CN101448760A - Max相粉末和用于制备所述粉末的方法 - Google Patents

Max相粉末和用于制备所述粉末的方法 Download PDF

Info

Publication number
CN101448760A
CN101448760A CNA2007800185415A CN200780018541A CN101448760A CN 101448760 A CN101448760 A CN 101448760A CN A2007800185415 A CNA2007800185415 A CN A2007800185415A CN 200780018541 A CN200780018541 A CN 200780018541A CN 101448760 A CN101448760 A CN 101448760A
Authority
CN
China
Prior art keywords
powder
precursor
alc
preparation
sic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2007800185415A
Other languages
English (en)
Inventor
J·卡内尔
F·特内加尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
US Atomic Energy Commission (AEC)
Original Assignee
US Atomic Energy Commission (AEC)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by US Atomic Energy Commission (AEC) filed Critical US Atomic Energy Commission (AEC)
Publication of CN101448760A publication Critical patent/CN101448760A/zh
Pending legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00Nitrogen; Compounds thereof
    • C01B21/06Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0602Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with two or more other elements chosen from metals, silicon or boron
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/90Carbides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/56Shaped 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
    • C04B35/5607Shaped 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 refractory metal carbides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/56Shaped 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
    • C04B35/5607Shaped 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 refractory metal carbides
    • C04B35/5611Shaped 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 refractory metal carbides based on titanium carbides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/56Shaped 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
    • C04B35/5607Shaped 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 refractory metal carbides
    • C04B35/5611Shaped 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 refractory metal carbides based on titanium carbides
    • C04B35/5615Shaped 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 refractory metal carbides based on titanium carbides based on titanium silicon carbides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/56Shaped 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
    • C04B35/5607Shaped 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 refractory metal carbides
    • C04B35/5611Shaped 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 refractory metal carbides based on titanium carbides
    • C04B35/5618Shaped 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 refractory metal carbides based on titanium carbides based on titanium aluminium carbides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/56Shaped 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
    • C04B35/5607Shaped 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 refractory metal carbides
    • C04B35/5622Shaped 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 refractory metal carbides based on zirconium or hafnium carbides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/58Shaped 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
    • C04B35/58007Shaped 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 refractory metal nitrides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/58Shaped 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
    • C04B35/58007Shaped 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 refractory metal nitrides
    • C04B35/58014Shaped 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 refractory metal nitrides based on titanium nitrides, e.g. TiAlON
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/58Shaped 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
    • C04B35/58007Shaped 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 refractory metal nitrides
    • C04B35/58014Shaped 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 refractory metal nitrides based on titanium nitrides, e.g. TiAlON
    • C04B35/58021Shaped 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 refractory metal nitrides based on titanium nitrides, e.g. TiAlON based on titanium carbonitrides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/58Shaped 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
    • C04B35/58007Shaped 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 refractory metal nitrides
    • C04B35/58028Shaped 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 refractory metal nitrides based on zirconium or hafnium nitrides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/58Shaped 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
    • C04B35/58007Shaped 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 refractory metal nitrides
    • C04B35/58028Shaped 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 refractory metal nitrides based on zirconium or hafnium nitrides
    • C04B35/58035Shaped 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 refractory metal nitrides based on zirconium or hafnium nitrides based on zirconium or hafnium carbonitrides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605Treating the starting powders individually or as mixtures
    • C04B35/6261Milling
    • C04B35/6262Milling of calcined, sintered clinker or ceramics
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64Burning or sintering processes
    • C04B35/645Pressure sintering
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71Ceramic products containing macroscopic reinforcing agents
    • C04B35/78Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80Fibres, filaments, whiskers, platelets, or the like
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/62Submicrometer sized, i.e. from 0.1-1 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/5216Inorganic
    • C04B2235/522Oxidic
    • C04B2235/5224Alumina or aluminates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/5216Inorganic
    • C04B2235/524Non-oxidic, e.g. borides, carbides, silicides or nitrides
    • C04B2235/5244Silicon carbide
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/5216Inorganic
    • C04B2235/524Non-oxidic, e.g. borides, carbides, silicides or nitrides
    • C04B2235/5248Carbon, e.g. graphite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54Particle size related information
    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5454Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80Phases present in the sintered or melt-cast ceramic products other than the main phase
    • C04B2235/81Materials characterised by the absence of phases other than the main phase, i.e. single phase materials
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2918Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
    • Y10T428/292In coating or impregnation
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982Particulate matter [e.g., sphere, flake, etc.]

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Powder Metallurgy (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Luminescent Compositions (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

本发明涉及一种粉末,其包含至少一种元素M、至少一种元素A和至少一种元素X,比例分别为(n+1±ε1)、1±ε2和n±ε3,其中:A选自Cd、Al、Ga、In、Tl、Si、Ge、Sn、Pb、P、As和S;M是过渡金属;X选自B、C和N;n是等于1、2或3的整数;且ε1、ε2和ε3各自独立地表示0-0.2的数值,所述粉末的平均粒径小于500nm。

