CN115180960A - 一种氮化硅陶瓷烧结体及其制备方法 - Google Patents

一种氮化硅陶瓷烧结体及其制备方法 Download PDF

Info

Publication number
CN115180960A
CN115180960A CN202210941639.4A CN202210941639A CN115180960A CN 115180960 A CN115180960 A CN 115180960A CN 202210941639 A CN202210941639 A CN 202210941639A CN 115180960 A CN115180960 A CN 115180960A
Authority
CN
China
Prior art keywords
tungsten
silicon nitride
sintered body
grain boundary
phase
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.)
Granted
Application number
CN202210941639.4A
Other languages
English (en)
Other versions
CN115180960B (zh
Inventor
乔竹辉
王鲁杰
李彤阳
王梓岳
于源
汤华国
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.)
Yantai Advanced Materials And Green Manufacturing Shandong Laboratory
Yantai Zhongke Advanced Materials And Green Chemical Industry Technology Research Institute
Lanzhou Institute of Chemical Physics LICP of CAS
Original Assignee
Yantai Advanced Materials And Green Manufacturing Shandong Laboratory
Yantai Zhongke Advanced Materials And Green Chemical Industry Technology Research Institute
Lanzhou Institute of Chemical Physics LICP of CAS
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 Yantai Advanced Materials And Green Manufacturing Shandong Laboratory, Yantai Zhongke Advanced Materials And Green Chemical Industry Technology Research Institute, Lanzhou Institute of Chemical Physics LICP of CAS filed Critical Yantai Advanced Materials And Green Manufacturing Shandong Laboratory
Priority to CN202210941639.4A priority Critical patent/CN115180960B/zh
Publication of CN115180960A publication Critical patent/CN115180960A/zh
Application granted granted Critical
Publication of CN115180960B publication Critical patent/CN115180960B/zh
Priority to US18/199,423 priority patent/US11919824B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C04B35/587—Fine 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/4505—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application
    • C04B41/455—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application the coating or impregnating process including a chemical conversion or reaction
    • C04B41/4556—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application the coating or impregnating process including a chemical conversion or reaction coating or impregnating with a product reacting with the substrate, e.g. generating a metal coating by surface reduction of a ceramic substrate
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6261—Milling
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—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
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/74—Ceramic products containing macroscopic reinforcing agents containing shaped metallic materials
    • C04B35/76—Fibres, filaments, whiskers, platelets, or the like
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/0072—Heat treatment
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
    • C04B41/5062—Borides, Nitrides or Silicides
    • C04B41/5064—Boron 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
    • C04B41/5062—Borides, Nitrides or Silicides
    • C04B41/5066—Silicon nitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/16—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides 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
    • C04B2235/32—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
    • C04B2235/32—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
    • C04B2235/3227—Lanthanum 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3258—Tungsten oxides, tungstates, 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
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3804—Borides
    • C04B2235/3813—Refractory metal borides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—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
    • C04B2235/3891—Silicides, e.g. molybdenum disilicide, iron silicide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—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
    • C04B2235/424—Carbon black
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/425—Graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—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
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5216—Inorganic
    • 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
    • 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
    • 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
    • C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
    • 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
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • C04B2235/85—Intergranular or grain boundary phases
    • 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

Abstract

本发明属于陶瓷材料技术领域，具体涉及一种氮化硅陶瓷烧结体及其制备方法。本发明提供的氮化硅陶瓷烧结体，包括烧结主体和形成于所述烧结主体表面的硬质表层；硬质表层的厚度为10～1000μm；烧结主体包括氮化硅结晶相和第一晶界相，第一晶界相包括金属钨相，金属钨相为钨单质和/或钨合金；硬质表层包括氮化硅结晶相和第二晶界相，第二晶界相包括碳化钨颗粒；第一晶界相中，金属钨相中的钨元素占第一晶界相中总钨元素的质量百分含量为80～100wt％；第二晶界相中，碳化钨颗粒中的钨元素占第二晶界相中总钨元素的质量百分含量为60～100wt％。本发明提供的氮化硅陶瓷烧结体能够实现兼具有高韧性、高硬度及耐磨损的特点。

