A high conductivity gradient copper alloy groove wire and its preparation method

Abstract

This invention discloses a high conductivity gradient copper alloy channel wire and its preparation method, relating to the field of copper alloy material technology. The composition, by mass percentage, includes: Ag 0.3-0.6%, rare earth elements 0.01-0.1%, Co 0.05-0.15%, Ni 0.02-0.12%, Ba 0.01-0.03%, Nb 0.05-0.8%, Ta 0.01-0.05%, Re 0.003-0.007%, Hf 0.08-0.2%, Mg 0.2-0.6%, carbon nanotubes 0.01-0.05%, fullerene 0.01-0.03%, with the balance being Cu and other unavoidable impurities. The rare earth elements are Ce, La, and Y mixed in a mass ratio of (1-2):1:(0.8-1.2). The grooved wire exhibits excellent mechanical properties, fatigue resistance, corrosion resistance, and electrical conductivity.

Description

Technical Field

[0001] This invention relates to the field of copper alloy materials technology, and in particular to a high conductivity gradient copper alloy channel wire and its preparation method. Background Technology

[0002] Copper alloy cable trays are copper alloy materials with specific shapes (usually channel-shaped), generally made by smelting and processing pure copper with other metallic elements such as zinc, tin, lead, aluminum, and nickel through specific processes. Due to their excellent electrical and thermal conductivity, high strength and hardness, superior corrosion resistance, and machinability, they are widely used in power transmission, electrical equipment, electronic information, machinery manufacturing, and architectural decoration. With the rapid development of modern high-end manufacturing, the performance requirements for copper alloy cable trays have reached unprecedented levels.

[0003] Traditional copper alloy cable trays employ static composition design, which, while meeting basic performance requirements, suffer from a significant increase in surface resistance due to the skin effect under high-frequency signal transmission and high-current-density conditions. This makes it difficult to meet the demands of next-generation electronic devices for low-loss, high-speed transmission. To improve the conductivity of copper alloy cable trays, trace alloying elements such as silver and magnesium are often added. However, improper selection of the type and amount of alloying elements can lead to limited mechanical and fatigue resistance, and the corrosion resistance and conductivity of the manufactured cable trays still require further improvement.

[0004] Chinese invention patent application CN119811777A discloses a method for preparing grooved wire for superconducting wires, comprising: drawing copper rods into copper flat wires using a drawing process; soaking the copper flat wires in flux, followed by washing and air drying to obtain pre-formed copper flat wires; combining multiple pre-formed copper flat wires according to the cross-sectional structure of the superconducting wire; induction heating welding the combined multiple pre-formed copper flat wires through a welding mold to obtain copper grooved wires; water cooling, cleaning, and drying the copper grooved wires to obtain clean copper grooved wires; and screening the copper grooved wires using a laser diameter gauge and eddy current flaw detection equipment to obtain finished copper grooved wires. This invention obtains copper grooved wires with grooved surfaces by welding copper flat wires, achieving integrated molding of the structural grooved wires, improving production efficiency. By designing molds with different structures for welding and finishing, the surface quality of the copper grooved wires is improved, resulting in high-precision, complex-structured grooved wires. The drawing speed is relatively fast, which is conducive to the large-scale production of copper grooved wires. However, this method only processes the groove lines in terms of manufacturing process without improving the material formulation, so the mechanical properties, fatigue resistance, corrosion resistance and electrical conductivity of the products made by this method still need to be further improved.

[0005] It is evident that developing a copper alloy channel wire with excellent mechanical properties, fatigue resistance, corrosion resistance, and electrical conductivity, as well as its preparation method, meets market demands, has broad market value and application prospects, and is of great significance to promoting the development of the copper alloy channel wire field. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of the prior art and provide a high conductivity gradient copper alloy channel wire with excellent mechanical properties, fatigue resistance, corrosion resistance and electrical conductivity, as well as its preparation method.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is: a high conductivity gradient copper alloy channel wire, the composition of which, by mass percentage, includes: Ag 0.3-0.6%, rare earth elements 0.01-0.1%, Co 0.05-0.15%, Ni 0.02-0.12%, Ba 0.01-0.03%, Nb 0.05-0.8%, Ta 0.01-0.05%, Re 0.003-0.007%, Hf 0.08-0.2%, Mg 0.2-0.6%, carbon nanotubes 0.01-0.05%, fullerene 0.01-0.03%, with the balance being Cu and other unavoidable impurities.

[0008] Preferably, the rare earth elements are Ce, La, and Y mixed in a mass ratio of (1-2):1:(0.8-1.2).

[0009] Preferably, the carbon nanotubes are multi-walled carbon nanotubes with an outer diameter of 6-13 nm and a length of 2.5-20 μm, with product number 698849, and are provided by Merck Chemicals.

[0010] Preferably, the fullerene is fullerene-C 60 It has an average diameter of 0.7 nm, part number 379646, and is supplied by Merck Chemicals.

[0011] Another object of the present invention is to provide a method for preparing the high conductivity gradient copper alloy trench wire, comprising the following steps:

[0012] Step S1, Pretreatment of carbon nanotubes and fullerenes: Carbon nanotubes and fullerenes are ultrasonically dispersed in a 3-5% nitric acid solution for 25-35 minutes to remove surface impurities; then, surface modification is performed using silane coupling agent KH-550, and the reaction is carried out in an 80℃ water bath for 2-4 hours. After drying, surface-activated carbon nanotubes and fullerenes are obtained.

