CN115057706A - Ultrahigh-porosity complex-phase high-entropy ultrahigh-temperature ceramic material and preparation method thereof - Google Patents

Ultrahigh-porosity complex-phase high-entropy ultrahigh-temperature ceramic material and preparation method thereof Download PDF

Info

Publication number
CN115057706A
CN115057706A CN202210502274.5A CN202210502274A CN115057706A CN 115057706 A CN115057706 A CN 115057706A CN 202210502274 A CN202210502274 A CN 202210502274A CN 115057706 A CN115057706 A CN 115057706A
Authority
CN
China
Prior art keywords
entropy
ultrahigh
ultra
temperature ceramic
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210502274.5A
Other languages
Chinese (zh)
Other versions
CN115057706B (en
Inventor
王京阳
邵卓杰
吴贞
孙鲁超
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.)
Institute of Metal Research of CAS
Original Assignee
Institute of Metal Research of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Metal Research of CAS filed Critical Institute of Metal Research of CAS
Priority to CN202210502274.5A priority Critical patent/CN115057706B/en
Publication of CN115057706A publication Critical patent/CN115057706A/en
Application granted granted Critical
Publication of CN115057706B publication Critical patent/CN115057706B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—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
    • 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
    • C04B35/58007—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 refractory metal nitrides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/10—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam
    • 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
    • C04B2235/3821—Boron carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3826—Silicon carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3839—Refractory metal carbides
    • C04B2235/3843—Titanium carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3839—Refractory metal carbides
    • C04B2235/3847—Tungsten carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3865—Aluminium nitrides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3873—Silicon nitrides, e.g. silicon carbonitride, silicon oxynitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3891—Silicides, e.g. molybdenum disilicide, iron silicide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/425—Graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—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
    • C04B2235/70—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
    • C04B2235/96—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

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)
  • Ceramic Products (AREA)

Abstract

The invention relates to the field of porous ultrahigh-temperature ceramic heat insulation materials, in particular to a complex-phase high-entropy ultrahigh-temperature ceramic material with ultrahigh porosity and a preparation method thereof. Two phases in the porous complex-phase high-entropy ultrahigh-temperature ceramic are high-entropy boride with a close-packed hexagonal crystal structure and high-entropy carbide with a face-centered cubic crystal structure respectively. Ball-milling and uniformly mixing various transition metal boride and carbide powder, preparing the mixed powder into slurry, foaming and injection molding, freezing and drying, and finally sintering at high temperature to obtain the porous complex-phase high-entropy ultrahigh-temperature ceramic heat-insulating material. The method has simple process and strong operability, and is easy to realize large-scale industrial production. The prepared porous complex phase high entropy is ultrahighThe thermal insulation material has ultrahigh porosity (80-97%) and low density (0.20-1.87 g/cm) 3 ) High strength (0.17 to 30.19MPa), low thermal conductivity (0.10 to 0.49W/(m.K)), and ultra-high temperature resistance (>2000 ℃ and has wide application prospect in the aerospace thermal protection field.

