CrMnFeCoNi / cuCr alloy composite net structure material and preparation method thereof

Abstract

The application provides a preparation method of a CrMnFeCoNi / CuCr alloy composite net structure material, copper is liquefied and diffused to a grain boundary position in a CrMnFeCoNi high-entropy alloy particle, the grain is refined, and substructure strengthening is obtained through deformation, the powder metallurgy-micro-liquefaction hot-pressing sintering method adopted in the method is synergistic, the two composite phases are matched with each other, and after trace liquid phase is generated through rapid high-temperature hot-pressing sintering, a relatively dense sample can be obtained. The application also provides a CrMnFeCoNi / CuCr alloy composite net structure material, in the CrMnFeCoNi / CuCr alloy composite net structure material, Cr alloy penetrates into the grain boundary position in the CrMnFeCoNi alloy particle, the alloy powder particle size is small, through rapid heating and solidification of rapid high-temperature hot-pressing sintering, there is almost no segregation, and the grain is ensured to be fine.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of new materials, and relates to a CrMnFeCoNi / CuCr alloy composite reticular structure material and a preparation method thereof. BACKGROUND

[0002] Since Professor Ye Quanwei defined high-entropy alloys in 1995, and Professor Cantor discovered a single solid solution CrMnFeCoNi alloy at the beginning of this century, such an alloy prepared by using multiple metal elements as main elements has random atomic arrangement, the mixing of different elements causes serious lattice distortion in the alloy, and the different effects of different elements make the high-entropy alloy exhibit many excellent properties different from other alloys, thereby having great research value and development potential. The known high-entropy alloys exhibit excellent performance in mechanical properties, physical properties, corrosion resistance and the like. The high-entropy alloy is often composed of multiple metal and non-metal elements and is often prepared by arc melting and powder metallurgy. When the high-entropy alloy is prepared by arc melting, multiple remelting is needed to achieve internal organization homogenization. The cost of arc melting is relatively high, and the initial performance of the prepared sample is often difficult to achieve internal organization homogenization and is poor. In the production process, it is difficult to ensure repeatability, and the stability and controllability of continuous production are poor, and it is often difficult to achieve industrialization. By using mechanical alloying to prepare the high-entropy alloy by the powder metallurgy method, the yield of the material can be effectively improved, and the internal organization of the material is uniform. However, the sphericity of the powder prepared by the powder metallurgy and mechanical alloying is reduced, and the sintering density in the sintering process is reduced obviously. In the powder hot-pressing sintering process, the material is also prone to anti-densification. In addition, mechanical alloying often needs to add a binder, and the processing technology is relatively complex, the process exploration period is long, and it is difficult to completely remove the organic binder. Therefore, the plastic deformation degree of the material prepared by powder hot-pressing sintering is extremely low, and it is difficult to realize the performance of the material by deformation strengthening in industry, which greatly limits the actual application. For example, a high-strength FeCoNiCrMn high-entropy alloy prepared by the high-strength FeCoNiCrMn high-entropy alloy and the preparation method disclosed in patent CN 108103381 A has an ultimate tensile strength of 981 MPa, and the plasticity is only 4.8%. SUMMARY

[0003] The technical problems to be solved by the present application are to overcome the deficiencies and defects mentioned in the above background art, and the present application is a CrMnFeCoNi / CuCr alloy composite network structure material and a preparation method thereof, which is prepared by compounding CrMnFeCoNi high-entropy alloy with excellent ductility and CuCr alloy, diffusing copper into the grain boundary position of CrMnFeCoNi high-entropy alloy particles, refining the grains, and obtaining substructure strengthening through deformation.

[0004] To solve the above technical problems, the technical solution provided by the present application is:

[0005] A preparation method of a CrMnFeCoNi / CuCr alloy composite network structure material, which diffuses copper into the grain boundary position of CrMnFeCoNi high-entropy alloy particles, refines the grains, and obtains substructure strengthening through deformation, specifically comprising the following steps:

[0006] (1) Take chromium source, manganese source, iron source, cobalt source and nickel source to prepare CrMnFeCoNi alloy powder by inert gas atomization method; take copper source and copper-chromium intermediate alloy (Cu 10 Cr intermediate alloy) to prepare CuCr alloy powder by inert gas atomization method;

[0007] (2) The CrMnFeCoNi alloy powder and CuCr alloy powder obtained in step (1) are sieved respectively, and then mixed to obtain a composite material mixed powder; the two kinds of alloy powders are compounded, which is beneficial to improve the stability of the material in sintering and improve the performance after preparation;

[0008] (3) The composite material mixed powder obtained in step (2) is vacuum sintered, heat treated and cooled to obtain a sintered sample; the sintered sample is heat treated by rapid high-temperature hot pressing sintering, and the CuCr phase is liquefied and penetrated into the grain boundary of the CrMnFeCoNi high-entropy alloy particles through the unique liquid phase separation phenomenon between the two phases, which effectively refines the high-entropy alloy particles and further improves the toughness and strength of the composite material;

[0009] (4) The sintered sample obtained in step (3) is subjected to solid solution treatment, and then subjected to hot rolling treatment and cold rolling treatment in sequence to obtain a CrMnFeCoNi / CuCr alloy composite network structure material. The hot rolling treatment is multiple isothermal hot rolling treatment.

