CN112030030B - High-strength high-conductivity copper alloy wire and preparation method thereof - Google Patents
High-strength high-conductivity copper alloy wire and preparation method thereof Download PDFInfo
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 claims abstract description 39
- 239000010949 copper Substances 0.000 claims abstract description 39
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052709 silver Inorganic materials 0.000 claims abstract description 34
- 239000004332 silver Substances 0.000 claims abstract description 33
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 30
- 239000010941 cobalt Substances 0.000 claims abstract description 30
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000003723 Smelting Methods 0.000 claims abstract description 17
- 238000005266 casting Methods 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 229910000531 Co alloy Inorganic materials 0.000 claims description 47
- WGLUFVNYIRPMST-UHFFFAOYSA-N [Co].[Cu].[Ag] Chemical compound [Co].[Cu].[Ag] WGLUFVNYIRPMST-UHFFFAOYSA-N 0.000 claims description 45
- 238000005491 wire drawing Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 238000007731 hot pressing Methods 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 18
- 238000005728 strengthening Methods 0.000 abstract description 6
- 230000001427 coherent effect Effects 0.000 abstract description 5
- 238000004220 aggregation Methods 0.000 abstract description 4
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- 239000000956 alloy Substances 0.000 description 31
- 229910045601 alloy Inorganic materials 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 21
- 229910001316 Ag alloy Inorganic materials 0.000 description 11
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 11
- 229910017770 Cu—Ag Inorganic materials 0.000 description 9
- 230000007547 defect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910002701 Ag-Co Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 1
- 229910017985 Cu—Zr Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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Abstract
The invention discloses a high-strength high-conductivity copper alloy wire, belonging to the field of electrical materials, wherein the wire comprises the following raw materials in percentage by mass: 0.1-1.5 wt% of silver, 0.1-1 wt% of cobalt, and the balance of copper and inevitable impurities, wherein the purities of the silver, the copper and the cobalt are not lower than 99.99%, and twin crystals are contained in a wire crystal grain structure; the invention also discloses a preparation method of the high-strength and high-conductivity copper alloy wire, which comprises the steps of smelting, casting and extruding copper, silver and cobalt, then drawing at-300 to-100 ℃ and in a 0.5 to 5T magnetic field, and finally annealing to obtain the copper alloy conductive wire. The invention has the advantages that the advantages of copper, silver and cobalt are fully utilized, and the aggregation and growth of a large amount of twin crystals are induced under the combined action of a magnetic field and low-temperature deformation to form twin crystal strengthening; meanwhile, the coherent twin crystal boundary has extremely low scattering capacity to electrons, so that the copper alloy wire keeps higher conductivity and has higher strength.
Description
Technical Field
The invention belongs to the field of electrical materials, and relates to a high-strength high-conductivity copper alloy conductive wire and a preparation method thereof.
Background
The high-strength high-conductivity copper alloy is a functional material with excellent physical and mechanical properties, is widely applied to switches, circuit breakers and contactors of medium load and light load, and is also used as a sliding electric contact material of a micro-motor slip ring, a commutator segment and the like; meanwhile, the high-strength and high-conductivity copper alloy is also applied to a plurality of fields such as high-pulse magnetic field conductor materials, integrated circuit lead frames, trolley buses and overhead conductors of electric trains, contact wires for high-speed railways and the like. The developed high-strength and high-conductivity copper alloy is a series of materials such as Cu-Cr, Cu-Zr, Cu-Cr-Zr, Cu-Ag, Cu-Nb and the like. The Cu-Ag alloy has low melting point and is easy to melt, and the microstructure is easy to control; the conductivity of Ag is higher than that of copper, and the high-conductivity copper alloy is more favorably obtained. Therefore, the Cu-Ag alloy has become one of the first choice materials for high strength and high conductivity copper alloy material.