Description

MAX相粉末和用于制备所述粉末的方法
技术领域
本发明涉及纳米级粉末(或纳米粉末),特别是MAX相粉末,及其制备方法。
MAX相代表很宽范围的材料。它们一般满足通式:Mn+1AXn,其中M是过渡金属(比如Ti、V、Cr、Zr、Nb、Hf或Ta),A是选自Cd、Al、Ga、In、Tl、Si、Ge、Sn、Pb、P、As和S的元素,X是选自B、C和N的非金属元素。
此类材料的特征为含有堆积的纳米层和较小比例的非金属原子(当n等于1、2和3时分别为25%、33%和37.5%)的六方晶体结构。
这些材料具有金属性质,并且就它们能够在很高的温度下保持其形状的意义上说,还具有接近于陶瓷的性能。
因此,它们可应用于比如电子(例如使用化合物Ti2SnC)、自润滑涂层(例如在农业食品工业中)、模塑或浇铸模板、航空中的结构部件的广阔领域中。
背景技术
MAX-型材料一般由物理汽相淀积(PVD)或化学汽相淀积(CVD)以薄膜形式获得,或以粉末(例如通过电弧熔化随后研磨,或通过元素粉末的热处理获得)形式,或者直接以松散材料形式使用粉末冶金作为生产方法(例如通过烧结元素粉末)获得。
因此,在1967年,Jeitschko和Novotny通过将氢化钛、硅和石墨粉在2000℃下加热20分钟,并将其迅速冷却到1200℃制备了Ti3SiC2
其他作者在真空中,在约1300-1600℃下通过反应性烧结Ti、TiC和Si粉末的混合物制备了Ti3SiC2。然而,此方法存在硅蒸发的缺点,致使化学计量发生改变。调整初始硅比例的尝试不能获得纯净的Ti3SiC2。该缺陷通常归因于Ti3SiC2在高温下按照下列方案进行的分解:
Ti3SiC2(s)→3TiC0.67(s)+Si(g)。
随后进行的其他方法,基于合成后通过化学过程去除不需要的产物。因此,已使用氟化氢处理来去除TiS2,通过在空气中在450℃下氧化10小时,将TiC转化成TiO2,随后在100℃下使用硫酸铵/硫酸混合物溶解TiO2。这些方法繁重,而且还有产量低并严重危害环境的缺点。
另一种方法包括Ti、Si和C粉末的混合物的冷压加工,任选地将其电弧熔化并在预先抽空的石英管中将其加热至900℃24小时,然后在1400℃下加热5小时或在1200℃下加热100小时。在两种情况中都形成Ti3SiC2,但存在其他相。最好的是,必须在过程最后用氢氟酸去除TiS2,以获得纯度超过99%的粉末。
最后,用于合成Ti3SiC2的另一方法包括混合钛、碳化硅和石墨粉末,在反应性烧结处理过程中严格控制氧分压,以防止Ti3SiC2通过下列机理的分解:
Ti3SiC2(s)+(1/2)O2(g)→3TiC0.67(s)+SiO(g)。
然而,该控制需要使用气流(例如氩气或氢气),以及用于捕获氧气的牺牲粉末(sacrificial powder)(例如钛粉),并且其量和分布需要通过系列预先试验,随后对获得的产物化学分析来确定。在最佳条件下,不需要的化合物的比例可高达2体积%。
因此,一般而言,所有与MAX-型材料形成有关的方法是起始于含有最终产物中所需的各种化学物质的粉末混合物,能够获得松散材料的方法。这在很大程度上具有损害最终产物纯度的缺点。这是因为,一方面,起始粉末必须尽可能地纯净,以保证最终产物的纯度,但另一方面,为了使反应能够在固相中迅速、完全和均匀地进行,各种粉末必须充分混合,因此必须是细粉末。然而,由于其延展性,细金属粉末难以获得,并且因为其高自燃性质而存储是危险的。此外,它们更易于氧化,因此与高纯度的目的不相容。此外,所述粉末必须在特定条件下进行混合,其中必须对气压和由用于研磨的装置引起的任何污染进行控制。另外,因此没有方法回避与用于形成所需物质的固相反应的局部性质有关的问题,并因此防止所述形成反应不均匀且易于形成含有所需物质之外的产物的复合物。
此外,至今没有获得粒径小于500nm的纳米粉末的方法,这种纳米粉末将赋予能够通过烧结促进其固结的粉末反应性,产生细微结构(不可能由常规粉末获得),并将因而增强性能。纳米粉末还意味着预计可以通过用纳米颗粒的悬浮物渗透来制备含有长纤维的复合物,纳米颗粒的尺寸确保了纤维间空隙的高填充系数,从而使基体具有低孔隙率。
因此本发明人设定的目的是开发用于获得具有高纯度、平均粒径小于500nm的纳米粉末的方法,该方法操作简单并且在经济上适于工业大规模生产,并且在组成的选择上具有很大灵活性,化学计量上十分精确且均匀性在小于一微米的量级。
发明内容
因此,根据第一主旨,本发明提供了一种粉末,其包含至少一种元素M、至少一种元素A和至少一种元素X,比例分别为(n+1±ε1)、1±ε2和n±ε3,其中:
*A选自Cd、Al、Ga、In、Tl、Si、Ge、Sn、Pb、P、As和S;
*M是过渡金属;
*X选自B、C和N;
*n是等于1、2或3的整数;且
*ε1、ε2和ε3各自独立地表示0-0.2的数值,
所述粉末的平均粒径小于500nm。
粉末中的元素M、A和X可以是:
-分离形式,即未组合的形式,从而形成具有限定的分子式的相;
-不形成Mn+1±ε1A1±ε2X1±ε3相的部分组合形式;
-具有Mn+1±ε1A1±ε2X1±ε3相区的部分组合形式;或
-Mn+1±ε1A1±ε2X1±ε3相的完全组合形式。
有利的平均粒径范围在10—200nm。
所述平均粒径可以小于100nm,例如在10—50nm。
粉末的平均粒径可以通过两种不同的技术进行评价:通过气体吸附进行的比表面积测定(单分子厚度的层上粉末颗粒表面上吸附的气体量使得表面积可以测定,并且在已知质量和密度的条件下,由此可推导出粉末颗粒的平均粒径)和透射电子显微术(将粉末悬浮在溶剂中并用超声分散,将粉末沉积在显微镜载体上,并在至少十个区中观测——对于每个区,各可见颗粒的直径通常使用图像处理软件自动测量)。
根据本发明,M是过渡金属。术语“过渡金属”一般理解为指在中性原子状态下或在其一种一般氧化态中具有未完全填充的d壳层的金属。这些元素分布在三个过渡系列中:
-第一过渡系列从钪到锌;
-第二过渡系列从钇到镉;和
-第三过渡系列从铪到汞。
特别地,M可以是选自Sc、Ti、Zr、Hf、V、Nb、Ta、Cr和Mo的元素。
除了元素M、A和X,所述粉末可含有其他化学物质。所述化学物质的含量比例可调(相对于粉末总重一般在10重量%以下)并尽可能均匀地分布,即在各颗粒中均匀分布。这些添加的化学物质的性质根据目标用途而决定。它们可以是例如烧结剂,其作用是促进粉末固结以获得致密的散装材料。
根据本发明的一项,本发明的粉末可分别以(n+1)、1和n的比例包含元素M、A和X。
例如,本发明的粉末可分别以3、1和2的比例包含元素M、A和X,用式M3AX2象征性地表示。
有利地,M可以是Ti,A可以是Si、Al或Ge,并且X可以是C,因而相应的物相是Ti3SiC2、Ti3AlC2或Ti3GeC2