[0010] The Cu and CrMnFeCoNi high-entropy alloy cannot be co-melted, so that the copper is liquefied and diffused into the grain boundary position of the CrMnFeCoNi high-entropy alloy particles, the grains are refined, and the strength and toughness of the material are effectively improved through the deformation to obtain the substructure strengthening. Since the thermal expansion coefficients of the two materials are similar, the CuCr alloy is equivalent to the binder to further strengthen the high-entropy alloy phase, and the diffusion between the composite double phases achieves the common strengthening effect of the two phases, so that the material can achieve high strength while improving the plasticity of the material prepared by the powder metallurgy method. In addition, the high thermal conductivity of the Cu alloy and the rapid high-temperature hot-pressing sintering of the micro-liquid phase powder make the composite double phase achieve a network structure, thereby improving the thermal conductivity of the composite material. In the specific preparation process, the preparation method is relatively simple and clear, and can achieve continuous industrial production of the material, thereby ensuring the possibility of industrialization of the material.

[0011] Preferably, in step (1), the chromium source is Cr, the manganese source is Mn, the iron source is Fe, the cobalt source is Co, and the nickel source is Ni, and the mass fractions are respectively Cr: 20-28 parts, Mn: 19-27 parts, Fe: 19-27 parts, Co: 22-32 parts, and Ni: 19-28 parts.

[0012] Preferably, in step (1), the copper-chromium intermediate alloy is Cu 10 The copper source is electrolytic pure copper. The mass fraction of the copper-chromium intermediate alloy is 10-15 parts, and the mass fraction of the electrolytic pure copper is 85-90 parts. Obtaining copper-chromium intermediate alloy powder with different mass percentages will be more suitable for adjusting the composition percentage of the CuCr alloy powder, which is beneficial to prevent impurity elements from affecting the material performance. Using electrolytic pure copper can effectively avoid the influence of impurities in the as-cast material on the alloy composition.

[0013] Preferably, in step (1), the preparation of the CrMnFeCoNi alloy powder and the preparation of the CuCr alloy powder both adopt the inert gas atomization method, and the reaction parameters are as follows: the inert gas is Ar, the melt temperature of the holding furnace is 1100-1200℃, the holding time is 10-15 minutes, and the gas atomization pressure is 2-5MPa.

[0014] Preferably, in step (2), the mixing mass ratio of the CrMnFeCoNi alloy powder and the CuCr alloy powder is (1:1)-(3:7), the mixing is physically mixed by a V-type mixer for 3-7 hours, and the particle size of the sieved powder is 10-52μm.

[0015] Preferably, the vacuum sintering in step (3) is performed by a hot-press sintering furnace at 50 MPa or less, the pressure on the green compact during the vacuum sintering is 20-50 MPa, the sintering temperature is 800-1000℃, and the sintering heating rate is 50-100℃ / min. Here, it is a rapid high-temperature hot-press sintering, the temperature is raised rapidly, so the time is also very short, the sintering time is only 10 min, and the product is taken out after furnace cooling. The micro-liquid-phase powder high-temperature hot-press sintering adopted in the present application has the following advantages: the activity of the fine-particle-size powder itself is large, under high pressure and high vacuum, the powder is melted to form a micro-liquid phase due to reaching the melting point, and a small amount of liquidization occurs during the sintering process, which can further increase the density of the material compared with traditional solid-phase sintering. At the same time, the liquid phase of the Cu alloy penetrates into the original particle boundaries and grain boundaries of the high-entropy alloy through diffusion, and it is found in previous studies that the Cu element is difficult to enter the interior of the CrMnFeCoNi high-entropy alloy due to the positive mixing enthalpy, and thus is segregated at the grain boundaries.

[0016] Preferably, the holding time in step (3) is 5-60 min, and the cooling is performed by furnace cooling.

[0017] Preferably, the solid solution treatment in step (4) is performed in a muffle furnace for 4-8 hours, and the solid solution temperature is 800-1000℃. The solid solution treatment can diffuse Mn, Ni, Fe, and Co in the high-entropy alloy to the CuCr alloy, and further diffuse Cu to the grain boundaries of the high-entropy alloy and a small amount of Cu to the interior of the high-entropy alloy, the interface bonding strength between the two kinds of particles is high, and the Cu alloy composition is improved to CuCrMnNiFeCo alloy. The solid solution of Mn and Ni can effectively improve the initial solid solution strength of the Cu alloy, and the main strengthening mechanism is solid solution strengthening mechanism, while the diffusion of other elements is mainly concentrated in the Cr precipitate particles. The solid solution treatment itself can dissolve the Cr particles precipitated during the furnace cooling process back into the matrix, thereby ensuring the controllability of the material industrialization and the stability of the subsequent deformation.

