CN109678523B - High-entropy ceramic with high-temperature strength and hardness and preparation method and application thereof - Google Patents

High-entropy ceramic with high-temperature strength and hardness and preparation method and application thereof Download PDF

Info

Publication number
CN109678523B
CN109678523B CN201910040601.8A CN201910040601A CN109678523B CN 109678523 B CN109678523 B CN 109678523B CN 201910040601 A CN201910040601 A CN 201910040601A CN 109678523 B CN109678523 B CN 109678523B
Authority
CN
China
Prior art keywords
temperature
powder
equal
entropy ceramic
ceramic
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.)
Active
Application number
CN201910040601.8A
Other languages
Chinese (zh)
Other versions
CN109678523A (en
Inventor
郭伟明
张岩
吴利翔
张威
林华泰
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.)
Guangdong University of Technology
Original Assignee
Guangdong University of Technology
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 Guangdong University of Technology filed Critical Guangdong University of Technology
Priority to CN201910040601.8A priority Critical patent/CN109678523B/en
Publication of CN109678523A publication Critical patent/CN109678523A/en
Application granted granted Critical
Publication of CN109678523B publication Critical patent/CN109678523B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/5805Shaped 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
    • C04B35/58064Shaped 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
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64Burning or sintering processes
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66Monolithic refractories or refractory mortars, including those whether or not containing clay
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232Titanium oxides or titanates, e.g. rutile or anatase
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3256Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3258Tungsten oxides, tungstates, or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661Multi-step sintering
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/666Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74Physical characteristics
    • C04B2235/77Density
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Abstract

The invention belongs to the technical field of ceramic materials, and discloses a high-entropy ceramic with high-temperature strength and hardness, and a preparation method and application thereof. The ceramic is HfO2、ZrO2、WO3、MoO3、TiO2And amorphous boron powder as raw materials, ball-milling and mixing the raw materials, and pressing the mixture into a green body; placing into a graphite crucible and vacuum heat treating to obtain (Hf)xZryWzMonTim)B2Solid solution powder; and (3) heating the solid solution powder to 1000-1400 ℃ by adopting spark plasma sintering, filling protective atmosphere, and then heating to 1800-2200 ℃ for calcining to obtain the solid solution powder. The molecular formula of the ceramic is (Hf)xZryWzMonTim)B2Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 1, and m is more than or equal to 0 and less than or equal to 1; and x + y + z + n + m is 1; the hardness of the ceramic is 28-42 GPa, and the fracture toughness is 5-10 MPa.m1/2The bending strength and the high-temperature strength are both 800-1500MPa, and the weight change rate after heat treatment is 0.3-0.5%.