例如,本发明的粉末可分别以2、1和1的比例包含元素M、A和X,用式M2AX象征性地表示。作为实例,可提及对应于下列物相的粉末:
-当M对应于Ti时:Ti2AlC、Ti2AlN、Ti2InN、Ti2GeC、Ti2SC、Ti2GaN、Ti2InC、Ti2TlC、Ti2SnC、Ti2GaC、Ti2CdC、Ti2PbC;
-当M对应于Zr时:Zr2InN、Zr2SnC、Zr2SC、Zr2InC、Zr2TlC、Zr2PbC、Zr2TlN;
-当M对应于Hf时:Hf2PbC、Hf2InN、Hf2SnN、Hf2SnC、Hf2SC、Hf2TlC、Hf2InC;
-当M对应于Cr时:Cr2GaC、Cr2AlC、Cr2GaN;
-当M对应于V时:V2AsC、V2AlC、V2PC、V2GaN、V2GaC、V2GeC;
-当M对应于Nb时:Nb2AlC、Nb2GaC、Nb2AsC、Nb2SnC、Nb2PC、Nb2InC、Nb2SC;
-当M对应于Ta时:Ta2AlC、Ta2GaC;
-当M对应于Mo时:Mo2GaC。
例如,本发明的粉末也可分别以4、1和3的比例包含元素M、A和X,用式M4AX3象征性地表示。作为实例,可提及对应于选自物相Ti4AlN3和Ta4AlC3的粉末。
根据本发明的一个具体实施方案,M可部分地被另一过渡金属或另一金属(比如Al)所替代,和/或A可部分地被上述A的可选元素中的另一元素替代,和/或X可部分地被上述X的可选元素中的另一元素所替代。
符合特征的粉末可以是对应于下列物相的粉末:(Ti,Zr)3SiC2、(Ti,Hf)3SiC2、(Ti,Hf)3(Si,Ge)C2、(Ti,Zr)3(Si,Ge)(C,N)2、(Ti,V)3SiC2、(Ti,V)3Si(C,N)2、Ti3(Si,Al)C2、(Ti,V)3(Si,Ge)(C,N)2、(Ti,V,Hf)3(Si,Ge)(C,N)2、(Ti,V,Hf)3(Si,Ge,Al)(C,N)2、(Nb,Ti)2AlC和TiAlN0.5C0.5。一个具体化学式可以是(Ti2.8Al0.2)SiC2。一个具体的可用于核应用的化合物是(Ti,Zr)3SiC2
在第二方面,本发明还涉及用于制备如上限定的粉末的方法,其包括下列步骤:
a)混合步骤,在不加热和没有氧气的条件下,将至少一种M的前体、至少一种A的前体和至少一种X的前体一起混合,所述前体为气体、气体悬浮物中的固体和/或气体悬浮物中的液体的形式;和
b)加热步骤,其中将步骤a)中获得的所述混合物加热到可有效形成粉末的温度。
有利地,该方法可用于获得多元素粉末,其化学组成可以通过独立地改变各前体的流速来变化。此外,由于混合步骤以气体形式、气体悬浮物中的固体和/或气体悬浮物中的液体形式进行,随后是加热步骤,本方法因而产生具有以上限定的特性的粉末。
有利地,在所述混合步骤内,所述前体由作为原料的单独的流相互接触,即由包含M的前体的流、包含A的前体的流和包含X的前体的流进行混合。
M的前体,即过渡金属,可以是M的卤化物(比如TiCl4)、M的卤氧化物(比如CrOCl2或VOCl3)、M的羰基合物(比如Mo(CO)6)、M的烷氧基化物(比如[OCH(CH3]2Nb)或M的硼氢化物(比如Zr(BH4)4)。
A的前体可以是A的氢化物(比如SiH4、Si2H6和GeH4)、A的氢卤化物(比如SiH2Cl2)或烷基化M络合物(比如Al(CH3)3)。
最后,X的前体是碳、硼或氮前体。
适当的碳前体可以是乙炔(C2H2)和乙烯(C2H4)。
适当的硼前体可以是硼卤化物(比如BCl3)或硼烷(比如B2H6和B4H6)。
适当的氮前体可以是氨(NH3)。
如果M、A或X的前体为粉末或液体的形式,它们将有利地在称作“载气”的气体悬浮物中混合,以形成适当的流。在固体的情况中,它们也可呈液体溶液的形式,然后将该液体放入载气悬浮物中,以形成气溶胶。术语“载气”理解为指任何不进入获得的产品的组成的气体。这优选为惰性气体(比如氩气),或尽管参与了反应,但在方法的最后以气态形式完全去除的气体。载气的作用是可以以控制的流速传输液体和固体反应物。
当M的前体为卤化物形式时,它们可在混合步骤a)前原位制备。
更确切地说,所述卤化物可以在卤化装置(比如氯化装置)中制备,在该装置中在氢卤酸存在下,在有利于获得相应气态M卤化物的温度下加热M的金属粉末。该温度有利地在1000℃以下并优选在500℃以下。使用该原位制备的优点是成本低,因为金属粉末比常规前体便宜。
例如,前体ZrCl4可通过在1000℃以下的温度下将锆金属粉末暴露于氢氯酸蒸汽中来制备。
引入这类形式的前体(即气体、悬浮液体或悬浮固体)的优点在于确保对流速的有效控制和对化学计量的调节。
这是因为,当为气体、悬浮液体或悬浮固体形式时,前体的化学式使测定反应物质(M、A和X)的摩尔数和粉末组成中元素的摩尔数之间的对应关系成为可能(例如,每摩尔C2H2气体含有两摩尔碳)。已知在给定压力下每单位体积的前体摩尔数,控制含有前体的流体的流速等同于控制用于形成粉末的原子的比例,并因此控制其化学计量,从而避免副产物(secondaryspecies)的形成(例如当形成Ti3SiC2粉末时的TiC)。
当替代某些M、A和X以形成固体溶液时,也以选自气体、悬浮液和悬浮固体的形式引入含有取代元素的前体。
还应当注意,当处理后粉末必须含有其他化学物质时,这些物质可以有利地在混合步骤过程中同样以气体或载气悬浮物中的固体或液体的形式引入。
根据本发明,在不加热并且无氧的条件下,将适当形式(气体、悬浮液体、悬浮固体)的各种前体一起混合。
该混合可在反应器中进行,借助由前体流入反应器室产生的湍流和/或利用反应器中的混合器。该混合步骤确保各种前体间相对均匀。该混合在无氧条件下进行是重要的,以免损害处理后获得的粉末的纯度。
一旦得到混合物,根据本发明,直接将其引入到反应区,在反应区中将其加热到可有效形成粉末的温度。当使用的加热技术是等离子体加热时,此温度可相当于产生等离子体必需的温度,或者当使用的加热技术是激光加热时,所述温度在1000—2000℃范围内。上述温度使粉末反应非常迅速并几乎瞬间进行,并且防止多数挥发性化学物质在能够参加反应前以气体形式逸出。在反应过程中释放的热量引起分子扰动,因此,如果在前面的混合步骤过程中尚未实现均匀性,高频碰撞保证了介质的化学均匀性。
本领域技术人员可以调整反应参数,比如由热源传递的混合物或粉末的流速。
通过改变混合物的流速,可以调整粉末的粒径,所述流速决定反应区中混合物的停留时间(一般地在数毫秒的数量级)。
通过改变由热源传递的能量,可以调整粉末的结晶度,温度越低形成的粉末结构将越接近无定形结构,而温度越高晶体结构越多。
有利地,反应步骤是以流动模式进行的步骤,也就是说在反应器中形成的粉末不断地经抽吸而移出,给进入的反应物的混合物留出空间。该特征意味着可以预计大量粉末的生产。
