A copper alloy with TiC and TiB2 hybrid reinforcing phase and preparation method and application

Abstract

The application belongs to the technical field of copper alloy, and particularly relates to a copper alloy with TiC and TiB2 hybrid reinforcing phase, a preparation method and application. The preparation method of the copper alloy with TiC and TiB2 hybrid reinforcing phase provided in the application is to mix Ti, SiC and CuB and then sinter into a hybrid reinforcing phase body, so as to introduce the reinforcing phase such as TiC and TiB2 into the copper alloy by means of the reaction wetting method, avoid the defects such as poor wettability, weak interface bonding and uneven dispersion between the added reinforcing phase and the copper matrix, reduce the reaction between the Ti powder and the Si powder in the copper alloy raw material, increase the generation amount of the hybrid reinforcing phase such as TiC and TiB2, and improve the copper alloy. By using the spark plasma sintering and controlling the amount of Ti, SiC and CuB in the copper alloy raw material, the performance of the copper alloy is further improved, so as to solve the technical problem of low performance of the copper alloy prepared in the prior art.

Description

Technical Field

[0001] This application belongs to the field of copper alloy technology, and particularly relates to a copper alloy with TiC and TiB2 mixed reinforcing phases, its preparation method and application. Background Technology

[0002] Copper and copper alloys are among the earliest non-ferrous metal materials to be used on a large scale in human history.

[0003] Its application history can be traced back to the Bronze Age thousands of years ago, serving as the core material carrier for human civilization's transition from the Stone Age to the Metal Age. From early weapons, ritual objects, and production tools to core materials covering the entire industrial chain in modern industrial systems, including aerospace, marine vessels, metallurgy, power electronics, and machinery manufacturing, copper and copper alloys have always occupied a central position throughout the entire cycle of human industrial development due to their irreplaceable combination of physical and mechanical properties. Even today, with the continuous emergence of new materials such as titanium alloys, aluminum alloys, and special engineering plastics, copper and copper alloys remain irreplaceable basic materials in power transmission, heat exchange, wear and friction reduction, and corrosion resistance service scenarios, and their industrial scale and technological iteration speed have always kept pace with the development of modern industry.

[0004] Pure copper (also known as red copper), as the base material of copper alloy systems, derives its core performance advantages from its unique atomic structure and crystal lattice characteristics. Copper is located in the fourth period, group IB of the periodic table, with atomic number 29. It has a face-centered cubic crystal structure and no allotropic transformation. This crystallographic characteristic endows pure copper with extremely excellent plastic processing properties. It can be formed into various complex shapes such as foils, wires, tubes, and profiles through various processes such as cold working and hot working. The minimum processing size can reach the micrometer or even nanometer scale, meeting the processing needs of high-end applications such as precision electronic devices and micro-wires. The most core performance advantage of pure copper lies in its excellent electrical and thermal conductivity due to its extremely high free electron mobility, making it the preferred material for conductive and thermally conductive functional components in the industrial field. However, its strength, hardness, and wear resistance are relatively low, making it difficult to directly use as structural components under complex stress conditions. In order to overcome the performance limitations of pure copper... In the fields of science, technology, and industry, a technical approach centered on alloy design and microstructure control has been developed. By introducing different types and amounts of alloying elements into a copper matrix, combined with casting, plastic processing, and heat treatment, copper alloy systems with varying properties are prepared. While retaining the excellent electrical and thermal conductivity and corrosion resistance of the copper matrix, the mechanical properties are directionally controlled and significantly improved. Currently, the mainstream copper alloy systems in the industrial field can be divided into three main categories: brass, bronze, and cupronickel. Bronze is a copper-based alloy with tin, aluminum, beryllium, and other alloying elements as the main alloying elements, possessing excellent wear resistance and corrosion resistance. Cupronickel is a copper-based alloy with nickel as the main alloying element, characterized by extremely high corrosion resistance and antimagnetic properties. Brass, with its advantages of low cost, excellent processing performance, wide range of performance control, and high industrial maturity, has become the most widely used and highest-volume alloy category among the three major copper alloy systems.

[0005] Brass is a copper-based alloy with copper and zinc as the main alloying elements. The addition of zinc not only significantly improves the alloy's strength and hardness but also enhances casting fluidity and machinability. Depending on the zinc content, brass exhibits significant differences in mechanical and processing properties, making it suitable for various applications. To further push the performance limits of binary brass, research and industry often introduce alloying elements such as aluminum, manganese, silicon, iron, and nickel into the copper-zinc binary system to prepare multi-element copper alloys. The synergistic effect of these multiple elements enhances the performance of the copper alloy. Different alloying elements play differentiated modifying roles in multi-element brass, requiring precise composition design. This process enables targeted optimization of brass properties. Manganese has extremely high solid solubility in the copper-zinc matrix, further enhancing the solid solution strengthening effect of the alloy, significantly improving its strength and hardness. Simultaneously, it inhibits grain growth at high temperatures, greatly improving the alloy's thermal stability and impact resistance, while maintaining good toughness at low temperatures and preventing brittle cracking. Silicon, one of the core alloying elements in multi-element wear-resistant brass, has low solid solubility in the brass matrix, forming high-hardness intermetallic compounds. These hard second-phase particles, with a hardness exceeding HV450, are dispersed throughout the copper matrix, forming a stable "microscopic wear-resistant skeleton." Through the... The two-phase strengthening mechanism significantly improves the hardness and wear resistance of the alloy. Simultaneously, these hard particles effectively reduce the contact area between the alloy and its mating parts during frictional service, reducing adhesive wear and endowing the alloy with excellent friction-reducing and wear-resistant properties. Under dry friction and boundary lubrication conditions, the wear rate of silicon-containing multi-element brass can be reduced by more than an order of magnitude compared to binary brass. Furthermore, silicon can further improve the casting fluidity of the alloy, enhancing the forming quality of complex thin-walled castings. The core role of iron in brass is grain refinement. Its solubility in solid copper is extremely low, and it precipitates as iron-rich phase particles. These dispersed particles can act as... Heterogeneous nucleation cores significantly refine the as-cast grains of the alloy. Simultaneously, during hot working, they pin grain boundaries, inhibiting grain growth. Through a grain refinement strengthening mechanism, both the strength and toughness of the alloy are simultaneously improved. Adding iron to brass refines the grain size, achieving a simultaneous increase in strength and toughness. Furthermore, when iron is added synergistically with manganese and aluminum, it forms composite intermetallic compounds, further enhancing the alloy's wear resistance and making it suitable for high-load wear-resistant applications. The core value of aluminum in multi-element brass lies in improving the alloy's corrosion resistance and strength. Aluminum dissolved in the copper matrix further enhances the solid solution strengthening effect, increasing the alloy's strength and hardness.During the alloy's service life, aluminum preferentially forms a dense alumina oxide film on the surface, with a density and stability far exceeding that of pure copper oxide films. This effectively blocks corrosive media, significantly improving the alloy's resistance to atmospheric and seawater corrosion. It also inhibits dezincification corrosion in binary brass, reducing the alloy's annual corrosion rate. The addition of nickel further broadens the alloy's passivation range, enhancing its corrosion resistance in acidic media, while optimizing its hot and cold working properties, achieving a good balance of strength, corrosion resistance, and plasticity. Based on this multi-element copper alloy design, brass can achieve a significant improvement in strength, hardness, and wear resistance through the synergistic effect of various strengthening mechanisms such as solid solution strengthening, second-phase strengthening, and grain refinement. Simultaneously, it maintains good electrical and thermal conductivity and corrosion resistance, making it the preferred material for wear-resistant and friction-reducing components such as traditional friction pairs, sliding bearings, bushings, and linings in industrial applications.

