CN114956826A - (TiNbCrWTa) C x High-entropy ceramic and preparation method thereof - Google Patents
(TiNbCrWTa) C x High-entropy ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention relates to (TiNbCrWTa) C x The high-entropy ceramic is a ceramic with a single-phase face-centered cubic structure; the preparation method comprises the following steps: s1: uniformly mixing a metal and four carbide raw material powders to obtain mixed powder A; s2: putting the mixed powder A into a graphite die with good heat-conducting property for solid-phase reaction sintering to obtain high-entropy ceramic (TiNbCrWTa) C x . The invention selects Ti powder and Cr 3 C 2 The powder combination not only reduces the sintering temperature in the sintering process, but also ensures the carbon source of the high-entropy carbide, is beneficial to the diffusion of each element, and ensures that the final product hasHigher compactness and uniformity, finally forming a single-phase solid solution, and the prepared high-entropy ceramic has excellent mechanical, physical and chemical properties.
Description
Technical Field
The invention relates to (TiNbCrWTa) C x A high-entropy ceramic and a preparation method thereof belong to the technical field of high-entropy carbide ceramics.
Background
Ceramic materials have attracted extensive research interest due to superior mechanical, physical and chemical properties, such as high hardness, strength and wear resistance in mechanical properties, high temperature stability in chemical properties, low thermal conductivity and electrical conductivity, compared to metallic materials. Transition metal carbides are a class of compound materials with high melting points and excellent mechanical properties, and the materials have wide application in the aspects of machinery, aviation, metallurgy and the like. The appearance of the concept of "high entropy" provides a new material design theory, becomes one of the hot spots in the field of material research, and the concept of "high entropy" begins to expand to the field of transition metal carbide along with the deep development of high entropy alloys for over a decade.
In the prior art, methods for manufacturing a high-entropy carbide block are classified into a carbide processing method using a metal carbide as a raw material, an oxidation process using a metal oxide and graphite as raw materials to perform a carbothermic reduction reaction, and an elemental method using metal powder and graphite as raw materials, according to the kind of raw materials used. But studies have shown that the temperature required for the carbide processing is higher and the relative density of the final product is lower; the high-entropy carbide prepared by carbothermic reduction is difficult to disperse due to the irregular shape of the carbon powder, so that the uniformity and compactness are influenced, and oxygen elements are easy to remain; the element method is adopted for preparation, because the particle size difference of the metal powder and the carbon powder is large, the element distribution is not uniform, and the uniformity of the product can be influenced. The influence on the high-entropy carbide sintering process and the structural performance is mainly a carbon source, so the preparation process of the high-entropy carbide ceramic needs to be further improved by starting from the carbon source of the raw material powder.
Disclosure of Invention
The invention aims to provide (TiNbCrWTa) C x High-entropy ceramic and its preparation method, selecting Ti powder and Cr 3 C 2 The powder is combined, so that the sintering temperature in the sintering process can be reduced, the carbon source of the high-entropy carbide can be ensured, and the prepared high-entropy ceramic has excellent mechanical, physical and chemical properties.
In order to achieve the purpose, the invention adopts the technical scheme that:
(TiNbCrWTa) C x The high-entropy ceramic is a single-phase face-centered cubic structure ceramic and comprises the following simple substances and carbides in atomic ratio: 23% of Ti, 23% of NbC, 23% of WC, 23% of TaC and the balance of Cr 3 C 2 。
(TiNbCrWTa) C x The preparation method of the high-entropy ceramic comprises the following steps:
s1: uniformly mixing a metal and four carbide raw material powders to obtain mixed powder A;
s2: through a vacuum hot-pressing sintering technology, the mixed powder A is placed into a graphite die with good heat-conducting property for solid-phase reaction sintering to obtain high-entropy ceramic (TiNbCrWTa) C x 。
The technical scheme of the invention is further improved as follows: the raw material powder is Ti powder, NbC powder and Cr powder 3 C 2 The purity of the powder, WC powder and TaC powder is higher than 99.5%.