Copper and silver are mixed and smelted, and deformation and heat treatment are adopted, so that the common preparation method of the high-strength high-conductivity copper-silver alloy material is provided, for example, the invention with the Chinese patent publication number of CN101643866A and the publication date of 2010, 2 months and 10 days creates a high-strength high-conductivity CuAg alloy material and a preparation method thereof, the application discloses a high-strength high-conductivity Cu-Ag alloy material and a preparation method thereof, the material consists of Cu, Ag and other elements, a copper-silver alloy ingot with a columnar structure is obtained by a directional solidification technology, and then a continuous fiber structure is obtained by processes of extrusion, drawing and the like; the alloy material comprises 5-10 wt% of Ag and the balance of copper. The preparation process of the copper-silver alloy comprises the steps of preparing chemical components, vacuumizing a smelting chamber and a directional solidification chamber, smelting the alloy, directionally solidifying, hot extruding, thermally treating, drawing or rolling to obtain the high-strength and high-conductivity Cu-Ag alloy wire/plate. The method prepares the Cu-Ag alloy by utilizing the directional solidification and deformation matched heat treatment, not only keeps the excellent conductivity of the Cu-Ag alloy, but also improves the alloy strength. The method has the disadvantages that interface scattering formed by the continuous fiber tissue generated by the method and lattice distortion scattering caused by solid solution alloying sacrifice certain conductivity while obtaining high strength, and simultaneously, directional solidification equipment is required, and the equipment and cost requirements are high.
In order to improve the strength of the Cu-Ag alloy, some researchers try to improve the strength of the material while maintaining high conductivity by adding a small amount of silver to prepare the nanocrystalline Cu-Ag alloy, for example, chinese patent publication No. CN111101008A, published as 2020, 5 and 5 days, create "a high-strength and high-conductivity copper-silver alloy material and a preparation method thereof", which discloses a method for preparing a high-strength and high-conductivity copper-silver alloy material, the preparation steps of which include: ball-milling copper powder and silver powder into nano powder in a ball-milling tank; pressing and molding the nano powder to obtain a blank; and sintering the blank at 350-550 ℃ for 0-3 min to obtain the copper-silver alloy material. According to the invention, the high conductivity of the formed copper-silver alloy material is realized by adding less silver powder, and the nanocrystalline structure is obtained by controlling the growth of crystal grains in the sintering process through lower sintering temperature, so that the copper-silver alloy material keeps higher strength. But has the disadvantages that: firstly, in order to obtain a nanocrystalline structure, the mixed powder of copper and silver needs to be subjected to ball milling for a long time (60-180 hours); secondly, in order to obtain the nanocrystalline, a low-temperature sintering mode is adopted, so that the compactness of the nanocrystalline is limited to a certain extent; thirdly, the nanocrystalline structure provides high strength, but the increase in conductivity thereof is limited due to interface scattering caused by the presence of a large number of grain boundaries, and the conductivity thereof is found to be distributed between 75% and 90% IACS from examples.
In summary, in the development of high-strength and high-conductivity copper-silver alloys, the strength is usually enhanced by fine grain strengthening, solid solution strengthening, work hardening, etc., and the conductivity is reduced by introducing a large amount of defects such as dislocations, grain boundaries, etc., so that the defect increase and the conductivity decrease, and therefore, in order to maintain the high strength of the copper-silver alloy and obtain good conductivity, it is a research focus at present, which requires a new preparation method to obtain the high-strength and high-conductivity copper-silver alloy.
The twin boundary is a special low-energy coherent boundary, which can effectively block dislocation movement, especially the strengthening effect begins to appear when the twin crystal layer is thinned to nanometer level, and meanwhile, the scattering ability of the coherent twin boundary to electrons is extremely small, and the resistance value is one order of magnitude lower than that of the common boundary. In 2004, researchers at the institute of metals in the department of Chinese academy of sciences used pulsed electrodeposition technology to produce pure copper films with High density and nano-sized grown twins, and obtained pure copper samples with ultra-High Strength and High Conductivity, tensile Strength of 1068MPa, and room temperature Conductivity comparable to oxygen-free High Conductivity copper (ultra High Strength and High electric Conductivity in copper science,304(2004) 422-. However, due to the limitation of the pulse electrolytic deposition technology, the thickness of the prepared film is only in the micron level, and the bulk material with wider application is difficult to prepare.
