CN115057706B - Complex-phase high-entropy superhigh-temperature ceramic material with superhigh porosity and preparation method thereof - Google Patents

Complex-phase high-entropy superhigh-temperature ceramic material with superhigh porosity and preparation method thereof Download PDF

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CN115057706B
CN115057706B CN202210502274.5A CN202210502274A CN115057706B CN 115057706 B CN115057706 B CN 115057706B CN 202210502274 A CN202210502274 A CN 202210502274A CN 115057706 B CN115057706 B CN 115057706B
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entropy
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temperature ceramic
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CN115057706A (en
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王京阳
邵卓杰
吴贞
孙鲁超
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Institute of Metal Research of CAS
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Abstract

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

Description

Complex-phase high-entropy superhigh-temperature ceramic material with superhigh porosity and preparation method thereof
Technical Field
The invention relates to the field of light porous ultrahigh-temperature ceramic heat insulation materials, in particular to an ultrahigh-porosity complex-phase high-entropy ultrahigh-temperature ceramic material and a preparation method thereof.
Background
The ultra-high temperature ceramic has excellent physical and chemical properties, such as ultra-high melting point (> 3000 ℃), high strength and modulus, and good thermochemical stability and ablation resistance, and is a candidate system of the ultra-high temperature heat insulation material with excellent properties. However, the intrinsic thermal conductivity of the ultra-high temperature boride and carbide is relatively high, and effective measures are needed to reduce the thermal conductivity of the ultra-high temperature boride and carbide so as to meet the use requirements of the aerospace thermal insulation material. The current methods for significantly reducing thermal conductivity are: the lattice distortion caused by the high entropy effect can effectively inhibit heat transmission, introduce a pore structure to reduce the solid phase volume ratio and effectively reduce the heat transmission, thereby realizing the aim of efficient heat insulation.
Research shows that the high-entropy superhigh-temperature ceramic with low thermal conductivity can be obtained by introducing lattice distortion and enhancing phonon scattering by means of high-entropy effect and can obviously inhibit heat transmission. Such as high entropy boride (Hf, zr, ta, nb, ti) B 2 And high entropy carbides (Hf, zr, ta, nb, ti) C having thermal conductivities of only 24.8 and 13.2W/(mK), respectively, far below that of the five single metal principal 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 average thermal conductivities of the ceramics were 72.1 and 26.3W/(mK) as shown in Table 1, (M.D.Qin et al J.Eur.Ceram. Soc. (journal of European ceramic 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 above-mentioned ultra-high temperature ceramic block, the introduction of a porous structure can further effectively reduce its thermal conductivity (l.gong et al int.j.heat Mass tran.) 2013 (67): 253-259. Therefore, the preparation of the high-entropy and ultrahigh-temperature ceramic material with ultrahigh porosity (more than 90%) is expected to solve the inherent problem of high heat conductivity of the ultrahigh-temperature ceramic and meet the urgent requirement of ultrahigh-temperature heat insulation in the aerospace field.
For the ultra-high temperature ceramics of boride and carbide which are more researched at present, the two ceramics have advantages and disadvantages. As shown in Table 1, boride has the advantages of relatively low density, strong oxidation resistance, but high thermal conductivity; while carbide has the advantages of relatively low thermal conductivity, high melting point, but has a slightly weaker oxidation resistance than boride. Therefore, the advantages of the two can be combined to develop the complex-phase ultra-high temperature ceramic of boride and 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 ultra-high temperature ceramic material with high melting point, low thermal conductivity, low density and good oxidation resistance is obtained. On the basis, the high entropy and the ultra-high porosity of the material are further realized, so that the novel complex-phase high-entropy ultra-high-temperature heat insulation material with more excellent comprehensive performance can be developed, and the strategic requirements of national security are met.