根据该方法得到的粉末可用于形成松散材料,该散装材料可以是纳米结构的单相材料或纳米结构的复合物。
术语“单相材料”理解为指基本上仅包含一个物相的材料,在本发明范围内,其分别以(n+1±ε1)、1±ε2和n±ε3的比例包含至少一种元素M、至少一种元素A和至少一种元素X,n、ε1、ε2和ε3如上限定。术语“基本上”理解为指所述相构成材料的至少95%、或97%或甚至99%。
术语“纳米结构的材料”理解为指包含尺寸大体小于100纳米的颗粒的材料。
术语“复合物”理解为指包含基体的材料,所述基体中分散有增强成分(reinforcing elements)。
因此,本发明涉及制备纳米结构单相材料的方法,其包括,优选在室温下压缩如上限定的粉末的步骤,和烧结步骤以使材料固结。为了促进烧结,在固结前可将烧结剂添加到粉末中。应该注意也可如上所述将此烧结剂添加到粉末的制备中。
根据实施该方法的一种具体方法,可以使用下列次序的步骤来制备材料:
-压缩如上面限定的粉末的步骤,在室温下,优选在500—1500MPa的压力下进行,之后得到第一预压缩物;
-研磨步骤,其中将所述第一预压缩物研磨,以获得优选为微米尺寸的聚集体;
-压缩步骤,其中将所述聚集体在室温下,优选200—400MPa的压力下压缩,之后得到第二预压缩物;
-任选地,机械加工步骤,其中将所述第二预压缩物机械加工以赋予其限定的形状;及
-固结步骤,其中将所述第二预压缩物通过烧结固结,优选在1000—2000℃的温度下,更优选1000—1500℃,任选地在优选0—200MPa的压力下进行,
所有这些步骤任选地在无氧条件下进行。
本发明还涉及可通过如上限定的方法获得的纳米结构的单相材料。在这些材料的情况中,因为它们是由本发明的粉末制备的,各颗粒的化学组成是均匀的,其尺寸可在5—500nm变化并控制其粒度分布,粒度分布可以是狭窄的(例如90%的颗粒的尺寸在20—50nm之间)。
本发明还涉及复合物的制备。
各种复合物可根据本发明进行区分:
-包含由本发明的粉末获得的基体的复合物,其中分散有基体微粒增强成分(例如那些平均粒径从数微米到数十微米的基体微粒增强成分);
-包含由本发明的粉末获得的基体的复合物,其中分散有基体短纤维(通常长度小于1cm,也称作晶须)作为增强成分,所述基体短纤维一般具有无规取向;和
-包含由本发明的粉末获得的基体和长纤维作为增强成分的复合物。所述长纤维的长度通常为1cm到数厘米(或具有该部分所需数量级的长度)。它们在复合物形成之前,可以形成预制体。
当所述增强成分是微粒增强成分和/或短纤维时,本发明的方法通常包括将本发明的粉末与增强成分混合的步骤和烧结步骤。
根据实施该方法的一种具体方法,特别是当增强成分是短纤维时,上述复合物可根据下列次序的步骤进行制备:
-压缩步骤,其中将根据本发明的粉末在室温下在优选500—1500MPa的压力下进行压缩,之后得到第一预压缩物;
-研磨步骤,其中将所述第一预压缩物研磨以获得优选为微米尺寸的聚集体;
-混合步骤,其中将所述聚集体与增强成分混合;
-压缩步骤,其中将所述混合物在室温下在优选200—400MPa的压力下进行压缩,之后得到第二预压缩物;
-任选地,机械加工步骤,其中将所述第二预压缩物机械加工以赋予其限定的形状;和
-固结步骤,其中将所述第二预压缩物通过烧结而固结,优选在1000—2000℃的温度下,并更优选1000—1500℃,任选地在优选0—200MPa的压力下进行,
所有这些步骤优选在无氧条件下进行。
特别地,所述增强成分可以是碳、碳化硅(SiC)或其他陶瓷(氧化物、碳化物、氮化物、碳氧化物、碳氮化物、硅化物或硼化物)(比如氧化铝)的颗粒或短纤维。应当指出短纤维(或晶须)通常理解为指在弹性模量和抗拉强度方面具有特别优异的机械性能的纤维状单晶。
本发明还涉及可由上述方法获得的纳米结构的复合物。
当所述增强成分是长纤维时,用于制备复合物的方法通常包括悬浮根据本发明的粉末的步骤,用所述悬浮物渗透由所述长纤维组成的预制体的步骤,和烧结步骤以固结材料。
根据实施该方法的一种具体方法,上述复合物可根据下列次序的步骤进行制备:
-将根据本发明的粉末悬浮在水或有机介质中的步骤,任选地使用分散剂和/或粘合剂,并任选地对该悬浮物进行超声以分离任何聚集体;
-对由长纤维(可能是织物纤维)组成的预制体进行渗透的步骤,所述渗透步骤可能用电泳或压力渗透进行;
-将渗透后获得的集合体(assembly)干燥的步骤;
-将干燥后获得的所述集合体固结的步骤,优选在1000—2000℃的温度下,更优选1000—1500℃,任选地在优选0—200MPa的压力下通过烧结进行,
所有这些步骤优选在无氧条件下进行。
当所述烧结在压力下进行时,垂直于纤维织物施加压力是有利的,以免损伤纤维。
所述增强成分可以是长的碳纤维或碳化硅(SiC)纤维或陶瓷(氧化物、碳化物、氮化物、碳氧化物、碳氮化物、硅化物或硼化物)纤维,比如氧化铝纤维。
本发明还涉及可由上述方法获得的纳米结构的复合物。
无论它们的增强成分的性质如何,所述复合物可应用于涉及耐火材料使用的所有领域中,比如核工业或航空工业。
附图说明
唯一的附图显示了用于实施实施例中说明的实施方案的装置。
具体实施方式
实施例1
该实施例说明在图1所示装置中通过激光热解制备Ti3SiC2粉末。
硅、碳和钛前体分别是硅烷(SiH4)、乙炔(C2H2)和四氯化钛(TiCl4)。
将上述前体分别以1、1和3的比例引入到混合室中(参考1),SiH4和C2H2为气体形式而TiCl4为在蒸发器(参考3)中获得的蒸气形式,所述蒸发器具有惰性气体入口(参考2)。将得到的混合物引入激光热解反应器5中,其中压力是900mbar,火焰温度在1000—2000℃之间,所述混合室具有供排出形成的粉末的出口(参考7)。将TiCl4蒸气传输到反应器的管线保持在150℃的温度,从而防止蒸气再凝结。对于1、1和3的比例,通过简单调整引入的反应物流速,确保制备的纳米粉末的Ti3SiC2化学计量。在此粉末中可以观测到,Ti、Si和C元素在纳米级别以至原子级别上均匀分布。通过将SiH4、C2H2和TiCl4的流速分别设为1.5、1.5和4.5 l/min,Ti3SiC2的产率升至600g/h。
得到的粉末的粒径小于100nm。
实施例2
该实施例说明在如单一附图所示装置中通过激光热解制备Ti2SnC粉末。
钛、锡和碳前体分别是四氯化钛(TiCl4)、四氯化锡(SnCl4)和乙炔(C2H2)。
以与前述同样的方式,将上述前体分别以2、1和1/2的比例引入。
实施例3
该实施例说明在类似于单一附图所示装置中通过激光热解制备Ti4AlC3粉末。
钛、铝和碳前体分别是四氯化钛(TiCl4)、三氯化铝(AlCl3)和乙炔(C2H2)。
以与前述同样的方式,将上述前体分别以4、1和3/2的比例引入。

