Preparation method of high-entropy metal ceramic material and high-entropy metal ceramic material

Abstract

The present disclosure provides a method for preparing a high-entropy cermet material and a high-entropy cermet material, relating to the field of ceramic technology. The method comprises: preparing a CuzFeNiCryX high-entropy alloy powder; configuring a cermet composite powder based on the CuzFeNiCryX high-entropy alloy powder and MC carbide; and ball-milling the cermet composite powder to obtain a MC-CuzFeNiCryX cermet powder having a dispersed distribution of carbide particles; and using a powder thermoforming technique to prepare the MC-CuzFeNiCryX cermet powder into a cermet block to obtain a high-entropy cermet material. The present disclosure improves the corrosion resistance of the high-entropy cermet material and increases the service life and stability of the reactor.

Description

Technical Field

[0001] The embodiments of the present disclosure relate to the technical field of ceramic powders, and in particular to a preparation method of a high-entropy metal ceramic material and a high-entropy metal ceramic material. Background Art

[0002] Lead-based reactors, using liquid lead or lead-bismuth alloys as coolant, currently offer significant advantages in safety, affordability, miniaturization, and sustainability. Dynamic and static load-bearing components, such as supports and guide tubes, play a critical role in maintaining stable reactor operation. However, these components are prone to corrosion failure during service, seriously impacting reactor operational stability.

[0003] To address these issues, developing structural materials with superior corrosion resistance is an effective approach. WC-based cermets, known for their exceptional hardness, corrosion resistance, and wear resistance, are known to be effective. However, under long-term radiation exposure, the Co binder phase in WC-based cermets gradually excites and forms Co-60 isotopes, extending the radiation half-life. This increases maintenance time and nuclear fuel shielding costs, significantly limiting their widespread application in the nuclear power sector. Summary of the Invention

[0004] The purpose of the present disclosure is to provide a preparation method of a high-entropy metal-ceramic material and a high-entropy metal-ceramic material, thereby overcoming, at least to a certain extent, the problem of poor performance of high-entropy metal-ceramic materials caused by the limitations and defects of related technologies.

[0005] According to one aspect of the present disclosure, a method for preparing a high entropy metal ceramic material is provided, comprising:

[0006] Preparation of Cu z FeNiCr y X high entropy alloy powder, based on Cu z FeNiCr y X high entropy alloy powder and MC carbide are used to prepare metal ceramic composite powder, and the metal ceramic composite powder is ball milled to obtain MC-Cu with dispersed carbide particles. z FeNiCr y X metal ceramic powder;

[0007] MC-Cu is formed by powder hot forming technology z FeNiCr y X cermet powder is prepared into cermet blocks to obtain high entropy cermet materials.

[0008] In an exemplary embodiment of the present disclosure, the Cu z FeNiCr yX high entropy alloy powder is prepared by vacuum atomization method and is used to prepare Cu z FeNiCr y The process parameters of X high entropy alloy powder include: air pressure 1~10 MPa, air flow velocity 100~200 mm / s, and air flow injection angle 30~90°.

[0009] In an exemplary embodiment of the present disclosure, the Cu z FeNiCr y X in the X high entropy alloy powder includes any one of Co, Al and Ti; Cu z FeNiCr y The range of z and y in X high entropy alloy powder is 0~1.0 at%, Cu z FeNiCr y The particle size of X high entropy alloy powder is 0.1~15 μm.

[0010] In an exemplary embodiment of the present disclosure, the MC carbide is WC, WC-Cr3C2 or WC-B4C, and the particle size of the MC carbide is 1-3 μm.

[0011] In an exemplary embodiment of the present disclosure, the MC-Cu z FeNiCr y X cermet powder contains 5~40wt% Cu z FeNiCr y X high entropy alloy powder and 60~95 ​​wt% MC carbide.

[0012] In an exemplary embodiment of the present disclosure, 0.1-1.0 wt % of a grain inhibitor and 0.1-1.0 wt % of an antioxidant are added during the ball milling mixing process, and the grain inhibitor includes chromium carbide and vanadium carbide.

[0013] In an exemplary embodiment of the present disclosure, the ball milling time is 20 to 40 hours, the ball milling rotation mode is in a cyclic forward-reverse alternation, the ball milling speed is 100 to 300 r / min, and the MC-Cu obtained after ball milling is z FeNiCr y The particle size of X metal ceramic powder is 0.5~5 μm.

[0014] In an exemplary embodiment of the present disclosure, the MC-Cu z FeNiCr y X metal ceramic powder is prepared into a metal ceramic block, comprising:

[0015] MC-Cu zFeNiCr y X metal ceramic powder is dried and kept warm, and MC-Cu is formed by powder hot forming technology. z FeNiCr y The X metal ceramic powder is sintered to prepare the high entropy metal ceramic material.

[0016] In an exemplary embodiment of the present disclosure, the sintering pressure is 10-40 MPa, the sintering temperature is 900-1400° C., and the holding time is 5-120 min.

[0017] According to one aspect of the present disclosure, a high-entropy metal-ceramic material is provided. The high-entropy metal-ceramic material is prepared according to any one of the above-mentioned methods for preparing a high-entropy metal-ceramic material.