Description

一种氮化硅陶瓷烧结体及其制备方法
技术领域
本发明属于陶瓷材料技术领域，具体涉及一种氮化硅陶瓷烧结体及其制备方法。
背景技术
氮化硅以高强度、高韧性、高硬度、高抗热震等性能被广泛应用于机械、冶金、航空等领域，其性能取决于氮化硅的致密度、晶粒尺寸分布及长径比、晶界相的性质等。
通过采用不同的制备工艺可以实现氮化硅陶瓷的弯曲强度、断裂韧性、硬度的提升，但往往会出现一种性能提升带来了另一种性能下降的现象，例如降低陶瓷的平均粒径尺寸可以提高氮化硅陶瓷强度但也带来的氮化硅陶瓷韧性的降低，而提高氮化硅陶瓷晶粒尺寸会增加韧性降低强度。若引入一些提高韧性的第二相如氮化硼颗粒等则会降低陶瓷材料硬度。综上，陶瓷材料的性能之间存在一定的相互制约，往往难以同时提高。
但是，作为结构材料，氮化硅陶瓷在实际应用过程中的弯曲强度、断裂韧性、硬度都是非常重要的指标。高强度可以保证承受大载荷，高韧性能够阻止陶瓷材料缺陷情况下失效以提高其稳定性，而高硬度可以赋予陶瓷材料优异的耐磨耐侵彻性能。因此，同时提高陶瓷材料的强度、韧性、硬度变得非常重要。
发明内容
本发明的目的在于提供一种氮化硅陶瓷烧结体及其制备方法，本发明提供的氮化硅陶瓷烧结体具有表层高硬度且主体高韧性的特点。
为了实现上述目的，本发明提供如下技术方案：
本发明提供了一种氮化硅陶瓷烧结体，包括烧结主体和形成于所述烧结主体表面的硬质表层；所述硬质表层的厚度为10～1000μm；所述烧结主体包括氮化硅结晶相和第一晶界相，所述第一晶界相包括金属钨相，所述金属钨相为钨单质和/或钨合金；所述硬质表层包括氮化硅结晶相和第二晶界相，所述第二晶界相包括碳化钨颗粒；所述第一晶界相中，所述金属钨相中的钨元素占所述第一晶界相中总钨元素的质量百分含量为80～100wt％；所述第二晶界相中，所述碳化钨颗粒中的钨元素占所述第二晶界相中总钨元素的质量百分含量为60～100wt％。
优选的，所述金属钨相和碳化钨颗粒的总体积占所述氮化硅陶瓷烧结体的体积百分含量为0.5～35vol％。
优选的，所述烧结主体的氮化硅结晶相和所述硬质表层的氮化硅结晶相的总体积占所述氮化硅陶瓷烧结体的体积百分含量为50～90vol％。
优选的，所述碳化钨颗粒的平均粒径为0.5～50μm。
本发明提供了上述技术方案所述的氮化硅陶瓷烧结体的制备方法，包括以下步骤：
将钨增韧的氮化硅陶瓷烧结体埋入埋粉中进行热处理发生碳化反应，得到所述氮化硅陶瓷烧结体；所述钨增韧的氮化硅陶瓷烧结体包括氮化硅结晶相和金属钨晶界相，所述金属钨晶界相为钨单质和/或钨合金；所述埋粉包括碳源。
优选的，所述埋粉中，碳源的质量百分含量为20～100wt％。
优选的，所述热处理的温度为1100～1450℃，所述热处理的保温时间为0.5～5h。
优选的，所述钨增韧的氮化硅陶瓷烧结体的制备方法包括以下步骤：
将氮化硅源、金属钨晶界相前驱体和烧结助剂球磨混合，得到混合粉体；所述金属钨晶界相前驱体为钨单质、钨合金和有机钨化合物中的一种或多种；
将所述混合粉体成型得到成型体，将所述成型体在氮气气氛中烧结，得到所述钨增韧的氮化硅陶瓷烧结体。
优选的，所述混合粉体中，氮化硅源的体积百分含量为60～90wol％，所述金属钨晶界相前驱体的体积百分含量为0.5～35vol％。
优选的，所述烧结的温度优选为1600～1900℃；所述氮气气氛的氮气气压为≥0.3MPa。
本发明提供了一种氮化硅陶瓷烧结体，包括烧结主体和形成于所述烧结主体表面的硬质表层；所述硬质表层的厚度为10～1000μm；所述烧结主体包括氮化硅结晶相和第一晶界相，所述第一晶界相包括金属钨相，所述金属钨相为钨单质和/或钨合金；所述硬质表层包括氮化硅结晶相和第二晶界相，所述第二晶界相包括碳化钨颗粒；所述第一晶界相中，所述金属钨相中的钨元素占所述第一晶界相中总钨元素的质量百分含量为80～100wt％；所述第二晶界相中，所述碳化钨颗粒中的钨元素占所述第二晶界相中总钨元素的质量百分含量为60～100wt％。本发明以硬质表层中的碳化钨颗粒提高氮化硅陶瓷烧结体表面硬度，而且表层硬度的提高也有利于提高氮化硅陶瓷烧结体的耐磨损性能；本发明的烧结主体中的金属钨相有利于氮化硅陶瓷烧结体主体断裂韧性的提升，而且断裂韧性的提高同样有利于提高氮化硅陶瓷烧结体的耐磨损性能；同时本发明控制所述硬质表层的厚度为10～1000μm，且所述金属钨相中的钨元素占所述第一晶界相中总钨元素的质量百分含量为80～100wt％，所述碳化钨颗粒中的钨元素占所述第二晶界相中总钨元素的质量百分含量为60～100wt％，由此，本发明提供的氮化硅陶瓷烧结体通过表层成分和内部成分的差异，最终实现表层高硬度且主体高韧性的效果，能够实现兼具有高韧性、高硬度及耐磨损的特点。
本发明提供了上述技术方案所述的氮化硅陶瓷烧结体的制备方法，包括以下步骤：将钨增韧的氮化硅陶瓷烧结体埋入埋粉中进行热处理发生碳化反应，得到所述氮化硅陶瓷烧结体；所述钨增韧的氮化硅陶瓷烧结体中包括氮化硅结晶相和金属钨晶界相，所述金属钨晶界相为钨单质和/或钨合金；所述埋粉包括碳源。本发明提供的制备方法以钨增韧的氮化硅陶瓷烧结体作为包埋热处理的原料，其中金属钨晶界相有利于提高钨增韧的氮化硅陶瓷烧结体的韧性，在包埋热处理时钨增韧的氮化硅陶瓷烧结体表面的金属钨晶界相与埋粉中的碳源反应，形成包含有碳化钨颗粒的硬质表层，从而提高氮化硅陶瓷烧结体的表面硬度。本发明提供的制备方法简单易行，适宜工业化生产。
附图说明
图1为本发明实施例1制备的氮化硅烧结体的成分示意图。
具体实施方式
本发明提供了一种氮化硅陶瓷烧结体，包括烧结主体和形成于所述烧结主体表面的硬质表层；所述硬质表层的厚度为10～1000μm；所述烧结主体包括氮化硅结晶相和第一晶界相，所述第一晶界相包括金属钨相，所述金属钨相为钨单质和/或钨合金；所述硬质表层包括氮化硅结晶相和第二晶界相，所述第二晶界相包括碳化钨颗粒；所述第一晶界相中，所述金属钨相中的钨元素占所述第一晶界相中总钨元素的质量百分含量为80～100wt％；所述第二晶界相中，所述碳化钨颗粒中的钨元素占所述第二晶界相中总钨元素的质量百分含量为60～100wt％。