Disclosure of Invention
The invention aims to provide a complex-phase high-entropy ultrahigh-temperature ceramic material with ultrahigh porosity and a preparation method thereof, wherein the complex-phase high-entropy ultrahigh-temperature ceramic material with ultrahigh porosity and controllable preparation of the material are realized by adopting a foaming-condensation-freeze drying technology, and the porous complex-phase high-entropy ultrahigh-temperature ceramic material with low density, high strength, low thermal conductivity, good oxidation resistance and the like is prepared by pressureless in-situ reaction sintering, and meanwhile, the complex-phase high-entropy ultrahigh-temperature ceramic material has a phase composition of two crystal structures of HCP and FCC, so that the problem of high thermal conductivity of the existing ultrahigh-temperature ceramic is solved.
The technical scheme of the invention is as follows:
the porous composite phase high-entropy superhigh-temperature ceramic skeleton has matrix material of 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 structures f Hf g Nb h Ta i Y j ) C, ceramic; wherein, the value range of a, b, c, d, e, f, g, h, i and j is 0-50%, and a+b+c+d+e=1, f+g+h+i+j=1, X or Y is one or more than two metal elements of W, V, ti, cr or Mo; in addition, the molar ratio of the high-entropy boride phase to the high-entropy carbide phase is 1:m,0.05<m<20。
The porous composite phase high-entropy superhigh-temperature ceramic material with superhigh porosity has porosity of 80-97% and density of 0.20-1.87 g/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 phase high-entropy superhigh-temperature ceramic material with superhigh porosity comprises the following steps:
(1) Ball milling and blending the boride powder and the carbide powder of the 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, injection molding, and freeze-drying 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.
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 particle size of boride powder and carbide powder is 0.1-10 mu m.
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.
The preparation method of the composite phase high-entropy superhigh-temperature ceramic material with superhigh porosity comprises the following steps of: 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 gel is 0.5-10 wt%, and the balance of the deionized water.
The preparation method of the ultra-high porosity composite phase high-entropy ultra-high temperature ceramic material comprises the steps of preparing a dispersing agent from polyethylenimine, citric acid, polyethylene glycol or ammonium citrate, preparing a sintering aid from graphite, boron carbide, silicon carbide, molybdenum silicide, zirconium silicide, silicon nitride, zirconium nitride or aluminum nitride, preparing a foaming agent from sodium dodecyl sulfate or sodium dodecyl sulfonate, and preparing a gel from agar, gelatin, sodium hydroxymethyl cellulose or acrylamide.
In the step (2), the freeze-drying temperature is-70 to-20 ℃ and the freeze-drying time is 6 to 72 hours.
The preparation method of the composite phase high-entropy superhigh-temperature ceramic material with superhigh porosity comprises the following steps of: 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; then heating to 1800-2150 ℃ at a heating rate of 3-10 ℃/min under vacuum or atmosphere protection, and keeping the temperature for 1-3.5 h.
The design idea of the invention is as follows:
according to the invention, multi-principal-element ultrahigh-temperature boride and carbide composite ceramic with ultrahigh melting point is selected as a matrix, the ultrahigh porosity of the material is realized through a foaming-injection-freeze drying technology, then the high entropy of multi-principal-element components is realized through high-temperature in-situ reaction sintering, and finally the porous composite-phase high-entropy ultrahigh-temperature ceramic heat insulation material with low heat conductivity is prepared, so that the material and the technical support are provided for innovation of a thermal protection system for aerospace.
The invention has the advantages and beneficial effects that:
1. the porous material prepared by the method has an isotropic multi-stage pore structure, and the porosity is high (80% -97%) and controllable.
2. The porous complex-phase high-entropy superhigh-temperature ceramic block material is directly generated by sintering the multi-principal-component mixed raw material powder through high-temperature in-situ reaction, and simultaneously contains high-entropy boride with HCP crystal structure and high-entropy carbide with FCC crystal structure, and the two phases are uniformly distributed and have stable thermal and mechanical properties.
