Alloy material for high-strength alloy bar production and method for producing the same

Abstract

This invention discloses an alloy material and its preparation method for high-strength alloy bars, belonging to the field of alloy material preparation technology. It addresses the technical problem that the hardness and strength of alloy materials prepared from alloy bars in existing technologies need further improvement. This invention adds three functional materials—a melt purifier, a melt homogenizer, and a as-cast stabilizer—to a copper-based multi-principal-element alloy system, forming a coordinated control system for the melt and solidification stages. The melt purifier regulates the micro-region distribution and interface state of the multi-principal-element components; the melt homogenizer promotes liquid phase homogeneity and coordinated local component migration; and the as-cast stabilizer stabilizes the interface and microstructure continuity at the solidification front. The synergistic effect of these three materials enables the copper-based multi-principal-element alloy to form a more uniform and continuous microstructure during solidification and microstructure evolution, ultimately achieving a coordinated match between performance indicators such as grain size, hardness, strength, and bar fatigue.

Description

Technical Field

[0001] This invention relates to the field of alloy materials technology, specifically to an alloy material for preparing high-strength alloy bars and its preparation method. Background Technology

[0002] Currently, the alloy materials used for high-strength alloy bars mainly include high-strength and high-conductivity copper alloy systems such as Cu-Cr-Zr, Cu-Ni-Si, Cu-Fe-Si, Cu-Ti, Cu-Ag, and Cu-Mg. In recent years, complex concentrated alloys or multi-principal element alloys designed by combining three or more main elements in high content have also emerged. These alloy materials are usually made into bars by combining processes such as melting, casting, homogenization, hot working, and subsequent aging to obtain higher strength by utilizing solid solution strengthening, precipitation strengthening, grain refinement strengthening, and work hardening. They are then used for conductive load-bearing, connecting components, and other applications where high bar strength is required.

[0003] However, for alloy materials for bars with a high degree of alloying and a large number of components, the existing technology often has the problem of unstable composition distribution during the melt and solidification stages. Due to the differences in melting point, enthalpy of mixing and diffusion behavior among different elements, interdendritic segregation, grain boundary enrichment and local enrichment phase formation are prone to occur during solidification. Some copper alloy as-cast materials may also be accompanied by shrinkage cavities, inclusions or coarse second phases. The above problems will cause the as-cast structure to be inhomogeneous in the cross-sectional and length directions, and further affect the continuity of the structure and the consistency of the material after subsequent bar processing.

[0004] Furthermore, in pursuing strength improvement, existing high-strength alloy bar materials often face the problem of the transfer of microstructural defects to service performance. Public research shows that the fatigue response of copper and copper alloys is closely related to grain size, metallurgical state, and loading mode. Defects, inclusions, and second-phase particles near the surface of the bar are prone to become fatigue crack initiation sites. For high-strength copper alloy bars, cracks can also directly start in the weak area of ​​the surface and near the second-phase particles. Therefore, simply improving the static load strength is still insufficient to guarantee the microstructural stability and service compatibility of the bar material under cyclic loading conditions.

[0005] To address this technical deficiency, a solution is proposed. Summary of the Invention

[0006] The purpose of this invention is to provide an alloy material and its preparation method for high-strength alloy rods, thereby solving the technical problem that the hardness and strength of alloy materials prepared from alloy rods in the prior art need to be further improved.

[0007] The objective of this invention can be achieved through the following technical solutions: An alloy material for preparing high-strength alloy bars comprises the following raw material composition by weight: 645-725 parts of base molten metal, 220-235 parts of active regulating metal, 60-80 parts of supplementary metal, 10-14 parts of melt purifier, 5-7 parts of melt homogenizer and 1-2 parts of as-cast stabilizer. The preparation method of the melt purifier is as follows: formamide and urea are added to the reaction vessel and stirred. After mixing evenly, boron-phosphorus purification composite material is added. The reaction vessel is then heated to 135-145℃ and stirred for 2-3 hours. The melt purifier is then obtained through post-treatment.

[0008] Furthermore, the ratio of formamide, urea and boron-phosphorus purification composite material is 130-170mL:18-22g:16-20g. The post-treatment includes: after the reaction is completed, vacuum distillation is carried out until no liquid is collected, the material is taken out, dried, pulverized and passed through a 100-140 mesh sieve to obtain melt purification agent.

[0009] Furthermore, the base molten metal material is obtained by mixing copper, nickel, tin, silicon, chromium and titanium in a ratio of 420-450g:175-205g:35-45g:10-15g:5-10g:1.5-2.5g; the activity regulating metal material is obtained by mixing manganese and aluminum in a ratio of 125-145g:75-90g; and the supplementary metal material is zinc.

[0010] Furthermore, the boron-phosphorus purification composite material is prepared by the following method: A1. Add anhydrous ethanol and deionized water to the reaction vessel and stir. After mixing evenly, add metal hydrate I, phytic acid and citric acid. Then heat the reaction vessel to 55-65℃ and stir for 2-3 hours. After the reaction is completed, cool to room temperature, filter and collect the filter cake, wash and dry to obtain the acid-treated purification precursor. A2. Add glycerol and boric acid to the reaction vessel and stir. After mixing evenly, add the acid treatment purification precursor material, then heat the reaction vessel to 105-115℃ and keep it at that temperature for 2-3 hours. After the reaction is completed, cool it to 35-45℃, filter and collect the filter cake, wash and dry it to obtain the boron-phosphorus purification composite material.

[0011] Further, in step A1, the ratio of anhydrous ethanol, deionized water, metal hydrate, phytic acid, and citric acid is 160-200mL:50-70mL:32-42g:8-12g:5-7g, wherein the metal hydrate I is obtained by mixing copper nitrate trihydrate, zirconium oxychloride octahydrate, and magnesium acetate tetrahydrate in a ratio of 16-20g:10-14g:6-9g; Furthermore, in step A2, the ratio of glycerol, boric acid, and acid-treated purification precursor is 100-140 mL: 10-14 g: 18-22 g.

