EP1922354A2 - Ceramique resistante et procede de fabrication - Google Patents

Ceramique resistante et procede de fabrication

Info

Publication number
EP1922354A2
EP1922354A2 EP06780403A EP06780403A EP1922354A2 EP 1922354 A2 EP1922354 A2 EP 1922354A2 EP 06780403 A EP06780403 A EP 06780403A EP 06780403 A EP06780403 A EP 06780403A EP 1922354 A2 EP1922354 A2 EP 1922354A2
Authority
EP
European Patent Office
Prior art keywords
sic
ceramic material
solid solution
resistant ceramic
aln
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.)
Withdrawn
Application number
EP06780403A
Other languages
German (de)
English (en)
Inventor
Avigdor Zangvil
Michael Katz
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.)
Carboshield Ltd
Original Assignee
Carboshield Ltd
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 Carboshield Ltd filed Critical Carboshield Ltd
Publication of EP1922354A2 publication Critical patent/EP1922354A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C04B35/591—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 obtained by reaction sintering
    • 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
    • C04B35/593—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 obtained by pressure sintering
    • 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
    • C04B35/593—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 obtained by pressure sintering
    • C04B35/5935—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 obtained by pressure sintering obtained by gas pressure sintering
    • 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
    • C04B35/62615—High energy or reactive ball 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6261—Milling
    • C04B35/6262—Milling of calcined, sintered clinker or ceramics
    • 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
    • C04B35/62695—Granulation or pelletising
    • 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
    • C04B35/63—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 using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
    • 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
    • C04B35/63—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 using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/638—Removal thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F41H5/04—Plate construction composed of more than one layer
    • F41H5/0414—Layered armour containing ceramic material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F41H5/04—Plate construction composed of more than one layer
    • F41H5/0414—Layered armour containing ceramic material
    • F41H5/0428—Ceramic layers in combination with additional layers made of fibres, fabrics or plastics
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • 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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • 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
    • C04B2235/3817—Carbides
    • C04B2235/3839—Refractory metal 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
    • C04B2235/3839—Refractory metal carbides
    • C04B2235/3843—Titanium carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3856—Carbonitrides, e.g. titanium carbonitride, zirconium carbonitride
    • 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
    • C04B2235/3865—Aluminium nitrides
    • 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
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3886—Refractory metal nitrides, e.g. vanadium nitride, tungsten nitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3895—Non-oxides with a defined oxygen content, e.g. SiOC, TiON
    • 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
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/404—Refractory metals
    • 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
    • C04B2235/50—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
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • 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
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6565—Cooling rate
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6587—Influencing the atmosphere by vaporising a solid material, e.g. by using a burying of sacrificial powder
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
    • 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
    • C04B2235/94—Products characterised by their shape
    • 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
    • C04B2235/95—Products characterised by their size, e.g. microceramics
    • 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