3. The invention has simple and convenient operation, the high-temperature sintering is pressureless sintering under vacuum condition or atmosphere protection condition, and the sintering temperature is lower than the preparation temperature (2200 ℃) in most 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 superhigh temperature ceramic prepared in example 1.
FIG. 2 is an XRD spectrum of the porous complex phase high entropy superhigh temperature ceramic prepared in example 2.
Fig. 3 (a) -3 (b) are scanning electron micrographs of the porous complex phase high-entropy superhigh temperature ceramic prepared in example 3 and EDS spectra of the respective elements. Wherein, fig. 3 (a) is the macro-pore morphology of the sample, and fig. 3 (b) is the particle morphology and EDS spectra of the corresponding elements.
Detailed Description
In the specific implementation process, the mixed powder of various transition metal borides and carbides is taken as a raw material, water is taken as a dispersion medium, a dispersing agent and a sintering aid are added to prepare slurry with uniform components of the mixed powder, then a foaming agent is added to foam, a gelling agent is added to foam, injection molding is carried out, and then freezing and drying are carried out. Finally, preparing the porous complex phase high entropy boron carbide ultra-high temperature ceramic heat insulation material through pre-sintering and high temperature in-situ reaction sintering. Two phases in the porous complex-phase high-entropy superhigh-temperature ceramic are respectively high-entropy boride with a close-packed hexagonal crystal structure and high-entropy carbide with a face-centered cubic crystal structure. The matrix material of the porous complex phase high-entropy superhigh temperature ceramic skeleton is 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 structures f Hf g Nb h Ta i Y j ) C, ceramic; wherein, the value range of a, b, c, d, e, f, g, h, i and j is 0-50%, and a+b+c+d+e=1, f+g+h+i+j=1, X or Y is one or more than two metal elements of W, V, ti, cr or Mo; in addition, 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 by way of examples, but the scope and embodiments of the present invention are not limited thereto.
Example 1
In this embodiment, the composite phase high-entropy superhigh-temperature ceramic material with superhigh 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, pour Si 3 N 4 And (3) adding 50ml of acetone into a ball milling tank, performing ball milling, and performing ball milling for 40 hours by using a planetary ball mill at a rotating speed of 200rpm to obtain the multi-principal component mixed raw material with uniform components and fine particles.
Adding the multi-principal component mixed raw material, 60g of deionized water, 1g of dispersing agent ammonium citrate and 1g of sintering aid graphite into a beaker, and continuously stirring to form slurry; adding 0.4g of sodium dodecyl sulfate serving as a foaming agent into the obtained slurry, rapidly stirring for foaming, adding 4g of gel agar, uniformly stirring to obtain foam slurry, performing injection molding, performing freeze drying, and drying at-60 ℃ for 10 hours to obtain a blank;
then heating the blank to 1300 ℃ at 3 ℃/min under the protection atmosphere of argon, and preserving heat for 1h; finally, heating to 1850 ℃ at the speed of 3 ℃/min, and preserving heat for 3.5h to perform in-situ reaction sintering, thus finally preparing the porous complex phase high-entropy superhigh temperature ceramic (Zr) 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 room temperature compression strength is 0.52MPa, the room temperature thermal conductivity is 0.19W/(m.K), the phase composition is shown as XRD pattern in figure 1, it can be seen from the figure that the prepared porous complex phase high-entropy ultrahigh-temperature material consists of high-entropy boride with HCP crystal structure and high-entropy carbide with FCC crystal structure, wherein the mol 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 this embodiment, the composite phase high-entropy superhigh-temperature ceramic material with superhigh 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 Pouring the powder into a WC ball milling tank, adding 60ml of water, performing ball milling, and using a planetary typeBall milling is carried out for 20 hours at the rotating speed of 460rpm, and the uniform multi-principal component mixed raw material is obtained.