[0012] Furthermore, the preparation method of the as-cast stabilizer is as follows: deionized water and sodium molybdate dihydrate are added to a reaction vessel and stirred. After mixing evenly, the reaction vessel is cooled to 8-12°C, 30wt% hydrogen peroxide aqueous solution is added and stirred for 10-20 min, then metal hydrate II and ammonium bicarbonate are added. Subsequently, the reaction vessel is heated to 60-70°C and stirred for 1-2 h. The as-cast stabilizer is obtained after post-treatment.

[0013] Furthermore, in the preparation of the as-cast stabilizer, the ratio of deionized water and sodium molybdate dihydrate, 30wt% hydrogen peroxide aqueous solution, metal hydrate II and ammonium bicarbonate is 220mL:7-9g:8-12mL:8-10g:7-9g. Among them, metal hydrate II is obtained by mixing cerium nitrate hexahydrate, yttrium nitrate hexahydrate and stannous chloride dihydrate in a ratio of 3-4g:2g:3-4g. The post-treatment includes: cooling to room temperature after the reaction, filtering to collect the filter cake, washing and drying, and then grinding through a 120-160 mesh sieve to obtain the as-cast stabilizer.

[0014] Furthermore, the melt homogenizer is prepared by the following method: B1. Add anhydrous ethanol and deionized water to the reactor and stir. After mixing evenly, add metal hydrate III and then add tetraethyl orthosilicate in ten equal batches with an interval of 5 minutes between additions. After the addition is complete, heat the reactor to 46-54℃ and keep it at the temperature for 2-3 hours. The post-processing yields the silicon source homogenization precursor. B2. Add deionized water and anhydrous ethanol to the reaction vessel and stir. After mixing evenly, add furfural and ethylenediamine, then add silicon source homogenization precursor. First, keep the mixture at 35-40℃ and stir for 40-60 minutes, then raise the temperature to 75-85℃ and keep stirring for 1-2 hours. The post-treatment yields the melt homogenizer.

[0015] Further, in step B1, the ratio of anhydrous ethanol, deionized water, metal hydrate III, and tetraethyl orthosilicate is 140-180 mL: 35-45 mL: 24-32 g: 16-20 mL, wherein the metal hydrate III is obtained by mixing nickel acetate tetrahydrate, manganese acetate tetrahydrate, and aluminum nitrate nonahydrate in a ratio of 12-16 g: 9-11 g: 5-7 g. The post-treatment includes: cooling to room temperature after the reaction, filtering to collect the filter cake, washing and drying to obtain the silicon source homogenization precursor. Furthermore, in step B2, the ratio of deionized water, anhydrous ethanol, furfural, ethylenediamine, and silicon source homogenizing precursor is 70-90 mL: 35-45 mL: 10-14 mL: 8-12 mL: 14-18 g. The post-treatment includes: cooling to room temperature after the reaction, filtering to collect the filter cake, washing and drying, and then grinding through a 100-120 mesh sieve to obtain the melt homogenizer.

[0016] This invention also discloses a method for preparing alloy materials for high-strength alloy rods, comprising the following steps: adding basic molten metal to a melting furnace, heating and melting under argon protection, mixing evenly, adding active regulating metal, holding the temperature until the melt is uniform, adding melt purifying agent, controlling the furnace temperature to 1190-1210℃ and holding for 4-8 minutes, then adding melt homogenizing agent, controlling the furnace temperature to 1165-1185℃ and holding for 2-4 minutes, continuing to lower the furnace temperature to 1105-1135℃, adding supplementary metal and as-cast stabilizer, holding for 1-3 minutes, and post-processing to obtain a copper-based multi-principal element alloy.

[0017] Further post-processing includes: removing slag and letting it stand for 1-3 minutes, then pouring it into a mold preheated to 220-280℃ to cool and solidify, thus obtaining a copper-based multi-principal element alloy.

[0018] The present invention has the following beneficial effects: 1. In the process configuration of this invention, the melt purifier is arranged in the pre-melt treatment stage. Its function is not limited to the general purification treatment, but to first regulate the liquid phase environment so that the subsequent distribution adjustment of multi-components is based on a relatively stable melt. On this basis, a melt homogenizer is added, and the spatial distribution of each component in the liquid phase tends to be coordinated, and the pulling effect of local segregation on the solidification initiation state is correspondingly weakened. Subsequently, a casting stabilizer is configured so that the aforementioned liquid phase conditions are continued in the solidification transformation stage, and the local fluctuations in the formation process of the casting structure are constrained. Through the combined effect of this structural configuration and the operating sequence, a good correspondence is formed between grain size, grain boundary morphology and regional microstructure consistency, and the microstructure characterization shows a more convergent state.

[0019] 2. After the melt homogenizer prepared by this invention enters the melt system, the multi-components formed by the base molten metal and the active regulating metal do not remain in a local enrichment state. The spatial expression of each strengthening factor in the liquid phase is more continuous. The resulting microstructure no longer mainly relies on individual regions to bear the load response of the material body. The previously configured melt purifier constrains the impurity background and interface anomalies, providing lower interference conditions for this distribution state. The subsequently added as-cast stabilizer makes the equilibrium pattern formed in the liquid phase less likely to be disrupted again during solidification. The resulting internal structure of the material exhibits more consistent response characteristics in terms of hardness characterization, tensile load transfer, and deformation connection before and after yielding. The various bulk mechanical characteristics are also easier to maintain coordination.