[0006] As modern industrial equipment develops towards higher power, higher load, miniaturization, and integration, higher demands are placed on the service performance of materials under complex conditions such as high load, high friction, and high-speed sliding. In the field of power electronics, equipment such as ultra-high voltage power transmission, high-power drive motors for new energy vehicles, and high-power energy storage converters require conductive materials to withstand higher contact stress and high-speed sliding friction while carrying large currents, and to simultaneously maintain excellent heat dissipation and resistance to arc erosion. In the field of metallurgy and heavy machinery, transmission components of large equipment such as continuous casting machines and rolling mills need to operate stably for a long time under coupled conditions of high load, impact load, and continuous friction and wear, placing higher demands on the strength, hardness, wear resistance, and fatigue resistance of materials. In the fields of aerospace and marine propulsion, the lightweight and high-power design of equipment makes the working environment of core moving components increasingly harsh, requiring them to withstand the combined effects of high-speed sliding friction, instantaneous high temperature, corrosive media, and alternating loads. Under these complex and extreme conditions, traditional copper alloys and multi-component brass materials are gradually becoming unable to meet the performance requirements. In order to break through... To address the performance bottlenecks of traditional copper alloys, researchers have turned their attention to particle-reinforced copper matrix composites. By introducing high-performance ceramic reinforcing phases into the copper alloy matrix, and combining the excellent electrical and thermal conductivity of the copper matrix with the high strength, high hardness, and wear resistance of the ceramic phase, advanced composite materials with both functional and structural properties can be prepared. This has become a research hotspot and core development direction in the field of copper alloy materials. Among the many selectable ceramic reinforcing phases, TiC and TiB2 have become one of the preferred reinforcing agents for copper alloys due to their high hardness (28~34GPa) and other advantages, which help improve properties such as strength, hardness, and wear resistance. The traditional mechanical stirring method mainly involves introducing the added reinforcing phase into the molten copper alloy by generating shear force through a mechanical stirrer. However, due to defects such as poor wettability, weak interfacial bonding, and uneven dispersion between the molten copper and the reinforcing phase, the added reinforcing phase is difficult to significantly improve the performance of the copper alloy. However, with the help of active metal elements such as Ti, TiC and other reinforcing phases can be synthesized in situ in the copper alloy with SiC through reactive wetting method, thereby improving the performance of the copper alloy.The core value of the reactive wetting method lies in solving the inherent wetting bottleneck between the copper matrix and the SiC ceramic reinforcing phase. Simultaneously, through the in-situ synthesis of the endogenous reinforcing phase, it achieves a synergistic improvement in the strength, hardness, wear resistance, and electrical and thermal conductivity of the copper alloy. It is one of the core preparation technologies with significant industrial potential in the field of high-performance copper-based composite materials. However, there is a natural problem of extremely poor wettability between pure copper and the SiC ceramic reinforcing phase. In the high-temperature range above the melting point of copper (1100~1300℃), the wetting angle between the pure copper melt and SiC ceramic is large, belonging to a completely non-wetting system. This makes it impossible for the copper melt to effectively spread and encapsulate the SiC ceramic particles, resulting in difficulty in forming a uniform composite material structure and weak interfacial bonding leading to load... The extremely low charge transfer efficiency makes the interface a channel for crack initiation and propagation, ultimately deteriorating the overall performance of the material. The synergistic introduction of reactive wetting and Ti active elements is the key to breaking through this core bottleneck. Reactive wetting is a core technical means to improve the wettability of the interface between metal and ceramic systems. It belongs to the category of reactive wetting and is different from non-reactive physical wetting that relies solely on physical adsorption at the interface. Its core is to introduce active elements into the metal melt and trigger a controllable in-situ chemical reaction at high temperature to generate a thermodynamically stable interfacial transition phase. Through the release of Gibbs free energy and reconstruction of interfacial energy by the chemical reaction, the metal melt completely wets the ceramic phase and at the same time constructs a strongly bonded interfacial structure, laying the foundation for the in-situ synthesis and performance improvement of the endogenous reinforcing phase.

[0007] However, the active metal elements such as Ti used in the reaction wetting method, in addition to reacting with SiC, are also prone to reacting with Si in the copper alloy raw materials to form intermetallic compounds such as Ti5Si3, which consumes the active metal elements such as Ti and adversely affects the reaction of active metal elements such as Ti and SiC to form reinforcing phases such as TiC, thus reducing the performance of copper alloys prepared by the reaction wetting method; it is necessary to develop a new preparation process to improve the performance of copper alloys. Summary of the Invention

[0008] In view of this, this application provides a copper alloy with TiC and TiB2 hybrid reinforcing phases, a preparation method and applications, to solve the technical problem of low performance of copper alloys prepared in the prior art.

[0009] The first aspect of this application provides a method for preparing a copper alloy with a mixed reinforcing phase of TiC and TiB2, comprising the following steps:

[0010] Weighing steps for copper alloy raw materials: Weigh the corresponding pure copper, zinc ingots, Al blocks, Mn powder, Si powder, Fe powder, CuPb master alloy, Ti powder, SiC powder, and CuB powder as raw materials for the copper alloy according to the following proportions: Cu: 61.5~64.0wt.%, Zn: 13.15~22.87wt.%, Al: 5.5~7.0wt.%, Mn: 7.5~9.0wt.%, Si: 0.5~2.0wt.%, Fe: 0.5~2.0wt.%, Pb: 0.35~0.80wt.%, Ti: 0.2~1.5wt.%, SiC: 0.06~0.40wt.%, B: 0.02~0.15wt.%.

[0011] Preparation steps of silicon-magnesium composite blocks: Weighed Mn powder and Si powder are mixed and then pressed into silicon-magnesium composite blocks;

[0012] Sintering steps of the hybrid reinforced phase body: Weighed Ti powder, SiC powder and CuB powder are mixed and then sintered into a hybrid reinforced phase body;

[0013] The smelting steps of copper alloy melt are as follows: Weigh pure copper, zinc ingots, Al blocks, Fe powder, CuPb master alloy, mixed reinforcing phases and silicon-magnesium composite blocks are completely smelted to obtain copper alloy melt;

[0014] The casting and forming steps of copper alloy melt are as follows: the copper alloy melt is poured into a mold and cooled to form a copper alloy with TiC and TiB2 mixed reinforcing phases.

[0015] Preferably, in the weighing step of the copper alloy raw material in the method for preparing a copper alloy with TiC and TiB2 mixed reinforcing phases provided in the first aspect of this application, the weighed copper alloy raw material includes: Cu: 61.5~64.0 wt.%, Zn: 13.38~22.87 wt.%, Al: 5.5~7.0 wt.%, Mn: 7.5~9.0 wt.%, Si: 0.5~2.0 wt.%, Fe: 0.5~2.0 wt.%, Pb: 0.35~0.80 wt.%, Ti: 0.2~1.3 wt.%, SiC: 0.06~0.39 wt.%, B: 0.02~0.13 wt.%.

[0016] Preferably, in the weighing step of the copper alloy raw material in the method for preparing a copper alloy with TiC and TiB2 mixed reinforcing phases provided in the first aspect of this application, the weighed copper alloy raw material includes: Cu: 61.5~64.0 wt.%, Zn: 13.8~22.87 wt.%, Al: 5.5~7.0 wt.%, Mn: 7.5~9.0 wt.%, Si: 0.5~2.0 wt.%, Fe: 0.5~2.0 wt.%, Pb: 0.35~0.80 wt.%, Ti: 0.2~1.0 wt.%, SiC: 0.06~0.30 wt.%, B: 0.02~0.10 wt.%.

[0017] Preferably, in the preparation step of the silicon-magnesium composite block of the method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases provided in the first aspect of this application, the pressing pressure is 10~30MPa.

[0018] Preferably, in the sintering step of the mixed-reinforced phase substrate in the method for preparing a copper alloy having a TiC and TiB2 mixed-reinforced phase provided in the first aspect of this application, the sintering process includes hot pressing sintering or spark plasma sintering.

[0019] Preferably, in the method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases provided in the first aspect of this application, the heating rate of the hot pressing sintering is 5~15℃ / min, the sintering temperature is 350~500℃, the sintering pressure is 50~60MPa, and the time is 20~40min.

[0020] Preferably, in the method for preparing a copper alloy with a TiC and TiB2 hybrid reinforcing phase provided in the first aspect of this application, the heating rate of the spark plasma sintering is 100~150℃ / min, the sintering temperature is 900~950℃, the sintering pressure is 30~50MPa, and the time is 6~10min.

[0021] Preferably, in the sintering step of the mixed-reinforced phase body of the method for preparing a copper alloy having a TiC and TiB2 mixed reinforcing phase provided in the first aspect of this application, the mixing process includes: ball milling weighed Ti powder, SiC powder and CuB powder at a speed of 50~150 r / min for 4~6 h to mix them.

[0022] The second aspect of this application provides a copper alloy having a TiC and TiB2 hybrid reinforcing phase, prepared by the method for preparing a copper alloy having a TiC and TiB2 hybrid reinforcing phase as described in the first aspect.

[0023] The third aspect of this application provides the application of a copper alloy with TiC and TiB2 hybrid reinforcing phases as described in the second aspect in the manufacture of sliding bearings, pump and valve parts, brush holders or high-load friction components.