The technical scheme of the invention is further improved as follows: the raw material powder comprises Ti, NbC, Cr3C2, WC and TaC, wherein the ratio of the raw material powder to the raw material powder is 3:3:1:3: 3.
The technical scheme of the invention is further improved as follows: the specific steps of step S1 are:
s11: weighing the raw material powder according to equal metal atom ratio;
s12: putting the raw material powder weighed by S11 into an agate ball milling tank, wherein the ball powder ratio is 6:1, sealing the ball milling tank by adopting vacuum silicone grease, and filling argon into the ball milling tank;
s13: ball milling is carried out by adopting a planetary ball mill, the rotating speed is 200r/min, and the ball milling time is 10 hours.
The technical scheme of the invention is further improved as follows: the granularity of the Ti powder is 45 mu m, the granularity of the NbC powder is 4 mu m, and the Cr powder is 3 C 2 The particle size of the powder was 1 μm, that of the WC powder was 1 μm and that of the TaC powder was 4 μm.
The technical scheme of the invention is further improved as follows: and graphite paper is arranged on the inner wall of the S2 graphite die and the position contacted with the powder.
The technical scheme of the invention is further improved as follows: in the solid-phase reaction sintering process of the step S2, 10MPa of pre-pressure is adopted firstly, then the pressure is gradually increased, 30MPa of pressure maintaining is adopted, and the vacuum degree of the graphite mold is always kept lower than that in the sintering process1.8×10 -2 Pa。
The technical scheme of the invention is further improved as follows: in the step S2, the solid-phase reaction sintering temperature is 1350-1650 ℃, the heating rate is 10 ℃/min, and the heat preservation time is 2 h; and after sintering, cooling to room temperature along with the furnace, and taking out the sample.
Due to the adoption of the technical scheme, the invention has the following technical effects:
the invention selects Ti powder and Cr 3 C 2 The powder is combined, so that the sintering temperature in the sintering process is reduced, the carbon source of the high-entropy carbide is ensured, the diffusion of each element is facilitated, the final product has higher density and uniformity, a single-phase solid solution is finally formed, and the prepared high-entropy ceramic has excellent mechanical, physical and chemical properties.
The invention uses the metal simple substance Ti and simultaneously uses NbC and Cr 3 C 2 The WC powder and the TaC powder can be used as a carbon source in the high-entropy carbide ceramic, the carbon content and the formation of the high-entropy carbide can be effectively controlled, the diffusion among elements is facilitated, and the prepared high-entropy ceramic has good comprehensive performance.
The high-entropy ceramic (TiNbCrWTa) C prepared by the invention x The ceramic is of a single-phase face-centered cubic structure, and has good compactness, high hardness and high application value.
Drawings
FIG. 1 shows (TiNbCrWTa) C prepared according to the present invention x XRD pattern of high entropy carbide ceramic;
FIG. 2 shows (TiNbCrWTa) C prepared according to the present invention x SEM and EDS images of high entropy carbide ceramics;
FIG. 3 shows (TiNbCrWTa) C prepared according to the present invention x The change curve of the ceramic hardness along with the sintering temperature.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific embodiments:
(TiNbCrWTa) C x The high-entropy ceramic is of a single-phase face-centered cubic structure.
The (TiNbCrWTa) C x The preparation method of the high-entropy ceramic comprises the following steps:
s1 preparation of Mixed powder A
S11: weighing raw material powders according to equal metal atomic ratio, wherein the raw material powders are respectively Ti powder, NbC powder and Cr powder 3 C 2 Powder, WC powder and TaC powder, wherein the purity of each powder is higher than 99.5%; the particle size of the Ti powder is 45 mu m, the particle size of the NbC powder is 4 mu m, and the Cr is 3 C 2 The granularity of the powder is 1 mu m, the granularity of the WC powder is 1 mu m, and the granularity of the TaC powder is 4 mu m;
s12: putting raw material powder weighed by S11 into an agate ball milling tank, wherein the ball powder ratio is 6:1, sealing the ball milling tank by adopting vacuum silicone grease, and filling argon into the ball milling tank;
s13: ball milling is carried out by adopting a planetary ball mill, the rotating speed is 200r/min, and the ball milling time is 10 hours.