Description

Ultrahigh-porosity complex-phase high-entropy ultrahigh-temperature ceramic material and preparation method thereof
Technical Field
The invention relates to the field of light porous ultrahigh-temperature ceramic heat insulation materials, in particular to a complex-phase high-entropy ultrahigh-temperature ceramic material with ultrahigh porosity and a preparation method thereof.
Background
The ultrahigh-temperature ceramic has excellent physicochemical properties, such as ultrahigh melting point (>3000 ℃), high strength and high modulus, and good thermochemical stability and ablation resistance, and is a candidate system of an ultrahigh-temperature heat-insulating material with excellent properties. However, the intrinsic thermal conductivity of the ultrahigh-temperature boride and carbide is relatively high, and effective measures need to be taken to reduce the thermal conductivity of the ultrahigh-temperature boride and carbide so as to meet the use requirements of aerospace thermal insulation materials. Currently, methods for significantly reducing thermal conductivity include: the lattice distortion caused by the high entropy effect can effectively inhibit heat transfer, and the solid phase volume ratio can be reduced by introducing a pore structure, so that the heat conduction can be effectively reduced, and the aim of high-efficiency heat insulation is fulfilled.
Researches show that lattice distortion is introduced by virtue of a high entropy effect, phonon scattering is enhanced, and heat transmission can be obviously inhibited, so that the high entropy ultra-high temperature ceramic with low thermal conductivity is obtained. Such as high entropy boride (Hf, Zr, Ta, Nb, Ti) B 2 And high entropy carbides (Hf, Zr, Ta, Nb, Ti) C have thermal conductivities of only 24.8 and 13.2W/(m.K), respectively, which are much lower than those of the five single metal main elements
TABLE 1 melting point, density and thermal conductivity of common ultra-high temperature ceramic materials
Material Melting Point (. degree.C.) Density (g/cm) 3 ) Thermal conductivity (W/(m.K))
HfB 2 3380 11.16 104.0
ZrB 2 3250 6.10 120.0
TaB 2 3037 12.54 16.1
NbB 2 2990 6.94 24.0
TiB 2 3225 4.49 96.0
(Hf,Zr,Ta,Nb,Ti)B 2 / 8.29 24.8
HfC 3890 12.67 29.3
ZrC 3540 6.73 33.5
TaC 3880 14.30 33.5
NbC 3500 7.79 14.3
TiC 3140 6.93 21.0
(Hf,Zr,Ta,Nb,Ti)C / 9.34 13.2
The corresponding average thermal conductivities of the ceramics were 72.1 and 26.3W/(m.K), as shown in Table 1, (M.D.Qin et al.J.Eur.Ceram.Soc. (J.Eur. ceramics society) 2020(40): 5037-5050.). Since the thermal conductivity of air is only 0.026W/(m.K) which is far lower than that of the ultra-high temperature ceramic block, the introduction of the porous structure can further effectively reduce the thermal conductivity (L.Gong et al. int.J.Heat Mass. Tran. (International journal of Heat and Mass transfer) 2013 (67: 253-259). Therefore, the high-entropy ultrahigh-temperature ceramic material with ultrahigh porosity (90%) is expected to solve the inherent problem of high thermal conductivity of the ultrahigh-temperature ceramic, and meets the urgent demand of ultrahigh-temperature heat insulation in the aerospace field.
For the two types of ultrahigh-temperature ceramics, boride and carbide which are researched more at present, the boride and carbide respectively have advantages and disadvantages. As shown in table 1, the boride has the advantages of relatively low density, strong oxidation resistance, but high thermal conductivity; carbide has the advantage of relatively low thermal conductivity, high melting point, but somewhat less oxidation resistance than boride. Therefore, the advantages of the boride and the carbide can be combined to develop the complex phase ultrahigh temperature ceramic of the boride and the carbide, and a large number of grain boundaries of the complex phase ceramic can cause more interface thermal resistance and contribute to reducing the thermal conductivity, so that the novel ultrahigh temperature ceramic material with high melting point, low thermal conductivity, low density and good oxidation resistance is obtained. On the basis, high entropy and ultrahigh porosity of the material are further realized, and a novel complex phase high entropy ultrahigh temperature heat insulating material with more excellent comprehensive performance can be developed, so that the strategic requirements of national safety are met.
Disclosure of Invention
The invention aims to provide a composite high-entropy ultrahigh-temperature ceramic material with ultrahigh porosity and a preparation method thereof, which adopt a foaming-coagulating injection-freezing drying technology to realize ultrahigh porosity and controllable preparation of the material, prepare a porous composite high-entropy ultrahigh-temperature ceramic material with the characteristics of low density, high strength, low thermal conductivity, good oxidation resistance and the like by pressureless in-situ reaction sintering, and simultaneously have phase compositions of two crystal structures, namely HCP and FCC, thereby solving the problem of high thermal conductivity of the existing ultrahigh-temperature ceramic.
The technical scheme of the invention is as follows:
