CN118108512A - Preparation method of high-entropy boride-silicon carbide composite ceramic - Google Patents
Preparation method of high-entropy boride-silicon carbide composite ceramic Download PDFInfo
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- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 106
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 52
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- 238000002289 liquid silicon infiltration Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 23
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 23
- 238000000498 ball milling Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 23
- 229910052796 boron Inorganic materials 0.000 claims description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims description 20
- 150000004706 metal oxides Chemical class 0.000 claims description 20
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- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910052580 B4C Inorganic materials 0.000 claims description 9
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical group B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
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- 238000004321 preservation Methods 0.000 description 18
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- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 12
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- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 6
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- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 6
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- 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
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Abstract
The invention belongs to the technical field of ceramics, and particularly relates to a preparation method of high-entropy boride-silicon carbide composite ceramic, which comprises the following steps: mixing high-entropy boride powder with carbon source powder, and preparing a ceramic blank by adopting a ceramic forming method; embedding the ceramic blank with silicon powder, and performing liquid silicon infiltration treatment in a vacuum environment to obtain the high-entropy boride-silicon carbide composite ceramic. The invention utilizes the high-entropy boride to be mixed with the carbon source and then carries out liquid phase siliconizing, the process is simpler, the residual Si content is relatively less, and the high-entropy boride-silicon carbide composite ceramic with the density of more than 99 percent can be obtained, thereby being suitable for large-scale production and application.
Description
Technical Field
The invention belongs to the technical field of ceramics, and particularly relates to a preparation method of high-entropy boride-silicon carbide composite ceramic.
Background
Hypersonic aircraft have a high flight speed, and the nose cone or the front edge part of the wing is impacted by airflow to cause the surface temperature to rise sharply, so that serious ablation is generated. In order to effectively protect the aircraft, the high temperature resistance, high thermal conductivity and oxygen ablation resistance of the thermal protection material become particularly important. The superhigh temperature ceramic is widely used in a heat protection system due to the characteristics of high melting point, high heat conductivity, ablation resistance and the like, but is easy to oxidize and ablate to cause material failure in a complex flying environment. To further accommodate the demand for aircraft thermal protection materials, it is imperative to develop new materials.
The high entropy ceramic is a single-phase solid solution compound composed of anions or cations of not less than four elements in equimolar or approximately equimolar ratio. The unique high entropy effect, lattice distortion effect, delayed diffusion effect and cocktail effect make it possess better physical and chemical performance than single component or two component compound. The high-entropy boride powder of four different components such as Ti 0.2Hf0.2Zr0.2Nb0.2Ta0.2)B2 and the like is prepared by a fusion auxiliary synthesis method in literature 1"Ye B,Fan C,et al.Synthesis of high-entropy diboride nanopowders via molten salt-mediated magnesiothermic reduction[J].Journal of the American Ceramic Society,2020,103(9):4738-4741."Beilin Ye and the oxidation resistance of the powder is tested by utilizing thermogravimetric analysis, and the result shows that the initial oxidation temperature and the obvious weight increase temperature of the high-entropy boride ceramic are obviously higher than those of single-component boride, the literature 2"Gild J,Zhang Y,Harrington T,et al.High-entropy metal diborides:a new class of high-entropy materials and a new type of ultrahigh temperature ceramics[J].Scientific reports,2016,6(1):1-10."Gild J and the like prepare 6 high-entropy metal boride ceramics (such as Ti 0.2Hf0.2Zr0.2Nb0.2Ta0.2)B2 and the like) which have single-phase close-packed hexagons and have uniform element distribution through a mechanical alloying combined discharge plasma sintering method, and the high-entropy ceramics are found to have small weight increase and improved oxidation resistance after being oxidized compared with single-component ceramics due to the hysteresis diffusion effect.
In order to further improve the oxidation and ablation resistance of the high-entropy boride, the high-entropy boride-silicon carbide composite ceramic is prepared by introducing silicon carbide. In the oxidation process, the SiC is actively oxidized and the SiO is outwards diffused to form a glassy SiO 2 protective layer, so that further corrosion of oxygen is prevented, and the antioxidation ablation performance of the complex-phase ceramic can be better improved. The preparation method of the complex phase ceramic mainly includes pressureless sintering method, pressure assisted sintering method, field assisted sintering method, etc., for example, patent CN109987941B is a high entropy ceramic composite material with oxidation resistance and its preparation method and application, the (Ti 0.2Hf0.2Zr0.2Mo0.2Cr0.2)B2 powder and SiC powder are uniformly mixed according to a certain proportion, then SPS sintering is adopted to make them compact, the relative density of the prepared complex phase ceramic can reach 95% -99.9%, after heat treatment the weight change is less.