在本发明中，若无特殊说明，所有制备原料/组分均为本领域技术人员熟知的市售产品。
本发明提供的氮化硅陶瓷烧结体包括烧结主体。
在本发明中，所述烧结主体包括氮化硅结晶相和第一晶界相，所述第一晶界相包括金属钨相，所述金属钨相为钨单质和/或钨合金。
在本发明中，所述第一晶界相式弥散分布于所述烧结主体中。
在本发明中，所述钨单质优选包括钨单质颗粒和/或钨单质纤维。
在本发明中，所述钨单质颗粒的平均粒径优选为0.5～50μm，更优选为10～40μm。
在本发明中，所述钨单质纤维的直径优选为0.2～20μm，优选为0.5～15μm。
在本发明中，所述钨合金优选包括钨掺钾合金、钨掺二氧化钍合金、钨铼合金、钨掺铪碳合金、钨掺钼合金、W5Si3和WB中的一种或多种。
在本发明中，所述钨合金优选包括钨合金颗粒和/或钨合金纤维。
在本发明中，所述钨合金颗粒的平均粒径优选为0.5～50μm，更优选为10～40μm。
在本发明中，所述钨合金纤维的直径优选为0.2～20μm，优选为0.5～15μm。
在本发明中，所述第一晶界相中，所述金属钨相中的钨元素占所述第一晶界相中总钨元素的质量百分含量为80～100wt％，优选为85～100wt％。
在本发明中，所述第一晶界相中，所述金属钨相中的钨元素占所述第一晶界相中总钨元素的质量百分含量优选为80～100wt％，有利于氮化硅陶瓷烧结体断裂韧性的提升，而断裂韧性的提高也有利于提高氮化硅陶瓷烧结体的耐磨损性能。
本发明提供的氮化硅陶瓷烧结体包括形成于所述烧结主体表面的硬质表层。
在本发明中，所述硬质表层包括氮化硅结晶相和第二晶界相，所述第二晶界相包括碳化钨颗粒。
在本发明中，所述硬质表层的厚度为10～1000μm，优选为10～500μm。
在本发明中，所述第二晶界相中，所述碳化钨颗粒中的钨元素占所述第二晶界相中总钨元素的质量百分含量为60～100wt％，优选为65～100wt％。
在本发明中，所述第二结晶相中，所述碳化钨颗粒中的钨元素占所述第二晶界相中总钨元素的质量百分含量优选≥60wt％，且＜100wt％时，所述第二晶界相中优选还包括金属钨相，所述金属钨相为钨单质和/或钨合金；所述第二晶界相由碳化钨颗粒和金属钨相组成。
在本发明中，所述碳化钨颗粒的平均粒径优选为0.5～50μm，更优选为1～45μm。
在本发明中，所述硬质表层的碳化钨颗粒有利于提高氮化硅陶瓷烧结体材料表层硬度，硬度的提高也有利于提高氮化硅陶瓷烧结体的耐磨损性能。
在本发明中，所述金属钨相和碳化钨颗粒的总体积占所述氮化硅陶瓷烧结体的体积百分含量优选为0.5～35vol％，更优选为1～25vol％。
在本发明中，所述烧结主体的氮化硅结晶相和所述硬质表层的氮化硅结晶相的总体积占所述氮化硅陶瓷烧结体的体积百分含量优选为60～90vol％，更优选为62～90vol％。
本发明提供的氮化硅陶瓷烧结体中，氮化硅结晶相的体积百分含量优选为60～90vol％，第一晶界相和第二晶界相的总体积的体积百分含量优选为0.5～35vol％，且本发明提供的氮化硅陶瓷烧结体形成烧结主体和硬质表层的机构，由于氮化硅陶瓷烧结体表层成分和内部成分的差异，可实现兼具有高韧性、高硬度及耐磨损的特点。
本发明提供了上述技术方案所述的氮化硅陶瓷烧结体的制备方法，包括以下步骤：
将钨增韧的氮化硅陶瓷烧结体埋入埋粉中进行热处理发生碳化反应，得到所述氮化硅陶瓷烧结体；所述钨增韧的氮化硅陶瓷烧结体包括氮化硅结晶相和金属钨晶界相，所述金属钨晶界相为钨单质和/或钨合金；所述埋粉包括碳源。
在本发明中，所述碳源优选包括石墨粉体、炭黑粉体、含碳有机物、金刚石粉体中的一种或多种。
在本发明中，所述含碳有机物优选包括糖和/或酚醛树脂。
在本发明中，所述钨增韧的氮化硅陶瓷烧结体中金属钨晶界相的体积百分含量优选为0.5～35vol％，更优选为0.8～35vol％。
在本发明中，所述钨增韧的氮化硅陶瓷烧结体的制备方法优选包括以下步骤：
将氮化硅源、金属钨晶界相前驱体和烧结助剂球磨混合，得到混合粉体；所述金属钨晶界相前驱体为钨单质、钨合金和有机钨化合物中的一种或多种；
将所述混合粉体成型得到成型体，将所述成型体在氮气气氛中烧结，得到所述钨增韧的氮化硅陶瓷烧结体。
本发明采用氮气气氛烧结，通过氮气抑制金属钨相前驱体中的钨元素与氮化硅反应，从而使金属钨晶界相与氮化硅结晶相之间形成弱界面作用，能够有效偏转裂纹，提高氮化硅陶瓷烧结体的断裂韧性。
本发明将氮化硅源、金属钨晶界相前驱体和烧结助剂球磨混合，得到混合粉体；所述金属钨相前驱体为钨单质、钨合金和有机钨化合物中的一种或多种。
在本发明中，所述氮化硅源优选包括氮化硅原料和/或硅单质。
在本发明中，所述氮化硅原料的平均粒径优选为0.2～50μm，更优选为1～45μm，进一步优选为5～40μm。
在本发明中，所述硅单质的平均粒径优选为0.2～100μm，更优选为0.5～80μm，进一步优选为2～75μm。
在本发明的具体实施例中，所述硅单质具体优选为硅粉体。
在本发明中，所述金属钨晶界相前驱体为钨单质、钨合金和有机钨化合物中的一种或多种。
在本发明中，所述钨单质优选包括钨单质颗粒和/或钨单质纤维。
在本发明中，所述钨单质颗粒的平均粒径优选为0.5～50μm，更优选为10～40μm。
在本发明中，所述钨单质纤维的直径优选为0.2～20μm，优选为0.5～15μm。
在本发明中，所述钨合金优选包括钨掺钾合金、钨掺二氧化钍合金、钨铼合金、钨掺铪碳合金、钨掺钼合金、W5Si3和WB中的一种或多种中的一种或多种。
在本发明中，所述钨合金优选包括钨合金颗粒和/或钨合金纤维。
在本发明中，所述钨合金颗粒的平均粒径优选为0.5～50μm，更优选为10～40μm。
在本发明中，所述钨合金纤维的直径优选为0.2～20μm，优选为0.5～15μm。
