CN110407213B - (Ta, nb, ti, V) C high-entropy carbide nano powder and preparation method thereof - Google Patents
(Ta, nb, ti, V) C high-entropy carbide nano powder and preparation method thereof Download PDFInfo
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Abstract
The invention discloses (Ta, nb, ti, V) C high-entropy carbide nano powder and a preparation method thereof. The preparation method comprises the following steps: (1) Grinding and mixing Ta powder, nb powder, ti powder, V powder, C powder and KCl; (2) Sintering the mixed powder at a high temperature, introducing Ar gas for protection in the sintering process, and cooling to room temperature after sintering; (3) And washing, filtering and drying the sintered mixed powder by using deionized water to finally obtain the (Ta, nb, ti, V) C high-entropy carbide nano powder. The method disclosed by the invention has the advantages that the adopted raw materials are low in price, the synthesis temperature is low, the equipment requirement is low, the grain size of the synthesized (Ta, nb, ti, V) C high-entropy carbide nano-powder is small (the average grain size is 80-90 nm), the purity is high, and the components are uniform, so that the method has the potential of being developed into large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of high-entropy compounds, and particularly relates to (Ta, nb, ti, V) C high-entropy carbide nano powder and a preparation method thereof.
Background
The concept of the high-entropy material is firstly proposed by professor yu yi of Qinghua university in Taiwan in 2004, and the concept is defined that the element type is more than or equal to 4, no leading element exists, and the content of each element is between 5% and 35%. At present, research on high-entropy materials by domestic and foreign researchers is mainly focused on the field of alloys, and research on the field of ceramics is less. Since the concept of high-entropy oxide ceramic materials was first reported in 2015, high-entropy ceramic materials have become a research hotspot in recent years, and various high-entropy oxide, boride, nitride and carbide ceramic materials are reported successively. Among them, the high-entropy carbide ceramic material has been widely noticed by researchers at home and abroad due to its characteristics of extremely high melting point, relatively low thermal conductivity, excellent mechanical properties, and good high-temperature physical and chemical stability. However, the high-entropy carbide ceramic materials prepared at present generally have the problems of large grain size, high porosity, non-uniform element components and the like. The synthesis of the high-purity ultra-fine high-entropy carbide ceramic powder plays an important role in solving the problems. However, few reports are made at home and abroad about the synthesis method of the high-purity superfine high-entropy carbide ceramic powder.
The document discloses a method for preparing (Hf, ta, ti, zr, nb) C High-entropy carbide powder at 2000 ℃ by using five carbide powders of TiC, zrC, hfC, nbC and TaC as raw materials and adopting an SPS sintering technology, wherein the five carbide powders are Zhou J, zhang J, zhang F and et al, A novel class of metals of A novel class of multi-component Ceramics, ceramics International, 2018 and 44 (17) 22014-22018. The method has the advantages of high raw material price, high preparation temperature (2000 ℃) and high equipment requirement, and the synthesized (Hf, ta, ti, zr, nb) C high-entropy carbide powder has large grain size (micron order), uneven components and low purity, so the popularization and the application of the method are seriously limited by the defects.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide (Ta, nb, ti, V) C high-entropy carbide nano powder and a preparation method thereof. According to the method, ta powder, nb powder, ti powder, V powder and C powder are used as raw materials, KCl is used as a molten salt medium, and the raw materials are directly reacted in molten salt at a low temperature to prepare the (Ta, nb, ti, V) C high-entropy carbide nano powder, so that the method is low in raw material price, low in synthesis temperature and low in equipment requirement, and the prepared (Ta, nb, ti, V) C high-entropy carbide nano powder is uniform in component, high in purity and small in grain size (the average grain size is 80-90 nm).
The purpose of the invention is realized by at least one of the following technical solutions.
A preparation method of (Ta, nb, ti, V) C high-entropy carbide nano-powder comprises the following steps:
(1) Grinding and mixing Ta powder, nb powder, ti powder, V powder, C powder and KCl;
(2) Sintering the mixed powder at a high temperature, introducing Ar gas for protection in the sintering process, and cooling to room temperature after sintering;
(3) And washing the sintered mixed powder with deionized water, filtering and drying to finally obtain the (Ta, nb, ti, V) C high-entropy carbide nano powder.
Further, in the step (1), the particle diameters of the Ta powder, the Nb powder, the Ti powder and the V powder are all 1-3 μm, the purities are all more than or equal to 99.5%, the particle diameter of the C powder is 0.7-0.9 μm, and the purity is more than or equal to 99.9%.
Further, in the step (1), the molar ratio of Ta powder, nb powder, ti powder and V powder is 1; the mass of the KCl salt is 10-20 times of the total mass of the Ta powder, the Nb powder, the Ti powder, the V powder and the C powder.