Disclosure of Invention
In order to solve the technical problems, the invention provides the preparation method of the high-entropy boride-silicon carbide composite ceramic, the high-entropy boride is mixed with a carbon source, and then liquid phase siliconizing is carried out, so that the process is simpler, the residual Si content is relatively less, the high-entropy boride-silicon carbide composite ceramic with the density of more than 99% can be obtained, the preparation process and the preparation principle are simple, the temperature is low, and the method is suitable for large-scale production and application.
The invention is realized by the following technical scheme.
The preparation method of the high-entropy boride-silicon carbide composite ceramic comprises the following steps:
Mixing high-entropy boride powder with carbon source powder, and preparing a ceramic blank by adopting a ceramic forming method;
embedding the ceramic blank with silicon powder, and performing liquid silicon infiltration treatment in a vacuum environment to obtain the high-entropy boride-silicon carbide composite ceramic.
When the silicon melting point is reached, liquid silicon and part of gas silicon can infiltrate into the ceramic body from all directions, silicon carbide is formed in a carbon source, and the silicon carbide is uniformly distributed among high-entropy borides.
In a preferred embodiment of the present invention, the carbon source includes graphite, carbon black, and resin carbon, and the carbon source is added in an amount of 10 to 30wt.%.
In a preferred embodiment of the present invention, the ceramic molding method includes dry press molding, isostatic molding, slip casting, and hot press molding.
In a preferred embodiment of the invention, the conditions of the liquid silicon infiltration treatment are: the vacuum environment is under the pressure of 1-10 MPa, the heating rate is 5-20 ℃/min, the heat preservation temperature is 1500-1650 ℃ and the heat preservation time is 30-150 min.
In a preferred embodiment of the present invention, the high entropy boride powder and the carbon source powder are mixed in the steps of: mixing the five-component high-entropy boride powder with a carbon source, immersing in alcohol, performing wet grinding treatment, and drying.
In a preferred embodiment of the present invention, the five-component high-entropy boride has a chemical formula (D x1Ex2Fx3Gx4Hx5)B2 or (D y1Ey2Fy3Gy4)B2) in which D, E, F, G, H elements are any five of Ti, zr, hf, V, nb, ta, cr, mo, W nine metal elements, respectively, wherein x1+x2+x3+x4+x5=1, y1+y2+y3+y4=1, and the stoichiometric ratio between x1, x2, x3, x4, x5 may be an equimolar ratio or a non-equimolar ratio, the stoichiometric ratio between y1, y2, y3, y4 is an equimolar ratio or a non-equimolar ratio, preferably, x1+x2+x3+x4+x5=1, and 0.1.ltoreq.x1.5, 0.1.ltoreq.x2.ltoreq.0.5, 0.1.ltoreq.x3.5, and 0.1.ltoreq.y5, and the stoichiometric ratio between x 1+y2+y3+y4=1, and y1, y 1+y3, y4 is an equimolar ratio or a non-equimolar ratio between y1, y 1+x3+x4+x5, and the stoichiometric ratio between y1 and y 1.ltoreq.1.ltoreq.3, y4 is 0.5, 0.ltoreq.5, 0.1.ltoreq.1.ltoreq.x3, 0.5, 0.1.ltoreq.5, 0.1.ltoreq.3, and the average molar ratio between y1 and y2, y1 and y4, and the ceramic body is 0.6, and the stoichiometric ratio between y1 and y 1.3, x4, and y1 is 0.6, and 3.
In a preferred embodiment of the invention, the high entropy boride is prepared by a borocarbothermic reaction process:
uniformly mixing metal oxide powder with a boron source, performing heat treatment at 1700-2000 ℃, and performing ball milling on the heat-treated powder to obtain the required high-entropy boride powder;
in a preferred embodiment of the invention, the metal oxide powders are all higher than 90% pure, and the particle size is in the order of nanometers to micrometers.
In a preferred embodiment of the invention, the boron source is boron carbide powder and/or boron powder, and the ratio of the total number of moles of metal oxides to the number of moles of boron source at the time of dosing is between 7.5 and 9, since the reduction rate of each oxide is different, and when all oxides are reduced, more boron source than theoretically is required.
In a preferred embodiment of the present invention, the heat treatment time is 30 to 240 minutes; the rotating speed of the ball mill is 150-400 r/min, and the ball milling time is 5-40 h.
In the ceramic forming and sintering process, any binder or sintering aid is not used.
