WO2020133928A1 - 一种致密HfC(Si)-HfB2复相陶瓷的制备方法 - Google Patents

一种致密HfC(Si)-HfB2复相陶瓷的制备方法 Download PDF

Info

Publication number
WO2020133928A1
WO2020133928A1 PCT/CN2019/090157 CN2019090157W WO2020133928A1 WO 2020133928 A1 WO2020133928 A1 WO 2020133928A1 CN 2019090157 W CN2019090157 W CN 2019090157W WO 2020133928 A1 WO2020133928 A1 WO 2020133928A1
Authority
WO
WIPO (PCT)
Prior art keywords
hfc
hfb
dense
sintering
powder
Prior art date
Application number
PCT/CN2019/090157
Other languages
English (en)
French (fr)
Inventor
郝巍
赵晓峰
倪娜
蔡黄越
姚尧
易妹玉
郭芳威
Original Assignee
上海交通大学
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 上海交通大学 filed Critical 上海交通大学
Publication of WO2020133928A1 publication Critical patent/WO2020133928A1/zh
Priority to US17/187,725 priority Critical patent/US11180419B2/en

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
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
    • C04B35/5622—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on zirconium or hafnium 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
    • C04B35/58064—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
    • C04B35/58078—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides based on zirconium or hafnium borides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—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
    • C04B35/626—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
    • C04B35/62625—Wet mixtures
    • C04B35/6264—Mixing media, e.g. organic solvents
    • 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
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying
    • 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
    • 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
    • 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
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3804—Borides
    • C04B2235/3813—Refractory metal borides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3839—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
    • C04B2235/42—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
    • C04B2235/428—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
    • C04B2235/02—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
    • C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
    • 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
    • C04B2235/606—Drying
    • 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
    • C04B2235/6567—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
    • C04B2235/6581—Total pressure below 1 atmosphere, e.g. vacuum
    • 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
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C—CHEMISTRY; METALLURGY
    • 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
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
    • C04B2235/9615—Linear firing shrinkage