Description

High-entropy ceramic with high-temperature strength and hardness and preparation method and application thereof
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to high-entropy ceramic with high-temperature strength and hardness, and a preparation method and application thereof.
Background
Ultrahigh-temperature ceramic boride ZrB2、TiB2、HfB2The like have good thermal stability and chemical stability, and attract great attention of researchers, and the high-temperature-resistant high-pressure-resistant high-temperature-resistant highAnd (3) candidate materials under extreme environments such as atomic and nitrogen atom environments at 2000 ℃ or higher), rocket engines (chemical reaction atmospheres at 3000 ℃ or higher), and the like. The melting points of the alloy are more than 3000 ℃, and the alloy still has good strength and good thermal shock resistance at more than 1200 ℃, so the alloy is hopefully applied to components such as wing leading edges and the like which need to be used in extreme environments. Researchers are now working on how to further improve their performance to accommodate applications in extreme environments. The prepared solid solution can effectively improve the performance of the material, the high-entropy ceramic material arouses the interest of researchers in recent years, and the high-entropy material has a large amount of dislocation in the system due to a large entropy value, has the excellent properties of high hardness, high toughness, corrosion resistance and the like, and is a very promising material applied to the fields of aerospace, ultrahigh-speed reentry vehicles, nuclear reactors and the like.
It has been reported in literature that most of high-entropy ceramics are prepared by sintering commercially available powder after high-energy ball milling to obtain high-entropy ceramic materials, and although the high-energy ball milling can reduce the particle size of the powder, the high-energy ball milling inevitably introduces ball milling media due to high energy to pollute the powder, and impurities mostly exist in the grain boundary position of the ceramics, which can reduce the high-temperature performance of the materials and limit the application thereof. W is one of the most hard alloys, if WB2The performance of the material must be greatly improved by adding the high-entropy ceramic (Hf reported by Gild research)0.2Zr0.2W0.2Mo0.2Ti0.2) The density of the B material is only 92.4 percent, and the hardness is only 17.5 GPa. Since there is little WB in commerce2Powder of W2B5Powder instead of (Hf)0.2Zr0.2W0.2Mo0.2Ti0.2)B2The material is not a single-phase high-entropy ceramic but exists (Ti)1.6W2.4)B4Phase, W2B5Powder of other boron compound (ZrB)2、TiB2、HfB2、TaB2、CrB2And the like) the lattice structures are different, so that the single-phase high-entropy ceramic is difficult to form by solid solution, the performance of the single-phase high-entropy ceramic is reduced, and the application of the single-phase high-entropy ceramic at high temperature is influenced. In the literatureThe introduction of W is reported to remove impurities in the material, purify grain boundaries and improve the high-temperature performance of the material.
Disclosure of Invention
In order to solve the disadvantages and shortcomings of the prior art, the present invention provides a high-entropy ceramic having high-temperature strength and hardness. The ceramic has a uniform solid solution phase, stable components, stable high-temperature performance, and excellent mechanical property and oxidation resistance.
Another object of the present invention is to provide a method for preparing the above high-entropy ceramic having high-temperature strength and hardness.
Still another object of the present invention is to provide the use of the above high-entropy ceramic having high-temperature strength and hardness.
The purpose of the invention is realized by the following technical scheme:
a high-entropy ceramic having high-temperature strength and hardness, characterized in that the molecular formula of the high-entropy ceramic is (Hf)xZryWzMonTim)B2Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, m is more than or equal to 0 and less than or equal to 1, and x + y + z + n + m is equal to 1; the high-entropy ceramic is HfO2、ZrO2、WO3、MoO3、TiO2Mixing the amorphous boron powder and the amorphous boron powder serving as raw material powder, adding a solvent and a ball milling medium for mixing, drying to obtain mixed powder, carrying out heat treatment on a mixed powder blank prepared by die pressing the mixed powder under a vacuum condition, firstly heating to 800-1200 ℃, keeping the temperature I, then heating to 1400-1600 ℃, keeping the temperature II, grinding and sieving to obtain the (Hf) powderxZryWzMonTim)B2And (2) heating the ultrahigh-temperature high-entropy ceramic powder to 1000-1400 ℃ by adopting spark plasma sintering, filling protective atmosphere, and heating to 1800-2200 ℃ for calcining to obtain the ultrahigh-temperature high-entropy ceramic powder.
Preferably, the molecular formula of the high-entropy ceramic is (Hf)xZryWzMonTim)B2Wherein x is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.1 and less than or equal to 0.9, z is more than or equal to 0.1 and less than or equal to 0.9, n is more than or equal to 0.1 and less than or equal to 0.9, m is more than or equal to 0.1 and less than or equal to 0.9, andx + y + z + n + m is 1.
Preferably, the HfO2、ZrO2、WO3、MoO3And TiO2The purity of the HfO is more than or equal to 99.9 percent, and the HfO2、ZrO2、WO3、MoO3And TiO2The particle size of the particles is 1 to 2 μm.
Preferably, the relative density of the ceramic>98 percent, hardness of 28-42 GPa and fracture toughness of 5-10 MPa.m1/2The room temperature bending strength is 800-1500MPa, the high temperature strength is 800-1500MPa at 1000-1600 ℃, and the weight change rate of the ceramic after heat treatment at 1000-1500 ℃ is 0.3-0.5%.