Definitions

  • the present invention relates to a method of preparing a resistant ceramic material by consolidation of SiC-AlN solution powder, and to novel resistant ceramic material comprising primarily a homogeneous SiC-AlN solid solution or a homogeneous SiC-AlN solid solution that underwent phase separation, used for military and civil armor, and products that can withstand dynamic loading and are also wear resistant.
  • SiC silicon carbide
  • AlN aluminum nitride
  • Al 2 O 3 aluminum oxide
  • B 4 C boron carbide
  • Aluminum Nitride is resistant to attack by most molten metals, most notably aluminum, lithium and copper. AlN is resistant to attack from most molten salts including chlorides and cryolite; it has high thermal conductivity for a ceramic material (second only to beryllia); AlN has high electrical resistivity; and has high dielectric strength; AlN may be attacked by acids and alkalis; and in the powder form is susceptible to hydrolysis by water or humidity.
  • Silicon Carbide is highly wear resistant and also has good mechanical properties, including high temperature strength and thermal shock resistance.
  • Bulk SiC as a technical ceramic, is produced in two main ways. Reaction bonded SiC is made by infiltrating compacts made of mixtures of SiC and Carbon with liquid Silicon. The Silicon reacts with the Carbon forming SiC. The reaction product bonds the SiC particles.
  • Sintered SiC is produced from pure SiC powder with oxide or non-oxide sintering aids. Conventional ceramic forming processes are used and the material is sintered in an inert atmosphere at temperatures up to 2000 0 C or higher.
  • the aim of the present invention is the development of an impact resistant ceramic material, which is applicable for manufacture of inexpensive, uniform, controllable and lightweight armor tiles and other articles.
  • this invention provides a method of preparing a resistant ceramic material by consolidation of a SiC-AlN solid solution powder comprising a. synthesis of a SiC-AlN solid solution, followed by b. processing steps comprising part or all of: crushing, milling, sinter-aid addition, binder addition, granulation (if cold-pressed or hot-pressed), cold forming, consolidation and heat treatment.
  • this invention provides a resistant ceramic material comprising primarily a homogeneous SiC-AlN solid solution. [009] hi one embodiment, this invention provides a resistant ceramic material comprising primarily a homogeneous SiC-AlN solid solution, which underwent phase separation.
  • Fig. 1 is an X-ray diffraction pattern of the synthesized and milled SiC-AlN solution powder, similar to that obtained in EXAMPLE 3 below, but with a 1 :1 ratio of SiC:AlN in the solid solution. It shows the typical peaks (at the correct locations and relative intensities) of a SiC-AlN solid solution with approximately 50% SiC and 50% AlN.
  • Fig. 2 is an X-ray diffraction pattern of the synthesized and milled SiC-AlN solution powder with Ti(QN) particles, similar to that obtained in EXAMPLE 2 below. It shows the typical peaks (at the correct locations and relative intensities) of a SiC-AlN solid solution with approximately 60% SiC and 40% AlN and also of Ti(QN).
  • Fig. 3 is an optical micrograph of a polished and etched sample from a tile, similar to that obtained in EXAMPLE 3 below. It shows a dense, fined grained microstructure of the solid solution without visible porosity.
  • Fig. 4 shows square and hexagonal SiC-AlN sintered armor tiles, similar to those described in EXAMPLE 3, on an aluminum alloy block.
  • the present invention relates to a method of preparing a resistant ceramic material by consolidation of SiC-AlN solid solution powder, and to novel resistant ceramic material comprising primarify a homogeneous SiC-AlN solid solution or a homogenous SiC-AlN solid solution that underwent phase separation, that may be used for military and civil armor, and products that can withstand dynamic loading and are also wear resistant.
  • SiC and AlN are promising armor materials, although AlN has been of much less interest.
  • SiC is a highly covalent compound (82%), while AlN is less covalent (57%).
  • Solid solutions and composites of the two materials have several important advantages for ballistic applications.
  • the sintering temperature necessary for densification is lower for a SiC-AlN solid solution than for SiC alone.
  • AlN can help reduce the amount of additives necessary for pressureless sintering (AlN itself can be used a sintering aid to SiC).