a composite phase high-entropy superhigh-temperature ceramic material with ultrahigh porosity is prepared from the transition metal high-entropy boride (Zr) with hexagonal close-packed (HCP) crystal structure a Hf b Nb c Ta d X e )B 2 Transition metal high entropy carbides (Zr) of ceramic and Face Centered Cubic (FCC) crystal structure f Hf g Nb h Ta i Y j ) C, ceramic; wherein, the value ranges of a, b, c, d, e, f, g, h, i and j are 0-50%, a + b + c + d + e is 1, f + g + h + i + j is 1, and X or Y is one or more than two metal elements of W, V, Ti, Cr or Mo; furthermore, the molar ratio of the high-entropy boride phase to the high-entropy carbide phase is 1: m, 0.05<m<20。
The complex phase high-entropy ultra-high temperature ceramic material with ultrahigh porosity has the porosity range of 80-97 percent and the density of 0.20 percent～1.87g/cm 3 The compression strength is 0.17-30.19 MPa, the room temperature thermal conductivity is 0.10-0.49W/(m.K), and the temperature resistance is higher than 2000 ℃.
The preparation method of the composite high-entropy ultrahigh-temperature ceramic material with ultrahigh porosity comprises the following steps:
(1) carrying out ball milling and blending on boride powder and carbide powder of transition metal, drying and sieving to obtain mixed raw material powder;
(2) weighing the mixed raw material powder obtained in the step (1), adding deionized water, a dispersing agent and a sintering aid, and stirring to obtain slurry; sequentially adding a foaming agent and a gelling agent, uniformly stirring to obtain foam slurry, carrying out injection molding, and then carrying out freeze drying on the foam slurry to obtain a blank;
(3) and (3) performing high-temperature reaction sintering on the blank obtained in the step (2) to finally obtain the porous complex-phase high-entropy ultrahigh-temperature ceramic.
The preparation method of the composite phase high-entropy ultrahigh-temperature ceramic material with ultrahigh porosity comprises the step (1), wherein boride powder and carbide powder of transition metal are respectively selected from ZrB 2 、HfB 2 、WB、NbB 2 、TaB 2 、VB 2 、TiB 2 、CrB 2 、MoB 2 And ZrC, HfC, WC, NbC, TaC, VC, TiC, Cr 3 C 2 、Mo 2 And C, the grain diameters of the boride powder and the carbide powder are 0.1-10 mu m.
In the preparation method of the multiphase high-entropy ultrahigh-temperature ceramic material with ultrahigh porosity, in the step (1), the ball milling mode is wet planetary ball milling, the ball milling medium is water, ethanol or acetone, the rotating speed is 50-550 rpm, and the mixing time is 6-72 h.
In the step (2), the foam slurry comprises the following components in percentage by mass: the addition amount of the mixed raw material powder is 10-50 wt%, the addition amount of the dispersing agent is 0.1-10 wt%, the addition amount of the sintering aid is 0.1-10 wt%, the addition amount of the foaming agent is 0.1-5 wt%, the addition amount of the gelling agent is 0.5-10 wt%, and the balance is deionized water.
According to the preparation method of the ultrahigh-porosity complex-phase high-entropy ultrahigh-temperature ceramic material, the dispersing agent is polyethyleneimine, citric acid, polyethylene glycol or ammonium citrate, the sintering aid is graphite, boron carbide, silicon carbide, molybdenum silicide, zirconium silicide, silicon nitride, zirconium nitride or aluminum nitride, the foaming agent is sodium dodecyl sulfate or sodium dodecyl sulfate, and the gelling agent is agar, gelatin, sodium hydroxymethyl cellulose or acrylamide.
The preparation method of the composite high-entropy ultrahigh-temperature ceramic material with ultrahigh porosity comprises the step (2), wherein the freeze drying temperature is-70 to-20 ℃, and the freeze drying time is 6 to 72 hours.
The preparation method of the composite high-entropy ultrahigh-temperature ceramic material with ultrahigh porosity comprises the following sintering parameters in the step (3): firstly, under the vacuum condition or the atmosphere protection condition, heating to 1300-1600 ℃ at the heating rate of 3-10 ℃/min, and keeping the temperature for 0.5-4 h; and then heating to 1800-2150 ℃ at a heating rate of 3-10 ℃/min under a vacuum condition or an atmosphere protection condition, and keeping the temperature for 1-3.5 h.
The design idea of the invention is as follows:
the invention selects multi-principal element ultra-high temperature boride and carbide complex phase ceramic with ultra-high melting point as a substrate, realizes the ultra-high porosity of the material by foaming, injection coagulation and freeze drying technology, and then realizes the high entropy of multi-principal element components by high temperature in-situ reaction sintering, finally prepares the porous complex phase high entropy ultra-high temperature ceramic heat insulation material with low heat conductivity, and provides material and technical support for the innovation of the thermal protection system of aerospace.
The invention has the advantages and beneficial effects that:
1. the invention prepares the complex phase high entropy ultra-high temperature ceramic with ultra-high porosity and low thermal conductivity by foaming-pouring coagulation-freeze drying process, the porous material prepared by the method presents isotropic hierarchical pore structure, and in addition, the porosity is high (80-97%) and controllable.