Preferably, the ultrahigh-temperature high-entropy ceramic powder (Hf)xZryWzMonTim)B2The purity of the ultra-high temperature high entropy ceramic powder is 99.0-99.9wt%, the grain size of the ultra-high temperature high entropy ceramic powder is 0.1-1 mu m, and the oxygen content of the ultra-high temperature high entropy ceramic powder is 0.1-0.5 wt%.
Preferably, the solvent is ethanol, propanol, methanol or acetone.
Preferably, the protective atmosphere is N2Or Ar.
Preferably, the heating rates of the temperature rise to 800-1200 ℃ and the temperature rise to 1400-1600 ℃ are both 5-20 ℃/min, and the time of the heat preservation I and the heat preservation II is 0.5-2 h; the calcining time is 1-30 min, the calcining pressure is 10-100 MPa, and the heating rate when the temperature is raised to 1800-2200 ℃ is 100-400 ℃/min.
The preparation method of the high-entropy ceramic with high-temperature strength and hardness comprises the following specific steps:
s1, using HfO2、ZrO2、WO3、MoO3、TiO2Adding a solvent and a ball milling medium into the amorphous boron powder serving as raw materials, mixing the amorphous boron powder and the ball milling medium on a roller ball mill for 10-48 hours, and drying to obtain mixed powder;
s2, placing the blank body formed by die pressing the mixed powder into a graphite crucible, heating to 800-1200 ℃ at the speed of 5-20 ℃/min, preserving heat for 0.5-2 h, and then heating to 1400-1600 ℃ at the speed of 5-20 ℃/minKeeping the temperature for 0.5-2 h to obtain (Hf DEG C)xZryWzMonTim)B2Ultra-high temperature high entropy ceramic powder;
s3. will (Hf)xZryWzMonTim)B2Putting the ultrahigh-temperature high-entropy ceramic powder into a graphite mold, heating to 1000-1400 ℃ at the speed of 100-400 ℃/min by adopting spark plasma sintering, filling a protective atmosphere, heating to 1800-2200 ℃ at the speed of 100-400 ℃/min, preserving heat for 1-30 min, and pressurizing to 10-100 MPa for calcination to obtain (Hf)xZryWzMonTim)B2Ultrahigh-temperature high-entropy ceramic.
The high-entropy ceramic with high-temperature strength and hardness is applied to the field of ultra-high temperature limit.
The high-entropy ceramic with high-temperature strength and hardness is prepared from HfO2、ZrO2、WO3、MoO3、TiO2And amorphous boron powder as raw materials to prepare (Hf)xZryWzMonTim)B2The ultrahigh-temperature high-entropy ceramic powder solves the problem that W is difficult to dissolve in a solid manner by introducing high-performance W in situ. After spark plasma sintering, solid solution precipitation phase is difficult to appear due to high cooling speed, and single-phase (Hf) is obtainedxZryWzMonTim)B2Ultrahigh-temperature high-entropy ceramic due to ultrahigh-temperature transition metal boride HfB2、ZrB2、WB2、MoB2And TiB2The ultrahigh-temperature high-entropy ceramic prepared by mutual solid solution has the properties of uniform solid solution phase, stable component, stable high-temperature performance, excellent mechanical property and excellent oxidation resistance.
Compared with the prior art, the invention has the following beneficial effects:
1. the high-entropy ceramic prepared by the invention has high purity of original powder and small particle size, can promote atomic diffusion in the process of forming a solid solution, can realize compact sintering at low temperature, improves sintering performance and improves material performance. The synthesized high-entropy ceramic powder has fine grains and uniform components. The ceramic has the advantages of uniform solid solution phase, stable components, stable high-temperature performance, excellent mechanical property and excellent oxidation resistance.
2. The invention adopts the ultrahigh-temperature high-entropy ceramic powder self-synthesized by the borothermic reduction method as the raw material to prepare the ultrahigh-temperature high-entropy ceramic, can effectively solve the defect that boride purchased commercially is difficult to dissolve in solid, can more easily prepare single-phase ultrahigh-temperature high-entropy ceramic,
3. the method of the invention can prepare single-phase (Hf)xZryWzMonTim)B2The ultra-high temperature high entropy ceramic solves the problem that W is difficult to dissolve in solid, and high performance W is added to ensure that (Hf)xZryWzMonTim)B2The performance of the ultrahigh-temperature high-entropy ceramic is greatly improved.
4. Compared with the reported method for mixing the raw material powder by high-energy ball milling of a plurality of borides in order to improve the powder activity, the raw material mixing method of the method adopts the roller ball mill, realizes high efficiency, simplicity and energy conservation, and avoids the oxidation of impurities and powder generated in the high-energy ball milling process. Compared with the physical mixing uniformity, the method achieves the chemical uniformity of the raw material components. It is also beneficial to the formation of a uniform solid melt phase of the sintered material, and also saves energy and cost.
Drawings
FIG. 1 (Hf) prepared in example 40.2Zr0.2W0.2Mo0.2Ti0.2)B2XRD patterns of the ultrahigh-temperature high-entropy ceramic powder and the ceramic.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. With HfO2(purity of powder 99.9%, particle diameter 2 μm), ZrO2(purity of powder 99.9%, particle diameter 2 μm), MoO3(purity of powder 99.9%, particle diameter 2 μm) and TiO2(purity of powder 99%, particle size 2 μm) powder was blended in equal atomic ratio with amorphous boron powder (purity 96%, particle size 2 μm) as raw material to obtain (Hf)0.25Zr0.25Mo0.25Ti0.25)B2Mixing the above oxides with amorphous boron powder.