Adding the multi-principal component mixed raw material, 50g of deionized water, 2g of dispersing agent polyethylenimine 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, adding 3.7g of gel gelatin, uniformly stirring to obtain foam slurry, injection molding, freeze-drying, and drying at-35 ℃ for 25 hours to obtain a blank;
heating the blank to 1450 ℃ at a speed of 5 ℃/min in vacuum, and preserving heat for 1h; finally, heating to 1900 ℃ at the speed of 5 ℃/min, and preserving heat for 2h to perform high-temperature in-situ reaction sintering, thus finally preparing the porous complex-phase high-entropy superhigh-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), the phase composition is shown as XRD pattern in figure 2, it can be seen from the figure that the prepared porous complex phase high-entropy ultrahigh-temperature material consists of high-entropy boride with HCP crystal structure and high-entropy carbide with FCC crystal structure, wherein the mol ratio of the high-entropy boride phase to the high-entropy carbide phase is 1:1.05, and the highest temperature resistance reaches 2400 ℃.
Example 3
In this embodiment, the composite phase high-entropy superhigh-temperature ceramic material with superhigh porosity and the preparation method thereof are as follows:
17.4g ZrB with the grain diameter of 1-5 mu m is weighed 2 、28.0g HfB 2 、11.9g NbB 2 、6.9g TiB 2 11.3g of ZrC, 15.2g of HfC, 12.6g of NbC, 16.1g of TaC and 6.6g of VC, adding 40ml of absolute ethyl alcohol, performing ball milling, and performing ball milling for 62 hours by using a planetary ball mill at a rotating speed of 110rpm to obtain a uniform multi-principal component mixed raw material.
Adding the multi-principal component 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 sulfonate into the obtained slurry for foaming, then adding 7.2g of gelling agent sodium hydroxymethyl cellulose, uniformly stirring to obtain foam slurry, performing injection molding, and then performing freeze drying, and drying at the temperature of-20 ℃ for 50 hours to obtain a blank;
then heating the blank to 1550 ℃ at 10 ℃/min under the protection atmosphere of argon, and preserving heat for 0.5h; finally, heating to 2100 ℃ at the speed of 10 ℃/min, and preserving heat for 1h to perform high-temperature in-situ reaction sintering, thus finally preparing the porous complex-phase high-entropy superhigh-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 this example, the porosity of the porous complex phase high entropy superhigh temperature ceramic prepared was 81.6% and the density was 1.47g/cm 3 The room temperature compression 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, as can be seen from fig. 3 (a), pore size distribution of the samples is uniform, and the porous complex phase high entropy superhigh temperature ceramic material synthesized under the conditions has a typical multi-stage pore structure. As seen from fig. 3 (b), the distribution of each metal element in the sample was uniform, indicating that each metal element in the prepared sample was sufficiently solid-dissolved. The prepared porous complex-phase high-entropy ultrahigh-temperature material consists of a high-entropy boride with a HCP crystal structure and a 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 example results show that the composite phase high entropy boron carbide ultrahigh temperature ceramic heat insulation material with ultrahigh porosity is prepared by combining a foaming-injection-freeze drying process with a high temperature pressureless in-situ reaction sintering technology. The novel ultra-high temperature heat insulation 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 (0.17-30.19 MPa, preferably 0.20-25.10 MPa), low thermal conductivity (0.10-0.49W/(mK), preferably0.10 to 0.29W/(m.K)) and good ultra-high temperature heat stability>2000 ℃ and has wide application prospect in the field of aviation thermal protection.

