WO2006080936A1 - Corps composites contenant des nanotubes et leurs procedes de fabrication - Google Patents

Corps composites contenant des nanotubes et leurs procedes de fabrication Download PDF

Info

Publication number
WO2006080936A1
WO2006080936A1 PCT/US2005/014275 US2005014275W WO2006080936A1 WO 2006080936 A1 WO2006080936 A1 WO 2006080936A1 US 2005014275 W US2005014275 W US 2005014275W WO 2006080936 A1 WO2006080936 A1 WO 2006080936A1
Authority
WO
WIPO (PCT)
Prior art keywords
nanotubes
carbon
composite body
silicon
composite
Prior art date
Application number
PCT/US2005/014275
Other languages
English (en)
Inventor
Prashant G. Karandikar
Original Assignee
M Cubed Technologies
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
Priority claimed from US10/832,823 external-priority patent/US20050181209A1/en
Application filed by M Cubed Technologies filed Critical M Cubed Technologies
Publication of WO2006080936A1 publication Critical patent/WO2006080936A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/111—Fine ceramics
    • C04B35/117—Composites
    • 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
    • C04B35/56—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 carbides or oxycarbides
    • C04B35/563—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 carbides or oxycarbides based on boron carbide
    • 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
    • C04B35/56—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 carbides or oxycarbides
    • C04B35/565—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 carbides or oxycarbides based on silicon carbide
    • 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
    • C04B35/56—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 carbides or oxycarbides
    • C04B35/565—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 carbides or oxycarbides based on silicon carbide
    • C04B35/573—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 carbides or oxycarbides based on silicon carbide obtained by reaction sintering or recrystallisation
    • 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
    • C04B35/58—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/5805—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
    • C04B35/58064—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
    • C04B35/58071—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides based on titanium borides
    • 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
    • C04B35/58—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon 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
    • 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
    • C04B35/6261—Milling
    • 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
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62844—Coating fibres
    • C04B35/62857—Coating fibres with non-oxide ceramics
    • C04B35/6286—Carbides
    • C04B35/62863—Silicon carbide
    • 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
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62844—Coating fibres
    • C04B35/62857—Coating fibres with non-oxide ceramics
    • C04B35/62873—Carbon
    • 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
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • 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
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • C04B35/83—Carbon fibres in a carbon matrix
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • 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
    • C04B2235/3804—Borides
    • C04B2235/3813—Refractory metal borides
    • 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
    • C04B2235/3821—Boron 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
    • C04B2235/3817—Carbides
    • C04B2235/3826—Silicon 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
    • C04B2235/3873—Silicon nitrides, e.g. silicon carbonitride, silicon oxynitride
    • 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
    • C04B2235/402—Aluminium
    • 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
    • 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
    • C04B2235/428—Silicon
    • 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
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • 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
    • C04B2235/5208—Fibers
    • C04B2235/5216—Inorganic
    • C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
    • C04B2235/5244—Silicon carbide
    • 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
    • C04B2235/5208—Fibers
    • C04B2235/5216—Inorganic
    • C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
    • C04B2235/5248—Carbon, e.g. 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
    • C04B2235/5208—Fibers
    • C04B2235/5264—Fibers characterised by the diameter of the fibers
    • 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
    • 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
    • C04B2235/02—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
    • C04B2235/54—Particle size related information
    • C04B2235/5463—Particle size distributions
    • C04B2235/5472—Bimodal, multi-modal or multi-fraction
    • 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
    • C04B2235/604—Pressing at temperatures other than sintering temperatures
    • 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
    • C04B2235/616—Liquid infiltration of green bodies or pre-forms
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C22C2026/002—Carbon nanotubes
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity

Definitions

  • the present invention relates to metal and/or ceramic containing composite materials featuring a particular kind of fibrous reinforcement.
  • the invention relates to composites having a matrix featuring metal, ceramic and/or polymer, and being reinforced with nanotubes, and preferably carbon nanotubes.
  • Carbon fibers can be manufactured with high degrees of anisotropy.
  • the graphite form of carbon in particular features a hexagonal crystallographic structure, with the covalent bonds within the ⁇ 001 ⁇ planes being strong, and the bonds between the ⁇ 001 ⁇ planes consisting of weak van der Waals bonds. It is possible to preferentially align the crystallographic planes in a graphite fiber such that the ⁇ 001 ⁇ planes tend to be parallel to the graphite fiber axis. By increasing the relative amount of covalent bonds in the fiber axis direction, a fiber possessing high strength and high elastic modulus in the direction of the fiber axis is produced.
  • U.S. Patent No. 3,807,996 to Sara teaches a carbon fiber reinforced nickel matrix composite material. Sara discloses the use of high strength, high modulus carbon fibers, as well as various geometrical arrangements of the fibers, such as arrays (plates) of parallel fibers and cross-plies (laminates) of such arrays.
  • U.S. Patent No. 4,791,076 Leggett et al. discloses a graphite fiber/silica matrix composite composition having a near-zero overall CTE.
  • the matrix contains boron phosphate and beta-spodumene, and Leggett states that the composite CTE is tailorable between -1 and +1 ppm/K by varying the matrix composition.
  • This glass matrix composite material exhibited much less thermal distortion than did other laser mirror materials such as single crystal molybdenum or silicon.
  • glass matrix composites have been used in environments where low expansion polymer composites would be insufficiently durable. Many of these applications, however, require high thermal conductivity, and most glasses are deficient in this area. Thus, composites workers have attempted to address the thermal conductivity problem by relying on the carbon fibers to carry this responsibility, the carbon fibers possessing relatively high thermal conductivity in the fiber axis direction. Another problem with glass matrix composites, though, is that they tend to be brittle. In many applications in which such composites are subjected to accelerations and stresses, such as with semiconductor fabrication equipment, it would be preferable to have a tougher, more impact resistant material.
  • Silicon carbide composites have been produced by reactive infiltration techniques for more than thirty-five years.
  • a reactive infiltration process comprises contacting molten silicon with a porous mass containing silicon carbide plus carbon in a vacuum or an inert atmosphere environment.
  • a wetting condition is created, with the result that the molten silicon is pulled by capillary action into the mass, where it reacts with the carbon to form additional silicon carbide.
  • This in-situ silicon carbide typically is interconnected.
  • a dense body usually is desired, so the process typically occurs in the presence of excess silicon.
  • the resulting composite body thus comprises silicon carbide and unreacted silicon (which typically also is interconnected), and may be referred to in shorthand notation as Si/SiC or RBSC (denoting "reaction-bonded silicon carbide").
  • Heyroth U.S. Patent No. 2,431,326 subjected a carbon body, in which at least a substantial portion of the carbon formed a continuous skeletal structure, to the action of elemental silicon at a temperature well above the melting point of silicon.
  • the silicon rapidly infiltrated the whole carbon body.
  • it reacted with the carbon to form a body featuring a continuous, reticular, skeletal body of crystalline silicon carbide, with the interstices of the silicon carbide skeletal structure substantially filled with silicon-rich material.
  • Popper U.S. Patent No. 3,275,722 produced a self-bonded silicon carbide body by infiltrating silicon into a porous mass of silicon carbide particulates and powdered graphite in vacuo at a temperature in the range of 1800 to 2300 0 C.
  • the infiltrant metal used to make a reaction-formed silicon carbide body so that the metal phase of the formed body includes a constituent other than silicon.
  • the infiltrant may comprise an alloy of silicon and aluminum to yield a phase in the formed silicon carbide body comprising metallic aluminum or aluminum plus silicon.
  • Such bodies containing an alloy infiltrant phase advantageously permit certain properties of the body to be tailored to meet specific needs. For example, by replacing some of the residual silicon infiltrant with aluminum, the thermal conductivity and the fracture toughness of the composite body each may be increased.
  • reaction-bonded SiC composite suitable for braking applications, e.g., disk and pad, for motor vehicles, consisting of carbon fibers arranged isotropically and embedded in a matrix of 40-50 volume percent SiC and not more than 15 volume percent Si.
  • U.S. Patent No.6,030,913 to Heine discloses a similar technology.
  • the long or short high-strength graphite fibers are impregnated or coated with synthetic resin to form a prepreg, which is then carbonized.
  • the carbonized prepreg is then re-subjected to further resin infiltration, and recarbonization, followed by graphitization, which is then followed by comminution to yield a dry material, which is then mixed with a high carbon content binder and compression molded to form a green article.
  • the green article is then carbonized once more, and then infiltrated with molten silicon.
  • the formed composite body features a matrix substantially consisting of SiC, and being reinforce with short graphite fibers.
  • the fibers are enclosed by at least two shells of graphitized carbon, the outermost shell being partially converted into SiC.
  • U.S. Patent No. 4,944,904 to Singh et al. discloses a similar composite material system intended mostly for high temperature, aerospace applications, such as a turbine engine component, but also mentioning applications such as wear parts and acoustic parts.
  • the matrix comprises at least 5 volume percent SiC but preferably at least 45 percent, and 1-30 volume percent Si but preferably 1-2 percent.
  • the fibers may be carbon or SiC, but are not disclosed as being arranged isotropically or quasi-isotropically.
  • the fibers are protected from attack by the molten silicon using boron nitride plus an overcoat of a silicon- wettable material such as carbon or metal carbides such as SiC.
  • the BN also provides a debond layer so that the fibers can move relative to the matrix under mechanical loading, thereby providing a toughening aspect to the resulting composite body.
  • Nanomaterials such as carbon nanotubes, sometimes abbreviated as "CNTs", are relatively new materials that have attracted the attention of materials investigators, in part due to the potential for achieving extremes of properties.
  • CNTs carbon nanotubes
  • a review of the carbon nanotube literature indicates or at least suggests elastic modulus approaching that of diamond, thermal conductivity being about double that of diamond, strength being one to two orders of magnitude larger than that of steel, and electric current carrying capacity being three orders of magnitude greater than that of copper. See, for example:
  • Table I compares some physical properties of carbon nanotubes to macroscopic carbon fibers.
  • the carbon fibers and carbon nanotubes are considered fairly representative of their respective species.
  • Table 1. Comparison of axial properties of carbon fibers and carbon nanotubes (CNTs)
  • T300 and P120 are BP Amoco carbon fibers.
  • Carbon Nanotubes are from Iljin Nanotech Co. Ltd., Seoul, S. Korea.
  • CNTs While carbon fibers have low CTE in axial directions, they have high CTE in radial directions (12 ppm/K). CNTs, on the other hand, have low CTE in both axial and radial directions. Moreover, CNTs also have much higher strain capability and as a result, they should have higher toughness than carbon fibers.
  • Carbon nanotubes have the graphitic structure, e.g., each carbon atom having three nearest neighbors, and can be thought of as a graphite sheet rolled up but with the ends offset to produce a helicity or chirality.
  • Ma et al formed a composite of 10 wt% carbon nanotubes in a silicon carbide matrix via a hot pressing route, and achieved a ten percent increase in strength and fracture toughness versus monolithic SiC ceramics.
  • Chen et al. produced a carbon nanotube reinforced metal matrix composite by an electroplating route.
  • X. Chen, J. Xia, J. Peng, W. Li, and S. Xie “Carbon-nanotube metal- matrix composites prepared by electroless plating", Composites Science and Technology: 60 [2], (2000) pp. 301-306.
  • Figure 1 shows the relative sizes of coated carbon fibers and carbon nanotubes in cross- section.
  • the sizes or thicknesses of the fiber, coating and nanotube of about 7 microns, 500 nanometers and about 50 nanometers, respectively, are typical for these bodies.
  • Figure 1 clearly shows that even the protective coating on the carbon fibers is an order of magnitude larger than the carbon nanotubes.
  • a small fiber-matrix reaction could be permitted in the case of fibers; however, the slightest reaction would annihilate the carbon nanotubes.
  • the CNTs are often only tens of atoms in diameter. Thus, another technique(s) may be required.
  • nanotube-reinforced composite body in which the nanotubes are well dispersed, and well distributed throughout the body, and not agglomerated or clumped into high concentration clusters of nanotubes.
  • nanotubes are initially provided in an agglomerated form, then preferably the agglomerations are broken up, or the nanotubes otherwise untangled and separated from one another to a significant extent prior to embedment or encapsulation by matrix material.
  • this detachment, dispersal or untangling of nanotubes can be realized, for example, by comminuting or milling, prior to organizing them into a preform or other porous mass.
  • the matrix component may be metal, glass, ceramic and/or polymer, and in a preferred embodiment is made by infiltrating the matrix component, or one or more matrix precursors, into a porous mass or preform containing the nanotubes.
  • the infiltrating process may be conducted in a pressureless manner, or with the assistance of pressure or vacuum to assist in the infiltration.
  • the infiltrant features molten silicon metal or an alloy thereof which infiltrates by capillarity into a porous mass or preform containing the nanotubes to form a matrix containing silicon metal or alloy, and optionally silicon carbide.
  • the nanotubes feature elemental carbon, and the carbonaceous nanotubes are at least partially protected from chemical reaction with the molten silicon metal by one or more substances such as carbon disposed between the nanotubes and the developing matrix component.
  • the carbon nanotubes may feature one or more coatings that serve to prevent chemical reaction with the molten infiltrant material, which coating(s) may be the above-mentioned carbon.