2. Ethanol is used as solvent, Si is used as solvent3N4The balls are used as ball milling media, and are mixed for 24 hours on a roller ball mill, and mixed and dried to obtain mixed powder.
3. Placing the powder blank after the mixed powder mould pressing into a graphite crucible, heating to 1100 ℃ at the speed of 10 ℃/min, preserving heat for 2h, then heating to 1600 ℃ at the speed of 10 ℃/min, preserving heat for 1h, wherein the whole sintering process is vacuum, the pressure is 0.1Pa, grinding and sieving the obtained powder to obtain (Hf) (Hf is obtained0.25Zr0.25Mo0.25Ti0.25)B2Ultrahigh-temperature high-entropy ceramic powder.
4. Will (Hf)0.25Zr0.25Mo0.25Ti0.25)B2Putting the ultrahigh-temperature high-entropy ceramic powder into a graphite mould, heating to 2000 ℃ at the heating rate of 200 ℃/min, keeping the temperature for 5min, pressurizing to 30MPa, filling Ar gas at 1200 ℃, and sintering by discharge plasma (SPS) to obtain the ultrahigh-temperature high-entropy ceramic.
This example (Hf) was determined by laser particle size analysis0.25Zr0.25Mo0.25Ti0.25)B2The grain diameter of the ultra-high temperature high entropy ceramic powder is 0.75 μm, and the oxygen content of the solid solution powder is 0.5wt% measured by a carbon-oxygen analyzer. The prepared ultrahigh-temperature high-entropy ceramic forms a uniform single-phase solid solution. The relative density is 98 percent, the hardness is 28GPa, and the fracture toughness is 5 MPa.m1/2The bending strength at room temperature is 920MPa, the high-temperature performance of the ceramic is stable, the bending strength at high temperature of 1200 ℃ is 800MPa, the oxidation resistance of the ceramic is good, and the ceramic is heavy after heat treatment at 1200 DEG CThe amount increased by 0.5%.
Example 2
1. With HfO2(purity of powder 99.9%, particle diameter 2 μm), ZrO2(purity of powder 99.9%, particle diameter 2 μm), WO3(purity of powder 99.9%, particle diameter 2 μm), MoO3(purity of powder 99.9%, particle diameter 2 μm) and TiO2(purity of powder 99%, particle size 2 μm) powder was blended in equal atomic ratio with amorphous boron powder (purity 96%, particle size 2 μm) as raw material to obtain (Hf)0.1Zr0.2W0.3Mo0.2Ti0.2)B2Mixing the above oxides with amorphous boron powder.
2. Ethanol is used as solvent, Si is used as solvent3N4The balls are used as ball milling media, and are mixed for 24 hours on a roller ball mill, and mixed and dried to obtain mixed powder.
3. Placing the powder blank after the mixed powder is molded into a graphite crucible, heating to 1100 ℃ at the speed of 10 ℃/min, keeping the temperature for 1h, heating to 1500 ℃ at the speed of 10 ℃/min, keeping the temperature for 1h, wherein the whole sintering process is vacuum and the pressure is 0.1Pa, grinding and sieving the obtained powder to obtain (Hf)0.1Zr0.2W0.3Mo0.2Ti0.2)B2Ultrahigh-temperature high-entropy ceramic powder.
4. Will (Hf)0.1Zr0.2W0.3Mo0.2Ti0.2)B2Placing the ultrahigh-temperature high-entropy ceramic powder into a graphite mold, heating to 2000 deg.C at a heating rate of 300 deg.C/min, maintaining the temperature for 5min, pressurizing to 80MPa, charging Ar gas at 1200 deg.C, and sintering by discharge plasma (SPS) to obtain (Hf)0.1Zr0.2W0.3Mo0.2Ti0.2)B2Ultrahigh-temperature high-entropy ceramic.
This example (Hf) was determined by laser particle size analysis0.1Zr0.2W0.3Mo0.2Ti0.2)B2The grain diameter of the ultra-high temperature high entropy ceramic powder is 0.55 mu m, and the oxygen content of the solid solution powder is 0.3 wt% measured by a carbon-oxygen analyzer. The prepared ultrahigh-temperature high-entropy ceramic forms a uniform single-phase solid solution. The relative density is 99 percent, and the hardness is 40GPa, fracture toughness 8MPa m1/2The bending strength at room temperature is 1060MPa, the high-temperature performance of the ceramic is stable, the bending strength at high temperature of 1200 ℃ is 980MPa, the oxidation resistance of the ceramic is good, and the weight is increased by 0.5 percent after heat treatment at 1200 ℃.
Example 3
1. With HfO2(purity of powder 99.9%, particle diameter 2 μm), ZrO2(purity of powder 99.9%, particle diameter 2 μm), WO3(purity of powder 99.9%, particle diameter 2 μm), MoO3(purity of powder 99.9%, particle diameter 2 μm) and TiO2(purity of powder 99%, particle size 2 μm) powder was blended in equal atomic ratio with amorphous boron powder (purity 96%, particle size 2 μm) as raw material to obtain (Hf)0.2Zr0.3W0.1Mo0.2Ti0.2)B2Mixing the above oxides with amorphous boron powder.
2. Ethanol is used as solvent, Si is used as solvent3N4The balls are used as ball milling media, and are mixed for 24 hours on a roller ball mill, and mixed and dried to obtain mixed powder.
3. Placing the powder blank after the mixed powder mould pressing into a graphite crucible, heating to 1000 ℃ at the speed of 10 ℃/min, keeping the temperature for 1h, then heating to 1550 ℃ at the speed of 10 ℃/min, keeping the temperature for 1h, wherein the whole sintering process is vacuum, the pressure is 0.1Pa, grinding and sieving the obtained powder to obtain (Hf)0.2Zr0.3W0.1Mo0.2Ti0.2)B2Ultrahigh-temperature high-entropy ceramic powder.
4. Will (Hf)0.2Zr0.3W0.1Mo0.2Ti0.2)B2Placing the ultrahigh-temperature high-entropy ceramic powder into a graphite mold, heating to 2000 deg.C at a heating rate of 200 deg.C/min, maintaining the temperature for 5min, pressurizing to 50MPa, charging Ar gas at 1200 deg.C, and sintering by discharge plasma (SPS) to obtain (Hf)0.2Zr0.3W0.1Mo0.2Ti0.2)B2Ultrahigh-temperature high-entropy ceramic.
