CN113816747A - TiC enhanced MAX phase high-entropy ceramic matrix composite material and preparation method thereof - Google Patents

TiC enhanced MAX phase high-entropy ceramic matrix composite material and preparation method thereof Download PDF

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CN113816747A
CN113816747A CN202110998353.5A CN202110998353A CN113816747A CN 113816747 A CN113816747 A CN 113816747A CN 202110998353 A CN202110998353 A CN 202110998353A CN 113816747 A CN113816747 A CN 113816747A
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max phase
powder
tic
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entropy
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钟志宏
刘成友
欧阳维
林俐菁
宋奎晶
吴玉程
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Hefei University of Technology
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Abstract

The invention relates to a method for preparing a TiC enhanced MAX phase high-entropy ceramic material matrix composite material with excellent comprehensive mechanical properties, and the TiC enhanced MAX phase high-entropy ceramic material matrix composite material prepared by the method. The method comprises the following steps: 1) mixing TiC powder and MAX phase powder, wherein the MAX phase powder is any more than three transition metal MAX phase carbide powder; 2) dispersing the mixed powder obtained in the step one in a grinding aid, carrying out ball milling to obtain ceramic slurry, carrying out vacuum drying, and sieving; 3) placing the mixed powder obtained in the step two in a steel die, and performing pre-pressing forming to obtain a ceramic biscuit; 4) and (4) placing the ceramic biscuit obtained in the step three in a graphite mold, and performing pressure sintering in a vacuum environment. The performance of the material is further improved by introducing a TiC second phase into the MAX phase high-entropy ceramic matrix.

Description

TiC enhanced MAX phase high-entropy ceramic matrix composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of structural ceramic materials, and particularly relates to a method for preparing a TiC enhanced MAX phase high-entropy ceramic material matrix composite material with excellent comprehensive mechanical properties, and the TiC enhanced MAX phase high-entropy ceramic material matrix composite material prepared by the method.
Background
MAX phase ceramics are a class of hexagonal structure ceramics with high long axis ratios and chemical bond anisotropy. The composite material has the advantages of metal and ceramic, such as low density, high modulus, high damage tolerance, good thermal shock resistance, good electrical conductivity and the like, has wide application prospect, and is expected to be used for high-temperature sealing elements, nuclear fuel cladding materials, novel electric brushes, electrodes and the like. However, compared with the traditional ceramic material, the MAX phase has lower hardness (2-6 GPa) and strength, which greatly limits the application of the MAX phase in engineering practice, so that the improvement of the mechanical property is necessary.
In recent years, many researchers have attempted to improve the mechanical properties of the MAX phase by strengthening means such as solid solution strengthening, second phase grain strengthening, and texture strengthening.
"high entropy" is a new material design theory appearing in recent years, and has become a big hot spot in the field of material research, and the concept of the high entropy alloy is originally developed. The high-entropy alloy is a solid solution formed by solid dissolving a plurality of alloy elements together at a nearly equal atomic ratio to form a single phase. With the continuous and deep research, the concept of high entropy is gradually expanded to other materials, such as high entropy metallic glass, high entropy ceramics, high entropy thermoelectric materials, high entropy polymers and the like. The high-entropy effect caused by the multi-principal element can effectively improve the thermodynamic stability of the material and reduce the sintering temperature of the material, the high-entropy effect is adopted to synthesize the MAX-phase high-entropy ceramic material of the multi-principal element system, and the effects of solid solution strengthening, lattice distortion and the like caused by high-entropy synthesis further improve the comprehensive performance of the MAX-phase ceramic material and provide more possibilities for the application of the MAX-phase material in practical engineering.