[0018] In the technical solution provided in the embodiments of the present disclosure, on the one hand, high entropy alloy powder is prepared based on the unique characteristics of high entropy alloy such as resistance to radiation damage, high oxidation resistance and good wettability. The use of high entropy alloy as the metal phase can reduce the proportion of active element components inside the coating and greatly improve the material's resistance to radiation damage. Taking full account of the high wettability, high toughness, corrosion resistance and radiation damage resistance of the bonding phase of the composite material, four elements with similar atomic radius, Fe, Ni, Cr and Cu, are selected as the basic elements of high entropy alloy powder to form a high entropy alloy with FCC structure. Among them, the three elements Fe, Ni and Cr can increase the chaotic entropy of the alloy and promote the formation of high entropy alloy; the addition of Cr element is also beneficial to the formation of Cr2O3, which improves the corrosion resistance of the alloy; the addition of Cu element improves the wettability of high entropy alloy and carbide hard phase, and improves the density and cohesive strength of the composite material; the doping of elements such as Co, Al and Ti can adjust the degree of lattice distortion of the FCC phase of the high entropy alloy, change the mechanical properties of the alloy, and realize the functional diversification of the composite material. On the other hand, the use of Cu z FeNiCr y X high-entropy alloy powder replaces the Co binding phase. Compared with traditional metal ceramics, the metal phase is high-entropy to obtain a high-entropy metal-ceramic composite material with high strength and toughness and excellent resistance to radiation damage. The prepared high-entropy metal-ceramic material has better corrosion resistance, which can significantly improve the service life and stability of the reactor and expand its application range. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The accompanying drawings are incorporated into and constitute a part of the specification, illustrate embodiments consistent with the present disclosure, and together with the specification, are used to explain the principles of the present disclosure. Obviously, the drawings described below are only some embodiments of the present disclosure, and those skilled in the art can derive other drawings based on these drawings without inventive effort.

[0020] Figure 1 A flow chart schematically illustrates a method for preparing a high entropy metal ceramic material in an embodiment of the present disclosure.

[0021] Figure 2 The schematic diagram of the process of preparing metal ceramic blocks is shown schematically.

[0022] Figure 3 This is a surface morphology of the high entropy alloy powder prepared in Example 1 of the present disclosure.

[0023] Figure 4 This is a cross-sectional morphology diagram of the high-entropy metal ceramic block prepared according to Example 1 in the embodiments of the present disclosure.

[0024] Figure 5 These are the test results of friction and wear rates of the high-entropy metal ceramic blocks prepared according to Examples 1 to 3.

[0025] Figure 6 These are the neutral salt spray corrosion performance test results of the metal ceramic blocks prepared according to Example 3 and Example 4 in the embodiments of the present disclosure.

[0026] Figure 7 The hardness and bending strength test results of the metal ceramic blocks prepared according to Example 3 and the comparative example are shown. DETAILED DESCRIPTION

[0027] Example embodiments will now be described more fully with reference to the accompanying drawings. However, example embodiments can be implemented in a variety of forms and should not be construed as limited to the examples set forth herein; rather, these embodiments are provided so that the present disclosure will be more comprehensive and complete and will fully convey the concepts of the example embodiments to those skilled in the art. The described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. In the following description, many specific details are provided to provide a full understanding of the embodiments of the present disclosure. However, those skilled in the art will appreciate that the technical solutions of the present disclosure may be practiced while omitting one or more of the specific details, or that other methods, components, devices, steps, etc. may be employed. In other cases, well-known technical solutions are not shown or described in detail to avoid obscuring various aspects of the present disclosure.

[0028] The terms "a", "an", "the" and "said" are used in this specification to indicate the presence of one or more elements / components, etc.; the terms "including" and "having" are used to express open-ended inclusion and mean that additional elements / components, etc. may exist in addition to the listed elements / components, etc.; the terms "first" and "second" are used only as labels and are not intended to limit the quantity of their objects.

[0029] In order to solve the above technical problems, the present disclosure provides a method for preparing a high entropy metal ceramic material, which is used to prepare a high entropy metal ceramic material. Figure 1 As shown in , it mainly includes the following steps:

[0030] In step S110, Cu z FeNiCr y X high entropy alloy powder is ball-milled with MC carbide to obtain MC-Cu with dispersed carbide particles. z FeNiCr y X metal ceramic powder;

[0031] In step S120, MC-Cu is formed by powder hot forming technology. z FeNiCr y X cermet powder is prepared into cermet blocks to obtain high entropy cermet materials.

[0032] Next, the preparation method of the high entropy metal ceramic material in the embodiment of the present disclosure is described in detail.

[0033] In step S110, Cu z FeNiCr y X high entropy alloy powder is ball-milled with MC carbide to obtain MC-Cu with dispersed carbide particles. z FeNiCr y X cermet powder.

[0034] In the embodiment of the present disclosure, Cu z FeNiCr y X high entropy alloy powder is a powder prepared by vacuum atomization. z FeNiCr y The process of preparing CuX high entropy alloy powder z FeNiCr y The process parameters of X high entropy alloy powder include: air pressure of 1~10 MPa, air flow velocity of 100~200 mm / s, and air flow injection angle of 30~90°.

[0035] In some embodiments, high entropy alloy is a new type of multi-principal alloy material, which has high strength, high hardness, excellent corrosion resistance, high temperature softening resistance and unique radiation resistance. z FeNiCr y The element X in the X high entropy alloy powder includes any one of Co, Al and Ti, which is determined according to actual needs. z FeNiCr yThe range of z in X high entropy alloy powder is 0~1.0 at%, Cu z FeNiCr y The range of y in X high entropy alloy powder is 0~1.0 at%, Cu z FeNiCr y The particle size of X high-entropy alloy powder ranges from 0.1 to 15 μm. High-entropy alloys offer resistance to radiation damage, high oxidation resistance, and good wettability. Using high-entropy alloy powder as the metal phase can reduce the proportion of active elements within the coating, significantly improving the material's resistance to radiation damage.

[0036] In the embodiment of the present disclosure, MC-Cu is prepared based on the unique characteristics of high entropy alloy such as resistance to radiation damage, high oxidation resistance and good wettability. z FeNiCr y X new metal-ceramic composite powder. The use of high entropy alloy as the metal phase can reduce the proportion of active element components inside the coating and greatly improve the material's resistance to radiation damage. Furthermore, the disclosed embodiment fully considers the high wettability, high toughness, corrosion resistance and radiation damage resistance of the composite material's bonding phase, and selects Fe, Ni, Cr and Cu, four elements with similar atomic radius, as the basic elements of the high entropy alloy powder to form a high entropy alloy with FCC structure. Among them, the three elements Fe, Ni and Cr can increase the chaotic entropy of the alloy and promote the formation of high entropy alloys; the addition of Cr elements is also beneficial to the formation of Cr2O3, which improves the corrosion resistance of the alloy; the addition of Cu elements can increase the wettability of the high entropy alloy and the carbide hard phase, and improve the density and cohesive strength of the composite material; the doping of elements such as Co, Al and Ti can adjust the degree of lattice distortion of the FCC phase of the high entropy alloy, change the mechanical properties of the alloy, and achieve functional diversification of the composite material.