[0020] 3. After the as-cast stabilizer prepared in this invention is introduced into the solidification stage, the ingot structure maintains good continuity and convergence during the formation process. Differences between dendrites, local structural fluctuations, and initial defect sources are less likely to accumulate further in the as-cast stage. This preserves a smoother structural starting point for subsequent homogenization, hot extrusion, solution treatment, cold drawing, and aging processes. The control of inclusions and impurities left by the melt purifier reduces the potential crack initiation sites inside the bar. The continuity of component distribution maintained by the melt homogenizer makes the structural transformation and local performance connection after hot working more natural. The internal load-bearing path of the bar formed along this process chain is more coherent. Under cyclic loading, there is less likely to be abrupt mismatch between crack initiation, propagation, and stress transmission, and the corresponding service characterization is more stable. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 This is a SEM image of the melt purifying agent prepared in Example 3 of the present invention; Figure 2 This is an SEM image of the melt homogenizer prepared in Example 6 of the present invention. Detailed Implementation

[0023] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] Example 1 This embodiment provides a method for preparing a melt purifying agent, including the following steps: Step I: Preparation of acid treatment purification precursor Weigh out 16.0g of copper nitrate trihydrate, 10.0g of zirconium oxychloride octahydrate and 6.0g of magnesium acetate tetrahydrate and mix them to obtain metal hydrate I; Weigh out 160.0 mL of anhydrous ethanol and 50.0 mL of deionized water and add them to the reaction vessel. Stir and mix well. Then add 32.0 g of metal hydrate I, 8.0 g of phytic acid and 5.0 g of citric acid. Heat the reaction vessel to 55 °C and keep it at that temperature for 2 hours. After the reaction is complete, cool it to room temperature, filter and collect the filter cake, wash and dry it to obtain the acid-treated purification precursor.

[0025] Step II: Preparation of boron-phosphorus purification composite material Weigh out 100.0 mL of glycerol and 10.0 g of boric acid and add them to the reaction vessel. Stir and mix well. Then add 18.0 g of acid treatment purification precursor. Heat the reaction vessel to 105°C and keep it at that temperature for 2 hours. After the reaction is complete, cool it to 35°C, filter and collect the filter cake, wash and dry it to obtain boron-phosphorus purification composite material.

[0026] Step III: Preparation of melt purification agent Weigh out 130.0 mL of formamide and 18.0 g of urea and add them to the reaction vessel. Stir and mix evenly. Then add 16.0 g of boron-phosphorus purification composite material. Heat the reaction vessel to 135°C and keep it at that temperature for 2 hours. After the reaction is complete, distill under reduced pressure until no liquid is collected. Take out the material, dry it, crush it, and pass it through a 100-mesh sieve to obtain the melt purification agent.

[0027] The reaction principle for preparing melt purifying agent is as follows: In an ethanol-water mixture, the metal ions formed by the dissociation of copper nitrate trihydrate, zirconium oxychloride octahydrate, and magnesium acetate tetrahydrate undergo hydrolytic coordination, multi-site complexation, and condensation association with phytic acid and citric acid, gradually forming a precursor structure with metal-oxygen-organic ligand bonding characteristics. Boric acid in a glycerol medium undergoes esterification, coordination association, and condensation rearrangement with the phosphate, hydroxyl, and carboxyl groups in the precursor system, transforming the system into a composite solid phase containing boron and phosphorus structural units. In the presence of formamide and urea, the residual oxygen-containing groups in the system further undergo condensation and association with nitrogen-containing small molecules, forming an organic-inorganic composite solid product with boron and phosphorus components.

[0028] The working principle of melt purifiers in copper-based multi-principal alloys is as follows: The melt purifier prepared by this process is an organic-inorganic composite functional material with multiple active sites. Its structure includes a metal-oxygen coordination framework and boron, phosphorus, and nitrogen-containing functional units, which endow it with the ability to regulate the composite structure in copper-based multi-principal alloy melts. After entering the melt, the melt purifier can adsorb, bind, or migrate oxide inclusions, impurity enrichment areas, and locally unstable interfaces, reducing the melt's defect sensitivity. On the other hand, it can slow down and coordinate the local distribution of multi-principal components, interface states, and microstructure evolution near the solidification front, thereby reducing local segregation and abrupt changes in microstructure. Based on this mechanism, the melt is more likely to form a more uniform and continuous microstructure during solidification, resulting in a more coordinated matching relationship between the final copper-based multi-principal alloy in terms of grain size, hardness, tensile strength, specified plastic elongation strength, and subsequent bar fatigue response.

[0029] Example 2 This embodiment provides a method for preparing a melt purifying agent, including the following steps: Step I: Preparation of acid treatment purification precursor Weigh out 20.0g of copper nitrate trihydrate, 14.0g of zirconium oxychloride octahydrate and 9.0g of magnesium acetate tetrahydrate and mix them to obtain metal hydrate I; Weigh out 200.0 mL of anhydrous ethanol and 70.0 mL of deionized water and add them to the reaction vessel. Stir and mix well. Then add 42.0 g of metal hydrate I, 12.0 g of phytic acid and 7.0 g of citric acid. Heat the reaction vessel to 65 °C and keep it at that temperature for 3 hours. After the reaction is complete, cool to room temperature, filter and collect the filter cake, wash and dry it to obtain the acid-treated purified precursor material.

[0030] Step II: Preparation of boron-phosphorus purification composite material Weigh out 140.0 mL of glycerol and 14.0 g of boric acid and add them to the reaction vessel. Stir and mix well. Then add 22.0 g of acid treatment purification precursor. Heat the reaction vessel to 115°C and keep it at that temperature for 3 hours. After the reaction is complete, cool it to 45°C, filter and collect the filter cake, wash and dry it to obtain boron-phosphorus purification composite material.

[0031] Step III: Preparation of melt purification agent Weigh out 170.0 mL of formamide and 22.0 g of urea and add them to the reaction vessel. Stir and mix evenly. Then add 20.0 g of boron-phosphorus purification composite material. Heat the reaction vessel to 145°C and keep it at that temperature for 3 hours. After the reaction is completed, distill under reduced pressure until no liquid is collected. Take out the material, dry it, crush it, and pass it through a 140-mesh sieve to obtain the melt purification agent.