Compared with the prior art, the invention has the following beneficial effects:
The invention adopts boron/carbothermic reaction to prepare high-entropy boride powder, and adopts a ceramic forming method to prepare a ceramic blank after the high-entropy boride powder is mixed with carbon source powder. Embedding the ceramic blank with silicon powder, and performing liquid silicon infiltration treatment in a vacuum environment to obtain the high-entropy boride-silicon carbide composite ceramic. The invention can generate SiC in situ, the distribution of substances in the prepared ceramic is relatively uniform, the reaction of Si and C can be generated in the sintering process, a large amount of atom migration phenomenon occurs in the ceramic, and all phases in the sintered ceramic are uniformly dispersed. The prepared ceramic block has high density (more than 99 percent), is not easy to change in shape, and can effectively improve the oxidation and ablation resistance and prepare the component.
The invention solves the problems of complex preparation process, high preparation temperature and the like of the prior method for introducing silicon carbide into the high-entropy boride, can ensure that the density of the prepared ceramic is up to more than 99 percent, and is beneficial to further improving the antioxidation ablation performance of the ultrahigh-temperature ceramic. In addition, the preparation temperature of the method is lower, the process is simple, the experimental environment requirement is low, the requirements on the particle size and activity of the powder are low, the purity of the silicon powder used for embedding is not particularly required, and the method can be used for low-cost large-scale production.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of the high-entropy boride-silicon carbide composite ceramic.
FIG. 2 is a BSE and point sweep spectrum of the (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 -SiC complex phase ceramic) prepared in example 2.
FIG. 3 is a cross-sectional morphology of a sample of the composite phase ceramic of Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 -SiC prepared in example 2 (after 100h oxidation at 1550 ℃ C. With a corresponding EDS spectrum).
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the present invention will be further described with reference to the specific examples and the accompanying drawings, but the examples are not intended to be limiting.
The experimental methods and the detection methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.
The high-entropy boride combines excellent oxidation and ablation resistance of the boride with four high-entropy effects of the high-entropy material, so that the boride has more excellent oxidation and ablation resistance and high-temperature mechanical properties. The high-entropy boride-silicon carbide composite ceramic prepared by the RMI method has the advantages of high density, low cost and low sintering temperature, and is a method for preparing the composite ceramic rapidly and efficiently. The principle is as follows:
And (3) impregnating the Si melt into a ceramic blank containing a carbon source by utilizing a high-temperature environment, and generating SiC by the reaction of Si and C, thereby preparing the high-entropy boride-silicon carbide composite ceramic. The method comprises the steps of preparing high-entropy boride powder by utilizing a boron/carbothermic reaction, mixing a carbon source with the high-entropy boride powder, preparing a ceramic blank, and finally densifying the ceramic blank by utilizing an RMI (RMI) process.
The preparation method of the invention comprises the following steps:
Mixing high-entropy boride powder with carbon source powder, and preparing a ceramic blank by adopting a ceramic forming method;
embedding the ceramic blank with silicon powder, and performing liquid silicon infiltration treatment in a vacuum environment to obtain the high-entropy boride-silicon carbide composite ceramic.
When the melting point of silicon is reached, liquid silicon and part of gas silicon can infiltrate into the ceramic from all directions of a ceramic blank body, silicon carbide is formed in a carbon source, and the silicon carbide is uniformly distributed among high-entropy borides.
The RMI method can be used for preparing the high-entropy boride-silicon carbide composite ceramic with high density and good mechanical property at a lower temperature by using simpler equipment, but the report on the method is rare at present. Patent 3' Liu Wei, sun Tongchen, etc. a high entropy ceramic matrix composite and a method for preparing the same [ P ]. Beijing city: CN113321510B,2022-06-03 et al, "Liu Wei et al impregnated the slurry of high-entropy carbide powder mixed with phenolic resin into a semi-dense composite material, and then siliconized the semi-dense composite material by RMI process to obtain a high-entropy ceramic matrix composite material with excellent mechanical properties and high-temperature oxidation resistance. However, this method may have a problem in that the high entropy carbide reacts with silicon, while the high entropy boride does not react with silicon. The invention utilizes the RMI technology to prepare the high-entropy boride-silicon carbide ceramic with excellent output mechanical property and high-temperature ablation resistance at low cost.
In a preferred embodiment of the present invention, the carbon source includes graphite, carbon black, and resin carbon, and the carbon source is added in an amount of 10 to 30wt.%.
In a preferred embodiment of the present invention, the ceramic molding method includes dry press molding, isostatic molding, slip casting, and hot press molding.