在本发明中，所述有机钨化合物优选包括W(NH4)6和/或H2W12O40。
在本发明中，所述金属钨晶界相前驱体的平均粒径优选为0.1～100μm，更优选为1～80μm，进一步优选为5～70μm。
在本发明中，所述烧结助剂优选包括金属氧化物，更优选为包括Al2O3、MgO和稀土氧化物中的一种或多种，进一步优选包括Y2O3、Yb2O3、Sm2O3和La2O3中的至少一种。
在本发明中，所述烧结助剂的平均粒径优选为0.1～30μm，更优选为5～25μm。
在本发明中，所述烧结助剂的质量优选为氮化硅源、含钨晶界相前驱体和烧结助剂总体积的3～15vol％，更优选为6～10vol％。
在本发明中，所述混合粉体中，氮化硅源的体积百分含量优选为50～90vol％，所述金属钨晶界相前驱体的体积百分含量优选为0.5～35vol％。
在本发明中，所述球磨混合优选在行星式球磨机中进行。
在本发明中，所述球磨混合优选湿磨。
在本发明中，所述球磨混合使用的球磨介质优选为乙醇或水。
在本发明中，所述水优选为去离子水。
在本发明中，所述球磨混合使用的球磨珠优选为三氧化二铝球磨珠、氮化硅球磨珠或玛瑙球磨珠。
在本发明中，所述球磨混合时，粉体原料、球磨介质和球磨珠的质量比优选为1:3:2。
在本发明中，所述球磨混合的转速优选为150～300rpm。
在本发明中，所述球磨混合的时间优选为0.5～8h。
得到混合粉体后，本发明将所述混合粉体成型得到成型体，将所述成型体在氮气气氛中烧结，得到所述钨增韧的氮化硅陶瓷烧结体。
在本发明中，所述成型之前，本发明优选对所述混合粉体进行干燥。在本发明中，所述干燥的具体实施方式优选为喷雾干燥或烘干。
在本发明中，所述烘干的温度优选为40～120℃。
在本发明中，所述烘干的保温时间优选为1～8h。
本发明对所述喷雾干燥的具体实施过程没有特殊要求。
本发明优选通过干燥对所述混合体进行造粒。在本发明中，所述干燥的具体实施过程优选为喷雾干燥时，所述喷雾干燥后直接得到混合粉体。
在本发明中，所述干燥的具体实施方式优选为烘干时，本发明优选对所述烘干得到的物料进行筛分，得到混合粉体。在本发明中，所述筛分的筛孔直径优选为20～200目，具体优选为20目、60目、80目或200目。
在本发明中，所述成型优选按照方式一或方式二进行；
在本发明中，所述方式一具体优选为：将所述混合粉体进行冷等静压，所述冷等静压的气压优选为100～300MPa，更优选为150～250MPa。
在本发明中，所述方式二具体优选为：将所述混合粉体依次进行干压和冷等静压，所述干压的气压优选为10～80MPa，更优选为15～70MPa；所述冷等静压的气压优选为100～300MPa，更优选为150～250MPa。
在本发明中，所述烧结的温度优选为1600～1900℃，具体优选为1600℃、1700℃、1750℃、1800℃或1850℃。
在本发明中，所述氮气气氛的氮气气压为≥0.3MPa。
在本发明中，所述烧结温度优选为1600℃时，所述氮气气压优选≥0.3MPa，更优选≥0.5MPa。
在本发明中，所述烧结温度优选为1700℃时，所述氮气气压优选≥2.5MPa。
在本发明中，所述烧结温度优选为1750℃时，所述氮气气压优选≥4MPa。
在本发明中，所述烧结温度优选为1800℃时，所述氮气气压优选≥6MPa。
在本发明中，所述烧结温度优选为1850℃时，所述氮气气压≥11MPa。
在本发明中，调节不同烧结温度条件下的氮气气压，即较低烧结温度条件下选择较低的氮气压力，较高烧结温度条件下须采用相对较高的氮气压力，使得含钨晶界相前驱体能够形成钨单质或钨合金，并保证直接加入的含钨晶界相前驱体形成的含钨晶界相与氮化硅之间共存或无化学反应发生。
在本发明中，所述烧结优选为热压烧结或放电等离子结合气压进行烧结。
在本发明中，碳源包括无机碳源和/或有机碳源。
在本发明中，所述碳源优选包括石墨粉体、炭黑粉体、果糖、酚醛树脂和金刚石粉体等的一种或多种。
在本发明中，所述埋粉中，碳源的质量百分含量优选为20～100wt％，更优选为25～100wt％。
在本发明中，所述埋粉中，碳源的质量百分含量优选为≥20wt％，且小于100wt％时，所述埋粉优选还包括氮化硅粉体和/或氮化硼粉体，所述埋粉由氮化硅粉体和/或氮化硼粉体与碳源组成。
在本发明中，所述埋粉优选还包括氮化硅粉体和/或氮化硼粉体时，所述埋粉的制备方法优选包括以下步骤：将所述氮化硅粉体和/或氮化硼粉体与所述碳源进行湿法球磨。在本发明中，所述湿法球磨混合优选在行星式球磨机中进行。在本发明中，所述湿法球磨使用的球磨介质优选为乙醇或水。在本发明中，所述水优选为去离子水。在本发明中，所述湿法球磨使用的球磨珠优选为三氧化二铝球磨珠、氮化硅球磨珠或玛瑙球磨珠。在本发明中，所述湿法球磨时，钨增韧的氮化硅陶瓷烧结体和所述埋粉的总质量、球磨介质和球磨珠的质量比优选为2:3:2。在本发明中，所述球湿法球磨的转速优选为150～300rpm。在本发明中，所述湿法球磨的时间优选为0.5～8h。
在本发明中，所述氮化硅粉体和/或氮化硼粉体与所述碳源湿法球磨后得到混合浆料，本发明优选将所述混合浆料进行干燥和筛分，得到所述埋粉。在本发明中，所述干燥的具体实施方式优选为烘干。在本发明中，所述烘干的温度优选为40～120℃。在本发明中，所述烘干的保温时间优选为1～8h。在本发明中，所述筛分的筛孔直径优选为20目。
在本发明中，所述热处理的温度优选为1100～1450℃，更优选为1150～1400℃。
在本发明中，所述热处理的保温时间优选为0.5～5h，更优选为1～4.5h。
在本发明中，所述热处理的气氛优选为氮气、氩气或真空气氛。
本发明首先采用含钨晶界相作为增韧相，制备钨增韧的氮化硅陶瓷烧结体。其中金属钨晶界相前驱体在烧结过程中全部或大部分形成金属钨单质或合金。由于含钨晶界相在高温下容易与氮化硅烧结体发生反应，氮气气氛或氮气压力可以抑制反应生成，因此在烧结过程中需要氮气气氛或压力，且随着温度升高所需相应的氮气气压应升高以有效抑制反应发生，最终金属钨与氮化硅烧结之间的弱界面可以偏转裂纹提高氮化硅陶瓷烧结体断裂韧性。在所述热处理过程中烧结体表层的含钨晶界相与碳发生反应生成碳化钨颗粒可以提高表层的硬度。