In addition, the introduction of the second phase particles with high hardness and high melting point into the MAX phase matrix is a relatively common strengthening mode, and the mode can effectively improve the mechanical property of the material. Mainly due to the following points: (1) the second phase particles have higher hardness and modulus, and can enhance the deformation resistance of the MAX phase matrix; (2) adding second phase particles to refine the crystal grains of the MAX phase matrix; (3) the second phase particles are well combined with the MAX phase matrix interface, and have the function of pinning dislocation of the matrix. (As to how et al, MAX phase ceramic strengthening methods and mechanism research progress [ J ] Chinese ceramics, 2019, 55(09): 1-9.).
The MAX phase high-entropy ceramic material is a new MAX phase material recently, and has higher strength and hardness than a common MAX phase material, but the MAX phase high-entropy ceramic material has less research on strengthening machines and an unclear strengthening mechanism, different elements are solid-dissolved at different positions to obtain different strengthening effects, and the MAX phase high-entropy ceramic material meeting the comprehensive mechanical properties of practical engineering application cannot be obtained. The MAX phase high-entropy ceramic material is currently in a starting stage of research at home and abroad, and no report on the enhancement modification of the MAX high-entropy ceramic material is found. The difficulty of enhancing and modifying the MAX phase high-entropy ceramic material mainly lies in obtaining a single-phase MAX phase high-entropy ceramic matrix, the added second-phase particles cannot react with the MAX phase matrix to influence the structure and the high-entropy process of the MAX phase matrix, and the second-phase particles are uniformly distributed in the ceramic matrix to play a role in dispersion strengthening.
TiC, a typical transition metal carbide, has a very high melting point, good high temperature strength and ablation resistance, while it also has a high elastic modulus and hardness, and bonds well and stably with the MAX phase interface, and does not interface-react with the MAX phase at high temperatures. Therefore, the nano or submicron TiC is selected to strengthen the MAX phase high-entropy ceramic, and the comprehensive performance of the MAX phase high-entropy ceramic is expected to be further improved.
Disclosure of Invention
Technical problem
In order to further improve the comprehensive performance of the MAX phase ceramic, the invention provides a method for preparing a TiC enhanced MAX phase high-entropy ceramic matrix composite material and the TiC enhanced MAX phase high-entropy ceramic matrix composite material prepared by the method.
Technical scheme
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for preparing MAX phase high-entropy ceramic matrix composite material comprises the following steps:
the method comprises the following steps: mixing TiC powder and MAX phase powder, wherein the MAX powder is any more than three transition metal MAX phase carbide powder;
step two: dispersing the mixed powder obtained in the step one in a grinding aid, carrying out ball milling to obtain ceramic slurry, carrying out vacuum drying, and sieving;
step three: placing the mixed powder obtained in the step two in a steel die, and performing pre-pressing forming to obtain a ceramic biscuit;
step four: and (4) placing the ceramic biscuit obtained in the step three in a graphite mold, and performing pressure sintering in a vacuum environment to obtain the TiC enhanced MAX phase high-entropy ceramic matrix composite.
Compared with the prior art, the preparation method of the MAX-phase high-entropy ceramic-based composite material provided by the invention has the advantages that various MAX-phase powders are selected for sintering, the MAX-phase ceramics are subjected to high entropy by using the high entropy effect of multiple principal elements, so that excellent performance is obtained, and the performance of the MAX-phase high-entropy ceramic material is further improved by introducing the TiC second phase on the basis of high entropy reinforcement, so that the TiC enhanced MAX-phase high-entropy ceramic-based composite material with excellent mechanical properties is obtained. The TiC particles are added into the MAX phase high-entropy ceramic as a second phase, so that crystal grains of a matrix can be effectively refined, and dislocation movement is hindered, so that the mechanical properties of the MAX phase high-entropy ceramic, such as strength, toughness and the like, are enhanced, and the TiC and MAX phase interface are well and stably combined, so that interface reaction does not occur, and the high entropy of the MAX phase ceramic matrix is not influenced.