In a preferred embodiment of the invention, the conditions of the liquid silicon infiltration treatment are: the vacuum environment is under the pressure of 1-10 MPa, the heating rate is 5-20 ℃/min, the heat preservation temperature is 1500-1650 ℃ and the heat preservation time is 30-150 min.
In a preferred embodiment of the present invention, the high entropy boride powder and the carbon source powder are mixed in the steps of: mixing the five-component high-entropy boride powder with a carbon source, immersing in alcohol, performing wet grinding treatment, and drying.
In a preferred embodiment of the present invention, the high-entropy boride has a chemical formula (D x1Ex2Fx3Gx4Hx5)B2 or (D y1Ey2Fy3Gy4)B2, wherein D, E, F, G, H is any five of Ti, zr, hf, V, nb, ta, cr, mo, W nine metal elements, respectively; wherein x1, x2, x3, x4, x5 are the molar ratios of the elements, respectively, y1, y2, y3, y4 are the molar ratios of the elements, respectively, x1+x2+x3+x4+x5=1, y1+y2+y3+y4=1, and the stoichiometric ratio between x1, x2, x3, x4, x5 is an equimolar ratio or a non-equimolar ratio; the stoichiometric ratio between y1, y2, y3 and y4 is equal molar ratio or non-equal molar ratio, preferably, x1+x2+x3+x4+x5=1, and 0.1.ltoreq.x1.ltoreq.0.5, 0.1.ltoreq.x2.ltoreq.0.5, 0.1.ltoreq.x4.ltoreq.0.5, 0.1.ltoreq.x5.ltoreq.0.5, y1+y2+y3+y4=1, and 0.1.ltoreq.y1.ltoreq.0.5, 0.1.ltoreq.y2.ltoreq.0.5, 0.1.ltoreq.y4.ltoreq.0.5, more preferably, the stoichiometric ratio between x1, x2, x3, x4 and x5 is equal molar ratio, and the stoichiometric ratio between y1, y2, y3 and y4 is equal molar ratio, the average grain size of the high entropy ceramic powder is 0.2-6 mu m.
In a preferred embodiment of the invention, the high entropy boride is prepared by a borocarbothermic reaction process:
uniformly mixing metal oxide powder with a boron source, performing heat treatment at 1700-2000 ℃, and performing ball milling on the heat-treated powder to obtain the required high-entropy boride powder;
in a preferred embodiment of the invention, the metal oxide powders are all higher than 90% pure, and the particle size is in the order of nanometers to micrometers.
In a preferred embodiment of the invention, the boron source is boron carbide powder and/or boron powder, and the ratio of the total number of moles of metal oxides to the number of moles of boron source at the time of dosing is between 7.5 and 9, since the reduction rate of each oxide is different, and when all oxides are reduced, more boron source than theoretically is required.
In a preferred embodiment of the present invention, the heat treatment time is 30 to 240 minutes; the rotating speed of the ball mill is 150-400 r/min, and the ball milling time is 5-40 h.
In the ceramic forming and sintering process, any binder or sintering aid is not used.
The invention adopts boron/carbothermic reaction to prepare high-entropy boride powder, and adopts a ceramic forming method to prepare a ceramic blank after the high-entropy boride powder is mixed with carbon source powder. The ceramic body is embedded with silicon powder and subjected to liquid silicon infiltration treatment in a vacuum environment to prepare the high-entropy boride-silicon carbide composite ceramic, and the prepared ceramic block has high density (more than 99 percent) and is not easy to change in shape. The method has the advantages of low preparation temperature, simple process, low experimental environment requirement, low powder particle size and activity requirement, no special requirement on the purity of the embedded silicon powder, and low cost and large-scale production. The invention can generate SiC in situ, the distribution of substances in the prepared ceramic is relatively uniform, the reaction of Si and C can be generated in the sintering process, a large amount of atom migration phenomenon occurs in the ceramic, and all phases in the sintered ceramic are uniformly dispersed. The invention solves the problems of high cost, high preparation temperature and high requirement on experimental equipment, ensures that the density of the prepared ceramic is up to more than 99 percent, and further improves the antioxidation ablation performance of the ultra-high temperature ceramic.
The following examples and comparative examples are provided to illustrate the present invention.
Example 1
A preparation method of high-entropy boride-silicon carbide composite ceramic, specifically a preparation method of a 10wt.% graphite sample (S1) is shown in FIG. 1, and comprises the following steps:
Step1, (preparation of Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 powder):
Five metal oxide powders (TiO 2、ZrO2、HfO2、Nb2O5、Ta2O5) and boron carbide powder are mixed according to the element mole ratio of 1:1:1:1:1:8, adding the mixture into a ball milling tank, uniformly mixing, carrying out boron/carbon thermal reduction reaction at 1800 ℃ for 120min, and finally carrying out ball milling on the reacted powder by using a planetary ball mill to obtain the required (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 powder, wherein the rotating speed of the ball mill is 300r/min, the ball milling time is 24h, and the purity of the metal oxide powder is higher than 90%.