Definitions

  • the invention relates to a method for preparing ultra-high temperature ceramics, in particular to a method for preparing dense HfC(Si)-HfB 2 multiphase ceramics.
  • Ultra-high temperature ceramics (UHTCs) materials are a new type of high-temperature ablation-resistant structural materials, which have a high melting point (> 2000 °C), high hardness and Young's modulus, under high temperature conditions It has high strength, low coefficient of thermal expansion and good thermal physical and chemical stability, high thermal conductivity and electrical conductivity. The most important thing is that it has good ablative resistance and is used in thermal structural parts of supersonic aircraft and solid rockets, such as nozzles, wing leading edges, and hot end parts of engines; it is also used in high-temperature electrodes and cutting tools , So it has received much attention.
  • UHT ceramics are mostly carbides (HfC, ZrC, TaC, NbC), borides (HfB 2 , ZrB 2 , TaB 2 ) and nitrides (HfN, ZrN) of Group IV and V transition metal elements in the periodic table. ), as well as some refractory metal alloys and carbon/carbon composite materials (Ta, W, Ir and C/C composite materials).
  • HfC has the following defects that prevent it from being widely used in the aerospace field.
  • the main points are as follows: on the one hand, ceramics have a high melting point and a low self-diffusion coefficient, which is difficult to sinter and densify; second, it is used as a high-temperature structural material In terms of fracture toughness (2.1-3.4MPa ⁇ m 1/2 ); finally, as a high-temperature anti-ablation material, it is easy to be oxidized, that is, the material begins to oxidize when the service temperature reaches 500°C or more in an aerobic environment, which also Limit its application in the field of high temperature.
  • HfB 2 ceramic also has a high melting point (3380°C), high hardness (29GPa) and Young's modulus (480GPa), high electrical conductivity (9.1 ⁇ 10 6 S ⁇ m -1 ) and thermal conductivity (74 -114W ⁇ (m K) -1 ), however, it has a low coefficient of thermal expansion of 6.3 ⁇ 10 -6 /°C and a low fracture toughness (3.0-6.0MPa ⁇ m 1/2 ).
  • single-phase HfB 2 has good oxidation resistance below 1200°C, which is due to the formation of liquid B 2 O 3 glass phase which plays a good anti-oxidation role.
  • the preparation of multi-phase ceramics is considered to be the most effective method to improve the sintering and fracture toughness of ultra-high temperature ceramics.
  • in-situ reaction sintering can be introduced to promote the diffusion and migration of elements at high temperatures, thereby achieving rapid sintering and densification.
  • the reported preparation methods for preparing HfC and HfB 2 ceramics are as follows, for example, carbon black, graphite and HfO 2 are used as raw materials, and the powder is prepared by carbon thermal reduction method and then sintered to make HfC ceramics [Ji- Xuan Liu, Yan-Mei Kan, Guo-Jun Zhang.
  • HfC anti-ablation coatings Jincui Ren, Yulei Zhang, Jinhua Li, et al., Effects of deposition temperature and time on HfC nanowires synthesized by CVD on SiC-coated C/C composites [J].
  • the above methods of preparing HfC and HfB 2 ceramics and coating methods all require a reaction under conditions above 1500°C to first produce a powder and then sintering under high temperature conditions above 2000°C. It takes two steps to complete and the phase composition and grain size cannot be controlled at high temperature. At the same time, the refractory HfO 2 raw material is difficult to diffuse at low temperature ( ⁇ 1500°C). In addition, the CVD method is limited to the deposition of HfC coatings or nanowires and the preparation efficiency is low, making the process difficult to control. CVI, RMI and PIP are used to prepare ultra-high temperature ceramic composite materials. It is difficult to obtain a denser sintered body, and impurities may also be introduced.
  • the sintering methods of UHTCs in recent years include discharge plasma sintering (SPS) [Omar Cedillos-Barraza, Salvatore Grasso, Nasrin Al Nasiri, et al., Sintering behavior, solid solution formation and characterization of TaC, HfC and TaC -HfC fabricated by spark plasma sintering[J].Journal of the European Ceramic Society.36(2016)1539–1548.], Hot pressing[Liuyi Xiang,Laifei Cheng,Yi Hou,et al.,Fabrication and mechanical properties of laminated HfC-SiC/BN ceramics[J].Journal of the European Ceramic Society 34(2014)3635-3640] and [E.Zapata-Solvas,DDJ
  • Chinese patent CN100378035C discloses a boride-silicon carbide composite ceramic and its preparation method, which is characterized by using the activity of silicon carbide generated during the cracking of polycarbosilane, and hot pressing at a moderate temperature of 1700 ⁇ 1900°C to prepare dense boron Compound-silicon carbide composite ceramic;
  • the boride mainly includes zirconium boride, titanium boride and hafnium boride; this process does not need to add other burning aids to ensure the high temperature performance of the material; add 1- in the preparation process 12wt% of silicon, zirconium, titanium, hafnium and other metal powders, or any combination of these metal powders, to absorb the residual carbon in the cracking process of polycarbosilane can increase the density of the composite material and improve the mechanical properties of the material.
  • the reaction system is different, which results in the carbon-boron thermal reduction reaction sintering process and mechanism under the temperature condition of 1500-1850 °C
  • the final product is also different, so this
  • the application is a special reaction system and composition, structural design, in order to produce HfC(Si)-HfB 2 multiphase ceramics in a one-step process of carbon-boron thermal reduction reaction sintering at a temperature of 1500-1850°C, not only can it improve the multiphase ceramics Sintering densification, and greatly improve the fracture toughness of the composite ceramics.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art that the ultra-high temperature ceramic powder is difficult to synthesize and the bulk ceramic is difficult to sinter.
  • SiB 6 as a boron source and a silicon source
  • nano carbon black as a carbon source
  • nano hafnium oxide As a hafnium source
  • HfC(Si)-HfB 2 composite ceramics are prepared in one step by in-situ carbon-boron thermal reduction sintering, and during the discharge plasma sintering process, SiB 6 and carbon black have good high-temperature electrical conductivity, Effectively improve the discharge sintering efficiency of the reaction system, and the B, C, Si elements, diffusion and migration rate are fast, and the in-situ carbonization, boronization and diffusion solution solution are efficiently and quickly realized.
  • the phase composition and grain size of the sintered preparation are evenly distributed.
  • the ceramic sintered body has high density and fracture toughness, which avoids the difficulty of controlling the composition and grain size in the traditional process of preparing the powder first, and it is difficult in the later sintering ceramic process Densification. Therefore, the present invention provides not only a simple process but also efficient and rapid sintering to prepare HfC(Si)-HfB 2 multiphase ceramics, which realizes the in-situ compounding of hafnium carbide and hafnium boride ceramics to optimize their performance and has broad applications prospect.
  • a method for preparing dense HfC(Si)-HfB 2 composite ceramics adopts the following steps:
  • the mixed powder in step (1) is ball-milled using a planetary ball mill, and isopropyl alcohol is used as the ball-milling medium, so that the above HfO 2 , carbon black, and SiB 6 are uniformly mixed, and the mass ratio of the mixed powder to ball stone is 1: (4 ⁇ 20), the ball mill speed is 200-500 rpm, the ball mill is 6-24h, and then dried in a 50-80°C electric blast drying oven for 4-10h to form a uniform mixed powder;
  • step (3) Take out the uniformly mixed powder finally obtained in step (3), put it into a graphite mold (diameter 32mm) covered with graphite paper, perform discharge plasma sintering, control the sintering temperature to 1500-1850°C, and keep the temperature for 5-30min, sintering applied pressure is 20-60MPa, heating rate is 50-200°C/min, vacuum degree is controlled at 0-1.0mbar, then HfC with density of 94.0% ⁇ 100% and uniform dispersion of grains can be obtained (Si)-HfB 2 multiphase ceramics.
  • this application uses hafnium oxide powder, nano carbon black and silicon hexaboride powder as raw materials, whether in terms of chemical thermodynamics or kinetics, these raw materials can be at a temperature of 1500-1850°C
  • the carbon-boron thermal reduction reaction sintering process occurs at the same time, accompanied by the solution dissolution doping process.
  • the reactant system is simple and reaction sintering is easy to produce the required HfC(Si)-HfB 2 multiphase ceramics, and the composition, microstructure and purity of the resulting product are easy to control and no impurities are generated;
  • this application adopts the discharge plasma sintering method, and the dense HfC(Si)-HfB 2 ceramic can be quickly prepared through the carbon-boron thermal reduction reaction sintering process.
  • the different sintering heating mechanisms lead to the final reactant reaction mechanism different.
  • this application introduces nano-carbon black as a carbon source, on the one hand, as a carbon source, to promote the carbon-boron thermal reduction reaction; on the other hand, as a grain boundary phase, to adjust the electrical conductivity of the reaction system and thus the discharge plasma sintering efficiency, to promote complex
  • the rapid sintering and densification of ceramics is beneficial to improve the fracture toughness of complex ceramics;
  • the target product of this application is a HfC-based composite ceramics
  • the dense HfC(Si)-HfB 2 is prepared by introducing SiB 6 and nano carbon black and sintering through a carbon-boron thermal reduction reaction
  • complex ceramics there are HfC and HfB 2 grains dispersed in the product and Si element diffuses into the HfC lattice to form a solid solution.
