High-entropy alloy particle reinforced copper-based composite material with interface diffusion layer structure and preparation method of high-entropy alloy particle reinforced copper-based composite material

Abstract

The invention discloses a high-entropy alloy particle reinforced copper-based composite material with an interface diffusion layer structure and a preparation method of the high-entropy alloy particle reinforced copper-based composite material, and relates to the technical field of copper-based composites.The preparation method comprises the following steps that copper plating treatment is conducted on the surfaces of high-entropy alloy particles, then deionized water is used for cleaning and drying, and then diffusion heat treatment is conducted on the high-entropy alloy particles; the high-entropy alloy particles are provided with interface diffusion layer structures and the surfaces of the high-entropy alloy particles are plated with copper; the high-entropy alloy particles serve as a reinforcing phase, a pure copper plate serves as a base body, and the high-entropy alloy particle reinforced copper-based composite material with the interface diffusion layer structure is prepared through a stirring friction machining method; the method is simple to operate, solves the problem of poor interface diffusivity of reinforced particles and a matrix when the composite material is prepared through stirring friction processing, avoids the adverse effect of the heat treatment process on the copper matrix in the composite material, realizes the synergistic improvement of the strength and plasticity of the composite material, and remarkably improves the overall performance of the composite material.

Description

Technical Field

[0001] The present invention relates to the technical field of copper-based composite materials, and in particular to a method for preparing a high-entropy alloy particle-reinforced copper-based composite material with an interface diffusion layer structure. Background Art

[0002] Copper-based composites retain the excellent thermal conductivity, electrical conductivity, and corrosion resistance of pure copper while also offering high strength and wear resistance, making them widely used in fields such as aerospace and power electronics. Among the commonly used reinforcing particles, ceramic particles can effectively improve the strength and hardness of composites, but their poor wettability with the pure copper matrix leads to a significant loss of ductility. While pure metal particles exhibit good wettability with the matrix, their inherent strength limitations result in minimal improvement in the overall strength of the composite.

[0003] High-entropy alloys (HEAs), due to their unique alloying effect, exhibit ultrahigh strength, hardness, wear resistance, excellent ductility, and thermal stability. Furthermore, their unique solid solution structure enables them to maintain excellent interfacial bonding with the metal matrix, making them highly promising reinforcement materials. In recent years, friction stir processing (FSP) has demonstrated unique advantages in the preparation of copper-based composites. Multi-pass processing promotes uniform distribution of the reinforcement particles within the copper matrix, while the vigorous stirring action promotes grain refinement within the copper matrix.

[0004] However, as a solid-phase processing method, friction stir processing (FSP) requires relatively low temperatures during the preparation of composite materials. This results in insufficient interdiffusion between the high-entropy alloy particles and the pure copper matrix, leading to poor interfacial bonding strength and compromising the composite's performance. Heat treatment of the composite material can promote interfacial diffusion, but high temperatures also increase the copper matrix grain size and reduce dislocation density, ultimately reducing its overall performance. Summary of the Invention

[0005] The purpose of the present invention is to provide a method for preparing a high entropy alloy particle reinforced copper-based composite material with an interface diffusion layer structure, and to solve the following technical problems: How to improve the interfacial bonding strength of high entropy alloy particle reinforced copper-based composites without changing the matrix structure.

[0006] The purpose of the present invention can be achieved through the following technical solutions: In a first aspect, the present invention discloses a method for preparing a high entropy alloy particle reinforced copper-based composite material having an interface diffusion layer structure, comprising the following steps: Step 1: copper plating the surface of the high entropy alloy particles. After the copper plating is completed, the high entropy alloy particles are separated from the copper plating solution, and then washed with deionized water and dried to obtain high entropy alloy particles with copper plating on the surface. Step 2: performing a diffusion heat treatment on the surface copper-plated high entropy alloy particles to obtain surface copper-plated high entropy alloy particles with an interface diffusion layer structure; Step 3: Using surface copper-plated high-entropy alloy particles with an interface diffusion layer structure as the reinforcement phase and pure copper plate as the matrix, a stir friction processing method is used to prepare a high-entropy alloy particle-reinforced copper-based composite material with an interface diffusion layer structure.

[0007] Preferably, in step 1, the copper plating method is a chemical copper plating method or a mechanical alloying method.

[0008] Preferably, the chemical copper plating method comprises the following steps: Step 1: The high entropy alloy particles are acid-washed in a H2SO4 solution for 0.5 h, and then washed with deionized water to obtain clean high entropy alloy particles; Step 2: The clean high-entropy alloy particles are first added to the HCHO aqueous solution to wet them, and then transferred to the chemical copper plating solution, stirred evenly at 40-60° C. to form a mixed solution, and at the same time, the mixed solution is adjusted to a pH greater than 12 with a NaOH solution until the reaction is completed.