S2, preparing high-entropy ceramic (TiNbCrWTa) C by vacuum hot-pressing sintering x
And putting the mixed powder A into a graphite mould with good heat conductivity, and coating graphite paper on the inner wall of the graphite mould and the position contacted with the powder. Putting the graphite mould into a vacuum hot-pressing sintering furnace, and vacuumizing to less than 1.8 multiplied by 10 -2 Pa; setting the sintering temperature to 1350-1650 ℃, setting the temperature rise speed to 10 ℃/min, adopting 10MPa of pre-pressure in a sintering furnace in the sintering process, then gradually increasing the pressure, controlling the pressure to 30MPa when the temperature is increased to the sintering temperature, and preserving the heat for 2 h.
And after the sintering process is finished, cooling the sintering furnace along with the furnace, and taking out the sample after the temperature reaches the room temperature.
Example 1
(TiNbCrWTa) C x The high-entropy ceramic is of a single-phase face-centered cubic structure.
The (TiNbCrWTa) C x The preparation method of the high-entropy ceramic comprises the following steps:
s1 preparation of Mixed powder A
Selecting required mixed powder: preparing initial powders of Ti powder, NbC powder and Cr 3 C 2 18g of powder, WC powder and TaC powder are weighed according to the atomic ratio of metal and the like, and the molar ratio is Ti, NbC and Cr 3 C 2 WC: TaC: 3:3:1:3: 3. Respectively weighing by means of balances1.43g Ti powder, 3.13g NbC powder, 1.79g Cr powder 3 C 2 Powder, 5.86g of WC powder and 5.77g of TaC powder, the powder is placed in an agate ball milling tank, 108g of agate balls are added according to the ball powder ratio of 6:1, the mass ratio of large balls to small balls is 1:1, in order to prevent the mixed powder from being oxidized, argon gas is filled into the ball milling tank, the agate ball milling tank is placed in a planetary ball mill to be mixed for 10 hours, and the rotating speed is 200 r/min.
S2, preparing high-entropy ceramic (TiNbCrWTa) C by vacuum hot-pressing sintering x
And putting the mixed powder A into a graphite mould with good heat conductivity, and coating graphite paper on the inner wall of the graphite mould and the position contacted with the powder. Putting the graphite mould into a vacuum hot-pressing sintering furnace, and vacuumizing to less than 1.8 multiplied by 10 -2 Pa. The sintering temperature is 1450 ℃, the heating rate is 10 ℃/min, and the temperature is respectively kept at 600 ℃, 900 ℃ and 1250 ℃ for 10min in the heating process. In the sintering process, a sintering furnace adopts 10MPa of pre-pressure, then the pressure is gradually increased, the pressure is controlled to be 30MPa when the temperature is 1450 ℃, and the temperature is kept for 2 h.
And after the sintering process is finished, cooling the sintering furnace along with the furnace, and taking out the sample after the temperature reaches the room temperature. The cake product was cut by wire cutting according to the dimensions required for the subsequent experiments. (TiNbCrWTa) C prepared by the process x The Vickers hardness of the ceramic is 1745HV 0.5 。
Example 2:
(TiNbCrWTa) C x The high-entropy ceramic is of a single-phase face-centered cubic structure.
The (TiNbCrWTa) C x The preparation method of the high-entropy ceramic comprises the following steps:
s1 preparation of Mixed powder A
Selecting required mixed powder: preparing small amount of Ti powder, NbC powder and Cr powder 3 C 2 18g of powder, WC powder and TaC powder are weighed according to the atomic ratio of metal and the like, and the ratio is Ti, NbC and Cr 3 C 2 WC: TaC: 3:3:1:3: 3. 1.43g of Ti powder, 3.13g of NbC powder and 1.79g of Cr powder were weighed on a balance 3 C 2 Powder, 5.86g WC powder and 5.77g TaC powder, placing the powders in an agate ball milling tank, and adding 108g of the agate powder according to the ball powder ratio of 6:1The mass ratio of big balls to small balls of the agate balls is 1:1, and in order to prevent the mixed powder from being oxidized, argon gas is filled into a ball milling tank; and putting the agate jar into a planetary ball mill to mix for 10 hours at the rotating speed of 200 r/min.