  • Nano carbon black is evenly distributed at the grain boundaries, effectively improving the fracture toughness of the complex ceramics.
  • the present invention has the following advantages:
  • HfC(Si)-HfB 2 complex ceramics are dense and grains of different phases are evenly distributed, and solid solution is formed along with element diffusion, which greatly improves the ceramic sintering densification process.
  • the fracture toughness of the HfC(Si)-HfB 2 composite ceramics prepared by this method has been significantly improved.
  • the fracture toughness of the three-point bending single-sided open beam test can reach 8.52-14.3MPa ⁇ m 1/ 2. At the same time, it can be ablated at 2500°C for 180s, and its linear ablation rate is less than 6 ⁇ m ⁇ s -1 .
  • Too high temperature and excessive pressure will cause abnormal growth of crystal grains, resulting in poor ceramic structure and performance; too low temperature and too low pressure will cause in-situ carbon-boron
  • the one-step thermal reduction reaction sintering densification process cannot be achieved, and the activation energy of the starting raw material reaction cannot be achieved; in addition, the material with too little pressure cannot be sintered and densified. Finally, the composition and microstructure of the material are affected, which further deteriorates the mechanical properties and anti-ablation properties of the material at high temperature.
  • Example 1 is the XRD pattern of the HfC(Si)-HfB 2 composite ceramic prepared in Example 3;
  • FIG. 2 is an SEM image of the HfC(Si)-HfB 2 composite ceramic prepared in Example 3.
  • FIG. 1 is an SEM image of the HfC(Si)-HfB 2 composite ceramic prepared in Example 3.
  • a method for preparing dense HfC(Si)-HfB 2 composite ceramics adopts the following steps:
  • HfO 2 hafnium oxide powder
  • SiB 6 silicon hexaboride powder
  • the mixed powder in step (1) is ball-milled using a planetary ball mill, and isopropyl alcohol is used as the ball-milling medium, so that the above HfO 2 , carbon black, and SiB 6 are uniformly mixed, and the mass ratio of the mixed powder to ball stone is 1: (4 ⁇ 20), the ball mill speed is 200-500 rpm, the ball mill is 6-24h, and then dried in a 50-80°C electric blast drying oven for 4-10h to form a uniform mixed powder;
  • step (3) Take out the uniformly mixed powder finally obtained in step (3), put it into a graphite mold (diameter 32mm) covered with graphite paper, perform discharge plasma sintering, control the sintering temperature to 1500-1850°C, and keep the temperature for 5-30min, sintering applied pressure is 20-60MPa, heating rate is 50-200°C/min, vacuum degree is controlled at 0-1.0mbar, then HfC with density of 94.0% ⁇ 100% and uniform dispersion of grains can be obtained (Si)-HfB 2 multiphase ceramics.
  • the HfO 2 nano-powder used in the above method is produced by Shanghai Superfine Nano Technology Co., Ltd. with a purity of ⁇ 99.9%.
  • Nano carbon black is produced by Beijing Yinuokai Technology Co., Ltd. with a purity of ⁇ 99.9%.
  • the silicon hexaboride powder is produced by Alfa Aesar Company, with a purity ⁇ 98%.
  • the ball milling process uses a planetary ball mill, which is a model QM-3SP4 planetary ball mill produced by Nanjing University.
  • the electric heating blast drying oven is used for drying, which is DHG-9075A type produced by Shanghai Yiheng Scientific Instrument Co., Ltd.
  • the discharge plasma sintering furnace (SPS) is the HPD-25 discharge plasma sintering system produced by the German FCT company.
  • a method for preparing dense HfC(Si)-HfB 2 composite ceramics adopts the following steps:
  • step (1) The mixed powder in step (1) is ball-milled using a planetary ball mill, and isopropyl alcohol is used as the ball-milling medium, so that the above HfO 2 , carbon black, and SiB 6 are uniformly mixed, and the mass ratio of the mixed powder to ball stone is 1:10, the speed of the ball mill is 300 rpm, the ball is milled for 8 hours, and then dried in a 50 °C electric blast drying oven for 6 hours to form a uniform mixed powder;
  • step (3) Take out the uniformly mixed powder finally obtained in step (3), put it into a graphite mold (diameter 32mm) covered with graphite paper, perform discharge plasma sintering, control the sintering temperature to 1600°C, and keep the temperature for 10 minutes.
  • the sintering applied pressure is 45MPa
  • the heating rate is 200°C/min
  • the vacuum degree is controlled at 0mbar
  • the HfC(Si)-HfB 2 multiphase ceramics with a density of 96% and uniformly dispersed grains can be obtained.
  • a method for preparing dense HfC(Si)-HfB 2 composite ceramics adopts the following steps:
  • the mixed powder in step (1) is ball-milled using a planetary ball mill, and isopropyl alcohol is used as the ball-milling medium, so that the above HfO 2 , carbon black, and SiB 6 are uniformly mixed, and the mass ratio of the mixed powder to ball stone is 1:15, the speed of the ball mill is 350 rpm, the ball mill is 12h, and then dried in a 60°C electric blast drying oven for 8h to form a uniform mixed powder;
  • step (3) Take out the uniformly mixed powder finally obtained in step (3), put it into a graphite mold (diameter 32mm) covered with graphite paper, perform discharge plasma sintering, control the sintering temperature to 1700°C, and keep the temperature for 20 minutes.
  • the sintering applied pressure is 35MPa
  • the heating rate is 100°C/min
  • the vacuum degree is controlled at 0.5mbar
  • the HfC(Si)-HfB 2 multiphase ceramics with a density of 98% and uniformly dispersed grains can be obtained.
  • a method for preparing dense HfC(Si)-HfB 2 composite ceramics adopts the following steps:
  • the mixed powder in step (1) is ball-milled using a planetary ball mill, and isopropyl alcohol is used as the ball-milling medium, so that the above HfO 2 , carbon black, and SiB 6 are uniformly mixed, and the mass ratio of the mixed powder to ball stone is 1:20, the speed of the ball mill is 400 rpm, the ball mill is 16h, and then dried in a 70°C electric blast drying oven for 10h to form a uniform mixed powder;
  • step (3) Take out the uniformly mixed powder finally obtained in step (3), put it into a graphite mold (diameter 32mm) covered with graphite paper, perform discharge plasma sintering, control the sintering temperature at 1850°C, and keep the temperature at 30min.
  • the sintering applied pressure is 60MPa
  • the heating rate is 80°C/min
  • the vacuum degree is controlled at 0.2mbar
  • the HfC(Si)-HfB 2 multiphase ceramics with a density of 99% and uniformly dispersed grains can be obtained.
  • a method for preparing dense HfC(Si)-HfB 2 composite ceramics adopts the following steps:
  • the mixed powder in step (1) is ball-milled using a planetary ball mill, and isopropyl alcohol is used as the ball-milling medium, so that the above HfO 2 , carbon black, and SiB 6 are uniformly mixed, and the mass ratio of the mixed powder to ball stone is 1:4, the speed of the ball mill is 200 rpm, the ball mill is 24h, and then dried in a 50°C electric blast drying oven for 10h to form a uniform mixed powder;
  • step (3) Take out the uniformly mixed powder finally obtained in step (3), put it into a graphite mold (diameter 32mm) covered with graphite paper, perform discharge plasma sintering, control the sintering temperature to 1500°C, and keep the temperature for 30 minutes.
  • the sintering applied pressure is 20MPa
  • the heating rate is 50°C/min
  • the vacuum degree is controlled at 0mbar
  • the HfC(Si)-HfB 2 multiphase ceramics with a density of 94.0% and uniformly dispersed grains can be obtained.
  • a method for preparing dense HfC(Si)-HfB 2 composite ceramics adopts the following steps:
  • the mixed powder in step (1) is ball-milled using a planetary ball mill, and isopropyl alcohol is used as the ball-milling medium, so that the above HfO 2 , carbon black, and SiB 6 are uniformly mixed, and the mass ratio of the mixed powder to ball stone is 1:12, the speed of the ball mill is 200-500 rpm, the ball is milled for 12h, and then dried in a 60°C electric blast drying oven for 6h to form a uniform mixed powder;
  • step (3) Take out the uniformly mixed powder finally obtained in step (3), put it into a graphite mold (diameter 32mm) covered with graphite paper, perform discharge plasma sintering, control the sintering temperature to 1650°C, and keep the temperature for 20 minutes.
  • the sintering applied pressure is 40MPa
  • the heating rate is 100°C/min
  • the vacuum degree is controlled at 0.5mbar
  • the HfC(Si)-HfB 2 multiphase ceramics with a density of 98% and uniformly dispersed grains can be obtained.
  • a method for preparing dense HfC(Si)-HfB 2 composite ceramics adopts the following steps:
  • the mixed powder in step (1) is ball-milled using a planetary ball mill, and isopropyl alcohol is used as the ball-milling medium, so that the above HfO 2 , carbon black, and SiB 6 are uniformly mixed, and the mass ratio of the mixed powder to ball stone is 1:20, the speed of the ball mill is 500 rpm, the ball mill is 6h, and then dried in an electric blast drying oven at 80°C for 4h to form a uniform mixed powder;
  • step (3) Take out the uniformly mixed powder finally obtained in step (3), put it into a graphite mold (diameter 32mm) covered with graphite paper, perform discharge plasma sintering, control the sintering temperature to 1850°C, and keep the temperature for 5 minutes.
  • the sintering applied pressure is 60MPa
  • the heating rate is 200°C/min
  • the vacuum degree is controlled at 1.0mbar
  • the HfC(Si)-HfB 2 multiphase ceramics with a density of 100% and uniformly dispersed grains can be obtained.
  • FIG. 1 is the XRD pattern of the HfC(Si)-HfB 2 composite ceramic prepared in Example 3. From FIG. 1, it can be seen that the XRD pattern of the HfC(Si)-HfB 2 composite ceramic prepared by the present invention: main crystal phase It is HfC and HfB 2 and has good crystallinity, in which a small amount of HfO 2 is present . The HfC and HfB 2 crystal phases are in agreement with PDFNO.65-8747 and PDF NO.65-8678, respectively.
  • 2 is an SEM image of the HfC(Si)-HfB 2 composite ceramic prepared in Example 3. FIG. It can be seen from FIG.
  • the HfC and HfB 2 grains are evenly distributed and the ceramic is denser, with a grain size of about 600 nm and grain boundaries. There is a small amount of free carbon.