[0032] Example 3 This embodiment provides a method for preparing a melt purifying agent, including the following steps: Step I: Preparation of acid treatment purification precursor Weigh out 18.0g of copper nitrate trihydrate, 12.0g of zirconium oxychloride octahydrate and 7.5g of magnesium acetate tetrahydrate and mix them to obtain metal hydrate I; Weigh out 180.0 mL of anhydrous ethanol and 60.0 mL of deionized water and add them to the reaction vessel. Stir and mix well. Then add 36.0 g of metal hydrate I, 10.0 g of phytic acid and 6.0 g of citric acid. Heat the reaction vessel to 60 °C and keep it at that temperature for 3 hours. After the reaction is complete, cool to room temperature, filter and collect the filter cake, wash and dry it to obtain the acid-treated purification precursor.

[0033] Step II: Preparation of boron-phosphorus purification composite material Weigh 120.0 mL of glycerol and 12.0 g of boric acid and add them to the reaction vessel. Stir and mix evenly. Then add 20.0 g of acid treatment purification precursor. Heat the reaction vessel to 110°C and keep it at that temperature for 3 hours. After the reaction is complete, cool it to 40°C, filter and collect the filter cake, wash and dry it to obtain boron-phosphorus purification composite material.

[0034] Step III: Preparation of melt purification agent Weigh out 150.0 mL of formamide and 20.0 g of urea and add them to the reaction vessel. Stir and mix evenly. Then add 18.0 g of boron-phosphorus purification composite material. Heat the reaction vessel to 140°C and keep it at that temperature for 3 hours. After the reaction is complete, distill under reduced pressure until no liquid is collected. Take out the material, dry it, crush it, and pass it through a 120-mesh sieve to obtain the melt purification agent.

[0035] Example 4 This embodiment provides a method for preparing a melt homogenizer, including the following steps: Step ①: Preparation of silicon source homogenization precursor Weigh out 12.0 g of nickel acetate tetrahydrate, 9.0 g of manganese acetate tetrahydrate and 5.0 g of aluminum nitrate nonahydrate and mix them to obtain metal hydrate hydrate III; Weigh out 140.0 mL of anhydrous ethanol and 35.0 mL of deionized water and add them to the reaction vessel. Stir and mix well. Then add 24.0 g of metal hydrate III and add tetraethyl orthosilicate in ten equal batches. The total amount added is 16.0 mL with an interval of 5 min between additions. After the addition is complete, heat the reaction vessel to 46 °C and keep it at this temperature for 2 h with stirring. After the reaction is complete, cool to room temperature, filter and collect the filter cake, wash and dry it to obtain the silicon source homogenization precursor.

[0036] Step 2: Preparation of melt homogenizer Weigh out 70.0 mL of deionized water and 35.0 mL of anhydrous ethanol and add them to the reaction vessel. Stir and mix well. Then add 10.0 mL of furfural and 8.0 mL of ethylenediamine, followed by 14.0 g of silicon source homogenizing precursor. First, keep the mixture at 35 °C and stir for 40 min, then raise the temperature to 75 °C and stir for 1 h. After the reaction is complete, cool to room temperature, filter and collect the filter cake, wash and dry it, and then grind it through a 100-mesh sieve to obtain the melt homogenizer.

[0037] The reaction principle for preparing melt homogenizers is as follows: In an ethanol-water mixed medium, metal ions formed by the dissociation of nickel acetate tetrahydrate, manganese acetate tetrahydrate, and aluminum nitrate nonahydrate undergo hydrolysis, hydroxyl condensation, and coordination association with silanol species generated by the hydrolysis of tetraethyl orthosilicate, gradually constructing an inorganic precursor structure characterized by metal-oxygen-silicon bonds. Furfural and ethylenediamine undergo condensation in the water-ethanol medium, and adsorption, coordination, and local condensation occur between them and hydroxyl groups, unsaturated metal sites, and siloxy groups on the surface of the precursor system, thereby forming a composite solid phase composition with organic components involved.

[0038] The working principle of melt homogenizers in copper-based multi-principal element alloys is as follows: The melt homogenizer prepared by this process is a composite functional material with multiple coordination sites and silicon-oxygen structural units. Its structural origin includes a metal-oxygen structural basis formed by nickel, manganese, and aluminum-related components, as well as silicon-oxygen network characteristics formed by the introduction of silicon sources. Combined with a surface-active structure containing organic coordination groups, it endows the melt with the ability to regulate components and homogenize micro-regions in copper-based multi-principal alloy melts. After entering the melt, the melt homogenizer does not act in a single purification manner, but rather weakens component enrichment and local fluctuations by coordinating and regulating the local distribution, micro-region diffusion state, and interface migration behavior of multi-principal components. This makes the composition field and structural evolution inside the melt more uniform and continuous. Based on this mode of action, it is easier to form a more uniform microstructure during solidification, reducing the discontinuity of microstructure and performance fluctuations caused by local mismatch. As a result, the final copper-based multi-principal alloy exhibits a better coordination and matching relationship between grain size, hardness, tensile strength, specified plastic elongation strength, and subsequent bar fatigue response.

[0039] Example 5 This embodiment provides a method for preparing a melt homogenizer, including the following steps: Step ①: Preparation of silicon source homogenization precursor Weigh out 16.0 g of nickel acetate tetrahydrate, 11.0 g of manganese acetate tetrahydrate and 7.0 g of aluminum nitrate nonahydrate and mix them to obtain metal hydrate hydrate III; Weigh out 180.0 mL of anhydrous ethanol and 45.0 mL of deionized water and add them to the reaction vessel. Stir and mix thoroughly. Then add 32.0 g of metal hydrate III and add tetraethyl orthosilicate in ten equal batches, with a total addition of 20.0 mL and an interval of 5 min between additions. After the addition is complete, heat the reaction vessel to 54 °C and keep it at that temperature for 3 h with stirring. After the reaction is complete, cool to room temperature, filter and collect the filter cake, wash and dry it to obtain the silicon source homogenization precursor.