  • SiC and AlN allow good control of the microstructure (e.g., size and shape of crystallites, structure modulation), both during the initial formation of the microstructure and in subsequent treatments.
  • the SiC-AlN system is among only a few ceramic systems (another important one is the Si-Al-O-N system) where extensive solid solutions can form.
  • the SiC-AlN system possesses a miscibility gap, where precipitation or spinodal decomposition can occur by soaking the solid solution at certain temperatures, thus improving mechanical properties.
  • the addition of AlN can potentially improve antiballistic performance, because it is known to possess a structural transition at high shock wave velocity. Because of all these reasons, materials in the SiC-AlN system can have superior ballistic performance (a synergistic effect), if engineered properly, in spite of the fact that AlN itself has lower performance than that of SiC. At the same time, these materials can be processed more easily and more effectively than SiC itself.
  • the formation of the SiC-AlN solid solution from SiC and AlN requires temperatures of 2100° to 2300 0 C. if powders having particle sizes in the order of micrometers or larger are used. TWs can be achieved only by hot-pressing, because pressureless sintering is not practical at such temperatures due to material loss. Hot-pressing is a very expensive process, and renders the articles produced by it unaffordable for many armor or wear applications. In addition, hot-pressing does not allow the production of large or complicated parts. In addition, even at such high temperatures, the solid solution that is obtained is inhomogeneous: it contains regions with considerably variable SiC: AlN ratios, a fact that makes it extremely difficult to obtain reproducible microstructures and properties.
  • such homogeneous solid solution powders are produced by an in situ reactive process from certain precursors, rather than from mixtures of SiC and AlN.
  • the resulting solid solution product undergoes processing steps such as milling, sinter- aid addition, binder addition, granulation, cold forming, and final consolidation.
  • processing steps such as milling, sinter- aid addition, binder addition, granulation, cold forming, and final consolidation.
  • the parameters of each of these steps are specifically determined so as to fit the solid solution composition, and are generally different from parameters used for processing of SiC, AlN, or SiC+ AlN mixtures.
  • the present invention provides a method of preparing a resistant ceramic material by consolidation of a SiC-AlN solid solution powder comprising a) synthesis of a SiC-AlN solid solution, followed by b) processing steps comprising part or all of: crushing, milling, sinter-aid addition, binder addition, granulation (if cold-pressed or hot-pressed), cold forming, consolidation and heat treatment.
  • carbide, nitride, or carbo-nitride of a transition metal is embedded in step (a) or step (b).
  • the transition metal is Titanium or Zirconium.
  • the SiC-AlN solid solution may be homogeneous.
  • homogeneous solid solution of non-modulated structure includes SiC:AlN constant ratios within 10% error.
  • homogeneous solid solution of modulated structure includes SiC: AlN constant ratios within 10% error, when local composition is measured over areas larger than the modulation wavelength.
  • the microstructure of a SiC-AlN solid solution may consist of single- phase crystallites, homogeneous, without large deviation of composition from point to point within each crystallite; in another embodiment crystallites that exhibit a phase-separated structure, including modulation of compositions, with alternating regions that are richer and poorer in AlN content. In another embodiment, such modulated structures have been reported to contribute to the fracture toughness of the material.
  • the average crystallite size (or grain size) of a SiC-AlN solid solution is between about 0.1 micrometers and 10 micrometers.
  • a SiC-AlN solid solution constitutes between 60 and 99% of the weight of the article.
  • LQ another embodiment the method of preparation of homogeneous SiC-AlN solid solution including self propagating high temperature synthesis (SHS) via combustion nitridation of aluminum, silicon and carbon (Al-Si-C) or aluminum and silicon carbide (Al-SiC) under nitrogen gas pressure of up to 50 bar.
  • SHS high temperature synthesis
  • the raw dry-mixed powder of aluminum, silicon and carbon or aluminum and SiC is poured into a carbon felt-lined perforated stainless steel reactor or a similar gas-permeable reactor, then pressed or shaken to achieve a desirable bulk density and the reactor placed in a pressure chamber, where nitrogen gas pressure is applied.