Further, in the step (1), the manual grinding time is 10-30 min.
Further, in the step (2), the heating rate is 5-10 ℃/min in the sintering process, the sintering temperature is 1200-1300 ℃, the heat preservation time is 30-90 min, and the flow of the introduced Ar gas is 300-400 sccm.
Further, in the step (3), the temperature of the deionized water is 80-100 ℃.
Further, in the step (3), the drying temperature is 40-80 ℃, and the drying time is 2-5 hours.
The (Ta, nb, ti, V) C high-entropy carbide nano powder prepared by the preparation method.
The preparation method comprises the steps of taking Ta powder, nb powder, ti powder, V powder and C powder as raw materials, taking KCl as a molten salt medium, uniformly mixing the raw materials according to a certain proportion, then carrying out heat treatment for 30-90 min at 1200-1300 ℃, preparing (Ta, nb, ti, V) C high-entropy carbide nano powder through direct reaction of the raw materials in molten salt, then cleaning with hot deionized water to remove KCl salt, and finally obtaining the (Ta, nb, ti, V) C high-entropy carbide nano powder.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The raw materials adopted by the preparation method are low in price, low in synthesis temperature, low in equipment requirement and low in production cost, and large-scale industrial production is facilitated;
(2) The (Ta, nb, ti, V) C high-entropy carbide nano-powder synthesized by the preparation method disclosed by the invention has the advantages of small grain size (the average grain size is 80-90 nm), high purity and uniform components, and the method has the potential of being developed into large-scale industrial production.
Drawings
FIG. 1 is an XRD spectrum of the (Ta, nb, ti, V) C high-entropy nanopowder synthesized in example 2;
FIG. 2 is SEM image and EDS energy spectrum element distribution diagram of (Ta, nb, ti, V) C high-entropy nano-powder synthesized in example 2.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, but the scope and implementation of the present invention are not limited thereto.
In the specific embodiment of the invention, the Ta powder, the Nb powder, the Ti powder and the V powder have the particle sizes of 1-3 mu m and the purities of more than or equal to 99.5 percent, and the C powder has the particle size of 0.7-0.9 mu m and the purity of more than or equal to 99.9 percent; the purity of the KCl salt used was analytical grade.
Example 1
(1) Respectively weighing 0.45 g of Ta powder, 0.23 g of Nb powder, 0.12 g of Ti powder, 0.13 g of V powder, 0.12 g of C powder and 10.50 g of KCl salt, putting the powder into an agate mortar, manually grinding for 10 min to uniformly mix the powder, and transferring the powder into a corundum ark;
(2) Putting the square boat into an atmosphere furnace, vacuumizing the atmosphere furnace for 10 min to ensure that the vacuum degree reaches 10 -1 And (5) maintaining the vacuum for 10 min under MPa, observing whether the indication of the vacuum meter changes or not, if the indication does not change, indicating that the system is sealed well, and repeating the process for three times. Introducing Ar gas to normal pressure, then heating the furnace temperature from room temperature to 1200 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 30 min; then, turning off the power supply, naturally cooling to room temperature, and introducing Ar gas for protection in the whole process, wherein the flow of the Ar gas is kept at 300 sccm;
(3) And washing the obtained mixture in deionized water at 80 ℃, filtering, and drying in an oven at 40 ℃ for 2 h to obtain the target product. The (Ta, nb, ti, V) C high-entropy carbide powder synthesized under the condition is pure phase, the appearance is granular, and the average grain size is about 85 nm.
Example 2
(1) Respectively weighing 0.45 g of Ta powder, 0.23 g of Nb powder, 0.12 g of Ti powder, 0.13 g of V powder, 0.13 g of C powder and 15.90 g of KCl salt, putting the materials into an agate mortar, manually grinding the materials for 20 min to uniformly mix the materials, and transferring the materials into a corundum ark;
(2) Putting the ark into an atmosphere furnace, vacuumizing the atmosphere furnace for 10 min to make the vacuum degree reach 10 -1 And (5) maintaining the vacuum for 10 min under MPa, observing whether the indication of the vacuum meter changes or not, if the indication does not change, indicating that the system is sealed well, and repeating the process for three times. Introducing Ar gas to normal pressure, then heating the furnace temperature from room temperature to 1250 ℃ at the heating rate of 8 ℃/min, and preserving the temperature for 60 min; then, turning off the power supply, naturally cooling to room temperature, and introducing Ar gas for protection in the whole process, wherein the flow of the Ar gas is kept at 350 sccm;
(3) And washing the obtained mixture in deionized water at 90 ℃, filtering, and drying in an oven at 60 ℃ for 4 h to obtain the target product.