Disclosure of Invention
The invention aims to solve at least one of the technical problems in the prior art, and provides a high-strength and high-conductivity copper alloy wire and a preparation method thereof, wherein the wire has high strength while good conductivity is maintained.
The technical solution of the invention is as follows:
the invention provides a high-strength high-conductivity copper alloy wire, which comprises the following raw materials in percentage by mass: 0.1-1.5 wt% of silver, 0.1-1 wt% of cobalt, and the balance of copper and inevitable impurities, wherein the purities of the silver, the copper and the cobalt are not lower than 99.99%, and twin crystals are contained in the grain structure of the copper alloy wire.
Furthermore, the average width of twin crystals of the copper alloy wire rod is 20-100 nm, and the average length of twin crystals is 200-800 nm.
Further, the average grain size of the copper alloy wire rod is 1-10 μm.
Further, the tensile strength of the copper alloy wire is more than 600MPa, and the electrical conductivity is more than 90% IACS.
The invention provides a preparation method of the high-strength and high-conductivity copper alloy wire, which comprises the following steps:
s1, smelting and casting the three raw materials of copper, silver and cobalt to obtain a copper-silver-cobalt alloy cast ingot;
s2, extruding the copper-silver-cobalt alloy cast ingot to obtain a copper-silver-cobalt alloy bar;
s3, carrying out wire drawing treatment on the copper-silver-cobalt alloy bar at-300 to-100 ℃, and simultaneously applying a magnetic field to the copper-silver-cobalt alloy bar, wherein the strength of the magnetic field is 0.5 to 5T;
and S4, annealing the copper-silver-cobalt alloy bar processed in the step S3 to obtain the copper alloy conductive wire.
Further, in the step S2, the copper-silver-cobalt alloy cast ingot is placed into a vacuum hot pressing furnace and heated to 400-600 ℃, heat preservation is carried out for 1-3 hours, and then extrusion is carried out, wherein the extrusion ratio is 5-10: 1.
Further, in the step S3, adding the copper silver cobalt alloy bar into a wire drawing die, and soaking the wire drawing die and the copper silver cobalt alloy bar in liquid nitrogen for wire drawing.
Further, in the step S3, in the wire drawing process, the deformation amount of each pass is 10 to 30%, and the total deformation amount is not less than 80%.
Further, the annealing process in step S4 includes: and (4) processing the copper-silver-cobalt alloy bar processed in the step S3 for 1-2 hours at 200-300 ℃ under the protection of vacuum or inert gas.
Further, in the step S1, smelting the copper, silver and cobalt raw materials in a medium-frequency induction smelting mode, after the three raw materials are completely molten, controlling the casting temperature to be 1150-1350 ℃ and the casting speed to be 0.3-0.6 Kg/S, and obtaining a copper-silver-cobalt alloy cast ingot; and (4) carrying out surface processing on the copper-silver-cobalt alloy cast ingot to obtain the copper-silver-cobalt alloy cast ingot with a smooth surface.