本发明首次结合金属钨晶界相和碳化钨各自的优势，首先引入金属钨晶界相前驱体制备具有高韧性的钨增韧的氮化硅陶瓷烧结体，然后采用热处理方式使表面的金属钨晶界相形成高硬度碳化钨颗粒，提高氮化硅陶瓷烧结体表面硬度，最终达到表层高硬度而基体高韧性的效果。
本发明提供的氮化物陶瓷烧结体具有良好的抗弯强度、断裂韧性、耐摩擦磨损性能，可用于机械、冶金、航空等领域。
本发明采用万能试验机测试样品的三点抗弯强度。
本发明采用开槽法测试样品的室温断裂韧性。
本发明采用维氏硬度计测试样品的维氏硬度。
本发明采用自配副方式球盘式摩擦磨损测试样品的耐磨性能。
需要说明的是，硬度和摩擦磨损测试前需表面抛光，抛光深度应低于表面硬化表层深度，否则起不到表面硬化和提高耐磨性的效果。
为了进一步说明本发明，下面结合附图和实施例对本发明提供的技术方案进行详细地描述，但不能将它们理解为对本发明保护范围的限定。
实施例1
按照氮化硅粉体80vol％、金属钨粉体10vol％、氧化铝粉体6vol％、氧化钇粉体4vol％共100g置于氮化硅球磨罐中，添加200g氮化硅研磨球，300g无水乙醇，行星式球磨机(rpm＝300)混合2h，得到浆料；
浆料经60℃烘箱干燥5h，过80目筛，得到粉体；
粉体10MPa干压后经过200MPa冷等静压成型后在10MPa氮气气压下1750℃烧结2h得到钨增韧的氮化硅陶瓷烧结体；
采用氮化硅粉体50wt％、石墨粉体50wt％共200g置于氮化硅球磨罐中，添加200g氮化硅研磨球，300g无水乙醇，行星式球磨机(rpm＝300)混合0.5h，浆料经60℃烘箱干燥5h，过20目筛，得到埋粉；
将钨增韧的氮化硅陶瓷烧结体埋入上述埋粉中在氮气气氛1300℃热处理2h得到表面硬化的氮化硅陶瓷烧结体。
将材料进行弯曲强度、断裂韧性、硬度及摩擦磨损测试。
实施例2
按照硅粉体20vol％、氮化硅粉体62vol％、金属钨纤维12vol％、氧化镁粉体3vol％、氧化钇粉体3vol％共100g置于聚四氟乙烯球磨罐中，添加200g氮化硅研磨球，300g无水乙醇，行星式球磨机(rpm＝300)混合2h，得到浆料；
浆料经40℃烘箱干燥5h，过100目筛，得到粉体；
粉体直接200MPa冷等静压成型后在10MPa氮气气压下1800℃烧结2h得到钨增韧的氮化硅陶瓷烧结体；
采用氮化硼粉体60wt％、无定形炭黑粉体40wt％共200g置于氮化硅球磨罐中，添加200g氮化硅研磨球，300g无水乙醇，行星式球磨机(rpm＝300)混合0.5h，浆料经60℃烘箱干燥5h，过20目筛，得到埋粉；
将钨增韧的氮化硅陶瓷烧结体埋入上述埋粉中在氩气气氛1100℃热处理5h得到表面硬化的氮化硅陶瓷烧结体。
将材料进行弯曲强度、断裂韧性、硬度及摩擦磨损测试。
实施例3
按照硅粉体81vol％、金属钨铼合金(铼含量5wt％)粉体5vol％、氧化镁粉体8vol％、氧化镱粉体6vol％共100g置于氮化硅球磨罐中，添加200g氧化铝研磨球，300g无水乙醇，行星式球磨机(rpm＝300)混合2h，得到浆料；
浆料经50℃烘箱干燥4h，过60目筛，得到粉体；
粉体10MPa干压后经过200MPa冷等静压成型后在0.5MPa氮气气压1600℃烧结8h得到钨增韧的氮化硅陶瓷烧结体；
将上述钨增韧的氮化硅陶瓷烧结体埋入纯石墨粉中在真空气氛1200℃热处理1h得到表面硬化的氮化硅陶瓷烧结体。
将材料进行弯曲强度、断裂韧性、硬度及摩擦磨损测试。
实施例4
按照硅粉体62vol％、二硅化钨(WSi2)粉体20vol％、钨粉体15vol％、氧化镁粉体2vol％、氧化镧粉体1vol％共100g置于尼龙球磨罐中，添加200g氮化硅研磨球，300g无水乙醇，行星式球磨机(rpm＝150)混合8h，得到浆料；
浆料经40℃烘箱干燥12h，过100目筛，得到粉体；
粉体40MPa干压后经过150MPa冷等静压成型后在1MPa氮气气压下1600℃烧结6h得到钨增韧的氮化硅陶瓷烧结体；
采用氮化硅粉体80wt％、酚醛树脂20wt％共200g置于氮化硅球磨罐中，添加200g玛瑙研磨球，300g无水乙醇，行星式球磨机(rpm＝300)混合0.5h，浆料经60℃烘箱干燥5h，真空600℃裂解2h后，过20目筛，得到埋粉；
将钨增韧的氮化硅陶瓷烧结体埋入上述埋粉中在氮气气氛1400℃热处理1h得到表面硬化的氮化硅陶瓷烧结体。
将材料进行弯曲强度、断裂韧性、硬度及摩擦磨损测试。
实施例5
按照氮化硅粉体80vol％、W(NH4)6(H2W12O40)粉体5vol％、氧化铝粉体6vol％、氧化钐粉体9vol％共100g置于氮化硅球磨罐中，添加200g氮化硅研磨球，300g无水乙醇，行星式球磨机(rpm＝200)混合6h，得到浆料；
浆料经直接喷雾造粒得到粉体；
粉体20MPa干压后经过200MPa冷等静压成型后在3MPa氮气气压下1700℃烧结4h得到钨增韧的氮化硅陶瓷烧结体；
采用氮化硅粉体50wt％、石墨粉体50wt％共200g置于氮化硅球磨罐中，添加200g氮化硅研磨球，300g去离子水，行星式球磨机(rpm＝300)混合0.5h，浆料经80℃烘箱干燥5h，过20目筛，得到埋粉；
将钨增韧的氮化硅陶瓷烧结体埋入上述埋粉中在氮气气氛1450℃热处理1h得到表面硬化的氮化硅烧结体。
将材料进行弯曲强度、断裂韧性、硬度及摩擦磨损测试。
实施例6
按照氮化硅粉体90vol％、硼化钨(WB)粉体1vol％、氧化铝粉体3vol％、氧化镱粉体6vol％共100g置于氮化硅球磨罐中，添加200g氮化硅研磨球，300g去离子水，行星式球磨机(rpm＝300)混合4h，得到浆料；
浆料经80℃烘箱干燥2h，过80目筛，得到粉体；
