CN117430423A - Preparation method of carbon vacancy high-entropy carbide (TiVNbMoW) Cx - Google Patents
Preparation method of carbon vacancy high-entropy carbide (TiVNbMoW) Cx Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 39
- 239000000919 ceramic Substances 0.000 claims abstract description 33
- 239000011812 mixed powder Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002490 spark plasma sintering Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 229910052786 argon Inorganic materials 0.000 claims abstract description 3
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 21
- 238000007254 oxidation reaction Methods 0.000 abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 150000001247 metal acetylides Chemical class 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000004584 weight gain Effects 0.000 description 3
- 235000019786 weight gain Nutrition 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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Abstract
The invention relates to a preparation method of carbon vacancy high-entropy carbide (TiVNbMoW) Cx, which comprises the steps of taking Ti powder, V powder, nb powder, mo powder, W powder and carbon powder as raw materials, mixing, adding a small amount of ethanol, and grinding in an argon protective atmosphere to obtain mixed powder; drying the obtained mixed powder, pressing and forming to obtain a green body, then carrying out spark plasma sintering on the green body, and naturally cooling to room temperature to obtain the high-entropy carbide ceramic (Ti) 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C x (x is more than or equal to 0.7 and less than 1). The invention introduces carbon vacancy into the high entropy carbide by controlling the dosage of carbon and the preparation process skillfully, and the carbon vacancy containing a large amount of carbon vacancy can preferentially adsorb oxygen to generate carbonaceous oxide, and the carbonaceous oxide can prevent oxygen from diffusing inwards to further improve oxidation resistance, thereby effectively improving oxidation resistanceThe high entropy carbide oxidation resistance is improved.
Description
Technical Field
The invention belongs to the technical field of high-entropy compound preparation, relates to a preparation method of high-entropy carbide, and in particular relates to a carbon vacancy high-entropy carbide (TiVNbMoW) C x The preparation method of the high-entropy carbide is used for improving the oxidation resistance of the high-entropy carbide, so that the application of the high-entropy carbide is expanded.
Background
The high-entropy alloy has no less than five main metal element compositions, each metal component being in equimolar or near equimolar ratio. The research on the high-entropy ceramics is stimulated by the teaching of the high-entropy alloy. The high-entropy ceramic is a novel single-phase ceramic. Currently, it mainly includes carbides, oxides, nitrides, diborides and the like. High Entropy Carbides (HECs) are solid solutions composed mainly of group IVB-VIB transition metal carbides, which are of great interest due to their ultra-high melting point, good thermal stability, high temperature creep resistance and radiation resistance. High entropy carbides generally have equimolar metal ratios and non-carbon stoichiometric deviations. Recently, researchers have reported non-equimolar ratios of high entropy carbides with carbon vacancies. At the same time, due to the typical face-centered cubic structure, high entropy carbides containing carbon vacancies can still exist in a stable form. Many studies in the past have shown that the presence of carbon vacancies contributes to a reduction in the sintering temperature and thermal conductivity of high entropy carbides. At the same time, carbon vacancies are also beneficial for increasing hardness, young's modulus and flexural strength. However, high entropy carbides are often used in high temperature environments due to their ultra-high melting point (> 3000 ℃). The oxidation resistance of high entropy carbides limits their use. Therefore, the improvement of the oxidation resistance of the high-entropy carbide is of great significance.
Disclosure of Invention
The invention aims to provide a preparation method of carbon vacancy high-entropy carbide (TiVNbMoW) Cx.
1. Preparation of carbon vacancy high entropy carbide (TiVNbMoW) Cx
The preparation method of the carbon vacancy high-entropy carbide comprises the following steps:
(1) Taking Ti powder, V powder, nb powder, mo powder, W powder and carbon powder as raw materials, mixing, adding a small amount of ethanol, and grinding in an argon protective atmosphere to obtain mixed powder.
The purities of the raw materials Ti powder, V powder, nb powder, mo powder, W powder and C powder are all more than or equal to 99 percent, and the particle sizes are all less than 10 mu m. The mol ratio of Ti, V, nb, mo, W to C is 1:1:1:1:1 (3.5-5).
In grinding, the mass ratio of grinding balls to raw materials is 3:1-10:1, and the rotating speed of the ball mill is 200-800 r/min; the ball milling time is 3-20 h.
(2) Drying the obtained mixed powder, pressing and forming at 30MPa by a hydraulic press to obtain a green body, then performing spark plasma sintering on the green body, and naturally cooling to room temperature to obtain the high-entropy carbide ceramic (Ti) 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C x 。
The sintering process has a great influence on the structure and performance of the high-entropy carbide ceramic. The sintering temperature is low, the heat preservation time is too short, the pressure is low, and the high-entropy carbide ceramic (Ti) 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C x The sintering temperature is higher, the heat preservation time is longer, the pressure is higher, so that the grain growth is larger, and the mechanical property is poorer. Therefore, the process of the invention in discharge plasma burning is as follows: the temperature rising rate is 20-300 ℃/min, the sintering temperature is 1800-2300 ℃, the heat preservation time is 0.1-1 h, the pressure is 1.5-30 MPa, and the vacuum degree is less than 10 1 Pa。
The invention skillfully introduces carbon vacancy into the high-entropy carbide by controlling the dosage of carbon and the preparation process, and the prepared high-entropy carbide ceramic (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C x X is more than or equal to 0.7 and less than 1).