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)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Ceramic Products (AREA)

Abstract

一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，将氧化铪粉体、纳米碳黑以及六硼化硅粉体按摩尔比为1～10∶1～20∶1～5的比例混合，获得混合粉体，经过球磨混合均匀，然后进行干燥，形成均匀的混合粉体；将得到的均匀混合粉体装入石墨模具中进行放电等离子体烧结，即原位碳-硼热还原反应-烧结致密化一步工艺完成，制备得到致密度为94.0％～100％且晶粒均匀弥散分布的HfC(Si)-HfB 2复相陶瓷。烧结制备得到的物相组成和晶粒尺寸均匀分布，同时具有较高的致密性和断裂韧性。

Description

一种致密HfC(Si)-HfB 2复相陶瓷的制备方法 技术领域
本发明涉及超高温陶瓷的制备方法，尤其是涉及一种致密HfC(Si)-HfB 2复相陶瓷的制备方法。
背景技术
超高温陶瓷(Ultra-high temperature ceramics，UHTCs)材料是一种新型的高温耐烧蚀的结构材料，其具有很高的熔点(>2000℃)，高的硬度和杨氏模量，在高温条件下具有高的强度，低的热膨胀系数以及具有较好的热物理化学稳定性，高的热导率和电导率。最重要其具有较好的抗烧蚀性能而被应用于超音速飞机和固体火箭的热结构部件，例如喷管，机翼前缘以及发动机的热端部件；同时还应用于高温电极和切削刀具，因此备受广泛的关注。超高温陶瓷大多是元素周期表中第Ⅳ族和Ⅴ族过渡金属元素的碳化物(HfC，ZrC，TaC，NbC)，硼化物(HfB 2，ZrB 2，TaB 2)以及氮化物(HfN，ZrN)，以及一些难熔金属合金和碳/碳复合材料(Ta，W，Ir和C/C复合材料)。目前，碳化物是熔点最高且更耐高温的超高温陶瓷材料，尤其是HfC材料其熔点最高可达到3980℃，热膨胀系数仅为6.73×10 -6/℃，密度与其他碳化物相比较为适中(ρ＝12.7g·cm -3)。但是HfC具有以下缺陷而阻止其被广泛应用于航空航天领域，主要有以下几点：一方面，陶瓷熔点较高，具有较低的自扩散系数，难以烧结致密化；其次，其作为高温结构材料而言，断裂韧性较低(2.1-3.4MPa·m 1/2)；最后，其作为高温抗烧蚀材料，容易被氧化即当服役温度达到500℃以上有氧环境下材料开始氧化，这也限制了其在高温领域的应用。同时，HfB 2陶瓷也具有高的熔点(3380℃)、高硬度(29GPa)和杨氏模量(480GPa)，高的电导率(9.1×10 6S·m -1)和热导率(74-114W·(m K) -1)， 然而具有低的热膨胀系数为6.3×10 -6/℃，较低的断裂韧性(3.0-6.0MPa·m 1/2)。与HfC相比，单相HfB 2在1200℃以下具有良好的抗氧化性能，这是由于液态B 2O 3玻璃相生成起到了良好的抗氧化作用。无论是HfC陶瓷还是HfB 2陶瓷的难以烧结致密化和断裂韧性低成为当前研究应用的瓶颈。因此HfC和HfB 2等UTHCs的烧结和韧性问题成为近年来国内外研究的热点之一。同时烧结制备固溶体复相超高温陶瓷对其烧结和力学方面的应用具有重要的意义。
因此，制备复相陶瓷被认为是提高超高温陶瓷烧结和断裂韧性的最有效的方法，并且同时可以引入原位反应烧结促使元素在高温中扩散迁移，进而达到快速烧结致密化。到目前为止，已报道的制备HfC和HfB 2陶瓷制备方法有以下几种，例如以炭黑、石墨和HfO 2为原料，采用碳热还原法先制备粉体后烧结制成HfC陶瓷[Ji-Xuan Liu,Yan-Mei Kan,Guo-Jun Zhang.Synthesis of Ultra-Fine Hafnium Carbide Powder and its Pressureless Sintering[J].Journal of the American Ceramic Society,93(2010)980-986.]、以HfO 2和WC为原料，采用反应烧结法制备HfC-W金属陶瓷和HfC-SiC陶瓷[Shi-Kuan Sun,Guo-Jun Zhang,Ji-Xuan Liu,et al.Reaction Sintering of HfC/W Cermets with High Strength and Toughness[J].Journal of the American Ceramic Society,96(2013)867-872.]和[Lun Feng,Sea-Hoon Lee,Jie Yin.Low-Temperature Sintering of HfC/SiC Nanocomposites Using HfSi 2-C Additives[J].Journal of the American Ceramic Society,99(2016)2632-2638.]。以及采用HfCl 4和酚醛树脂分别作为Hf源和碳源，用溶胶-凝胶法制备纳米HfC粉体及涂层[S.Venugopal1,A.Paul1,B.Vaidhyanathan et al.,Nano-crystalline ultra high temperature HfB 2 and HfC powders and coatings using a Sol-Gel approach[J].Advanced Ceramic Coatings and Materials for Extreme Environments.32(2011)151-160.]。另外采用化学气相沉积法(CVD)制备HfC抗烧蚀涂层[Jincui Ren,Yulei Zhang,Jinhua Li,et al.,Effects of deposition temperature and time on HfC nanowires synthesized by  CVD on SiC-coated C/C composites[J].Ceramics International.42(2016)5623-5628.]和化学气相渗透法(CVI)，反应熔融浸渗法(RMI)以及前驱体浸渍裂解法(PIP)制备超高温陶瓷复合材料[Sufang Tang,Chenglong Hu.Design,Preparation and Properties of Carbon Fiber Reinforced Ultra-HighTemperature Ceramic Composites for Aerospace Applications:A Review[J].Journal of Materials Science&Technology.33(2017)117-130.]。以上采用的方法制备HfC和HfB 2陶瓷和涂层的方法，均需要在高于1500℃的条件下发生反应先制得粉体，然后在高于2000℃的高温条件下烧结。需要两步完成且高温下无法控制其物相组成和晶粒尺寸，同时难熔的HfO 2原料难以在低温下(<1500℃)扩散反应。另外，CVD法仅限于沉积HfC涂层或者纳米线且制备效率低，工艺难以控制。CVI，RMI和PIP用于制备超高温陶瓷复合材料，很难获得较为致密的烧结体，并且还可能引入杂质，同时对设备要求较高，工艺时间长和成本高。同时所制备HfC的前驱体难以获得，成本较高。除此之外，近年来UHTCs的烧结方法有放电等离子体烧结(SPS)[Omar Cedillos-Barraza,Salvatore Grasso,Nasrin Al Nasiri,et al.,Sintering behavior,solid solution formation and characterization of TaC,HfC and TaC-HfC fabricated by spark plasma sintering[J].Journal of the European Ceramic Society.36(2016)1539–1548.]，热压烧结(Hot pressing)[Liuyi Xiang,Laifei Cheng,Yi Hou,et al.,Fabrication and mechanical properties of laminated HfC-SiC/BN ceramics[J].Journal of the European Ceramic Society 34(2014)3635-3640]和[E.Zapata-Solvas,D.D.Jayaseelan,H.T.Lin,P.Brown,W.E.Lee.Mechanical properties of ZrB 2-and HfB 2-based ultra-high temperature ceramics fabricated by spark plasma sintering[J].Journal of the European Ceramic Society 33(2013)1373–1386.]以及无压烧结[Ji-Xuan Liu,Yan-Mei Kan,Guo-Jun Zhang.Synthesis of Ultra-Fine Hafnium Carbide Powder and its Pressureless Sintering[J].Journal  of the American Ceramic Society 93(2010)980–986.]。以上已报道的HfC和HfB 2陶瓷的烧结方法仅仅是陶瓷烧结过程，并没有原位反应过程，并且均需要较高的烧结温度(1800-2400℃)，进而烧结工艺难以控制。因此，原位反应烧结可以有效解决HfC和HfB 2超高温陶瓷烧结的问题，同时低温制备可以有效调控晶粒尺寸。并且到目前为止，引入耐高温的SiB 6作为原位反应的硼源和硅源，以纳米碳黑为碳源，采用放电等离子体烧结法(SPS)，通过原位碳-硼热还原反应烧结法一步制备HfC(Si)-HfB 2复相陶瓷方面的研究还很少见报道。
中国专利CN100378035C公开了一种硼化物—碳化硅复相陶瓷及其制备方法，其特征在于利用聚碳硅烷裂解时生成的碳化硅的活性，在1700～1900℃温和温度下热压制备致密的硼化物—碳化硅复合陶瓷；所述硼化物主要包括硼化锆，硼化钛和硼化铪；这种工艺不需添加其他助烧剂，保证了材料的高温性能；在制备过程中加入1-12wt％的硅，锆，钛，铪等金属粉末，或者这些金属粉末的任意组合，以吸收聚碳硅烷裂解过程中的残留碳，则可以提高复合材料的致密度，改善材料的力学性能。但是由于起始原料与本申请的完全不同，所述反应体系不同，导致其在1500-1850℃的温度条件下发生碳-硼热还原反应烧结过程以及机理不同，最终产物也就不同，因此本申请是特殊的反应体系和组成、结构设计，才能在1500-1850℃的温度条件下发生碳-硼热还原反应烧结一步法制备HfC(Si)-HfB 2复相陶瓷，不仅可以提高复相陶瓷的烧结致密化，并且大幅度提高复相陶瓷的断裂韧性。
发明内容
本发明的目的在于克服上述超高温陶瓷粉末难以合成和块体陶瓷难以烧结的现有技术缺点，在引入耐高温氧化的SiB 6作为硼源和硅源，纳米碳黑作为碳源，纳米氧化铪作为铪源，通过原位碳-硼热还原反应烧结一步完成制备HfC(Si)-HfB 2复相陶瓷，并且在放电等离子体烧结过程中，SiB 6和碳黑具有 较好的高温电导率，有效提高反应体系放电烧结效率，并且B、C、Si元素、扩散迁移速率快，高效快速地实现原位碳化、硼化以及扩散固溶反应。烧结制备得到物相组成和晶粒尺寸均匀分布，同时其陶瓷烧结体具有较高的致密性和断裂韧性，避免传统先制备粉体过程中难以控制成分和晶粒尺寸，后期烧结陶瓷过程中难以致密化。因此，本发明提供了一种不仅工艺简单而且高效快速烧结制备HfC(Si)-HfB 2复相陶瓷，实现了碳化铪和硼化铪陶瓷的原位复合进而优化提升其性能，具有广阔的应用前景。
本发明的目的可以通过以下技术方案来实现：
一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，采用以下步骤：
(1)取颗粒尺寸为50-500nm氧化铪粉体((HfO 2)、纳米碳黑(50nm)以及颗粒尺寸为1-5μm的六硼化硅粉体(SiB 6)，按照摩尔比为：HfO 2∶C∶SiB 6＝(1～10)∶(1～20)∶(1～5)的比例混合，获得混合粉体；
(2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，采用异丙醇为球磨介质，使得上述HfO 2、炭黑以及SiB 6均匀混合，混合粉体与球石的质量比为1∶(4～20)，球磨机转速为200-500转，球磨6-24h，然后在50-80℃电热鼓风干燥箱中干燥4-10h，形成均匀的混合粉体；