[0018] Preferably, the hot rolling temperature of the hot rolling treatment in step (4) is 800-1000 DEG C, the pass reduction of the hot rolling is 5%-40%, and the total deformation of the hot rolling is 50-70%; the pass deformation of the cold rolling treatment is 10-20%; the total deformation of the hot rolling and the cold rolling in step (4) is 80-90%. In the powder metallurgy method in the application, the sample itself is deformed by hot rolling and cold rolling with copper wrapping, the hot rolling and the cold rolling are performed by using a two-roller reversible hot rolling machine, the curvature radius can be effectively reduced, the sample is directly hot-rolled after the solid solution treatment, the cylindrical sample is cut from both sides after high-temperature hot-pressing sintering of the micro-liquid phase powder, the stress effect of the wide spreading part on the material can be reduced during the rolling process, the copper wrapping can effectively prevent the hot-pressed sample from being oxidized at high temperature during the solid solution process, the copper wrapping can effectively improve the lubricating effect of the material during the rolling process, and the copper wrapping can prevent the material from sticking to the roller, so that the material can be well reduced and the surface cracks during the deformation process can be reduced.

[0019] Based on the overall inventive concept, the application further provides a CrMnFeCoNi / CuCr alloy composite net structure material, wherein the CuCr alloy penetrates into the grain boundary of the CrMnFeCoNi alloy particles, and has a layer structure, and contains the following components in parts by weight: Cr: 10-14 parts, Mn: 9.5-13.5 parts, Fe: 9.5-13.5 parts, Co: 11-16 parts, Ni: 9.5-14 parts, and Cu: 30-50 parts.

[0020] The powder metallurgy-micro-liquid hot-pressing sintering method used in the prepared CrMnFeCoNi / CuCr alloy composite net structure material in the application has a synergistic effect of each step and a mutual cooperation between the two composite phases, the alloy powder particles have a small size, the rapid heating and solidification during the rapid high-temperature hot-pressing sintering can hardly cause segregation, and the fine grains are difficult to grow. After the trace liquid phase is generated by the rapid high-temperature hot-pressing sintering, a relatively dense sample can be obtained, and at the same time, the subsequent deformation heat treatment process is combined, so that the final product has more excellent performance indexes, the comprehensive performance of the material is improved, and a good design concept and an innovative scheme are provided for the industrialization of the same material and similar materials.

[0021] Compared with the prior art, the application has the following beneficial effects:

[0022] 1. The powder metallurgy-micro-liquefaction hot-pressing sintering method adopted in the preparation method in the present application, the various steps synergistically act, the two composite phases cooperate with each other, due to the small size of the alloy powder particles, through the rapid heating and solidification of rapid high-temperature hot-pressing sintering, there is almost no segregation, and the grain is fine, which is difficult to grow rapidly or recrystallize, after the micro-liquid phase is generated by rapid high-temperature hot-pressing sintering, a relatively dense sample can be obtained, at the same time combined with the subsequent deformation heat treatment process, the performance indicators of the final product are more excellent, the comprehensive performance of the material is improved, the present application can greatly improve the plasticity of the alloy sample prepared by traditional powder metallurgy and rapid high-temperature hot-pressing sintering by reasonably setting the process steps and optimizing the process parameters, and realize deformation treatment, so that the strength of the material is greatly improved.

[0023] 2. The near-liquid phase sintered material obtained by using Cu and CrMnFeCoNi high-entropy alloy which cannot be co-melted, and adjusting the temperature, the CuCr phase and the CrMnFeCoNi high-entropy alloy phase have good wettability, and penetrate into the grain boundary inside the particles, greatly refining the particle size, and improving the bonding strength between the phases and the grain boundaries, thereby filling the defects of the material.

[0024] 3. The preparation method of the present application has a short process flow, simple operation, continuous production, and is suitable for industrial production, in the specific preparation process, the present preparation method is simple and clear, and can achieve continuous industrial production of materials, thereby ensuring the possibility of material industrialization.

[0025] 4. The CrMnFeCoNi / CuCr alloy composite network structure material prepared by the present application, through a large number of stacking faults formed during the deformation process of the high-entropy alloy, the alloy strength and plasticity are effectively strengthened, the inherent influence of traditional Cu addition on the toughness and strength of the material is broken, through reasonable regulation of the composition, the five elements in the high-entropy alloy powder particles are uniformly distributed, and the composition is uniform, mainly by solid solution strengthening and interface strengthening; in addition, the Cr element in the copper alloy powder itself is uniformly distributed in the matrix after gas atomization, and the mixing also effectively ensures the uniformity of the powder during the mixing process, thereby improving the uniformity of the sample after sintering, and further improving the mechanical properties of the material, the tensile strength of the composite material reaches 900-1200 MPa, and the elongation rate is 15%-20%. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, the drawings described below are only some embodiments of the present application, and for those skilled in the art, other drawings can also be obtained without creative labor based on these drawings.