The invention has at least one of the following beneficial effects:
(1) the copper alloy conductive wire rod integrates the advantages of copper, silver and cobalt, takes copper with good conductivity as a substrate, and is added with low-layer fault energy metal (16 mJ/m)2) Silver and mesoscopic energy metals (78 mJ/m)2) Copper can not only enhance the conductivity and the oxidation resistance of the alloy, but also reduce the stacking fault energy of the alloy, and is more beneficial to the generation of twin crystals; and a small amount of magnetic cobalt is added and dissolved in the alloy, and can induce aggregation and growth of a large amount of twin crystals under the combined action of a magnetic field and low-temperature deformation to form twin crystal strengthening, so that twin boundaries exist in the copper alloy conductive wire rod prepared by the invention, the twin boundaries are special low-energy state coherent boundaries, and the scattering capacity of the coherent twin boundaries on electrons is extremely small, so that the copper alloy conductive wire rod can keep higher conductivity and higher strength, the tensile strength of the copper alloy wire rod prepared by the invention is more than 600MPa, and the conductivity of the copper alloy wire rod is more than 90% IACS.
(2) The preparation method of the invention obtains cast ingots by smelting copper, silver and cobalt; then obtaining a copper alloy bar by adopting a medium-temperature extrusion mode; then, the bar is drawn under the external magnetic field and low temperature environment and is annealed, the deformation under the low temperature is beneficial to the twinning deformation (twinning formation) of the medium and low-layer fault energy metal and the alloy, and meanwhile, under the action of the external magnetic field, the alloy is easy to induce the aggregation and growth of the twins in the drawing deformation process, so that the high-strength and high-conductivity nanometer twin crystal copper alloy wire is finally prepared; the equipment used in the method is common material processing equipment, the preparation method is simple, the period is short, the application range is wide, and the method can be widely used for preparing high-strength high-conductivity alloy wires.
Drawings
FIG. 1 is a TEM image of a longitudinal section of a Cu-Ag-Co alloy wire rod prepared in example 1 of the present invention and a corresponding diffraction pattern of selected areas;
FIG. 2 is a transmission electron micrograph of a longitudinal section of a Cu-Ag-Co alloy wire rod prepared according to comparative example 1 of the present invention and a corresponding diffraction pattern of a selected area.
Detailed Description
The invention provides a high-strength high-conductivity copper alloy wire, which comprises the following raw materials in percentage by mass: 0.1-1.5 wt% of silver, 0.1-1 wt% of cobalt, and the balance of copper and unavoidable impurities, wherein the purities of the silver, the copper and the cobalt are not lower than 99.99%, the grain structure of the copper alloy wire rod contains twin crystals, the average width of the twin crystals with the average grain size of 1-10 μm of the copper alloy wire rod is 20-100 nm, the average length of the twin crystals is 200-800 nm, the tensile strength of the copper alloy wire rod can reach more than 600MPa, and the conductivity can reach more than 90% IACS.
The preparation method of the high-strength high-conductivity copper alloy wire rod comprises the following steps:
(1) selecting copper, silver and cobalt raw materials with the purity of 4N (99.99%) or more, proportioning according to 0.1-1.5 wt% of silver, 0.1-1 wt% of cobalt, the balance of copper and inevitable impurities, smelting in a medium-frequency induction smelting mode, controlling the casting temperature to 1150-1350 ℃ after the raw materials are completely molten, and obtaining a copper-silver-cobalt alloy cast ingot at the casting speed of 0.3-0.6 Kg/s;
(2) processing the surface of the copper-silver-cobalt alloy cast ingot, specifically turning and the like, so as to remove the defects of surface looseness, holes and the like and obtain a copper alloy cylinder with a smooth surface;
(3) putting the copper-silver-cobalt alloy cylinder treated in the step (2) into a vacuum hot pressing furnace, heating to 400-600 ℃, preserving heat for 1-3 hours, then extruding at an extrusion ratio of 5: 1-10: 1 to obtain a bar material, and obtaining a copper alloy bar material;
(4) and (3) carrying out wire drawing treatment on the copper alloy bar treated in the step (3) at the temperature of-300 to-100 ℃, specifically, soaking a wire drawing die and the bar in liquid nitrogen, setting a strong magnetic field on the wire drawing die, setting the magnetic field strength to be 0.5 to 5T, and setting the deformation of each pass to be 10 to 30 percent and the total deformation to be not less than 80 percent in the wire drawing process.