Step2, preparing a ceramic blank:
Respectively weighing 18g of the (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 and 2g of pure graphite powder prepared in the step 1, putting the powder in an agate mortar for uniform mixing and granulating, then weighing 5g of the mixed powder, putting the powder in a die, and obtaining a molded blank by a tablet press;
the mixing mode is as follows: weighing high-entropy boride and a carbon source in proportion, putting the mixture into a sealed bottle, adding a large amount of alcohol to dissolve powder into the alcohol, putting the mixture into a roller ball mill for wet grinding treatment, and taking the mixture out and drying the mixture in an oven.
Step 3, liquid silicon infiltration:
Embedding the ceramic blank in the step 2 with silicon powder, placing the ceramic blank in a graphite crucible, placing the ceramic blank wrapped with the silicon powder in a siliconizing furnace, and performing liquid silicon infiltration treatment in a vacuum environment to finally obtain the (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 -SiC complex phase ceramic, wherein the pressure is 10MPa, the heating rate is 5 ℃/min, the heat preservation temperature is 1500 ℃, and the heat preservation time is 60min.
Example 2
The preparation method of the high-entropy boride-silicon carbide composite ceramic, specifically the preparation of a 20wt.% graphite sample (S2), comprises the following steps:
Step1, (preparation of Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 powder):
Five metal oxide powders (TiO 2、ZrO2、HfO2、Nb2O5、Ta2O5) and boron carbide powder are mixed according to the element mole ratio of 1:1:1:1:1:8, adding the mixture into a ball milling tank, uniformly mixing, carrying out boron/carbon thermal reduction reaction at 1800 ℃ for 120min, and finally carrying out ball milling on the reacted powder by using a planetary ball mill to obtain the required (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 powder, wherein the rotating speed of the ball mill is 300r/min, the ball milling time is 24h, and the purity of the metal oxide powder is higher than 90%.
Step2, preparing a ceramic blank:
Respectively weighing 16g of the (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 and 4g of pure graphite powder prepared in the step 1, putting the powder in an agate mortar for uniform mixing and granulating, then weighing 4.5g of the mixed powder, putting the powder in a die, and obtaining a molded blank by a tablet press, wherein the mixing mode is that high-entropy boride and a carbon source are weighed according to a proportion, then the powder is put in a sealed bottle, a large amount of alcohol is added, the powder is dissolved in the alcohol, then the powder is put in a roller ball mill for wet grinding treatment, and then the powder is taken out and dried in an oven.
Step 3, liquid silicon infiltration:
Embedding the ceramic blank in the step 2 with silicon powder, placing the ceramic blank in a graphite crucible, placing the ceramic blank wrapped with the silicon powder in a siliconizing furnace, and performing liquid silicon infiltration treatment in a vacuum environment to finally obtain the (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 -SiC complex phase ceramic, wherein the pressure is 10MPa, the heat preservation temperature is 1500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 60min.
Example 3
The preparation method of the high-entropy boride-silicon carbide composite ceramic, in particular to the preparation of a 30wt.% graphite sample (S3), comprises the following steps:
Step1, (preparation of Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 powder):
Five metal oxide powders (TiO 2、ZrO2、HfO2、Nb2O5、Ta2O5) and boron carbide powder are mixed according to the element mole ratio of 1:1:1:1:1:8, adding the mixture into a ball milling tank, uniformly mixing, carrying out boron/carbon thermal reduction reaction at 1800 ℃ for 120min, and finally carrying out ball milling on the reacted powder by using a planetary ball mill to obtain the required (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 powder, wherein the rotating speed of the ball mill is 300r/min, the ball milling time is 24h, and the purity of the metal oxide powder is higher than 90%.
Step2, preparing a ceramic blank:
14g of the (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 and 6g of pure graphite powder prepared in the step 1 are respectively weighed, uniformly mixed and granulated in an agate mortar, then 4g of the mixed powder is weighed and put in a die, a molded blank is obtained by a tablet press, and the mixing mode is that high-entropy boride and a carbon source are weighed according to a proportion, then the mixture is put in a sealed bottle, a large amount of alcohol is added, so that the powder is dissolved in the alcohol, then the mixture is put in a roller ball mill for wet grinding treatment, and then the mixture is taken out and dried in an oven.