2. According to the invention, the multi-principal element mixed raw material powder is subjected to high-temperature in-situ reaction sintering to directly generate the porous complex-phase high-entropy ultrahigh-temperature ceramic block material, and meanwhile, the porous complex-phase high-entropy ultrahigh-temperature ceramic block material contains high-entropy boride with an HCP crystal structure and high-entropy carbide with an FCC crystal structure, the two phases are uniformly distributed, and the thermal and mechanical properties are stable.
3. The method is simple and convenient to operate, the high-temperature sintering is pressureless sintering under a vacuum condition or an atmosphere protection condition, and the sintering temperature is lower than the preparation temperature (2200 ℃) in most of documents.
4. The method has simple process and strong operability, and is easy to realize large-scale industrial production.
Drawings
FIG. 1 is an XRD spectrum of the porous complex-phase high-entropy ultra-high temperature ceramic prepared in example 1.
FIG. 2 is an XRD spectrum of the porous complex-phase high-entropy ultra-high temperature ceramic prepared in example 2.
FIGS. 3(a) -3 (b) are scanning electron micrographs of the porous complex-phase high-entropy ultra-high temperature ceramic prepared in example 3 and EDS spectra of the corresponding elements. Wherein, fig. 3(a) is the appearance of the macroscopic hole of the sample, and fig. 3(b) is the appearance of the particle and the EDS map of each element corresponding to the particle.
Detailed Description
In the specific implementation process, the mixed powder of multiple transition metal borides and carbides is used as a raw material, water is used as a dispersion medium, a dispersing agent and a sintering aid are added simultaneously to prepare a slurry with uniform components of the mixed powder, then a foaming agent is added to foam, a gelling agent is added to mold, and then freezing and drying are carried out. And finally, preparing the porous complex-phase high-entropy boron carbide ultra-high temperature ceramic heat insulating material through pre-sintering and high-temperature in-situ reaction sintering. Two phases in the porous complex-phase high-entropy ultrahigh-temperature ceramic are high-entropy boride with a close-packed hexagonal crystal structure and high-entropy carbide with a face-centered cubic crystal structure respectively. The matrix material of the porous complex-phase high-entropy ultrahigh-temperature ceramic skeleton is a transition metal high-entropy boride (Zr) with a close-packed Hexagonal (HCP) crystal structure a Hf b Nb c Ta d X e )B 2 Transition metal high entropy carbides (Zr) of ceramic and Face Centered Cubic (FCC) crystal structure f Hf g Nb h Ta i Y j ) C, ceramic; wherein a, b, c, d, e, f, g, h, i and j have a value ranging from 0% to 50%, and a + b + c + d + e is 1,f + g + h + i + j is 1, and X or Y is one or more than two metal elements of W, V, Ti, Cr or Mo; furthermore, the molar ratio of the high-entropy boride phase to the high-entropy carbide phase is 1: m, 0.05<m<20 (preferably 0.2)<m<5)。
The present invention is described in detail below with reference to examples, but the scope and embodiments of the present invention are not limited thereto.
Example 1
In this embodiment, the composite high-entropy ultrahigh-temperature ceramic material with ultrahigh porosity and the preparation method thereof are as follows:
weighing 17.6g ZrB with the grain diameter of 0.1-6 mu m 2 、21.7g HfB 2 、10.1g WB、8.6g CrB 2 、2.3g ZrC、3.6g HfC、2.1g VC、0.9g TiC、1.0g Cr 3 C 2 And 2.6g Mo 2 C powder, pouring Si 3 N 4 Adding 50ml of acetone into a ball milling tank, carrying out ball milling, and carrying out ball milling for 40h by using a planetary ball mill at the rotating speed of 200rpm to obtain a multi-principal-element mixed raw material with uniform components and fine particles.
Adding the multi-principal-element mixed raw material, 60g of deionized water, 1g of ammonium citrate dispersant and 1g of graphite sintering aid into a beaker, and continuously stirring to form slurry; adding 0.4g of foaming agent sodium dodecyl sulfate into the obtained slurry, quickly stirring for foaming, adding 4g of gel agar, uniformly stirring to obtain foam slurry, injection molding, freeze drying, and drying at-60 ℃ for 10 hours to obtain a blank;
heating the blank to 1300 ℃ at the speed of 3 ℃/min under the protection atmosphere of argon, and preserving heat for 1 h; finally, the temperature is raised to 1850 ℃ at the speed of 3 ℃/min and is kept for 3.5 hours for in-situ reaction sintering, and finally the porous complex-phase high-entropy ultra-high temperature ceramic (Zr) is prepared 0.36 Hf 0.25 W 0.12 Cr 0.27 )B 2 -(Zr 0.17 Hf 0.14 V 0.25 Ti 0.12 Cr 0.13 Mo 0.19 )C。
In this example, the porosity of the material prepared was 95.7% and the density was 0.34g/cm 3 The compression strength at room temperature is 0.52MPa, the thermal conductivity at room temperature is 0.19W/(m.K), the phase composition is shown in an XRD pattern in figure 1, and as can be seen from the figure,the prepared porous complex-phase high-entropy ultrahigh-temperature material consists of two phases of high-entropy boride with a HCP crystal structure and high-entropy carbide with an FCC crystal structure, wherein the molar ratio of the high-entropy boride phase to the high-entropy carbide phase is 1:0.24, and the highest temperature resistance reaches 2200 ℃.
Example 2
In the embodiment, the composite high-entropy ultrahigh-temperature ceramic material with ultrahigh porosity and the preparation method thereof are as follows:
weighing 8.2g ZrB with the grain diameter of 0.5-8 mu m 2 、11.3g HfB 2 、12.9g WB、3.6g VB 2 、10.1g MoB 2 7.7g ZrC, 13.8g WC, 10.0g NbC, 10.4g TaC, 3.5g TiC and 3.7g Cr 3 C 2 And pouring the powder into a WC ball milling tank, adding 60ml of water, carrying out ball milling, and carrying out ball milling for 20 hours by using a planetary ball mill at the rotating speed of 460rpm to obtain a uniform multi-principal-element mixed raw material.
Adding the multi-principal-element mixed raw material, 50g of deionized water, 2g of dispersant polyethyleneimine and 0.9g of aluminum nitride into a beaker and continuously stirring to form slurry; adding 1g of foaming agent sodium dodecyl sulfate into the obtained slurry for foaming, then adding 3.7g of gel gelatin, uniformly stirring to obtain foam slurry, carrying out injection molding, then carrying out freeze drying, and drying at the temperature of-35 ℃ for 25 hours to obtain a blank;
then heating the blank body to 1450 ℃ at the speed of 5 ℃/min in vacuum, and preserving the heat for 1 h; finally heating to 1900 ℃ at the speed of 5 ℃/min and preserving heat for 2h for high-temperature in-situ reaction sintering to finally prepare the porous complex-phase high-entropy ultrahigh-temperature ceramic (Zr) 0.22 Hf 0.17 W 0.20 V 0.15 Mo 0.26 )B 2 -(Zr 0.18 W 0.17 Nb 0.23 Ta 0.13 Ti 0.14 Cr 0.15 )C。
In this example, the porosity of the material prepared was 85.2% and the density was 1.35g/cm 3 The room-temperature compression strength is 14.7MPa, the room-temperature thermal conductivity is 0.27W/(m.K), and the phase composition is shown in an XRD pattern in figure 2, and the prepared porous complex phase high-entropy ultra-high temperature material is composed of two phases of high-entropy boride with an HCP crystal structure and high-entropy carbide with an FCC crystal structure, wherein the high-entropy boride is high in density and the high-entropy carbide is high in densityThe molar ratio of the boride phase to the high-entropy carbide phase is 1:1.05, and the highest temperature resistance is up to 2400 ℃.
Example 3
In the embodiment, the composite high-entropy ultrahigh-temperature ceramic material with ultrahigh porosity and the preparation method thereof are as follows:
weighing 17.4g ZrB with the grain diameter of 1-5 mu m 2 、28.0g HfB 2 、11.9g NbB 2 、6.9g TiB 2 11.3g ZrC, 15.2g HfC, 12.6g NbC, 16.1g TaC and 6.6g VC, 40ml absolute ethyl alcohol is added for ball milling, and a planetary ball mill is used for ball milling for 62 hours at the rotating speed of 110rpm, so that a uniform multi-principal-element mixed raw material is obtained.
Adding the multi-principal-element mixed raw material, 45g of deionized water, 1.5g of dispersant citric acid and 0.7g of molybdenum silicide into a beaker and continuously stirring to form slurry; adding 0.9g of foaming agent sodium dodecyl sulfate into the obtained slurry for foaming, then adding 7.2g of gelling agent sodium carboxymethyl cellulose, uniformly stirring to obtain foam slurry, carrying out injection molding, then carrying out freeze drying, and drying at the temperature of-20 ℃ for 50 hours to obtain a blank;
then heating the blank to 1550 ℃ at a speed of 10 ℃/min under the protection atmosphere of argon, and preserving heat for 0.5 h; finally heating to 2100 ℃ at the speed of 10 ℃/min and preserving heat for 1h for high-temperature in-situ reaction sintering to finally prepare the porous complex-phase high-entropy ultrahigh-temperature ceramic (Zr) 0.31 Hf 0.28 Nb 0.21 Ti 0.20 )B 2 -(Zr 0.22 Hf 0.16 Nb 0.24 Ta 0.17 V 0.21 )C。
In the embodiment, the porosity of the prepared porous complex-phase high-entropy ultrahigh-temperature ceramic is 81.6%, and the density is 1.47g/cm 3 The room temperature compressive strength is 26.5MPa, and the room temperature thermal conductivity is 0.39W/(m.K). As shown in fig. 3(a) -3 (b), SEM photographs of the samples prepared in this example and EDS spectra of the respective elements show from fig. 3(a), that the pore size distribution of the samples is uniform, and the porous complex-phase high-entropy ultra-high temperature ceramic material synthesized under the conditions has a typical multi-level pore structure. As seen from fig. 3(b), the distribution of each metal element in the sample was uniform, indicating that each metal element was sufficiently solid-solubilized in the prepared sample. PreparedThe porous complex-phase high-entropy ultrahigh-temperature material consists of two phases of high-entropy boride with an HCP crystal structure and high-entropy carbide with an FCC crystal structure, wherein the molar ratio of the high-entropy boride phase to the high-entropy carbide phase is 1:0.77, and the highest temperature resistance reaches 2200 ℃.
The embodiment result shows that the composite high-entropy boron carbide ultrahigh-temperature ceramic heat-insulating material with ultrahigh porosity is prepared by combining a foaming-injection-freezing drying process and a high-temperature pressureless in-situ reaction sintering technology. The novel ultra-high temperature heat-insulating material synthesized by the invention has high porosity (80-97%, preferably 90-97%) and low density (0.20-1.87 g/cm) 3 Preferably 0.20 to 1.00g/cm 3 ) High strength (0.17 to 30.19MPa, preferably 0.20 to 25.10MPa), low thermal conductivity (0.10 to 0.49W/(m.K), preferably 0.10 to 0.29W/(m.K)), and good ultra-high temperature thermal stability (>2000 ℃) and has wide application prospect in the aerospace aviation thermal protection field.