(3)取出步骤(3)最终得到的均匀混合粉体，装入铺着石墨纸的石墨模具(直径为32mm)中，进行放电等离子体烧结，控制烧结温度为1500-1850℃，保温时间为5-30min，烧结施加压力为20-60MPa，升温速率为50-200℃/min，真空度控制在0-1.0mbar，即可得到致密度为94.0％～100％且晶粒均匀弥散分布的HfC(Si)-HfB 2复相陶瓷。
与目前现有公开的技术，例如CN100378035C相比，本申请存在以下区 别技术特征：
(1)起始原料不同：本申请采用氧化铪粉体、纳米碳黑以及六硼化硅粉体作为原料，无论在化学热力学还是动力学方面，这些原料都可以在1500-1850℃的温度条件下发生碳-硼热还原反应烧结过程，同时伴随固溶掺杂过程。通过大量实验验证，反应物体系简单且易发生反应烧结，制备出所需要的HfC(Si)-HfB 2复相陶瓷，且生成产物的组成、微观结构和纯度容易控制且无杂质产生；
(2)工艺制备方法不同：本申请采用放电等离子体烧结法，通过碳-硼热还原反应烧结过程可以快速制备致密的HfC(Si)-HfB 2陶瓷，烧结加热机制不同导致最终反应物反应机理不同。另外本申请通过引入纳米碳黑为碳源，一方面作为碳源，促进碳-硼热还原反应；另一方面作为晶界相，调控反应体系的电导率进而放电等离子体烧结效率，促进复相陶瓷快速烧结致密化，有利于提高复相陶瓷断裂韧性；
(3)最终生成物的组成和微观结构不同：本申请目标产物是HfC基复相陶瓷，通过引入SiB 6和纳米碳黑经过碳-硼热还原反应烧结制备致密的HfC(Si)-HfB 2复相陶瓷，生成物中有HfC和HfB 2晶粒弥散分布且Si元素扩散进入HfC晶格形成固溶体，纳米碳黑均匀分布在晶界处，有效提高复相陶瓷的断裂韧性。
与现有技术相比，本发明具有以下优点：
(1)采用原位碳-硼热还原一步反应烧结法制备成分和晶粒尺寸可控的HfC(Si)-HfB 2复相陶瓷。
(2)同时结合SPS低温高效快速反应烧结获得HfC(Si)-HfB 2复相陶瓷致密 且不同物相晶粒均匀分布、并且伴随元素扩散形成固溶体，这样大大提高了陶瓷烧结致密化过程。
(3)这种一步法反应烧结制备HfC(Si)-HfB 2复相陶瓷工艺简单，两相成分可控，原料易得，效率高。
(4)这种方法制备的HfC(Si)-HfB 2复相陶瓷的断裂韧性具有明显的提高，采用三点弯曲单边开口梁的方法测试其断裂韧性可以达到8.52-14.3MPa·m 1/2，同时能在2500℃的乙氧炔火焰烧蚀180s，其线烧蚀率均小于6μm·s -1。
(5)本申请所涉及的技术参数，例如起始反应粉体颗粒尺寸、配比、球磨工艺参数以及放电等离子体烧结时采用的温度、压力、真空度等都是通过大量实验和基于化学热力学以及动力学反应机制后总结的结果。只有在上述技术参数：配比、烧结温度、压力和保温时间的条件下才能发生原位碳-硼热还原一步反应烧结，制备出致密的HfC(Si)-HfB 2复相陶瓷。反之，颗粒尺寸和配比不是上述参数，温度太高，压力过大，会导致晶粒异常长大，导致陶瓷结构和性能变差；温度太低、压力太小，会导致原位碳-硼热还原一步反应烧结致密化过程无法实现，未能达到起始原料反应的活化能；另外，压力过小材料无法烧结致密化。最后影响材料的组成和微观结构，进而使得材料的力学性能和高温抗烧蚀性能变差。真空度过高，氧分压过高会导致反应物氧化，原位碳-硼热还原反应无法进行；真空度过低，对设备要求过高，也无法正常获得目标产物。
附图说明
图1为实施例3制备的HfC(Si)-HfB 2复相陶瓷的XRD图谱；
图2为实施例3制备的HfC(Si)-HfB 2复相陶瓷的SEM图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，采用以下步骤：
(1)取颗粒尺寸为50-500nm氧化铪粉体(HfO 2)、纳米碳黑(50nm)以及颗粒尺寸为1-5μm的六硼化硅粉体(SiB 6)，按照摩尔比为：HfO 2∶C∶SiB 6＝(1～10)∶(1～20)∶(1～5)的比例混合，获得混合粉体；
(2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，采用异丙醇为球磨介质，使得上述HfO 2、炭黑以及SiB 6均匀混合，混合粉体与球石的质量比为1∶(4～20)，球磨机转速为200-500转，球磨6-24h，然后在50-80℃电热鼓风干燥箱中干燥4-10h，形成均匀的混合粉体；
(3)取出步骤(3)最终得到的均匀混合粉体，装入铺着石墨纸的石墨模具(直径为32mm)中，进行放电等离子体烧结，控制烧结温度为1500-1850℃，保温时间为5-30min，烧结施加压力为20-60MPa，升温速率为50-200℃/min，真空度控制在0-1.0mbar，即可得到致密度为94.0％～100％且晶粒均匀弥散分布的HfC(Si)-HfB 2复相陶瓷。
以上方法中使用的HfO 2纳米粉体是由上海超微纳米科技有限公司生产的，纯度≥99.9％。异丙醇的纯度≥99.8％。纳米碳黑是由北京伊诺凯科技有 限公司生产的，纯度≥99.9％。六硼化硅粉体是由阿法埃莎公司生产的，纯度≥98％。
球磨工艺采用的是行星球磨机，是由南京大学生产的型号为QM-3SP4型行星球磨机。干燥采用的是电热鼓风干燥箱，是由上海一恒科学仪器有限公司生产的DHG-9075A型。放电等离子体烧结炉(SPS)为德国FCT公司生产的HPD-25放电等离子体烧结系统。
以下是更加详细的实施案例，通过以下实施案例进一步说明本发明的技术方案以及所能够获得的技术效果。
实施例1：
一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，采用以下步骤：
(1)取颗粒尺寸为50nm氧化铪粉体(HfO 2)、纳米碳黑(50nm)以及颗粒尺寸为5μm的六硼化硅粉体(SiB 6)，按照摩尔比为：HfO 2∶C∶SiB 6＝5∶2∶1的比例混合，获得混合粉体；
(2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，采用异丙醇为球磨介质，使得上述HfO 2、炭黑以及SiB 6均匀混合，混合粉体与球石的质量比为1∶10，球磨机转速为300转，球磨8h，然后在50℃电热鼓风干燥箱中干燥6h，形成均匀的混合粉体；
(3)取出步骤(3)最终得到的均匀混合粉体，装入铺着石墨纸的石墨模具(直径为32mm)中，进行放电等离子体烧结，控制烧结温度为1600℃，保温时间为10min，烧结施加压力为45MPa，升温速率为200℃/min，真空度控制在0mbar，即可得到致密度为96％且晶粒均匀弥散分布的HfC(Si)-HfB 2复相陶 瓷。
实施例2：
一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，采用以下步骤：
(1)取颗粒尺寸为100nm氧化铪粉体(HfO 2)、纳米碳黑(50nm)以及颗粒尺寸为4μm的六硼化硅粉体(SiB 6)，按照摩尔比为：HfO 2∶C∶SiB 6＝10∶5∶3的比例混合，获得混合粉体；
(2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，采用异丙醇为球磨介质，使得上述HfO 2、炭黑以及SiB 6均匀混合，混合粉体与球石的质量比为1∶15，球磨机转速为350转，球磨12h，然后在60℃电热鼓风干燥箱中干燥8h，形成均匀的混合粉体；
(3)取出步骤(3)最终得到的均匀混合粉体，装入铺着石墨纸的石墨模具(直径为32mm)中，进行放电等离子体烧结，控制烧结温度为1700℃，保温时间为20min，烧结施加压力为35MPa，升温速率为100℃/min，真空度控制在0.5mbar，即可得到致密度为98％且晶粒均匀弥散分布的HfC(Si)-HfB 2复相陶瓷。
实施例3：
一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，采用以下步骤：
(1)取颗粒尺寸为200nm氧化铪粉体((HfO 2)、纳米碳黑(50nm)以及颗粒尺寸为1μm的六硼化硅粉体(SiB 6)，按照摩尔比为：HfO 2∶C∶SiB 6＝2∶1∶1的比例混合，获得混合粉体；
(2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，采用异丙醇为球磨 介质，使得上述HfO 2、炭黑以及SiB 6均匀混合，混合粉体与球石的质量比为1∶20，球磨机转速为400转，球磨16h，然后在70℃电热鼓风干燥箱中干燥10h，形成均匀的混合粉体；
(3)取出步骤(3)最终得到的均匀混合粉体，装入铺着石墨纸的石墨模具(直径为32mm)中，进行放电等离子体烧结，控制烧结温度为1850℃，保温时间为30min，烧结施加压力为60MPa，升温速率为80℃/min，真空度控制在0.2mbar，即可得到致密度为99％且晶粒均匀弥散分布的HfC(Si)-HfB 2复相陶瓷。
实施例4：
一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，采用以下步骤：
(1)取颗粒尺寸为80nm氧化铪粉体(HfO 2)、纳米碳黑(50nm)以及颗粒尺寸为1μm的六硼化硅粉体(SiB 6)，按照摩尔比为：HfO 2∶C∶SiB 6＝1∶1∶1的比例混合，获得混合粉体；
(2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，采用异丙醇为球磨介质，使得上述HfO 2、炭黑以及SiB 6均匀混合，混合粉体与球石的质量比为1∶4，球磨机转速为200转，球磨24h，然后在50℃电热鼓风干燥箱中干燥10h，形成均匀的混合粉体；
(3)取出步骤(3)最终得到的均匀混合粉体，装入铺着石墨纸的石墨模具(直径为32mm)中，进行放电等离子体烧结，控制烧结温度为1500℃，保温时间为30min，烧结施加压力为20MPa，升温速率为50℃/min，真空度控制在0mbar，即可得到致密度为94.0％且晶粒均匀弥散分布的HfC(Si)-HfB 2复相陶 瓷。
实施例5：
一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，采用以下步骤：
(1)取颗粒尺寸为200nm氧化铪粉体(HfO 2)、纳米碳黑(50nm)以及颗粒尺寸为4μm的六硼化硅粉体(SiB 6)，按照摩尔比为：HfO 2∶C∶SiB 6＝10∶15∶3的比例混合，获得混合粉体；
(2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，采用异丙醇为球磨介质，使得上述HfO 2、炭黑以及SiB 6均匀混合，混合粉体与球石的质量比为1∶12，球磨机转速为200-500转，球磨12h，然后在60℃电热鼓风干燥箱中干燥6h，形成均匀的混合粉体；
(3)取出步骤(3)最终得到的均匀混合粉体，装入铺着石墨纸的石墨模具(直径为32mm)中，进行放电等离子体烧结，控制烧结温度为1650℃，保温时间为20min，烧结施加压力为40MPa，升温速率为100℃/min，真空度控制在0.5mbar，即可得到致密度为98％且晶粒均匀弥散分布的HfC(Si)-HfB 2复相陶瓷。
实施例6：
一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，采用以下步骤：
(1)取颗粒尺寸为500nm氧化铪粉体(HfO 2)、纳米碳黑(50nm)以及颗粒尺寸为5μm的六硼化硅粉体(SiB 6)，按照摩尔比为：HfO 2∶C∶SiB 6＝8∶20∶5的比例混合，获得混合粉体；
(2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，采用异丙醇为球磨 介质，使得上述HfO 2、炭黑以及SiB 6均匀混合，混合粉体与球石的质量比为1∶20，球磨机转速为500转，球磨6h，然后在80℃电热鼓风干燥箱中干燥4h，形成均匀的混合粉体；
(3)取出步骤(3)最终得到的均匀混合粉体，装入铺着石墨纸的石墨模具(直径为32mm)中，进行放电等离子体烧结，控制烧结温度为1850℃，保温时间为5min，烧结施加压力为60MPa，升温速率为200℃/min，真空度控制在1.0mbar，即可得到致密度为100％且晶粒均匀弥散分布的HfC(Si)-HfB 2复相陶瓷。
图1为实施例3制备的HfC(Si)-HfB 2复相陶瓷的XRD图谱，由图1可看出本发明所制备的HfC(Si)-HfB 2复相陶瓷的XRD图谱：主晶相为HfC和HfB 2，并且结晶性较好，其中存在少量HfO 2。HfC和HfB 2晶相分别与PDFNO.65-8747和PDF NO.65-8678相吻合。图2为实施例3所制备HfC(Si)-HfB 2复相陶瓷的SEM图。由图2可看出本发明实施例3所制备的HfC(Si)-HfB 2复相陶瓷中，HfC和HfB 2晶粒均匀弥散分布且陶瓷致密较高，晶粒尺寸约为600nm，晶界处存在少量游离的碳。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (10)