Step 3, liquid silicon infiltration:
Embedding the ceramic blank in the step 2 with silicon powder, placing the ceramic blank in a graphite crucible, placing the ceramic blank wrapped with the silicon powder in a siliconizing furnace, and performing liquid silicon infiltration treatment in a vacuum environment to finally obtain the (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 -SiC complex phase ceramic, wherein the pressure is 10MPa, the heat preservation temperature is 1500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 60min.
Example 4
The preparation method of the high-entropy boride-silicon carbide composite ceramic, specifically the preparation of a graphite sample (S3) doped with 30wt.%, compared with example 3, the liquid silicon infiltration heat preservation time is 30min, and the preparation method comprises the following steps:
Step1, (preparation of Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 powder):
Five metal oxide powders (TiO 2、ZrO2、HfO2、Nb2O5、Ta2O5) and boron carbide powder are mixed according to the element mole ratio of 1:1:1:1:1:8, adding the mixture into a ball milling tank, uniformly mixing, carrying out boron/carbon thermal reduction reaction at 1800 ℃ for 120min, and finally carrying out ball milling on the reacted powder by using a planetary ball mill to obtain the required (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 powder, wherein the rotating speed of the ball mill is 300r/min, the ball milling time is 24h, and the purity of the metal oxide powder is higher than 90%.
Step2, preparing a ceramic blank:
14g of the (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 and 6g of pure graphite powder prepared in the step 1 are respectively weighed, uniformly mixed and granulated in an agate mortar, then 4g of the mixed powder is weighed and put in a die, a molded blank is obtained by a tablet press, and the mixing mode is that high-entropy boride and a carbon source are weighed according to a proportion, then the mixture is put in a sealed bottle, a large amount of alcohol is added, so that the powder is dissolved in the alcohol, then the mixture is put in a roller ball mill for wet grinding treatment, and then the mixture is taken out and dried in an oven.
Step 3, liquid silicon infiltration:
Embedding the ceramic blank in the step 2 with silicon powder, placing the ceramic blank in a graphite crucible, placing the ceramic blank wrapped with the silicon powder in a siliconizing furnace, and performing liquid silicon infiltration treatment in a vacuum environment to finally obtain the (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 -SiC complex phase ceramic, wherein the pressure is 10MPa, the heat preservation temperature is 1500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 30min.
Example 5
The preparation method of the high-entropy boride-silicon carbide composite ceramic, specifically the preparation of a 30wt.% graphite sample (S3), is characterized in that compared with the preparation of the example 3, the liquid silicon infiltration heat preservation time is 150min, and the preparation method comprises the following steps:
Step1, (preparation of Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 powder):
Five metal oxide powders (TiO 2、ZrO2、HfO2、Nb2O5、Ta2O5) and boron carbide powder are mixed according to the element mole ratio of 1:1:1:1:1:8, adding the mixture into a ball milling tank, uniformly mixing, carrying out boron/carbon thermal reduction reaction at 1800 ℃ for 120min, and finally carrying out ball milling on the reacted powder by using a planetary ball mill to obtain the required (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 powder, wherein the rotating speed of the ball mill is 300r/min, the ball milling time is 24h, and the purity of the metal oxide powder is higher than 90%.
Step2, preparing a ceramic blank:
14g of the (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 and 6g of pure graphite powder prepared in the step 1 are respectively weighed, uniformly mixed and granulated in an agate mortar, then 4g of the mixed powder is weighed and put in a die, a molded blank is obtained by a tablet press, and the mixing mode is that high-entropy boride and a carbon source are weighed according to a proportion, then the mixture is put in a sealed bottle, a large amount of alcohol is added, so that the powder is dissolved in the alcohol, then the mixture is put in a roller ball mill for wet grinding treatment, and then the mixture is taken out and dried in an oven.
Step 3, liquid silicon infiltration:
Embedding the ceramic blank in the step 2 with silicon powder, placing the ceramic blank in a graphite crucible, placing the ceramic blank wrapped with the silicon powder in a siliconizing furnace, and performing liquid silicon infiltration treatment in a vacuum environment to finally obtain the (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 -SiC complex phase ceramic, wherein the pressure is 10MPa, the heat preservation temperature is 1500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 150min.
Example 6
The preparation method of the high-entropy boride-silicon carbide composite ceramic, specifically the preparation of a 30wt.% graphite sample (S3), has a liquid silicon infiltration pressure of 1MPa compared with that of example 3, and comprises the following steps:
Step1, (preparation of Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 powder):
Five metal oxide powders (TiO 2、ZrO2、HfO2、Nb2O5、Ta2O5) and boron carbide powder are mixed according to the element mole ratio of 1:1:1:1:1:8, adding the mixture into a ball milling tank, uniformly mixing, carrying out boron/carbon thermal reduction reaction at 1800 ℃ for 120min, and finally carrying out ball milling on the reacted powder by using a planetary ball mill to obtain the required (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 powder, wherein the rotating speed of the ball mill is 300r/min, the ball milling time is 24h, and the purity of the metal oxide powder is higher than 90%.