This example (Hf) was determined by laser particle size analysis0.2Zr0.3W0.1Mo0.2Ti0.2)B2Particles of ultrahigh-temperature high-entropy ceramic powderThe particle size was 0.35 μm, and the oxygen content of the solid solution powder was 0.3% by weight as measured by a carbon-oxygen analyzer. The prepared ultrahigh-temperature high-entropy ceramic forms a uniform single-phase solid solution. The relative density is 99 percent, the hardness is 30GPa, and the fracture toughness is 6 MPa.m1/2The room temperature bending strength is 1160MPa, the high temperature performance of the ceramic is stable, the bending strength at the high temperature of 1300 ℃ is 1080MPa, the oxidation resistance of the ceramic is good, and the weight is increased by 0.5 percent after the heat treatment at the temperature of 1300 ℃.
Example 4
1. With HfO2(purity of powder 99.9%, particle diameter 2 μm), ZrO2(purity of powder 99.9%, particle diameter 2 μm), WO3(purity of powder 99.9%, particle diameter 2 μm), MoO3(purity of powder 99.9%, particle diameter 2 μm) and TiO2(purity of powder 99%, particle size 2 μm) powder was blended in equal atomic ratio with amorphous boron powder (purity 96%, particle size 2 μm) as raw material to obtain (Hf)0.2Zr0.2W0.2Mo0.2Ti0.2)B2Mixing the above oxides with amorphous boron powder.
2. Ethanol is used as solvent, Si is used as solvent3N4The balls are used as ball milling media, and are mixed for 24 hours on a roller ball mill, and mixed and dried to obtain mixed powder.
3. Placing the powder blank after the mixed powder mould pressing into a graphite crucible, heating to 1100 ℃ at the speed of 10 ℃/min, preserving heat for 2h, then heating to 1600 ℃ at the speed of 10 ℃/min, preserving heat for 2h, wherein the whole sintering process is vacuum, the pressure is 0.1Pa, grinding and sieving the obtained powder to obtain (Hf) (Hf is obtained0.2Zr0.2W0.2Mo0.2Ti0.2)B2Ultrahigh-temperature high-entropy ceramic powder.
4. Will (Hf)0.2Zr0.2W0.2Mo0.2Ti0.2)B2Placing the ultrahigh-temperature high-entropy ceramic powder into a graphite mold, heating to 2000 deg.C at a heating rate of 150 deg.C/min, maintaining the temperature for 10min, pressurizing to 30MPa, charging Ar gas at 1200 deg.C, and sintering by discharge plasma (SPS) to obtain (Hf)0.2Zr0.2W0.2Mo0.2Ti0.2)B2Ultrahigh-temperature high-entropy ceramic.
FIG. 1 shows (Hf) prepared in this example0.2Zr0.2W0.2Mo0.2Ti0.2)B2XRD patterns of the ultrahigh-temperature high-entropy ceramic powder and the ceramic. Wherein, (a) is ultrahigh-temperature high-entropy ceramic powder, and (b) is ultrahigh-temperature high-entropy ceramic; as can be seen from (a) in the figure, (Hf) produced in the present example0.2Zr0.2W0.2Mo0.2Ti0.2)B2No HfO is detected in the ultrahigh-temperature high-entropy ceramic powder2、ZrO2、WO3、MoO3And TiO2Phase, amorphous boron powder is amorphous, so XRD cannot detect the boron powder, and only a small amount of W is detected2B5、WB、(Hf,Zr)O2And (Hf)0.2Zr0.2W0.2Mo0.2Ti0.2)B2A solid solution phase in which W is hardly solid-dissolved with other substances to form a single-phase solid solution, and (Hf, Zr) O2Difficult to remove, proving HfO2、ZrO2、WO3、MoO3And TiO2Has undergone boron thermal reaction with boron and is converted into ultrahigh-temperature high-entropy ceramic powder. And with HfB2And ZrB2The comparison between the standard PDF cards 65-8678 and 65-8704 shows that (Hf)0.2Zr0.2W0.2Mo0.2Ti0.2)B2The peak of (2) was shifted to a high angle, and it was confirmed that five elements were dissolved in each other to decrease the lattice constant, and thus the diffraction peak was shifted. When (Hf)0.2Zr0.2W0.2Mo0.2Ti0.2)B2After the ultra-high temperature high entropy ceramic powder was sintered by SPS, as shown in FIG. 1(b), it detected only (Hf)0.2Zr0.2W0.2Mo0.2Ti0.2)B2(ii) a diffraction peak of (1), no other impurity peak, and (Hf) in comparison with FIG. 1(a)0.2Zr0.2W0.2Mo0.2Ti0.2)B2Further shift toward high angles, proving W2B5And WB phase is solid-dissolved in the high-entropy ceramic matrix, the lattice constant is reduced, and the diffraction peak is shifted to a high angle. This example resulted in a homogeneous single-phase ultra-high temperature high entropy ceramic solid solution.
By laser particle size divisionAnalysis of this example (Hf)0.2Zr0.2W0.2Mo0.2Ti0.2)B2The grain diameter of the ultra-high temperature high entropy ceramic powder is 0.25 μm, and the oxygen content of the solid solution powder is 0.2 wt% measured by a carbon-oxygen analyzer. The prepared ultrahigh-temperature high-entropy ceramic forms a uniform single-phase solid solution. The relative density is 99 percent, the hardness is 42GPa, and the fracture toughness is 10 MPa.m1/2The room temperature bending strength is 1500MPa, the high temperature performance of the ceramic is stable, the high temperature bending strength of the ceramic is 1480MPa at the temperature of 1200 ℃, the oxidation resistance of the ceramic is good, and the weight is increased by 0.3 percent after heat treatment at the temperature of 1200 ℃.
Example 5
The difference from example 1 is that: separately prepare TiB2、MoB2、WB2、ZrB2And HfB2Ultra-high temperature ceramics.
Example 6
The difference from example 1 is that: prepare (Hf)0.1Ti0.9)B2Ultra-high temperature ceramics.
Example 7
The difference from example 1 is that: prepare (Zr)y0.1Mo0.9)B2Ultra-high temperature ceramics.
Example 8
The difference from example 1 is that: prepare (Hf)0.1Ti0.9)B2Ultra-high temperature ceramics.
Example 9
The difference from example 1 is that: prepare (W)0.2Mo0.8)B2Ultra-high temperature ceramics.
Example 10
The difference from example 1 is that: prepare (Hf)0.3Mo0.7)B2Ultra-high temperature ceramics.
Example 11
The difference from example 1 is that: prepare (Hf)0.4Zr0.2W0.1Mo0.1Ti0.2)B2Ultra-high temperature ceramics.
Example 12
The difference from example 1 is that: prepare a(Hf0.5Zr0.1W0.1Mo0.2Ti0.1)B2Ultra-high temperature ceramics.
Example 13
The difference from example 1 is that: prepare (Hf)0.6Zr0.1W0.1Mo0.1Ti0.1)B2Ultra-high temperature ceramics.
Example 14
The difference from example 1 is that: prepare (Hf)0.8Zr0.05W0.05Mo0.1Ti0.1)B2Ultra-high temperature ceramics.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.