Claims (9)

1. The composite phase high-entropy ultrahigh-temperature ceramic material with ultrahigh porosity is characterized in that a matrix material of a porous composite phase high-entropy ultrahigh-temperature ceramic skeleton is a transition metal high-entropy boride (Zr) with a close-packed Hexagonal (HCP) crystal structure a Hf b Nb c Ta d X e )B 2 Transition metal high entropy carbides (Zr) of ceramic and Face Centered Cubic (FCC) crystal structure f Hf g Nb h Ta i Y j ) C, ceramic; wherein, the value ranges of a, b, c, d, e, f, g, h, i and j are 0-50%, a + b + c + d + e is 1, f + g + h + i + j is 1, and X or Y is one or more than two metal elements of W, V, Ti, Cr or Mo; furthermore, the molar ratio of the high-entropy boride phase to the high-entropy carbide phase is 1: m, 0.05<m<20。
2. The ultra-high porosity complex phase high entropy ultra-high temperature ceramic material as claimed in claim 1, wherein the complex phase high entropy ultra-high temperature ceramic material has a porosity ranging from 80% to 97%, and a density of 0.20 to 1.87g/cm 3 Compressive strength of 0.17 to 30.19MPa, room temperature thermal conductivity of 0.10 to 0.49W/(m.K), and resistance to heatThe temperature is higher than 2000 ℃.
3. The preparation method of the ultra-high porosity complex phase high entropy ultra high temperature ceramic material as claimed in claim 1 or 2, characterized by comprising the following steps:
(1) carrying out ball milling and blending on boride powder and carbide powder of transition metal, drying and sieving to obtain mixed raw material powder;
(2) weighing the mixed raw material powder obtained in the step (1), adding deionized water, a dispersing agent and a sintering aid, and stirring to obtain slurry; sequentially adding a foaming agent and a gelling agent, uniformly stirring to obtain foam slurry, carrying out injection molding, and then carrying out freeze drying on the foam slurry to obtain a blank;
(3) and (3) performing high-temperature reaction sintering on the blank obtained in the step (2) to finally obtain the porous complex-phase high-entropy ultrahigh-temperature ceramic.
4. The method for preparing the ultra-high porosity complex phase high entropy ultra high temperature ceramic material as claimed in claim 3, wherein in the step (1), boride powder and carbide powder of transition metal are respectively selected from ZrB 2 、HfB 2 、WB、NbB 2 、TaB 2 、VB 2 、TiB 2 、CrB 2 、MoB 2 And ZrC, HfC, WC, NbC, TaC, VC, TiC, Cr 3 C 2 、Mo 2 And C, the grain diameters of the boride powder and the carbide powder are 0.1-10 mu m.
5. The preparation method of the ultra-high-porosity complex-phase high-entropy ultra-high-temperature ceramic material as claimed in claim 3, wherein in the step (1), the ball milling mode is wet planetary ball milling, the ball milling medium is water, ethanol or acetone, the rotation speed is 50-550 rpm, and the mixing time is 6-72 h.
6. The preparation method of the ultra-high porosity complex phase high entropy ultra-high temperature ceramic material as claimed in claim 3, wherein in the step (2), the foam slurry comprises the following components by mass percent: the addition amount of the mixed raw material powder is 10-50 wt%, the addition amount of the dispersing agent is 0.1-10 wt%, the addition amount of the sintering aid is 0.1-10 wt%, the addition amount of the foaming agent is 0.1-5 wt%, the addition amount of the gelling agent is 0.5-10 wt%, and the balance is deionized water.
7. The preparation method of the ultra-high porosity complex phase high entropy ultra-high temperature ceramic material as claimed in claim 6, wherein the dispersant is polyethyleneimine, citric acid, polyethylene glycol or ammonium citrate, the sintering aid is graphite, boron carbide, silicon carbide, molybdenum silicide, zirconium silicide, silicon nitride, zirconium nitride or aluminum nitride, the foaming agent is sodium dodecyl sulfate or sodium dodecyl sulfate, and the gelling agent is agar, gelatin, sodium hydroxymethyl cellulose or acrylamide.
8. The preparation method of the ultra-high porosity complex phase high entropy ultra-high temperature ceramic material as claimed in claim 3, wherein in the step (2), the temperature of freeze drying is-70 to-20 ℃, and the time of freeze drying is 6 to 72 hours.
9. The preparation method of the ultra-high porosity complex phase high entropy ultra-high temperature ceramic material as claimed in claim 3, wherein in the step (3), the sintering parameters are as follows: firstly, under the vacuum condition or the atmosphere protection condition, heating to 1300-1600 ℃ at the heating rate of 3-10 ℃/min, and keeping the temperature for 0.5-4 h; and then heating to 1800-2150 ℃ at a heating rate of 3-10 ℃/min under a vacuum condition or an atmosphere protection condition, and keeping the temperature for 1-3.5 h.
CN202210502274.5A 2022-05-09 2022-05-09 Complex-phase high-entropy superhigh-temperature ceramic material with superhigh porosity and preparation method thereof Active CN115057706B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210502274.5A CN115057706B (en) 2022-05-09 2022-05-09 Complex-phase high-entropy superhigh-temperature ceramic material with superhigh porosity and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210502274.5A CN115057706B (en) 2022-05-09 2022-05-09 Complex-phase high-entropy superhigh-temperature ceramic material with superhigh porosity and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115057706A true CN115057706A (en) 2022-09-16
CN115057706B CN115057706B (en) 2023-10-10

