CN110616342B - Short-process continuous preparation method of high-performance copper-chromium alloy wire - Google Patents

Short-process continuous preparation method of high-performance copper-chromium alloy wire Download PDF

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CN110616342B
CN110616342B CN201910749619.5A CN201910749619A CN110616342B CN 110616342 B CN110616342 B CN 110616342B CN 201910749619 A CN201910749619 A CN 201910749619A CN 110616342 B CN110616342 B CN 110616342B
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copper
annealing
alloy
extrusion
temperature
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CN110616342A (en
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黄国杰
彭丽军
解浩峰
杨振
冯雪
张文婧
米绪军
尹向前
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GRIMN Engineering Technology Research Institute Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
    • B21C37/047—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire of fine wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • B22D11/004—Copper alloys
    • 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
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • 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
    • 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 relates to a short-process continuous preparation method of a high-performance copper-chromium alloy wire rod, belonging to the field of nonferrous metal processing. The method comprises the following steps: a. the copper-chromium alloy is prepared by the following components in percentage by weight: 0.1-0.6% of Cr, one or two of Zr, Ti, Ag, Mg, Sn, Fe, Si and Zn, the total content of alloy elements is 0.08-0.4%, the content of each alloy element is 0.05-0.2%, and the balance is Cu; b. continuous extrusion; c. drawing; d. performing bell-type intermediate annealing; e. drawing; f. and (4) carrying out online annealing treatment. The invention omits the high-temperature solution treatment and multiple aging treatment processes in the traditional process, is easy to realize short-flow continuous preparation, can meet the requirement of high-end precise cables on the large length of wire rods, shortens the production process flow and improves the production efficiency of alloy materials.

Description

Short-process continuous preparation method of high-performance copper-chromium alloy wire
Technical Field
The invention relates to a short-process continuous preparation method of a high-performance copper-chromium alloy wire rod, belonging to the field of nonferrous metal processing.
Background
The Cu-Cr alloy has high strength, good electric and thermal conductivity, good weldability, oxidation resistance, wear resistance and other excellent comprehensive properties, is widely applied to the fields of lead frames of large-scale integrated circuits, overhead conductors of large-scale electric locomotives, crystallizer linings of continuous casting machines in heat exchange environments, resistance welding electrodes, aerospace high-end cables and the like, and becomes a structural functional material in the fields of high strength and high conductivity of the electronic circuit industry.
Because chromium elements which are easy to oxidize and segregate exist in the copper-chromium alloy, the traditional preparation and processing method of the alloy wire generally adopts vacuum semi-continuous casting, hot extrusion, cold drawing and corresponding heat treatment processes, and the method cannot realize the production of large length (the length is more than 300km) of the wire due to the limitation of the capacity of a vacuum smelting furnace. In order to realize the preparation of the long-length copper-chromium wire material, the up-drawing continuous casting copper-chromium alloy is developed subsequently, and the continuous casting of the alloy is realized. However, because the copper-chromium alloy belongs to a solid solution aging strengthening type alloy, the improvement of the comprehensive performance of the copper-chromium alloy is caused by the fact that the alloy undergoes a solid solution aging treatment process, so that in order to obtain the high-performance copper-chromium alloy wire rod, the high-performance copper-chromium alloy wire rod can be obtained only by carrying out cold rolling, solid solution treatment, acidity and multistage aging treatment processes on an up-lead continuously cast rod, the process passes are multiple, the route is long, and the production efficiency of the alloy wire rod is low.
Disclosure of Invention
The invention mainly aims to make up the defects of the existing copper-chromium wire preparation process, develop a short-process continuous preparation method of a high-performance copper-chromium wire, and easily realize the long-length industrial production of the high-performance alloy wire.
The invention realizes the short-flow continuous preparation of the high-performance copper-chromium alloy wire rod, and simultaneously, the length of the alloy wire rod can meet the requirement of a high-end cable on large length, thereby effectively saving energy consumption and improving the production efficiency of alloy materials.
A short-flow continuous preparation and processing method of a high-performance copper-chromium wire rod comprises the following steps: a. the method comprises the following steps of proportioning, feeding, smelting and casting according to the mass percent of the copper-chromium alloy, b, continuously extruding, c, drawing, d, bell-type intermediate annealing, e, drawing and f, carrying out online annealing treatment.