[0024] Compared with the prior art, the method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases provided in this application has at least the following beneficial effects:

[0025] 1. This application provides a method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases. In this method, TiC and TiB2 hybrid reinforcing phases are introduced into the copper alloy by means of a reaction wetting method. This avoids defects such as poor wettability, weak interfacial bonding and uneven dispersion between the added TiC and TiB2 hybrid reinforcing phases and the copper matrix. Combined with reinforcing phases such as [Mn(Fe)]5Si3 and reinforcing phases of different morphologies such as granular and whisker in the copper alloy matrix, the distribution of multi-scale and multi-type hybrid reinforcing phases in the copper matrix significantly improves the tensile strength, friction coefficient and hardness of the copper alloy.

[0026] 2. This application provides a method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases. In this method, Ti powder, SiC powder, and CuB powder in the copper alloy raw material are sintered into a hybrid reinforcing phase substrate in advance. This reduces the formation of intermetallic compounds such as Ti5Si3 between Ti powder and Si powder in the copper alloy raw material, and increases the amount of TiC and TiB2 hybrid reinforcing phases. Furthermore, by using a rapid heating and short-time sintering discharge plasma sintering process, the excessive reaction of Ti and SiC at high temperatures and the defects of grain growth during long-term sintering in hot pressing sintering processes are avoided. This improves the tensile strength, friction coefficient, and hardness of the copper alloy.

[0027] 3. This application provides a method for preparing a copper alloy with TiC and TiB2 mixed reinforcing phases. In the preparation method, by controlling the amount of Ti powder, SiC powder and CuB powder in the copper alloy raw materials, the agglomeration of TiC and TiB2 mixed reinforcing phases is avoided, which is detrimental to the improvement of alloy performance. As a result, the tensile strength, friction coefficient and hardness of the copper alloy are improved. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the specific embodiments of this application or the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0029] Figure 1 A method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases provided in Example 1 of this application, and a microstructure diagram of the copper alloy with TiC and TiB2 hybrid reinforcing phases prepared therefrom;

[0030] Figure 2 Example 2 of this application provides a method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases, and a microstructure diagram of the prepared copper alloy with TiC and TiB2 hybrid reinforcing phases.

[0031] Figure 3 Example 3 of this application provides a method for preparing a copper alloy with a mixed reinforcing phase of TiC and TiB2, and a microstructure diagram of the prepared copper alloy with a mixed reinforcing phase of TiC and TiB2.

[0032] Figure 4 Example 4 of this application provides a method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases, and a microstructure diagram of the prepared copper alloy with TiC and TiB2 hybrid reinforcing phases.

[0033] Figure 5 Example 5 of this application provides a method for preparing a copper alloy with TiC and TiB2 mixed reinforcing phases, and a microstructure diagram of the prepared copper alloy with TiC and TiB2 mixed reinforcing phases.

[0034] Figure 6 A method for preparing a copper alloy with a reinforcing phase is provided for Comparative Example 1 of this application, and the microstructure of the copper alloy with a reinforcing phase is shown in the image.

[0035] Figure 7 This is a method for preparing a copper alloy, as provided in Comparative Example 2 of this application, and the microstructure of the prepared copper alloy is shown in the image. Detailed Implementation

[0036] This application provides a copper alloy with TiC and TiB2 hybrid reinforcing phases, its preparation method, and its application, to solve the technical problem of low performance of copper alloys prepared in the prior art.

[0037] The technical solutions of this application will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this application. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0038] Example 1

[0039] This embodiment provides a method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases. The preparation method includes a step of weighing copper alloy raw materials, a step of preparing a silicon-magnesium composite block, a step of sintering the hybrid reinforcing phase bulk, a step of melting the copper alloy melt, and a step of casting the copper alloy melt.

[0040] The weighing steps for copper alloy raw materials include:

[0041] According to the proportions of Cu: 63.0 wt.%, Zn: 19.7 wt.%, Al: 6.0 wt.%, Mn: 8.0 wt.%, Si: 1.0 wt.%, Fe: 1.0 wt.%, Pb: 0.40 wt.%, Ti: 0.64 wt.%, SiC: 0.20 wt.%, and B: 0.06 wt.%, the corresponding industrial pure copper, zinc ingots, Al blocks, Mn powder, Si powder, Fe powder, CuPb master alloy, Ti powder, SiC powder, and CuB powder were weighed as copper alloy raw materials. The CuPb master alloy in the copper alloy raw materials is CuPb10, and the CuB powder is CuB5 alloy powder. CuPb10 represents that the master alloy contains 10 wt.% Pb, while CuB5 represents that it contains 5 wt.% B.

[0042] The preparation steps of the silicon-magnesium composite bulk material include:

[0043] After weighing Mn powder and Si powder, they are mixed in a three-dimensional mixer and then pressed into blocks using a powder press at 20 MPa. The three-dimensional mixer used in this step, also called a three-dimensional motion mixer, is designed to mix two or more metal powders in different proportions into a homogeneous mixture. Its unique mechanical structure ensures extremely high mixing uniformity even between alloy powders with significant differences in density and specific gravity, preventing segregation. When the three-dimensional mixer is started, the drive shaft is driven by a motor, rotating through two special Y-shaped universal joints. This drives the mixing drum to simultaneously perform translation, rotation, and tumbling motions in space. This composite motion is transmitted to the metal powder inside the drum, causing simultaneous axial movement (movement along the length of the mixing drum), radial movement (flow within the drum's cross-section), and circumferential movement (similar to circular motion, causing the material to tumble near the drum wall). These three movements superimpose each other, resulting in... The container has almost no dead zones, allowing materials to constantly collide, diffuse, and convection, ultimately achieving a completely homogeneous mixture. The powder tablet press used in this step serves to press the homogeneously mixed metal powder into a mold by applying enormous pressure, causing the particles to bind tightly together and forming a "compact" or "block" with a certain strength, shape, and density. After the mixed metal powder is filled into the mold cavity of the powder tablet press, the machine is started. The upper punch slowly descends under hydraulic drive, contacts the powder, and begins to apply pressure. Under pressure, the powder particles shift and rearrange, the gaps between the particles are compressed, and the internal air is expelled along the gaps between the particles, making the pressed block more uniform in density and stronger, preventing cracks or delamination after demolding, and obtaining the formed block. After forming, the upper punch retracts, and the lower punch rises, ejecting the pressed metal block from the mold, resulting in a silicon-magnesium composite block.

[0044] The sintering steps of the hybrid reinforced phase substrate include:

[0045] Argon was used as a protective gas. Weighed Ti powder, SiC powder, and CuB powder were added to a ball mill, with a ball-to-powder ratio of 10:1 and a milling speed of 100 r / min. After milling for 5 hours, the mixture was then subjected to spark plasma sintering to obtain a hybrid reinforced phase. The heating rate during spark plasma sintering was 150℃ / min, the sintering temperature was 900℃, the sintering pressure was 40 MPa, and the time was 6 minutes. The sintering process used in this step was spark plasma sintering, a novel powder metallurgy sintering technology. It involves directly passing a pulsed current between powder particles, utilizing the Joule heating of the powder itself and the plasma effect generated by interparticle discharge for heating, while simultaneously applying axial pressure, thereby achieving rapid densification of the powder. The spark plasma sintering process, with its rapid heating and short sintering time, avoids the defects of excessive grain growth during long-term sintering and the defects of excessive reaction between Ti and SiC at high temperatures, which is beneficial to improving the performance of the hybrid reinforced phase.

[0046] The smelting steps for copper alloy melt include:

[0047] Weighed industrial pure copper is melted in a medium-frequency induction furnace. After the industrial pure copper is completely melted, a hybrid reinforcing phase, silicon-magnesium composite block, Al block, Fe powder, and CuPb master alloy are added and melted completely at 1300℃. This allows the copper alloy raw materials to fully dissolve and diffuse, resulting in a uniform liquid melt. After cooling to 1125℃, zinc ingots are added and rapidly stirred to ensure complete melting and uniform diffusion into the melt, resulting in a fully melted copper alloy melt. The melting principle of the medium-frequency induction furnace used in this step is a non-contact energy conversion process based on the laws of electromagnetic induction and Joule heating. When a medium-frequency alternating current is passed through the induction coil, according to Faraday's law of electromagnetic induction, an alternating magnetic field of the same frequency is excited inside the coil. The conductive furnace material placed in the magnetic field generates an induced electromotive force due to the change in magnetic flux, which in turn excites eddy currents inside the material. According to the Joule-Lenz law, the eddy currents do work to overcome the intrinsic resistance of the material, converting electrical energy into heat energy, achieving volumetric heating from the inside out, thereby melting the alloy.