[0013] Step S2, Alloy Melting and Nanocomposite: Electrolytic copper, Ag-Cu master alloy, rare earth element-Cu master alloy, Co-Cu master alloy, Ni-Cu master alloy, Ba-Cu master alloy, Nb-Cu master alloy, Ta-Cu master alloy, Re-Cu master alloy, Hf-Cu master alloy, and Mg-Cu master alloy are used as raw materials and added to a vacuum induction melting furnace for melting; surface-activated carbon nanotubes and fullerenes are added to the melt in three batches with a 5-minute interval between each batch, while electromagnetic stirring is turned on to stir evenly, to obtain an alloy liquid;

[0014] Step S3, Gradient Solidification and Texture Control: The molten alloy is poured into a directional solidification mold with a temperature gradient and directional solidification is carried out at a cooling rate of 10℃ / min to form an ingot with columnar crystal orientation; a pulsed magnetic field is applied during solidification to initially form a composition gradient.

[0015] Step S4, Hot Isostatic Pressing: The ingot is placed in a hot isostatic pressing apparatus for hot isostatic pressing to obtain a billet;

[0016] Step S5, Composite Processing and Gradient Strengthening: The billet is rolled using a cumulative rolling process. During the rolling process, a 60nm thick silver-copper-indium gradient alloy layer is deposited on the surface using ion beam sputtering technology. Subsequently, deep cryogenic treatment is performed to obtain the initial product of the groove line.

[0017] Step S6, Laser-assisted processing: Use a high-power pulsed laser to scan and process the surface of the initial grooved product;

[0018] Step S7, Heat treatment: Annealing is performed in a furnace under a high-purity argon protective atmosphere to obtain a high conductivity gradient copper alloy groove wire.

[0019] Preferably, the mass of the silane coupling agent KH-550 in step S1 is 0.8-1.5% of the total mass of carbon nanotubes and fullerenes.

[0020] Preferably, the melting temperature in step S2 is 1200-1220℃, and the vacuum degree is 1×10⁻⁶. -5 Pa.

[0021] Preferably, the frequency of the electromagnetic stirring in step S2 is 20-25Hz and the intensity is 0.5-0.6T.

[0022] Preferably, the bottom temperature of the directional solidification mold with temperature gradient described in step S3 is 275-285°C, and the top temperature is 515-525°C.

[0023] Preferably, the magnetic induction intensity of the pulsed magnetic field in step S3 is 0.8-0.9T, the frequency is 10-12Hz, and the pulse width is 500-550ms.

[0024] Preferably, the pressure of the hot isostatic pressing in step S4 is 100-110 MPa, the temperature is 890-910 °C, and the time is 5-7 h.

[0025] Preferably, the rolling temperature in step S5 is 300-320°C, and the rolling process is performed in 8 passes with a deformation of 20% per pass.

[0026] Preferably, in step S5, the mass ratio of silver, copper, and indium on the surface of the silver-copper-indium gradient alloy layer is 85:10:5; the silver content in the alloy layer gradually decreases from 85% on the surface to close to the silver content of the substrate at the interface with the substrate; the indium content gradually decreases from 5% on the surface to below 1% at a distance of about 20nm from the surface, while the copper content gradually increases from 10% on the surface to connect with the copper content of the substrate.

[0027] Preferably, the cryogenic treatment in step S5 is performed at a temperature of -195℃ to -200℃ for 10-12 hours.

[0028] Preferably, the high-power pulsed laser in step S6 has a wavelength of 1064 nm, a pulse width of 100 ns, a frequency of 10 Hz, and a power density of 5 × 10⁻⁶. 8 W / cm 2 .

[0029] Preferably, the scanning speed of the scanning process in step S6 is 50 mm / s and the spot diameter is 1 mm.

[0030] Preferably, the annealing process in step S7 adopts a three-stage annealing process: first, the temperature is held at 410-430℃ for 1-1.2 hours, then the temperature is raised to 560-590℃ and held for 0.5-0.7 hours, and finally the temperature is lowered to 470-490℃ and held for 0.8-0.9 hours.

[0031] Due to the application of the above technical solution, the present invention has the following beneficial effects:

[0032] (1) The method for preparing high conductivity gradient copper alloy groove wire disclosed in this invention is simple, easy to operate and control, has high preparation efficiency and high finished product qualification rate, is suitable for continuous large-scale production, and has high promotion and application value.

[0033] (2) The high conductivity gradient copper alloy channel wire disclosed in this invention comprises, by mass percentage: Ag 0.3-0.6%, rare earth elements 0.01-0.1%, Co 0.05-0.15%, Ni 0.02-0.12%, Ba 0.01-0.03%, Nb 0.05-0.8%, Ta 0.01-0.05%, Re 0.003-0.007%, Hf 0.08-0.2%, Mg 0.2-0.6%, carbon nanotubes 0.01-0.05%, fullerenes 0.01-0.03%, with the balance being Cu and other unavoidable impurities. Through the rational selection of component types and dosage ratios, the components can synergistically improve the mechanical properties, fatigue resistance, corrosion resistance, and conductivity of the channel wire. By incorporating carbon nanotubes and fullerenes into a copper alloy system and precisely controlling their dosage, as well as subjecting them to surface modification, the problem of uniform dispersion and effective utilization of nanomaterials in copper alloys has been solved. With their high specific surface area and excellent conductivity, they effectively reduce electron scattering, thereby significantly improving the surface conductivity of the alloy.

[0034] (3) The high conductivity gradient copper alloy groove wire disclosed in this invention adopts gradient solidification and pulsed magnetic field control to promote the dynamic segregation of alloying elements with carbon nanotubes and fullerenes, and builds the composition gradient from the solidification stage; it adopts laser-assisted surface treatment and introduces high-power pulsed laser treatment technology, and uses the rapid heating and cooling characteristics of laser to form a nanoscale recrystallization layer on the surface, which not only significantly improves the surface conductivity, but also enhances the surface hardness, thereby effectively improving the surface properties of the material.