(5) And (4) carrying out final annealing treatment on the bar treated in the step (4), wherein the annealing treatment condition is that the treatment time is 1-2 h at 200-300 ℃ under the protection of vacuum or inert gas, so as to obtain the copper alloy wire.
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
Copper, silver and cobalt with the purity of 4N (99.99%) are used as raw materials, and the mixture ratio is as follows: 0.5 wt% of silver, 1.0 wt% of cobalt, and the balance of copper and inevitable impurities, smelting by adopting a medium-frequency induction smelting mode, controlling the casting temperature to 1150 ℃ and the casting speed to be 0.3Kg/s after the raw materials are completely molten, and obtaining a copper-silver-cobalt alloy cast ingot; turning and processing the copper-silver-cobalt alloy cast ingot, and removing the defects of surface looseness, holes and the like to obtain a copper-silver-cobalt alloy cylinder with a smooth surface; then, putting the copper-silver-cobalt alloy cylinder into a vacuum hot pressing furnace, heating to 400 ℃, preserving heat for 3 hours, and then extruding with an extrusion ratio of 5:1 to obtain a bar material, thus obtaining a copper-silver-cobalt alloy bar material; then, carrying out wire drawing treatment on the copper-silver-cobalt alloy bar, wherein a wire drawing die and the bar are both soaked in liquid nitrogen in the wire drawing process, a strong magnetic field is arranged on the wire drawing die, the magnetic field intensity is set to be 2T, the deformation of each pass is 10% and the total deformation is 80% in the wire drawing process; and finally annealing the bar, wherein the annealing condition is vacuum, and the treatment time is 1h at 200 ℃, so that the copper alloy conductive wire is obtained.
Example 2
The method adopts copper, silver and cobalt with the purity of 4N5 (99.995%), and comprises the following steps: 0.1 wt% of silver, 0.5 wt% of cobalt, and the balance of copper and inevitable impurities, smelting by adopting a medium-frequency induction smelting mode, and after the raw materials are completely molten, controlling the casting temperature to 1250 ℃ and the casting speed to be 0.4Kg/s to obtain a copper-silver-cobalt alloy cast ingot; turning and processing the copper-silver-cobalt alloy cast ingot, and removing the defects of surface looseness, holes and the like to obtain a copper-silver-cobalt alloy cylinder with a smooth surface; then, putting the copper-silver-cobalt alloy cylinder into a vacuum hot pressing furnace, heating to 500 ℃, preserving heat for 2 hours, and then extruding with an extrusion ratio of 7:1 to obtain a bar material, thus obtaining a copper-silver-cobalt alloy bar material; then, carrying out wire drawing treatment on the bar, wherein a wire drawing die and the copper-silver-cobalt alloy bar are both soaked in liquid nitrogen in the wire drawing process, a strong magnetic field is arranged on the wire drawing die, the magnetic field intensity is set to be 0.5T, the deformation of each pass is 15% and the total deformation is 90% in the wire drawing process; and finally annealing the copper-silver-cobalt alloy bar under the condition of argon protection for 1.5h at 250 ℃ to obtain the copper alloy conductive wire.
Example 3
The method adopts copper, silver and cobalt with the purity of 5N (99.999%), and comprises the following steps: 1.5 wt% of silver, 0.1 wt% of cobalt, and the balance of copper and inevitable impurities, smelting by adopting a medium-frequency induction smelting mode, controlling the casting temperature to 1350 ℃ and the casting speed to be 0.6Kg/s after the raw materials are completely melted, and obtaining a copper-silver-cobalt alloy cast ingot; turning and processing the copper-silver-cobalt alloy cast ingot, and removing the defects of surface looseness, holes and the like to obtain a copper-silver-cobalt alloy cylinder with a smooth surface; putting the copper-silver-cobalt alloy cylinder into a vacuum hot pressing furnace, heating to 600 ℃, preserving heat for 1h, and then extruding with an extrusion ratio of 10:1 to obtain a bar material, thereby obtaining a copper-silver-cobalt alloy bar material; then, carrying out wire drawing treatment on the copper-silver-cobalt alloy bar, wherein a wire drawing die and the bar are both soaked in liquid nitrogen in the wire drawing process, a strong magnetic field is arranged on the wire drawing die, the magnetic field intensity is set to be 5T, the deformation of each pass is 30% and the total deformation is 90% in the wire drawing process; and finally annealing the bar, wherein the annealing condition is that the treatment time is 1h at 300 ℃ under the protection of argon gas, so as to obtain the copper alloy conductive wire.
Comparative example 1
The difference between comparative example 1 and example 1 is that: the drawing process in comparative example 1 was performed at room temperature, i.e., the drawing die and the rod were not immersed in liquid nitrogen during the drawing process, and the other was the same as in example 1.
Comparative example 2
The difference between comparative example 2 and example 1 is that: the drawing process in comparative example 2 was the same as example 1 except that a strong magnetic field was not applied.
Comparative example 3
The difference between comparative example 3 and example 2 is that: in comparative example 3, the raw material without cobalt, namely the raw materials of copper and silver with the purity of 4N5 (99.995%) are adopted, and the mixture ratio is as follows: silver 0.1 wt%, balance copper and inevitable impurities, the others being the same as in example 2.
Testing
1. The microstructure of the copper alloy wires obtained in example 1 and comparative example 1 was observed under a transmission electron microscope, and the results of the transmission electron microscope photograph of the longitudinal section of the copper silver cobalt alloy wire and the corresponding diffraction pattern of the selected area are shown in fig. 1 and fig. 2, respectively:
as can be seen from FIG. 1, the copper alloy wire rod obtained in example 1 had a uniform microstructure mainly composed of dense twin crystals parallel to each other, and the alloy had an average crystal grain size of 8 μm, an average twin crystal width of 90nm and an average twin crystal length of 500 nm. As can be seen from fig. 2, the microstructure of the copper alloy wire rod prepared in comparative example 1 exhibited a non-uniform deformed grain structure, some grains had a dense dislocation cell structure inside and contained a small amount of twin crystals crossing each other, the twin crystals had no significant directionality, and some grains had relatively few dislocation cells inside, and the average grain size of the alloy was 30 μm. It can be seen that the microstructure of the copper alloy prepared in example 1 is significantly different from that of the copper alloy prepared in comparative example 1, and the microstructure uniformity and twin orientation of the alloy prepared in example 1 are significantly better than those of comparative example 1.
2. The tensile strength and the electrical conductivity of the copper alloy wires prepared in the examples 1 to 3 and the comparative examples 1 to 3 were measured, the tensile strength was measured by using GB/T228.1-2010 "metal material tensile test part 1: room temperature test method", and the electrical conductivity was measured by using GB/T3048.2-2007 "electric wire and cable electrical property test method part 2: metal material resistivity test", and the results are shown in the following table 1:
TABLE 1 Properties of copper alloy wire rods obtained in examples 1 to 3 and comparative examples 1 to 3
As can be seen from table 1, the average grain size of the copper alloy wire rods obtained in examples 1 to 3 is smaller than 8 μm, and there are many twin structures, the tensile strength is 600MPa or more, and the electrical conductivity is 91% IACS or more, and thus the copper alloy wire rods obtained in examples 1 to 3 have high strength while maintaining high electrical conductivity, and can be applied to circuit breakers, contactors, and the like; further, it can be seen that the copper alloy wire rod obtained in example 3 is excellent in both tensile strength and electrical conductivity. Compared with the comparative example, the average grain size of the comparative examples 1 to 3 is more than 20 μm, twin structures rarely exist, the tensile strength is less than 470MPa, the conductivity is less than 85% IACS, the tensile strength and the conductivity of the copper alloy wire rods prepared in the examples 1 to 3 are obviously superior to those of the comparative example 1 (wire drawing is carried out at room temperature), the comparative example 2 (no magnetic field is added in the wire drawing treatment) and the comparative example 3 (no cobalt is added in the raw materials), therefore, the invention induces the aggregation and growth of a large amount of twin crystals to form twin crystal strengthening under the combined action of the magnetic field and low-temperature deformation of the alloy by adding a small amount of silver and cobalt in the raw materials, thereby realizing that the wire rods have good conductivity and also have higher strength.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.