FIG. 1 shows the high entropy carbide (Ti) 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C x XRD pattern of the ceramic. XRD patterns showed that the prepared high entropy (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C x The high entropy ceramic is a pure phase and does not contain other impurity phases.
FIG. 2 is the presentHigh entropy carbide (Ti) 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C x SEM images of the ceramic polished surface and corresponding EDS element profile. SEM images and EDS elemental profiles showed that the prepared (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C x The five constituent elements in the ceramic are approximately uniformly distributed.
2. Oxidation resistance of carbon vacancy high entropy carbide (TiVNbMoW) Cx
The testing method comprises the following steps: first, a high entropy carbide (TiVNbMoW) Cx block was pulverized by a pulverizer and screened into powder. The oxidation resistance of HE-TMCx powder was measured in a thermogravimetric analyzer with a heating rate of 10 ℃/min in air, heating to 1000 ℃, stopping heating, and then naturally cooling. To illustrate the improvement in oxidation resistance of the carbon vacancy high entropy carbide (TiVNbMoW) Cx, this experiment was compared to conventional high entropy carbide (TiVNbMoW) C.
FIG. 3 is a high entropy carbide (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C x TG curve of (b). The TG curve of the high entropy carbide (TiVNbMoW) C was first mass changed by thermogravimetry in the oxidation zone from room temperature to 1000 ℃, indicating that oxidation was first occurring. High entropy (Ti) 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.7 Ceramics exhibit the most excellent oxidation resistance. At the same time, compared with ceramics (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.8 And (Ti) 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.9 High entropy (Ti) 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.7 The initial oxidation temperature of (a) was highest, the rate of increase was lowest (25.2%), and the oxidation rate was also lowest (0.1577%/. Degree. C.).
FIG. 4 is a high entropy carbide (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C x Is a DSC curve of (C). From the figure, it can be obtained that the high entropy carbide (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 ) C and (Ti) 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.7 Initially an exothermic reaction starts, high entropy carbides (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 ) C has excessive carbon, and is high in entropy carbide (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.7 Since a large number of carbon vacancies preferentially adsorb oxygen to form carbonaceous oxides, the carbonaceous oxides can prevent oxygen from diffusing into the interior and thereby improve oxidation resistance.
Drawings
FIG. 1 shows a high entropy (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C x XRD pattern of the ceramic.
FIG. 2 shows a high entropy (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C x SEM images of the polished surface and corresponding EDS element profiles.
FIG. 3 shows a high entropy (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C x TG curve of (b).
FIG. 4 shows a high entropy (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C x Is a DSC curve of (C).
Detailed Description
The following description of the specific examples and the accompanying drawings refers to the carbon vacancy high entropy (Ti) 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C x The preparation and properties of the ceramic are described in detail.
Example 1, high entropy (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.7 Preparation of ceramics
(1) Mixing Ti, V, nb, mo, W and C powder according to a molar ratio of 1:1:1:1:1:3.5, adding a small amount of ethanol, and placing in a tungsten carbide ball milling tank (tungsten carbide balls: mixed powder=5:1); placing the ball milling tank into a ball mill, and ball milling at a rotating speed of 200 r/min for 8 h to obtain mixed powder;
(2) Mixing the powder obtained in the step (1)After the body is dried, the green body is obtained by prepressing and shaping under 30MPa by a hydraulic press, and then the green body is sintered by spark plasma. The process conditions of spark plasma sintering are as follows: vacuumizing the atmosphere furnace to make the vacuum indication number less than 10 1 Pa, then raising the furnace temperature from room temperature to 2150 ℃ at a heating rate of 100 ℃/min, and preserving heat for 10min; then the power is turned off and naturally cooled to room temperature, thus obtaining (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.7 High entropy ceramic. XRD patterns (FIG. 1) showed that the prepared (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.7 The high-entropy ceramic is a pure phase and does not contain other impurity phases; SEM images and elemental distribution maps show the synthesized high entropy (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.7 The five constituent elements of the ceramic are approximately uniformly distributed;
(3) High entropy (Ti) 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.7 Oxidation resistance of ceramic: the oxidation rate is 0.1577 percent/DEG C, and the weight gain rate is 25.2 percent.