[0035] (4) The high conductivity gradient copper alloy channel wire disclosed in this invention comprehensively utilizes cumulative rolling, ion beam sputtering, and cryogenic treatment processes. It leverages the difference in thermal expansion coefficients to induce the dispersion and precipitation of nano-phases, achieving deep gradient strengthening from the surface to the core. This significantly improves the mechanical properties, fatigue resistance, corrosion resistance, and conductivity of the manufactured channel wire. The three-stage annealing process effectively improves production efficiency and enhances the conductivity and mechanical properties of the channel wire. Detailed Implementation

[0036] The following description is intended to disclose the invention and enable those skilled in the art to implement it. The preferred embodiments described below are merely examples, and other obvious variations will occur to those skilled in the art.

[0037] Example 1

[0038] A high conductivity gradient copper alloy channel wire, by mass percentage, comprises: Ag 0.3%, rare earth elements 0.01%, Co 0.05%, Ni 0.02%, Ba 0.01%, Nb 0.05%, Ta 0.01%, Re 0.003%, Hf 0.08%, Mg 0.2%, carbon nanotubes 0.01%, fullerene 0.01%, with the balance being Cu and other unavoidable impurities.

[0039] The rare earth elements are Ce, La, and Y mixed in a mass ratio of 1:1:0.8; the carbon nanotubes are multi-walled carbon nanotubes with an outer diameter of 6-13 nm and a length of 2.5-20 μm, with product number 698849, supplied by Merck Chemicals; the fullerene is fullerene-C 60 It has an average diameter of 0.7 nm, part number 379646, and is supplied by Merck Chemicals.

[0040] A method for preparing the high conductivity gradient copper alloy groove wire includes the following steps:

[0041] Step S1, Pretreatment of carbon nanotubes and fullerenes: Carbon nanotubes and fullerenes were ultrasonically dispersed in a 3% nitric acid solution for 25 minutes to remove surface impurities; then, surface modification was performed using silane coupling agent KH-550, and the reaction was carried out in an 80℃ water bath for 2 hours. After drying, surface-activated carbon nanotubes and fullerenes were obtained.

[0042] Step S2, Alloy Melting and Nanocomposite: Electrolytic copper, Ag-Cu master alloy, rare earth element-Cu master alloy, Co-Cu master alloy, Ni-Cu master alloy, Ba-Cu master alloy, Nb-Cu master alloy, Ta-Cu master alloy, Re-Cu master alloy, Hf-Cu master alloy, and Mg-Cu master alloy are used as raw materials and added to a vacuum induction melting furnace for melting; surface-activated carbon nanotubes and fullerenes are added to the melt in three batches with a 5-minute interval between each batch, while electromagnetic stirring is turned on to stir evenly, to obtain an alloy liquid;

[0043] Step S3, Gradient Solidification and Texture Control: The molten alloy is poured into a directional solidification mold with a temperature gradient and directional solidification is carried out at a cooling rate of 10℃ / min to form an ingot with columnar crystal orientation; a pulsed magnetic field is applied during solidification to initially form a composition gradient.

[0044] Step S4, Hot Isostatic Pressing: The ingot is placed in a hot isostatic pressing apparatus for hot isostatic pressing to obtain a billet;

[0045] Step S5, Composite Processing and Gradient Strengthening: The billet is rolled using a cumulative rolling process. During the rolling process, a 60nm thick silver-copper-indium gradient alloy layer is deposited on the surface using ion beam sputtering technology. Subsequently, deep cryogenic treatment is performed to obtain the initial product of the groove line.

[0046] Step S6, Laser-assisted processing: Use a high-power pulsed laser to scan and process the surface of the initial grooved product;

[0047] Step S7, Heat treatment: Annealing is performed in a furnace under a high-purity argon protective atmosphere to obtain a high conductivity gradient copper alloy groove wire.

[0048] In step S1, the mass of the silane coupling agent KH-550 is 0.8% of the total mass of carbon nanotubes and fullerenes; in step S2, the melting temperature is 1200℃ and the vacuum degree is 1×10⁻⁶. -5 Pa; the frequency of the electromagnetic stirring in step S2 is 20 Hz and the intensity is 0.5 T; the bottom temperature of the directional solidification mold with temperature gradient in step S3 is 275 ℃ and the top temperature is 515 ℃; the magnetic induction intensity of the pulsed magnetic field in step S3 is 0.8 T, the frequency is 10 Hz, and the pulse width is 500 ms.

[0049] In step S4, the hot isostatic pressing pressure is 100 MPa, the temperature is 890℃, and the time is 5 hours. In step S5, the rolling temperature is 300℃, and the rolling is performed in 8 passes with a deformation of 20% per pass. In step S5, the mass ratio of silver, copper, and indium on the surface of the silver-copper-indium gradient alloy layer is 85:10:5. The silver content in the alloy layer gradually decreases from 85% on the surface to close to the silver content of the substrate at the interface with the substrate. The indium content gradually decreases from 5% on the surface to below 1% at a distance of about 20 nm from the surface, while the copper content gradually increases from 10% on the surface to connect with the copper content of the substrate.