[0027] Figure 1 、 Figure 2 is a CrMnFeCoNi / CuCr alloy composite reticular structure material deformed state scanning electron microscope photograph; Figure 3 is a flowchart of the preparation method of the present application. DETAILED DESCRIPTION

[0028] In order to facilitate the understanding of the present application, the following will combine the drawings of the specification and the preferred embodiments to make a more comprehensive and detailed description of the present application, but the protection scope of the present application is not limited to the following specific embodiments.

[0029] Unless otherwise defined, all professional terms used in the following have the same meaning as generally understood by those skilled in the art. The professional terms used in this paper are only for the purpose of describing specific embodiments and are not intended to limit the protection scope of the present application.

[0030] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present application can be purchased from the market or can be prepared by existing methods.

[0031] Example 1:

[0032] A CrMnFeCoNi / CuCr alloy composite reticular structure material, scanning electron microscope photographs of different positions (position a, position b) of the deformed sample are shown in Figure 1 、 Figure 2 The components and contents are shown in Table 1:

[0033] The preparation method of the CrMnFeCoNi / CuCr alloy composite reticular structure material in this proportion, the batching ratio is shown in Table 1, which includes the following steps, as shown in Figure 3

[0034] (1) Take 9.87 kg of copper source, 1 kg of copper-chromium intermediate alloy source to prepare CuCr alloy powder by inert gas atomization method; take 1.845 kg of chromium, 1.959 kg of manganese, 1.992 kg of iron, 2.102 kg of cobalt and 2.093 kg of nickel to prepare high-entropy alloy with the same atomic percentage by inert gas atomization method. The reaction parameters of inert gas atomization method are: inert gas Ar, holding furnace melt temperature 1100℃, holding for 10 minutes, gas atomization pressure 2MPa.​

[0035] (2) The CrMnFeCoNi high-entropy alloy powder and the CuCr alloy powder obtained in step (1) are mixed in a mass ratio of 7:3, physically mixed for 3 hours, sieved, and the powder particles with a particle size of 10-52 μm are obtained, and then micro-liquid phase powder rapid high-temperature hot pressing sintering is performed through a rapid high-temperature hot pressing sintering furnace, the pressure of the compact is 50 MPa during the rapid high-temperature hot pressing sintering, the sintering temperature is 950℃, the sintering heating rate is 100℃ / min, the sintering holding time is 10 mins, and the furnace is cooled.

[0036] Example 2:

[0037] A CrMnFeCoNi / CuCr alloy composite network structure material contains the components and contents shown in Table 1 in mass percentage:

[0038] The preparation method of the CrMnFeCoNi / CuCr alloy composite network structure material in this ratio comprises the following steps:

[0039] (1) 9.87 kg of copper source and 1 kg of copper-chromium intermediate alloy source are used to prepare CuCr alloy powder by inert gas atomization method; 1.845 kg of chromium, 1.959 kg of manganese, 1.992 kg of iron, 2.102 kg of cobalt, and 2.093 kg of nickel are used to prepare high-entropy alloy with the same atomic percentage by inert gas atomization method. The reaction parameters of the inert gas atomization method are as follows: Ar is used as the inert gas, the melt temperature of the holding furnace is 1200℃, the holding time is 15 minutes, and the gas atomization pressure is 3 MPa.

[0040] (2) The CrMnFeCoNi high-entropy alloy powder and the CuCr alloy powder obtained in step (1) are sieved and mixed in a mass ratio of 1:1, physically mixed for 3 hours, sieved, and the powder particles with a particle size of 10-52 μm are obtained, and then micro-liquid phase powder rapid high-temperature hot pressing sintering is performed through a rapid high-temperature hot pressing sintering furnace, the pressure of the compact is 50 MPa during the rapid high-temperature hot pressing sintering, the sintering temperature is 950℃, the sintering heating rate is 100℃ / min, the sintering holding time is 10 mins, and the furnace is cooled.

[0041] (3) The sample after step (2) is wire cut and wrapped with copper skin, solid solution treatment is performed for 4.5 h at a solid solution temperature of 950℃, and then multi-stage holding hot rolling deformation is performed with a total reduction of 60%, the hot rolling temperature is 950℃, and the pass reduction is 20%; then cold rolling deformation is performed with a total strain of 80% and a pass deformation of 20%, to obtain the CrMnFeCoNi / CuCr alloy composite network structure material.

[0042] The performance test results of the CrMnFeCoNi / CuCr alloy composite reticular structure material treated by steps (1-3) are shown in Table 2.

[0043] Example 3:

[0044] A CrMnFeCoNi / CuCr alloy composite reticular structure material contains the components and contents in mass percentage as shown in Table 1:

[0045] The preparation method of the CrMnFeCoNi / CuCr alloy composite reticular structure material in this proportion includes the following steps:

[0046] (1) Take 9.87 kg of copper source and 1 kg of copper-chromium intermediate alloy to prepare CuCr alloy powder by inert gas atomization method; take 1.845 kg of chromium, 1.959 kg of manganese, 1.992 kg of iron, 2.102 kg of cobalt and 2.093 kg of nickel to prepare high-entropy alloy with the same atomic percentage by inert gas atomization method. The reaction parameters of the inert gas atomization method are as follows: the inert gas is Ar, the melt temperature of the holding furnace is 1100℃, the holding time is 15 minutes, and the gas atomization pressure is 4 MPa.