粉体40MPa干压后经过200MPa冷等静压成型后在20MPa氮气气压下1900℃烧结2h得到钨增韧的氮化硅陶瓷烧结体；
采用氮化硅粉体50wt％、果糖粉体50wt％共200g置于氮化硅球磨罐中，添加200g氮化硅研磨球，300g无水乙醇，行星式球磨机(rpm＝300)混合0.5h，浆料经60℃烘箱干燥5h，过20目筛，得到埋粉；
将钨增韧的氮化硅陶瓷烧结体埋入上述埋粉中在氮气气氛1300℃热处理2h得到表面硬化的氮化硅陶瓷烧结体。
将材料进行弯曲强度、断裂韧性、硬度及摩擦磨损测试。
实施例7
按照氮化硅粉体86vol％、金属钨粉体0.5vol％、氧化铝粉体3.5vol％、氧化钇粉体10vol％共100g置于氮化硅球磨罐中，添加200g玛瑙研磨球，300g去离子水，行星式球磨机(rpm＝300)混合2h，得到浆料；
浆料经40℃烘箱干燥8h，过200目筛，得到粉体；
粉体采用40MPa热压在1500℃氮气气氛中完成烧结，得到钨增韧的氮化硅陶瓷烧结体；
采用氮化硼粉体80wt％、金刚石粉体20wt％共200g置于氮化硅球磨罐中，添加200g氮化硅研磨球，300g无水乙醇，行星式球磨机(rpm＝300)混合0.5h，浆料经60℃烘箱干燥5h，过20目筛，得到埋粉；
将钨增韧的氮化硅陶瓷烧结体埋入上述埋粉中在氮气气氛1450℃热处理1h得到表面硬化的氮化硅陶瓷烧结体。
将材料进行弯曲强度、断裂韧性、硬度及摩擦磨损测试。
实施例8
按照氮化硅粉体80vol％、金属钨粉体8vol％、氧化铝粉体7vol％、氧化钇粉体5vol％共100g置于氮化硅球磨罐中，添加200g氮化硅研磨球，300g去离子水，行星式球磨机(rpm＝300)混合4h，得到浆料；
浆料经直接喷雾造粒得到粉体；
粉体采用40MPa放电等离子烧结工艺在1500℃氮气气氛中完成烧结，得到钨增韧的氮化硅陶瓷烧结体；
采用氮化硅粉体70wt％、石墨粉体30wt％共200g置于氮化硅球磨罐中，添加200g氮化硅研磨球，300g无水乙醇，行星式球磨机(rpm＝300)混合0.5h，浆料经60℃烘箱干燥5h，过20目筛，得到埋粉；
将钨增韧的氮化硅陶瓷烧结体埋入上述埋粉中在氮气气氛1450℃热处理0.5h得到表面硬化的氮化硅烧结体。
将材料进行弯曲强度、断裂韧性、硬度及摩擦磨损测试。
对比例1
按照氮化硅粉体90vol％、氧化铝粉体6vol％、氧化钇粉体4vol％共100g置于氮化硅球磨罐中，添加200g氮化硅研磨球，300g无水乙醇，行星式球磨机(rpm＝300)混合2h，得到浆料；
浆料经60℃烘箱干燥5h，过80目筛，得到粉体；
粉体10MPa干压后经过200MPa冷等静压成型后在10MPa氮气气压下1750℃烧结2h得到氮化硅烧结体。
将未经埋粉包埋热处理的氮化硅烧结体直接进行弯曲强度、断裂韧性、硬度及摩擦磨损测试。
对比例2
按照氮化硅粉体80vol％、金属钨粉体10vol％、氧化铝粉体6vol％、氧化钇粉体4vol％共100g置于氮化硅球磨罐中，添加200g氮化硅研磨球，300g无水乙醇，行星式球磨机(rpm＝300)混合2h，得到浆料；
浆料经60℃烘箱干燥5h，过80目筛，得到粉体；
粉体10MPa干压后经过200MPa冷等静压成型后在10MPa氮气气压下1750℃烧结2h得到钨增韧的氮化硅陶瓷烧结体。
将未经埋粉包埋热处理的钨增韧的氮化硅陶瓷烧结体直接进行弯曲强度、断裂韧性、硬度及摩擦磨损测试。
对比例3
按照氮化硅粉体90vol％、氧化铝粉体6vol％、氧化钇粉体4vol％共100g置于氮化硅球磨罐中，添加200g氮化硅研磨球，300g无水乙醇，行星式球磨机(rpm＝300)混合2h，得到浆料；
浆料经60℃烘箱干燥5h，过80目筛，得到粉体；
粉体10MPa干压后经过200MPa冷等静压成型后在10MPa氮气气压下1750℃烧结2h得到氮化硅烧结体；
采用氮化硅粉体50wt％、石墨粉体50wt％共200g置于氮化硅球磨罐中，添加200g氮化硅研磨球，300g无水乙醇，行星式球磨机(rpm＝300)混合0.5h，浆料经60℃烘箱干燥5h，过20目筛，得到埋粉。
将氮化硅烧结体埋入上述埋粉中在氮气气氛1300℃热处理2h得到氮化硅烧结体进行弯曲强度、断裂韧性、硬度及摩擦磨损测试。
表1给出了实施例1～8和对比例1～3得到氮化硅陶瓷烧结体的弯曲强度、断裂韧性、硬度及摩擦磨损测试。实施例1～8采用本发明提供的技术方案制备，对比例1采用不引入含钨晶界相也未经过碳源包埋得到埋粉热处理制备氮化硅烧结体，对比例2采用引入含钨晶界相后未进行碳源包埋得到埋粉热处理表面硬化制备氮化硅烧结体，对比例3采用未引入含钨晶界相但进行了碳源包埋得到埋粉热处理制备氮化硅烧结体。将实施例1～8与对比例1对比发现，经过引入金属钨和埋粉处理后，氮化硅烧陶瓷结体的弯曲强度变化不大，断裂韧性、维氏硬度、耐磨损性能均得到有效提升。将对比例1与对比例2对比发现，单纯引入含钨晶界相能够提升氮化硅陶瓷烧结体的断裂韧性和耐磨损性能，但其维氏硬度一定程度降低，这是因为表面没有形成包括碳化钨颗粒的硬质表层。结合实施例1～8分析认为，埋粉热处理形成碳化钨颗粒相是提高维氏硬度的关键。通过对比例3发现，不引入含钨晶界相单纯碳源包埋热处理不能提高氮化硅烧结体的维氏硬度，引入含钨晶界相后再进行碳源包埋热处理过程中在表层形成碳化钨是表层硬度提高的关键。经过微观分析表明在实施例1～8中烧结体表层(厚度500μm左右)中钨主要以碳化钨(WC)形式存在，而内部主要以金属钨相形式存在。对比例2中表层和内部的钨均以金属钨单质形式存在。
表1为各实施例和对比例制备的氮化硅烧结体所对应的强度、韧性、抗热等性能
Figure BDA0003785897130000161
尽管上述实施例对本发明做出了详尽的描述，但它仅仅是本发明一部分实施例，而不是全部实施例，还可以根据本实施例在不经创造性前提下获得其他实施例，这些实施例都属于本发明保护范围。