[0048] The casting process for copper alloy melt includes:

[0049] After skimming off the slag from the surface of the fully smelted copper alloy melt, the melt is thoroughly stirred with a carbon rod until homogeneous. It is then poured into a graphite mold to cool and solidify, resulting in a copper alloy with TiC and TiB2 mixed reinforcing phases. Skimming off the slag in this step is to physically remove the solid oxide slag formed by the reaction of alloying elements with oxygen in the air during the smelting process. This prevents these oxides from remaining in the casting, becoming stress concentration points, and affecting the mechanical properties of the copper alloy. Furthermore, the copper alloy melt contains multiple elements... The density of copper alloys often differs from that of copper. To avoid density differences and resulting segregation, carbon rod stirring is a forced convection method. Using carbon rods, the fully smelted copper alloy melt is thoroughly stirred and homogenized. In addition, graphite has advantages such as good thermal shock resistance, thermal conductivity, and self-lubricating properties. The copper alloy melt has good fluidity in the graphite mold and can accurately replicate the shape of the mold cavity, resulting in a smooth casting surface. Thus, the slag skimming in this step ensures the purity of the copper alloy melt, stirring ensures the consistency of the copper alloy melt, and graphite mold casting lays the foundation for obtaining copper alloys with excellent microstructure and properties.

[0050] Example 2

[0051] This embodiment provides a method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases. The preparation method includes a step of weighing copper alloy raw materials, a step of preparing a silicon-magnesium composite block, a step of sintering the hybrid reinforcing phase bulk, a step of melting the copper alloy melt, and a step of casting the copper alloy melt.

[0052] The weighing steps for copper alloy raw materials include:

[0053] According to the proportions of Cu: 63.0 wt.%, Zn: 19.92 wt.%, Al: 6.0 wt.%, Mn: 8.0 wt.%, Si: 1.0 wt.%, Fe: 1.0 wt.%, Pb: 0.40 wt.%, Ti: 0.48 wt.%, SiC: 0.14 wt.%, and B: 0.06 wt.%, the corresponding industrial pure copper, zinc ingots, Al blocks, Mn powder, Si powder, Fe powder, CuPb master alloy, Ti powder, SiC powder, and CuB powder were weighed as copper alloy raw materials. The CuPb master alloy in the copper alloy raw materials is CuPb10, and the CuB powder is CuB5 alloy powder. CuPb10 represents that the master alloy contains 10 wt.% Pb, while CuB5 represents that it contains 5 wt.% B.

[0054] The preparation steps of the silicon-magnesium composite bulk material include:

[0055] After weighing Mn powder and Si powder, they are mixed in a three-dimensional mixer and then pressed into blocks using a powder press at 20 MPa. The three-dimensional mixer used in this step, also called a three-dimensional motion mixer, is designed to mix two or more metal powders in different proportions into a homogeneous mixture. Its unique mechanical structure ensures extremely high mixing uniformity even between alloy powders with significant differences in density and specific gravity, preventing segregation. When the three-dimensional mixer is started, the drive shaft is driven by a motor, rotating through two special Y-shaped universal joints. This drives the mixing drum to simultaneously perform translation, rotation, and tumbling motions in space. This composite motion is transmitted to the metal powder inside the drum, causing simultaneous axial movement (movement along the length of the mixing drum), radial movement (flow within the drum's cross-section), and circumferential movement (similar to circular motion, causing the material to tumble near the drum wall). These three movements superimpose each other, resulting in... The container has almost no dead zones, allowing materials to constantly collide, diffuse, and convection, ultimately achieving a completely homogeneous mixture. The powder tablet press used in this step serves to press the homogeneously mixed metal powder into a mold by applying enormous pressure, causing the particles to bind tightly together and forming a "compact" or "block" with a certain strength, shape, and density. After the mixed metal powder is filled into the mold cavity of the powder tablet press, the machine is started. The upper punch slowly descends under hydraulic drive, contacts the powder, and begins to apply pressure. Under pressure, the powder particles shift and rearrange, the gaps between the particles are compressed, and the internal air is expelled along the gaps between the particles, making the pressed block more uniform in density and stronger, preventing cracks or delamination after demolding, and obtaining the formed block. After forming, the upper punch retracts, and the lower punch rises, ejecting the pressed metal block from the mold, resulting in a silicon-magnesium composite block.

[0056] The sintering steps of the hybrid reinforced phase substrate include:

[0057] Argon was used as a protective gas. Weighed Ti powder, SiC powder, and CuB powder were added to a ball mill, with a ball-to-powder ratio of 10:1 and a milling speed of 100 r / min. After milling for 5 hours, the mixture was then subjected to spark plasma sintering to obtain a hybrid reinforced phase. The heating rate during spark plasma sintering was 150℃ / min, the sintering temperature was 900℃, the sintering pressure was 40 MPa, and the time was 6 minutes. The sintering process used in this step was spark plasma sintering, a novel powder metallurgy sintering technology. It involves directly passing a pulsed current between powder particles, utilizing the Joule heating of the powder itself and the plasma effect generated by interparticle discharge for heating, while simultaneously applying axial pressure, thereby achieving rapid densification of the powder. The spark plasma sintering process, with its rapid heating and short sintering time, avoids the defects of excessive grain growth during long-term sintering and the defects of excessive reaction between Ti and SiC at high temperatures, which is beneficial to improving the performance of the hybrid reinforced phase.

[0058] The smelting steps for copper alloy melt include:

[0059] Weighed industrial pure copper is melted in a medium-frequency induction furnace. After the industrial pure copper is completely melted, a hybrid reinforcing phase, silicon-magnesium composite block, Al block, Fe powder, and CuPb master alloy are added and melted completely at 1300℃. This allows the copper alloy raw materials to fully dissolve and diffuse, resulting in a uniform liquid melt. After cooling to 1125℃, zinc ingots are added and rapidly stirred to ensure complete melting and uniform diffusion into the melt, resulting in a fully melted copper alloy melt. The melting principle of the medium-frequency induction furnace used in this step is a non-contact energy conversion process based on the laws of electromagnetic induction and Joule heating. When a medium-frequency alternating current is passed through the induction coil, according to Faraday's law of electromagnetic induction, an alternating magnetic field of the same frequency is excited inside the coil. The conductive furnace material placed in the magnetic field generates an induced electromotive force due to the change in magnetic flux, which in turn excites eddy currents inside the material. According to the Joule-Lenz law, the eddy currents do work to overcome the intrinsic resistance of the material, converting electrical energy into heat energy, achieving volumetric heating from the inside out, thereby melting the alloy.

[0060] The casting process for copper alloy melt includes:

[0061] After skimming off the slag from the surface of the fully smelted copper alloy melt, the melt is thoroughly stirred with a carbon rod until homogeneous. It is then poured into a graphite mold to cool and solidify, resulting in a copper alloy with TiC and TiB2 mixed reinforcing phases. Skimming off the slag in this step is to physically remove the solid oxide slag formed by the reaction of alloying elements with oxygen in the air during the smelting process. This prevents these oxides from remaining in the casting, becoming stress concentration points, and affecting the mechanical properties of the copper alloy. Furthermore, the copper alloy melt contains multiple elements... The density of copper alloys often differs from that of copper. To avoid density differences and resulting segregation, carbon rod stirring is a forced convection method. Using carbon rods, the fully smelted copper alloy melt is thoroughly stirred and homogenized. In addition, graphite has advantages such as good thermal shock resistance, thermal conductivity, and self-lubricating properties. The copper alloy melt has good fluidity in the graphite mold and can accurately replicate the shape of the mold cavity, resulting in a smooth casting surface. Thus, the slag skimming in this step ensures the purity of the copper alloy melt, stirring ensures the consistency of the copper alloy melt, and graphite mold casting lays the foundation for obtaining copper alloys with excellent microstructure and properties.

[0062] Example 3

[0063] This embodiment provides a method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases. The preparation method includes a step of weighing copper alloy raw materials, a step of preparing a silicon-magnesium composite block, a step of sintering the hybrid reinforcing phase bulk, a step of melting the copper alloy melt, and a step of casting the copper alloy melt.

[0064] The weighing steps for copper alloy raw materials include:

[0065] According to the proportions of Cu: 63.0 wt.%, Zn: 19.32 wt.%, Al: 6.0 wt.%, Mn: 8.0 wt.%, Si: 1.0 wt.%, Fe: 1.0 wt.%, Pb: 0.40 wt.%, Ti: 0.92 wt.%, SiC: 0.27 wt.%, and B: 0.09 wt.%, the corresponding industrial pure copper, zinc ingots, Al blocks, Mn powder, Si powder, Fe powder, CuPb master alloy, Ti powder, SiC powder, and CuB powder were weighed as copper alloy raw materials. The CuPb master alloy in the copper alloy raw materials is CuPb10, and the CuB powder is CuB5 alloy powder. CuPb10 represents that the master alloy contains 10 wt.% Pb, while CuB5 represents that it contains 5 wt.% B.

[0066] The preparation steps of the silicon-magnesium composite bulk material include:

[0067] After weighing Mn powder and Si powder, they are mixed in a three-dimensional mixer and then pressed into blocks using a powder press at 20 MPa. The three-dimensional mixer used in this step, also called a three-dimensional motion mixer, is designed to mix two or more metal powders in different proportions into a homogeneous mixture. Its unique mechanical structure ensures extremely high mixing uniformity even between alloy powders with significant differences in density and specific gravity, preventing segregation. When the three-dimensional mixer is started, the drive shaft is driven by a motor, rotating through two special Y-shaped universal joints. This drives the mixing drum to simultaneously perform translation, rotation, and tumbling motions in space. This composite motion is transmitted to the metal powder inside the drum, causing simultaneous axial movement (movement along the length of the mixing drum), radial movement (flow within the drum's cross-section), and circumferential movement (similar to circular motion, causing the material to tumble near the drum wall). These three movements superimpose each other, resulting in... The container has almost no dead zones, allowing materials to constantly collide, diffuse, and convection, ultimately achieving a completely homogeneous mixture. The powder tablet press used in this step serves to press the homogeneously mixed metal powder into a mold by applying enormous pressure, causing the particles to bind tightly together and forming a "compact" or "block" with a certain strength, shape, and density. After the mixed metal powder is filled into the mold cavity of the powder tablet press, the machine is started. The upper punch slowly descends under hydraulic drive, contacts the powder, and begins to apply pressure. Under pressure, the powder particles shift and rearrange, the gaps between the particles are compressed, and the internal air is expelled along the gaps between the particles, making the pressed block more uniform in density and stronger, preventing cracks or delamination after demolding, and obtaining the formed block. After forming, the upper punch retracts, and the lower punch rises, ejecting the pressed metal block from the mold, resulting in a silicon-magnesium composite block.

[0068] The sintering steps of the hybrid reinforced phase substrate include:

[0069] Argon was used as a protective gas. Weighed Ti powder, SiC powder, and CuB powder were added to a ball mill, with a ball-to-powder ratio of 10:1 and a milling speed of 100 r / min. After milling for 5 hours, the mixture was then subjected to spark plasma sintering to obtain a hybrid reinforced phase. The heating rate during spark plasma sintering was 150℃ / min, the sintering temperature was 900℃, the sintering pressure was 40 MPa, and the time was 6 minutes. The sintering process used in this step was spark plasma sintering, a novel powder metallurgy sintering technology. It involves directly passing a pulsed current between powder particles, utilizing the Joule heating of the powder itself and the plasma effect generated by interparticle discharge for heating, while simultaneously applying axial pressure, thereby achieving rapid densification of the powder. The spark plasma sintering process, with its rapid heating and short sintering time, avoids the defects of excessive grain growth during long-term sintering and the defects of excessive reaction between Ti and SiC at high temperatures, which is beneficial to improving the performance of the hybrid reinforced phase.

[0070] The smelting steps for copper alloy melt include:

[0071] Weighed industrial pure copper is melted in a medium-frequency induction furnace. After the industrial pure copper is completely melted, a hybrid reinforcing phase, silicon-magnesium composite block, Al block, Fe powder, and CuPb master alloy are added and melted completely at 1300℃. This allows the copper alloy raw materials to fully dissolve and diffuse, resulting in a uniform liquid melt. After cooling to 1125℃, zinc ingots are added and rapidly stirred to ensure complete melting and uniform diffusion into the melt, resulting in a fully melted copper alloy melt. The melting principle of the medium-frequency induction furnace used in this step is a non-contact energy conversion process based on the laws of electromagnetic induction and Joule heating. When a medium-frequency alternating current is passed through the induction coil, according to Faraday's law of electromagnetic induction, an alternating magnetic field of the same frequency is excited inside the coil. The conductive furnace material placed in the magnetic field generates an induced electromotive force due to the change in magnetic flux, which in turn excites eddy currents inside the material. According to the Joule-Lenz law, the eddy currents do work to overcome the intrinsic resistance of the material, converting electrical energy into heat energy, achieving volumetric heating from the inside out, thereby melting the alloy.

[0072] The casting process for copper alloy melt includes:

[0073] After skimming off the slag from the surface of the fully smelted copper alloy melt, the melt is thoroughly stirred with a carbon rod until homogeneous. It is then poured into a graphite mold to cool and solidify, resulting in a copper alloy with TiC and TiB2 mixed reinforcing phases. Skimming off the slag in this step is to physically remove the solid oxide slag formed by the reaction of alloying elements with oxygen in the air during the smelting process. This prevents these oxides from remaining in the casting, becoming stress concentration points, and affecting the mechanical properties of the copper alloy. Furthermore, the copper alloy melt contains multiple elements... The density of copper alloys often differs from that of copper. To avoid density differences and resulting segregation, carbon rod stirring is a forced convection method. Using carbon rods, the fully smelted copper alloy melt is thoroughly stirred and homogenized. In addition, graphite has advantages such as good thermal shock resistance, thermal conductivity, and self-lubricating properties. The copper alloy melt has good fluidity in the graphite mold and can accurately replicate the shape of the mold cavity, resulting in a smooth casting surface. Thus, the slag skimming in this step ensures the purity of the copper alloy melt, stirring ensures the consistency of the copper alloy melt, and graphite mold casting lays the foundation for obtaining copper alloys with excellent microstructure and properties.

[0074] Example 4

[0075] This embodiment provides a method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases. The preparation method includes a step of weighing copper alloy raw materials, a step of preparing a silicon-magnesium composite block, a step of sintering the hybrid reinforcing phase bulk, a step of melting the copper alloy melt, and a step of casting the copper alloy melt.

[0076] The weighing steps for copper alloy raw materials include:

[0077] According to the proportions of Cu: 63.0 wt.%, Zn: 18.78 wt.%, Al: 6.0 wt.%, Mn: 8.0 wt.%, Si: 1.0 wt.%, Fe: 1.0 wt.%, Pb: 0.40 wt.%, Ti: 1.3 wt.%, SiC: 0.39 wt.%, and B: 0.13 wt.%, the corresponding industrial pure copper, zinc ingots, Al blocks, Mn powder, Si powder, Fe powder, CuPb master alloy, Ti powder, SiC powder, and CuB powder were weighed as copper alloy raw materials. The CuPb master alloy in the copper alloy raw materials is CuPb10, and the CuB powder is CuB5 alloy powder. CuPb10 represents that the master alloy contains 10 wt.% Pb, while CuB5 represents that it contains 5 wt.% B.

[0078] The preparation steps of the silicon-magnesium composite bulk material include:

[0079] After weighing Mn powder and Si powder, they are mixed in a three-dimensional mixer and then pressed into blocks using a powder press at 20 MPa. The three-dimensional mixer used in this step, also called a three-dimensional motion mixer, is designed to mix two or more metal powders in different proportions into a homogeneous mixture. Its unique mechanical structure ensures extremely high mixing uniformity even between alloy powders with significant differences in density and specific gravity, preventing segregation. When the three-dimensional mixer is started, the drive shaft is driven by a motor, rotating through two special Y-shaped universal joints. This drives the mixing drum to simultaneously perform translation, rotation, and tumbling motions in space. This composite motion is transmitted to the metal powder inside the drum, causing simultaneous axial movement (movement along the length of the mixing drum), radial movement (flow within the drum's cross-section), and circumferential movement (similar to circular motion, causing the material to tumble near the drum wall). These three movements superimpose each other, resulting in... The container has almost no dead zones, allowing materials to constantly collide, diffuse, and convection, ultimately achieving a completely homogeneous mixture. The powder tablet press used in this step serves to press the homogeneously mixed metal powder into a mold by applying enormous pressure, causing the particles to bind tightly together and forming a "compact" or "block" with a certain strength, shape, and density. After the mixed metal powder is filled into the mold cavity of the powder tablet press, the machine is started. The upper punch slowly descends under hydraulic drive, contacts the powder, and begins to apply pressure. Under pressure, the powder particles shift and rearrange, the gaps between the particles are compressed, and the internal air is expelled along the gaps between the particles, making the pressed block more uniform in density and stronger, preventing cracks or delamination after demolding, and obtaining the formed block. After forming, the upper punch retracts, and the lower punch rises, ejecting the pressed metal block from the mold, resulting in a silicon-magnesium composite block.

[0080] The sintering steps of the hybrid reinforced phase substrate include:

[0081] Argon was used as a protective gas. Weighed Ti powder, SiC powder, and CuB powder were added to a ball mill, with a ball-to-powder ratio of 10:1 and a milling speed of 100 r / min. After milling for 5 hours, the mixture was then subjected to spark plasma sintering to obtain a hybrid reinforced phase. The heating rate during spark plasma sintering was 150℃ / min, the sintering temperature was 900℃, the sintering pressure was 40 MPa, and the time was 6 minutes. The sintering process used in this step was spark plasma sintering, a novel powder metallurgy sintering technology. It involves directly passing a pulsed current between powder particles, utilizing the Joule heating of the powder itself and the plasma effect generated by interparticle discharge for heating, while simultaneously applying axial pressure, thereby achieving rapid densification of the powder. The spark plasma sintering process, with its rapid heating and short sintering time, avoids the defects of excessive grain growth during long-term sintering and the defects of excessive reaction between Ti and SiC at high temperatures, which is beneficial to improving the performance of the hybrid reinforced phase.

[0082] The smelting steps for copper alloy melt include:

[0083] Weighed industrial pure copper is melted in a medium-frequency induction furnace. After the industrial pure copper is completely melted, a hybrid reinforcing phase, silicon-magnesium composite block, Al block, Fe powder, and CuPb master alloy are added and melted completely at 1300℃. This allows the copper alloy raw materials to fully dissolve and diffuse, resulting in a uniform liquid melt. After cooling to 1125℃, zinc ingots are added and rapidly stirred to ensure complete melting and uniform diffusion into the melt, resulting in a fully melted copper alloy melt. The melting principle of the medium-frequency induction furnace used in this step is a non-contact energy conversion process based on the law of electromagnetic induction and the Joule heating effect. When a medium-frequency alternating current is passed through the induction coil, according to Faraday's law of electromagnetic induction, an alternating magnetic field of the same frequency is excited inside the coil. The conductive furnace material placed in the magnetic field generates an induced electromotive force due to the change in magnetic flux, which in turn excites eddy currents inside the material. According to the Joule-Lenz law, the eddy currents do work to overcome the intrinsic resistance of the material, converting electrical energy into heat energy, achieving volume heating from the inside out, thereby melting the alloy.

[0084] The casting process for copper alloy melt includes:

[0085] After skimming off the slag from the surface of the fully smelted copper alloy melt, the melt is thoroughly stirred with a carbon rod until homogeneous. It is then poured into a graphite mold to cool and solidify, resulting in a copper alloy with TiC and TiB2 mixed reinforcing phases. Skimming off the slag in this step is to physically remove the solid oxide slag formed by the reaction of alloying elements with oxygen in the air during the smelting process. This prevents these oxides from remaining in the casting, becoming stress concentration points, and affecting the mechanical properties of the copper alloy. Furthermore, the copper alloy melt contains multiple elements... The density of copper alloys often differs from that of copper. To avoid density differences and resulting segregation, carbon rod stirring is a forced convection method. Using carbon rods, the fully smelted copper alloy melt is thoroughly stirred and homogenized. In addition, graphite has advantages such as good thermal shock resistance, thermal conductivity, and self-lubricating properties. The copper alloy melt has good fluidity in the graphite mold and can accurately replicate the shape of the mold cavity, resulting in a smooth casting surface. Thus, the slag skimming in this step ensures the purity of the copper alloy melt, stirring ensures the consistency of the copper alloy melt, and graphite mold casting lays the foundation for obtaining copper alloys with excellent microstructure and properties.

[0086] Example 5

[0087] This embodiment provides a method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases. The preparation method includes a step of weighing copper alloy raw materials, a step of preparing a silicon-magnesium composite block, a step of sintering the hybrid reinforcing phase bulk, a step of melting the copper alloy melt, and a step of casting the copper alloy melt.

[0088] The weighing steps for copper alloy raw materials include:

[0089] According to the proportions of Cu: 63.0 wt.%, Zn: 19.7 wt.%, Al: 6.0 wt.%, Mn: 8.0 wt.%, Si: 1.0 wt.%, Fe: 1.0 wt.%, Pb: 0.40 wt.%, Ti: 0.64 wt.%, SiC: 0.20 wt.%, and B: 0.06 wt.%, the corresponding industrial pure copper, zinc ingots, Al blocks, Mn powder, Si powder, Fe powder, CuPb master alloy, Ti powder, SiC powder, and CuB powder were weighed as copper alloy raw materials. The CuPb master alloy in the copper alloy raw materials is CuPb10, and the CuB powder is CuB5 alloy powder. CuPb10 represents that the master alloy contains 10 wt.% Pb, while CuB5 represents that it contains 5 wt.% B.

[0090] The preparation steps of the silicon-magnesium composite bulk material include:

[0091] After weighing Mn powder and Si powder, they are mixed in a three-dimensional mixer and then pressed into blocks using a powder press at 20 MPa. The three-dimensional mixer used in this step, also called a three-dimensional motion mixer, is designed to mix two or more metal powders in different proportions into a homogeneous mixture. Its unique mechanical structure ensures extremely high mixing uniformity even between alloy powders with significant differences in density and specific gravity, preventing segregation. When the three-dimensional mixer is started, the drive shaft is driven by a motor, rotating through two special Y-shaped universal joints. This drives the mixing drum to simultaneously perform translation, rotation, and tumbling motions in space. This composite motion is transmitted to the metal powder inside the drum, causing simultaneous axial movement (movement along the length of the mixing drum), radial movement (flow within the drum's cross-section), and circumferential movement (similar to circular motion, causing the material to tumble near the drum wall). These three movements superimpose each other, resulting in... The container has almost no dead zones, allowing materials to constantly collide, diffuse, and convection, ultimately achieving a completely homogeneous mixture. The powder tablet press used in this step serves to press the homogeneously mixed metal powder into a mold by applying enormous pressure, causing the particles to bind tightly together and forming a "compact" or "block" with a certain strength, shape, and density. After the mixed metal powder is filled into the mold cavity of the powder tablet press, the machine is started. The upper punch slowly descends under hydraulic drive, contacts the powder, and begins to apply pressure. Under pressure, the powder particles shift and rearrange, the gaps between the particles are compressed, and the internal air is expelled along the gaps between the particles, making the pressed block more uniform in density and stronger, preventing cracks or delamination after demolding, and obtaining the formed block. After forming, the upper punch retracts, and the lower punch rises, ejecting the pressed metal block from the mold, resulting in a silicon-magnesium composite block.

[0092] The sintering steps of the hybrid reinforced phase substrate include:

[0093] Argon was used as a protective gas. Weighed Ti powder, SiC powder and CuB powder were added to a ball mill, and the ball-to-material ratio was controlled at 10:1. The ball milling speed was 100 r / min. After ball milling for 5 hours, the mixture was hot-pressed and sintered to obtain a hybrid reinforced phase matrix. The heating rate during the hot-pressing and sintering process was 10℃ / min, the sintering temperature was 400℃, the sintering pressure was 50 MPa, and the time was 30 min.

[0094] The smelting steps for copper alloy melt include:

[0095] Weighed industrial pure copper is melted in a medium-frequency induction furnace. After the industrial pure copper is completely melted, a hybrid reinforcing phase, silicon-magnesium composite block, Al block, Fe powder, and CuPb master alloy are added and melted completely at 1300℃. This allows the copper alloy raw materials to fully dissolve and diffuse, resulting in a uniform liquid melt. After cooling to 1125℃, zinc ingots are added and rapidly stirred to ensure complete melting and uniform diffusion into the melt, resulting in a fully melted copper alloy melt. The melting principle of the medium-frequency induction furnace used in this step is a non-contact energy conversion process based on the law of electromagnetic induction and the Joule heating effect. When a medium-frequency alternating current is passed through the induction coil, according to Faraday's law of electromagnetic induction, an alternating magnetic field of the same frequency is excited inside the coil. The conductive furnace material placed in the magnetic field generates an induced electromotive force due to the change in magnetic flux, which in turn excites eddy currents inside the material. According to the Joule-Lenz law, the eddy currents do work to overcome the intrinsic resistance of the material, converting electrical energy into heat energy, achieving volume heating from the inside out, thereby melting the alloy.

[0096] The casting process for copper alloy melt includes:

[0097] After skimming off the slag from the surface of the fully smelted copper alloy melt, the melt is thoroughly stirred with a carbon rod until homogeneous. It is then poured into a graphite mold to cool and solidify, resulting in a copper alloy with TiC and TiB2 mixed reinforcing phases. Skimming off the slag in this step is to physically remove the solid oxide slag formed by the reaction of alloying elements with oxygen in the air during the smelting process. This prevents these oxides from remaining in the casting, becoming stress concentration points, and affecting the mechanical properties of the copper alloy. Furthermore, the copper alloy melt contains multiple elements... The density of copper alloys often differs from that of copper. To avoid density differences and resulting segregation, carbon rod stirring is a forced convection method. Using carbon rods, the fully smelted copper alloy melt is thoroughly stirred and homogenized. In addition, graphite has advantages such as good thermal shock resistance, thermal conductivity, and self-lubricating properties. The copper alloy melt has good fluidity in the graphite mold and can accurately replicate the shape of the mold cavity, resulting in a smooth casting surface. Thus, the slag skimming in this step ensures the purity of the copper alloy melt, stirring ensures the consistency of the copper alloy melt, and graphite mold casting lays the foundation for obtaining copper alloys with excellent microstructure and properties.

[0098] Comparative Example 1

[0099] This comparative example provides a method for preparing a copper alloy with a reinforcing phase. The method includes a step of weighing copper alloy raw materials, a step of smelting copper alloy melt, and a step of casting copper alloy melt.

[0100] The weighing steps for copper alloy raw materials include:

[0101] According to the proportions of Cu: 63.0 wt.%, Zn: 19.7 wt.%, Al: 6.0 wt.%, Mn: 8.0 wt.%, Si: 1.0 wt.%, Fe: 1.0 wt.%, Pb: 0.40 wt.%, Ti: 0.64 wt.%, SiC: 0.20 wt.%, and B: 0.06 wt.%, the corresponding industrial pure copper, zinc ingots, Al blocks, Mn powder, Si powder, Fe powder, CuPb master alloy, Ti powder, SiC powder, and CuB powder were weighed as copper alloy raw materials. The CuPb master alloy in the copper alloy raw materials is CuPb10, and the CuB powder is CuB5 alloy powder. CuPb10 represents that the master alloy contains 10 wt.% Pb, while CuB5 represents that it contains 5 wt.% B.

[0102] The smelting steps for copper alloy melt include:

[0103] Weighed industrial pure copper is melted in a medium-frequency induction furnace. After the industrial pure copper is completely melted, Al blocks, Mn powder, Si powder, Fe powder, CuPb master alloy, Ti powder, SiC powder, and CuB powder are added and melted completely at 1300℃. This allows the copper alloy raw materials to fully dissolve and diffuse, resulting in a uniform liquid melt. After cooling to 1125℃, zinc ingots are added and stirred rapidly to ensure complete melting and uniform diffusion into the melt, resulting in a fully melted copper alloy melt. The melting principle of the medium-frequency induction furnace used in this step is a non-contact energy conversion process based on the law of electromagnetic induction and the Joule heating effect. When a medium-frequency alternating current is passed through the induction coil, according to Faraday's law of electromagnetic induction, an alternating magnetic field of the same frequency is excited inside the coil. The conductive furnace material placed in the magnetic field generates an induced electromotive force due to the change in magnetic flux, which in turn excites eddy currents inside the material. According to the Joule-Lenz law, the eddy currents do work to overcome the intrinsic resistance of the material, converting electrical energy into heat energy, achieving volume heating from the inside out, thereby melting the alloy.

[0104] The casting process for copper alloy melt includes:

[0105] After skimming off the slag from the surface of the fully smelted copper alloy melt, the melt is thoroughly stirred with a carbon rod until homogeneous. It is then poured into a graphite mold to cool and solidify, resulting in a copper alloy with reinforcing phases. Skimming off the slag in this step physically removes the solid oxide slag formed by the reaction of alloying elements with oxygen in the air during the smelting process. This prevents these oxides from remaining in the casting, becoming stress concentration points, and affecting the mechanical properties of the copper alloy. Simultaneously, the density of the copper alloy melt, containing multiple elements, is similar to that of copper... Unlike other methods, carbon rod stirring is a forced convection method used to avoid density differences and resulting segregation. The carbon rod thoroughly stirs the fully melted copper alloy to ensure uniformity. In addition, graphite has advantages such as good thermal shock resistance, thermal conductivity, and self-lubrication. The copper alloy melt has good fluidity in the graphite mold and can accurately replicate the shape of the mold cavity, resulting in a smooth casting surface. Therefore, the slag skimming in this step ensures the purity of the copper alloy melt, stirring ensures the consistency of the copper alloy melt, and graphite mold casting lays the foundation for obtaining copper alloys with excellent structure and properties.

[0106] Comparative Example 2

[0107] This comparative example provides a method for preparing a copper alloy, which includes a step of weighing copper alloy raw materials, a step of smelting copper alloy melt, and a step of casting copper alloy melt.

[0108] The weighing steps for copper alloy raw materials include:

[0109] According to the proportions of Cu: 63.0 wt.%, Zn: 20.6 wt.%, Al: 6.0 wt.%, Mn: 8.0 wt.%, Si: 1.0 wt.%, Fe: 1.0 wt.%, and Pb: 0.40 wt.%, the corresponding industrial pure copper, zinc ingots, Al blocks, Mn powder, Si powder, Fe powder, and CuPb master alloy were weighed as copper alloy raw materials; the CuPb master alloy in the copper alloy raw materials was CuPb10, which represents that the master alloy contains 10 wt.% Pb.

[0110] The smelting steps for copper alloy melt include:

[0111] Weighed industrial pure copper is melted in a medium-frequency induction furnace. After the industrial pure copper is completely melted, Al blocks, Mn powder, Si powder, Fe powder, and CuPb master alloy are added and melted completely at 1300℃. This allows the copper alloy raw materials to fully dissolve and diffuse, resulting in a uniform liquid melt. After cooling to 1125℃, zinc ingots are added and stirred rapidly to ensure complete melting and uniform diffusion into the melt, resulting in a fully melted copper alloy melt. The melting principle of the medium-frequency induction furnace used in this step is a non-contact energy conversion process based on the law of electromagnetic induction and the Joule heating effect. When a medium-frequency alternating current is passed through the induction coil, according to Faraday's law of electromagnetic induction, an alternating magnetic field of the same frequency is excited inside the coil. The conductive furnace material placed in the magnetic field generates an induced electromotive force due to the change in magnetic flux, which in turn excites eddy currents inside the material. According to the Joule-Lenz law, the eddy currents do work to overcome the intrinsic resistance of the material, converting electrical energy into heat energy, achieving volume heating from the inside out, thereby melting the alloy.

[0112] The casting process for copper alloy melt includes:

[0113] After skimming off the slag from the surface of the fully smelted copper alloy melt, the melt is thoroughly stirred with a carbon rod until homogeneous. It is then poured into a graphite mold to cool and solidify, yielding the copper alloy. Skimming off the slag in this step physically removes the solid oxide slag formed during the smelting process by the reaction of alloying elements with oxygen in the air. This prevents these oxides from remaining in the casting, becoming stress concentration points, and affecting the mechanical properties of the copper alloy. Furthermore, the density of the various elements in the molten copper alloy often differs from that of copper itself. To avoid density differences leading to specific gravity segregation, carbon rod stirring is a forced convection method. Using carbon rods, the fully smelted copper alloy melt is thoroughly stirred and homogenized. In addition, graphite has advantages such as good thermal shock resistance, thermal conductivity, and self-lubricating properties. The copper alloy melt has good fluidity in the graphite mold, which can accurately replicate the shape of the mold cavity, resulting in a smooth casting surface. Thus, the slag skimming in this step ensures the purity of the copper alloy melt, stirring ensures the consistency of the copper alloy melt, and graphite mold casting lays the foundation for obtaining copper alloys with excellent microstructure and properties.

[0114] Experimental Example 1

[0115] This experimental example demonstrates the structural characterization and performance testing of the copper alloys provided in Examples 1-5 and Comparative Examples 1-2; the microstructure of the copper alloys under structural characterization is as follows: Figure 1-7 As shown in Table 1, the performance tests included the tensile strength, coefficient of friction, and hardness of the copper alloy.