  • ignition of the powder is achieved by tungsten wire heating, graphite strip heating, laser heating or similar means; the reaction propagates downwards and complete reaction is achieved.
  • the reactor and reaction propagation is in horizontal direction.
  • the SHS method of solid solution can be described by the following two exothermic reaction paths: xAl +x/2.N 2 (g) + (l-x)Si + (l-x)C ⁇ xAlN + (l-x)SiC (1) xAl +x/2.N 2 (g) + (l-x)SiC ⁇ xAIN + (l-x)SiC (2)
  • a transition metal powder is added and mixed with the Al-Si-C powders, to obtain, for example, Ti(C 5 N) as separate particles along with or embedded in the SiC-AlN solid solution particles.
  • This additional reaction path is:
  • Addition of a transition metal powder provides (a) the formation of TiC from Ti and C is more exothermic than the formation of SiC from Si and C, although less exothermic than the formation of AlN from Al and N 2 .
  • the addition of Ti allows to obtain a stable reaction with higher Si: Al ratios,
  • the Ti carbonitride particles can act as a toughening phase.
  • the molecular ratio (which is also close to the weight ratio) of the SiC-AlN solid solution obtained is between about 92:8 to about 50:50.
  • the solid solution can be processed in water, in contrast to mixtures containing AlN powder (not in solid solution), which react with water.
  • the reaction product of (a) (sponge-like product, SiC-AlN solid solution in the SHS process) is crushed in a jaw crusher or by other means, and sieved to ⁇ 250 ⁇ m size powder.
  • the powder particles themselves are composed of micrometer-sized crystallites, and this fine grained material is easy (relative to SiC) to further comminute.
  • milling includes wet-vibration-milling in cylindrical rubber-lined steel containers with water or alcohol, and either tungsten carbide or SiC or SiC-AlN milling media such as WC, SiC or SiC-AlN.
  • the water is de-ionized water
  • the alcohol is isopropanol.
  • the containers are mounted on a vibrating plate, activated by a vibratory motor, for a time sufficient to reduce the average particle size to around 1 micrometer.
  • milling is done in rubber-lined containers or in SiC containers on an attrition miller.
  • wet bead milling with 1-2 mm ceramic beads is used.
  • sub-micron powder is obtained by a high energy milling method, such as those mentioned above.
  • sintering aids for liquid phase sintering are a mixture of oxides of aluminum and yttrium and/or a rare earth (RE) element which are added to the powder.
  • the mixture is homogenized in a ball mill using steel balls and de-ionized water.
  • total quantities of oxide additives for liquid phase sintering ranges between 4wt% and 25wt%, or smaller amounts (usually ⁇ 2%) of oxides, carbon, boron and/or boron compounds are added for non-liquid phase sintering.
  • the final materials contain oxide or oxynitride intergranular phases, which are essentially products of the oxide sintering aid.
  • the weight ratio between alumina and the sum of [yttria + RE] is between 2 and 0.4.
  • a binder is added if cold-pressing follows this step.
  • a binder mixture based on polyethylene glycol (PEG) or polyvinyl alcohol (PVA) is added.
  • a plasticizer such as glycerin is included in the binder mixture; in another embodiment, additional minor additives are included in the binder mixture to improve lubrication.
  • the weight percent of binder mixture, relative to powder weight can be from about 2% to about 14%.
  • granulation includes squeezing a moisture controlled mixture through mesh, in another embodiment it includes palletizing, in another embodiment it includes a spray drying process, in another embodiment achieving a granulated ready-to-press material with free pouring density of about 600-800 kg/m 3 and a tap density of about 800-1200 kg/m 3 .
  • granule sizes are generally between 40 and 400 micrometers.
  • uniaxial cold pressing in hardened steel dies (which may be equipped with harder inserts to reduce wear) is performed at pressures in the order of 1 ,000 bar.
  • cold isostatic pressing at up to 4,000 bar may be added if higher final properties are desired.
  • usable molding compositions include, in addition to the ceramic powder and major binder component, several minor organic components such as plasticizers for the main polymer which are intended as flow modifiers, and in another embodiment processing aids which are supposed to act as surfactants, to the ceramic and improve particle wetting.