S2, preparing high-entropy ceramic (TiNbCrWTa) C by vacuum hot-pressing sintering x
And putting the mixed powder A into a graphite die with good heat conductivity, and coating graphite paper on the position where the inner wall of the graphite die is contacted with the powder. Putting the graphite mould into a vacuum hot-pressing sintering furnace, and vacuumizing to less than 1.8 multiplied by 10 -2 Pa. The sintering temperature is set to 1550 ℃, the heating rate is 10 ℃/min, and the temperature is respectively kept at 600 ℃, 900 ℃ and 1250 ℃ for 10min in the heating process. In the sintering process, a sintering furnace adopts 10MPa of pre-pressure, then the pressure is gradually increased, the pressure is controlled to be 30MPa when the temperature reaches 1550 ℃, and the temperature is kept for 2 h.
And after the sintering process is finished, cooling the sintering furnace along with the furnace, and taking out the sample after the temperature reaches the room temperature. The cake product was cut by wire cutting according to the dimensions required for the subsequent experiments. (TiNbCrWTa) C prepared by the process x The Vickers hardness of the ceramic is 2214HV 0.5 。
Example 3:
(TiNbCrWTa) C x The high-entropy ceramic is of a single-phase face-centered cubic structure.
The (TiNbCrWTa) C x The preparation method of the high-entropy ceramic comprises the following steps:
s1 preparation of Mixed powder A
Selecting required mixed powder: preparing small amount of Ti powder, NbC powder and Cr powder 3 C 2 18g of powder, WC powder and TaC powder are weighed according to the atomic ratio of metal and the like, and the ratio is Ti, NbC and Cr 3 C 2 WC: TaC: 3:3:1:3: 3. 1.43g of Ti powder, 3.13g of NbC powder and 1.79g of Cr powder were weighed on a balance 3 C 2 Powder, 5.86g of WC powder and 5.77g of TaC powder, the powder is placed in an agate ball milling tank, 108g of agate balls are added according to the ball powder ratio of 6:1, the mass ratio of big balls to small balls is 1:1, and in order to prevent the mixed powder from being oxidized, argon gas is filled into the ball milling tank. Putting an agate ball milling pot into a planetary ball mill to mix powder for 10h at a rotating speed200r/min。
S2, preparing high-entropy ceramic (TiNbCrWTa) C by vacuum hot-pressing sintering x
And putting the mixed powder into a graphite die with good heat conductivity, and coating graphite paper on the inner wall of the graphite die and the position contacted with the powder. Putting the graphite mould into a vacuum hot-pressing sintering furnace, and vacuumizing to less than 1.8 multiplied by 10 -2 Pa. The sintering temperature is set to 1650 ℃, the heating rate is 10 ℃/min, and the temperature is respectively kept at 600 ℃, 900 ℃ and 1250 ℃ for 10min in the heating process. In the sintering process, a sintering furnace adopts 10MPa of pre-pressure, then the pressure is gradually increased, the pressure is controlled to be 30MPa when the temperature reaches 1650 ℃, and the temperature is kept for 2 h.
And after the sintering process is finished, cooling the sintering furnace along with the furnace, and taking out the sample after the temperature reaches the room temperature. The cake product was cut by wire cutting according to the dimensions required for the subsequent experiments. (TiNbCrWTa) C prepared by the process x The Vickers hardness of the ceramic is 2501HV 0.5 。
FIG. 1 shows (TiNbCrWTa) C prepared in example 1 of the present invention x The high-entropy carbide ceramic is shown by the figure, the diffraction peak of a single face-centered cubic structure phase is mainly in the map, and the diffraction peak of other substances is not existed, so that the prepared (TiNbCrWTa) C is illustrated x The high-entropy carbide ceramic has high purity. FIG. 2 shows (TiNbCrWTa) C prepared in example 1 of the present invention x SEM and EDS images of the high-entropy carbide ceramic show that the material has high compactness and almost has no air holes. The EDS chart shows that the elements are uniformly distributed, and segregation of the elements does not occur. Fig. 3 shows the hardness changes of three examples of the present invention, and it can be found that the hardness of the high-entropy ceramic is in direct proportion to the temperature, and the hardness value between 1450 ℃ and 1650 ℃ has a significant change because the densification degree of the material is greatly increased in the temperature range, and the material begins to form a single solid solution phase structure.