[0116] Table 1: Performance test results of the copper alloys provided in Examples 1-5 and Comparative Examples 1-2

[0117]

[0118] From Table 1 and in combination Figure 1-7 As shown in the microstructure diagrams, the copper alloys prepared by the methods provided in Examples 1-5 and Comparative Example 1 mainly consist of β phase, [Mn(Fe)]5Si3, eutectic phase Mn5Si3, lead-rich phase, TiC, and TiB2 mixed reinforcing phases. In contrast, the copper alloy prepared by the method provided in Comparative Example 1 lacks TiC and TiB2 mixed reinforcing phases in its microstructure. Therefore, compared to the copper alloy provided in Comparative Example 2, the copper alloys prepared by the methods provided in Examples 1-5 and Comparative Example 1 exhibit superior tensile strength, coefficient of friction, and hardness. This indicates that the methods provided in Examples 1-5 and Comparative Example 1, by using Ti, SiC, and CuB as raw materials, generate TiC in situ within the copper alloy during the preparation process. Hybrid reinforcing phases such as iC and TiB2 are introduced into copper alloys using a reactive wetting method. This avoids defects such as poor wettability, weak interfacial bonding, and uneven dispersion between the added iC and TiB2 hybrid reinforcing phases and the copper matrix. Combined with the β phase, primary phase [Mn(Fe)]5Si3, eutectic phase Mn5Si3, lead-rich phase, and other reinforcing phases in the copper matrix, as well as different morphologies of the reinforcing phases, such as granular reinforcing phases dispersed in the copper matrix, they effectively hinder dislocation movement and significantly improve the strength and wear resistance of the material. Whisker-like reinforcing phases, with their high aspect ratio and excellent rigidity, play a bridging and load transfer role. These multi-scale and multi-type hybrid reinforcing phases distributed in the copper matrix improve the tensile strength, friction coefficient, and hardness of the copper alloy.

[0119] Table 1 further shows that, although the copper alloy prepared by the method provided in Comparative Example 1 uses Ti, SiC, and CuB as raw materials and introduces mixed reinforcing phases such as TiC and TiB2 into the copper alloy through reaction wetting, its tensile strength, coefficient of friction, and hardness are still lower than those of the copper alloy prepared by the method provided in Example 1. This indicates that different ways of introducing Ti, SiC, and CuB into the copper alloy raw materials also affect the performance of the copper alloy. This is because, in the preparation method provided in Comparative Example 1, Ti powder, SiC powder, and CuB powder were not sintered into a mixed reinforcing phase matrix beforehand. As a result, Ti powder and Si powder (1.0 wt.%) in the copper alloy raw materials generated intermetallic compounds such as Ti5Si3 during the smelting process, consuming some Ti and reducing the amount of Ti that can react with SiC and CuB. The number of reinforcing phases such as TiC / TiB2 observed in the microstructure of the copper alloy decreased, the tensile strength decreased from 767.6 MPa to 658.1 MPa, and the coefficient of friction and hardness also decreased.

[0120] Table 1 further shows that although the copper alloy prepared by the method provided in Example 5 uses Ti, SiC, and CuB as raw materials, and pre-sintersects Ti powder, SiC powder, and CuB powder into a hybrid reinforcing phase, reducing the formation of intermetallic compounds such as Ti5Si3 from the Si powder (1.0 wt.%) in the copper alloy raw materials during smelting, its tensile strength, coefficient of friction, and hardness are still lower than those of the copper alloy prepared by the method provided in Example 1. This is because the method provided in Example 5... The preparation method of the copper alloy involves sintering Ti powder, SiC powder, and CuB powder into a hybrid reinforced phase using a hot pressing sintering process. However, Example 1 uses a spark plasma sintering process, which has the advantages of rapid heating (150℃ / min) and short sintering time (usually 6 minutes). This avoids the excessive reaction and grain growth of Ti and SiC at high temperatures during the long sintering process (30 minutes) of the hot pressing sintering process, thereby improving the tensile strength, friction coefficient, and hardness of the copper alloy.

[0121] Table 1 further shows that the copper alloys prepared by the methods provided in Examples 1-4 have their tensile strength, coefficient of friction, and hardness affected by adjusting the amounts of Si powder, Fe powder, and CuPb powder in the raw materials. The copper alloy prepared by the method provided in Example 4 has a slightly decreased performance due to the agglomeration of the reinforcing phases in the microstructure caused by the introduction of more Si powder, Fe powder, and CuPb powder. Combining the performance test results of the copper alloys provided in Examples 1-4, the copper alloys prepared by introducing Si powder, Fe powder, and CuPb powder in the following proportions are superior: Ti: 0.64 wt.%, SiC: 0.20 wt.%, B: 0.06 wt.%, Ti: 0.48 wt.%, SiC: 0.14 wt.%, B: 0.06 wt.%.

[0122] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

Claims

1. A method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases, characterized in that, Includes the following steps: According to the proportions of Cu: 61.5~64.0wt.%, Zn: 13.15~22.87wt.%, Al: 5.5~7.0wt.%, Mn: 7.5~9.0wt.%, Si: 0.5~2.0wt.%, Fe: 0.5~2.0wt.%, Pb: 0.35~0.80wt.%, Ti: 0.2~1.5wt.%, SiC: 0.06~0.40wt.%, and B: 0.02~0.15wt.%, the corresponding pure copper, zinc ingots, Al blocks, Mn powder, Si powder, Fe powder, CuPb master alloy, Ti powder, SiC powder, and CuB powder are weighed as raw materials for copper alloys. After weighing and mixing Mn powder and Si powder, the mixture is pressed into a silicon-magnesium composite block. Weighed Ti powder, SiC powder and CuB powder are mixed and sintered into a hybrid reinforced phase matrix; The weighed pure copper, zinc ingots, Al blocks, Fe powder, CuPb master alloy, hybrid reinforcing phases and silicon-magnesium composite blocks are completely melted to obtain copper alloy melt; The copper alloy melt is poured into a mold and cooled to form a copper alloy with TiC and TiB2 mixed reinforcing phases.

2. The method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases according to claim 1, characterized in that, The raw materials of the weighed copper alloy include: Cu: 61.5~64.0 wt.%, Zn: 13.38~22.87 wt.%, Al: 5.5~7.0 wt.%, Mn: 7.5~9.0 wt.%, Si: 0.5~2.0 wt.%, Fe: 0.5~2.0 wt.%, Pb: 0.35~0.80 wt.%, Ti: 0.2~1.3 wt.%, SiC: 0.06~0.39 wt.%, B: 0.02~0.13 wt.%.

3. The method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases according to claim 1, characterized in that, The raw materials of the weighed copper alloy include: Cu: 61.5~64.0 wt.%, Zn: 13.8~22.87 wt.%, Al: 5.5~7.0 wt.%, Mn: 7.5~9.0 wt.%, Si: 0.5~2.0 wt.%, Fe: 0.5~2.0 wt.%, Pb: 0.35~0.80 wt.%, Ti: 0.2~1.0 wt.%, SiC: 0.06~0.30 wt.%, B: 0.02~0.10 wt.%.

4. The method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases according to claim 1, characterized in that, The pressing pressure is 10~30MPa.

5. The method for preparing a copper alloy with a TiC and TiB2 hybrid reinforcing phase according to claim 1, characterized in that, The sintering process includes hot pressing sintering or spark plasma sintering.

6. The method for preparing a copper alloy with a TiC and TiB2 hybrid reinforcing phase according to claim 5, characterized in that, The heating rate of the hot pressing sintering is 5~15℃ / min, the sintering temperature is 350~500℃, the sintering pressure is 50~60MPa, and the time is 20~40min.

7. The method for preparing a copper alloy with a TiC and TiB2 hybrid reinforcing phase according to claim 5, characterized in that, The heating rate of the discharge plasma sintering is 100~150℃ / min, the sintering temperature is 900~950℃, the sintering pressure is 30~50MPa, and the time is 6~10min.

8. The method for preparing a copper alloy with TiC and TiB2 hybrid reinforcing phases according to claim 1, characterized in that, The mixing process includes: ball milling the weighed Ti powder, SiC powder and CuB powder at a speed of 50~150 r / min for 4~6 h.

9. A copper alloy having a TiC and TiB2 hybrid reinforcing phase, characterized in that, It is prepared by the preparation method according to any one of claims 1-8.

10. The application of the copper alloy with TiC and TiB2 hybrid reinforcing phases as described in claim 9 in the manufacture of sliding bearings, pump and valve parts, brush holders or high-load friction components.

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