additive manufacturing and liquid silicon infiltration
JP7201401B2 (ja) 粉末積層造形に用いるための粉末材料、これを用いた粉末積層造形法および造形物
Bala et al. A review on binder jetting fabrication: Materials, characterizations and challenges

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16849787

Country of ref document: EP

Kind code of ref document: A2