The above-disclosed preferred embodiments of the present invention are provided primarily for the purpose of illustrating the principles of preparation, the organization and configuration of materials, and the advantages of the invention. The preferred examples are not exhaustive of all experimental details and do not limit the invention to the only specific implementation steps. The foregoing examples are illustrative of the principles of this invention and numerous modifications and variations, as well as variations and improvements, may be made without departing from the scope and spirit of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. (TiNbCrWTa) C x High entropy ceramics, its characterized in that: the high-entropy ceramic is a single-phase face-centered cubic structure ceramic, and comprises the following simple substances and carbides in atomic ratio: 23% of Ti, 23% of NbC, 23% of WC, 23% of TaC and the balance of Cr 3 C 2 。
2. A method for preparing the (TiNbCrWTa) C of claim 1 x The method for preparing the high-entropy ceramic is characterized by comprising the following steps: the method comprises the following steps:
s1: uniformly mixing a metal and four carbide raw material powders to obtain mixed powder A;
s2: through a vacuum hot-pressing sintering technology, the mixed powder A is placed into a graphite die with good heat-conducting property for solid-phase reaction sintering to obtain high-entropy ceramic (TiNbCrWTa) C x 。
3. A (TiNbCrWTa) C according to claim 2 x The preparation method of the high-entropy ceramic is characterized by comprising the following steps: the raw material powder is Ti powder, NbC powder and Cr powder 3 C 2 The purity of the powder, WC powder and TaC powder is higher than 99.5%.
4. A (TiNbCrWTa) C according to claim 3 x The preparation method of the high-entropy ceramic is characterized by comprising the following steps: the raw material powder comprises the following components in an atomic ratio of metal and the like, wherein the ratio of Ti to NbC to Cr3C2 to WC to TaC =3:3:1:3: 3.
5. A (TiNbCrWTa) C according to claim 4 x The preparation method of the high-entropy ceramic is characterized by comprising the following steps: the specific steps of step S1 are:
s11: weighing the raw material powder according to equal metal atom ratio;
s12: putting the raw material powder weighed by S11 into an agate ball milling tank, wherein the ball powder ratio is 6:1, sealing the ball milling tank by adopting vacuum silicone grease, and filling argon into the ball milling tank;
s13: ball milling is carried out by adopting a planetary ball mill, the rotating speed is 200r/min, and the ball milling time is 10 hours.
6. A (TiNbCrWTa) C according to claim 5 x The preparation method of the high-entropy ceramic is characterized by comprising the following steps: the granularity of the Ti powder is 45 mu m, the granularity of the NbC powder is 4 mu m, and the Cr powder is 3 C 2 The particle size of the powder was 1 μm, that of the WC powder was 1 μm and that of the TaC powder was 4 μm.
7. A (TiNbCrWTa) C according to claim 2 x The preparation method of the high-entropy ceramic is characterized by comprising the following steps: and graphite paper is arranged on the inner wall of the S2 graphite die and the position contacted with the powder.
8. A (TiNbCrWTa) C according to claim 2 x The preparation method of the high-entropy ceramic is characterized by comprising the following steps: in the solid-phase reaction sintering process of the step S2, 10MPa of pre-pressure is adopted firstly, then the pressure is gradually increased, 30MPa of pressure maintaining is adopted, and the vacuum degree of the graphite mold is kept lower than 1.8 multiplied by 10 all the time in the sintering process -2 Pa。
9. A (TiNbCrWTa) C according to claim 8 x The preparation method of the high-entropy ceramic is characterized by comprising the following steps: in the step S2, the solid-phase reaction sintering temperature is 1350-1650 ℃, the heating rate is 10 ℃/min, and the heat preservation time is 2 h; and after sintering, cooling to room temperature along with the furnace, and taking out the sample.
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