[0040] Step 2: Preparation of melt homogenizer Weigh out 90.0 mL of deionized water and 45.0 mL of anhydrous ethanol and add them to the reaction vessel. Stir and mix well. Then add 14.0 mL of furfural and 12.0 mL of ethylenediamine, followed by 18.0 g of silicon source homogenizing precursor. First, keep the mixture at 40 °C and stir for 60 min. Then, raise the temperature to 85 °C and keep stirring for 2 h. After the reaction is complete, cool to room temperature, filter and collect the filter cake. Wash and dry the cake, and then grind it through a 120-mesh sieve to obtain the melt homogenizer.

[0041] Example 6 This embodiment provides a method for preparing a melt homogenizer, including the following steps: Step ①: Preparation of silicon source homogenization precursor Weigh out 15.0 g of nickel acetate tetrahydrate, 10.0 g of manganese acetate tetrahydrate and 6.0 g of aluminum nitrate nonahydrate and mix them to obtain metal hydrate hydrate III; Weigh out 160.0 mL of anhydrous ethanol and 40.0 mL of deionized water and add them to the reaction vessel. Stir and mix thoroughly. Then add 27.0 g of metal hydrate III and add tetraethyl orthosilicate in ten equal batches, with a total addition of 18.0 mL at 5 min intervals. After the addition is complete, heat the reaction vessel to 50 °C and keep it at that temperature for 3 h with stirring. After the reaction is complete, cool to room temperature, filter and collect the filter cake, wash and dry it to obtain the silicon source homogenization precursor.

[0042] Step 2: Preparation of melt homogenizer Weigh out 80.0 mL of deionized water and 40.0 mL of anhydrous ethanol and add them to the reaction vessel. Stir and mix well. Then add 12.0 mL of furfural and 10.0 mL of ethylenediamine, followed by 16.0 g of silicon source homogenizing precursor. First, keep the mixture at 40 °C and stir for 50 min, then raise the temperature to 80 °C and stir for 2 h. After the reaction is complete, cool to room temperature, filter and collect the filter cake, wash and dry it, and then grind it through a 110-mesh sieve to obtain the melt homogenizer.

[0043] Example 7 This embodiment provides a method for preparing alloy materials for high-strength alloy rods, including the following steps: Step 1: Preparation of the as-cast stabilizer Weigh out 3.0 g of cerium nitrate hexahydrate, 2.0 g of yttrium nitrate hexahydrate and 3.0 g of stannous chloride dihydrate and mix them to obtain metal hydrate II; Weigh out 220.0 mL of deionized water and 7.0 g of sodium molybdate dihydrate and add them to the reaction vessel. Stir and mix thoroughly. Then, cool the reaction vessel to 8°C, add 8.0 mL of 30 wt% hydrogen peroxide aqueous solution and stir for 10 min. Then, add 8.0 g of metal hydrate II and 7.0 g of ammonium bicarbonate. Subsequently, heat the reaction vessel to 60°C and keep it at that temperature for 1 h. After the reaction is complete, cool to room temperature, filter and collect the filter cake, wash and dry it, and then grind it through a 120-mesh sieve to obtain the as-cast stabilizer.

[0044] The reaction principle for preparing as-cast stabilizers is as follows: Under low-temperature aqueous conditions, sodium molybdate and hydrogen peroxide form peroxymolybdenum-oxygen species. After dissociation, cerium salt, yttrium salt, and tin salt undergo coordination association with these molybdenum-oxygen species. Simultaneously, in a weakly alkaline environment regulated by ammonium bicarbonate, each metal component gradually undergoes hydrolysis, hydroxylation, and oxygen-containing anion bridging. Inorganic bonding relationships characterized by metal-oxygen-metal and metal-oxygen-molybdenum are established between different metal centers. The resulting solid-phase product exhibits a composite composition consisting of multi-metal oxygen-containing structural units such as cerium, yttrium, molybdenum, and tin.

[0045] The working principle of as-cast stabilizers in copper-based multi-principal element alloys is as follows: The as-cast stabilizer prepared by this process has a composite structure composed of oxygen-containing structural units of multiple metals such as cerium, yttrium, tin, and molybdenum. After entering the copper-based multi-principal alloy system, it mainly plays a role in the solidification and as-cast microstructure formation process. It can coordinate and regulate the interface state, micro-region solute redistribution behavior, and microstructure evolution process near the solidification front, reduce local component fluctuations and microstructure abrupt changes, and promote the formation of a more uniform and continuous microstructure. Based on this mechanism, the resulting copper-based multi-principal alloy is more likely to form a stable as-cast microstructure and exhibits a better coordination relationship between strength, plasticity, and subsequent bar performance.

[0046] Step 2: Preparation of copper-based multi-principal-element alloys Weigh out 420.0g copper, 175.0g nickel, 35.0g tin, 10.0g silicon, 5.0g chromium and 1.5g titanium and mix them to obtain the basic molten metal material; Weigh out 125.0g of manganese and 75.0g of aluminum and mix them to obtain an activity-regulating metal material; By weight, 645 parts of basic molten metal were weighed and added to the melting furnace. Under argon protection, the mixture was heated and melted. After being mixed evenly, 220 parts of active regulating metal were added and the mixture was kept at a constant temperature until the melt was homogeneous. Then, 10 parts of the melt purifier prepared in Example 1 were added, and the furnace temperature was controlled at 1190℃ and held for 4 minutes. Subsequently, 5 parts of the melt homogenizer prepared in Example 4 were added, and the furnace temperature was controlled at 1165℃ and held for 2 minutes. After the furnace temperature was lowered to 1105℃, 60 parts of supplementary metal and 1 part of as-cast stabilizer were added. After holding for 1 minute, the slag was removed and the mixture was allowed to stand for 1 minute. The mixture was then poured into a mold preheated to 220℃ and cooled to solidify, thus obtaining a copper-based multi-principal element alloy.