[0050] The cryogenic treatment in step S5 is carried out at a temperature of -195℃ for 10 hours; the high-power pulsed laser in step S6 has a wavelength of 1064nm, a pulse width of 100ns, a frequency of 10Hz, and a power density of 5×10⁻⁶. 8 W / cm 2 The scanning speed of the scanning process in step S6 is 50 mm / s and the spot diameter is 1 mm. The annealing process in step S7 adopts a three-stage annealing process: first, it is heated at 410℃ for 1 hour, then heated to 560℃ for 0.5 hours, and finally cooled to 470℃ for 0.8 hours.

[0051] Example 2

[0052] A high conductivity gradient copper alloy channel wire, by mass percentage, comprises: Ag 0.4%, rare earth elements 0.03%, Co 0.08%, Ni 0.05%, Ba 0.015%, Nb 0.2%, Ta 0.02%, Re 0.004%, Hf 0.12%, Mg 0.3%, carbon nanotubes 0.02%, fullerene 0.015%, with the balance being Cu and other unavoidable impurities.

[0053] The rare earth elements are Ce, La, and Y mixed in a mass ratio of 1.3:1:0.9; the carbon nanotubes are multi-walled carbon nanotubes with an outer diameter of 6-13 nm and a length of 2.5-20 μm, with product number 698849, supplied by Merck Chemicals; the fullerene is fullerene-C 60 It has an average diameter of 0.7 nm, part number 379646, and is supplied by Merck Chemicals.

[0054] A method for preparing the high conductivity gradient copper alloy groove wire includes the following steps:

[0055] Step S1, Pretreatment of carbon nanotubes and fullerenes: Carbon nanotubes and fullerenes were ultrasonically dispersed in a 3.5% nitric acid solution for 28 minutes to remove surface impurities; then, surface modification was performed using silane coupling agent KH-550, and the reaction was carried out in an 80°C water bath for 2.5 hours. After drying, surface-activated carbon nanotubes and fullerenes were obtained.

[0056] Step S2, Alloy Melting and Nanocomposite: Electrolytic copper, Ag-Cu master alloy, rare earth element-Cu master alloy, Co-Cu master alloy, Ni-Cu master alloy, Ba-Cu master alloy, Nb-Cu master alloy, Ta-Cu master alloy, Re-Cu master alloy, Hf-Cu master alloy, and Mg-Cu master alloy are used as raw materials and added to a vacuum induction melting furnace for melting; surface-activated carbon nanotubes and fullerenes are added to the melt in three batches with a 5-minute interval between each batch, while electromagnetic stirring is turned on to stir evenly, to obtain an alloy liquid;

[0057] Step S3, Gradient Solidification and Texture Control: The molten alloy is poured into a directional solidification mold with a temperature gradient and directional solidification is carried out at a cooling rate of 10℃ / min to form an ingot with columnar crystal orientation; a pulsed magnetic field is applied during solidification to initially form a composition gradient.

[0058] Step S4, Hot Isostatic Pressing: The ingot is placed in a hot isostatic pressing apparatus for hot isostatic pressing to obtain a billet;

[0059] Step S5, Composite Processing and Gradient Strengthening: The billet is rolled using a cumulative rolling process. During the rolling process, a 60nm thick silver-copper-indium gradient alloy layer is deposited on the surface using ion beam sputtering technology. Subsequently, deep cryogenic treatment is performed to obtain the initial product of the groove line.

[0060] Step S6, Laser-assisted processing: Use a high-power pulsed laser to scan and process the surface of the initial grooved product;

[0061] Step S7, Heat treatment: Annealing is performed in a furnace under a high-purity argon protective atmosphere to obtain a high conductivity gradient copper alloy groove wire.

[0062] The mass of the silane coupling agent KH-550 mentioned in step S1 is 1% of the total mass of carbon nanotubes and fullerenes; the melting temperature in step S2 is 1205℃, and the vacuum degree is 1×10⁻⁶. -5 Pa; the frequency of the electromagnetic stirring in step S2 is 22 Hz and the intensity is 0.52 T; the bottom temperature of the directional solidification mold with temperature gradient in step S3 is 278 ℃ and the top temperature is 518 ℃; the magnetic induction intensity of the pulsed magnetic field in step S3 is 0.83 T, the frequency is 10.5 Hz, and the pulse width is 520 ms.

[0063] In step S4, the hot isostatic pressing pressure is 103 MPa, the temperature is 895℃, and the time is 5.5 h. In step S5, the rolling temperature is 305℃, and the rolling is performed in 8 passes with a deformation of 20% per pass. In step S5, the mass ratio of silver, copper, and indium on the surface of the silver-copper-indium gradient alloy layer is 85:10:5. The silver content in the alloy layer gradually decreases from 85% on the surface to close to the silver content of the substrate at the interface with the substrate. The indium content gradually decreases from 5% on the surface to below 1% at a distance of about 20 nm from the surface, while the copper content gradually increases from 10% on the surface to connect with the copper content of the substrate.

[0064] The cryogenic treatment in step S5 is performed at a temperature of -197℃ for 10.5 hours; the high-power pulsed laser in step S6 has a wavelength of 1064 nm, a pulse width of 100 ns, a frequency of 10 Hz, and a power density of 5 × 10⁻⁶. 8 W / cm 2 The scanning speed of the scanning process in step S6 is 50 mm / s and the spot diameter is 1 mm. The annealing process in step S7 adopts a three-stage annealing process: first, it is heated at 415℃ for 1.1 hours, then heated to 570℃ for 0.55 hours, and finally cooled to 475℃ for 0.83 hours.

[0065] Example 3

[0066] A high conductivity gradient copper alloy channel wire, by mass percentage, comprises: Ag 0.45%, rare earth elements 0.06%, Co 0.1%, Ni 0.08%, Ba 0.02%, Nb 0.5%, Ta 0.035%, Re 0.005%, Hf 0.15%, Mg 0.4%, carbon nanotubes 0.035%, fullerene 0.02%, with the balance being Cu and other unavoidable impurities.