Step a, before smelting, adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are molten, adding one or two of copper-zirconium intermediate alloy, pure silicon, sponge titanium, pure magnesium, copper-iron intermediate alloy, pure zinc, pure silver and pure tin, optionally adding one of copper lanthanum, copper cerium, copper yttrium, copper scandium, copper gadolinium and copper samarium intermediate alloy into the alloy, raising the temperature to 1300-1350 ℃, uniformly stirring after the melt is completely molten, controlling the casting temperature to 1200-1250 ℃, keeping the temperature for 20-25 min, then carrying out upward continuous casting, and casting into a copper rod with the diameter of 18-20 mm.
The continuous upward casting is carried out by adopting a non-vacuum power frequency induction furnace, the smelting temperature is 1300-1350 ℃, the casting temperature is controlled to be 1200-1250 ℃, the pitch is 1-6 mm, the stopping time is 0.15-0.30 s, the pulling time is 0.05-0.20 s, the stopping-pulling time ratio is 1.5-6, and the upward casting speed is 300-600 mm/min.
And b, continuously extruding the alloy copper rod on a Conform continuous extruder for multiple times, wherein the heating temperature of an extrusion wheel is 400-450 ℃, the extrusion speed is 5-10 r/min, the extrusion times are 1-3 times, the extrusion ratio is 1-25, and cooling is carried out by using a mixed solution of alcohol and water (the volume ratio of the alcohol to the water is preferably 1: 4).
And c, performing multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 85-99%.
In the step d, the cold-drawn copper wire is placed in a bell jar type annealing furnace for intermediate annealing, the annealing temperature is 500-600 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is preferably 3:1) is cooled.
And e, performing multi-pass drawing on the annealed copper wire, wherein the processing rate is 85-99%.
In the step f, carrying out online annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 400-550 ℃, the annealing speed is 5-30 cm/s, and the residence time of the copper wire in an annealing area is 5-60 s; the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
The preparation method of the copper alloy wire rod is suitable for the following copper-chromium alloy materials, and the materials comprise the following components in percentage by weight: 0.1 to 0.6 percent of Cr, the balance of Cu, and one or two of Zr, Ti, Ag, Mg, Sn, Fe, Si, Zn and the like in the alloy, wherein the content of each alloy element is 0.05 to 0.2 percent, and the total content of the alloy elements is 0.08 to 0.4 percent. The copper-chromium alloy can also simultaneously comprise one of rare earth elements such as La, Ce, Y, Sc, Gd, Sm and the like, and the content of the rare earth alloy elements is 0.005-0.01 percent.
The technical principle and the advantages of the invention are as follows: on the basis of the up-drawing continuous casting technology, core technological parameters and a casting forming die structure are adjusted, the cooling strength of a melt is increased, the alloy obtains large supersaturation degree in the up-drawing continuous casting process, and the alloy elements realize solid solution treatment through the up-drawing continuous casting process as far as possible. By adopting a continuous extrusion technology, the alloy is subjected to high-temperature short-time effective treatment while being subjected to a severe shearing action through a severe friction action between the copper rod and an extrusion die in the continuous extrusion process, and the grain size and the nano precipitated phase distribution uniformity of the alloy can be effectively improved through multi-pass continuous extrusion. And through subsequent multi-pass drawing and annealing treatment, the comprehensive performance of the alloy wire can be effectively regulated and controlled, and the use requirement of the high-end precise cable on the performance of the copper alloy wire is met. The technology of the invention has the advantages that the high-temperature solution treatment and multiple aging treatment processes in the traditional process are saved, the short-flow continuous preparation of the copper alloy wire rod can be easily realized, the requirement of high-end precise cables on the large length of the wire rod can be met, the production process flow is shortened, and the production efficiency of the alloy material is improved.