Claims (30)

1.粉末,其包含至少一种元素M、至少一种元素A和至少一种元素X,比例分别为(n+1±ε1)、1±ε2和n±ε3,其中:
* A选自Cd、Al、Ga、In、Tl、Si、Ge、Sn、Pb、P、As和S;
* M是过渡金属;
* X选自B、C和N;
* n是等于1、2或3的整数;且
* ε1、ε2和ε3各自独立地表示0-0.2的数值,
所述粉末的平均粒径小于500nm。
2.权利要求1的粉末,其中所述粉末的平均粒径小于100nm。
3.权利要求1的粉末,其中所述粉末的平均粒径为10—200nm。
4.权利要求1的粉末,其中所述粉末的平均粒径为10—50nm。
5.权利要求1—4任一项的粉末,其中所述元素M、A和X的比例分别为3、1和2。
6.权利要求5的粉末,其中所述粉末对应于选自Ti3SiC2、Ti3AlC2和Ti3GeC2的物相。
7.权利要求6的粉末,其中所述粉末对应于Ti3SiC2相。
8.权利要求1—4任一项的粉末,其中所述元素M、A和X的比例分别为2、1和1。
9.权利要求8的粉末,其中所述粉末对应于选自Ti2AlC、Ti2AlN、Ti2InN、Ti2GeC、Ti2SC、Ti2GaN、Ti2InC、Ti2TlC、Ti2SnC、Ti2GaC、Ti2CdC、Ti2PbC、Zr2InN、Zr2SnC、Zr2SC、Zr2InC、Zr2TlC、Zr2PbC、Zr2TlN、Hf2PbC、Hf2InN、Hf2SnN、Hf2SnC、Hf2SC、Hf2TlC、Hf2InC、Cr2GaC、Cr2AlC、Cr2GaN、V2AsC、V2AlC、V2PC、V2GaN、V2GaC、V2GeC、Nb2AlC、Nb2GaC、Nb2AsC、Nb2SnC、Nb2PC、Nb2InC、Nb2SC、Ta2AlC、Ta2GaC、Mo2GaC和Nb2SC的物相。
10.权利要求1—4任一项的粉末,其中所述元素M、A和X的比例分别为4、1和3。
11.权利要求10的粉末,其中所述粉末对应于选自Ti4AlN3和Ta4AlC3的物相。
12.权利要求1的粉末,其中M部分地被另一过渡金属或另一金属所替代,和/或A部分地被权利要求1中A的可选元素中的另一元素所替代,和/或X部分地被权利要求1中X的可选元素中的另一元素所替代。
13.权利要求12的粉末,其中所述粉末对应于选自(Ti,Zr)3SiC2、(Ti,Hf)3SiC2、(Ti,Hf)3(Si,Ge)C2、(Ti,Zr)3(Si,Ge)(C,N)2、(Ti,V)3SiC2、(Ti,V)3Si(C,N)2、Ti3(Si,Al)C2、(Ti,V)3(Si,Ge)(C,N)2、(Ti,V,Hf)3(Si,Ge)(C,N)2、(Ti,V,Hf)3(Si,Ge,Al)(C,N)2、(Nb,Ti)2AlC和TiAlN0.5C0.5的物相。
14.前述权利要求任一项的粉末,其还包括烧结剂。
15.用于制备权利要求1所限定的粉末的方法,其包括下列步骤:
a)混合步骤,在不加热和没有氧气的条件下进行,其中将至少一种M的前体、至少一种A的前体和至少一种X的前体一起混合,所述前体为气体、气体悬浮物中的固体和/或气体悬浮物中的液体的形式;和
b)加热步骤,其中将在步骤a)中获得的所述混合物加热到可有效形成粉末的温度。
16.权利要求15的制备方法,其中所述混合步骤从包含M的前体的流、包含A的前体的流和包含X的前体的流开始进行。
17.权利要求15或16的制备方法,其中所述M的前体选自M的卤化物、M的卤氧化物、M的羰基合物、M的烷氧化物和M的硼氢化物。
18.权利要求15—17任一项的制备方法,其中所述A的前体选自A的氢化物、A的氢卤化物和烷基化M的络合物。
19.权利要求15—18任一项的制备方法,其中碳前体选自乙炔(C2H2)和乙烯(C2H4)。
20.权利要求15—19任一项的制备方法,其中硼前体选自硼卤化物和硼烷。
21.权利要求15—20任一项的制备方法,其中氮前体是NH3
22.权利要求15的制备方法,其包括,当所述M的前体是M卤化物时,在步骤a)前,制备所述前体的步骤,其包括在氢卤酸存在下,在可有效得到相应M卤化物的温度下加热M的金属粉末。
23.权利要求15—22任一项的制备方法,其中所述加热步骤在产生等离子体所需温度或1000—2000℃的温度下进行。
24.用于制备纳米结构单相材料的方法,其包括压缩如权利要求1—14任一项所限定的粉末的步骤和烧结步骤以使材料固结。
25.纳米结构单相材料,其可用权利要求24所限定的方法获得。
26.用于制备具有微粒增强成分和/或短纤维作为增强成分的复合物的方法,其包括将如权利要求1—14任一项所限定的粉末与增强成分混合的步骤和烧结步骤。
27.权利要求26的制备方法,其中所述增强成分选自碳的颗粒或短纤维、碳化硅(SiC)的颗粒或短纤维或其他陶瓷的颗粒或短纤维。
28.复合物,其可通过权利要求26和27任一项所限定的方法获得。
29.用于制备具有长纤维作为增强成分的复合物的方法,其包括悬浮如权利要求1—14任一项所限定的粉末的步骤,用所述悬浮物渗透由所述长纤维组成的预制体的步骤,和烧结步骤从而使所述复合物固结。
30.复合物,其可通过权利要求29所限定的方法获得。
CNA2007800185415A 2006-05-30 2007-05-29 Max相粉末和用于制备所述粉末的方法 Pending CN101448760A (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0651960 2006-05-30
FR0651960A FR2901721B1 (fr) 2006-05-30 2006-05-30 Poudres de phase max et procede de fabrication des dites poudres