[0037] The MC carbide includes any one of WC, WC-Cr3C2 and WC-B4C, and is determined according to actual needs. The particle size of the MC carbide is 1~3 μm.

[0038] In some embodiments, Cu z FeNiCr y The weight percentage of the X high entropy alloy powder is 5-40 wt%, and the weight percentage of the MC carbide is 60-95 wt%.

[0039] After obtaining Cu z FeNiCr y After X high entropy alloy powder and MC carbide, Cu z FeNiCr y X high entropy alloy powder and MC carbide are ball milled to prepare MC-Cu z FeNiCry X Metal Ceramic Powder, MC-Cu z FeNiCr y X metal ceramic powder can be MC-Cu with dispersed carbide particles. z FeNiCr y X metal ceramic powder. MC-Cu z FeNiCr y X cermet powder mainly contains 5~40 wt% Cu z FeNiCr y X high entropy alloy powder and 60~95 ​​wt% MC carbide. z FeNiCr y X high entropy alloy powder is used as the metal phase.

[0040] During the ball milling process, 0.1~1.0 wt% of a grain inhibitor and 0.1~1.0 wt% of an antioxidant may also be added. The grain inhibitor is used to inhibit grain growth during sintering, and the antioxidant is used to inhibit oxidation during sintering. Excessively large grains and oxidation will weaken the hardness, fracture toughness and wear resistance of the material. The grain inhibitor may include two complex carbides. The two complex carbides may include chromium carbide and vanadium carbide, wherein the ratio of chromium carbide to vanadium carbide may be any suitable ratio, as long as the weight percentage of chromium carbide and vanadium carbide is 0.1~1.0 wt%. The antioxidant may be carbohydrazide. It should be noted that when adding a grain inhibitor and an antioxidant during the ball milling process, the amount of the grain inhibitor and the antioxidant added may be the same.

[0041] Furthermore, the metal-ceramic composite powder can be weighed and proportioned, and the metal-ceramic composite powder includes Cu z FeNiCr y X high entropy alloy powder and MC carbide, in addition to the grain inhibitor and antioxidant. Of course, the metal ceramic composite powder can also contain only Cu z FeNiCr y X high entropy alloy powder and MC carbide, without grain inhibitors and antioxidants. Based on this, the prepared metal-ceramic composite powder can be ball-milled with deionized water in a preset ratio, which can be 1:2 or other suitable ratios, depending on actual needs.

[0042] During the ball milling process, the ball milling method can be wet milling. For example, the ball milling time can be 20 to 40 hours, and the rotation method during the ball milling process is to rotate in a forward-reverse alternating manner according to a cycle, and 2 to 5 hours can be used as a cycle for forward-reverse alternating rotation. The rotation speed during the ball milling process is 100 to 300 r / min, and the MC-Cu obtained after ball milling is z FeNiCr y The particle size of X metal ceramic powder is 0.5~5 μm.

[0043] The embodiment of the present disclosure adopts measures such as long aging, forward-reverse alternation and wet ball milling to achieve uniform distribution of WC particles and high entropy alloy phases, which not only effectively solves the problem of WC particle segregation in the process of mixing WC-based powder by traditional ball milling, but also avoids the problem of sticking of high entropy alloy phases at high temperatures, ensuring the stability of the content of each phase in the composite powder. Furthermore, the embodiment of the present disclosure adopts a grain inhibitor to inhibit the growth of carbide grains during high-temperature sintering, which can simultaneously inhibit the excessive growth of nano-scale and submicron-scale carbide particles during the sintering process, and effectively improve the mechanical properties of the composite material. The embodiment of the present disclosure adds an antioxidant to the composite powder to eliminate oxide impurities generated during the ball milling of the composite powder, which not only helps to improve the density of the sintered block, but also can inhibit crack initiation and expansion behavior under high external stress, thereby improving the overall fracture toughness of the material. In addition, by inhibiting crack expansion behavior, the number of corrosion channels can be reduced, further improving the corrosion resistance of the material.

[0044] Next, in step S120, MC-Cu is formed by powder hot forming technology. z FeNiCr y X cermet powder is prepared into cermet blocks to obtain high entropy cermet materials.

[0045] In the embodiment of the present disclosure, the powder hot forming technology includes any one of hot pressing sintering, hot isostatic pressing and spark plasma sintering. For example, MC-Cu z FeNiCr y X metal ceramic powder is dried and kept warm, and MC-Cu is formed by powder hot forming technology. z FeNiCr y X metal ceramic powder is sintered to prepare high entropy metal ceramic material. z FeNiCr y The X metal ceramic powder is placed in a blast drying oven for heat preservation. The drying temperature can be 80° C. to 90° C., and the heat preservation time can be 10 to 12 hours.

[0046] Furthermore, the MC-Cu after heat preservation can be z FeNiCry The X metal ceramic powder is sieved, and the sieve used for sieving can be 200 mesh or 300 mesh, etc., which is determined according to actual needs, as long as the powder particles can be fine and evenly dispersed.

[0047] On this basis, MC-Cu can be formed by powder hot forming technology. z FeNiCr y X metal ceramic powder is prepared into metal ceramic blocks. In some embodiments, MC-Cu z FeNiCr y The X cermet powder is sintered to prepare a cermet block, so that the cermet block is used as a high entropy cermet material.