[0009] Preferably, in step 1, the mass fraction of the H2SO4 solution is ≥98%.

[0010] Preferably, in step 2, the concentration of the HCHO aqueous solution is 200 mL / L.

[0011] Preferably, in step 2, the chemical copper plating solution is a mixed solution of CuSO4·5H2O and KNaC4H4O6·5H2O, wherein the concentration of CuSO4·5H2O is 70 g / L and the concentration of KNaC4H4O6·5H2O is 170 g / L.

[0012] Preferably, in step 2, the concentration of the NaOH solution is 50 g / L.

[0013] Preferably, in step 1, the high entropy alloy particles include FeCoNiCrAl series high entropy alloy particles, CoCrFeNi series high entropy alloy particles, and / or.

[0014] Preferably, in step 1, the particle size of the high entropy alloy particles is 15-50 μm.

[0015] Preferably, in step 2, the diffusion heat treatment method is: placing the high entropy alloy particles with copper plating on the surface in a vacuum heating furnace and treating them at 800-900° C. for 0.5-2 hours.

[0016] Preferably, in step three, the method of the friction stir processing method is: using a milling cutter to open a groove with a width of 0.5-2 mm and a depth less than the length of the stirring needle on the surface of the pure copper plate; filling the groove with high-entropy alloy particles with a surface copper-plated interface diffusion layer structure, using a needle-free stirring head to perform friction stir processing along the direction of the groove, and sealing the groove surface; using a needle stirring head to perform multiple reciprocating friction stir processing along the direction of the sealed groove.

[0017] Preferably, in step three, the purity of the pure copper plate is ≥99.8%.

[0018] In a second aspect, the present invention further discloses a copper-based composite material, which is prepared by the above-mentioned method for preparing a high-entropy alloy particle-reinforced copper-based composite material with an interface diffusion layer structure.

[0019] Beneficial effects of the present invention: In the preparation method of the high-entropy alloy particle-reinforced copper-based composite material with an interface diffusion layer structure of the present invention, the interface diffusion layer structure is pre-generated by copper plating and heat treating the surface of the high-entropy alloy particles, and a stir friction processing method is combined to prepare the high-entropy alloy particle-reinforced copper-based composite material with the interface diffusion layer structure; the method is simple to operate, solves the problem of poor interface diffusion ability between the reinforcing particles and the matrix when the composite material is prepared by stir friction processing, and improves the bonding strength between the interfaces; at the same time, avoids the adverse effects of the heat treatment process on the copper matrix in the composite material, and achieves a synergistic improvement in the strength and plasticity of the composite material; significantly improves the overall performance of the composite material; multi-pass processing achieves uniform distribution of the high-entropy alloy particles in the pure copper matrix; the preparation process is green and clean, and avoids pollution such as dust, light, and smoke. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The present invention will be further described below with reference to the accompanying drawings.

[0021] Figure 1 3. This is a schematic diagram of the structure of the interface diffusion layer generated by the FeCoNiCrAl high entropy alloy particles after copper plating and heat treatment in Example 1 of the present invention; Figure 2 This is a microstructure morphology of the FeCoNiCrAl high entropy alloy particle reinforced copper-based composite material with an interface diffusion layer structure prepared in Example 1 of the present invention; Figure 3 This is a microstructure morphology of the FeCoNiCrAl high entropy alloy particle reinforced copper-based composite material with an interface diffusion layer structure prepared in Comparative Example 1 of the present invention; Figure 4 This is a microstructure morphology diagram of the FeCoNiCrAl high entropy alloy particle reinforced copper-based composite material with an interface diffusion layer structure prepared in Comparative Example 2 of the present invention. DETAILED DESCRIPTION

[0022] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0023] Unless otherwise specified, the experimental methods in the following examples are conventional methods and were performed according to the techniques or conditions described in the literature in the field or according to the product instructions. The materials and reagents used in the following examples, unless otherwise specified, were all commercially available.