Claims (8)

1. The composite phase high-entropy superhigh-temperature ceramic material with superhigh porosity is characterized in that the matrix material of the porous composite phase high-entropy superhigh-temperature ceramic skeleton is transition metal high-entropy boride ceramic with a close-packed Hexagonal (HCP) crystal structure and transition metal high-entropy carbide ceramic with a face-centered cubic (FCC) crystal structure, and the composite material is one of the following combinations:
(1) The transition metal high entropy boride ceramic is (Zr) a Hf b W c Cr d )B 2 The transition metal high entropy carbide ceramic is (Zr) e Hf f V g Ti h Cr i Mo j ) C, wherein: the value range of a is 0.36-0.50, the value range of b is 0.25-0.50, the value range of c is 0.12-0.50, the value range of d is 0.27-0.50, and a+b+c+d=1; e ranges from 0.17 to 0.50, f ranges from 0.14 to 0.50, g ranges from 0.25 to 0.50, h ranges from 0.12 to 0.50, i ranges from 0.13 to 0.50, j ranges from 0.19 to 0.50, and e+f+g+h+i+j=1;
(2) The transition metal high entropy boride ceramic is (Zr) a Hf b W c V d Mo e )B 2 The transition metal high entropy carbide ceramic is (Zr) f W g Nb h Ta i Ti j Cr k ) C, wherein: the value range of a is 0.22-0.50, the value range of b is 0.17-0.50, the value range of c is 0.20-0.50, the value range of d is 0.15-0.50, the value range of e is 0.26-0.50, and a+b+c+d+e=1; f is 0.18-0.50, g is 0.17-0.50, h is 0.23-0.50, i is 0.13-0.50, j is 0.14-0.50, k is 0.15-0.50, and f+g+h+i+j+k=1;
(3) The transition metal high entropy boride ceramic is (Zr) a Hf b Nb c Ti d )B 2 High transition metalEntropy carbide ceramic is (Zr) e Hf f Nb g Ta h V i ) C, wherein: the value range of a is 0.31-0.50, the value range of b is 0.28-0.50, the value range of c is 0.21-0.50, the value range of d is 0.20-0.50, and a+b+c+d=1; e ranges from 0.22 to 0.50, f ranges from 0.16 to 0.50, g ranges from 0.24 to 0.50, h ranges from 0.17 to 0.50, i ranges from 0.21 to 0.50, and e+f+g+h+i=1;
in addition, the mol ratio of the high-entropy boride phase to the high-entropy carbide phase is 1:m, and m is 0.05< m < 1.05;
the porosity range of the complex phase high entropy superhigh temperature ceramic material is 80% -97%, and the density is 0.20-1.87 g/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 ℃.
2. A method for preparing the ultra-high porosity composite phase high entropy ultra-high temperature ceramic material according to claim 1, comprising the steps of:
(1) Ball milling and blending the boride powder and the carbide powder of the 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, injection molding, and freeze-drying 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.
3. The method for preparing a composite phase high entropy superhigh temperature ceramic material with superhigh porosity according to claim 2, wherein in the step (1), boride powder and carbide powder of transition metal are respectively selected from ZrB 2 、HfB 2 、WB、NbB 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 particle size of boride powder and carbide powder is 0.1-10 mu m.
4. The method for preparing the ultra-high porosity composite phase high-entropy ultra-high temperature ceramic material according to claim 2, wherein 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.
5. The method for preparing the ultra-high porosity composite phase high entropy ultra-high temperature ceramic material according to claim 2, wherein in the step (2), the composition and content of the foam slurry are as follows 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 gel is 0.5-10 wt%, and the balance of the deionized water.
6. The method for preparing the ultra-high porosity composite phase high entropy ultra-high temperature ceramic material according to claim 5, wherein the dispersing agent is polyethylenimine, 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 sulfonate, and the gelling agent is agar, gelatin, sodium hydroxymethyl cellulose or acrylamide.
7. The method for preparing a composite phase high-entropy superhigh-temperature ceramic material with superhigh porosity according to claim 2, wherein in the step (2), the freeze-drying temperature is-70 to-20 ℃, and the freeze-drying time is 6 to 72 hours.
8. The method for preparing a composite phase high entropy superhigh temperature ceramic material with superhigh porosity according to claim 2, wherein in the step (3), 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; then heating to 1800-2150 ℃ at a heating rate of 3-10 ℃/min under vacuum or atmosphere protection, and keeping the temperature for 1-3.5 h.
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