[0047] (2) The CrMnFeCoNi high-entropy alloy powder and the CuCr alloy powder obtained in step (1) are mixed in a mass percentage of 7:3, the physical mixing time is 3 hours, and the powder particles with a particle size of 10-52 μm are obtained by screening, and then the micro-liquid phase powder is rapidly high-temperature hot-pressed by a rapid high-temperature hot-pressing sintering furnace. The pressure of the green compact during rapid high-temperature hot-pressing is 50 MPa, the sintering temperature is 900℃, the sintering temperature rising rate is 100℃ / min, the sintering holding time is 10 mins, and the furnace cooling is carried out.

[0048] (3) The sample after step (2) is line-cut and wrapped with copper skin, and then solid solution treatment is carried out in a muffle furnace for 4.5 h at a solid solution temperature of 900℃, and then multi-stage holding hot rolling deformation is carried out with a total reduction of 60%, and the hot rolling temperature is 900℃, and the pass reduction is 20%; then cold rolling deformation is carried out with a total strain of 80% and a pass deformation of 20%, to obtain the CrMnFeCoNi / CuCr alloy composite reticular structure material.

[0049] The performance test results of the CrMnFeCoNi / CuCr alloy composite reticular structure material treated by steps (1-3) are shown in Table 2.

[0050] Example 4:

[0051] A CrMnFeCoNi / CuCr alloy composite reticular structure material contains the components and contents in mass percentage as shown in Table 1:

[0052] The preparation method of the CrMnFeCoNi / CuCr alloy composite network structure material in this proportion includes the following steps:

[0053] (1) Take copper source 9.87 kg, copper-chromium intermediate alloy source 1 kg, and use inert gas atomization method to prepare CuCr alloy powder; prepare high-entropy alloy with the same atomic percentage by inert gas atomization method according to the mass percentage of the elements of chromium 1.845 kg, manganese 1.959 kg, iron 1.992 kg, cobalt 2.102 kg, and nickel 2.093 kg. The reaction parameters of the inert gas atomization method are: the inert gas is Ar, the melt temperature of the holding furnace is 1100°C, the holding time is 10 minutes, and the gas atomization pressure is 5 MPa.

[0054] (2) The CrMnFeCoNi high-entropy alloy powder and CuCr alloy powder obtained in step (1) are mixed in a mass ratio of 1:1, the physical mixing time is 3 hours, and the powder particles with a particle size of 10-52 μm are obtained by screening, and then the micro-liquid phase powder is rapidly high-temperature hot-pressed and sintered in a rapid high-temperature hot-pressing sintering furnace. The pressure of the green compact during rapid high-temperature hot-pressing sintering is 50 MPa, the sintering temperature is 900°C, the sintering temperature rising rate is 100°C / min, the sintering holding time is 10 mins, and the furnace cooling is carried out.

[0055] (3) The sample after step (2) is line-cut and wrapped with copper skin, and then solid solution treatment is carried out for 4.5 h at a solid solution temperature of 900°C, and then multi-stage holding hot rolling deformation is carried out, the total amount of reduction is 60%, the hot rolling temperature is 900°C, and the pass reduction is 20%; then cold rolling deformation is carried out, the total strain is 80%, and the pass deformation is 20%, to obtain the CrMnFeCoNi / CuCr alloy composite network structure material.

[0056] The performance test results of the CrMnFeCoNi / CuCr alloy composite network structure material treated by steps (1-3) are shown in Table 2.

[0057] Comparative Example 1:

[0058] A CrMnFeCoNi / CuCr alloy composite network structure material contains the components and contents shown in Table 1 in mass percentage:

[0059] The preparation method of the CrMnFeCoNi / CuCr alloy composite network structure material in this proportion includes the following steps:

[0060] (1) CuCr alloy powder was prepared from copper source and copper-chromium intermediate alloy source with mass percentage of element composition, and the mass of the two was 9.87 kg and 1 kg respectively; high-entropy alloy with the same atomic percentage was prepared from chromium source, manganese source, iron source, cobalt source and nickel source with mass percentage of element composition, and the mass of the five was 1.845 kg, 1.959 kg, 1.992 kg, 2.102 kg and 2.093 kg respectively.

[0061] (2) The CrMnFeCoNi high-entropy alloy powder and the CuCr alloy powder obtained in step (1) were mixed in a mass ratio of 9:1 for 3 hours, and then sieved to obtain powder particles with a particle size of 10-52 μm. Then, the micro-liquid phase powder was subjected to rapid high-temperature hot-pressing sintering in a rapid high-temperature hot-pressing sintering furnace. The pressure of the green compact was 50 MPa, the sintering temperature was 900℃, the sintering heating rate was 100℃ / min, the sintering holding time was 10 mins, and the furnace was cooled.