Preferably, in step one, the MAX phase powder is selected from Ti2AlC、Nb2AlC、V2AlC、Cr2AlC and Ta2Any three or more of AlC, and the MAX phase powder is preferably Ti2AlC、V2AlC and Nb2AlC。
Preferably, in step one, the molar ratio of the MAX phase powders to each other is equal molar ratio, the MAX phase powders have a particle size not greater than 15 μm and a purity not lower than 98%.
Preferably, in the step one, the mass fraction of the TiC powder is 5 wt% to 20 wt%, more preferably 10 wt% to 15 wt%, of the total mass of the mixed powder; and the particle size of the TiC powder is 0.6-0.9 mu m, and the purity is not lower than 99%.
If the content of TiC is lower than 5 wt%, the improvement on the material performance is not obvious; if the content of TiC is more than 20 wt%, the density is reduced, and the performance of the material is adversely affected by the reduction of the density.
The high purity of the reaction raw materials can reduce impurity phases; the small particle size of the reaction raw materials is beneficial to the rapid and sufficient uniform mixing of the reaction raw materials in the ball milling process.
Preferably, in the second step, the ball-material ratio is (5-10): 1, the ball milling rotation speed is 200-400 rpm/min, and the ball milling time is 6-10 h.
Preferably, in the second step, the grinding balls are agate balls, and the grinding aid is absolute ethyl alcohol.
The agate balls are good in wear resistance and low in possibility of polluting samples, materials can be mixed more sufficiently due to the addition of the absolute ethyl alcohol, the powder agglomeration phenomenon is prevented to a certain extent, and the absolute ethyl alcohol is high in volatility, can be removed easily and cannot pollute the materials.
Preferably, in the second step, the volume fraction of the solid phase in the ceramic slurry is 60-75%.
Preferably, in the second step, the vacuum drying oven is vacuumized to a pressure of less than 0.1MPa, and the temperature of vacuum drying is set to be 55-60 ℃. Vacuumizing once every two hours, removing volatilized gas, turning off heating after 6-10 hours, maintaining the vacuum state, and taking out the sample after the sample is cooled to room temperature.
Preferably, in the second step, the size of the sieved screen is 200-225 meshes, and the powder particles which can not pass through the screen are pulverized by using a mortar and then pass through the screen.
Preferably, in the third step, the BN coating is sprayed on the inner wall of the steel mould and the surface of the pressure head before sample loading, so that demoulding is facilitated. And (3) loading the processed reaction sintering mixed powder into a steel mould, prepressing under the pressure of 15-30 MPa, maintaining the pressure for 5-10 min, and then demoulding.
Preferably, in the fourth step, the ceramic green body obtained after the pre-pressing is placed in a graphite mold lined with graphite paper, and sintering is performed.
Preferably, in the fourth step, the ceramic green body is sintered by using spark plasma sintering technology.
More preferably, the spark plasma sintering conditions are: and under the vacuum state of the sintering furnace, raising the temperature to 750-800 ℃ at the temperature rise rate of 80-120 ℃/min, preserving the heat for 10min, loading the pressure to 10-15 MPa, raising the temperature to 1350-1500 ℃ at the temperature rise rate of 50-100 ℃/min, preserving the heat for 8-15 min, wherein the loading pressure is 45-55 MPa, reducing the pressure and the temperature after the heat preservation, and cooling the sample along with the furnace.
The TiC enhanced MAX phase high-entropy ceramic matrix composite material prepared by the method has the relative density of more than 94 percent, the Vickers hardness of more than 7.0GPa and the fracture toughness of 12 MPa.m1/2The three-point bending strength at room temperature is 900MPa or more, preferably 1000MPa or more, and the three-point bending strength at a high temperature of 800 ℃ is 750MPa or more, preferably 800MPa or more.
According to a second aspect of the present invention, there is provided a MAX phase high entropy ceramic matrix composite, the MAX phase high entropy ceramic matrix composite being produced by the method for producing a TiC enhanced MAX phase high entropy ceramic matrix composite according to the present invention.