[0067] The rare earth elements are Ce, La, and Y mixed in a mass ratio of 1.5:1:1; the carbon nanotubes are multi-walled carbon nanotubes with an outer diameter of 6-13 nm and a length of 2.5-20 μm, with product number 698849, supplied by Merck Chemicals; the fullerene is fullerene-C 60 It has an average diameter of 0.7 nm, part number 379646, and is supplied by Merck Chemicals.

[0068] A method for preparing the high conductivity gradient copper alloy groove wire includes the following steps:

[0069] Step S1, Pretreatment of carbon nanotubes and fullerenes: Carbon nanotubes and fullerenes were ultrasonically dispersed in a 4% nitric acid solution for 30 minutes to remove surface impurities; then, surface modification was performed using silane coupling agent KH-550, and the reaction was carried out in an 80℃ water bath for 3 hours. After drying, surface-activated carbon nanotubes and fullerenes were obtained.

[0070] Step S2, Alloy Melting and Nanocomposite: Electrolytic copper, Ag-Cu master alloy, rare earth element-Cu master alloy, Co-Cu master alloy, Ni-Cu master alloy, Ba-Cu master alloy, Nb-Cu master alloy, Ta-Cu master alloy, Re-Cu master alloy, Hf-Cu master alloy, and Mg-Cu master alloy are used as raw materials and added to a vacuum induction melting furnace for melting; surface-activated carbon nanotubes and fullerenes are added to the melt in three batches with a 5-minute interval between each batch, while electromagnetic stirring is turned on to stir evenly, to obtain an alloy liquid;

[0071] Step S3, Gradient Solidification and Texture Control: The molten alloy is poured into a directional solidification mold with a temperature gradient and directional solidification is carried out at a cooling rate of 10℃ / min to form an ingot with columnar crystal orientation; a pulsed magnetic field is applied during solidification to initially form a composition gradient.

[0072] Step S4, Hot Isostatic Pressing: The ingot is placed in a hot isostatic pressing apparatus for hot isostatic pressing to obtain a billet;

[0073] Step S5, Composite Processing and Gradient Strengthening: The billet is rolled using a cumulative rolling process. During the rolling process, a 60nm thick silver-copper-indium gradient alloy layer is deposited on the surface using ion beam sputtering technology. Subsequently, deep cryogenic treatment is performed to obtain the initial product of the groove line.

[0074] Step S6, Laser-assisted processing: Use a high-power pulsed laser to scan and process the surface of the initial grooved product;

[0075] Step S7, Heat treatment: Annealing is performed in a furnace under a high-purity argon protective atmosphere to obtain a high conductivity gradient copper alloy groove wire.

[0076] In step S1, the mass of the silane coupling agent KH-550 is 1.3% of the total mass of carbon nanotubes and fullerenes; in step S2, the melting temperature is 1210℃ and the vacuum degree is 1×10⁻⁶. -5 Pa; the electromagnetic stirring frequency in step S2 is 23 Hz, and the intensity is 0.55 T; the bottom temperature of the directional solidification mold with temperature gradient in step S3 is 280℃, and the top temperature is 520℃; the magnetic induction intensity of the pulsed magnetic field in step S3 is 0.85 T, the frequency is 11 Hz, and the pulse width is 530 ms; the hot isostatic pressing pressure in step S4 is 105 MPa, the temperature is 900℃, and the time is 6 h; the rolling temperature in step S5 is 310℃, and it is an 8-pass rolling process with a deformation of 20% per pass.

[0077] In step S5, the mass ratio of silver, copper, and indium on the surface of the silver-copper-indium gradient alloy layer is 85:10:5. The silver content in the alloy layer gradually decreases from the surface (85%) to near the substrate silver content at the interface with the substrate. The indium content gradually decreases from 5% on the surface, dropping below 1% at approximately 20 nm from the surface, while the copper content gradually increases from 10% on the surface until it reaches the same level as the substrate copper content. The cryogenic treatment in step S5 is performed at -198°C for 11 hours. The high-power pulsed laser in step S6 has a wavelength of 1064 nm, a pulse width of 100 ns, a frequency of 10 Hz, and a power density of 5 × 10⁻⁶. 8 W / cm 2 The scanning speed of the scanning process in step S6 is 50 mm / s and the spot diameter is 1 mm. The annealing process in step S7 adopts a three-stage annealing process: first, it is heated at 420℃ for 1.1 hours, then heated to 575℃ for 0.6 hours, and finally cooled to 480℃ for 0.85 hours.

[0078] Example 4

[0079] A high conductivity gradient copper alloy channel wire, by mass percentage, comprises: Ag 0.55%, rare earth elements 0.09%, Co 0.13%, Ni 0.1%, Ba 0.025%, Nb 0.7%, Ta 0.04%, Re 0.006%, Hf 0.18%, Mg 0.55%, carbon nanotubes 0.04%, fullerene 0.025%, with the balance being Cu and other unavoidable impurities.

[0080] The rare earth elements are Ce, La, and Y mixed in a mass ratio of 1.8:1:1.1; the carbon nanotubes are multi-walled carbon nanotubes with an outer diameter of 6-13 nm and a length of 2.5-20 μm, with product number 698849, supplied by Merck Chemicals; the fullerene is fullerene-C 60 It has an average diameter of 0.7 nm, part number 379646, and is supplied by Merck Chemicals.