Claims (9)
1. The high-strength high-conductivity copper alloy wire is characterized by comprising the following raw materials in percentage by mass: 0.1-1.5 wt% of silver, 0.1-1 wt% of cobalt, and the balance of copper and unavoidable impurities, wherein the purity of the silver, the purity of the copper and the purity of the cobalt are not lower than 99.99%, the average grain size of the copper alloy wire is 1-10 mu m, and twin crystals are contained in the grain structure of the copper alloy wire.
2. The copper alloy wire rod as claimed in claim 1, wherein the average width of the twin crystal of the copper alloy wire rod is 20-100 nm, and the average length of the twin crystal is 200-800 nm.
3. A high strength and high conductivity copper alloy wire as recited in claim 1, wherein said copper alloy wire has a tensile strength of greater than 600MPa and an electrical conductivity of greater than 90% IACS.
4. The preparation method of the high-strength high-conductivity copper alloy wire is characterized by comprising the following steps of:
s1, smelting and casting three raw materials of copper, silver and cobalt to obtain a copper-silver-cobalt alloy cast ingot, wherein the mass fraction of silver is 0.1-1.5 wt%, the mass fraction of cobalt is 0.1-1 wt%, the balance is copper and unavoidable impurities, and the purities of silver, copper and cobalt are not lower than 99.99%;
s2, extruding the copper-silver-cobalt alloy cast ingot to obtain a copper-silver-cobalt alloy bar;
s3, carrying out wire drawing treatment on the copper-silver-cobalt alloy bar under liquid nitrogen, and simultaneously applying a magnetic field to the copper-silver-cobalt alloy bar, wherein the strength of the magnetic field is 0.5-5T;
and S4, annealing the copper-silver-cobalt alloy bar processed in the step S3 to obtain the copper alloy conductive wire.
5. The preparation method of the high-strength high-conductivity copper alloy wire rod according to claim 4, wherein in the step S2, the copper-silver-cobalt alloy cast ingot is placed into a vacuum hot pressing furnace and heated to 400-600 ℃, and is extruded after heat preservation for 1-3 hours, wherein the extrusion ratio is 5-10: 1.
6. The method of claim 4, wherein in step S3, the CuAg-Co alloy rod is added into a drawing die, and the drawing die and the CuAg-Co alloy rod are immersed in liquid nitrogen for drawing.
7. The method for preparing a high-strength high-conductivity copper alloy wire rod according to claim 4, wherein in the step S3, the deformation amount of each pass is 10-30% and the total deformation amount is not less than 80% in the wire drawing process.
8. The method as claimed in claim 4, wherein the annealing step S4 includes: and (4) processing the copper-silver-cobalt alloy bar processed in the step S3 for 1-2 hours at 200-300 ℃ under the protection of vacuum or inert gas.
9. The preparation method of the high-strength high-conductivity copper alloy wire rod according to claim 4, wherein in the step S1, the three raw materials of copper, silver and cobalt are smelted by adopting a medium-frequency induction smelting mode, after the three raw materials are completely melted, the casting temperature is controlled to be 1150-1350 ℃, the casting speed is controlled to be 0.3-0.6 Kg/S, and a copper-silver-cobalt alloy ingot is obtained.
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| US12000030B2 (en) * | 2021-05-07 | 2024-06-04 | Apple Inc. | Copper alloy film with high strength and high conductivity |
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