[0062] Comparative Example 2

[0063] A CrMnFeCoNi / CuCr alloy composite network structure material contained the following components and contents in mass percentage:

[0064] The preparation method of the CrMnFeCoNi / CuCr alloy composite network structure material in this ratio included the following steps:

[0065] (1) CuCr alloy powder was prepared from copper source and copper-chromium intermediate alloy source with mass percentage of element composition, and the mass of the two was 9.87 kg and 1 kg respectively; high-entropy alloy with the same atomic percentage was prepared from chromium source, manganese source, iron source, cobalt source and nickel source with mass percentage of element composition, and the mass of the five was 1.845 kg, 1.959 kg, 1.992 kg, 2.102 kg and 2.093 kg respectively.

[0066] (2) The CrMnFeCoNi high-entropy alloy powder and the CuCr alloy powder obtained in step (1) were mixed in a mass ratio of 8:2 for 3 hours, and then sieved to obtain powder particles with a particle size of 10-52 μm. Then, the micro-liquid phase powder was subjected to rapid high-temperature hot-pressing sintering in a rapid high-temperature hot-pressing sintering furnace. The pressure of the green compact was 50 MPa, the sintering temperature was 900℃, the sintering heating rate was 100℃ / min, the sintering holding time was 10 mins, and the furnace was cooled.

[0067] Comparative Example 3

[0068] A CrMnFeCoNi / CuCr alloy composite network structure material, which comprises the components and contents in mass percentage as shown in Table 1:

[0069] The preparation method of the CrMnFeCoNi / CuCr alloy composite network structure material in this proportion comprises the following steps:

[0070] (1) A copper source and a copper-chromium intermediate alloy source are prepared into CuCr alloy powder according to the mass percentage of element composition, and the mass of the two is 9.87 kg and 1 kg respectively; a chromium source, a manganese source, an iron source, a cobalt source and a nickel source are prepared into high-entropy alloy with the same atomic percentage according to the mass percentage of element composition, and the mass of the five is 1.845 kg, 1.959 kg, 1.992 kg, 2.102 kg and 2.093 kg respectively.

[0071] (2) The CrMnFeCoNi high-entropy alloy powder and the CuCr alloy powder obtained in step (1) are mixed according to a mass percentage of 7:3, the physical mixing time is 3 hours, and the powder particles with a particle size of 10-52 μm are obtained through screening, and then the micro-liquid phase powder is rapidly high-temperature hot-pressed and sintered through a rapid high-temperature hot-pressing sintering furnace, the pressure of the compact during rapid high-temperature hot-pressing sintering is 50 MPa, the sintering temperature is 900 ℃, the sintering temperature rising rate is 100 ℃ / min, the sintering holding time is 10 mins, and the furnace is cooled.

[0072] Comparative Example 4:

[0073] A CrMnFeCoNi / CuCr alloy composite network structure material, which comprises the components and contents in mass percentage as shown in Table 1:

[0074] The preparation method of the CrMnFeCoNi / CuCr alloy composite network structure material in this proportion comprises the following steps:

[0075] (1) A copper source and a copper-chromium intermediate alloy source are prepared into CuCr alloy powder according to the mass percentage of element composition, and the mass of the two is 9.87 kg and 1 kg respectively; a chromium source, a manganese source, an iron source, a cobalt source and a nickel source are prepared into high-entropy alloy with the same atomic percentage according to the mass percentage of element composition, and the mass of the five is 1.845 kg, 1.959 kg, 1.992 kg, 2.102 kg and 2.093 kg respectively.

[0076] (2) The CrMnFeCoNi high-entropy alloy powder obtained in step (1) and the CuCr alloy powder are mixed in a mass ratio of 7:3, and the physical mixing time is 3 hours. The powder is sieved, and the powder particles with a particle size of 10-52 μm are obtained. Then, the micro-liquid phase powder is subjected to rapid high-temperature hot pressing sintering in a rapid high-temperature hot pressing sintering furnace. The pressure of the compact is 50 MPa during the rapid high-temperature hot pressing sintering. The sintering temperature is 900°C. The sintering heating rate is 100°C / min. The sintering holding time is 10 mins. The furnace is cooled.

[0077] (3) The sample after step (2) is subjected to wire cutting and copper wrapping, and is subjected to cold rolling treatment. The pass reduction is 10%, and the total pass reduction is 35%, so that a plate is obtained.

[0078] Comparative Example 5:

[0079] A CrMnFeCoNi / CuCr alloy composite net structure material contains the components and contents shown in Table 1 in mass percentage:

[0080] The preparation method of the CrMnFeCoNi / CuCr alloy composite net structure material in this ratio includes the following steps:

[0081] (1) The copper source and the copper-chromium intermediate alloy source are prepared into CuCr alloy powder according to the mass percentage of element composition. The mass of the two is 9.87 kg and 1 kg, respectively. The chromium source, the manganese source, the iron source, the cobalt source, and the nickel source are prepared into high-entropy alloy with the same atomic percentage according to the mass percentage of element composition. The mass of the five is 1.845 kg, 1.959 kg, 1.992 kg, 2.102 kg, and 2.093 kg, respectively.

[0082] (2) The CrMnFeCoNi high-entropy alloy powder obtained in step (1) and the CuCr alloy powder are mixed in a mass ratio of 7:3, and the physical mixing time is 3 hours. The powder is sieved, and the powder particles with a particle size of 10-52 μm are obtained. Then, the micro-liquid phase powder is subjected to rapid high-temperature hot pressing sintering in a rapid high-temperature hot pressing sintering furnace. The pressure of the compact is 50 MPa during the rapid high-temperature hot pressing sintering. The sintering temperature is 900°C. The sintering heating rate is 100°C / min. The sintering holding time is 10 mins. The furnace is cooled.

[0083] (3) The sample after step (2) is subjected to wire cutting and copper wrapping, and is subjected to cold rolling treatment. The pass reduction is 10%, and the total pass reduction is 65%, so that a plate is obtained.

[0084] Comparative Example 6:

[0085] A CrMnFeCoNi / CuCr alloy composite network structure material, which comprises the components and contents in mass percentage as shown in Table 1:

[0086] The preparation method of the CrMnFeCoNi / CuCr alloy composite network structure material in this proportion comprises the following steps:

[0087] (1) A copper source and a copper-chromium intermediate alloy source are prepared into CuCr alloy powder according to the mass percentage of element composition, and the mass of the two is 9.87 kg and 1 kg respectively; a chromium source, a manganese source, an iron source, a cobalt source and a nickel source are prepared into high-entropy alloy with the same atomic percentage according to the mass percentage of element composition, and the mass of the five is 1.845 kg, 1.959 kg, 1.992 kg, 2.102 kg and 2.093 kg respectively.

[0088] (2) The CrMnFeCoNi high-entropy alloy powder and the CuCr alloy powder obtained in step (1) are mixed according to the mass percentage of 1:1, the physical mixing time is 3 hours, and the powder particles with a particle size of 10-52 μm are obtained through screening, and then the micro-liquid phase powder is rapidly high-temperature hot-pressed and sintered through a rapid high-temperature hot-pressing sintering furnace, the pressure of the compact during rapid high-temperature hot-pressing sintering is 50 MPa, the sintering temperature is 900 ℃, the sintering temperature rising rate is 100 ℃ / min, the sintering holding time is 10 mins, and the furnace is cooled.

[0089] Comparative example 7:

[0090] A CrMnFeCoNi / CuCr alloy composite network structure material, which comprises the components and contents in mass percentage as shown in Table 1:

[0091] The preparation method of the CrMnFeCoNi / CuCr alloy composite network structure material in this proportion comprises the following steps:

[0092] (1) A copper source and a copper-chromium intermediate alloy source are prepared into CuCr alloy powder according to the mass percentage of element composition, and the mass of the two is 9.87 kg and 1 kg respectively; a chromium source, a manganese source, an iron source, a cobalt source and a nickel source are prepared into high-entropy alloy with the same atomic percentage according to the mass percentage of element composition, and the mass of the five is 1.845 kg, 1.959 kg, 1.992 kg, 2.102 kg and 2.093 kg respectively.

[0093] (2) The CrMnFeCoNi high-entropy alloy powder obtained in step (1) and the CuCr alloy powder are mixed in a mass ratio of 1:1, and the physical mixing time is 3 hours, and then sieved, and the powder particles with a particle size of 10-52 μm are obtained, and then micro-liquid phase powder rapid high-temperature hot pressing sintering is carried out through a rapid high-temperature hot pressing sintering furnace, and the pressure of the compact during the rapid high-temperature hot pressing sintering is 50 MPa, the sintering temperature is 950°C, the sintering heating rate is 100°C / min, the sintering holding time is 10 mins, and the furnace is cooled.

[0094] (3) The sample after step (2) is linearly cut and wrapped with copper skin, and cold rolling treatment is carried out, the pass reduction is 10%, and the total pass reduction is 35%, and a plate is obtained.

[0095] Comparative Example 8:

[0096] A CrMnFeCoNi / CuCr alloy composite network structure material contains the components and contents shown in Table 1 in mass percentage:

[0097] The preparation method of the CrMnFeCoNi / CuCr alloy composite network structure material in this ratio includes the following steps:

[0098] (1) The copper source and copper-chromium intermediate alloy source are prepared into CuCr alloy powder according to the mass percentage of element composition, and the mass of the two is 9.87 kg and 1 kg, respectively; the chromium source, manganese source, iron source, cobalt source, and nickel source are prepared into high-entropy alloy with the same atomic percentage according to the mass percentage of element composition, and the mass of the five is 1.845 kg, 1.959 kg, 1.992 kg, 2.102 kg, and 2.093 kg, respectively.

[0099] (2) The CrMnFeCoNi high-entropy alloy powder obtained in step (1) and the CuCr alloy powder are mixed in a mass ratio of 1:1, and the physical mixing time is 3 hours, and then sieved, and the powder particles with a particle size of 10-52 μm are obtained, and then micro-liquid phase powder rapid high-temperature hot pressing sintering is carried out through a rapid high-temperature hot pressing sintering furnace, and the pressure of the compact during the rapid high-temperature hot pressing sintering is 50 MPa, the sintering temperature is 950°C, the sintering heating rate is 100°C / min, the sintering holding time is 10 mins, and the furnace is cooled.

[0100] (3) The sample after step (2) is linearly cut and wrapped with copper skin, and cold rolling treatment is carried out, the pass reduction is 10%, and the total pass reduction is 65%, and a plate is obtained.

[0101] Table 1: Components and contents of each example and comparative example

[0102]

[0103] Table 2: Performance test results of each example and comparative example

[0104]

[0105] The technical scheme of the present application, by reasonably designing the alloy components and contents of the two alloys of the composite material, makes the Cr particles in the copper alloy powder particles able to be precipitated, and the Mn, Ni, Fe diffused from the high-entropy alloy into the Cu alloy powder particles, while the Cu diffused in the high-entropy alloy particles, and since the mixing enthalpy of Cu in the CrMnFeCoNi high-entropy alloy is positive, the Cu particles diffused inside are relatively less, while a large amount of Cu-Mn phase will be gathered at the grain boundary, which can effectively bond the two particles together, thereby improving the plasticity of the material, and through the deformation treatment, the strength of the material will be greatly improved. Through the mutual diffusion of the elements between the two composite phases, the main strengthening mechanism of the material will be interface strengthening, solid solution strengthening, and subsequent deformation strengthening and aging strengthening.

Claims

1. A method for preparing a CrMnFeCoNi / CuCr alloy composite network structure material, characterized in that, The CuCr alloy penetrates into the grain boundary of the CrMnFeCoNi alloy particles in the CrMnFeCoNi / CuCr alloy composite net structure material, and has a layer structure, the tensile strength of the CrMnFeCoNi / CuCr alloy composite net structure material reaches 900-1200 MPa, and the elongation is 15%-20%; the method comprises the following steps: (1) taking a chromium source, a manganese source, an iron source, a cobalt source, a nickel source to prepare a CrMnFeCoNi alloy powder; taking a copper source, a copper-chromium intermediate alloy to prepare a CuCr alloy powder; the chromium source is Cr, the manganese source is Mn, the iron source is Fe, the cobalt source is Co, and the nickel source is Ni, and the mass fractions are respectively Cr: 20-28 parts, Mn: 19-27 parts, Fe: 19-27 parts, Co: 22-32 parts, and Ni: 19-28 parts; the copper-chromium intermediate alloy is Cu 10 Cr intermediate alloy, the copper source is electrolytic pure copper, and the mass fractions of the copper-chromium intermediate alloy and the electrolytic pure copper are respectively 10-15 parts and 85-90 parts; (2) mixing the CrMnFeCoNi alloy powder and the CuCr alloy powder obtained in step (1) to obtain a composite material mixed powder; the mixing mass ratio of the CrMnFeCoNi alloy powder and the CuCr alloy powder is (1:1)-(7:3); (3) vacuum sintering, heat preservation and cooling of the composite material mixed powder obtained in step (2) to obtain a sintered sample; (4) solid solution treatment of the sintered sample obtained in step (3), and then sequentially performing hot rolling treatment and cold rolling treatment to obtain a CrMnFeCoNi / CuCr alloy composite net structure material; wherein the hot rolling temperature is 800-1000 DEG C, the hot rolling pass reduction is 5%-40%, and the total deformation amount of hot rolling is 50-70%; the pass deformation amount of the cold rolling treatment is 10-20%; and the total deformation amount of the hot rolling treatment and the cold rolling treatment is 80-90%.

2. The production method according to claim 1, characterized by, In step (1), the preparation of the CrMnFeCoNi alloy powder and the preparation of the CuCr alloy powder are both carried out by using an inert gas atomization method, and the reaction parameters are as follows: Ar is used as the inert gas, the temperature of the heat preservation furnace melt is 1100-1200 DEG C, the heat preservation time is 10-15 minutes, and the gas atomization pressure is 2-5 MPa.

3. The preparation method according to claim 1, characterized in that, In step (2), the physical mixing is carried out by using a V-shaped mixer, and the mixing time is 3-7 hours; and the particle size of the composite material mixed powder is 10-52 microns.

4. The method of claim 1, wherein, In step (3), the vacuum sintering is carried out by using a hot pressing sintering furnace at 50 MPa or below, the pressure on the compact during the vacuum sintering is 20-50 MPa, the sintering temperature is 800 DEG C-1000 DEG C, and the sintering temperature is 800 DEG C-1000 DEG C.

5. The preparation method according to claim 1, characterized in that, In step (3), the heat preservation time is 5-60 minutes, and the cooling is carried out by using a furnace cooling method.

6. The method of claim 1, wherein, In step (4), the solid solution treatment is carried out in a muffle furnace for 4-8 hours, and the solid solution temperature is 800 DEG C-1000 DEG C.

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