Family

ID=83198110

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210502274.5A Active CN115057706B (en) 2022-05-09 2022-05-09 Complex-phase high-entropy superhigh-temperature ceramic material with superhigh porosity and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115057706B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116444297A (en) * 2023-06-12 2023-07-18 烟台奥森制动材料有限公司 Refining process of silicon-carbon composite brake disc
CN117024147A (en) * 2023-08-02 2023-11-10 昆明理工大学 (Ta, nb, hf) x ) 2 C medium entropy alloyed carbide ceramic and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111848177A (en) * 2020-07-08 2020-10-30 北京理工大学 Ultrahigh-temperature high-entropy boride ceramic powder and preparation method thereof
KR20210068250A (en) * 2019-11-29 2021-06-09 한국생산기술연구원 Manufacturing method of multi-phase high entropy ceramic powder and powder produced by the same
CN113045332A (en) * 2021-02-08 2021-06-29 中国科学院金属研究所 Ultrahigh-porosity high-entropy carbide ultrahigh-temperature ceramic and preparation method thereof
CN113698209A (en) * 2021-07-29 2021-11-26 安徽工业大学科技园有限公司 High-entropy diboride-silicon carbide composite ceramic, and preparation method and application thereof
CN114262229A (en) * 2022-01-04 2022-04-01 哈尔滨工业大学 Preparation method and application of high-strength and high-toughness diboride-carbide complex-phase high-entropy ceramic
CN114315359A (en) * 2022-01-04 2022-04-12 哈尔滨工业大学 Method for preparing high-strength and high-toughness complex-phase high-entropy ceramic by using solid solution coupling method and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20210068250A (en) * 2019-11-29 2021-06-09 한국생산기술연구원 Manufacturing method of multi-phase high entropy ceramic powder and powder produced by the same
CN111848177A (en) * 2020-07-08 2020-10-30 北京理工大学 Ultrahigh-temperature high-entropy boride ceramic powder and preparation method thereof
CN113045332A (en) * 2021-02-08 2021-06-29 中国科学院金属研究所 Ultrahigh-porosity high-entropy carbide ultrahigh-temperature ceramic and preparation method thereof
CN113698209A (en) * 2021-07-29 2021-11-26 安徽工业大学科技园有限公司 High-entropy diboride-silicon carbide composite ceramic, and preparation method and application thereof
CN114262229A (en) * 2022-01-04 2022-04-01 哈尔滨工业大学 Preparation method and application of high-strength and high-toughness diboride-carbide complex-phase high-entropy ceramic
CN114315359A (en) * 2022-01-04 2022-04-12 哈尔滨工业大学 Method for preparing high-strength and high-toughness complex-phase high-entropy ceramic by using solid solution coupling method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MINGDE QIN ET AL.: "Dual-phase high-entropy ultra-high temperature ceramics", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 *
MINGDE QIN ET AL.: "Dual-phase high-entropy ultra-high temperature ceramics", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》, vol. 40, no. 15, 19 May 2020 (2020-05-19), pages 2, XP086248378, DOI: 10.1016/j.jeurceramsoc.2020.05.040 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116444297A (en) * 2023-06-12 2023-07-18 烟台奥森制动材料有限公司 Refining process of silicon-carbon composite brake disc
CN116444297B (en) * 2023-06-12 2023-08-25 烟台奥森制动材料有限公司 Refining Process of Silicon-Carbon Composite Brake Disc
CN117024147A (en) * 2023-08-02 2023-11-10 昆明理工大学 (Ta, nb, hf) x ) 2 C medium entropy alloyed carbide ceramic and preparation method thereof
CN117024147B (en) * 2023-08-02 2024-02-06 昆明理工大学 (Ta, nb, hf) x ) 2 C medium entropy alloyed carbide ceramic and preparation method thereof