[0024] Example 1 Preparation of a FeCoNiCrAl high entropy alloy particle reinforced copper-based composite material with an interface diffusion layer structure, comprising the following steps: Step 1, placing FeCoNiCrAl high entropy alloy particles with a particle size range of 15-50 μm in a concentrated H2SO4 solution with a mass fraction of 98% for pickling for 0.5 h, and washing with deionized water to obtain clean FeCoNiCrAl high entropy alloy particles; CuSO4·5H2O and KNaC4H4O6·5H2O are mixed to form an electroless copper plating solution, wherein the concentration of CuSO4·5H2O is 70 g / L, and the concentration of KNaC4H4O6·5H2O is 170 g / L; then the clean FeCoNiCrAl high entropy alloy particles are first added to a 200 mL / L HCHO aqueous solution to wet them, and then transferred to the electroless copper plating solution, stirred uniformly at 50° C. to form a mixed solution, and at the same time, a NaOH solution is used to adjust the mixed solution to a pH>12, and copper plating is performed until the reaction is completed; after the copper plating is completed, the high entropy alloy particles are separated from the copper plating solution, and then washed with deionized water and dried to obtain FeCoNiCrAl high entropy alloy particles with surface copper plating; Step 2: Place the copper-plated FeCoNiCrAl high entropy alloy particles in a vacuum heating furnace and treat them at 850°C for 1 hour to obtain Figure 1 The surface copper-plated FeCoNiCrAl high entropy alloy particles with an interface diffusion layer structure are shown; Step 3: Using high-entropy alloy particles with surface copper plating having an interface diffusion layer structure as the reinforcing phase and pure copper plate as the matrix, a stir friction processing method is adopted: a milling cutter is used to open a groove with a width of 1 mm and a depth less than the length of the stirring needle on the surface of a pure copper plate with a purity of 99.8% and a size of 200 mm × 100 mm × 4 mm; the groove is filled with FeCoNiCrAl high-entropy alloy particles with surface copper plating having an interface diffusion layer structure, and a needle-free stirring head is used to stir friction process along the groove direction, and the groove surface is sealed; a needle stirring head is used to perform multiple reciprocating stir frictions along the sealed groove direction to prepare a FeCoNiCrAl high-entropy alloy particle-reinforced copper-based composite material with an interface diffusion layer structure, and its micromorphology is shown in the figure below. Figure 2 shown.

[0025] Example 2 Preparation of a FeCoNiCrAl high entropy alloy particle reinforced copper-based composite material with an interface diffusion layer structure, comprising the following steps: Step 1, placing FeCoNiCrAl high entropy alloy particles with a particle size range of 15-50 μm in a concentrated H2SO4 solution with a mass fraction of 98% for pickling for 0.5 h, and washing with deionized water to obtain clean FeCoNiCrAl high entropy alloy particles; CuSO4·5H2O and KNaC4H4O6·5H2O are mixed to form an electroless copper plating solution, wherein the concentration of CuSO4·5H2O is 70 g / L, and the concentration of KNaC4H4O6·5H2O is 170 g / L; then the clean FeCoNiCrAl high entropy alloy particles are first added to a 200 mL / L HCHO aqueous solution to wet them, and then transferred to the electroless copper plating solution, stirred uniformly at 50° C. to form a mixed solution, and at the same time, a NaOH solution is used to adjust the mixed solution to a pH>12, and copper plating is performed until the reaction is completed; after the copper plating is completed, the high entropy alloy particles are separated from the copper plating solution, and then washed with deionized water and dried to obtain FeCoNiCrAl high entropy alloy particles with surface copper plating; Step 2: placing the copper-plated FeCoNiCrAl high-entropy alloy particles in a vacuum heating furnace and treating them at 800° C. for 2 hours to obtain copper-plated FeCoNiCrAl high-entropy alloy particles with an interface diffusion layer structure; Step 3: Using high-entropy alloy particles with copper plating on the surface having an interface diffusion layer structure as the reinforcing phase and a pure copper plate as the matrix, a stir friction processing method is adopted: a milling cutter is used to open a groove with a width of 1 mm and a depth less than the length of the stirring needle on the surface of a pure copper plate with a purity of 99.8% and a size of 200 mm × 100 mm × 4 mm; the groove is filled with FeCoNiCrAl high-entropy alloy particles with copper plating on the surface having an interface diffusion layer structure, and a needle-free stirring head is used to stir friction processing along the direction of the groove, and the groove surface is sealed; a needle stirring head is used to perform multiple reciprocating stir friction along the direction of the sealed groove, and the processing thickness is the same as in Example 1, to prepare a FeCoNiCrAl high-entropy alloy particle reinforced copper-based composite material with an interface diffusion layer structure.

[0026] Example 3 Preparation of a FeCoNiCrAl high entropy alloy particle reinforced copper-based composite material with an interface diffusion layer structure, comprising the following steps: Step 1, placing FeCoNiCrAl high entropy alloy particles with a particle size range of 15-50 μm in a concentrated H2SO4 solution with a mass fraction of 98% for pickling for 0.5 h, and washing with deionized water to obtain clean FeCoNiCrAl high entropy alloy particles; CuSO4·5H2O and KNaC4H4O6·5H2O are mixed to form an electroless copper plating solution, wherein the concentration of CuSO4·5H2O is 70 g / L, and the concentration of KNaC4H4O6·5H2O is 170 g / L; then the clean FeCoNiCrAl high entropy alloy particles are first added to a 200 mL / L HCHO aqueous solution to wet them, and then transferred to the electroless copper plating solution, stirred uniformly at 50° C. to form a mixed solution, and at the same time, a NaOH solution is used to adjust the mixed solution to a pH>12, and copper plating is performed until the reaction is completed; after the copper plating is completed, the high entropy alloy particles are separated from the copper plating solution, and then washed with deionized water and dried to obtain FeCoNiCrAl high entropy alloy particles with surface copper plating; Step 2: placing the copper-plated FeCoNiCrAl high-entropy alloy particles in a vacuum heating furnace and treating them at 900° C. for 1.5 hours to obtain copper-plated FeCoNiCrAl high-entropy alloy particles with an interface diffusion layer structure; Step 3: Using high-entropy alloy particles with copper plating on the surface having an interface diffusion layer structure as the reinforcing phase and a pure copper plate as the matrix, a stir friction processing method is adopted: a milling cutter is used to open a groove with a width of 1 mm and a depth less than the length of the stirring needle on the surface of a pure copper plate with a purity of 99.8% and a size of 200 mm × 100 mm × 4 mm; the groove is filled with FeCoNiCrAl high-entropy alloy particles with copper plating on the surface having an interface diffusion layer structure, and a needle-free stirring head is used to stir friction processing along the direction of the groove, and the groove surface is sealed; a needle stirring head is used to perform multiple reciprocating stir friction along the direction of the sealed groove, and the processing thickness is the same as in Example 1, to prepare a FeCoNiCrAl high-entropy alloy particle reinforced copper-based composite material with an interface diffusion layer structure.

[0027] Comparative Example 1 Preparation of FeCoNiCrAl high entropy alloy particle reinforced copper-based composite material, comprising the following steps: FeCoNiCrAl high entropy alloy particles with a particle size range of 15-50um are used as the reinforcement phase and pure copper plate is used as the matrix. Stir friction processing is adopted: a milling cutter is used to open a groove with a width of 1mm and a depth less than the length of the stirring needle on the surface of a pure copper plate with a purity of 99.8% and a size of 200mm×100mm×4mm; FeCoNiCrAl high entropy alloy particles are filled into the groove, and a needle-free stirring head is used to stir friction process along the groove direction, and the groove surface is sealed; a needle stirring head is used to perform multiple reciprocating stir friction along the sealed groove direction to prepare a FeCoNiCrAl high entropy alloy particle reinforced copper-based composite material, the micromorphology of which is shown in the figure. Figure 3 shown.

[0028] Comparative Example 2 Preparation of FeCoNiCrAl high entropy alloy particle reinforced copper-based composite material, compared with Example 1, the only difference is that in step 2, "treatment at 850 ° C for 1 h" is changed to "treatment at 800 ° C for 4 h", and the other steps and conditions remain the same. Finally, FeCoNiCrAl high entropy alloy particle reinforced copper-based composite material is obtained, and its micromorphology is shown in the figure below. Figure 4 shown.

[0029] Comparative Example 3 Preparation of FeCoNiCrAl high-entropy alloy particle reinforced copper-based composite materials. Compared with Example 1, the only difference is that in step 2, "treatment at 850°C for 1 h" is changed to "treatment at 700°C for 0.5 h", and the other steps and conditions remain the same, and finally a FeCoNiCrAl high-entropy alloy particle reinforced copper-based composite material is obtained.

[0030] Comparative Example 4 Preparation of FeCoNiCrAl high-entropy alloy particle reinforced copper-based composite materials. Compared with Example 1, the only difference is that in step 2, "treatment at 850°C for 1 h" is changed to "treatment at 1000°C for 0.5 h", and the other steps and conditions remain the same, and finally a FeCoNiCrAl high-entropy alloy particle reinforced copper-based composite material is obtained.

[0031] The copper-based composite materials prepared in Examples 1-3 and Comparative Examples 1-4 were subjected to performance tests, including tensile performance tests, and the test methods were based on the national standard method GB / T228-2002.

[0032] The test results are listed in Table 1, which is as follows: Table 1 Tensile strength (MPa) Elongation (%) Example 1 377.6 34.1 Example 2 374.2 34.9 Example 3 375.8 34.4 Comparative Example 1 354.2 29.4 Comparative Example 2 347.8 34.6 Comparative Example 3 358.1 30.6 Comparative Example 4 363.5 31.4 By analyzing the data in Table 1, it can be seen that compared with Comparative Examples 1-4, the copper-based composite materials of Examples 1-3 have significantly stronger tensile strength and elongation, which shows that the presence or absence of an interface diffusion layer structure and the setting of heat treatment parameters have a great influence on the performance of the composite material.

[0033] The above describes in detail several embodiments of the present invention. However, the above contents are only preferred embodiments of the present invention and should not be considered as limiting the scope of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the present invention.

Claims

1. A method for preparing a high entropy alloy particle reinforced copper-based composite material with an interface diffusion layer structure, characterized in that: The following steps are involved: Step 1: copper plating the surface of the high entropy alloy particles. After the copper plating is completed, the high entropy alloy particles are separated from the copper plating solution, and then washed with deionized water and dried to obtain high entropy alloy particles with copper plating on the surface. Step 2: performing a diffusion heat treatment on the surface copper-plated high entropy alloy particles to obtain surface copper-plated high entropy alloy particles with an interface diffusion layer structure; Step 3: Using surface copper-plated high-entropy alloy particles with an interface diffusion layer structure as the reinforcement phase and pure copper plate as the matrix, a stir friction processing method is used to prepare a high-entropy alloy particle-reinforced copper-based composite material with an interface diffusion layer structure.

2. The method for preparing a high entropy alloy particle reinforced copper-based composite material having an interface diffusion layer structure according to claim 1, characterized in that: In step 1, the copper plating method is a chemical copper plating method or a mechanical alloying method.

3. The method for preparing a high entropy alloy particle reinforced copper-based composite material having an interface diffusion layer structure according to claim 2, characterized in that: The chemical copper plating method comprises the following steps: Step 1: The high entropy alloy particles are acid-washed in a H2SO4 solution for 0.5 h, and then washed with deionized water to obtain clean high entropy alloy particles; Step 2: The clean high-entropy alloy particles are first added to the HCHO aqueous solution to wet them, and then transferred to the chemical copper plating solution, stirred evenly at 40-60° C. to form a mixed solution, and at the same time, the mixed solution is adjusted to a pH greater than 12 with a NaOH solution until the reaction is completed.

4. The method for preparing a high entropy alloy particle reinforced copper-based composite material having an interface diffusion layer structure according to claim 3, characterized in that: In step 2, the chemical copper plating solution is a mixed solution of CuSO4·5H2O and KNaC4H4O6·5H2O, wherein the concentration of CuSO4·5H2O is 70 g / L and the concentration of KNaC4H4O6·5H2O is 170 g / L.

5. The method for preparing a high entropy alloy particle reinforced copper-based composite material having an interface diffusion layer structure according to claim 1, characterized in that: In step 1, the high entropy alloy particles include FeCoNiCrAl series high entropy alloy particles, CoCrFeNi series high entropy alloy particles, and / or.

6. The method for preparing a high entropy alloy particle reinforced copper-based composite material having an interface diffusion layer structure according to claim 1, characterized in that: In step 1, the particle size of the high entropy alloy particles is 15-50 μm.

7. The method for preparing a high entropy alloy particle reinforced copper-based composite material having an interface diffusion layer structure according to claim 1, characterized in that: In step 2, the diffusion heat treatment method is: placing the high entropy alloy particles with copper plating on the surface in a vacuum heating furnace and treating them at 800-900° C. for 0.5-2 hours.

8. The method for preparing a high entropy alloy particle reinforced copper-based composite material having an interface diffusion layer structure according to claim 1, characterized in that: In step three, the method of the friction stir processing method is: using a milling cutter to open a groove with a width of 0.5-2 mm and a depth less than the length of the stirring needle on the surface of the pure copper plate; filling the groove with high-entropy alloy particles with a surface copper-plated interface diffusion layer structure, using a needle-free stirring head to perform friction stir processing along the direction of the groove, and sealing the groove surface; using a needle stirring head to perform multiple reciprocating friction stir processing along the direction of the sealed groove.

9. The method for preparing a high entropy alloy particle reinforced copper-based composite material having an interface diffusion layer structure according to claim 1, characterized in that: In step three, the purity of the pure copper plate is ≥99.8%.

10. A copper-based composite material, characterized in that: The high entropy alloy particle reinforced copper-based composite material with an interface diffusion layer structure is prepared by the preparation method according to any one of claims 1 to 9.

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