[0048] During the sintering process, the sintering pressure is 10~40 MPa, the sintering temperature is 900~1400℃, and the holding time is 5~120 min.

[0049] Based on this, reference Figure 2 As shown in , the process of preparing the metal ceramic block in the embodiment of the present disclosure may mainly include the following steps:

[0050] First, the elemental metal is melted by vacuum atomization to obtain high entropy alloy powder. The high entropy alloy powder and MC carbide are mixed to obtain a batch, and a grain inhibitor and an antioxidant are added to the batch to obtain a metal-ceramic composite powder, which is then ball-milled. After the ball-milling process, the powder is dried and sieved, and then sintered to obtain MC-Cu z FeNiCr y X metal ceramic block, so as to use it as a high entropy metal ceramic material.

[0051] In the embodiment of the present disclosure, high performance MC-Cu is achieved by powder hot forming technology such as hot pressing sintering, hot isostatic pressing and spark plasma sintering. z FeNiCr y Stable preparation of X metal ceramic blocks. The appropriate sintering pressure and temperature ratio can avoid the overflow and loss of liquid high entropy alloy along the gap between the hot pressing mold and the sample, effectively ensuring the stability of the sample structure and performance. Under the process parameters disclosed in the present invention, the high entropy alloy bonding phase can be fully melted into a liquid phase to coat WC particles of different particle sizes and tightly bond each hard particle, effectively improving the density and mechanical properties of the composite material. In addition, the embodiment of the present disclosure combines the high corrosion resistance of carbides and the high resistance to radiation damage of high entropy alloys, and is supported by powder mixing technology and hot pressing molding technology with the characteristics of long aging, positive-reverse alternation and wet ball milling, and adopts Cu z FeNiCr yX high entropy alloy replaces the Co binder phase. Compared with traditional metal ceramics, high entropy metal ceramics have better corrosion resistance and can significantly improve the service life and stability of the reactor.

[0052] Next, the preparation method of the high entropy metal ceramic material provided by the present disclosure is described in detail with reference to the examples.

[0053] Example 1

[0054] In this example, a WC-10wt%CuFeNiCrCo metal ceramic block is prepared, and the specific implementation steps are as follows:

[0055] Step 1: Prepare CuFeNiCrCo high-entropy alloy powder using vacuum air atomization equipment. The vacuum air atomization process parameters include: air pressure of 3 MPa, air velocity of 150 mm / s, and air injection angle controlled at 45°. The resulting CuFeNiCrCo high-entropy alloy powder has a particle size of 0.1 to 15 μm.

[0056] Step 2: Weigh and mix a metal-ceramic composite powder, such as a WC-CuFeNiCrCo composite powder. When a grain suppressant and an antioxidant are added, the metal-ceramic composite powder includes 10 wt% of a CuFeNiCrCo high-entropy alloy powder, 90 wt% of a WC powder, 0.4 wt% of a grain suppressant (complex carbide), and 0.4 wt% of an antioxidant.

[0057] Step 3: The WC-CuFeNiCrCo composite powder and deionized water were ball-milled in a ratio of 1:2 for 30 h. The rotation mode of the ball mill was alternating forward and reverse (one cycle of 5 h) at a speed of 200 r / min. The particle size of the composite powder after ball milling was 0.5~5 μm.

[0058] Step 4: Place the ball-milled composite powder in a forced air drying oven at 80° C. for 10 h. After drying, sieve the composite powder using a 200-mesh sieve to ensure that the powder particles are fine and evenly dispersed.

[0059] Step 5: Prepare the WC-CuFeNiCrCo metal ceramic block by spark plasma sintering technology, wherein the sintering pressure is 30 MPa, the sintering temperature is 1300° C., and the holding time is 5 min.

[0060] Figure 3The figure shows the morphology of the prepared CuFeNiCrCo high-entropy alloy powder. As can be seen from the figure, the prepared CuFeNiCrCo high-entropy alloy powder is spherical, with a dense and smooth powder surface and no defects such as holes, indicating excellent powder preparation. The overall powder particle size is less than 15 μm, meeting the requirements of subsequent processing.

[0061] Figure 4 This is a cross-sectional SEM image of the WC-CuFeNiCrCo cermet block prepared according to Example 1. As can be seen from the image, most of the WC is tightly bonded to the CuFeNiCrCo high-entropy alloy, and the overall structure of the material is dense, with no obvious defects such as large pores and cracks.

[0062] Example 2

[0063] In this example, a WC-10wt%CuFeNiCrCo metal ceramic block was prepared. The specific implementation steps are as follows:

[0064] Step 1: Prepare CuFeNiCrCo high-entropy alloy powder using vacuum air atomization equipment. The vacuum air atomization process parameters include: air pressure of 5 MPa, air velocity of 100 mm / s, and air injection angle controlled at 45°. The resulting CuFeNiCrCo high-entropy alloy powder has a particle size of 0.1–15 μm.

[0065] Step 2: Weigh and mix the metal-ceramic composite powder. The metal-ceramic composite powder can be, for example, a WC-CuFeNiCrCo composite powder. When a grain inhibitor and an antioxidant are added, the metal-ceramic composite powder includes 10 wt% of CuFeNiCrCo high-entropy alloy powder, 90 wt% of WC powder, 0.8 wt% of grain inhibitor (complex phase carbide) and 0.8 wt% of antioxidant.

[0066] Step 3: The mixed metal-ceramic composite powder and deionized water were ball-milled in a ratio of 1:2 for 40 h. The rotation mode of the ball mill was alternating forward and reverse (one cycle was 5 h) at a speed of 300 r / min. The particle size of the composite powder after ball milling was 0.5~5 μm.

[0067] Step 4: The ball-milled composite powder is kept at 80° C. in a forced air drying oven for 5 h, and then sieved using a 400-mesh sieve to ensure that the powder particles are fine and evenly dispersed.