Preferably, the TiC enhanced MAX phase high-entropy ceramic matrix composite material has a relative density of more than 94%, a Vickers hardness of more than 7.0GPa, and a fracture toughness of 12 MPa-m1/2The three-point bending strength at room temperature is 900MPa or more, preferably 1000MPa or more, and the three-point bending strength at a high temperature of 800 ℃ is 750MPa or more, preferably 800MPa or more.
The invention uses various high-purity single-phase MAX ceramic powders and TiC powders, prepares the MAX phase structure through subsequent sintering, and the submicron TiC is dispersed and distributed in the MAX phase high-entropy ceramic material matrix, thereby improving the comprehensive performance.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method of the MAX phase ceramic selects Ti2AlC、Nb2AlC、V2AlC、Cr2AlC and Ta2Any three or more of the AlC powders. Three or more elements are solid-dissolved at the M site of the MAX phase ceramic, and the comprehensive performance of the MAX phase ceramic material is improved by utilizing the high entropy effect brought by the multi-principal element.
2. In the early stage of material preparation, TiC particles are introduced into mixed powder in a mechanical ball milling mode, and a TiC second phase is introduced into a MAX-phase high-entropy ceramic matrix after drying, sieving, pre-pressing and pressure sintering so as to further improve the performance of the material.
3. The sintering mode adopted by the invention is spark plasma sintering, and has the advantages of high temperature rise speed, short sintering time, low sintering temperature and the like. When the mixed powder is subjected to the combined action of pulse current and axial pressure, the sintering densification is carried out more quickly and thoroughly, and the TiC toughened MAX phase high-entropy ceramic matrix composite material with the relative density of more than 94% is finally obtained.
Drawings
FIG. 1 is a graph of (Ti) prepared according to comparative example 21/3V1/3Nb1/3)2Scanning electron microscope picture of room temperature fracture of AlC ceramic material.
FIG. 2 is a scanning electron micrograph of a fracture at room temperature of the TiC enhanced MAX phase high entropy ceramic matrix composite prepared according to example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The technical solution of the present invention is further illustrated by the following specific examples.
Raw materials of reagents
Ti2AlC、Nb2AlC、V2AlC、Cr2AlC、Ta2AlC and TiC. MAX phase powder is available from Fosmann scientific Beijing (Limited) company, and has a particle size of no more than 15 μm and a purity of no less than 98%. TiC is purchased from Henan Shai composite research institute Co., Ltd, the powder granularity is 0.6-0.9 μm, and the purity is not lower than 99%.
Device
An electronic balance: huazhi electronics technologies, Inc./HZK-FA 110S;
ball mill: omnibearing planet ball type mill, Nanjing Nanda instruments ltd produces/QM-QX 4;
electric heating constant temperature vacuum drying oven: shanghai leap-into medical devices, Inc./HZK-25;
discharge plasma sintering furnace: nippon Siji corporation/LABOX-350.
Test method
Testing the relative density of the product by adopting an Archimedes drainage method;
testing the room temperature and high temperature bending strength of the sample by adopting a three-point bending strength method;
measuring the hardness of the sample by adopting a Vickers hardness method;
and testing the fracture toughness of the sample by adopting a single-side notched beam three-point bending fracture method.