  • binder removal (also called debinding or dewaxing) is done in flowing Nitrogen gas by slow heating at 10° to 100 0 C per hour to temperatures between 450° and 600 0 C, holding up to 4 hours at the maximum temperature, and cooling down at a controlled slow rate or cooling down naturally with the furnace.
  • pressureless sintering is performed in Argon or Nitrogen atmosphere in a controlled atmosphere furnace at temperatures from 1850° to 2000 0 C and non-flowing gas pressure of less than 1 bar.
  • the temperature is preferably between 1870° and 1950 0 C.
  • the "green" tiles are enclosed in covered graphite containers; in another embodiment the "green” tiles are embedded in coarse SiC or SiC + Al 2 O 3 powder in covered graphite containers.
  • the heating rate is between 150° and 900 0 C per hour.
  • the holding time at the maximum temperature is between 10 minutes and 6 hours, preferably 30 minutes to 4 hours.
  • Green tiles refer to cold formed tiles before final consolidation.
  • phase separation is optionally performed in the last step of the sintering of the solid solution powder, while reducing the sintering temperature to 1500-1900 0 C for 1 to 24 hours or more, resulting in a modulated structure.
  • the phase separation may be performed as a separate step after the sintering step, by heating the sintering product to 1500-1900 0 C for 1-24 hours or more, resulting in a modulated structure.
  • a key to the success of this process is the homogeneity of the solid solution obtained in the preparation of a SiC-AlN solid solution.
  • hot isostatic pressing can be performed after the sintering step to provide higher density and better performance.
  • hot pressing of the homogeneous solid solution powder may be performed.
  • Hot isostatic pressing is done at high temperature under high gas pressure.
  • Hot pressing is a mechanical uniaxial pressure under heating conditions.
  • the ceramic bodies may be used as-sintered (and heat-treated, if applicable), or may undergo diamond wheel grinding to achieve more accurate shape and dimensions.
  • the consolidation of the SiC-AlN solid solution and Ti(C,N) powder into resistant ceramic material includes cold pressing and/or cold isostatic pressing followed by liquid phase assisted pressureless sintering or non-liquid-phase sintering.
  • the consolidation of the SiC-AlN solid solution and Ti(C 5 N) powder into resistant ceramic material comprises hot pressing.
  • the consolidation comprises cold- pressing and/or cold-isostatic-pressing followed by non-liquid-phase-assisted pressureless sintering.
  • the sintering additives may comprise small amounts of alumina, carbon, boron and boron compounds, and the sintering temperature may be higher than in liquid phase sintering.
  • the consolidation of the SiC-AlN solid solution powder into a resistant ceramic material is achieved by sintering followed by hot isostatic pressing.
  • the cold forming process comprises cold pressing and/or cold isostatic pressing followed by non-liquid-phase assisted pressureless sintering.
  • this invention provides a resistant ceramic material comprising primarily a homogeneous SiC-AlN solid solution.
  • the SiC-AlN solid solution may comprise carbide, nitride or carbo-nitride of a transition metal, in anther embodiment the transition metal is titanium or zirconium.
  • another way to improve fracture toughness and ballistic performance is to include reinforcing titanium carbo- nitride particles.
  • a resistant ceramic material of this invention may be used for the preparation of an armor material, in another embodiment for the preparation of a protective personal waistcoats, in another embodiment for the preparation of antiballistic resistance, in another embodiment for the preparation of a resisting to armor piercing bullets or in another embodiment for the preparation of an armor for light vehicles.
  • a resistant ceramic material comprising 65 to 94 wt % of a highly homogeneous SiC-AlN solid solution (wherein AlN content is from about 8 wt % to about 50 wt %).
  • a resistant ceramic composite material comprise 0.5 to 18 wt% titanium carbonitride Ti(C,N).
  • a resistant composite ceramic material comprise up to 25 wt % of multiphase product of reaction and crystallization of melt of the following oxides mixture: aluminum oxide (AI2O3), yttrium oxide (Y 2 O 3 ), a negligible amount of silica (SiO 2 ), and optionally ytterbium oxide (Yb2 ⁇ 3 ) or another rare earth (RE) oxide.
  • AI2O3 aluminum oxide
  • Y 2 O 3 yttrium oxide
  • SiO 2 a negligible amount of silica
  • Yb2 ⁇ 3 optionally ytterbium oxide
  • RE rare earth