[0047] The reaction principle for preparing copper-based multi-principal-element alloys is as follows: In the high-temperature liquid copper-based system, copper forms a continuous melt phase. Nickel, tin, silicon, chromium, titanium, and subsequently added manganese and aluminum enter the liquid phase under thermal action and undergo dissolution, diffusion, and redistribution. Multi-metallic bonding relationships are established between different components. The composite components in the melt purifier, melt homogenizer, and as-cast stabilizer undergo cracking, dissociation, coordination exchange, and oxygen-containing group reconstruction under high-temperature conditions. The boron, phosphorus, silicon, nitrogen, molybdenum, and rare earth-related species involved further participate in the local chemical equilibrium and interfacial association process in the melt, thereby forming a multi-component composite chemical system of copper-based multi-principal alloy.

[0048] Example 8 This embodiment provides a method for preparing alloy materials for high-strength alloy rods, including the following steps: Step 1: Preparation of the as-cast stabilizer Weigh out 4.0 g of cerium nitrate hexahydrate, 2.0 g of yttrium nitrate hexahydrate and 4.0 g of stannous chloride dihydrate and mix them to obtain metal hydrate II; Weigh 220.0 mL of deionized water and 9.0 g of sodium molybdate dihydrate and add them to the reaction vessel. Stir and mix thoroughly. Then, cool the reaction vessel to 12°C and add 12.0 mL of 30 wt% hydrogen peroxide aqueous solution. Stir for 20 min, then add 10.0 g of metal hydrate II and 9.0 g of ammonium bicarbonate. Subsequently, heat the reaction vessel to 70°C and keep it at that temperature for 2 h. After the reaction is complete, cool to room temperature, filter and collect the filter cake, wash and dry it, and then grind it through a 160-mesh sieve to obtain the as-cast stabilizer.

[0049] Step 2: Preparation of copper-based multi-principal-element alloys Weigh out 450.0g copper, 205.0g nickel, 45.0g tin, 15.0g silicon, 10.0g chromium and 2.5g titanium and mix them to obtain the basic molten metal material; Weigh out 145.0g of manganese and 90.0g of aluminum and mix them to obtain an activity-regulating metal material; Weigh out 725 parts of basic molten metal and add them to the melting furnace. Melt the metal under argon protection and mix it evenly. Then add 235 parts of active regulating metal and keep the temperature until the melt is uniform. Then add 14 parts of the melt purifier prepared in Example 2 and control the furnace temperature to 1210℃ and keep it at that temperature for 8 minutes. Then add 7 parts of the melt homogenizer prepared in Example 5 and control the furnace temperature to 1185℃ and keep it at that temperature for 4 minutes. Continue to lower the furnace temperature to 1135℃, then add 80 parts of supplementary metal and 2 parts of as-cast stabilizer. Keep the temperature at that temperature for 3 minutes, remove the slag and let it stand for 3 minutes. Then pour it into a mold with a preheated temperature of 280℃ to cool and solidify, and obtain a copper-based multi-principal element alloy.

[0050] Example 9 This embodiment provides a method for preparing alloy materials for high-strength alloy rods, including the following steps: Step 1: Preparation of the as-cast stabilizer Weigh out 3.5g of cerium nitrate hexahydrate, 2.0g of yttrium nitrate hexahydrate and 3.5g of stannous chloride dihydrate and mix them to obtain metal hydrate II; Weigh out 220.0 mL of deionized water and 8.0 g of sodium molybdate dihydrate and add them to the reaction vessel. Stir and mix thoroughly. Then, cool the reaction vessel to 10°C and add 10.0 mL of 30 wt% hydrogen peroxide aqueous solution. Stir for 15 min, then add 9.0 g of metal hydrate II and 8.0 g of ammonium bicarbonate. Subsequently, heat the reaction vessel to 65°C and keep it at that temperature for 2 h. After the reaction is complete, cool to room temperature, filter and collect the filter cake, wash and dry it, and then grind it through a 150-mesh sieve to obtain the as-cast stabilizer.

[0051] Step 2: Preparation of copper-based multi-principal-element alloys Weigh out 435.0g copper, 185.0g nickel, 40.0g tin, 12.0g silicon, 8.0g chromium and 2.0g titanium and mix them to obtain the basic molten metal material; Weigh out 135.0g of manganese and 80.0g of aluminum and mix them to obtain an activity-regulating metal material; By weight, 670 parts of basic molten metal were weighed and added to the melting furnace. Under argon protection, the mixture was heated and melted. After being mixed evenly, 230 parts of active regulating metal were added and the mixture was kept at a constant temperature until the melt was homogeneous. Then, 12 parts of the melt purifier prepared in Example 3 were added, and the furnace temperature was controlled at 1200℃ and held for 6 minutes. Subsequently, 6 parts of the melt homogenizer prepared in Example 6 were added, and the furnace temperature was controlled at 1175℃ and held for 3 minutes. After the furnace temperature was lowered to 1125℃, 70 parts of supplementary metal and 2 parts of as-cast stabilizer were added. After holding for 2 minutes, the slag was removed and the mixture was allowed to stand for 2 minutes. The mixture was then poured into a mold with a preheated temperature of 250℃ to cool and solidify, thus obtaining a copper-based multi-principal element alloy.

[0052] Comparative Example 1 The difference between this comparative example and comparative example 9 is that the melt purifier is omitted in step two.

[0053] Comparative Example 2 The difference between this comparative example and comparative example 9 is that the melt homogenizer is omitted in step two.

[0054] Comparative Example 3 The difference between this comparative example and comparative example 9 is that the casting stabilizer is omitted in step two.