  • the carbon source which may also make up the nanotube protective material, reacts with the silicon of the infiltrant to form at least some silicon carbide phase in-situ in the developing composite body.
  • the nanotubes can be mixed with one or more filler materials, such as silicon carbide or boron carbide particulate, and with any binders necessary for making a self- supporting preform.
  • the one or more protective coatings may be applied before, during or after mixing with the filler(s).
  • the resulting preferred embodiment composite body contains the carbon nanotubes as a reinforcement component of the composite, optionally one or more coatings protective of the nanotubes, a matrix featuring the silicon-containing infiltrant, and optionally one or more filler materials, also belonging to the reinforcement component.
  • the resulting composite also contains as part of the matrix component some in-situ formed silicon carbide replacing some, up to substantially all, of the elemental silicon constituent of the infiltrant component.
  • the one or more coatings are not entirely protective of the carbon nanotubes, chemical reaction could ensue, converting a carbon nanotube partially or completely to a silicon carbide nanotube, which might represent a desirable outcome.
  • Figure 1 is an illustration that shows the relative diameters of carbon fibers and carbon nanotubes.
  • Figure 2 is a scanning electron micrograph of carbon nanotubes in an "as- received" condition.
  • Figures 3 A and 3B are photographs of the composites formed in Example II and Comparative Example II, respectively, showing the macroscopic visual effect of the presence and absence, respectively, of carbon nanotubes on the outward appearance of the composite body.
  • Figure 4A is an optical photomicrograph taken at about 300X magnification of a polished cross section of the composite material produced in accordance with Example XVIIL
  • Figure 4B is a scanning electron micrograph of a fracture surface taken at about 50,000X magnification of the composite material produced in accordance with Example XVIII.
  • the instant invention focuses on a reinforcement component for the composite that is in the form of "nanotubes” and preferably those containing elemental carbon.
  • Carbon nanotubes in particular have been garnering attention recently in the materials science community.
  • the tubes are hollow and much smaller than a typical fiber, at least in terms of fiber diameter.
  • Nanotubes typically have diameters on the scale of nanometers. They often have very high aspect ratios; that is, the ratio of their length to their diameter can be quite large.
  • the long lengths, perhaps on the order of millimeters, can have utility for, among other properties, toughening, rapid heat transfer, and enhanced electrical conductivity.
  • a particularly preferred infiltrant in the instant invention is silicon metal or silicon alloy. Not only does silicon possess low CTE, important for many of the applications contemplated by the instant inventor, but, depending on the other processing conditions, one can use this infiltrant system to produce predominantly metal-based composite bodies, or predominantly ceramic-based composite bodies. For example, molten silicon can spontaneously wick into a porous mass of silicon carbide without the need to draw the molten silicon in under vacuum or to force it in under pressure. See, for example, U.S. Patent No. 3,951,587 to Alliegro et al. The instant invention refers to this product as "siliconized SiC", and to the process by which it is made as “siliconizing.” This infiltration works best in a vacuum atmosphere.
  • the infiltration usually is enhanced and the process generally is more robust.
  • the silicon component of the infiltrant chemically reacts with at least a portion of the carbon in the porous mass to form silicon carbide.
  • the body thus formed features the porous mass material, typically silicon carbide, distributed throughout the in-situ silicon carbide formed from the chemical reaction. Typically, some infiltrant material remains in the infiltrated body, and distributed throughout.
  • reaction-bonded SiC this metal-ceramic composite material product as "reaction-bonded SiC”
  • reaction-bonding the process by which it is made as “reaction-bonding”
  • reaction-bonding although other terms have been used in the literature over the years to mean substantially the same thing.
  • reaction forming the reaction forming
  • reaction sintering the reaction sintering
  • self bonding Both the siliconizing and the reaction-bonding processes are within the scope of the instant invention.
  • a common technique for producing metal composites by infiltration at least for example, for aluminum or magnesium-based metal composites, utilizes an externally applied force such as external pressure to help the molten metal permeate the preform. This, too, is within the scope of the instant invention.
  • the infiltration technique also embraces polymers and glass as candidate matrix materials.
  • the polymers may be thermoplastics such as polyethylenes, or thermosets such as the epoxies. Since polymers may be amorphous or "glassy", what is meant in the context of this disclosure by a "glass" matrix is an inorganic product of fusion cooled to a rigid condition, and more particularly, the class of glasses consisting of metal oxides such as those based on silica and boria, and containing their usual additives or modifying agents, e.g., calcia, zirconia, alumina, magnesia, etc.
  • the carbon nanotubes may possess higher-than-normal resistance to chemical attack by molten silicon, or at least a resistance that is higher than that of carbon fibers.
  • the instant invention has proceeded on the assumption (without further analysis) that the carbon nanotubes will not have increased corrosion resistance compared to macroscopic carbon fibers.
  • the instant inventor expects that, the nanotube diameter being many times smaller than that of a typical carbon fiber, a carbon nanotube would be completely reacted upon contact with molten silicon. Accordingly, the present work has focused on providing one or more protective coatings to the nanotubes.
  • the one or more coatings are placed directly onto the fibers.
  • coatings can be found that also permit the infiltrant metal (e.g., silicon or aluminum) to wet the reinforcement better. Wetting of the metal to the reinforcement may improve the mechanical properties of the resulting metal composite, and the wetting condition may also permit the metal to infiltrate a porous mass of the reinforcement material without the need to force the molten metal in under pressure, or to pull it in under applied vacuum.
  • a desirable additional coating is silicon carbide, and a widely known technique for depositing a coating of silicon carbide onto macroscopic carbon fibers is by chemical vapor deposition (CVD). It may be possible to similarly coat or encapsulate carbon nanotubes in such CVD SiC.
  • a technique that is particularly preferred according to the instant invention for protecting the carbon nanotubes when the infiltrant includes silicon is to coat the nanotubes with, or embed them in, additional carbon prior to infiltration.
  • Carbonaceous precursor materials such as pitch, phenolic resin, furfural alcohol, epoxy resin, etc. are acceptable choices in this regard.
  • One embodiment of this technique for coating nanotubes is to stir in the nanotubes into the liquid resin.
  • Another embodiment would be to provide the nanotubes to a porous mass or preform using standard techniques, and then soak the liquid resin into the porous mass.
  • One may adjust viscosity as needed for the type of processing used by "thinning" the mixture with a low viscosity liquid into which the resin is soluble, e.g., an organic solvent.
  • any solvents that may have been added are removed, for example, by a drying operation, and then the carbonaceous substance (e.g., resin) is decomposed to carbon, first by curing or crosslinking the resin, and then with further heating, generally in a non-oxidizing environment, to pyrolyze the resin to drive off the non-carbon constituents of the resin, leaving substantially pure carbon behind as a residue.
  • the residue carbon generally is porous, which may be important for a silicon infiltration operation. However, the pores are of such a size and amount and arrangement as to permit molten silicon infiltration into the pore space of the preform but not to permit complete chemical reaction of the silicon with carbon.
  • the pyrolyzed carbon limits the degree of reaction during infiltration of molten silicon is a manifestation of its protective function. It is not necessary that the pyrolyzed carbon be provided in multiple layers, or be in graphitized form for it to serve this chemical protective function.
  • this supplemental carbon may be provided for the purpose of reacting with the silicon metal of the infiltrant to form in-situ silicon carbide and/or for further reducing the propensity for the silicon to react with the nanotubes by saturating the silicon with carbon.
  • One means of accomplishing this carbon addition to the preform is to soak the preform in a carbonaceous resin such as furfuryl alcohol, and then pyrolyze the resin in a non-oxidizing atmosphere to decompose the resin to essentially elemental carbon. This soak-and-pyrolyze step can be repeated one or more times to increase the amount of carbon and decrease the amount of pore space in the preform.
  • the residual carbon also serves to permit some movement in the axial direction of the nanotubes relative to the matrix, e.g., serve as a nanotube debond layer or interface, should such behavior be desirable, for instance, if toughening is desired.
  • a composite body whose matrix is based on silicon metal typically is brittle, and thus any toughening mechanism that can be imparted to such a composite generally is desirable.
  • a silicon-containing polymer such as a polysilazane
  • a silicon-containing polymer such as a polysilazane
  • the silicon-containing polymer could also form all or part of the matrix of the composite.
  • the molten silicon or its alloy Upon contact with the molten silicon or its alloy, the latter can infiltrate the porous preform, and the silicon can react with at least a portion (generally only a portion when done correctly) of the carbon constituent of the preform to form at least some SiC in the resulting composite body, and typically leaving behind some residual Si or Si alloy. Often times, the free carbon is at least partially interconnected, which typically results in the in-situ formed SiC being at least partially interconnected. The interconnected SiC generally is thought of as forming a component of the matrix of the composite body. Ideally, the carbon nanotubes are protected from the molten silicon by the free carbon of the preform, which is generally interconnected.
  • the residual carbon coating also provides for toughening of the composite material by making a weak bond with the Si/SiC matrix, thereby permitting movement of the carbon nanotubes relative to the matrix upon application of mechanical stress.
  • the free carbon that embeds the carbon nanotubes can protect the underlying carbon nanotubes as a result of the large volume change associated with chemically converting carbon to silicon carbide.
  • a unit volume of carbon forms 2.3 unit volumes of SiC.
  • the space occupied by the formed SiC can help block off unreacted carbon from further ingress of this molten silicon.
  • a relatively small amount of reaction of the carbon can help "can off' the infiltration, and thwart continued reaction of carbon by molten silicon.
  • the carbon does not need to be in the "graphitic" form to provide adequate protection from the molten infiltrant.
  • the carbon nanotubes of the reinforcement component of the composite body may be supplemented with one or more other filler materials.
  • Filler materials are often provided in composite bodies to perform one or more functions such as tailor one or more properties of the composite body in a direction toward that property of the filler material, and/or to minimize the amount of space that must be occupied by matrix material.
  • the filler material(s) could be other forms of carbon not intended to react with the infiltrant to form silicon carbide, other non-elemental carbon materials such as metal carbides, or non-carbon-containing materials such as refractory metals, borides, nitrides or oxides, or complex compounds, e.g., oxycarbides.
  • a popular filler morphology is that of particulate because particulate is economical and readily available, but other non-limiting morphologies include fibers, spheres, platelets and flakes.
  • Useful sizes of particulate for metal-ceramic composite bodies made by infiltration of silicon-containing melts range from about 1 micron to about 1 millimeter.
  • the total volumetric loading of filler can range from about 5 or 10 vol% up to almost the limits where the pore space between bodies of filler begin to close off, about 90 or 95 vol%. More typically, a metal-infiltrated composite body that is highly loaded in filler might be expected to have between about 60 and 80 vol% filler.
  • the nanotubes and the other fillers may simply be placed into a common container and mixed together, such as by roll mixing or dry milling.
  • the mixture can then be shaped as a preform using techniques known in the art.
  • a more sophisticated approach might take into account that the bodies of filler material generally are going to be much larger in size than the diameter of a nano ⁇ ube (recall Figure 1). Accordingly, it may make sense to first mix the nanotubes into a liquid component if one is to be used in the preforming process. Even in a dry pressing operation, there is often a liquid component used, such as the binder.
  • the dry nanotubes can be in the form of a mass of tangled nanotubes. See, for example, Figure 2.
  • the mixture can then be processed in the usual way to make a preform, according to preforming techniques well-known in the art, e.g., pressing, casting (slip, sediment, tape, thixotropic, for example), injection molding, etc. If the preform is to contain free or reactable carbon, such can also be added at this time (if it has not been added already), such as by dipping the preform into a carbon-containing paint or slurry.
  • the one or more filler materials may be incorporated into the prepreg in the same way that the nanotubes are incorporated, that is, by mixing or stirring into carbonaceous resin.
  • the filler(s) may be placed between adjacent plies of prepreg material during preform development. Other incorporation techniques may occur to those skilled in the art.
  • the carbon nanotubes will have their greatest effect in terms of exhibiting their characteristic properties if they are dispersed or distributed throughout the resulting composite body as well and as evenly as is possible. Scanning electron microscopic examinations have confirmed that the nanotubes in the "as-received" condition from the manufacturer often are in the form of a mass of densely packed tangles. Breaking up such a tangled mass will help disperse the nanotubes.
  • One technique for dispersing the nanotubes is to comminute them, such as in a mill, which could be a ball mill. Other forms of comminuting or milling, such as jet milling, Muller mixing, etc., will readily occur to those skilled in the art.
  • a developing preform containing nanotubes and which is self-supporting, for example, as a result of the presence of skeletal carbonaceous material such as resin may be infiltrated with one or more fillers that are carried into the preform with a liquid carrier fluid.
  • a nanotube-containing preform can be infiltrated with a slurry or slip containing one or more fillers.
  • Preforms are useful because they more exactly define the final desired shape, and thus contribute to reducing the amount of final machining required to produce a nanotube reinforced composite article of some specific shape.
  • a preform usually is thought of as a porous mass containing the filler or reinforcement of the composite body that has been rendered self-supporting, such as with a binder or coating of some kind. Often times, the preform has the shape, or is made to conform to the shape of the final object desired, such as by molding or so-called "green" machining. Additionally, and particularly for complex shaped articles, one may build up the larger, more complex structure from two or more smaller, simpler-shaped preforms, for example by adhesive bonding the component preforms to one another.
  • Carbonaceous adhesives such as phenolic resin, epoxy, cyanate ester, etc. are well suited for this purpose. Further, one can add one or more filler materials, e.g., carbon fibers, SiC particulate, etc., including nanotubes, to the carbonaceous adhesive, for example, to more closely match one or more physical properties of the adhesive (e.g., CTE) to those of the component preforms.
  • one or more filler materials e.g., carbon fibers, SiC particulate, etc., including nanotubes
  • prepregs/n-stage bodies containing carbon nanotubes It should be possible to make such prepregs/n-stage bodies containing carbon nanotubes.
  • a preform such as a three-dimensional structure may be produced, again, in the usual way, e.g., laminating a plurality of such sheets or films.
  • the objective usually has been to maximize the amount of SiC and to minimize the amount of Si, e.g., for refractory applications.
  • the present invention embraces the infiltration of molten silicon-containing metal into a porous preform to produce a Si-containing composite body
  • the practitioner has wide latitude in the kind of composite body that he or she can process. For instance, one can maximize the amount of SiC produced by providing a preform that is highly loaded in SiC reinforcement and/or producing large quantities of in-situ SiC from reaction of molten Si with readable carbon in the preform.
  • the former approach may be more desirable than the latter.
  • problems that result from excessive reaction during the infiltration process are temperature spikes due to the exothermic nature of the chemical reaction of silicon and carbon. Such temperature spikes can cause cracking due to localized thermal expansion.
  • the instant invention is also amenable to producing composite materials having less ceramic and more metal in the matrix, for example, where something more akin to a metal matrix composite ("MMC") or dispersion strengthened metal is the objective.
  • MMC metal matrix composite
  • such composites can be produced according to the instant techniques by providing a preform that is not highly loaded in ceramic reinforcement material and by minimizing the degree of reaction that the molten Si undergoes with carbon sources as it infiltrates the preform.
  • the amount of free carbon in the preform is low or is substantially completely reacted, the amount of in-situ SiC formed will be relatively low, perhaps on the order of 1 to 10 vol% of the volume of the formed composite body.
  • the amount of free carbon is greater and extensive reaction ensues, the amount of residual infiltrant metal remaining in the formed body typically will be low, perhaps on the order of 5 to 20 vol% of the formed composite body.
  • the free carbon in the preform is interconnected and is incompletely reacted during infiltration, the situation is complex, as the matrix of the resulting composite body can contain carbon, silicon carbide and residual inf ⁇ ltrant metal.
  • One way for enhancing the toughness of the Si-based matrix composites is to enhance the toughness of the matrix, e.g., by alloying the silicon.
  • Commonly Owned U.S. Patent No. 6,503,572 discloses that aluminum may be alloyed with the silicon in amounts ranging from about 0.1 percent by weight or less up to about 90 percent.
  • the resulting alloy can still infiltrate by capillarity into a porous mass of reinforcement material containing some interconnected carbon to form a reaction bonded silicon carbide composite body.
  • the alloy generally does not need to be heated to a temperature greater than about 100 0 C above its liquidus temperature. If the body to be infiltrated contains no elemental carbon, however, the process may have to be carried out at higher temperatures, for example, in the 1600 0 C to 1800 0 C range.
  • Another technique to impart toughening is the technique commonly employed in CMC's—namely, to cause the fibers to debond from the matrix under applied load, or at least to be able to move axially with respect to the matrix under the influence of an applied load.
  • This technique is commonly achieved with a debond layer such as carbon (e.g., pyrolytic carbon) or boron nitride applied to the fibers.
  • carbon e.g., pyrolytic carbon
  • boron nitride boronitride
  • Si/SiC composite systems such carbon coatings are often reactive with the molten Si infiltrant, typically resulting in the loss of the debonding property.
  • some coatings, such as boron nitride in particular may not be wetted by molten Si, thus preventing infiltration.
  • the debond coating may be located between the nanotube and the coating that is protective of the nanotube.
  • the protective coating may protect both carbon nanotube and debond coating.
  • the debond coating can be applied or deposited by techniques known in the art, such as chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • the protective coating also may be applied by CVD.
  • U.S. Patent No. 5,015,540 discloses such a multiple fiber coating system.
  • carbon since carbon was earlier identified as a candidate protective coating, under the proper conditions it is possible that a single material, e.g., carbon, can serve the dual role of acting to chemically protect the underlying nanotube, as well as acting as the debond material for toughening purposes. Again, it seems as though carbon coating thicknesses that are merely on the order of the thickness of a single nanotube will not be sufficiently protective against chemical attack by molten silicon. Accordingly, the carbon "coating" may be provided in sufficient thickness and sufficient quantity that it might be thought of as forming a part of the matrix phase of the preform (e.g., interconnected), and not merely as a discrete coating on individual nanotubes.
  • FIG. 4A is an optical photomicrograph of a polished cross- section of a CNT composite specimen (from Example XVTII) that is fairly representative of all of the CNT-containing materials made according to the Examples.
  • Example I
  • This Example demonstrates, among other things, the successful incorporation of carbon nanotubes (CNTs) into a metal-ceramic composite material and in particular, the survivability of the CNTs during infiltration processing with the metal in a molten condition.
  • CNTs carbon nanotubes
  • CVD chemical vapor deposition
  • SC 1008 from Borden Chemical Inc., Louisville, KY
  • the mixture was poured in a rubber mold with a cavity measuring about 5 by 5 by 1.3 cm.
  • the rubber mold was placed on a vibrating table for about 12 hours.
  • a thin TEFLON® sheet measuring about 5 cm square was placed on the mixture in the mold.
  • a graphite block measuring about 5 by 5 by 2.5 cm (and having a mass of about 225 g) was placed on top of the TEFLON® sheet.
  • the mold was then placed in a curing oven and heated to about 14O 0 C for about 3 hours and then cooled to room temperature (about 20 0 C).
  • a cured, stand-alone preform was produced after demolding.
  • This preform was placed in a retort and heated to about 650 0 C for about 2 hours in an inert atmosphere to carbonize the phenolic. Carbonization of the phenolic left a pyrolytic carbon coating on the CNTs, which coating protects them during subsequent infiltration by molten Si.
  • This preform was then placed in a vacuum furnace, vacuum was drawn ( ⁇ 100 microns) and the preform was then heated to about 1520 0 C and brought into contact with molten silicon.
  • a fully dense composite resulted containing SiC, CNT, residual C and Si.
  • this example proves that a molten metal infiltration process can be used to make CNT/SiC composites and the pyrolytic carbon coating protects the CNTs during melt infiltration or reaction bonding.
  • This Example demonstrates, among other things, the successful incorporation of carbon nanotubes (CNTs) into a metal-ceramic composite material also containing another filler or reinforcement material.
  • CNTs carbon nanotubes
  • SiC powders consisting of a 70:30 weight ratio of 240 and 500 grit particulates (Saint Gobain/Norton Industrial Ceramics, Worcester, MA), 2g CNTs, about 20.93g phenolic and about 15.6 g THF (solvent) were hand mixed in a beaker to make a mixture.
  • the mixture was poured in a rubber mold with a cavity measuring about 5 by 5 by 1.3 cm.
  • the rubber mold was placed on a vibrating table for about 12 hours.
  • a thin TEFLON® sheet measuring about 5 cm square was placed on the mixture.
  • a graphite block measuring about 5 by 5 by 2.5 cm was placed on top of the TEFLON® sheet.
  • the mold was then placed in a curing oven and heated to about 14O 0 C for about 3 hours and then cooled to room temperature.
  • a cured, stand-alone preform was produced after demolding. This preform was placed in a retort and heated to about 650 0 C for about 2 hours in an inert atmosphere to carbonize the phenolic. Carbonization of the phenolic leaves a pyrolytic carbon coating on the CNTs which protects them during infiltration by molten Si.
  • This preform was then placed in a vacuum furnace, vacuum was drawn ( ⁇ 100 micron) and then heated to about 1520 0 C and brought in contact with molten silicon. Molten silicon spontaneously infiltrated into the preform. The pyrolytic carbon reacts with molten Si and provides the driving force for the infiltration. After initial reaction, a dense SiC coating is formed which prevents further reaction and protects the CNTs from reacting with molten Si.
  • a fully dense composite was obtained containing SiC (both as reinforcement and as matrix material), CNTs, Si and C.
  • the density of the composite was found to be 2.65 g/cc.
  • this Example proves that a metal infiltration process can be used to make a CNT-containing composite and that the pyrolytic carbon coating protects the CNTs during melt infiltration or reaction bonding. And further, the Example shows that a filler can be incorporated into the composite body without interfering with the CNTs.
  • Example II demonstrates, for comparative purposes, the manufacture of a SiC composite body not containing carbon nanotubes.
  • the technique of Example II was substantially repeated to produce a composite body containing SiC and Si.
  • the mixture to be cast had the following composition: about 100 grams SiC powder, about 15 grams of the phenolic resin, and about 15 grams of ethanol. This composition had about the same viscosity as the nanotube- containing mixture of Example II.
  • Example III [0087] Examples III and IV through X demonstrate, among other things, various methods for blending and distributing carbon nanotubes throughout a mass of preform material.
  • the mixture was poured out of the jar and into a rubber mold of nominal cavity size about 71mm square by about 13mm deep.
  • the rubber mold was placed on a vibrating table for about 18 hours, during which time, the excess liquid pooled at the top, and it was periodically removed.
  • the mold was placed in an oven and the temperature was raised to about 140 0 C at a rate of about 1O 0 C per hour, with about two 2-3 hour holds for temperature equilibration.
  • the oven and its contents were cooled at about 200 0 C per our to ambient temperature.
  • the preform was then demolded and placed on a graphite plate and was then placed in an inert atmosphere retort. The temperature was raised above 650 0 C, held for about 2 hours and reduced to room temperature to carbonize the preform.
  • the preform was then placed in a graphite boat along with chunks of silicon.
  • the boat was placed in a vacuum furnace.
  • the furnace was evacuated below 100 microns pressure.
  • the temperature of the furnace was raised to about 1450 0 C and held for 1 hour.
  • the temperature was then reduced to room temperature. As a result of this thermal processing, the silicon had melted and wicked into the preform forming a composite.
  • this Example does not have nanotubes in its composition.
  • Properties of this composite were as follows: Density- 3.04 g/cc, Elastic Modulus - 375 GPa, Flexural strength - 187 MPa, Electrical resistivity 1.097 Ohm-cm, and Knoop hardness - 1889 kg/mm2.
  • CNTs CVD grown multi-wall carbon nanotubes
  • alumina milling cylinders (1 inch diameter x 1 inch long).
  • the jar was placed on a jar mill for 4 hours.
  • the milled CNTs were mixed with lOOg SiC powders, from Saint Gobain (a mixture of 240 and 500/600 grit in 70:30 weight proportion) by rolling together in a plastic jar for 3 hours.
  • 5Og phenolic (details) was added to the mix and the mixed by hand.
  • the mix was screened through a wire mesh having openings of about 1.6 mm square.
  • Example 2 The mix was poured in a 2 x 2 inch (51 mm square) cold pressing die and pressed at 30,000 Ib load for 5 minutes. The pressed preform was removed from the die and placed on a graphite setter tray. The rest of the processing was the same as in Example 1 from the carbonization step forward.
  • Example VII This Example was conducted in substantially the same manner as Example VI except after the 600C carbonizing step, the preform was dipped in the phenolic for 2 hours to back soak it; that is, to add more carbonaceous resin to it. The back soaked preform was placed in an inert atmosphere retort and the temperature was raised above 600 0 C, held for 1 hour and then reduced to room temperature, to re-carbonize the preform. After that, the preform was infiltrated with molten silicon substantially as described in Example 1.
  • Example VIII This Example was performed in substantially the same manner as Example VI except the ball milling step with the alumina cylinders was carried out for 24 hours and only 35g phenolic was added to make the pressable admixture.
  • Example IX Same as Example VIII except after first carbonizing, the preform was dipped in the phenolic for 2 hours to back soak it. The back soaked preform was placed in an inert atmosphere retort and the temperature was raised above 600 0 C, held for 1 hour and then reduced to room temperature, to re-carbonize the preform. After that, the preform was infiltrated with molten silicon in substantially the same manner as described in Example 1.
  • Example IX The mix was then poured into a 51 mm square die cavity of a cold pressing die and pressed at about 30,000 Ib (1400 kgf) load for about 5 minutes.
  • the pressed preform was removed from the die and placed on a graphite setter tray. The rest of the processing was the same as in Example IX from the carbonizing step forward.
  • Example XIII is substantially same as Example XIII except, milling in step one was carried out for 24 hours, and no back soaking and second carbonizing was done.
  • Example XIV This example is substantially same as Example XIV except, 1Og of CNT were used instead of 5g.
  • Example XIV is substantially same as Example XIV except, 2Og of CNT were used instead of 5g.
  • Example XTV This example is substantially same as Example XTV except, 5Og of CNT were used instead of 5g.
  • Example XIV This example is substantially same as Example XIV except, 75g of CNT were used instead of 5g.
  • Example XTV This example is substantially same as Example XTV except, lOOg of CNT were used instead of 5g.
  • Example XIII is substantially same as Example XIII except, milling in step one was carried out for 24 hours.
  • Example XX is substantially same as Example XX except, 1Og of CNT were used instead of 5g.
  • Example XX is substantially same as Example XX except, 2Og of CNT were used instead of 5g.
  • Example XXIII is substantially same as Example XXIII except 1Og CNTs were used instead of 5g.
  • Example XXIII is substantially same as Example XXIII except 2Og CNTs were used instead of 5g.
  • Example XXHI This example is substantially same as Example XXHI except back-soaking and second carbonizing were carried out followed by infiltration similar to that in Example VII.
  • Example XXVI is substantially same as Example XXVI except 1Og of CNT were added instead of 5g.
  • Example XXVI is substantially same as Example XXVI except 2Og of CNT were added instead of 5g.
  • Example XVII is substantially same as Example XVII except B 4 C particulates were used in place of SiC.
  • the enhanced toughness of CNT composites most likely is due to (1) pull-out of the CNT from the matrix; (2) bridging of cracks by the CNT; and/or (3) deflection of cracks by the CNT.
  • compositions of the present invention should find utility in applications requiring or benefiting from the unusual properties offered by nanotubes, particularly carbon nanotubes, e.g., applications where high specific stiffness, low thermal expansion coefficient, enhanced toughness, high electrical conductivity, and/or high thermal conductivity are important
  • the carbon nanotube reinforced SiC composites of the instant invention seem to possess many of the desirable properties.
  • the instant nanotube-composites should also find application in large structures that must maintain size and shape within exacting tolerances, such as mirrors, e.g., land or space-based mirrors.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Composite Materials (AREA)
  • Nanotechnology (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Ceramic Products (AREA)

Abstract

L'invention porte sur des nanotubes constituant un matériau composite et renforçant un métal, un verre, une céramique et/ou un polymère formant une matrice. Selon une forme d'exécution préférée, des nanotubes sont constitués d'un carbone élémentaire et les composites peuvent être produits par une technique d'infiltration d'un métal de silicium fondu, ces nanotubes pouvant être mis ou non sous pression, par exemple, selon un processus de siliciuration ou de liaison par réaction. Selon cette forme d'exécution, on peut empêcher les nanotubes de carbone de réagir chimiquement avec un agent d'infiltration de silicium par le biais d'un revêtement interfacial disposé entre les nanotubes de carbone et l'agent d'infiltration. Un corps composite lié par réaction et contenant également un petit pourcentage de nanotubes de carbone présente une augmentation considérable de la conductivité électrique comparé à un composite lié par réaction et ne contenant par ces nanotubes, réfléchissant ainsi la haute conductivité électrique des nanotubes. Lorsque les nanotubes sont bien dispersés dans la totalité de la préforme, les améliorations apportées aux propriétés mécaniques commencent à devenir perceptibles, tels que le renforcement de la ténacité du matériau. Généralement, les nanotubes à l'état brut sont enchevêtrés ou agglomérés, mais il existe une technique efficace de division pour les désenchevêtrer, les séparer ou les disperser.
PCT/US2005/014275 2004-04-26 2005-04-26 Corps composites contenant des nanotubes et leurs procedes de fabrication WO2006080936A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US10/832,823 2004-04-26
US10/832,823 US20050181209A1 (en) 1999-08-20 2004-04-26 Nanotube-containing composite bodies, and methods for making same
US11/090,259 2005-03-25
US11/090,259 US20060062985A1 (en) 2004-04-26 2005-03-25 Nanotube-containing composite bodies, and methods for making same

Publications (1)

Publication Number Publication Date
WO2006080936A1 true WO2006080936A1 (fr) 2006-08-03

Family

ID=36593099

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2005/014275 WO2006080936A1 (fr) 2004-04-26 2005-04-26 Corps composites contenant des nanotubes et leurs procedes de fabrication

Country Status (2)

Country Link
US (1) US20060062985A1 (fr)
WO (1) WO2006080936A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008065446A1 (fr) * 2006-11-29 2008-06-05 Airbus Uk Limited Procédé amélioré de fabrication de composants composites
EP2139630A1 (fr) * 2007-03-21 2010-01-06 Höganäs Ab (publ) Composites polymères de métal en poudre
DE102009005629A1 (de) * 2009-01-21 2010-07-22 Technische Universität Bergakademie Freiberg Kohlenstoffgebundene feuerfeste Formkörper oder Massen mit einer hochfesten Bindephase und Verfahren zu ihrer Herstellung
WO2011024000A1 (fr) * 2009-08-25 2011-03-03 Isis Innovation Limited Matériaux composites contenant des nanotubes alignés et leur production
EP2371532A3 (fr) * 2006-11-06 2013-05-08 Hexcel Composites Limited Matériaux composites améliorés

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050064167A1 (en) * 2003-09-12 2005-03-24 Nano-Proprietary, Inc. Carbon nanotubes
US7592073B2 (en) * 2005-09-27 2009-09-22 The Boeing Company Rhenium composite alloys and a method of preparing same
CN101484397A (zh) * 2006-06-09 2009-07-15 克利夫兰州立大学 高强度复合材料和相关方法
CN101808819A (zh) * 2007-09-07 2010-08-18 无机专家公司 作为用于锂二次电池的阳极材料的硅改性纳米纤维纸
US8058364B2 (en) 2008-04-15 2011-11-15 Florida State University Research Foundation Method for functionalization of nanoscale fibers and nanoscale fiber films
US20090305489A1 (en) * 2008-06-05 2009-12-10 Fish Roger B Multilayer electrostatic chuck wafer platen
US9023175B2 (en) * 2008-08-04 2015-05-05 Lockheed Martin Corporation Carbon/carbon film adhesive
DE102009000888B4 (de) * 2009-02-16 2011-03-24 Semikron Elektronik Gmbh & Co. Kg Halbleiteranordnung
JP5678332B2 (ja) * 2009-09-04 2015-03-04 東洋炭素株式会社 セラミックス炭素複合材及びその製造方法並びにセラミックス被覆セラミックス炭素複合材及びその製造方法
US8225704B2 (en) 2010-01-16 2012-07-24 Nanoridge Materials, Inc. Armor with transformed nanotube material
CN102212967A (zh) * 2011-04-06 2011-10-12 东华大学 一种碳纳米管改性的碳纤维乳液上浆剂及其制备方法
US9957379B2 (en) 2012-01-03 2018-05-01 Lockheed Martin Corporation Structural composite materials with high strain capability
WO2013152144A1 (fr) * 2012-04-05 2013-10-10 The Research Foundation Of State University Of New York Structures carbonées tridimensionnelles
KR101334736B1 (ko) * 2012-10-09 2013-12-05 한국에너지기술연구원 탄소 섬유 강화 탄화규소 복합소재 및 이의 제조 방법
WO2016007889A1 (fr) * 2014-07-10 2016-01-14 Georgia Tech Research Corporation Compositions de nanotubes de carbone
CN104894869A (zh) * 2015-06-05 2015-09-09 中国科学院山西煤炭化学研究所 一种碳纤维增强体的快速制备方法
US20200399748A1 (en) * 2016-12-30 2020-12-24 American Boronite Corporation Metal Matrix Composite Comprising Nanotubes And Method Of Producing Same
PL3914744T3 (pl) * 2019-01-27 2024-05-06 Lyten, Inc. Urządzenie do wytwarzania materiałów typu covetic

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1084997A2 (fr) * 1999-09-16 2001-03-21 Sgl Technik Gmbh Matériau composite à matrice céramique renforcé par des faisceaux de fibres
US6299812B1 (en) * 1999-08-16 2001-10-09 The Board Of Regents Of The University Of Oklahoma Method for forming a fibers/composite material having an anisotropic structure
WO2002018296A1 (fr) * 2000-08-25 2002-03-07 Rensselaer Polytechnic Institute Nano-composites a matrice ceramique contenant des nanotubes de carbone conferant un comportement mecanique ameliore
JP2004010978A (ja) * 2002-06-07 2004-01-15 Sumitomo Electric Ind Ltd 高熱伝導性放熱材料及びその製造方法
US20040029706A1 (en) * 2002-02-14 2004-02-12 Barrera Enrique V. Fabrication of reinforced composite material comprising carbon nanotubes, fullerenes, and vapor-grown carbon fibers for thermal barrier materials, structural ceramics, and multifunctional nanocomposite ceramics
EP1400499A1 (fr) * 2002-09-13 2004-03-24 Sgl Carbon Ag Produit composite en céramique renforcée par des fibres et procédé de préparation
US6723279B1 (en) * 1999-03-15 2004-04-20 Materials And Electrochemical Research (Mer) Corporation Golf club and other structures, and novel methods for making such structures
EP1500677A2 (fr) * 2003-07-23 2005-01-26 Nissin Kogyo Co., Ltd. Matériau composite de fibres de carbone-mé tal et son procédé de fabrication

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2431326A (en) * 1942-10-29 1947-11-25 Carborundum Co Silicon carbide articles and method of making same
US3275722A (en) * 1959-07-08 1966-09-27 Power Jets Res & Dev Ltd Production of dense bodies of silicon carbide
GB1110791A (en) * 1964-04-24 1968-04-24 Nat Res Dev The production of carbon fibres
US3622283A (en) * 1967-05-17 1971-11-23 Union Carbide Corp Tin-carbon fiber composites
US3807996A (en) * 1972-07-10 1974-04-30 Union Carbide Corp Carbon fiber reinforced nickel matrix composite having an intermediate layer of metal carbide
US4082864A (en) * 1974-06-17 1978-04-04 Fiber Materials, Inc. Reinforced metal matrix composite
US4120731A (en) * 1976-02-23 1978-10-17 General Electric Company Method of making molten silicon infiltration reaction products and products made thereby
US4157409A (en) * 1978-08-28 1979-06-05 The United States Of America As Represented By The Secretary Of The Army Method of making metal impregnated graphite fibers
US4376803A (en) * 1981-08-26 1983-03-15 The Aerospace Corporation Carbon-reinforced metal-matrix composites
US4535035A (en) * 1984-01-17 1985-08-13 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Oxidation resistant slurry coating for carbon-based materials
US4791076A (en) * 1984-08-02 1988-12-13 Hughes Aircraft Company Graphite fiber reinforced silica matrix composite
JPS62244565A (ja) * 1986-04-16 1987-10-24 Toyota Motor Corp 閉ル−プ状炭素繊維強化部分を含む金属部材の製造方法
US4847220A (en) * 1986-09-17 1989-07-11 Lanxide Technology Company, Lp Method of making ceramic composites
US5015540A (en) * 1987-06-01 1991-05-14 General Electric Company Fiber-containing composite
US4944904A (en) * 1987-06-25 1990-07-31 General Electric Company Method of obtaining a fiber-containing composite
US4889686A (en) * 1989-02-17 1989-12-26 General Electric Company Composite containing coated fibrous material
US5723392A (en) * 1994-06-23 1998-03-03 Cercom, Inc. In-situ grown whisker reinforced ceramics
US5541006A (en) * 1994-12-23 1996-07-30 Kennametal Inc. Method of making composite cermet articles and the articles
US5834115A (en) * 1995-05-02 1998-11-10 Technical Research Associates, Inc. Metal and carbonaceous materials composites
EP0835853A1 (fr) * 1996-10-14 1998-04-15 Societe Europeenne De Propulsion Elément de friction en matériau composite carbone/carbone-carbure de silicium et procédé pour sa fabrication
DE19710105A1 (de) * 1997-03-12 1998-09-17 Sgl Technik Gmbh Mit Graphitkurzfasern verstärkter Siliciumcarbidkörper
DE19711829C1 (de) * 1997-03-21 1998-09-03 Daimler Benz Ag Verfahren zur Herstellung einer faserverstärkten Verbundkeramik
US6793873B2 (en) * 1997-03-21 2004-09-21 Daimlerchrysler Ag Melted-infiltrated fiber-reinforced composite ceramic
DE19727586C2 (de) * 1997-06-28 2002-10-24 Daimler Chrysler Ag Bremseinheit aus Bremsscheibe und Bremsbelag
US6203864B1 (en) * 1998-06-08 2001-03-20 Nec Corporation Method of forming a heterojunction of a carbon nanotube and a different material, method of working a filament of a nanotube
DE19834571C2 (de) * 1998-07-31 2001-07-26 Daimler Chrysler Ag Verfahren zur Herstellung von Körpern aus faserverstärkten Verbundwerkstoffen und Verwendung des Verfahrens
US6503572B1 (en) * 1999-07-23 2003-01-07 M Cubed Technologies, Inc. Silicon carbide composites and methods for making same
EP1178036A1 (fr) * 2000-08-04 2002-02-06 Aventis Cropscience S.A. Dérivés de phénylimidates fongicides
US6495258B1 (en) * 2000-09-20 2002-12-17 Auburn University Structures with high number density of carbon nanotubes and 3-dimensional distribution
US6949216B2 (en) * 2000-11-03 2005-09-27 Lockheed Martin Corporation Rapid manufacturing of carbon nanotube composite structures
US6782154B2 (en) * 2001-02-12 2004-08-24 Rensselaer Polytechnic Institute Ultrafast all-optical switch using carbon nanotube polymer composites
US6522446B2 (en) * 2001-04-25 2003-02-18 Research Frontiers Incorporated Anisometrically shaped metal particles, liquid suspensions and films thereof and light valves comprising same
AU2003235592A1 (en) * 2002-01-11 2003-07-30 The Trustees Of Boston College Reinforced carbon nanotubes
WO2003078316A1 (fr) * 2002-03-15 2003-09-25 Osaka Gas Company Limited Composite fer/carbone, matiere carbonee comprenant ce composite fer/carbone et procede de production correspondant
US7405854B2 (en) * 2002-03-21 2008-07-29 Cornell Research Foundation, Inc. Fibrous micro-composite material

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6723279B1 (en) * 1999-03-15 2004-04-20 Materials And Electrochemical Research (Mer) Corporation Golf club and other structures, and novel methods for making such structures
US6299812B1 (en) * 1999-08-16 2001-10-09 The Board Of Regents Of The University Of Oklahoma Method for forming a fibers/composite material having an anisotropic structure
EP1084997A2 (fr) * 1999-09-16 2001-03-21 Sgl Technik Gmbh Matériau composite à matrice céramique renforcé par des faisceaux de fibres
WO2002018296A1 (fr) * 2000-08-25 2002-03-07 Rensselaer Polytechnic Institute Nano-composites a matrice ceramique contenant des nanotubes de carbone conferant un comportement mecanique ameliore
US20040029706A1 (en) * 2002-02-14 2004-02-12 Barrera Enrique V. Fabrication of reinforced composite material comprising carbon nanotubes, fullerenes, and vapor-grown carbon fibers for thermal barrier materials, structural ceramics, and multifunctional nanocomposite ceramics
JP2004010978A (ja) * 2002-06-07 2004-01-15 Sumitomo Electric Ind Ltd 高熱伝導性放熱材料及びその製造方法
EP1400499A1 (fr) * 2002-09-13 2004-03-24 Sgl Carbon Ag Produit composite en céramique renforcée par des fibres et procédé de préparation
EP1500677A2 (fr) * 2003-07-23 2005-01-26 Nissin Kogyo Co., Ltd. Matériau composite de fibres de carbone-mé tal et son procédé de fabrication

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 2003, no. 12 5 December 2003 (2003-12-05) *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2371532A3 (fr) * 2006-11-06 2013-05-08 Hexcel Composites Limited Matériaux composites améliorés
CN107584843A (zh) * 2006-11-06 2018-01-16 赫克塞尔合成有限公司 改进的复合材料
CN107584843B (zh) * 2006-11-06 2019-09-24 赫克塞尔合成有限公司 改进的复合材料
WO2008065446A1 (fr) * 2006-11-29 2008-06-05 Airbus Uk Limited Procédé amélioré de fabrication de composants composites
US8137602B2 (en) 2006-11-29 2012-03-20 Airbus Operations Limited Method for manufacturing composite components
RU2451601C2 (ru) * 2006-11-29 2012-05-27 Эйрбас Оперейшнз Лимитед Улучшенный способ получения композиционных элементов
EP2139630A1 (fr) * 2007-03-21 2010-01-06 Höganäs Ab (publ) Composites polymères de métal en poudre
EP2139630A4 (fr) * 2007-03-21 2011-01-26 Hoeganaes Ab Publ Composites polymères de métal en poudre
US8475709B2 (en) 2007-03-21 2013-07-02 Hoganas Ab (Publ) Powder metal polymer composites
DE102009005629A1 (de) * 2009-01-21 2010-07-22 Technische Universität Bergakademie Freiberg Kohlenstoffgebundene feuerfeste Formkörper oder Massen mit einer hochfesten Bindephase und Verfahren zu ihrer Herstellung
WO2011024000A1 (fr) * 2009-08-25 2011-03-03 Isis Innovation Limited Matériaux composites contenant des nanotubes alignés et leur production

Also Published As

Publication number Publication date
US20060062985A1 (en) 2006-03-23

Similar Documents

Publication Publication Date Title
US20060062985A1 (en) Nanotube-containing composite bodies, and methods for making same
US20050181209A1 (en) Nanotube-containing composite bodies, and methods for making same
JP3942199B2 (ja) 金属窒化物で被覆された繊維強化材を有する炭化ケイ素複合材
US4944904A (en) Method of obtaining a fiber-containing composite
EP0564245B1 (fr) Revêtement protecteur avec intercouche réactive sur le renforcement de composite de carbure de silicium
US5552352A (en) Silicon carbide composite with coated fiber reinforcement
US9409823B2 (en) Microstructured high-temperature hybrid material, its composite material and method of making
US5021367A (en) Fiber-containing composite
US5316851A (en) Silicon carbide composite with metal boride coated fiber reinforcement
US5015540A (en) Fiber-containing composite
US7445095B2 (en) Brake system having a composite-material brake disc
US7169465B1 (en) Low expansion metal-ceramic composite bodies, and methods for making same
EP1326813A2 (fr) Composites de matrice en ceramique a base de carbure de bore
WO2002098819A1 (fr) Procede de production d'un materiau composite au carbure de silicium sic renforce de fibres sic
JP2009517313A (ja) 難分解性コンポジット
US7244034B1 (en) Low CTE metal-ceramic composite articles, and methods for making same
Arsecularatne et al. Carbon nanotube reinforced ceramic composites and their performance
EP0519643B1 (fr) Composé à base de carbure de silicium renforcé par fibres revêtue d'un carbure métallique
Gottlieb et al. Continuous fiber-reinforced ceramic matrix composites
GB2250516A (en) Fiber-containing composite
Tong et al. Thermally conductive ceramic matrix composites
JP3574583B2 (ja) 放熱材及びその製造方法
KR100298524B1 (ko) 규소-도핑된 붕소 질화물 피복된 섬유를 포함하는 규소 용융 침윤된 복합체
CA1321869C (fr) Composite a charge fibreuse
Tokarz et al. Compositions for preparing cement-adhesive reinforcing fibres

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
122 Ep: pct application non-entry in european phase