Also Published As

Publication number Publication date
CN115057706B (en) 2023-10-10

Similar Documents

Publication Publication Date Title
CN113045332B (en) Ultrahigh-porosity high-entropy carbide ultrahigh-temperature ceramic and preparation method thereof
CN115057706B (en) Complex-phase high-entropy superhigh-temperature ceramic material with superhigh porosity and preparation method thereof
CN109180188B (en) High-entropy boron-containing carbide ultra-high temperature ceramic powder and preparation method thereof
CN107739950B (en) WC-Co-cBN composite hard alloy and preparation method thereof
CN103145422B (en) High-hardness ceramic composite material of boron carbide-titanium boride-silicon carbide and preparation method thereof
CN109180189A (en) A kind of high entropy carbide ultra-high temperature ceramic powder and preparation method thereof
CN109608203B (en) High-entropy disilicide and preparation method thereof
CN102503427A (en) Preparation method of high-toughness boride-carbide composite ceramic
CN110396632A (en) A kind of Ti (C, N) based ceramic metal and preparation method thereof with homogeneous ring core structure
CN109180161B (en) High-purity titanium silicon carbide/alumina composite material and preparation method thereof
CN112645726B (en) Silicon carbide whisker ceramic with typical long particle morphology and rich in stacking faults and twin crystals and preparation method thereof
CN113443928B (en) Preparation method of zirconium and/or tungsten-based multiphase ceramic coating
CN114315359A (en) Method for preparing high-strength and high-toughness complex-phase high-entropy ceramic by using solid solution coupling method and application
Lei et al. Fabrication, microstructure and mechanical properties of co-continuous TiCx/Cu-Cu4Ti composites prepared by pressureless-infiltration method
CN108203302B (en) Silicon nitride ceramic with adjustable dielectric constant and medium-low dielectric constant and preparation method thereof
CN104926309A (en) Preparation method for compact silicon carbide ceramics free of boron or rare earth elements
CN112830810B (en) Ultrahigh-porosity hafnium-tantalum-niobium ternary carbide ultrahigh-temperature heat insulation material and preparation method thereof
CN111848170A (en) Boron carbide-based composite ceramic material and preparation method thereof
CN109133986B (en) Foaming-method-based AlN-SiC porous composite ceramic and preparation method thereof
CN115745620B (en) High-density titanium nitride ceramic material and preparation method thereof
CN112647029B (en) TiB enhanced TMCs with three-dimensional pellet composite structure and preparation method thereof
CN110129692A (en) A kind of cermet material
CN115215677A (en) Porous high-entropy carbide ultra-high-temperature heat-insulating material with uniform pore structure and preparation method thereof
CN106518085A (en) Carbon nanotube toughened hafnium diboride super-high-temperature ceramic composite material and preparing method thereof
CN113735591A (en) Method for preparing nitrogen-doped conductive silicon carbide ceramic by adopting spark plasma sintering

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