Claims (10)

1.一种氮化硅陶瓷烧结体，其特征在于，包括烧结主体和形成于所述烧结主体表面的硬质表层；所述硬质表层的厚度为10～1000μm；所述烧结主体包括氮化硅结晶相和第一晶界相，所述第一晶界相包括金属钨相，所述金属钨相为钨单质和/或钨合金；所述硬质表层包括氮化硅结晶相和第二晶界相，所述第二晶界相包括碳化钨颗粒；所述第一晶界相中，所述金属钨相中的钨元素占所述第一晶界相中总钨元素的质量百分含量为80～100wt％；所述第二晶界相中，所述碳化钨颗粒中的钨元素占所述第二晶界相中总钨元素的质量百分含量为60～100wt％。
2.根据权利要求1所述的氮化硅陶瓷烧结体，其特征在于，所述金属钨相和碳化钨颗粒的总体积占所述氮化硅陶瓷烧结体的体积百分含量为0.5～35vol％。
3.根据权利要求1或2所述的氮化硅陶瓷烧结体，其特征在于，所述烧结主体的氮化硅结晶相和所述硬质表层的氮化硅结晶相的总体积占所述氮化硅陶瓷烧结体的体积百分含量为50～90vol％。
4.根据权利要求1或2所述的氮化硅陶瓷烧结体，其特征在于，所述碳化钨颗粒的平均粒径为0.5～50μm。
5.权利要求1～4任一项所述的氮化硅陶瓷烧结体的制备方法，其特征在于，包括以下步骤：
将钨增韧的氮化硅陶瓷烧结体埋入埋粉中进行热处理发生碳化反应，得到所述氮化硅陶瓷烧结体；所述钨增韧的氮化硅陶瓷烧结体包括氮化硅结晶相和金属钨晶界相，所述金属钨晶界相为钨单质和/或钨合金；所述埋粉包括碳源。
6.根据权利要求5所述的制备方法，其特征在于，所述埋粉中碳源的质量百分含量为20～100wt％。
7.根据权利要求5或6所述的制备方法，其特征在于，所述热处理的温度为1100～1450℃，所述热处理的保温时间为0.5～5h。
8.根据权利要求5所述的制备方法，其特征在于，所述钨增韧的氮化硅陶瓷烧结体的制备方法包括以下步骤：
将氮化硅源、金属钨晶界相前驱体和烧结助剂球磨混合，得到混合粉体；所述金属钨晶界相前驱体为钨单质、钨合金和有机钨化合物中的一种或多种；
将所述混合粉体成型得到成型体，将所述成型体在氮气气氛中烧结，得到所述钨增韧的氮化硅陶瓷烧结体。
9.根据权利要求8所述的制备方法，其特征在于，所述混合粉体中，氮化硅源的体积百分含量为60～90wol％，所述金属钨晶界相前驱体的体积百分含量为0.5～35vol％。
10.根据权利要求8所述的制备方法，其特征在于，所述烧结的温度优选为1600～1900℃；所述氮气气氛的氮气气压为≥0.3MPa。
CN202210941639.4A 2022-08-08 2022-08-08 一种氮化硅陶瓷烧结体及其制备方法 Active CN115180960B (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202210941639.4A CN115180960B (zh) 2022-08-08 2022-08-08 一种氮化硅陶瓷烧结体及其制备方法
US18/199,423 US11919824B2 (en) 2022-08-08 2023-05-19 Silicon nitride ceramic sintered body and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210941639.4A CN115180960B (zh) 2022-08-08 2022-08-08 一种氮化硅陶瓷烧结体及其制备方法