[0081] A method for preparing the high conductivity gradient copper alloy groove wire includes the following steps:

[0082] Step S1, Pretreatment of carbon nanotubes and fullerenes: Carbon nanotubes and fullerenes were ultrasonically dispersed in a 4.5% nitric acid solution for 33 minutes to remove surface impurities; then, surface modification was performed using silane coupling agent KH-550, and the reaction was carried out in an 80℃ water bath for 3.5 hours. After drying, surface-activated carbon nanotubes and fullerenes were obtained.

[0083] Step S2, Alloy Melting and Nanocomposite: Electrolytic copper, Ag-Cu master alloy, rare earth element-Cu master alloy, Co-Cu master alloy, Ni-Cu master alloy, Ba-Cu master alloy, Nb-Cu master alloy, Ta-Cu master alloy, Re-Cu master alloy, Hf-Cu master alloy, and Mg-Cu master alloy are used as raw materials and added to a vacuum induction melting furnace for melting; surface-activated carbon nanotubes and fullerenes are added to the melt in three batches with a 5-minute interval between each batch, while electromagnetic stirring is turned on to stir evenly, to obtain an alloy liquid;

[0084] Step S3, Gradient Solidification and Texture Control: The molten alloy is poured into a directional solidification mold with a temperature gradient and directional solidification is carried out at a cooling rate of 10℃ / min to form an ingot with columnar crystal orientation; a pulsed magnetic field is applied during solidification to initially form a composition gradient.

[0085] Step S4, Hot Isostatic Pressing: The ingot is placed in a hot isostatic pressing apparatus for hot isostatic pressing to obtain a billet;

[0086] Step S5, Composite Processing and Gradient Strengthening: The billet is rolled using a cumulative rolling process. During the rolling process, a 60nm thick silver-copper-indium gradient alloy layer is deposited on the surface using ion beam sputtering technology. Subsequently, deep cryogenic treatment is performed to obtain the initial product of the groove line.

[0087] Step S6, Laser-assisted processing: Use a high-power pulsed laser to scan and process the surface of the initial grooved product;

[0088] Step S7, Heat treatment: Annealing is performed in a furnace under a high-purity argon protective atmosphere to obtain a high conductivity gradient copper alloy groove wire.

[0089] In step S1, the mass of the silane coupling agent KH-550 is 1.3% of the total mass of carbon nanotubes and fullerenes; in step S2, the melting temperature is 1215℃ and the vacuum degree is 1×10⁻⁶. -5 Pa; the electromagnetic stirring frequency in step S2 is 24 Hz and the intensity is 0.58 T; the bottom temperature of the directional solidification mold with temperature gradient in step S3 is 283℃ and the top temperature is 523℃; the magnetic induction intensity of the pulsed magnetic field in step S3 is 0.88 T, the frequency is 11 Hz, and the pulse width is 540 ms; the hot isostatic pressing pressure in step S4 is 108 MPa, the temperature is 905℃, and the time is 6.5 h.

[0090] The rolling temperature in step S5 is 315℃, with 8 passes and a deformation of 20% per pass; the mass ratio of silver, copper, and indium on the surface of the silver-copper-indium gradient alloy layer in step S5 is 85:10:5; the silver content in the alloy layer gradually decreases from 85% on the surface to close to the silver content of the substrate at the interface with the substrate; the indium content gradually decreases from 5% on the surface, dropping to below 1% at a distance of about 20nm from the surface, while the copper content gradually increases from 10% on the surface until it connects with the copper content of the substrate; the cryogenic treatment temperature in step S5 is -199℃, and the time is 12h; the wavelength of the high-power pulsed laser in step S6 is 1064nm, the pulse width is 100ns, the frequency is 10Hz, and the power density is 5×10⁻⁶. 8 W / cm 2 The scanning speed of the scanning process in step S6 is 50 mm / s and the spot diameter is 1 mm. The annealing process in step S7 adopts a three-stage annealing process: first, it is heated at 425℃ for 1.2 hours, then heated to 585℃ for 0.65 hours, and finally cooled to 485℃ for 0.88 hours.

[0091] Example 5

[0092] A high conductivity gradient copper alloy channel wire, by mass percentage, comprises: Ag 0.6%, rare earth elements 0.1%, Co 0.15%, Ni 0.12%, Ba 0.03%, Nb 0.8%, Ta 0.05%, Re 0.007%, Hf 0.2%, Mg 0.6%, carbon nanotubes 0.05%, fullerene 0.03%, with the balance being Cu and other unavoidable impurities.

[0093] The rare earth elements are Ce, La, and Y mixed in a mass ratio of 2:1:1.2; the carbon nanotubes are multi-walled carbon nanotubes with an outer diameter of 6-13 nm and a length of 2.5-20 μm, with product number 698849, supplied by Merck Chemicals; the fullerene is fullerene-C 60 It has an average diameter of 0.7 nm, part number 379646, and is supplied by Merck Chemicals.

[0094] A method for preparing the high conductivity gradient copper alloy groove wire includes the following steps:

[0095] Step S1, Pretreatment of carbon nanotubes and fullerenes: Carbon nanotubes and fullerenes were ultrasonically dispersed in a 5% nitric acid solution for 35 minutes to remove surface impurities; then, surface modification was performed using silane coupling agent KH-550, and the reaction was carried out in an 80°C water bath for 4 hours. After drying, surface-activated carbon nanotubes and fullerenes were obtained.