Publications (1)

Publication Number Publication Date
CN101448760A true CN101448760A (zh) 2009-06-03

Family

ID=37888107

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2007800185415A Pending CN101448760A (zh) 2006-05-30 2007-05-29 Max相粉末和用于制备所述粉末的方法

Country Status (7)

Country Link
US (1) US9023246B2 (zh)
EP (1) EP2038238B1 (zh)
JP (1) JP5101605B2 (zh)
CN (1) CN101448760A (zh)
AT (1) ATE537129T1 (zh)
FR (1) FR2901721B1 (zh)
WO (1) WO2007138052A1 (zh)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101747057B (zh) * 2009-10-27 2012-12-26 哈尔滨工业大学 一种Nb4AlC3陶瓷粉体的制备方法
CN101747049B (zh) * 2009-10-27 2012-12-26 哈尔滨工业大学 Nb4AlC3块体陶瓷的制备方法
CN101747048B (zh) * 2009-10-27 2013-03-13 哈尔滨工业大学 Nb2AlC块体陶瓷的制备方法
CN104003728A (zh) * 2014-05-19 2014-08-27 河南工业大学 一种无压烧结制备Ti2SC陶瓷的方法
WO2014154135A1 (zh) * 2013-03-26 2014-10-02 中国科学院金属研究所 三氧化二铝弥散强化钛四铝氮三陶瓷复合材料及制备方法
CN104192905A (zh) * 2014-08-04 2014-12-10 西华大学 连续合成Cr2AlC粉体的盐浴炉及合成方法
CN103910532B (zh) * 2013-01-05 2015-12-23 中国科学院宁波材料技术与工程研究所 涂层无机纤维增韧max相陶瓷复合材料、其制备方法及用途
CN105294106A (zh) * 2015-10-15 2016-02-03 河海大学 放电等离子烧结工艺制备的Ta2AlC块体陶瓷及其制备方法
CN106747536A (zh) * 2016-11-09 2017-05-31 哈尔滨东安发动机(集团)有限公司 一种纤维增强三元层状陶瓷零件的表面氮化方法
CN107686352A (zh) * 2017-08-14 2018-02-13 河海大学 一种高纯度Ti2SnC陶瓷材料的制备方法
CN108075135A (zh) * 2017-12-26 2018-05-25 盐城工学院 一种掺钒碳硫化钛电池负极材料的制备方法及其所得材料和应用
CN109369188A (zh) * 2018-12-13 2019-02-22 西南交通大学 一种超高纯度Cr2GaC陶瓷粉体的制备方法
CN109400171A (zh) * 2018-12-16 2019-03-01 冯良荣 一种制备max相材料的方法
CN110357633A (zh) * 2019-07-11 2019-10-22 上海交通大学 一种室温快速制备钛铝碳陶瓷的方法
CN111647769A (zh) * 2020-06-18 2020-09-11 超威电源集团有限公司 一种蓄电池板栅合金及其制备方法
CN112110731A (zh) * 2020-08-14 2020-12-22 河南理工大学 Sc2SC层状材料及其制备方法
CN114315357A (zh) * 2021-12-14 2022-04-12 长安大学 一种C/C-Ti3AlC2复合材料及其制备方法