Claims (9)

1. A high-entropy ceramic having high-temperature strength and hardness, characterized in that the molecular formula of the high-entropy ceramic is (Hf)xZryWzMonTim)B2Wherein, 0<x<1,0<y<1,0<z<1,0<n<1,0<m<1; and x + y + z + n + m = 1; the high-entropy ceramic is HfO2、ZrO2、WO3、MoO3、TiO2Mixing the amorphous boron powder and the amorphous boron powder serving as raw material powder, adding a solvent and a ball milling medium for mixing, drying to obtain mixed powder, carrying out heat treatment on a mixed powder blank prepared by die pressing the mixed powder under a vacuum condition, firstly heating to 800-1200 ℃, keeping the temperature I, then heating to 1400-1600 ℃, keeping the temperature II, grinding and sieving to obtain the (Hf) powderxZryWzMonTim)B2The method comprises the following steps of (1) heating the ultrahigh-temperature high-entropy ceramic powder to 1000-1400 ℃ by adopting spark plasma sintering, filling protective atmosphere, heating to 1800-2200 ℃, and calcining to obtain the ultrahigh-temperature high-entropy ceramic powder; the HfO2、ZrO2、WO3、MoO3And TiO2The purity of the HfO is more than or equal to 99.9 percent, and the HfO2、ZrO2、WO3、MoO3And TiO2The particle size of the particles is 1-2 mu m; the weight change rate of the ceramic after heat treatment at 1000-1500 ℃ is 0.3-0.5%; the hardness is 28-42 GPa, and the fracture toughness is 5-10 MPa.m1/2The room temperature bending strength is 800-1500MPa, and the high temperature strength at 1000-1600 ℃ is 800-1500 MPa.
2. A high entropy ceramic having high temperature strength and hardness according to claim 1, wherein the high entropy ceramic has a molecular formula of (Hf)xZryWzMonTim)B2Wherein x is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.1 and less than or equal to 0.9, z is more than or equal to 0.1 and less than or equal to 0.9, n is more than or equal to 0.1 and less than or equal to 0.9, m is more than or equal to 0.1 and less than or equal to 0.9, and x + y + z + n + m =1 is satisfied.
3. A high entropy ceramic having high temperature strength and hardness in accordance with claim 1, wherein the relative density of the ceramic is > 98%.
4. High-entropy ceramic with high-temperature strength and hardness according to claim 1, wherein the ultra-high-temperature high-entropy ceramic powder (Hf)xZryWzMonTim)B2The purity of the ultra-high temperature and high entropy ceramic powder is 99.0-99.9wt%, the particle size of the ultra-high temperature and high entropy ceramic powder is 0.1-1 mu m, and the oxygen content of the ultra-high temperature and high entropy ceramic powder is 0.1-0.5 wt%.
5. A high-entropy ceramic having high-temperature strength and hardness according to claim 1, wherein the solvent is ethanol, propanol, methanol or acetone.
6. A high-entropy ceramic having high-temperature strength and hardness according to claim 1, wherein the protective atmosphere is N2Or Ar.
7. The high-entropy ceramic with high-temperature strength and hardness according to claim 1, wherein the heating rates to 800-1200 ℃ and 1400-1600 ℃ are both 5-20 ℃/min, and the time for the heat preservation I and the heat preservation II is 0.5-2 h; the calcining time is 1-30 min, the calcining pressure is 10-100 MPa, and the heating rate when the temperature is raised to 1800-2200 ℃ is 100-400 ℃/min.
8. A preparation method of a high-entropy ceramic with high-temperature strength and hardness according to any one of claims 1 to 7, characterized by comprising the following specific steps:
s1, HfO2、ZrO2、WO3、MoO3、TiO2Adding a solvent and a ball milling medium into the amorphous boron powder serving as raw materials, mixing the amorphous boron powder and the ball milling medium on a roller ball mill for 10-48 hours, and drying to obtain mixed powder;
s2, placing the blank body of the mixed powder after mould pressing into a graphite crucible, heating to 800-1200 ℃ at the speed of 5-20 ℃/min, preserving heat for 0.5-2 h, then heating to 1400-1600 ℃ at the speed of 5-20 ℃/min, preserving heat for 0.5-2 h, and obtaining (Hf)xZryWzMonTim)B2Ultra-high temperature high entropy ceramic powder;
s3 (Hf)xZryWzMonTim)B2Putting the ultrahigh-temperature high-entropy ceramic powder into a graphite mold, heating to 1000-1400 ℃ at the speed of 100-400 ℃/min by adopting spark plasma sintering, filling a protective atmosphere, heating to 1800-2200 ℃ at the speed of 100-400 ℃/min, preserving heat for 1-30 min, and pressurizing to 10-100 MPa for calcination to obtain (Hf)xZryWzMonTim)B2High entropy ceramics.
9. Use of the high-entropy ceramic having high-temperature strength and hardness according to any one of claims 1 to 7 in the ultra-high temperature limit field.
CN201910040601.8A 2019-01-16 2019-01-16 High-entropy ceramic with high-temperature strength and hardness and preparation method and application thereof Active CN109678523B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910040601.8A CN109678523B (en) 2019-01-16 2019-01-16 High-entropy ceramic with high-temperature strength and hardness and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910040601.8A CN109678523B (en) 2019-01-16 2019-01-16 High-entropy ceramic with high-temperature strength and hardness and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109678523A CN109678523A (en) 2019-04-26
CN109678523B true CN109678523B (en) 2021-04-06