[0055] Performance testing: The average grain size of the copper-based multi-principal element alloys prepared in Examples 7-9 and Comparative Examples 1-3 was tested in accordance with the standard YS / T 347-2020 "Method for Determination of Average Grain Size of Copper and Copper Alloys". The Vickers hardness of the copper-based multi-principal element alloys prepared in Examples 7-9 and Comparative Examples 1-3 was tested in accordance with the standard GB / T 4340.1-2024 "Metallic materials - Vickers hardness test - Part 1: Test method". The tensile strength and specified plastic elongation strength of the copper-based multi-principal element alloys prepared in Examples 7-9 and Comparative Examples 1-3 were tested in accordance with the standard GB / T 3075-2021 "Method for controlling axial force in fatigue testing of metallic materials". The copper-based multi-principal-element alloy ingots prepared in Examples 7-9 and Comparative Examples 1-3 were processed into cylindrical billets with a diameter of 90 mm and a length of 180 mm. 2.5 mm of the surface layer was removed by turning. The billets were then placed in an argon-protected furnace for homogenization treatment. The protective gas purity was 99.99%, the homogenization temperature was 805 °C, and the holding time was 6 h. After holding, the billets were cooled in the furnace to 520 °C and then air-cooled to room temperature. The homogenized billets were then heated to 768 °C and held for 80 min. Hot extrusion was performed under conditions of an extrusion cylinder temperature of 438 °C and a die temperature of 426 °C. The extrusion ratio was controlled at 12.25:1, and the extrusion speed was controlled at 1.4 mm / s, yielding hot-extruded bars with a diameter of 20 mm. These hot-extruded bars were then subjected to solution treatment. The solution temperature was 905℃, and the holding time was 55 min. After being taken out of the furnace, the bar was immediately quenched and cooled in 24℃ water. The quenched bar was then subjected to three cold drawing processes: the first pass drew the bar from φ20.0mm to φ18.8mm, the second pass from φ18.8mm to φ17.4mm, and the third pass from φ17.4mm to φ16.0mm, with a total reduction in cross-section of 36.0%. After cold drawing, the bar underwent aging treatment at 452℃ for 3 h. After being taken out of the furnace, the bar was air-cooled to room temperature. Finally, after straightening, cutting to length, and surface finishing, the finished alloy bar was obtained with a specification of φ16mm×1000mm. The straightness of the bar was controlled to be ≤1.5mm / m, and the surface roughness was controlled to be Ra≤3.2μm. The fatigue strength of the alloy bars obtained by processing the copper-based multi-principal element alloys prepared in Examples 7-9 and Comparative Examples 1-3 was tested in accordance with the standard GB / T 3075-2021 "Method for controlling axial force in fatigue testing of metallic materials". See Table 1 for specific data; Table 1 - Performance Test Data for Each Sample Data Analysis: A comparative analysis of the data in Table 1 reveals that the copper-based multi-principal element alloy prepared in this invention has an average grain size of 26.7 μm, a Vickers hardness of 229 HV10, a tensile strength of 797 MPa, and a specified ductile elongation strength of 588 MPa. Furthermore, the alloy rod prepared using this copper-based multi-principal element alloy exhibits a fatigue strength of 249 MPa. All these data are superior to those of the comparative example, indicating that… In Comparative Example 1, since no melt purifier was added in step two, the melt lacked pretreatment of inclusions, oxygen-containing impurities, and local interface instability factors before entering the subsequent control stage. This resulted in insufficient stability of the initial reaction environment of the liquid phase system. Under these conditions, although the melt homogenizer added later could still promote component migration, its basis for action was continuously disturbed by the impurity background and local abnormal interfaces. It was difficult to fully establish the diffusion coordination and micro-region distribution continuity of the multi-components in the liquid phase. After entering the solidification stage, the above disturbances were easily transformed into local structural differences and transmitted into the interior of the as-cast structure. This resulted in a lack of balanced connection between grain nucleation, growth, and regional structural evolution processes, which in turn weakened the continuity of the load-bearing path inside the material and weakened the composite matching relationship between strength, plasticity, and fatigue-related characteristics. In Comparative Example 2, since no melt homogenizer was added in step two, the melt lacked a key link for intermediate coordination and continuous slow release of the spatial distribution of multi-components after the initial purification. Although the melt purifier had controlled the impurity background, the migration rate, local enrichment state, and interface distribution characteristics of each alloying element in the liquid phase were still difficult to become more consistent. As a result, different strengthening factors were difficult to form a coordinated expression in the overall structure. After this insufficiently balanced liquid phase entered the solidification zone, it was more likely to cause differences in the formation conditions of the structure in different regions. The subsequent as-cast stabilization process could only achieve limited convergence of the existing differences and it was difficult to rebuild a continuous and consistent structural basis from the source. As a result, the material was more likely to experience local mismatch in terms of load-bearing capacity, deformation transmission, and service response, and the degree of synergy of composite properties decreased accordingly. In Comparative Example 3, since no as-cast stabilizer was added in step two, the relatively coordinated liquid phase state formed by the melt after purification and homogenization failed to obtain effective support and stabilization constraints at the end of solidification. This resulted in a lack of necessary convergence mechanisms during the transformation of the liquid phase to the as-cast structure. In this case, the interdendritic differences, local structural fluctuations, and defect-sensitive areas that could have been suppressed during the solidification stage were more likely to be retained and solidified in the initial as-cast structure. After these initial differences entered the subsequent hot working and heat treatment processes, they were likely to further evolve into uneven local deformation, asynchronous structural transformation, and discontinuous stress transmission, which would damage the continuous load-bearing structure inside the material. As a result, it was difficult for the sample to maintain a stable connection between static load response and cyclic load response, and the strength-toughness relationship and service-related composite characterization also showed a tendency to weaken coordination. Ultimately, it is demonstrated that the melt purifier, melt homogenizer, and as-cast stabilizer in the material system are embedded in three interconnected operational stages: melt formation, component redistribution, and solidification convergence. Their interaction is more of a stage succession in the process chain than a parallel superposition of single additives. When the initial purification stage is missing, the subsequent component migration and microstructure evolution are established in a more disturbed liquid phase background. When the intermediate homogenization stage is missing, the lower defect state formed in the previous stage is difficult to further transform into a continuous and consistent component distribution. When the final stabilization stage is missing, the coordinated state formed in the liquid phase is difficult to be effectively preserved during solidification. Thus, although the steps of deletion vary in different comparative examples, their changes all reflect changes in the degree of connection in the microstructure construction process, which are further reflected in the matching tendency of the material's bulk response and service characterization.