Step2, preparing a ceramic blank:
14g of the (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 and 6g of pure graphite powder prepared in the step 1 are respectively weighed, uniformly mixed and granulated in an agate mortar, then 4g of the mixed powder is weighed and put in a die, a molded blank is obtained by a tablet press, and the mixing mode is that high-entropy boride and a carbon source are weighed according to a proportion, then the mixture is put in a sealed bottle, a large amount of alcohol is added, so that the powder is dissolved in the alcohol, then the mixture is put in a roller ball mill for wet grinding treatment, and then the mixture is taken out and dried in an oven.
Step 3, liquid silicon infiltration:
Embedding the ceramic blank in the step 2 with silicon powder, placing the ceramic blank in a graphite crucible, placing the ceramic blank wrapped with the silicon powder in a siliconizing furnace, and performing liquid silicon infiltration treatment in a vacuum environment to finally obtain the (Ti 0.2Zr0.2Hf0.2Nb0.2Ta0.2)B2 -SiC complex phase ceramic, wherein the pressure is 1MPa, the heat preservation temperature is 1500 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 150min.
The ceramics prepared in the above examples are described below.
Fig. 2 is a BSE and point sweep spectrum of the HEB-SiC ceramic prepared in example 2, and analysis of the internal morphology of the ceramic reveals that the degree of graphitization of the carbon is low and the reaction with silicon is insufficient, resulting in a small amount of residual carbon and residual silicon. When the liquid silicon permeates into the ceramic, a molten salt environment is created, the thermal motion of each atom is promoted, the further solid solution of the high-entropy boride becomes a uniform single-phase solid solution, and a layer of free silicon is dispersed around the high-entropy boride. Si has a slower diffusion rate than the reaction rate with carbon, and the graphitization degree of the carbon is lower, so that a layer of SiC is generated when Si does not reach the surface of the carbon, and Si is prevented from further reacting with the carbon in the silicon, so that a sandwich structure is formed on the SiC layer, silicon-rich SiC is generated near a silicon region, and a carbon-rich SiC region is generated near the carbon region.
FIG. 3 is a cross-sectional morphology of a sample oxidized at 1550℃for 100 hours and a corresponding EDS spectrum, and it is seen from FIG. 3 that the oxide thickness is about 45 μm, the oxide layer on the upper surface is more tightly bonded, and the oxide layer close to the substrate is more loosely bonded; the holes left on the Si outflow surface of the Si-rich region in the matrix indicate that the surface oxide layer is mainly a glassy oxide layer formed by the reaction of free Si diffused to the surface of the sample and oxygen. The ceramics prepared in the other examples are similar to the results and will not be described in detail.
As can be seen from fig. 2 and 3, the method of the present invention successfully prepares the high-entropy boride-silicon carbide composite ceramic, and successfully generates SiC in situ inside the ceramic, thereby realizing the introduction of SiC into the high-entropy boride. And it should be noted that, compared with the prior art mentioned in the background art, the preparation method provided by the invention is simpler: firstly, mixing high-entropy boride powder with carbon source powder, and preparing a ceramic blank by adopting a ceramic forming method; then embedding the ceramic blank with silicon powder, and performing liquid silicon infiltration treatment in a vacuum environment to obtain the high-entropy boride-silicon carbide composite ceramic. According to the preparation process, the method has low requirements on experimental environment, raw materials are easy to obtain, the requirements on the particle size and activity of powder are low, the purity of the embedded silicon powder is not particularly required, and the method can be used for low-cost large-scale production. The preparation process principle is simpler, the reaction condition is easy to control and regulate the product, and the method is very suitable for large-scale production application from the aspect. And through the simple preparation method provided by the invention, the ceramic with high density can be obtained, the density can be improved to more than 99%, and specifically, the density data of the ceramic prepared in the embodiment of the invention are shown in table 1:
Table 1 ceramic density data prepared in each example
| Group of | Density of the product |
| Example 1 | 99.5％ |
| Example 2 | 99.7％ |
| Example 3 | 99.7％ |
| Example 4 | 99.6％ |
| Example 5 | 99.3％ |
| Example 6 | 99.5％ |
In addition, the high-entropy boride powder and the carbon source powder are mixed, a ceramic blank is prepared by adopting a ceramic forming method, then the ceramic blank is embedded with silicon powder, and liquid silicon infiltration treatment is carried out in a vacuum environment, so that the high-entropy boride-silicon carbide composite ceramic is prepared. In the process, the high-entropy boride powder and the carbon source powder are mixed by wet grinding, the temperature is between 1500 and 1650 ℃ in the process of liquid silicon infiltration, and the high-quality ceramic can be prepared at 1500 ℃ as can be seen from the above examples and characterization results.