  1. 一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，其特征在于，该方法采用以下步骤：
    (1)将氧化铪粉体、纳米碳黑以及六硼化硅粉体按摩尔比为1～10∶1～20∶1～5的比例混合，获得混合粉体；
    (2)将步骤(1)中混合粉体采用行星式球磨机进行球磨，使氧化铪粉体、纳米碳黑以及六硼化硅粉体均匀混合，然后进行干燥，形成均匀的混合粉体；
    (3)将得到的均匀混合粉体装入石墨模具中进行放电等离子体烧结，制备得到致密度94.0％～100％且晶粒均匀弥散分布的HfC(Si)-HfB 2复相陶瓷。
  2. 根据权利要求1所述的一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，其特征在于，步骤(1)中所述氧化铪粉体的粒径为50-500nm，所述纳米碳黑的粒径为50nm，所述六硼化硅粉体的粒径为1-5μm。
  3. 根据权利要求1所述的一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，其特征在于，步骤(2)中采用行星式球磨机对混合粉体进行球磨。
  4. 根据权利要求1所述的一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，其特征在于，步骤(2)中球磨时采用的介质为异丙醇。
  5. 根据权利要求1所述的一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，其特征在于，步骤(2)中球磨时混合粉体与采用球石的质量比为1∶4～20。
  6. 根据权利要求3所述的一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，其特征在于，步骤(2)中球磨时控制球磨机转速为200-500转，球磨6-24h。
  7. 根据权利要求1所述的一种HfC(Si)-HfB 2致密复相陶瓷的制备方法，其特征在于，步骤(2)中球磨结束后在50-80℃电热鼓风干燥箱中干燥4-10h。
  8. 根据权利要求1所述的一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，其特征在于，步骤(3)中所述模具为铺有石墨纸的石墨模具。
  9. 根据权利要求1所述的一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，其特征在于，步骤(3)进行放电等离子体烧结时控制烧结温度为1500-1850℃， 保温时间为5-30min，烧结施加压力为20-60MPa，升温速率为50-200℃/min，真空度控制在0-1.0mbar。
  10. 根据权利要求1所述的一种致密HfC(Si)-HfB 2复相陶瓷的制备方法，其特征在于，步骤(3)进行放电等离子体烧结时控制烧结温度为1500-1850℃。
PCT/CN2019/090157 2018-12-23 2019-06-05 一种致密HfC(Si)-HfB2复相陶瓷的制备方法 WO2020133928A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US17/187,725 US11180419B2 (en) 2018-12-23 2021-02-26 Method for preparation of dense HfC(Si)—HfB2 composite ceramic