FIG. 1 is an XRD pattern of the (Ta, nb, ti, V) C high-entropy carbide powder prepared in this example, which shows that the synthesized powder consists of a single (Ta) 0.25 Nb 0.25 Ti 0.25 V 0.25 ) And the C phase consists, and other mixed phases are not found, so that the high-entropy carbide nano powder prepared by the method has high purity. FIG. 2 is an SEM photograph and an EDS energy spectrum element distribution chart of the (Ta, nb, ti, V) C high-entropy carbide powder synthesized in this example. As can be seen from fig. 2 (a), the (Ta, nb, ti, V) C high-entropy carbide powder synthesized in this example is a nano-powder, and the average crystal grain size thereof is about 80 nm, and as can be seen from EDS spectrum analysis (fig. 2 (b) - (e)), four metal elements of Ta, nb, ti, and V are uniformly distributed in the synthesized powder.
Example 3
(1) Respectively weighing 0.45 g of Ta powder, 0.23 g of Nb powder, 0.12 g of Ti powder, 0.13 g of V powder, 0.14 g of C powder and 25.00 g of KCl salt, putting the powder into an agate mortar, manually grinding for 30min to uniformly mix the powder, and transferring the powder into a corundum ark;
(2) Putting the square boat into an atmosphere furnace, vacuumizing the atmosphere furnace for 10 min to ensure that the vacuum degree reaches 10 -1 And (5) performing vacuum for 10 min under the MPa, observing whether the indication of the vacuum meter is changed or not, if the indication is not changed, indicating that the system is sealed completely, and repeating the process for three times. Introducing Ar gas to normal pressure, then heating the furnace temperature from room temperature to 1300 ℃ at the heating rate of 10 ℃/min, and preserving the temperature for 90 min; then, turning off the power supply, naturally cooling to room temperature, and introducing Ar gas for protection in the whole process, wherein the flow of the Ar gas is kept at 400 sccm;
(3) And washing the obtained mixture in deionized water at 100 ℃, filtering and drying in an oven at 80 ℃ for 5 hours to obtain the target product. The (Ta, nb, ti, V) C high-entropy carbide powder synthesized under the condition is pure phase, the morphology is nano-granular, and the average grain size is about 90 nm.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (7)
1. A preparation method of (Ta, nb, ti, V) C high-entropy carbide nano-powder is characterized by comprising the following steps:
(1) Grinding and mixing Ta powder, nb powder, ti powder, V powder, C powder and KCl; the molar ratio of the Ta powder, the Nb powder, the Ti powder and the V powder is 1; the mass of the KCl salt is 10 to 20 times of the total mass of the Ta powder, the Nb powder, the Ti powder, the V powder and the C powder;
(2) Sintering the mixed powder at a high temperature, introducing Ar gas for protection in the sintering process, and cooling to room temperature after sintering; the sintering temperature is 1200 to 1300 ℃, and the sintering time is 30 to 90 min;
(3) And washing, filtering and drying the sintered mixed powder by using deionized water to finally obtain the (Ta, nb, ti, V) C high-entropy carbide nano powder.
2. The preparation method according to claim 1, wherein in the step (1), the Ta powder, the Nb powder, the Ti powder and the V powder have the particle sizes of 1-3 μm and the purities of more than or equal to 99.5%, and the C powder has the particle size of 0.7-0.9 μm and the purities of more than or equal to 99.9%.
3. The method according to claim 1, wherein the grinding time in step (1) is 10 to 30min.
4. The preparation method according to claim 1, wherein in the step (2), the temperature rise rate is 5 to 10 ℃/min during sintering, and the flow rate of Ar gas is 300 to 400 sccm.
5. The method according to claim 1, wherein the temperature of the deionized water in the step (3) is 80 to 100 ℃.
6. The method according to claim 1, wherein in the step (3), the drying temperature is 40 to 80 ℃ and the drying time is 2 to 5 hours.
7. (Ta, nb, ti, V) C high-entropy carbide nano-powder prepared by the preparation method of any one of claims 1 to 6.
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| CN112851352A (en) * | 2021-01-27 | 2021-05-28 | 陕西科技大学 | Ultrahigh-temperature high-entropy carbide powder and preparation method thereof |
| CN113716580A (en) * | 2021-08-15 | 2021-11-30 | 吉林大学 | High-entropy boride micro-nano ceramic particle and preparation method thereof |
| CN113548898B (en) * | 2021-08-19 | 2023-03-21 | 郑州大学 | (Mo) 0.2 W 0.2 V 0.2 Cr 0.2 Ni 0.2 ) B high-entropy ceramic powder and preparation method thereof |
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