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5988030B2 (ja) * 2012-10-04 2016-09-07 国立研究開発法人物質・材料研究機構 大径Ti3SiC2層状粒子を含む粉体、大径Ti3Si1−xC2ナノシート及びそれらの製造方法
FR3024140B1 (fr) * 2014-07-28 2021-10-08 Centre De Transfert De Tech Ceramiques C T T C Materiau composite comprenant des objets ceramiques dans une matrice liante et procede de fabrication d'un tel materiau
CA2939288A1 (en) 2015-08-28 2017-02-28 Rolls-Royce High Temperature Composites, Inc. Ceramic matrix composite including silicon carbide fibers in a ceramic matrix comprising a max phase compound
CN106220181A (zh) * 2016-07-13 2016-12-14 东南大学 一种利用粉末冶金手段制备Ti2PbC陶瓷的方法
WO2018022999A1 (en) * 2016-07-28 2018-02-01 Seerstone Llc. Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same
US10812448B2 (en) * 2018-01-26 2020-10-20 Citrix Systems, Inc. Split-tunneling for clientless SSL-VPN sessions with zero-configuration
US11572298B2 (en) * 2018-05-11 2023-02-07 Entegris, Inc. Molds that include a ceramic material surface, and related methods for making and using the molds
RU2691181C1 (ru) * 2018-06-06 2019-06-11 Федеральное государственное бюджетное учреждение науки Институт электрофизики Уральского отделения Российской академии наук (ИЭФ УрО РАН) Способ изготовления высокоплотных объемных керамических элементов с использованием электрофоретического осаждения наночастиц (варианты)
CN112267048B (zh) * 2020-09-02 2022-02-25 上海交通大学 一种含纳米Ti2AlN粒子的铝基合金及其制备方法
CN114480902B (zh) * 2022-01-17 2023-04-28 东南大学 一种抑制max相中金属晶须生长的方法
CN114669747A (zh) * 2022-03-21 2022-06-28 四川大学 以Cr、Zr或Nb为基的MnAlCn-1相粉末的制备方法

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617358A (en) * 1967-09-29 1971-11-02 Metco Inc Flame spray powder and process
US5656138A (en) * 1991-06-18 1997-08-12 The Optical Corporation Of America Very high vacuum magnetron sputtering method and apparatus for precision optical coatings
US5942455A (en) * 1995-11-14 1999-08-24 Drexel University Synthesis of 312 phases and composites thereof
US6652967B2 (en) * 2001-08-08 2003-11-25 Nanoproducts Corporation Nano-dispersed powders and methods for their manufacture
US6569397B1 (en) * 2000-02-15 2003-05-27 Tapesh Yadav Very high purity fine powders and methods to produce such powders
US7384680B2 (en) * 1997-07-21 2008-06-10 Nanogram Corporation Nanoparticle-based power coatings and corresponding structures
US6461989B1 (en) * 1999-12-22 2002-10-08 Drexel University Process for forming 312 phase materials and process for sintering the same
US6500676B1 (en) * 2001-08-20 2002-12-31 Honeywell International Inc. Methods and apparatus for depositing magnetic films
WO2003046247A1 (en) * 2001-11-30 2003-06-05 Abb Ab METHOD OF SYNTHESIZING A COMPOUND OF THE FORMULA Mn+1AXn, FILM OF THE COMPOUND AND ITS USE
SE526336C2 (sv) * 2002-07-01 2005-08-23 Seco Tools Ab Skär med slitstark refraktär beläggning av MAX-fas
US20040250334A1 (en) * 2003-06-13 2004-12-16 Tamer El-Raghy Max phase glove and condom formers
WO2005038985A2 (en) * 2003-10-16 2005-04-28 Abb Research Ltd. COATINGS OF Mn+1AXn MATERIAL FOR ELECTRICAL CONTACT ELEMENTS
JP2005281084A (ja) * 2004-03-30 2005-10-13 Tungaloy Corp 焼結体およびその製造方法
JP2006001829A (ja) * 2004-05-20 2006-01-05 Japan Science & Technology Agency チタン炭化物焼結体又はチタンシリコン炭化物焼結体、同製造方法、同加工方法又はコーティング方法及び同用基板
US7553564B2 (en) * 2004-05-26 2009-06-30 Honeywell International Inc. Ternary carbide and nitride materials having tribological applications and methods of making same
JP4593173B2 (ja) * 2004-05-26 2010-12-08 株式会社アライドマテリアル ナノ粒径を備えた複合炭化物粉末およびその製造方法
US7572313B2 (en) * 2004-05-26 2009-08-11 Drexel University Ternary carbide and nitride composites having tribological applications and methods of making same
US20060051281A1 (en) * 2004-09-09 2006-03-09 Bhabendra Pradhan Metal carbides and process for producing same
US7510760B2 (en) * 2005-03-07 2009-03-31 Boardof Trustees Of The University Of Arkansas Nanoparticle compositions, coatings and articles made therefrom, methods of making and using said compositions, coatings and articles
FR2901714B1 (fr) * 2006-05-30 2008-09-05 Commissariat Energie Atomique Procede en phase gazeuse pour la production de particules nanometriques