Family

ID=66193457

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910040601.8A Active CN109678523B (en) 2019-01-16 2019-01-16 High-entropy ceramic with high-temperature strength and hardness and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109678523B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110194667B (en) * 2019-06-24 2021-09-17 哈尔滨工业大学 Superhard five-component transition metal carbide single-phase high-entropy ceramic material and preparation method thereof
CN110511035A (en) * 2019-08-05 2019-11-29 广东工业大学 A kind of high entropy ceramics of high-ductility high wear-resistant and its preparation method and application
CN110483058A (en) * 2019-08-07 2019-11-22 广东工业大学 A kind of boride ceramics and its preparation method and application of superhard high intensity
CN110734289A (en) * 2019-08-07 2020-01-31 郑州大学 boride high-entropy ceramic and preparation method thereof
CN110606748A (en) * 2019-09-04 2019-12-24 广东工业大学 Alumina-enhanced high-entropy boride ceramic and preparation method and application thereof
CN110606749A (en) * 2019-09-29 2019-12-24 石家庄铁道大学 High-entropy boride ceramic material and preparation method thereof

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006074595A1 (en) * 2005-01-14 2006-07-20 Genfa Li Eutectic powders for ceramics production and weld and method of producing the same
CN103011827A (en) * 2012-12-20 2013-04-03 复旦大学 Preparation method of zirconium diboride ceramic with in-situ-introduced boron as additive
CN103130508A (en) * 2011-12-02 2013-06-05 中国科学院上海硅酸盐研究所 Method for preparing texturing boride super-high-temperature ceramic
CN103710607A (en) * 2013-12-16 2014-04-09 北京科技大学 Oxygen-strengthened TiZrNbHfO high-entropy alloy and preparation method thereof
CN107746281A (en) * 2017-11-10 2018-03-02 中国矿业大学 A kind of preparation method of superhigh temperature ceramics boride solid solution powder
CN108455623A (en) * 2018-05-29 2018-08-28 广东工业大学 A kind of ultra fine transition metal boride powder and its preparation method and application
CN108585887A (en) * 2018-04-23 2018-09-28 华南理工大学 A kind of TixZr1-xB2Superhigh temperature solid solution ceramic raw powder's production technology
CN108911751A (en) * 2018-06-30 2018-11-30 华南理工大学 A kind of high entropy ceramic material of ZrHfTaNbTiC superhigh temperature and preparation method thereof
CN109180188A (en) * 2018-10-08 2019-01-11 中南大学 A kind of high entropy carbide containing boron ultra-high temperature ceramic powder and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH690129A5 (en) * 1994-09-29 2000-05-15 Kyocera Corp Silver-colored, sintered product, and process for its preparation.