After the short-flow preparation processing technology of the invention, the precipitation density of the soybean petal-shaped Cr phase with the face-centered cubic structure with the grain diameter of 10 nm-30 nm on the prepared copper-chromium alloy wire rod can be observed to be 1 multiplied by 1020～4×1023m-3The precipitation density of the body-centered cubic structure Moire fringe-like Cr phase with the grain diameter of 10nm to 15nm is 1 x 1021～5×1022m-3The alloy has tensile strength of 400-600 MPa, yield strength of 300-500 MPa, elongation of 6-20%, electrical conductivity of 80-95% IACS, softening temperature of 500-600 ℃, and repeated bending times of 1 × 106～1×109Next, the process is carried out.
The present invention is further illustrated by the following specific embodiments, which are not meant to limit the scope of the invention.
Detailed Description
The invention relates to a short-flow continuous preparation processing method of a high-performance copper-chromium wire rod, which comprises the technical processes of upward continuous casting, continuous extrusion, drawing, bell-type intermediate annealing, drawing, online annealing treatment and the like. The preparation method is suitable for the following copper-chromium alloy materials, and the materials comprise the following components in percentage by weight: 0.1-0.6% of Cr, the balance of Cu, and one or two of Zr, Ti, Ag, Mg, Sn, Fe, Si, Zn and the like in the alloy, wherein the content of the alloy elements is 0.05-0.2%, and the total content of the alloy elements is 0.1-0.4%. At the same time, at most one of rare earth elements such as La, Ce, Y, Sc, Gd, Sm and the like is included, and the content of the alloy elements is 0.005-0.01 percent.
The short-flow continuous preparation and processing method of the high-performance copper-chromium wire rod comprises the following steps: a. the method comprises the following steps of proportioning, feeding, smelting and casting according to mass percent, b, continuously extruding, c, drawing, d, bell-type intermediate annealing, e, drawing and f, carrying out online annealing treatment. The specific feeding sequence is as follows: before smelting, electrolytic copper and pure chromium are added into a non-vacuum power frequency induction furnace, after the materials are all melted, introducing high-purity argon for protection, adding one or two of copper-zirconium intermediate alloy/pure silicon/sponge titanium/pure magnesium/copper-iron intermediate alloy/pure zinc/pure silver/pure tin and one of copper-lanthanum/copper-cerium/copper-yttrium/copper-scandium/copper-gadolinium/copper-samarium intermediate alloy, raising the temperature to 1300-1350 ℃, after the melt is completely melted, uniformly stirring, controlling the casting temperature at 1200-1250 ℃, keeping the temperature for 20-25 min, then carrying out upward continuous casting, wherein the pitch is 1-6 mm, the stopping time is 0.15-0.30 s, the pulling time is 0.05-0.20 s, the stopping-pulling time ratio is 1.5-6, the upward speed is 300-600 mm/min, and the copper rod with the diameter of 18-20 mm is cast. The heating temperature of the extrusion wheel is 400-450 ℃, the extrusion speed is 5-10 r/min, the number of extrusion passes is 1-3, the extrusion ratio is 1-25, and the extrusion wheel is cooled by using a mixed solution of alcohol and water (the volume ratio of the alcohol to the water is 1: 4). The total processing rate of the primary drawing is 85-99%. The bell-type annealing temperature is 500-600 ℃, the temperature is raised for 6 hours, the heat is preserved for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3:1) is cooled. The total processing rate of the multi-pass drawing is 85-99%. The online annealing temperature is 400-550 ℃, the annealing speed is 5-30 cm/s, the residence time of the copper wire in the annealing area is 5-60 s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
Example 1
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, copper-zirconium master alloy, titanium sponge and copper-lanthanum master alloy. The composition of the alloy is shown in table 1, example 1.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding a copper-zirconium intermediate alloy, sponge titanium and a copper-lanthanum intermediate alloy, heating to 1300 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1250 ℃, carrying out upward continuous casting after heat preservation for 20min, wherein the pitch is 1mm, the stopping time is 0.30s, the pulling time is 0.20s, the stopping-pulling time ratio is 1.5, the upward speed is 300mm/min, and casting into a copper rod with the diameter of 18 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 450 ℃, the extrusion speed is 10r/min, the extrusion pass is 3 passes, the extrusion ratio is 1, and the alloy copper rod is cooled by using an alcohol and water mixed solution (the volume ratio of alcohol to water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 85%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell jar type annealing furnace for intermediate annealing, wherein the annealing temperature is 600 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3:1) is cooled.