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101747057B (zh) * 2009-10-27 2012-12-26 哈尔滨工业大学 一种Nb4AlC3陶瓷粉体的制备方法
CN101747049B (zh) * 2009-10-27 2012-12-26 哈尔滨工业大学 Nb4AlC3块体陶瓷的制备方法
CN101747048B (zh) * 2009-10-27 2013-03-13 哈尔滨工业大学 Nb2AlC块体陶瓷的制备方法
CN103910532B (zh) * 2013-01-05 2015-12-23 中国科学院宁波材料技术与工程研究所 涂层无机纤维增韧max相陶瓷复合材料、其制备方法及用途
WO2014154135A1 (zh) * 2013-03-26 2014-10-02 中国科学院金属研究所 三氧化二铝弥散强化钛四铝氮三陶瓷复合材料及制备方法
CN104003728A (zh) * 2014-05-19 2014-08-27 河南工业大学 一种无压烧结制备Ti2SC陶瓷的方法
CN104192905A (zh) * 2014-08-04 2014-12-10 西华大学 连续合成Cr2AlC粉体的盐浴炉及合成方法
CN104192905B (zh) * 2014-08-04 2015-08-12 西华大学 连续合成Cr2AlC粉体的盐浴炉及合成方法
CN105294106A (zh) * 2015-10-15 2016-02-03 河海大学 放电等离子烧结工艺制备的Ta2AlC块体陶瓷及其制备方法
CN106747536A (zh) * 2016-11-09 2017-05-31 哈尔滨东安发动机(集团)有限公司 一种纤维增强三元层状陶瓷零件的表面氮化方法
CN107686352A (zh) * 2017-08-14 2018-02-13 河海大学 一种高纯度Ti2SnC陶瓷材料的制备方法
CN108075135A (zh) * 2017-12-26 2018-05-25 盐城工学院 一种掺钒碳硫化钛电池负极材料的制备方法及其所得材料和应用
CN108075135B (zh) * 2017-12-26 2020-09-18 盐城工学院 一种掺钒碳硫化钛电池负极材料的制备方法及其所得材料和应用
CN109369188A (zh) * 2018-12-13 2019-02-22 西南交通大学 一种超高纯度Cr2GaC陶瓷粉体的制备方法
CN109400171A (zh) * 2018-12-16 2019-03-01 冯良荣 一种制备max相材料的方法
CN110357633A (zh) * 2019-07-11 2019-10-22 上海交通大学 一种室温快速制备钛铝碳陶瓷的方法
CN111647769A (zh) * 2020-06-18 2020-09-11 超威电源集团有限公司 一种蓄电池板栅合金及其制备方法
CN111647769B (zh) * 2020-06-18 2021-03-30 超威电源集团有限公司 一种蓄电池板栅合金及其制备方法
CN112110731A (zh) * 2020-08-14 2020-12-22 河南理工大学 Sc2SC层状材料及其制备方法
CN114315357A (zh) * 2021-12-14 2022-04-12 长安大学 一种C/C-Ti3AlC2复合材料及其制备方法

Also Published As

Publication number Publication date
JP2009538814A (ja) 2009-11-12
US9023246B2 (en) 2015-05-05
US20100247910A1 (en) 2010-09-30
FR2901721B1 (fr) 2008-08-22
WO2007138052A1 (fr) 2007-12-06
FR2901721A1 (fr) 2007-12-07
ATE537129T1 (de) 2011-12-15
EP2038238B1 (fr) 2011-12-14
JP5101605B2 (ja) 2012-12-19
EP2038238A1 (fr) 2009-03-25

Similar Documents

Publication Publication Date Title
CN101448760A (zh) Max相粉末和用于制备所述粉末的方法
US5514350A (en) Apparatus for making nanostructured ceramic powders and whiskers
CN102123967B (zh) 有序的中孔碳-硅纳米复合物的合成
Hahn Gas phase synthesis of nanocrystalline materials
KR20080108577A (ko) 다결정성 연마 컴팩트
KR20070083557A (ko) 다결정 연마 물질 및 그 제조방법
El-Sheikh et al. In situ synthesis of ZrC/SiC nanocomposite via carbothermic reduction of binary xerogel
Wu et al. Pyrolysis synthesis and microstructure of zirconium carbide from new preceramic polymers
US20060051281A1 (en) Metal carbides and process for producing same
Chen et al. Molten-salt nitridation synthesis of cubic ZrN nanopowders at low temperature via magnesium thermal reduction
Katea et al. Synthesis of nano-phase ZrC by carbothermal reduction using a ZrO2–carbon nano-composite
WO2002086451A2 (en) Organoboron route and process for preparation of boron nitride
Meng et al. Synthesis of “A β-SiC nanorod within a SiO2 nanorod” one dimensional composite nanostructures
Xu et al. Morphology and growth mechanism of silicon carbide chemical vapor deposited at low temperatures and normal atmosphere
Long et al. Synthesis of soluble and meltable pre‐ceramic polymers for Zr‐containing ceramic nanocomposites
Wu et al. Polymer precursor synthesis of novel ZrC–SiC ultrahigh-temperature ceramics and modulation of their molecular structure
US8246743B2 (en) Single crystal silicon carbide nanowire, method of preparation thereof, and filter comprising the same
JPH0617371A (ja) 現場化学反応により生じたノンオキサイド焼結ファイバーのための保護コーティング
Li et al. Interface structure and formation mechanism of BN/intergranular amorphous phase in pressureless sintered Si3N4/BN composites
Borek et al. Boron nitride coatings on oxide substrates: role of surface modifications
Zhou Ternary Si-Metal-N ceramics: single-source-precursor synthesis, nanostructure and properties characterization
Bouyer et al. Characterization of SiC and Si3N4 coatings synthesized by means of inductive thermal plasma from disilane precursors
Call et al. The density factor in the synthesis of carbon nanotube forest by injection chemical vapor deposition
Zhu et al. New route to synthesize ZrB2 coatings by reactive chemical vapor deposition method using Zr-BCl3-H2-Ar reagents
US5849360A (en) Tube chemical gas deposition method of preparing titanium nitride coated titanium carbide for titanium carbide/silicon nitride composites

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20090603