[0068] Step 5: Prepare the WC-CuFeNiCrCo metal ceramic block by spark plasma sintering technology, wherein the sintering pressure is 20 MPa, the sintering temperature is 900 °C, and the holding time is 10 min.

[0069] Example 3

[0070] This example is used to prepare a WC-10wt%CuFeNiCrCo cermet block, and the specific implementation steps are as follows:

[0071] Step 1: Prepare CuFeNiCrCo high-entropy alloy powder using vacuum air atomization equipment. The vacuum air atomization process parameters include: air pressure of 10 MPa, air velocity of 200 mm / s, and air injection angle controlled at 45°. The resulting CuFeNiCrCo high-entropy alloy powder has a particle size of 0.1–15 μm.

[0072] Step 2: Weigh and mix the metal-ceramic composite powder. The metal-ceramic composite powder can be, for example, a WC-CuFeNiCrCo composite powder. When a grain inhibitor and an antioxidant are added, the metal-ceramic composite powder includes 10 wt% of CuFeNiCrCo high-entropy alloy powder, 90 wt% of WC powder, 0.2 wt% of grain inhibitor (complex phase carbide) and 0.2 wt% of antioxidant.

[0073] Step 3: The mixed composite powder and deionized water were ball-milled in a ratio of 1:2 for 20 h. The rotation mode was alternating forward and reverse (one cycle was 5 h) at a speed of 200 r / min. The particle size of the powder after ball milling was 0.5~5 μm.

[0074] Step 4: The ball-milled composite powder was kept at 80° C. in a forced air drying oven for 10 h, and then sieved using a 200-mesh sieve to ensure that the powder particles were fine and evenly dispersed.

[0075] Step 5: Prepare the WC-CuFeNiCrCo metal ceramic block by spark plasma sintering technology, wherein the sintering pressure is 40 MPa, the sintering temperature is 1100° C., and the holding time is 10 min.

[0076] Figure 5 Figure 1 shows the friction and wear performance test results of the WC-CuFeNiCrCo cermet blocks prepared in Examples 1 to 3. The corresponding sample numbers for Examples 1 to 3 are WC-HEA-1, WC-HEA-2, and WC-HEA-3, respectively. As can be seen from the figure, the wear rates of the three groups of cermet blocks are more than four times lower than that of the control sample (316L stainless steel), demonstrating superior wear resistance. In particular, the wear rate of the sample in Example 1 is relatively low, at only 0.96×10 -6 mm 3 / Nm.

[0077] Furthermore, the corrosion resistance of the WC-CuFeNiCrCo cermet prepared in Example 3 was tested using a neutral salt spray corrosion test. The test conditions included a 5.0% NaCl solution, corrosion for 720 h, and five parallel specimens. Each specimen was sealed before testing. After the test, the corrosion resistance of the specimens was rated according to the GBT 6461-2002 standard. Figure 6 : The neutral salt spray corrosion performance test results of each sample. It can be seen from the figure that after 720 hours of corrosion, the corrosion level of the metal ceramic block prepared in Example 3 is stable at level 9, showing excellent corrosion resistance.

[0078] Example 4

[0079] This example is used to prepare a WC-10wt%CuFeNiCrCo cermet block, and the specific implementation steps are as follows:

[0080] Step 1: Prepare CuFeNiCrCo high-entropy alloy powder using vacuum air atomization equipment. The process parameters for preparing the CuFeNiCrCo high-entropy alloy powder include: air pressure of 10 MPa, air velocity of 200 mm / s, and an air injection angle of 45°. The resulting CuFeNiCrCo high-entropy alloy powder has a particle size of 0.1 to 15 μm.

[0081] Step 2: Weigh and mix the metal-ceramic composite powder. The metal-ceramic composite powder can be a WC-CuFeNiCrCo composite powder. Without adding a grain inhibitor and an antioxidant, the metal-ceramic composite powder includes 10 wt% of CuFeNiCrCo high entropy alloy powder and 90 wt% of WC powder.

[0082] Step 3: The metal-ceramic composite powder and deionized water are ball-milled in a ratio of 1:2. The ball-milling time is 20 hours. The rotation mode is forward-reverse alternation (one cycle is 5 hours). The speed is 200 r / min. The powder particle size after ball milling is 0.5~5 μm.

[0083] Step 4: The ball-milled metal-ceramic composite powder is kept at 80° C. in a forced air drying oven for 10 h, and then sieved using a 200-mesh sieve to ensure that the powder particles are fine and evenly dispersed.

[0084] Step 5: Prepare a WC-CuFeNiCrCo metal ceramic block by spark plasma sintering, wherein the sintering pressure is 40 MPa, the sintering temperature is 1100° C., and the holding time is 10 min.

[0085] Compared to Example 3, Example 4 did not add a grain inhibitor or antioxidant during the ball milling process. The deposited coatings of Examples 3 and 4 were subjected to neutral salt spray corrosion performance testing. The test conditions included: 5.0% NaCl solution, corrosion for 720 hours, five parallel specimens, and each specimen was sealed before testing. After the test, the corrosion resistance of the specimens was rated according to GBT 6461-2002. Figure 6 Figure 2 is the neutral salt spray corrosion performance test results of each sample. It can be seen from the figure that after 720 hours of corrosion, the corrosion level of the coating in Example 3 (level 9) is significantly higher than that of the coating in Example 4 (level 7), indicating that the addition of grain inhibitors and antioxidants is beneficial to improving the corrosion resistance of the coating.

[0086] Example 5

[0087] This example is used to prepare WC-40wt%Cu 0.5 FeNiCr metal ceramic block, the specific implementation steps are as follows:

[0088] Step 1: Prepare Cu using vacuum air atomization powder making equipment 0.5 FeNiCr high entropy alloy powder. Preparation of Cu 0.5 The process parameters of FeNiCr high entropy alloy powder include: air pressure of 5 MPa, air velocity of 200 mm / s, and air injection angle of 60°. 0.5 The particle size of FeNiCr high entropy alloy powder is 0.1~15 μm.