[0096] Step S2, Alloy Melting and Nanocomposite: Electrolytic copper, Ag-Cu master alloy, rare earth element-Cu master alloy, Co-Cu master alloy, Ni-Cu master alloy, Ba-Cu master alloy, Nb-Cu master alloy, Ta-Cu master alloy, Re-Cu master alloy, Hf-Cu master alloy, and Mg-Cu master alloy are used as raw materials and added to a vacuum induction melting furnace for melting; surface-activated carbon nanotubes and fullerenes are added to the melt in three batches with a 5-minute interval between each batch, while electromagnetic stirring is turned on to stir evenly, to obtain an alloy liquid;

[0097] Step S3, Gradient Solidification and Texture Control: The molten alloy is poured into a directional solidification mold with a temperature gradient and directional solidification is carried out at a cooling rate of 10℃ / min to form an ingot with columnar crystal orientation; a pulsed magnetic field is applied during solidification to initially form a composition gradient.

[0098] Step S4, Hot Isostatic Pressing: The ingot is placed in a hot isostatic pressing apparatus for hot isostatic pressing to obtain a billet;

[0099] Step S5, Composite Processing and Gradient Strengthening: The billet is rolled using a cumulative rolling process. During the rolling process, a 60nm thick silver-copper-indium gradient alloy layer is deposited on the surface using ion beam sputtering technology. Subsequently, deep cryogenic treatment is performed to obtain the initial product of the groove line.

[0100] Step S6, Laser-assisted processing: Use a high-power pulsed laser to scan and process the surface of the initial grooved product;

[0101] Step S7, Heat treatment: Annealing is performed in a furnace under a high-purity argon protective atmosphere to obtain a high conductivity gradient copper alloy groove wire.

[0102] In step S1, the mass of the silane coupling agent KH-550 is 1.5% of the total mass of carbon nanotubes and fullerenes; in step S2, the melting temperature is 1220℃ and the vacuum degree is 1×10⁻⁶. -5 Pa; the electromagnetic stirring frequency in step S2 is 25 Hz and the intensity is 0.6 T; the bottom temperature of the directional solidification mold with temperature gradient in step S3 is 285 ℃ and the top temperature is 525 ℃; the magnetic induction intensity of the pulsed magnetic field in step S3 is 0.9 T, the frequency is 12 Hz, and the pulse width is 550 ms; the pressure of the hot isostatic pressing in step S4 is 110 MPa, the temperature is 910 ℃, and the time is 7 h.

[0103] The rolling temperature in step S5 is 320℃, with 8 passes and a deformation of 20% per pass; the mass ratio of silver, copper, and indium on the surface of the silver-copper-indium gradient alloy layer in step S5 is 85:10:5; the silver content in the alloy layer gradually decreases from 85% on the surface to close to the silver content of the substrate at the interface with the substrate; the indium content gradually decreases from 5% on the surface, dropping to below 1% at a distance of about 20nm from the surface, while the copper content gradually increases from 10% on the surface until it connects with the copper content of the substrate; the cryogenic treatment temperature in step S5 is -200℃, and the time is 12h; the wavelength of the high-power pulsed laser in step S6 is 1064nm, the pulse width is 100ns, the frequency is 10Hz, and the power density is 5×10⁻⁶. 8 W / cm 2 The scanning speed of the scanning process in step S6 is 50 mm / s and the spot diameter is 1 mm. The annealing process in step S7 adopts a three-stage annealing process: first, it is heated at 430℃ for 1.2 hours, then heated to 590℃ for 0.7 hours, and finally cooled to 490℃ for 0.9 hours.

[0104] Comparative Example 1

[0105] This example provides a high conductivity gradient copper alloy groove wire and its preparation method, which is basically the same as that in Example 1. The difference is that Co, carbon nanotubes and Nb are not added, and there are no laser-assisted processing and cryogenic treatment steps.

[0106] Comparative Example 2

[0107] This example provides a high conductivity gradient copper alloy groove wire and its preparation method, which is basically the same as that in Example 1. The difference is that Ta, Hf and fullerene are not added, and no pulsed magnetic field is applied during the solidification process.

[0108] To further illustrate the beneficial technical effects of the high conductivity gradient copper alloy trench lines involved in the various embodiments of the present invention, relevant performance tests were conducted on the high conductivity gradient copper alloy trench lines involved in each example. The test results are shown in Table 1, and the test methods are as follows:

[0109] (1) Conductivity test: The test shall be conducted in accordance with GB / T 351–2019;

[0110] (2) Tensile properties: Tensile test at room temperature was conducted in accordance with GB / T 228.1-2021, with a tensile speed of 5 mm / min;

[0111] (3) Fatigue life: Refer to the fatigue test of JISZ 2273-1978, and count the number of repetitions until the test piece breaks when the load stress is 500MPa; the wire diameter of the test piece is 0.5mm; each case uses 3 pieces to carry out the above test, and calculate the average number of repetitions until the groove wire breaks.

[0112] (4) Corrosion performance test: Neutral salt spray test (5% NaCl solution, 35℃, continuous spraying for 120 hours) was conducted in accordance with GB / T 10125-2021, and the corrosion rate was calculated by the weight loss method.

[0113] Table 1. Performance test results of high conductivity gradient copper alloy cable.

[0114] project Surface conductivity tensile strength Fatigue life Corrosion rate unit %IACS MPa <![CDATA[×10 7 Next <![CDATA[g / (m 2 ·h)]]> Example 1 99.8 582 1.25 0.012 Example 2 101.2 585 1.30 0.010 Example 3 102.2 590 1.33 0.007 Example 4 103.0 592 1.35 0.006 Example 5 104.2 595 1.41 0.004 Comparative Example 1 93.8 540 1.01 0.032 Comparative Example 2 95.4 553 1.09 0.023

[0115] As can be seen from the table above, the high conductivity gradient copper alloy groove wires involved in the embodiments of the present invention have better conductivity, mechanical properties, fatigue resistance and corrosion resistance than the comparative product. The combined addition of Co, Nb, Ta, Hf, carbon nanotubes and fullerene, as well as laser-assisted treatment, cryogenic treatment and application of pulsed magnetic field during solidification, are beneficial to improving the above properties.