Publications (2)

Publication Number Publication Date
CN115180960A true CN115180960A (zh) 2022-10-14
CN115180960B CN115180960B (zh) 2023-03-24

Family

ID=83523461

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210941639.4A Active CN115180960B (zh) 2022-08-08 2022-08-08 一种氮化硅陶瓷烧结体及其制备方法

Country Status (2)

Country Link
US (1) US11919824B2 (zh)
CN (1) CN115180960B (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115930779A (zh) * 2022-12-05 2023-04-07 江苏富乐华功率半导体研究院有限公司 一种氮化硅陶瓷晶粒的量化评估测试方法
CN115959913A (zh) * 2022-12-20 2023-04-14 辽宁省轻工科学研究院有限公司 一种氮化硅手机背板的制备方法
CN117229067A (zh) * 2023-11-14 2023-12-15 中南大学 一种低压氮化-包埋制备氮化硅陶瓷的方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5908796A (en) * 1998-05-01 1999-06-01 Saint-Gobain Industrial Ceramics, Inc. Dense silicon nitride ceramic having fine grained titanium carbide
CN106392081A (zh) * 2016-09-18 2017-02-15 广东工业大学 一种表层富含陶瓷相的硬质合金及其制备方法
CN108455990A (zh) * 2018-04-17 2018-08-28 南京理工大学 一种氮化硅基复合陶瓷材料及其sps制备工艺
CN110117192A (zh) * 2018-02-07 2019-08-13 中国科学院上海硅酸盐研究所 一种氮化硅烧结体及其制备方法
CN114163244A (zh) * 2021-12-27 2022-03-11 中国科学院上海硅酸盐研究所 一种外硬内韧氮化硅陶瓷及其制备方法
CN114315358A (zh) * 2021-12-27 2022-04-12 海南大学 一种全致密无粘结剂碳化钨陶瓷及其制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4876148A (en) * 1984-10-29 1989-10-24 Ceramatec, Inc. Ceramic bodies having a plurality of stress zones
US6874942B2 (en) * 2001-03-02 2005-04-05 Nsk Ltd. Rolling device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5908796A (en) * 1998-05-01 1999-06-01 Saint-Gobain Industrial Ceramics, Inc. Dense silicon nitride ceramic having fine grained titanium carbide
CN106392081A (zh) * 2016-09-18 2017-02-15 广东工业大学 一种表层富含陶瓷相的硬质合金及其制备方法
CN110117192A (zh) * 2018-02-07 2019-08-13 中国科学院上海硅酸盐研究所 一种氮化硅烧结体及其制备方法
CN108455990A (zh) * 2018-04-17 2018-08-28 南京理工大学 一种氮化硅基复合陶瓷材料及其sps制备工艺
CN114163244A (zh) * 2021-12-27 2022-03-11 中国科学院上海硅酸盐研究所 一种外硬内韧氮化硅陶瓷及其制备方法
CN114315358A (zh) * 2021-12-27 2022-04-12 海南大学 一种全致密无粘结剂碳化钨陶瓷及其制备方法

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
LUJIE WANG ET AL.: "High tough W-added silicon nitride ceramics", 《CERAMICS INTERNATIONAL》 *
LUJIE WANG ET AL.: "Improving abrasive wear resistance of Si3N4 ceramics with self-matching through tungsten induced tribochemical wears", 《WEAR》 *
LUJIE WANG ET AL.: "The effect of tungsten introduction on the tribological properties of Si3N4 ceramics paired with GCr15 steel under nonlubricated conditions", 《WEAR》 *
LUJIE WANG ET AL.: "The fabrication of tungsten reinforced silicon nitride ceramics by altering nitrogen pressure", 《CERAMICS INTERNATIONAL》 *
中南矿冶学院粉末冶金教研室: "《粉末冶金基础》", 31 December 1974, 冶金工业出版社 *
卢茂华等: "添加WC对纳米Si3N4陶瓷组织和力学性能的影响", 《硬质合金》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115930779A (zh) * 2022-12-05 2023-04-07 江苏富乐华功率半导体研究院有限公司 一种氮化硅陶瓷晶粒的量化评估测试方法
CN115930779B (zh) * 2022-12-05 2023-11-14 江苏富乐华功率半导体研究院有限公司 一种氮化硅陶瓷晶粒的量化评估测试方法
CN115959913A (zh) * 2022-12-20 2023-04-14 辽宁省轻工科学研究院有限公司 一种氮化硅手机背板的制备方法
CN117229067A (zh) * 2023-11-14 2023-12-15 中南大学 一种低压氮化-包埋制备氮化硅陶瓷的方法
CN117229067B (zh) * 2023-11-14 2024-02-23 中南大学 一种低压氮化-包埋制备氮化硅陶瓷的方法

Also Published As

Publication number Publication date
CN115180960B (zh) 2023-03-24
US11919824B2 (en) 2024-03-05
US20240043349A1 (en) 2024-02-08

Similar Documents

Publication Publication Date Title
CN115180960B (zh) 一种氮化硅陶瓷烧结体及其制备方法
CN108484171B (zh) 一种碳化硼-硼化钛复相陶瓷材料及其无压烧结制备方法
CN109053206B (zh) 一种短纤维增强取向max相陶瓷基复合材料及制备方法
CN103613389B (zh) 碳化硼陶瓷烧结制备方法
CN101892411B (zh) 一种新型wc基硬质合金材料及其制备方法
CN106904977B (zh) 一种两步烧结法制备表硬心韧Si3N4陶瓷材料的方法
CN108796333A (zh) 一种W-Mo-Re-HfC合金材料及其制备方法
CN111410536A (zh) 一种常压烧结制备致密(HfZrTaNbTi)C高熵陶瓷烧结体的方法
CN106904985B (zh) 一种钛-硅-碳增强型氧化铝基多相复合材料及其制备方法
CN111018540A (zh) 一种基于低温热压烧结的高强度氮化硼陶瓷复合材料
CN108675797B (zh) 氮化硅基复合陶瓷材料及其微波烧结制备方法
CN115536403A (zh) 一种高韧氮化硅陶瓷材料及其制备方法
CN107746282A (zh) 一种原位碳化硅纤维增强液相烧结碳化硅陶瓷及制造方法
CN112851366B (zh) 一种Si3N4陶瓷材料及其制备方法
CN112062574B (zh) 一种高性能纳米碳化硅陶瓷及其制备方法和应用
CN116217233A (zh) 一种SiC晶须和高熵硼化物增硬增韧高熵碳化物的复相陶瓷及其制备方法和应用
CN110117192B (zh) 一种氮化硅烧结体及其制备方法
Santos et al. α-SiAlON–SiC composites obtained by gas-pressure sintering and hot-pressing
KR101972350B1 (ko) 탄화 지르코늄 복합체 및 이의 제조방법
CN110877980A (zh) 一种高强度碳化硅/氮化硅复相陶瓷及其制备方法
CN113149658B (zh) 一种氮化钛基复合陶瓷材料及其制备方法
CN108503370A (zh) 一种单相氮化硅陶瓷及其sps制备工艺
CN113121238B (zh) 一种高性能碳化硼基复合陶瓷材料及其制备方法
CN115073186A (zh) 一种氮化硅陶瓷烧结体及其制备方法
CN111018530A (zh) 高硬超轻陶瓷复合材料及其制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant