High-entropy boride ceramic particle reinforced copper-based composite material and preparation method thereof

Abstract

The invention discloses a high-entropy boride ceramic particle reinforced copper-based composite material and a preparation method thereof, high-entropy ceramic particles are single-phase ceramic particles generated by in-situ reaction of metal elements such as Ti, Zr, Hf, Cr, Ta, Nb, W, V, Mo and Sc and nonmetal element B, and the mass fraction of the high-entropy ceramic particles is 0.5-8 wt.%. The preparation method comprises the following steps of reactive casting, thermal deformation, thermomechanical treatment and the like. According to the copper-based composite material, the two important problems of macrosegregation and microcosmic agglomeration of a reinforced phase in the traditional casting process are solved, meanwhile, the copper-based composite material has the excellent performance of high conductivity, high strength, wear resistance and the like, prepared high-entropy ceramic particles are distributed in a dispersed mode, and compared with other in-situ preparation methods, the copper-based composite material has remarkable advantages and progress. The technical scheme provided by the invention is suitable for preparing the high-performance copper-based composite material with low cost and short process, and has obvious application prospects and technical benefits.

Description

Technical Field

[0001] The invention belongs to the technical field of copper-based composite materials, and particularly relates to a high-entropy boride ceramic particle reinforced copper-based composite material and a preparation method thereof. Technical Background

[0002] High-performance conductive copper-based composite materials have excellent conductivity and strength, as well as excellent high temperature resistance, wear resistance and ablation resistance. They are expected to become one of the key basic materials supporting the country's future major infrastructure and emerging industries. At present, high-performance conductive copper-based composite materials with better industrial application indicators have been prepared based on technologies such as powder metallurgy (CN 202110487939.5), aerosolization (CN202111247289.3), additive manufacturing and sol-gel-sintering (CN 201510330692.0). However, the above technologies all rely on cutting-edge equipment to varying degrees and face problems such as complex preparation processes and high preparation costs, which seriously restricts the widespread application of copper-based composite materials.

[0003] As we all know, casting technology is the most popular preparation technology for copper alloys, but its application in metal matrix composite forming is very limited. The fundamental reason is that it is mainly limited by the poor matching between the reinforcement phase and the matrix (such as large specific gravity difference and poor interface wettability, etc.), and it has only been industrially applied in a few composite systems with better matching, such as TiB / Ti and SiC / Al. These common problems are particularly evident in the liquid forming process of copper-based composites, which seriously restricts the development and application of copper-based composite casting forming technology. Although researchers have previously used casting technologies such as microalloying, dual melt mixing + rapid solidification (CN 200510032207.8) and field-assisted stirring casting to regulate and improve the performance of copper-based composites, and achieved good results, the composites prepared by such methods are either still limited to one-dimensional low-dimensional materials in ingot size, or have high requirements for material system and casting technology, and have not fundamentally solved the fundamental problem of large-size ingot forming. Based on this, it is imperative to develop a new type of copper-based composite material and its preparation technology suitable for traditional casting technology, so as to prepare large-sized copper-based composite materials with macro / micro uniform distribution of reinforcing phase, so as to meet the industrial needs of low-cost, short-cycle and batch preparation of high-performance conductive copper-based composite materials. Summary of the invention

[0004] To solve the above problems, the present invention provides two technical solutions, specifically a high-entropy boride ceramic particle reinforced copper-based composite material and a preparation method thereof, which solves the problems of poor macro / micro uniform distribution caused by poor matching between the reinforcing phase and the matrix in the traditional liquid forming process of copper-based composite materials. The high-entropy boride ceramic particle reinforced copper-based composite material of the present invention has excellent structural-functional integration performance.

[0005] The first technical solution of the present invention is a high entropy boride ceramic particle reinforced copper-based composite material, comprising: high entropy boride ceramic particles, wherein the high entropy boride ceramic particles are single-phase ceramic particles generated by an in-situ reaction of multiple metal elements and a boron element; in terms of mass percentage, the mass percentage of the high entropy boride ceramic particles is 0.5wt.% to 8wt.%, the remainder is Cu, and the sum of the mass percentages of Cu and the high entropy boride ceramic particles is 100%.

[0006] Furthermore, the plurality of metal elements include Ti, Zr, Cr, Hf, Ta, Nb, W, V, Mo or Sc.

[0007] The second technical solution of the present invention is a method for preparing a high entropy boride ceramic particle reinforced copper-based composite material, which is specifically implemented according to the following steps:

[0008] Step 1, preparation of composite material: weighing raw materials according to mass percentage, melting the raw materials within a reaction temperature range to obtain a composite material melt, and solidifying the melt in a mold to obtain a composite material ingot;

[0009] Step 2, thermal deformation: thermally deforming the sample obtained in step 1, wherein the thermal deformation temperature is 850° C. to 950° C., and the deformation amount is 5% to 90%;

[0010] Step 3, deformation heat treatment: the sample obtained in step 2 is subjected to deformation heat treatment, characterized in that the deformation amount in the deformation heat treatment is 0 to 90%, the heat treatment temperature is 300°C to 1000°C, and the heat treatment time is 5min to 15h.

[0011] The second technical solution of the present invention is also characterized in that: the raw materials in step 1 are pure Cu, Ti, Zr, Hf, Cr, Ta, B and other particles; the reaction temperature in step 1 is 1150°C to 1650°C, the composite material melt is kept at the reaction temperature for 3 to 15 minutes and then cast, and then solidified in a mold, and the mold can be a graphite mold, a water-cooled copper mold, a steel mold, etc.

[0012] The beneficial effects of the present invention are:

[0013] (1) The present invention utilizes the adjustable and designable properties of multi-component in-situ self-generated high-entropy ceramic particles in the liquid forming process to design high-entropy ceramic particles with a density close to that of copper, thereby solving the problem of macro-segregation of the reinforcing phase in the liquid forming of large-sized parts. By in-situ self-generating high-entropy boride ceramic particles with a density close to that of the copper matrix in liquid copper, the floating or sinking phenomenon of ceramic particles during the solidification process is avoided, solving the problem of macro-segregation of ceramic particles in the forming process of large-sized parts, and facilitating the preparation of large-sized copper-based composite materials;

[0014] (2) The present invention utilizes the element interface self-modification characteristics during the in-situ self-generation process of high-entropy ceramic particles to solve the problem of micro-agglomeration of traditional in-situ self-generated ceramic particles caused by poor interface wettability, and prepares a high-entropy boride ceramic particle reinforced copper-based composite material with fine size and uniform microscopic distribution;

[0015] (3) The high-entropy boride ceramic particle reinforced copper-based composite material of the present invention has the characteristics of simple process and short cycle, and has the performance characteristics of high strength, high conductivity, wear resistance, arc ablation resistance, etc. Compared with the copper-based composite material prepared by the existing public technology, its performance, preparation cost and process cycle advantages are obvious, and it is expected to be suitable for industrial preparation. Therefore, the copper-based composite material prepared by this technology is expected to be promoted and applied in the fields of cutting-edge weapons and equipment, new energy vehicles, advanced rail transportation, ultra-high voltage power grids, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a SEM microstructure of a high entropy boride ceramic particle reinforced copper-based composite material obtained in Example 4 of the present invention.

[0017] Figure 2 This is the quantitative statistical result of the high entropy ceramic particle size obtained in Example 4 of the present invention.

[0018] Figure 3 This is a tensile curve of a high entropy boride ceramic particle reinforced copper-based composite material obtained in Example 5 of the present invention. DETAILED DESCRIPTION

[0019] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0020] The following embodiment of the present invention provides a high entropy boride ceramic particle reinforced copper-based composite material, wherein the high entropy boride ceramic particle reinforced copper-based composite material can be (TiZrHfCrSc)B 2 / Cu、(TiZrHfCrTa)B 2 / Cu, etc.

[0021] A high entropy boride ceramic particle reinforced copper-based composite material, comprising high entropy boride ceramic particles, wherein the high entropy boride ceramic particles can be (TiZrHfCrSc)B 2 、(TiZrHfCrTa)B 2 etc., the (TiZrHfCrSc)B 2 and (TiZrHfCrTa)B 2 It is a new type of single-phase boride ceramic phase, which is obtained by the simultaneous in-situ reaction of Ti, Zr, Hf, Cr and Ta or Sc elements with B element, wherein the mass fraction of the above new ceramic phase is between 0.5wt.% and 8wt.%, the remainder is Cu, and the sum of the mass percentages is 100%.

[0022] Preparation of (TiZrHfCrSc)B in Example 2 / Cu and (TiZrHfCrTa)B 2 / Cu composite material, the Cu raw material is preferably oxygen-free Cu; the Ti raw material is preferably Cu-Ti master alloy; the Zr raw material is preferably Cu-Zr master alloy; the Hf raw material is preferably Cu-Hf master alloy; the Cr raw material is preferably Cu-Cr master alloy; the Ta raw material is preferably Cu-Ta master alloy; the Sc element is preferably Cu-Sc alloy; the B raw material is preferably Cu-B master alloy, wherein each master alloy is obtained by vacuum induction melting of pure raw materials; and the vacuum degree before the composite material is prepared needs to reach 5×10 -3 Pa, and the smelting process is protected by high purity argon gas.

[0023] Example 1

[0024] This example discloses a 3.8wt.% (TiZrHfCrSc)B 2 / Cu composite material and preparation method thereof, based on 100% by mass, in this embodiment (TiZrHfCrSc)B 2 The nominal content of Cu is 3.8 wt.%, with the remainder being Cu.

[0025] Step 1, composite material casting: The prepared Cu-Ti-Zr-Hf-Cr-Sc master alloy and Cu-B master alloy are induction melted, and the vacuum degree before melting is required to reach 5×10 -3 Pa, the smelting process is protected by argon; after the melt is kept at 1500℃ for 3 minutes, it is solidified in a water-cooled copper mold to obtain a composite material ingot;

[0026] Step 2, hot rolling: hot rolling the as-cast sample in step 1 at 900° C., with a hot forging deformation of 50%;

[0027] Step 3, cold rolling: cold rolling the sample obtained in step 2, with the cold rolling deformation amount being 20%;

[0028] Step 4, annealing: annealing the sample obtained in step 3 at a temperature of 500°C for 20 min;

[0029] Step 5, cold rolling: cold rolling the sample obtained in step 4, with a cold rolling deformation of 50%;

[0030] Step 6, annealing: annealing the sample obtained in step 5 at a temperature of 500°C for 40 min;

[0031] Step 7, cold rolling: cold rolling the sample obtained in step 6, with a cold rolling deformation of 60%;

[0032] The (TiZrHfCrSc)B obtained in this example 2 The room temperature tensile strength of the Cu / Cu composite is 587MPa and the electrical conductivity is 83.2%IACS.

[0033] Example 2

[0034] This embodiment discloses a 2.4wt.% (TiZrHfCrTa)B 2 / Cu composite material and preparation method thereof, based on 100% by mass, in this embodiment (TiZrHfCrTa)B 2 The nominal content of Cu is 2.4 wt.%, with the remainder being Cu.

[0035] In this embodiment, (TiZrHfCrTa)B 2 The preparation method of the / Cu composite material specifically comprises the following steps:

[0036] Step 1, composite material casting: The prepared Cu-Ti-Zr-Hf-Cr-Ta master alloy and Cu-B master alloy are induction melted, and the vacuum degree before melting is required to reach 5×10 -3 Pa, the melting process is protected by argon; after the melt is kept at 1250℃ for 10min, it is cast in a graphite mold and solidified to obtain a composite material ingot;

[0037] Step 2, hot forging: hot forging the as-cast sample in step 1 at 900°C, with a hot forging deformation of 50%; the 2.4wt.% (TiZrHfCrTa)B 2 The room temperature tensile strength of the Cu / Cu composite material is 325MPa, the electrical conductivity is 92.3%IACS, the elongation after fracture is 38.5%, and the softening temperature is >900℃.

[0038] Example 3

[0039] This embodiment discloses a 4.8wt.% (TiZrHfCrTa) B2 / Cu composite material and preparation method thereof, based on 100% by mass, in this embodiment (TiZrHfCrTa)B 2 The nominal content of Cu is 4.8 wt.%, with the remainder being Cu.

[0040] Step 1, composite material casting: The prepared Cu-Ti-Zr-Hf-Cr-Ta master alloy and Cu-B master alloy are induction melted, and the vacuum degree before melting is required to reach 5×10 -3 Pa, the melting process is protected by argon; after the melt is kept at 1500℃ for 3 minutes, it solidifies in a water-cooled copper mold to obtain a composite material ingot;

[0041] Step 2, hot rolling: hot rolling the as-cast sample in step 1 at 900° C., with a hot forging deformation of 50%;

[0042] Step 3, cold rolling: cold rolling the sample obtained in step 2, with the cold rolling deformation amount being 20%;

[0043] Step 4, annealing: annealing the sample obtained in step 3 at a temperature of 500°C for 20 min;

[0044] Step 5, cold rolling: cold rolling the sample obtained in step 4, with a cold rolling deformation of 50%;

[0045] Step 6, annealing: annealing the sample obtained in step 5 at a temperature of 500°C for 40 min;

[0046] Step 7, cold rolling: cold rolling the sample obtained in step 6, with a cold rolling deformation of 60%;

[0047] The (TiZrHfCrTa)B obtained in this example 2 The room temperature tensile strength of the / Cu composite material is 601MPa, and the conductivity is 85.1%IACS, which is a good match in conductivity and strength compared with Example 1. In addition, under the friction and wear conditions of 50N, 200r / min, and 100A current, the wear rate is 0.0877mg / m after 30min of friction, and the current carrying efficiency is 90.3%. Compared with imported copper materials under the same experimental conditions, it has obvious performance advantages, and the specific performance comparison is shown in Table 1.

[0048] Table 1 Performance comparison between the composite material of the present invention and imported high-performance copper material

[0049]

[0050] Example 4

[0051] This embodiment discloses a (TiZrHfCrTa)B2 / Cu composite material and preparation method thereof, in this embodiment (TiZrHfCrTa)B 2 The nominal content of Cu is 4.8 wt.%, with the remainder being Cu, totaling 100%.

[0052] Step 1, composite material casting: The prepared Cu-Ti-Zr-Hf-Cr-Ta master alloy and Cu-B master alloy are induction melted, and the vacuum degree before melting is required to reach 5×10 -3 Pa, the melting process is protected by argon; after the melt is kept at 1200℃ for 10min, it solidifies in a graphite mold to obtain a composite material ingot;

[0053] Step 2, hot forging: hot forging the as-cast sample in step 1 at 900° C. with a hot forging deformation of 50%;

[0054] The 4.8wt.% (TiZrHfCrTa) B 2 The high entropy ceramic particles of the / Cu composites are evenly distributed macroscopically, and there is no obvious macro / micro segregation at the bottom and top of the sample, such as Figure 1 Shown as white particles in the middle. Figure 2 The size of the high entropy ceramic particles was quantitatively analyzed, and the average size was 187 nm. The room temperature tensile strength of the composite material obtained in this example was 418 MPa, the electrical conductivity was 85.3% IACS, and the elongation after fracture was 25.6%.

[0055] Example 5

[0056] This example discloses a 5.2wt.% (TiZrHfCrTa)B 2 / Cu composite material and preparation method thereof, in this embodiment (TiZrHfCrTa)B 2 The nominal content of Cu is 5.2 wt.%, with the remainder being Cu, totaling 100%.

[0057] Step 1, composite material casting: The prepared Cu-Ti-Zr-Hf-Cr-Ta master alloy and Cu-B master alloy are induction melted, and the vacuum degree before melting is required to reach 5×10 -3 Pa, the melting process is protected by argon; after the melt is kept at 1500℃ for 3 minutes, it solidifies in a water-cooled copper mold to obtain a cast composite material ingot;

[0058] Step 2, hot forging: hot forging the as-cast sample in step 1 at 900° C. with a hot forging deformation of 50%;

[0059] Step 3, cold rolling: cold rolling the sample obtained in step 2, with the cold rolling deformation amount being 80%;

[0060] The 5.2wt.% (TiZrHfCrTa)B obtained in this example 2 The room temperature tensile strength of the / Cu composite material is 735MPa, the electrical conductivity is 76.9%IACS, and the tensile curve is shown in Figure 3 shown.

[0061] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A high entropy boride ceramic particle reinforced copper-based composite material, characterized in that: The invention comprises high entropy boride ceramic particles, wherein the high entropy boride ceramic particles are single-phase ceramic particles generated by in-situ reaction of multiple metal elements and boron element; in terms of mass percentage, the mass percentage of the high entropy boride ceramic particles is 0.5wt.% to 8wt.%, the remainder is Cu, and the sum of the mass percentages of Cu and the high entropy boride ceramic particles is 100%.

2. The high entropy boride ceramic particle reinforced copper-based composite material according to claim 1, characterized in that: The plurality of metal elements include Ti, Zr, Cr, Hf, Ta, Nb, W, V, Mo or Sc.

3. A method for preparing the high entropy boride ceramic particle reinforced copper-based composite material as claimed in claim 1, characterized in that: The following steps are involved: Step 1, preparation of composite material: weighing raw materials according to mass percentage, melting the raw materials within a reaction temperature range to obtain a composite material melt, and solidifying the melt in a mold to obtain a composite material ingot; Step 2, thermal deformation: thermally deforming the ingot obtained in step 1, wherein the thermal deformation temperature is 850° C. to 950° C. and the deformation amount is 5% to 90%; Step 3, deformation heat treatment: the sample obtained in step 2 is subjected to deformation heat treatment, the deformation amount in the deformation heat treatment is 0 to 90%, the heat treatment temperature is 300° C. to 1000° C., and the heat treatment time is 5 min to 15 h.

4. The preparation method according to claim 3, characterized in that: In the step 1, the reaction temperature is 1150° C. to 1650° C., the composite material melt is kept at the reaction temperature for 3 to 15 minutes and then cast, and then solidified in the mold.

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