Example 2 high entropy (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.8 Preparation of ceramics
(1) Mixing Ti, V, nb, mo, W and C powder according to a molar ratio of 1:1:1:1:1:4, adding a small amount of ethanol, and placing in a tungsten carbide ball milling tank (tungsten carbide balls: mixed powder=5:1); placing the ball milling tank into a ball mill, and ball milling at a rotating speed of 300 r/min for 5 h to obtain mixed powder;
(2) And (3) drying the mixed powder obtained in the step (1), prepressing and forming the mixed powder at 30MPa by using a hydraulic press to obtain a green body, and then performing spark plasma sintering on the green body. The process conditions of spark plasma sintering are as follows: vacuumizing the atmosphere furnace to make the vacuum indication number less than 10 0 Pa, then raising the furnace temperature from room temperature to 2200 ℃ at a heating rate of 150 ℃/min, and preserving heat for 5min; then the power is turned off and naturally cooled to room temperature, thus obtaining (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.8 High entropyAnd (3) ceramics. XRD patterns (FIG. 1) showed that the prepared (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.8 The high-entropy ceramic is a pure phase and does not contain other impurity phases; SEM images and elemental distribution maps show the synthesized high entropy (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.8 The five constituent elements of the ceramic are approximately uniformly distributed;
(3) High entropy (Ti) 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.8 Oxidation resistance of ceramic: the oxidation rate is 0.1586 percent/DEG C, and the weight gain rate is 29.4 percent.
Example 3 high entropy (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.9 Preparation of ceramics
(1) Mixing Ti, V, nb, mo, W and C powder according to a molar ratio of 1:1:1:1:4.5, adding a small amount of ethanol, and placing in a tungsten carbide ball milling tank (tungsten carbide balls: mixed powder=3:1); placing the ball milling tank in a ball mill, and ball milling for 9 hours at the rotating speed of 400 r/min to obtain mixed powder;
(2) And (3) drying the mixed powder obtained in the step (1), prepressing and forming the mixed powder at 30MPa by using a hydraulic press to obtain a green body, and then performing spark plasma sintering on the green body. The process conditions of spark plasma sintering are as follows: vacuumizing the atmosphere furnace to make the vacuum indication number less than 10 0 Pa, then raising the furnace temperature from room temperature to 2300 ℃ at a heating rate of 100 ℃/min, and preserving the heat for 10min; then the power is turned off and naturally cooled to room temperature, thus obtaining (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.9 High entropy ceramic. XRD patterns (FIG. 1) showed that the prepared (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.7 The high-entropy ceramic is a pure phase and does not contain other impurity phases; SEM images and elemental distribution maps show the synthesized high entropy (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.7 The five constituent elements of the ceramic are substantially uniformly distributed (fig. 2);
(3) High entropy (Ti) 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C 0.9 Oxidation resistance of ceramic: the oxidation rate is 0.1929 percent/DEG C, and the weight gain rate is 26.2 percent.
In each example, the purity of Ti powder, V powder, nb powder, mo powder, W powder and C powder is more than or equal to 99%, and the grain size is less than 10 mu m.
Claims (3)
1. A method for preparing a carbon vacancy high entropy carbide (TiVNbMoW) Cx, comprising the steps of:
(1) Taking Ti powder, V powder, nb powder, mo powder, W powder and carbon powder as raw materials, mixing, adding a small amount of ethanol, and grinding in an argon protective atmosphere to obtain mixed powder; the mol ratio of Ti, V, nb, mo, W to C is 1:1:1:1:1 (3.5-5);
(2) Drying the obtained mixed powder, pressing and forming at 30MPa by a hydraulic press to obtain a green body, then performing spark plasma sintering on the green body, and naturally cooling to room temperature to obtain the high-entropy carbide ceramic (Ti) 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C x The method comprises the steps of carrying out a first treatment on the surface of the The technological conditions of the discharge plasma burning are as follows: the temperature rising rate is 20-300 ℃/min, the sintering temperature is 1800-2300 ℃, the heat preservation time is 0.1-1 h, the pressure is 1.5-30 MPa, and the vacuum degree is less than 10 1 Pa; the prepared high-entropy carbide ceramic (Ti 0.2 V 0.2 Nb 0.2 Mo 0.2 W 0.2 )C x Wherein x is more than or equal to 0.7 and less than 1.
2. The method for preparing the carbon-vacancy high-entropy carbide (TiVNbMoW) Cx according to claim 1, wherein: the purities of the raw materials Ti powder, V powder, nb powder, mo powder, W powder and C powder are all more than or equal to 99 percent, and the particle sizes are all less than 10 mu m.
3. The method for preparing the carbon-vacancy high-entropy carbide (TiVNbMoW) Cx according to claim 1, wherein: in grinding, the mass ratio of grinding balls to raw materials is 3:1-10:1, and the rotating speed of the ball mill is 200-800 r/min; the ball milling time is 3-20 h.
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| CN116535215A (en) * | 2023-05-08 | 2023-08-04 | 中南大学 | Preparation method of non-stoichiometric multi-carbide ceramic |
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| CN109180189A (en) * | 2018-10-08 | 2019-01-11 | 中南大学 | A kind of high entropy carbide ultra-high temperature ceramic powder and preparation method thereof |
| CN109180188A (en) * | 2018-10-08 | 2019-01-11 | 中南大学 | A kind of high entropy carbide containing boron ultra-high temperature ceramic powder and preparation method thereof |
| CN111533559A (en) * | 2020-03-30 | 2020-08-14 | 东华大学 | Carbon-deficiency type high-entropy transition metal carbide ceramic material and preparation method thereof |
| CN113831133A (en) * | 2021-10-26 | 2021-12-24 | 燕山大学 | Non-stoichiometric high-entropy ceramic and preparation method thereof |
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