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006074595A1 (en) * 2005-01-14 2006-07-20 Genfa Li Eutectic powders for ceramics production and weld and method of producing the same
CN103130508A (en) * 2011-12-02 2013-06-05 中国科学院上海硅酸盐研究所 Method for preparing texturing boride super-high-temperature ceramic
CN103011827A (en) * 2012-12-20 2013-04-03 复旦大学 Preparation method of zirconium diboride ceramic with in-situ-introduced boron as additive
CN103710607A (en) * 2013-12-16 2014-04-09 北京科技大学 Oxygen-strengthened TiZrNbHfO high-entropy alloy and preparation method thereof
CN107746281A (en) * 2017-11-10 2018-03-02 中国矿业大学 A kind of preparation method of superhigh temperature ceramics boride solid solution powder
CN108585887A (en) * 2018-04-23 2018-09-28 华南理工大学 A kind of TixZr1-xB2Superhigh temperature solid solution ceramic raw powder's production technology
CN108455623A (en) * 2018-05-29 2018-08-28 广东工业大学 A kind of ultra fine transition metal boride powder and its preparation method and application
CN108911751A (en) * 2018-06-30 2018-11-30 华南理工大学 A kind of high entropy ceramic material of ZrHfTaNbTiC superhigh temperature and preparation method thereof
CN109180188A (en) * 2018-10-08 2019-01-11 中南大学 A kind of high entropy carbide containing boron ultra-high temperature ceramic powder and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《High-Entropy Metal Diborides:A New Class of high-Entropy Materials and a New Type of Ultrahigh Temperature Ceramics》;GILD J,Zhang Y;《Scientific Reports》;20161231;全文 *

Also Published As

Publication number Publication date
CN109678523A (en) 2019-04-26

Similar Documents

Publication Publication Date Title
CN109678523B (en) High-entropy ceramic with high-temperature strength and hardness and preparation method and application thereof
CN109516811B (en) Multi-element high-entropy ceramic and preparation method and application thereof
CN110002879B (en) Compact and superhard high-entropy boride ceramic and preparation method and application thereof
Sonber et al. Synthesis and consolidation of zirconium diboride
Roy et al. Pressureless sintering of boron carbide
CN105838913B (en) A kind of graphene/nickel based composites and preparation method thereof
CN109879669B (en) High-entropy ceramic composite material with high strength and preparation method and application thereof
Hotta et al. Densification and Phase Transformation of β‐SiAlON–Cubic Boron Nitride Composites Prepared by Spark Plasma Sintering
CN106517225B (en) Superfine M1-xTixB2Method for preparing powder
CN103130508A (en) Method for preparing texturing boride super-high-temperature ceramic
Li et al. Microstructure and mechanical properties of aluminum nitride co-doped with cerium oxide via hot-pressing sintering
Yin et al. High toughness in pressureless densified ZrB2-based composites co-doped with boron–titanium carbides
CN109665848B (en) Ultrahigh-temperature SiC-HfB2Composite ceramic and preparation method and application thereof
CN106747433B (en) Zirconia-based nano ceramic tool and die material and preparation method thereof
CN109354504B (en) Boron carbide-based composite ceramic sintering aid and sintering process
CN103194631A (en) Preparation method of high-volume fraction alumina ceramic particle enhanced composite material
CN109987941B (en) High-entropy ceramic composite material with oxidation resistance and preparation method and application thereof
Zhang et al. Densification, microstructure and mechanical properties of multicomponent (TiZrHfNbTaMo) C ceramic prepared by pressureless sintering
CN102731096A (en) Textured boride base ultra-high temperature ceramic material and its preparation method
Dai et al. Demonstrating low‐temperature sintering of boron carbide powders
CN110257684B (en) Preparation process of FeCrCoMnNi high-entropy alloy-based composite material
Mikeladze et al. Ceramic composites B4C–TiB2 in nanocrystalline state: Production, structure, and mechanical properties
CN103553631B (en) Method for obtaining compact titanium diboride material by using in-situ reaction between sintering aids
CN104163628B (en) A kind of method preparing HfC-SiC complex phase ceramic
CN110698204A (en) Preparation method of MAX phase ceramic

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