Comparative example 1
Preparing a MAX phase ceramic material by:
step one, selecting Ti2AlC powder;
step two, adding Ti2Dispersing AlC powder, drying in a vacuum drying oven at 55 deg.C, vacuumizing to below 0.1MPa, closing the heating device after 2 hr, and taking out after the sample is cooled to room temperature; grinding the dried powder into fine powder by using a mortar, and sieving the fine powder by using a 200-mesh sieve;
step three, preparing a steel mould with the diameter of 19.8mm, spraying BN coating on the inner wall of the mould and the surface of a pressure head, placing the reaction sintering mixed powder into a steel mould, loading the pressure of 15MPa, and keeping the pressure for 5min to obtain a ceramic biscuit;
step four, preparing a graphite die with the diameter of 20mm and embedding graphite paper with the thickness of 0.1mm, placing the ceramic biscuit obtained in the step three in the graphite die, and sintering in a discharge plasma sintering furnace, wherein the sintering mode is as follows: heating to 750 deg.C at a heating rate of 100 deg.C/min under vacuum condition in a sintering furnace, maintaining for 10min, loading under 10MPa, heating to 1400 deg.C at a heating rate of 80 deg.C/min, maintaining for 10min, loading under 50MPa, reducing pressure and temperature after the heat preservation is finished, cooling the sample in the furnace, and finally preparing Ti2AlC ceramic material. Tests show that the density, the Vickers hardness, the fracture toughness, the room temperature three-point bending strength and the 800 ℃ high temperature three-point bending strength are respectively 97.4 percent, 4.1GPa and 6.6 MPa.m1/2，362MPa，341MPa。
Comparative example 2
Preparing a MAX phase high entropy ceramic material by the following steps:
step one, Ti is mixed according to the mole ratio of molecules2AlC:V2AlC:Nb2Weighing the powder with AlC being 1:1:1, and mixing to prepare mixed powder.
And step two, pouring the mixed powder obtained in the step one into a ball milling tank, adding absolute ethyl alcohol serving as a grinding aid, and placing the mixture into a planetary ball mill for ball milling and mixing, wherein the mass ratio of the absolute ethyl alcohol to the mixed powder is 2: 1.
The grinding balls are agate balls, the grinding balls with the diameter of 10-15 mm account for 80% of the total number of the grinding balls, the grinding balls with the diameter of 5-8 mm account for 20% of the total number of the grinding balls, the ball-material ratio is 6:1, the ball-milling rotating speed is 360rpm/min, and the ball-milling time is 10 hours.
And then, placing the mixed slurry containing 65% of solid phase volume fraction obtained after ball milling into a porcelain plate, placing the porcelain plate into a vacuum drying oven for drying, setting the temperature at 60 ℃, vacuumizing to below 0.1MPa, vacuumizing every 2h, closing a heating device after 8h, and taking out the sample after the sample is cooled to room temperature. Grinding the dried powder into fine powder by using a mortar, and sieving the fine powder by using a 200-mesh sieve to obtain mixed powder.
And step three, preparing a steel mould with the diameter of 19.8mm, spraying BN coating on the inner wall of the mould and the surface of the pressure head, placing the reaction sintering mixed powder into a steel mould, loading the pressure of 15MPa, and keeping the pressure for 5min to obtain the ceramic biscuit.
Step four, preparing a graphite die with the diameter of 20mm and embedding graphite paper with the thickness of 0.1mm, placing the ceramic biscuit obtained in the step four into the graphite die, and sintering in a discharge plasma sintering furnace, wherein the sintering mode is as follows: heating to 750 deg.C at a heating rate of 100 deg.C/min under vacuum condition in sintering furnace, maintaining for 10min, loading under 10MPa, heating to 1400 deg.C at a heating rate of 80 deg.C/min, maintaining for 10min, loading under 50MPa, lowering pressure, cooling, and furnace cooling to obtain the final product (Ti)1/3V1/3Nb1/3)2AlC ceramic material. Tests show that the density, the Vickers hardness, the fracture toughness, the room temperature three-point bending strength and the 800 ℃ high temperature three-point bending strength are respectively 99.2 percent, 9.2GPa and 8.2 MPa.m1/2，806MPa，802MPa。
The MAX-phase high-entropy ceramic fracture picture obtained by observing through a scanning electron microscope can be seen to show that the synthesized ceramic presents a typical MAX-phase layered structure (as shown in figure 1), and the structure can enable cracks to deflect and kink in the fracture process, consume the energy of crack propagation, prolong the path of crack propagation and further improve the strength of the material.
Example 1
The TiC enhanced MAX phase high-entropy ceramic composite material is prepared by the following steps:
step one, Ti is mixed according to the mole ratio of molecules2AlC:V2AlC:Nb2Weighing TiC powder accounting for 10% of the total mass of the TiC powder in the AlC-1: 1 ratio, mixing the TiC powder with MAX-phase ceramic powder, and mixing to prepare mixed powder.
And step two, pouring the mixed powder obtained in the step one into a ball milling tank, adding absolute ethyl alcohol as a grinding aid, and placing the mixture into a planetary ball mill for ball milling and mixing, wherein the mass ratio of the absolute ethyl alcohol to the mixed powder is 2: 1.
The grinding balls are agate balls, the grinding balls with the diameter of 10-15 mm account for 80% of the total number of the grinding balls, the grinding balls with the diameter of 5-8 mm account for 20% of the total number of the grinding balls, the ball-material ratio is 6:1, the ball-milling rotating speed is 360rpm/min, and the ball-milling time is 10 hours.
And then, placing the mixed slurry containing 65% of solid phase volume fraction obtained after ball milling into a porcelain plate, placing the porcelain plate into a vacuum drying oven for drying, setting the temperature at 60 ℃, vacuumizing to below 0.1MPa, vacuumizing every 2h, closing a heating device after 8h, and taking out the sample after the sample is cooled to room temperature. Grinding the dried powder into fine powder by using a mortar, and sieving the fine powder by using a 200-mesh sieve to obtain mixed powder.
And step three, preparing a steel mould with the diameter of 19.8mm, spraying BN coating on the inner wall of the mould and the surface of the pressure head, placing the reaction sintering mixed powder into a steel mould, loading the pressure of 15MPa, and keeping the pressure for 5min to obtain the ceramic biscuit.
Step four, preparing a graphite die with the diameter of 20mm and embedding graphite paper with the thickness of 0.1mm, placing the ceramic biscuit obtained in the step four into the graphite die, and sintering in a discharge plasma sintering furnace, wherein the sintering mode is as follows: heating to 750 deg.C at a heating rate of 100 deg.C/min in vacuum state of sintering furnace, holding for 10min, loading under 10MPa, heating to 1400 deg.C at a heating rate of 80 deg.C/min, holding for 10min, loading under 50MPa, reducing pressure and temperature after holding, cooling sample in furnace, and finally preparing the product (Ti) containing 10 wt% TiC1/3V1/3Nb1/3)2AlC high-entropy ceramic composite material. Tests show that the density, the Vickers hardness, the fracture toughness, the room temperature three-point bending strength and the 800 ℃ high temperature three-point bending strength are respectively 97.2 percent, 8.3GPa and 13.2 MPa.m1/2，1110MPa，899MPa。
The sintering temperature, the heat preservation time, the heating rate and the loading pressure in the fourth step are in other ranges specified by the invention, and basically the same effect can be achieved.
The TiC enhanced MAX phase high-entropy ceramic matrix composite fracture picture obtained by observing through a scanning electron microscope can show that the synthesized ceramic presents a typical MAX phase layered structure (as shown in figure 2), and the structure can enable cracks to deflect and kink in the fracture process, consume crack propagation energy, prolong crack propagation paths and improve the strength of the material. In addition, fine and dispersed second-phase particles are uniformly distributed in the matrix of the composite ceramic, the second-phase particles can pin dislocation in the fracture process, the second-phase particles can be bypassed in the crack propagation process, and pores left after the second-phase particles are pulled out can also be seen from the figure, which can consume the energy of crack propagation, so that the mechanical property of the material is further improved.
Example 2
The TiC enhanced MAX phase high-entropy ceramic composite material is prepared by the following steps:
step one, Ti is mixed according to the mole ratio of molecules2AlC:V2AlC:Nb2Weighing powder with AlC being 1:1:1, weighing TiC powder with 15% of total mass of the powder, mixing the powder with MAX phase ceramic powder, and mixing to prepare mixed powder.
And step two, pouring the mixed powder obtained in the step one into a ball milling tank, adding absolute ethyl alcohol serving as a grinding aid, and placing the mixture into a planetary ball mill for ball milling and mixing, wherein the mass ratio of the absolute ethyl alcohol to the mixed powder is 2: 1.
The grinding balls are agate balls, the grinding balls with the diameter of 10-15 mm account for 80% of the total number of the grinding balls, the grinding balls with the diameter of 5-8 mm account for 20% of the total number of the grinding balls, the ball-material ratio is 6:1, the ball-milling rotating speed is 360rpm/min, and the ball-milling time is 10 hours.
However, the mixed slurry containing 65% of solid phase volume fraction obtained after ball milling is placed in a porcelain plate, is placed in a vacuum drying oven for drying, the temperature is set to be 60 ℃, the mixed slurry is vacuumized to be below 0.1MPa, the mixed slurry is vacuumized every 2 hours, after 8 hours, the heating device is closed, and the mixed slurry is taken out after the sample is cooled to the room temperature. Grinding the dried powder into fine powder by using a mortar, and sieving the fine powder by using a 200-mesh sieve to obtain mixed powder.
And step three, preparing a steel mould with the diameter of 19.8mm, spraying BN coating on the inner wall of the mould and the surface of the pressure head, placing the reaction sintering mixed powder into a steel mould, loading the pressure of 15MPa, and keeping the pressure for 5min to obtain the ceramic biscuit.
Step four, preparing a graphite die with the diameter of 20mm and embedding graphite paper with the thickness of 0.1mm, placing the ceramic biscuit obtained in the step four into the graphite die, and sintering in a discharge plasma sintering furnace, wherein the sintering mode is as follows: heating to 750 ℃ at a heating rate of 100 ℃/min under a vacuum state of a sintering furnace, preserving heat for 10min, loading pressure for 10MPa, heating to 1400 ℃ at a heating rate of 80 ℃/min, preserving heat for 10min, loading pressure for 50MPa, then reducing pressure and temperature after heat preservation, cooling a sample along with the furnace, and finally preparing the titanium carbide (Ti) containing 15 wt% of TiC1/3V1/3Nb1/3)2AlC high-entropy ceramic composite material. Tests show that the density, the Vickers hardness, the fracture toughness, the room-temperature three-point bending strength and the 800 ℃ high-temperature three-point bending strength are respectively 94.6 percent, 7.5GPa and 16.8 MPa.m1/2，1121MPa，839MPa。
The sintering temperature, the heat preservation time, the heating rate and the loading pressure in the fourth step are in other ranges specified by the invention, and basically the same effect can be achieved.
The results of the examples are summarized:
Figure BDA0003234596420000101
the MAX-phase high-entropy ceramic matrix composite with excellent comprehensive mechanical properties is obtained by utilizing mixed powder of various MAX-phase powders and TiC and carrying out in-situ reaction at high temperature. The composite material has a fine lamellar structure, and the phenomena of deflection, kinking and the like of cracks can exist in the fracture process, so that the energy of crack propagation is consumed, and the strength and the fracture toughness of the material are improved. The submicron TiC second phase has the characteristics of high hardness, high melting point, good high-temperature strength, good and stable combination with the MAX phase interface and the like, and the addition of TiC enables the crystal grains of the MAX phase matrix to be refined, so that the comprehensive mechanical property of the MAX phase high-entropy ceramic material is further improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A method for preparing MAX phase high-entropy ceramic matrix composite material comprises the following steps:
the method comprises the following steps: mixing TiC powder and MAX phase powder, wherein the MAX phase powder is any more than three transition metal MAX phase carbide powder;
step two: dispersing the mixed powder obtained in the step one in a grinding aid, carrying out ball milling to obtain ceramic slurry, carrying out vacuum drying, and sieving;
step three: placing the mixed powder obtained in the step two in a steel die, and performing pre-pressing forming to obtain a ceramic biscuit;
step four: and (4) placing the ceramic biscuit obtained in the step three in a graphite mold, and performing pressure sintering in a vacuum environment to obtain the TiC enhanced MAX phase high-entropy ceramic matrix composite.
2. The method of claim 1, wherein in step one, the MAX phase powder is selected from Ti2AlC、Nb2AlC、V2AlC、Cr2AlC and Ta2Any three or more of AlC;
preferably, in the step one, the mass fraction of the TiC powder is 5 wt% to 20 wt%, more preferably 10 wt% to 15 wt%, of the total mass of the mixed powder; and the particle size of the TiC powder is 0.6-0.9 mu m, and the purity is not lower than 99%.
3. The method of claim 1 or 2,
in the first step, the first step is carried out,
the molar ratio of the MAX phase powder to the molecule number is equal molar ratio, the particle size of the MAX phase powder is not more than 15 μm, and the purity is not less than 98%.
4. The method of any one of claims 1 to 3,
in the second step, the first step is carried out,
the ball-material ratio is (5-10): 1, the ball milling rotation speed is 200-400 rpm/min, and the ball milling time is 6-10 h;
preferably, the grinding balls are agate balls, and the grinding aid is absolute ethyl alcohol;
preferably, the vacuum drying oven is vacuumized until the pressure is less than 0.1MPa, and the temperature for vacuum drying is set to be 55-60 ℃;
preferably, vacuumizing once every two hours, removing volatilized gas, turning off heating after 6-10 hours, maintaining the vacuum state, and taking out after the sample is cooled to room temperature;
preferably, the size of the sieved screen is 200-225 meshes, and powder particles which cannot pass through the screen are pulverized by using a mortar and then pass through the screen.
5. The method of any one of claims 1 to 4,
in the third step, the first step is carried out,
spraying BN coating on the inner wall of the steel mould and the surface of the pressure head before sample loading; and (3) loading the processed reaction sintering mixed powder into a steel mould, prepressing under the pressure of 15-30 MPa, maintaining the pressure for 5-10 min, and then demoulding.
6. The method of any one of claims 1 to 5,
in the fourth step of the method, the first step of the method,
placing the ceramic biscuit body obtained after the pre-pressing in a graphite mould lined with graphite paper, and sintering;
preferably, the ceramic green body is sintered by spark plasma sintering.
7. The method of claim 6, wherein,
the discharge plasma sintering conditions are as follows: and under the vacuum state of the sintering furnace, raising the temperature to 750-800 ℃ at the temperature rise rate of 80-120 ℃/min, preserving the heat for 10min, loading the pressure to 10-15 MPa, raising the temperature to 1350-1500 ℃ at the temperature rise rate of 50-100 ℃/min, preserving the heat for 8-15 min, wherein the loading pressure is 45-55 MPa, reducing the pressure and the temperature after the heat preservation, and cooling the sample along with the furnace.
8. The method of any one of claims 1 to 7,
the prepared TiC enhanced MAX phase high-entropy ceramic matrix composite material has the relative density of more than 94 percent, the Vickers hardness of more than 7.0GPa and the fracture toughness of 12 MPa.m1/2The room-temperature three-point bending strength is 900MPa or more, preferably 1000MPa or more; and a three-point bending strength at a high temperature of 800 ℃ of 750MPa or more, preferably 800MPa or more.
9. A TiC enhanced MAX phase high entropy ceramic matrix composite material prepared according to the method of any one of claims 1 to 8.
10. The TiC enhanced MAX phase high-entropy ceramic-based composite of claim 9, wherein the TiC enhanced MAX phase high-entropy ceramic-based composite has a relative density of 94% or more, a vickers hardness of 7.0GPa or more, and a fracture toughness of 12 MPa-m1/2The three-point bending strength at room temperature is 900MPa or more, preferably 1000MPa or more, and the three-point bending strength at a high temperature of 800 ℃ is 750MPa or more, preferably 800MPa or more.
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