[0056] The above description is merely an example and illustration of the structure of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the structure of the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

[0057] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0058] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. An alloy material for high-strength alloy bar production, characterized by comprising, in mass %, The raw material composition includes the following parts by weight: 645-725 parts base molten metal, 220-235 parts active conditioning metal, 60-80 parts supplementary metal, 10-14 parts melt purifier, 5-7 parts melt homogenizer and 1-2 parts as-cast stabilizer. The preparation method of the melt purifier is as follows: formamide and urea are added to a reaction vessel and stirred. After mixing evenly, boron-phosphorus purification composite material is added. The reaction vessel is then heated to 135-145℃ and stirred for 2-3 hours. The melt purifier is obtained by post-treatment. The ratio of formamide, urea and boron-phosphorus purification composite material is 130-170mL:18-22g:16-20g.

2. An alloy material for high-strength alloy bar production according to claim 1, characterized by, The base molten metal is obtained by mixing copper, nickel, tin, silicon, chromium and titanium in a ratio of 420-450g:175-205g:35-45g:10-15g:5-10g:1.5-2.5g; the activity regulating metal is obtained by mixing manganese and aluminum in a ratio of 125-145g:75-90g; and the supplementary metal is zinc.

3. The alloy material for producing a high-strength alloy bar according to claim 1, characterized by The boron-phosphorus purification composite material is prepared by the following method: A1. Add anhydrous ethanol and deionized water to the reaction vessel and stir. After mixing evenly, add metal hydrate I, phytic acid and citric acid. Then heat the reaction vessel to 55-65℃ and stir for 2-3 hours. After the reaction is completed, cool to room temperature, filter and collect the filter cake, wash and dry to obtain the acid-treated purification precursor. A2. Add glycerol and boric acid to the reaction vessel and stir. After mixing evenly, add the acid treatment purification precursor material, then heat the reaction vessel to 105-115℃ and keep it at that temperature for 2-3 hours. After the reaction is completed, cool it to 35-45℃, filter and collect the filter cake, wash and dry it to obtain the boron-phosphorus purification composite material.

4. The alloy material for preparing high-strength alloy bars according to claim 3, characterized in that, In step A1, the ratio of anhydrous ethanol, deionized water, metal hydrate, phytic acid, and citric acid is 160-200 mL: 50-70 mL: 32-42 g: 8-12 g: 5-7 g, wherein metal hydrate I is obtained by mixing copper nitrate trihydrate, zirconium oxychloride octahydrate, and magnesium acetate tetrahydrate in a ratio of 16-20 g: 10-14 g: 6-9 g; in step A2, the ratio of glycerol, boric acid, and acid-treated purification precursor is 100-140 mL: 10-14 g: 18-22 g.

5. The alloy material for preparing high-strength alloy bars according to claim 1, characterized in that, The preparation method of the as-cast stabilizer is as follows: Deionized water and sodium molybdate dihydrate are added to a reaction vessel and stirred. After mixing evenly, the reaction vessel is cooled to 8-12℃, 30wt% hydrogen peroxide aqueous solution is added and stirred for 10-20min, then metal hydrate II and ammonium bicarbonate are added. Subsequently, the reaction vessel is heated to 60-70℃ and kept at this temperature for 1-2h. The as-cast stabilizer is obtained after post-treatment.

6. The alloy material for preparing high-strength alloy bars according to claim 5, characterized in that, In the preparation of the as-cast stabilizer, the ratio of deionized water and sodium molybdate dihydrate, 30wt% hydrogen peroxide aqueous solution, metal hydrate II and ammonium bicarbonate is 220mL:7-9g:8-12mL:8-10g:7-9g, wherein metal hydrate II is obtained by mixing cerium nitrate hexahydrate, yttrium nitrate hexahydrate and stannous chloride dihydrate in a ratio of 3-4g:2g:3-4g.

7. The alloy material for preparing high-strength alloy bars according to claim 1, characterized in that, The melt homogenizer is prepared by the following method: B1. Add anhydrous ethanol and deionized water to the reactor and stir. After mixing evenly, add metal hydrate III and then add tetraethyl orthosilicate in ten equal batches with an interval of 5 minutes between additions. After the addition is complete, heat the reactor to 46-54℃ and keep it at the temperature for 2-3 hours. The post-processing yields the silicon source homogenization precursor. B2. Add deionized water and anhydrous ethanol to the reaction vessel and stir. After mixing evenly, add furfural and ethylenediamine, then add silicon source homogenization precursor. First, keep the mixture at 35-40℃ and stir for 40-60 minutes, then raise the temperature to 75-85℃ and keep stirring for 1-2 hours. The post-treatment yields the melt homogenizer.

8. The alloy material for preparing high-strength alloy bars according to claim 7, characterized in that, In step B1, the ratio of anhydrous ethanol, deionized water, metal hydrate III, and tetraethyl orthosilicate is 140-180 mL: 35-45 mL: 24-32 g: 16-20 mL, wherein metal hydrate III is obtained by mixing nickel acetate tetrahydrate, manganese acetate tetrahydrate, and aluminum nitrate nonahydrate in a ratio of 12-16 g: 9-11 g: 5-7 g; in step B2, the ratio of deionized water, anhydrous ethanol, furfural, ethylenediamine, and silicon source homogenization precursor is 70-90 mL: 35-45 mL: 10-14 mL: 8-12 mL: 14-18 g.

9. A method for preparing an alloy material for producing high-strength alloy bars as described in any one of claims 1-8, characterized in that, Includes the following steps: The basic molten metal is added to the melting furnace and heated to melt under argon protection. After being mixed evenly, an active regulating metal is added and the temperature is maintained until the melt is homogeneous. Then, a melt purifier is added, and the furnace temperature is controlled at 1190-1210℃ and held for 4-8 minutes. Subsequently, a melt homogenizer is added, and the furnace temperature is controlled at 1165-1185℃ and held for 2-4 minutes. The furnace temperature is then further reduced to 1105-1135℃, and additional metal and as-cast stabilizer are added and held for 1-3 minutes. The post-processing yields a copper-based multi-principal element alloy.

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