In the prior art, the process route is complex, and the preparation temperature is high. For example, publication No. CN112028635A, an ultra-high temperature ceramic composite material and a preparation method thereof, which are characterized in that high-entropy boride and silicon carbide are directly mixed, then compression molding is carried out, and finally, the composite ceramic is prepared through a gas phase siliconizing process, wherein the temperature required by the adopted gas phase siliconizing process is 2073-2273K, which is significantly higher than 1500 ℃ in the application.
Publication No. CN109987941A, a high-entropy ceramic composite material with oxidation resistance, a preparation method and application thereof, which are characterized in that (Ti 0.2Hf0.2Zr0.2Mo0.2Cr0.2)B2 powder and SiC powder are uniformly mixed according to a certain proportion, SPS sintering is adopted, and the sintering temperature in the process is up to 1800-2200 ℃ and is obviously higher than 1500 ℃ of the invention.
Therefore, the invention can obviously reduce the temperature required by the preparation process and the energy consumption on the premise of ensuring that the prepared composite ceramic has high density and SiC is successfully introduced into the high-entropy boride matrix, thereby being beneficial to reducing the production cost and being beneficial to large-scale production and application from the aspect.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that such modifications and variations be included herein within the scope of the appended claims and their equivalents.
Claims (10)
1. The preparation method of the high-entropy boride-silicon carbide composite ceramic is characterized by comprising the following steps of:
mixing high-entropy boride powder with carbon source powder, and preparing a ceramic blank by adopting a ceramic forming method;
embedding the ceramic blank with silicon powder, and performing liquid silicon infiltration treatment in a vacuum environment to obtain the high-entropy boride-silicon carbide composite ceramic.
2. The method according to claim 1, wherein the carbon source is added in an amount of 10 to 30wt.% to the mixture of the high-entropy boride powder and the carbon source powder.
3. The method of claim 1, wherein the carbon source is graphite, carbon black or resin carbon.
4. The method according to claim 1, wherein the conditions of the liquid silicon infiltration treatment are: under the condition of vacuum environment and pressure of 1-10 MPa, the temperature is raised to 1500-1650 ℃ at the temperature rising rate of 5-20 ℃/min, and the temperature is kept at 1500-1650 ℃ for 30-150 min.
5. The method according to claim 1, wherein the high-entropy boride has a chemical formula (D x1Ex2Fx3Gx4Hx5)B2, wherein D, E, F, G and H are any five of Ti, zr, hf, V, nb, ta, cr, mo and W, wherein x1+x2+x3+x4+x5=1, and 0.1.ltoreq.x1.ltoreq.0.5, 0.1.ltoreq.x2.ltoreq.0.5, 0.1.ltoreq.x3.ltoreq.0.5, 0.1.ltoreq.x4.ltoreq.0.5, 0.1.ltoreq.x5.ltoreq.0.5;
Or the chemical formula of the high-entropy boride is (D y1Ey2Fy3Gy4)B2, wherein D, E, F and G are any four of Ti, zr, hf, V, nb, ta, cr, mo and W, wherein y1+y2+y3+y4=1, and y1 is more than or equal to 0.1 and less than or equal to 0.5, y2 is more than or equal to 0.1 and less than or equal to 0.5, y3 is more than or equal to 0.1 and less than or equal to 0.5, and y4 is more than or equal to 0.1 and less than or equal to 0.5).
6. The method according to claim 1, wherein the high-entropy boride powder has an average particle diameter of 0.2 to 6 μm.
7. The method according to claim 5, wherein the high entropy boride is prepared by a boron carbothermic reaction method, comprising the steps of:
uniformly mixing the required metal oxide powder with a boron source, performing heat treatment at 1700-2000 ℃, and performing ball milling on the heat-treated powder to obtain the required high-entropy boride powder.
8. The method according to claim 7, wherein the metal oxide powder has a purity of more than 90% and a particle size of the order of nanometers to micrometers.
9. The method according to claim 7, wherein the heat treatment time is 30 to 240 minutes.
10. The method according to claim 7, wherein the boron source is boron carbide powder and/or boron powder.
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