[0089] Step 2: weigh and mix the metal-ceramic composite powder, which can be WC-Cu 0.5 FeNiCr composite powder, metal ceramic composite powder including 10 wt% Cu 0.5 FeNiCr high entropy alloy powder, 90 wt% WC powder, 0.6 wt% grain inhibitor (complex phase carbide) and 0.6 wt% antioxidant.

[0090] Step 3: The metal-ceramic composite powder and deionized water are ball-milled in a ratio of 1:2. The ball-milling time is 30 h, the rotation mode is alternating forward and reverse (one cycle is 5 h), the speed is 300 r / min, and the powder particle size after ball milling is 0.5~5 μm.

[0091] Step 4: The ball-milled metal-ceramic composite powder is kept at 80°C in a blast drying oven for 10 h, and then sieved with a 200-mesh screen to ensure that the powder particles are fine and evenly dispersed. Step 5: Prepare WC-Cu by spark plasma sintering 0.5FeNiCr metal ceramic block, wherein the sintering pressure is 30 MPa, the sintering temperature is 1200 ℃, and the holding time is 10 min.

[0092] Example 6

[0093] This example is used to prepare WC-20wt%Cr3C2-10wt%Cu 0.2 The specific implementation steps of FeNiCrAl metal ceramic composite powder and metal ceramic block are as follows:

[0094] Step 1: Prepare Cu using vacuum air atomization powder making equipment 0.2 FeNiCrAl high entropy alloy powder. Preparation of Cu 0.2 The process parameters of FeNiCrAl high entropy alloy powder include: air pressure of 5 MPa, air velocity of 150 mm / s, and air injection angle of 30°. 0.2 The particle size of the FeNiCrAl high entropy alloy powder is 0.1~15μm.

[0095] Step 2: Weigh and proportion WC-Cr3C2-Cu 0.2 FeNiCrAl metal ceramic composite powder, with the addition of grain inhibitor and antioxidant, the metal ceramic composite powder includes 10 wt% Cu 0.2 FeNiCrAl high entropy alloy powder, 70 wt% WC powder, 20 wt% Cr3C2 powder, 0.6 wt% grain inhibitor (complex carbide) and 0.6 wt% antioxidant.

[0096] Step 3: The mixed metal-ceramic composite powder and deionized water were ball-milled in a ratio of 1:2. The ball-milling time was 30 h, the rotation mode was alternating forward and reverse (one cycle was 5 h), the speed was 300 r / min, and the particle size of the metal-ceramic composite powder after ball milling was 0.5~5 μm.

[0097] Step 4: The ball-milled metal-ceramic composite powder is kept at 80°C in a forced air drying oven for 10 hours, and then sieved with a 300-mesh screen to ensure that the powder particles are fine and evenly dispersed. Step 5: Hot isostatic pressing technology is used to sinter WC-Cr3C2-Cu 0.2 FeNiCrAl metal ceramic blocks were prepared with a sintering pressure of 30 MPa, a sintering temperature of 1200°C, and a holding time of 60 min.

[0098] Example 7

[0099] The process is the same as that of Example 1, except that the composition of the prepared metal ceramic block is WC-10wt%Cr3C2-40wt%Cu0.5 FeNiCrAl was prepared by hot isostatic pressing sintering technology, where the sintering pressure was 20 MPa, the sintering temperature was 1300℃, and the holding time was 90 min.

[0100] Example 8

[0101] The process is the same as that of Example 1, except that the composition of the prepared metal ceramic block is WC-20wt%Cr3C2-10wt%CuFeNiCr 0.2 Ti, the metal ceramic block was prepared by hot pressing sintering technology, wherein the sintering pressure was 25 MPa, the sintering temperature was 1000 ℃, and the holding time was 120 min.

[0102] Example 9

[0103] The process is the same as that of Example 1, except that the composition of the prepared metal ceramic block is WC-10wt%Cr3C2-40wt%Cu 0.2 FeNiCr 0.5 Ti, the metal ceramic block was prepared by hot pressing sintering technology, wherein the sintering pressure was 25 MPa, the sintering temperature was 1000 ℃, and the holding time was 120 min.

[0104] Example 10

[0105] The process is the same as that of Example 1, except that the composition of the prepared metal ceramic block is WC-20wt%B4C-20wt%CuFeNiCrCo, and the ball milling parameters of the metal ceramic composite powder include: ball milling time of 20 h, rotation mode of alternating forward and reverse rotation (one cycle of 2 h), rotation speed of 200 r / min, and powder particle size after ball milling of 0.5~5 μm.

[0106] Example 11

[0107] The process is the same as that of Example 1, except that the composition of the prepared metal ceramic block is WC-40wt%Cu 0.5 FeNiCr 0.5 Ti, the metal ceramic block was prepared by hot pressing sintering technology, wherein the sintering pressure was 40MPa, the sintering temperature was 900℃, and the holding time was 30min.

[0108] Example 12

[0109] The process is the same as that of Example 1, except that the composition of the metal ceramic block used to prepare is WC-20wt% Cu 0.5FeNiCrAl metal ceramic blocks were prepared by spark plasma sintering technology, with a sintering pressure of 40 MPa, a sintering temperature of 1100°C, and a holding time of 10 min.

[0110] Example 13

[0111] The process is the same as that of Example 1, except that the composition of the metal ceramic block used to prepare is WC-20wt% Cu 0.2 FeNiCr 0.5 Al, the metal ceramic block was prepared by spark plasma sintering technology, wherein the sintering pressure was 25 MPa, the sintering temperature was 1000℃, and the holding time was 8 min.

[0112] Example 14

[0113] The process is the same as that of Example 1, except that the composition of the metal ceramic block used to prepare is WC-10wt%Cr3C2-20wt%Cu 0.5 FeNiCr 0.5 Co; ball milling time was 30 h, the rotation mode was alternating forward and reverse (one cycle was 2 h), and the speed was 250 r / min; hot pressing technology was used to prepare the metal ceramic block, where the sintering pressure was 25 MPa, the sintering temperature was 1200 °C, and the holding time was 90 min.