[0116] The above embodiments are only for illustrating the technical concept and features of the present invention. Their purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing a high conductivity gradient copper alloy groove wire, characterized in that, Includes the following steps: Step S1, Pretreatment of carbon nanotubes and fullerenes: Carbon nanotubes and fullerenes are ultrasonically dispersed in a 3-5% nitric acid solution for 25-35 minutes to remove surface impurities; then, surface modification is performed using silane coupling agent KH-550, and the reaction is carried out in an 80℃ water bath for 2-4 hours. After drying, surface-activated carbon nanotubes and fullerenes are obtained. Step S2, Alloy Melting and Nanocomposite: Electrolytic copper, Ag-Cu master alloy, rare earth element-Cu master alloy, Co-Cu master alloy, Ni-Cu master alloy, Ba-Cu master alloy, Nb-Cu master alloy, Ta-Cu master alloy, Re-Cu master alloy, Hf-Cu master alloy, and Mg-Cu master alloy are added to a vacuum induction melting furnace for melting. Surface-activated carbon nanotubes and fullerenes are added to the melt in three batches at 5-minute intervals, while electromagnetic stirring is activated simultaneously to achieve uniform mixing and obtain an alloy liquid. Step S3, Gradient solidification and texture control: The alloy liquid is poured into a directional solidification mold with a temperature gradient and directional solidification is carried out at a cooling rate of 10℃ / min to form an ingot with columnar crystal orientation. A pulsed magnetic field is applied during solidification to initially form a composition gradient; the bottom temperature of the directional solidification mold with temperature gradient is 275-285℃, and the top temperature is 515-525℃; the magnetic induction intensity of the pulsed magnetic field is 0.8-0.9T, the frequency is 10-12Hz, and the pulse width is 500-550ms. Step S4, Hot Isostatic Pressing: The ingot is placed in a hot isostatic pressing apparatus for hot isostatic pressing to obtain a billet; Step S5, Composite Processing and Gradient Strengthening: The billet is rolled using a cumulative rolling process. During the rolling process, a 60nm thick silver-copper-indium gradient alloy layer is deposited on the surface using ion beam sputtering technology. Subsequently, deep cryogenic treatment is performed to obtain the initial product of the groove line. Step S6, Laser-assisted processing: The surface of the initial grooved product is scanned using a high-power pulsed laser; the high-power pulsed laser has a wavelength of 1064nm, a pulse width of 100ns, a frequency of 10Hz, and a power density of 5×10⁻⁶. 8 W / cm²; The scanning speed of the scanning process is 50 mm / s, and the spot diameter is 1 mm; Step S7, Heat treatment: Annealing is performed in a furnace under a high-purity argon protective atmosphere to obtain a high conductivity gradient copper alloy groove wire; The high conductivity gradient copper alloy channel wire comprises, by mass percentage: Ag 0.3-0.6%, rare earth elements 0.01-0.1%, Co 0.05-0.15%, Ni 0.02-0.12%, Ba 0.01-0.03%, Nb 0.05-0.8%, Ta 0.01-0.05%, Re 0.003-0.007%, Hf 0.08-0.2%, Mg 0.2-0.6%, carbon nanotubes 0.01-0.05%, fullerenes 0.01-0.03%, with the balance being Cu and other unavoidable impurities; the rare earth elements are Ce, La, and Y mixed in a mass ratio of (1-2):1:(0.8-1.2).

2. The method for preparing high conductivity gradient copper alloy groove wire according to claim 1, characterized in that, The carbon nanotubes are multi-walled carbon nanotubes with an outer diameter of 6-13 nm and a length of 2.5-20 μm; the fullerene is fullerene-C 60 The average diameter is 0.7 nm.

3. The method for preparing high conductivity gradient copper alloy groove wire according to claim 1, characterized in that, In step S1, the mass of the silane coupling agent KH-550 is 0.8-1.5% of the total mass of carbon nanotubes and fullerenes; in step S2, the melting temperature is 1200-1220℃ and the vacuum degree is 1×10⁻⁶. -5 Pa; the frequency of the electromagnetic stirring in step S2 is 20-25Hz, and the intensity is 0.5-0.6T.

4. The method for preparing high conductivity gradient copper alloy groove wire according to claim 1, characterized in that, In step S4, the hot isostatic pressing pressure is 100-110 MPa, the temperature is 890-910℃, and the time is 5-7 h; in step S5, the rolling temperature is 300-320℃, and the rolling is performed in 8 passes with a deformation of 20% per pass.

5. The method for preparing high conductivity gradient copper alloy groove wire according to claim 1, characterized in that, In step S5, the mass ratio of silver, copper, and indium on the surface of the silver-copper-indium gradient alloy layer is 85:10:5; the cryogenic treatment in step S5 is performed at a temperature of -195℃ to -200℃ for 10-12 hours.

6. The method for preparing high conductivity gradient copper alloy groove wire according to claim 1, characterized in that, The annealing process described in step S7 adopts a three-stage annealing process: first, it is held at 410-430℃ for 1-1.2 hours, then the temperature is raised to 560-590℃ and held for 0.5-0.7 hours, and finally the temperature is lowered to 470-490℃ and held for 0.8-0.9 hours.

7. A high conductivity gradient copper alloy channel wire prepared by the preparation method of the high conductivity gradient copper alloy channel wire according to any one of claims 1-6.