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811576879.9 2018-12-23
CN201811576879.9A CN109678511B (zh) 2018-12-23 2018-12-23 一种致密HfC(Si)-HfB2复相陶瓷的制备方法

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US17/187,725 Continuation US11180419B2 (en) 2018-12-23 2021-02-26 Method for preparation of dense HfC(Si)—HfB2 composite ceramic

Publications (1)

Publication Number Publication Date
WO2020133928A1 true WO2020133928A1 (zh) 2020-07-02

Family

ID=66188908

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/090157 WO2020133928A1 (zh) 2018-12-23 2019-06-05 一种致密HfC(Si)-HfB2复相陶瓷的制备方法

Country Status (3)

Country Link
US (1) US11180419B2 (zh)
CN (1) CN109678511B (zh)
WO (1) WO2020133928A1 (zh)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114276147A (zh) * 2021-11-24 2022-04-05 东华大学 一种弥散强化高熵十二硼化物基复合材料及其制备方法
CN114656274A (zh) * 2022-03-08 2022-06-24 西北工业大学 一种纳米线阵列改性石墨烯蜂窝增强纳米气凝胶隔热吸波复合材料
CN114671710A (zh) * 2022-03-10 2022-06-28 西北工业大学 一种双周期多层TaC/HfC超高温陶瓷抗烧蚀涂层及制备方法
CN114956832A (zh) * 2022-04-02 2022-08-30 有研资源环境技术研究院(北京)有限公司 一种超高温陶瓷致密化方法、超高温陶瓷
CN115557793A (zh) * 2022-09-19 2023-01-03 广东工业大学 一种具有细晶、高硬度和高韧性的高熵陶瓷及其制备方法和应用
CN116589305A (zh) * 2023-07-19 2023-08-15 中南大学 一种含超高温陶瓷复合涂层的碳陶复合材料及其制备方法

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109678511B (zh) 2018-12-23 2021-09-10 上海交通大学 一种致密HfC(Si)-HfB2复相陶瓷的制备方法
CN110372386B (zh) * 2019-08-14 2022-05-06 山东理工大学 一种低温液相热压烧结制备致密碳化钽陶瓷的方法
CN111732437A (zh) * 2020-07-08 2020-10-02 淄博星澳新材料研究院有限公司 超高温复相陶瓷粉体的制备方法及其致密化工艺
CN111777072B (zh) * 2020-07-23 2022-05-20 辽宁中色新材科技有限公司 一种二硅化铪的生产工艺
CN112358303A (zh) * 2020-10-27 2021-02-12 中国科学院金属研究所 一种HfCxNy超高温陶瓷粉体材料及其制备方法
CN113563080B (zh) * 2021-08-04 2022-11-25 合肥工业大学 一种制备高致密度的HfC制品的方法
CN113816392A (zh) * 2021-10-14 2021-12-21 北京华威锐科化工有限公司 一种硼化铪粉体的制备方法
CN113912407B (zh) * 2021-11-04 2023-03-03 航天特种材料及工艺技术研究所 一种C/HfC超高温陶瓷基复合材料及其制备方法
CN114481230B (zh) * 2022-02-25 2023-05-09 北京科技大学 一种高致密铪碳氧固溶体及其制备方法和一种电解制备金属铪的方法
CN115180981B (zh) * 2022-05-12 2023-02-14 湖北瑞宇空天高新技术有限公司 一种纳米线跨尺度增韧复相陶瓷抗氧化涂层及其制备方法与应用
CN116120095B (zh) * 2022-12-13 2024-04-19 西北工业大学 选区反应熔渗法制备梯度超高温陶瓷改性c/c复合材料的方法
CN116082065B (zh) * 2023-01-16 2024-03-26 中国科学院金属研究所 一种提高陶瓷基复合材料表面抗氧化涂层烧结致密度的方法及复合抗氧化涂层
CN117088692B (zh) * 2023-09-06 2024-08-02 西安交通大学 一种多相协同超高温陶瓷基复合材料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5750450A (en) * 1996-01-08 1998-05-12 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Ablation resistant zirconium and hafnium ceramics
CN102503427A (zh) * 2011-11-10 2012-06-20 哈尔滨工业大学 一种高韧性硼化物-碳化物复相陶瓷的制备方法
CN104671245A (zh) * 2015-02-28 2015-06-03 武汉理工大学 一种碳化铪纳米粉体的制备方法
CN109678511A (zh) * 2018-12-23 2019-04-26 上海交通大学 一种致密HfC(Si)-HfB2复相陶瓷的制备方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5296417A (en) * 1987-07-15 1994-03-22 Lanxide Technology Company, Lp Self-supporting bodies
US6979490B2 (en) * 2001-01-16 2005-12-27 Steffier Wayne S Fiber-reinforced ceramic composite material comprising a matrix with a nanolayered microstructure
CN100378035C (zh) 2006-01-26 2008-04-02 中国科学院上海硅酸盐研究所 硼化物-碳化硅复相陶瓷及其制备方法
CN100588637C (zh) * 2007-03-16 2010-02-10 中国科学院上海硅酸盐研究所 二硼化锆基复相陶瓷的原位反应制备方法
CA2770291C (en) * 2009-08-04 2023-08-08 Allomet Corporation Tough coated hard particles consolidated in a tough matrix material
WO2014070822A1 (en) * 2012-10-31 2014-05-08 Nano Labs Corp. Nanotechnological thermal insulating coating and uses thereof
CN103979974B (zh) * 2014-05-14 2016-02-24 西北工业大学 一种C/SiC-HfB2-HfC超高温陶瓷基复合材料的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5750450A (en) * 1996-01-08 1998-05-12 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Ablation resistant zirconium and hafnium ceramics
CN102503427A (zh) * 2011-11-10 2012-06-20 哈尔滨工业大学 一种高韧性硼化物-碳化物复相陶瓷的制备方法
CN104671245A (zh) * 2015-02-28 2015-06-03 武汉理工大学 一种碳化铪纳米粉体的制备方法
CN109678511A (zh) * 2018-12-23 2019-04-26 上海交通大学 一种致密HfC(Si)-HfB2复相陶瓷的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DILETTA SCITI ET AL: "Densification and Mechanical Behavior of HfC and HfB2 Fabricated by Spark Plasma Sintering", JOURNAL OF THE AMERICAN CERAMIC SOCIETY, vol. 91, no. 5, 6 May 2008 (2008-05-06), pages 1433 - 1440, XP055715453, ISSN: 0002-7820, DOI: 10.1111/j.1551-2916.2007.02248.x *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114276147A (zh) * 2021-11-24 2022-04-05 东华大学 一种弥散强化高熵十二硼化物基复合材料及其制备方法
CN114656274A (zh) * 2022-03-08 2022-06-24 西北工业大学 一种纳米线阵列改性石墨烯蜂窝增强纳米气凝胶隔热吸波复合材料
CN114656274B (zh) * 2022-03-08 2023-05-05 西北工业大学 一种纳米线阵列改性石墨烯蜂窝增强纳米气凝胶隔热吸波复合材料
CN114671710A (zh) * 2022-03-10 2022-06-28 西北工业大学 一种双周期多层TaC/HfC超高温陶瓷抗烧蚀涂层及制备方法
CN114956832A (zh) * 2022-04-02 2022-08-30 有研资源环境技术研究院(北京)有限公司 一种超高温陶瓷致密化方法、超高温陶瓷
CN114956832B (zh) * 2022-04-02 2023-10-03 有研科技集团有限公司 一种超高温陶瓷致密化方法、超高温陶瓷
CN115557793A (zh) * 2022-09-19 2023-01-03 广东工业大学 一种具有细晶、高硬度和高韧性的高熵陶瓷及其制备方法和应用
CN115557793B (zh) * 2022-09-19 2023-06-02 广东工业大学 一种具有细晶、高硬度和高韧性的高熵陶瓷及其制备方法和应用
CN116589305A (zh) * 2023-07-19 2023-08-15 中南大学 一种含超高温陶瓷复合涂层的碳陶复合材料及其制备方法
CN116589305B (zh) * 2023-07-19 2023-09-19 中南大学 一种含超高温陶瓷复合涂层的碳陶复合材料及其制备方法

Also Published As

Publication number Publication date
CN109678511A (zh) 2019-04-26
US11180419B2 (en) 2021-11-23
US20210179499A1 (en) 2021-06-17
CN109678511B (zh) 2021-09-10

Similar Documents

Publication Publication Date Title
WO2020133928A1 (zh) 一种致密HfC(Si)-HfB2复相陶瓷的制备方法
CN109180189B (zh) 一种高熵碳化物超高温陶瓷粉体及其制备方法
CN103910532B (zh) 涂层无机纤维增韧max相陶瓷复合材料、其制备方法及用途
CN114853477B (zh) 一种耐烧蚀高熵碳化物-高熵硼化物-碳化硅复相陶瓷及其制备方法
Liu et al. Microstructure and ablation behavior of SiC coated C/C–SiC–ZrC composites prepared by a hybrid infiltration process
CN110282976B (zh) 一种三维结构碳化铪-钛硅碳复相陶瓷的制备方法
JP2736380B2 (ja) 炭化珪素質材料の製造方法及び原料組成物
CN108503390B (zh) 碳/碳复合材料表面镶嵌SiC-ZrB2-ZrSi2复合抗氧化涂层的制备方法
CN109608203A (zh) 高熵二硅化物及其制备方法
CN106588018B (zh) 一种超高温碳化铪陶瓷纳米粉体的制备方法
CN112679213B (zh) 一种超多元高熵陶瓷及其制备方法和应用
WO2002081405A1 (fr) Procede de production de materiau composite sic renforce de fibres sic par presse a chaud
Yan et al. In situ synthesis of ultrafine ZrB2–SiC composite powders and the pressureless sintering behaviors
Mallick et al. Synthesis and consolidation of ZrC based ceramics: a review
Ge et al. Improving the electrical and microwave absorbing properties of Si3N4 ceramics with carbon nanotube fibers
CN108546130A (zh) 一种超高温陶瓷及其制备方法
CN101265106A (zh) 一种制备纳米/纳米型Si3N4/SiC纳米复相陶瓷的方法
Duan et al. Effect of MgO doping on densification and grain growth behavior of Gd 2 Zr 2 O 7 ceramics by microwave sintering process
Zhou et al. Polymer‐derived high‐temperature nonoxide materials: a review
CN117534495A (zh) 前驱体浸渍裂解结合反应熔渗制备陶瓷基复合材料的方法
CN115572164A (zh) 一种高韧性复合纳米陶瓷材料及其制备方法
CN105669231A (zh) 一种碳纤维增强MoSi2-SiC陶瓷基复合材料的制备方法
CN115385692B (zh) 一种多尺度孔结构的高熵碳化物陶瓷及其制备方法
CN114804869A (zh) 一种溶胶凝胶法合成Hf6Ta2O17粉体的制备方法
CN114853506A (zh) 碳/碳复合材料表面(HfZrTi)C3中熵碳化物抗烧蚀涂层及制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19904371

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19904371

Country of ref document: EP

Kind code of ref document: A1