  • the shapes and dimensions of the components can be: tiles in sizes from about 2" x 2" (about 50mm x 50mm) to 300mm x 300mm or more, with or without curvatures; hexagonal tiles; rods; spheres; or more complex shapes.
  • Example 1 Preparation of ceramic armor tiles including Ti (CN) EXAMPLE 1 [0055]
  • the tiles had a square shape with nominal dimensions 50 x 50 mm and thickness of 6 to 6.5 mm.
  • the armor tiles were manufactured from a material with the following nominal content of components:
  • SHS Self Propagating High-temperature Synthesis. Poured 37.5g of the powder mixture layer by layer into a cylindrical perforated stainless steel reactor (lined with graphite felt; inner diameter about 25 mm, height 70mm) and lightly tapped layer by layer to obtain a uniform bulk density of about 900 kg/m 3 . Mounted the reactor in the pressure chamber and sealed the chamber. Pressurized with nitrogen gas at 35 bar. Ignited using a tungsten filament at a distance of about 1 mm above the surface of the powder.
  • Reaction front downwards propagation was videotaped through the view port in the chamber wall, and temperatures were measured and recorded using 4 Type C thermocouples (one near the filament and 3 along the reaction path, inserted horizontally about 2mm deep into the powder). Ignition temperature was about 1350 0 C and the temperatures along the reaction path reached between 2000 and 2300 0 C. The reaction was complete within about 2 minutes.
  • Crushing of the reaction product The SHS reaction product was removed as one piece of a porous body from the carbon felt insulator. It was then crushed in a mortar and pestle, and sieved to obtain ⁇ 250 micrometer particles. d) Steps (b) and (c) were repeated for 2 more batches of 37.5g each.
  • the net weight of the product for each of the three runs was about 42 grams (the error being about 0.3 g due to some product adhering to the carbon felt insulation).
  • the weight addition of about 4.3-4.5 g (from the original 37.5 g) represents the added nitrogen, theoretically about
  • Vibratory milling was done in a rubber-lined steel container, having a volume of about 225cc.
  • the 3 batches of powder were loaded into the container, together with isopropyl alcohol (about 70cc) and about 600 grams of 8mm WC-6wt.°/ ⁇ Co balls as milling media.
  • the mill was operated for 48 hours at a frequency of 50Hz (3,000 R.P.M.) and amplitude of about 5mm.
  • the materials were then removed and dried in air at room temperature.
  • the dried powder was then dispersed in de-ionized water with 0.4% addition of DARV AN-C® dispersant, using an ultrasonic bath for 30 minutes.
  • X-ray diffraction has shown that the milled reaction products were 2H (wurtzite)-SiC-AlN solid solution, sometimes with a minor amount of residual silicon, depending on initial composition. The peak intensities are in agreement with reported values for the solid solution. No peaks of SiC or AlN are seen, and there is no indication of any deviation from a homogeneous solid solution. In addition, peaks of cubic titanium carbo-nitride [Ti(C 5 N)] are observed. g) Sintering aids addition. In this example, 7.2 grams (6wt%) of alumina and 4.8 grams
  • the "green” tiles were loaded into a covered graphite container, separated from each other with graphite felt sheets.
  • the sintering cycle was as follows: Heating to 1,000 0 C at 400 °C/h heating rate, then to 1900 0 C at 900 0 CZh, then to 1920 0 C at 50 0 CZIi; holding 1 hour at 1920 0 C; cooling at 600 0 CZIi to room temperature.
  • Example 2 the tiles had a square shape with nominal dimensions 50 x 50 mm and thickness of between 6mm and 7mm.
  • the armor tiles have been manufactured from material with following nominal content of components: (a) 85.4wt% of SiC-AlN solid solution, wherein AlN content was 30wt%; (b) 6.6wt% of Ti(C,N) particles; (c) 8wt % of multiphase product of crystallization of the melt of oxide mixture with the following composition: AI2O3 — 40wt %, and Y2O3 - 40wt%.
  • Steps (b) and (c) were repeated for 2 more batches of 33.0g each.
  • Vibratory milling, powder dispersion and XRD were done as in EXAMPLE 1, Item 5, with similar results.
  • 4.52 grams (4wt%) of alumina and 4.52 grams (4wt%) of yttria both with particle size of 0.5-1.0 micrometers were added to 104 grams of the SiC-AlN solid solution + Ti(CN) powder (in aqueous slurry), then mixed-homogenized in a ball mill using alumina cylinders as mixing media and de- ionized water for 16 hours.
  • Binder addition and granulation were used for 2 more batches of 33.0g each.
  • the tiles had a square shape with nominal dimensions 50 x 50 mm and thickness of between 6mm. and 9mm.
  • the armor tiles have been manufactured from material with the following nominal content of components:
  • Ig of the powder mixture layer by layer into an oval perforated stainless steel reactor (lined with carcon felt, inner cross section about 18cm 2 , height 100mm) and lightly pressed layer by layer to obtain a uniform bulk density of about 900kg/m 3 . Mounted the reactor in the pressure chamber and sealed the chamber. Pressurized with nitrogen gas at 35 bar.
  • the net weight of the product for each of the three runs was between 185 and 186 grams (the error being about 0.5 g due to some product adhering to the carbon felt insulation).
  • the weight addition of 25-26g represents the added nitrogen, theoretically 25.7g for a full reaction (1) shown above.
  • the yield of SiC-AlN solid solution could be determined by dividing the added weight by 25.7, showing values from 99 to 100%. This means that practically all the aluminum reacted with nitrogen (and all the Si with carbon) to form the solid solution, and also that practically no materials were lost as gaseous phases.
  • the bulk density of the sponge-like product was approximately 1,000 kg/m 3 . e) Vibratory milling to obtain micron-size particles.
  • Vibratory milling was done in 2 rubber-lined steel containers, having a volume of about 450cc each, attached vertically on the vibrating plate.
  • the 3 batches of powder were manually mixed in a bowl, divided into two equal parts (about 27Og each) and loaded into the two vibratory mill containers, together with isopropyl alcohol (about 200cc) and 8mm WC-6wt.%Co balls (about 1,300 grams).
  • the mill was operated for 54 hours at a frequency of 50Hz and amplitude of about 5mm. The materials were then removed and dried in air at room temperature.
  • X-ray diffraction has shown that the milled reaction products were 2H (wurtzite)-SiC-AlN solid solution, sometimes with a minor amount of residual silicon, depending on initial composition. The peak intensities are in agreement with reported values for the solid solution. No peaks of SiC or AlN are seen, and there is no indication of any deviation from a homogeneous solid solution.
  • Sedimentation was done by adding de-ionized water to the powder and adding 0.4% (relative to powder weight) of Darvan-C® as a dispersant, dispersing and mixing for 60 minutes in an ultrasonic bath, poured into a 400mm tall 2 liter measuring cylinders, then letting settle for 100 minutes and pumping out the top 95% of the volume of the slurry for use in the following steps.
  • Sintering aids addition was done by adding de-ionized water to the powder and adding 0.4% (relative to powder weight) of Darvan-C® as a dispersant, dispersing and mixing for 60 minutes in an ultrasonic bath, poured into a 400mm tall 2 liter measuring cylinders, then letting settle for 100 minutes and pumping out the top 95% of the volume of the slurry for use in the following steps.
  • Sintering aids addition was done by adding de-ionized water to the powder and adding 0.4% (relative to powder weight) of Darvan-C® as a dis
  • the RTP material was weighed (in an amount corresponding to the desired tile thickness) and manually poured into the die and pressed at 1 ,200 bar pressure, held for 90 seconds, and the green tile released from the die.
  • the sintering cycle was as follows: Heating to 1,000 0 C at 400 °C/h heating rate, then to 1900 0 C at 900 0 CZh, then to 1930 0 C at 60 0 CZh; holding 3 hours at 1930 0 C; cooling at 400 0 CZh to 1800 0 C, holding 4 hours at 1800 0 C for phase separation; cooling at 60O 0 CZh to room temperature.
  • Density measurements by the Archimedes method showed values from about 3200 to 3260 kgZm 3 , depending on additives and other processing parameters. These values corresponded to 98- 100% of the theoretical density.
  • Vickers micro-hardness tests (using 5N and ION loads) show mat the solid solution phase itself has hardness values of 2400 to over 2600 kgZm 3 . Vickers hardness using IOON load showed values of over 2000 kgZm 3 .
  • Ballistic tests were performed at a professional testing laboratory, by shooting 7.62 mm diameter 51mm long and 9.5 grams in weight Armor Piercing bullets (7.62x51 AP Type 61 IMI), at speeds of 830 to 860 mZsecond.
  • the tiles were lightly glued on Al 2024-T3 backing block, 30 mm thick. All tiles of thickness 6 mm to 9 mm stopped the bullets completely, as evidenced by the fact that no penetration of the bullet core into the Al backing block (witness block) occurred.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Products (AREA)

Abstract

La présente invention concerne un procédé de production d'une céramique résistante par consolidation d'une solution en poudre de SiC-AlN, par synthèse d'une solution solide de SiC-AlN, puis par broyage (le cas échéant), laminage, ajout d'aide au frittage, ajout de liant, granulation (cas du pressage à froid), formage à froid, et consolidation. L'invention concerne également une nouvelle céramique résistance à base essentiellement d'une solution solide de SiC-AlN ayant éventuellement subi une séparation des phases, et convenant pour les blindage de type militaire ou civil, ainsi que des produits résistant aux charges dynamiques, et résistants à l'usure.
EP06780403A 2005-08-15 2006-08-15 Ceramique resistante et procede de fabrication Withdrawn EP1922354A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US70794705P 2005-08-15 2005-08-15
PCT/IL2006/000943 WO2007020634A2 (fr) 2005-08-15 2006-08-15 Ceramique resistante et procede de fabrication

Publications (1)

Publication Number Publication Date
EP1922354A2 true EP1922354A2 (fr) 2008-05-21

Family

ID=37757960

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06780403A Withdrawn EP1922354A2 (fr) 2005-08-15 2006-08-15 Ceramique resistante et procede de fabrication

Country Status (3)

Country Link
EP (1) EP1922354A2 (fr)
AU (1) AU2006281014A1 (fr)
WO (1) WO2007020634A2 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11141919B2 (en) 2015-12-09 2021-10-12 Holo, Inc. Multi-material stereolithographic three dimensional printing
US10935891B2 (en) 2017-03-13 2021-03-02 Holo, Inc. Multi wavelength stereolithography hardware configurations
GB2564956B (en) 2017-05-15 2020-04-29 Holo Inc Viscous film three-dimensional printing systems and methods
US10245785B2 (en) 2017-06-16 2019-04-02 Holo, Inc. Methods for stereolithography three-dimensional printing
CN113474147A (zh) 2018-12-26 2021-10-01 霍洛公司 用于三维打印***和方法的传感器
EP3924320A4 (fr) 2019-02-11 2022-11-23 Holo, Inc. Procédés et systèmes pour impression tridimensionnelle
WO2021048875A1 (fr) * 2019-09-13 2021-03-18 Saint-Gobain Centre De Recherches Et D'etudes Europeen Composant de blindage comprenant une phase de carbonitrure de titane
CN112066380A (zh) * 2020-09-25 2020-12-11 江苏科环新材料有限公司 表面具有耐高温防磨蚀涂层的垃圾焚烧炉炉排片及其制备
WO2023286038A1 (fr) * 2021-07-16 2023-01-19 John Crane Inc. Matériau d'anneau d'étanchéité rotatif

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5272239A (en) * 1992-03-24 1993-12-21 Jensen James A Silicon-filled aluminum polymer precursors to SiC-AlN ceramics

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007020634A3 *

Also Published As

Publication number Publication date
WO2007020634A3 (fr) 2007-05-31
AU2006281014A1 (en) 2007-02-22
WO2007020634A2 (fr) 2007-02-22

Similar Documents

Publication Publication Date Title
WO2007020634A2 (fr) Ceramique resistante et procede de fabrication
CA1261887A (fr) Corps moules denses de nitrure d'aluminium polycristallin, et methode pour leur mise en forme sans apport d'agent de frittage
Ganesh Development of β-SiAlON based ceramics for radome applications
EP0780351B1 (fr) Corps fritte de nitrure d'aluminium et son procede de production
Zhu et al. Effect of sintering additive composition on the processing and thermal conductivity of sintered reaction‐bonded Si3N4
Wang et al. Dramatic effect of a small amount of MgO addition on the sintering of Al2O3-5 vol% SiC nanocomposite
US20150027065A1 (en) Diamond composite and a method of making a diamond composite
JP2013530914A (ja) 高強度ダイアモンド−ＳｉＣ圧密体及びその製造方法
KR102011586B1 (ko) 다결정성 연마 구조물
EP2189432B1 (fr) Corps fritté au nitrure d'aluminium à forte conductivité thermique
US8426043B2 (en) Boron suboxide composite materials
EP0676380A1 (fr) Poudres de composite en nitrure de silicium et carbure de silicium
Mei et al. Synthesis of high-purity Ti2AlC by spark plasma sintering (SPS) of the elemental powders
Kanai et al. Hot-Pressed BN-AlN Ceramic Composites with High Thermal Conductivity. Part III
CN106977198A (zh) 热压烧结氧化锆复合陶瓷绝缘件及其制备方法
Klement et al. Al2O3-SiC nanocomposites: Preparation, microstructure, and properties
JP2008156142A (ja) 窒化アルミニウム焼結体およびその製造方法
Cheng et al. Boron nitride–aluminum nitride ceramic composites fabricated by transient plastic phase processing
JP3694583B2 (ja) 粉砕機用部材
JP3413278B2 (ja) ＳｉＣ微粒子分散セラミックス焼結体の製造方法
JPH01246178A (ja) 溶鋼用耐火物の製造方法
JP3978789B2 (ja) ダイヤモンド焼結体及びその製造方法
JPH0379308B2 (fr)
JP2022032638A (ja) 窒化アルミニウム焼結体およびその製造方法
Itatani Properties of novel silicon nitride-based materials

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20080313

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20080821