[0114] Example 15

[0115] The process is the same as that of Example 1, except that the composition of the metal ceramic block used to prepare is WC-10wt%B4C-20wt%Cu 0.5 FeNiCr 0.5 Co; ball milling time was 20 h, the rotation mode was alternating forward and reverse (one cycle was 5 h), and the speed was 250 r / min; hot isostatic pressing technology was used to prepare the metal ceramic block, where the sintering pressure was 30 MPa, the sintering temperature was 900 ℃, and the holding time was 120 min.

[0116] Comparative Example

[0117] The material selected is ZrC-45wt%AlSiCrFeCoNi metal ceramic block, and the specific implementation steps are as follows:

[0118] Step 1: Prepare AlSiCrFeCoNi alloy powder using vacuum air atomization equipment. The process parameters for preparing the AlSiCrFeCoNi alloy powder include: air pressure of 10 MPa, air velocity of 200 mm / s, and an air injection angle of 45°. The prepared AlSiCrFeCoNi alloy powder has a particle size of 0.1 to 10 μm.

[0119] Step 2: Weigh and mix ZrC-AlSiCrFeCoNi composite powder, wherein the composite powder comprises 45 wt% of AlSiCrFeCoNi alloy powder and 55 wt% of ZrC powder.

[0120] Step 3: The mixed composite powder and deionized water were ball-milled in a ratio of 1:2. The ball-milling time was 20 h, the rotation mode was alternating forward and reverse (one cycle was 5 h), the speed was 200 r / min, and the powder particle size after ball milling was 0.5~5 μm.

[0121] Step 4: The ball-milled composite powder was kept at 80°C in a forced air drying oven for 10 h, and then sieved with a 200-mesh sieve to ensure that the powder particles were fine and evenly dispersed.

[0122] Step 5: Prepare the ZrC-AlSiCrFeCoNi metal ceramic block by vacuum sintering process. The specific steps of preparing the ZrC-AlSiCrFeCoNi metal ceramic block by vacuum sintering process include:

[0123] First, the treated powder was poured into a φ50 mm mold and pressed into a green body at a pressure of 200 MPa using a press. Subsequently, the pressed carbide green body was placed in a high-temperature furnace and heated under high vacuum conditions. The main parameters included: vacuum degree 10 -2 Pa, temperature 1100℃, holding time 60 min, heating rate 4℃ / min; finally, after the holding is completed, the furnace is cooled to room temperature to obtain a ZrC-AlSiCrFeCoNi metal ceramic block.

[0124] Figure 7 The test results for the coating hardness and flexural strength of the cermet blocks prepared in Example 3 and the comparative example are shown. The results show that Example 3 achieved a hardness of 94.5±0.9 HRA and a flexural strength of 1296±20 MPa, significantly higher than the hardness and flexural strength of the comparative example coating (90.3±0.7 HRA and 1132±35 MPa). The cermet blocks prepared in the disclosed examples exhibit superior overall mechanical properties.

[0125] In summary, in the embodiments of the present disclosure, MC-Cu is prepared based on the unique characteristics of high entropy alloys such as resistance to radiation damage, high oxidation resistance and good wettability. z FeNiCr y X is a new type of metal-ceramic composite powder. Using a high-entropy alloy as the metal phase can reduce the proportion of active elements within the coating and significantly improve the material's resistance to radiation damage. Taking into account the high wettability, high toughness, corrosion resistance, and radiation damage resistance of the composite's binder phase, four elements with similar atomic radii, Fe, Ni, Cr, and Cu, were selected as the base elements of the high-entropy alloy powder to form a high-entropy alloy with an FCC structure. Fe, Ni, and Cr increase the alloy's chaotic entropy and promote the formation of the high-entropy alloy. The addition of Cr also facilitates the formation of Cr2O3, improving the alloy's corrosion resistance. The addition of Cu enhances the wettability of the high-entropy alloy with the carbide hard phase, improving the density and cohesive strength of the composite. Doping with elements such as Co, Al, and Ti can adjust the degree of lattice distortion in the high-entropy alloy's FCC phase, altering the alloy's mechanical properties and achieving functional diversification of the composite material.

[0126] Furthermore, in the embodiments of the present disclosure, long-term aging, forward-reverse alternation and wet ball milling are used to achieve uniform distribution of WC particles as MC carbides and high entropy alloy phases, which not only effectively solves the problem of WC particle segregation in the process of mixing WC-based powders by traditional ball milling, but also avoids the problem of sticking of high entropy alloy phases at high temperatures, ensuring the stability of the content of each phase in the composite powder. In addition, a grain inhibitor is used to inhibit the growth of carbide grains during high-temperature sintering. By adding a grain inhibitor formed by a mixture of two complex phase carbides during the ball milling process, the excessive growth of nano-scale and submicron-scale carbide particles during the sintering process can be simultaneously inhibited, effectively improving the mechanical properties of the composite material. Adding an antioxidant to the composite powder during ball milling is used to eliminate oxide impurities generated during the ball milling of the composite powder, which helps to improve the density of the sintered block, and can inhibit crack initiation and expansion behavior under high external stress, thereby improving the overall fracture toughness of the material. In addition, by inhibiting crack expansion behavior, the number of corrosion channels can be reduced, further improving the corrosion resistance of the material.

[0127] High performance MC-Cu is achieved through powder hot forming technologies such as hot pressing, hot isostatic pressing and spark plasma sintering. z FeNiCr y Stable preparation of X-metal ceramic blocks. Under the process parameters described in the disclosed embodiments, the high-entropy alloy binder phase can fully melt into a liquid phase, coating WC particles of varying sizes and tightly bonding the hard particles, effectively improving the density and mechanical properties of the composite material. Furthermore, a suitable sintering pressure and temperature ratio prevents loss of liquid high-entropy alloy from spilling through the gap between the hot pressing die and the sample, effectively ensuring stable sample structure and performance.

[0128] The technical solution in the embodiment of the present disclosure combines the high corrosion resistance of carbides and the high radiation damage resistance of high entropy alloys, and is supported by powder mixing technology and hot pressing technology with the characteristics of long aging, forward-reverse alternation and wet ball milling. z FeNiCr y A corrosion-resistant high-entropy metal-ceramic composite material was designed and fabricated by replacing the Co binder phase with X high-entropy alloy. Compared with traditional metal-ceramics, high-entropy metal-ceramics have better corrosion resistance and can significantly improve the service life and stability of reactors.

[0129] In an embodiment of the present disclosure, a high-entropy metal-ceramic material is further provided. The high-entropy metal-ceramic material can be prepared according to the method of steps S110 to S120.

[0130] In the embodiment of the present disclosure, in order to meet the coupled harsh working conditions of lead-cooled fast reactor corrosion, wear and radiation damage, hard carbide with high corrosion resistance is combined with high entropy alloy with excellent radiation damage resistance, and MC-Co is prepared by vacuum atomization method and mechanical ball milling method. z AlFeNiCrX metal ceramic composite powder, and successfully prepared MC-Co using powder hot forming technology z AlFeNiCrX metal ceramic block. Prepared MC-Cu z FeNiCr y The X-cermet block has a dense structure and a hardness exceeding 90 HRA. After sealing, it withstands 720 hours of neutral salt spray corrosion, achieving a corrosion rating of 9. Compared to traditional cermets, high-entropy cermets offer superior corrosion resistance, significantly improving the service life and stability of reactors and enhancing their quality.

[0131] Furthermore, the figures above are merely illustrative of the processes included in the methods according to exemplary embodiments of the present disclosure and are not intended to be limiting. It is readily understood that the processes illustrated in the figures above do not indicate or limit the temporal order of these processes. Furthermore, it is readily understood that these processes may be executed synchronously or asynchronously, for example, in multiple modules.

[0132] Those skilled in the art will readily appreciate other embodiments of the present disclosure after considering the specification and practicing the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the present disclosure that follow the general principles of the present disclosure and include common knowledge or customary techniques in the art not disclosed herein. The description and examples are to be considered as exemplary only, with the true scope and spirit of the present disclosure being indicated by the appended claims.

[0133] It should be understood that the present disclosure is not limited to the exact structures that have been described above and shown in the drawings, and that various modifications and changes can be made without departing from the scope thereof. The scope of the present disclosure is limited only by the appended claims.

Claims

1. A method for preparing a high entropy metal ceramic material, characterized in that: include: Preparation of Cu z FeNiCr y X high entropy alloy powder, Cu z FeNiCr y X high entropy alloy powder is used as the metal phase to prepare metal-ceramic composite powder with MC carbide, and the metal-ceramic composite powder is ball-milled to obtain MC-Cu with dispersed carbide particles. z FeNiCr y X metal ceramic powder; the Cu z FeNiCr y X high entropy alloy powder is prepared by vacuum atomization method and is used to prepare Cu z FeNiCr y The process parameters of X high entropy alloy powder include: air pressure 1-10 MPa, air flow velocity 100-200 mm / s, air flow injection angle 30-90°; the Cu z FeNiCr y In the X high entropy alloy powder, X is Ti; Cu z FeNiCr y The particle size of X high entropy alloy powder is 0.1~15μm; Cu z FeNiCr y The range of z and y in the X high entropy alloy powder is 0 to 1.0 at%; the MC-Cu z FeNiCr y X cermet powder contains 5-40 wt% Cu z FeNiCr y X high entropy alloy powder; 0.1-1.0 wt% of a grain inhibitor and 0.1-1.0 wt% of an antioxidant are added during the ball milling mixing process, wherein the grain inhibitor is obtained by mixing two complex carbides, and the two complex carbides include chromium carbide and vanadium carbide; the antioxidant is carbohydrazide; the ball milling method is a wet milling method, and the ball milling rotation method is a forward-reverse alternating rotation with 2-5 hours as a cycle; the ball milling time is 20-40 hours, the ball milling speed is 100-300 r / min, and the MC-Cu obtained after ball milling z FeNiCr y The particle size of X metal ceramic powder is 0.5 to 5 μm; MC-Cu is formed by powder hot forming technology z FeNiCr y X metal ceramic powder is sintered to prepare a metal ceramic block to obtain a high-entropy metal ceramic material; the powder hot forming technology includes hot pressing sintering, hot isostatic pressing and spark plasma sintering; the sintering pressure is 10-40 MPa, and the sintering temperature is 900-1400°C.

2. The method for preparing a high entropy metal ceramic material according to claim 1, wherein: The MC carbide is WC, WC-Cr3C2 or WC-B4C, and the particle size of the MC carbide is 1 to 3 μm.

3. The method for preparing a high entropy metal ceramic material according to claim 1, wherein: The MC-Cu z FeNiCr y The X cermet powder contains 60 to 95 wt% of MC carbide.

4. The method for preparing a high entropy metal ceramic material according to claim 1, wherein: The MC-Cu z FeNiCr y X metal ceramic powder is prepared into a metal ceramic block, comprising: MC-Cu z FeNiCr y X metal ceramic powder is dried and kept warm, and MC-Cu is formed by powder hot forming technology. z FeNiCr y The X metal ceramic powder is sintered to prepare the high entropy metal ceramic material.

5. The method for preparing a high entropy metal ceramic material according to claim 4, wherein: The sintering pressure is 10-40 MPa, the sintering temperature is 900-1400° C., and the heat preservation time is 5-120 minutes.

6. A high entropy metal ceramic material, characterized in that: The high-entropy metal ceramic material is prepared according to the preparation method of the high-entropy metal ceramic material according to any one of claims 1-5.

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