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 99%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 400 ℃, the annealing speed is 30cm/s, the residence time of the copper wire in an annealing area is 5s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell-type annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 1 in table 2.
Example 2
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, copper-zirconium master alloy, titanium sponge and copper-lanthanum master alloy. The composition of the alloy is shown in table 1, example 2.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding a copper-zirconium intermediate alloy, sponge titanium and a copper-lanthanum intermediate alloy, raising the temperature to 1350 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1200 ℃, carrying out upward continuous casting after heat preservation for 20min, wherein the pitch is 6mm, the stopping time is 0.30s, the pulling time is 0.05s, the stopping-pulling time ratio is 6, the upward speed is 600mm/min, and casting the copper rod with the diameter of 20 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 400 ℃, the extrusion speed is 5r/min, the extrusion pass is 1 pass, the extrusion ratio is 25, and cooling is carried out by using an alcohol and water mixed solution (the volume ratio of alcohol to water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 99%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell jar type annealing furnace for intermediate annealing, wherein the annealing temperature is 500 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3:1) is cooled.
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 85%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 550 ℃, the annealing speed is 5cm/s, the residence time of the copper wire in an annealing area is 15s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell-type annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 2 in table 2.
Example 3
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, pure silver, titanium sponge and copper cerium intermediate alloy. The composition of the alloy is shown in table 1, example 3.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding pure silver, sponge titanium and copper cerium intermediate alloy, raising the temperature to 1320 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1220 ℃, carrying out upward continuous casting after keeping the temperature for 20min, wherein the pitch is 3mm, the stopping time is 0.15s, the pulling time is 0.05s, the stopping-pulling time ratio is 3, the upward speed is 400mm/min, and casting the copper rod with the diameter of 18 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 425 ℃, the extrusion speed is 7r/min, the extrusion pass is 2 passes, the extrusion ratio is 10, and cooling is carried out by using a mixed solution of alcohol and water (the volume ratio of the alcohol to the water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 90%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell jar type annealing furnace for intermediate annealing, wherein the annealing temperature is 550 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3:1) is cooled.
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 90%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 450 ℃, the annealing speed is 10cm/s, the residence time of the copper wire in an annealing area is 25s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell-type annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 3 in table 2.
Example 4
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, pure silver, pure magnesium and copper cerium intermediate alloy. The composition of the alloy is shown in table 1, example 4.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding pure silver, pure magnesium and copper cerium intermediate alloy, raising the temperature to 1330 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1230 ℃, carrying out upward continuous casting after keeping the temperature for 20min, wherein the pitch is 4mm, the stopping time is 0.15s, the pulling time is 0.1s, the stopping-pulling time ratio is 1.5, the upward speed is 450mm/min, and casting the copper rod with the diameter of 20 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 425 ℃, the extrusion speed is 10r/min, the extrusion pass is 3 passes, the extrusion ratio is 15, and cooling is carried out by using a mixed solution of alcohol and water (the volume ratio of the alcohol to the water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 90%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell-type annealing furnace for intermediate annealing, wherein the annealing temperature is 575 ℃, heating for 6 hours, keeping the temperature for 8 hours, and cooling the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3: 1).
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 99%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 500 ℃, the annealing speed is 20cm/s, the residence time of the copper wire in an annealing area is 35s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell-type annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 4 in table 2.
Example 5
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, pure silver, pure magnesium and copper yttrium master alloys. The composition of the alloy is shown in table 1, example 5.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding pure silver, pure magnesium and copper yttrium intermediate alloy, raising the temperature to 1300 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1250 ℃, carrying out upward continuous casting after preserving the heat for 20min, wherein the pitch is 4mm, the stopping time is 0.2s, the pulling time is 0.1s, the stopping-pulling time ratio is 2, the upward speed is 500mm/min, and casting the copper rod with the diameter of 20 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 450 ℃, the extrusion speed is 10r/min, the extrusion pass is 2 passes, the extrusion ratio is 20, and cooling is carried out by using a mixed solution of alcohol and water (the volume ratio of the alcohol to the water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 95%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell jar type annealing furnace for intermediate annealing, wherein the annealing temperature is 550 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3:1) is cooled.
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 85%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 550 ℃, the annealing speed is 25cm/s, the residence time of the copper wire in an annealing area is 60s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 5 in table 2.
Example 6
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, pure tin, pure magnesium and copper yttrium master alloys. The composition of the alloy is shown in table 1, example 6.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding pure tin, pure magnesium and copper yttrium intermediate alloy, raising the temperature to 1300 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1200 ℃, carrying out upward continuous casting after keeping the temperature for 20min, wherein the pitch is 5mm, the stopping time is 0.3s, the pulling time is 0.15s, the stopping-pulling time ratio is 2, the upward speed is 600mm/min, and casting the copper rod with the diameter of 20 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 425 ℃, the extrusion speed is 5r/min, the number of extrusion passes is 1, the extrusion ratio is 1, and cooling is carried out by using a mixed solution of alcohol and water (the volume ratio of the alcohol to the water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 90%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell jar type annealing furnace for intermediate annealing, wherein the annealing temperature is 530 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3:1) is cooled.
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 95%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 500 ℃, the annealing speed is 30cm/s, the residence time of the copper wire in an annealing area is 45s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 6 in Table 2.
Example 7
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, pure tin, copper-iron intermediate and copper-scandium intermediate alloys. The composition of the alloy is shown in table 1, example 7.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding pure tin, copper-iron intermediate alloy and copper-scandium intermediate alloy, raising the temperature to 1350 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1250 ℃, carrying out upward continuous casting after heat preservation for 20min, wherein the pitch is 3mm, the stopping time is 0.3s, the pulling time is 0.15s, the stopping-pulling time ratio is 2, the upward speed is 300mm/min, and casting the copper rod with the diameter of 19 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 400 ℃, the extrusion speed is 7r/min, the extrusion pass is 2 passes, the extrusion ratio is 5, and cooling is carried out by using an alcohol and water mixed solution (the volume ratio of alcohol to water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 90%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell jar type annealing furnace for intermediate annealing, wherein the annealing temperature is 500 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3:1) is cooled.
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 90%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 450 ℃, the annealing speed is 20cm/s, the residence time of the copper wire in an annealing area is 55s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 7 in Table 2.
Example 8
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, pure silicon, copper-iron intermediate and copper-scandium intermediate alloys. The composition of the alloy is shown in table 1, example 8.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding pure silicon, copper-iron intermediate alloy and copper-scandium intermediate alloy, raising the temperature to 1300 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1225 ℃, carrying out upward continuous casting after keeping the temperature for 20min, wherein the pitch is 4mm, the stopping time is 0.2s, the pulling time is 0.05s, the stopping-pulling time ratio is 4, the upward speed is 400mm/min, and casting the copper rod with the diameter of 20 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 400 ℃, the extrusion speed is 10r/min, the extrusion pass is 3 passes, the extrusion ratio is 15, and cooling is carried out by using an alcohol and water mixed solution (the volume ratio of alcohol to water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 85%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell jar type annealing furnace for intermediate annealing, wherein the annealing temperature is 500 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3:1) is cooled.
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 90%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 450 ℃, the annealing speed is 10cm/s, the residence time of the copper wire in an annealing area is 25s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 8 in table 2.
Example 9
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, pure silicon, pure zinc and copper gadolinium intermediate alloy. The composition of the alloy is shown in table 1, example 9.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding pure silicon, pure zinc and copper gadolinium intermediate alloy, raising the temperature to 1320 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1200 ℃, carrying out upward continuous casting after keeping the temperature for 20min, wherein the pitch is 3mm, the stopping time is 0.2s, the pulling time is 0.05s, the stopping-pulling time ratio is 4, the upward speed is 450mm/min, and casting the copper rod with the diameter of 20 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 450 ℃, the extrusion speed is 7r/min, the extrusion pass is 2 passes, the extrusion ratio is 15, and cooling is carried out by using an alcohol and water mixed solution (the volume ratio of alcohol to water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 90%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell jar type annealing furnace for intermediate annealing, wherein the annealing temperature is 550 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3:1) is cooled.
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 95%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 480 ℃, the annealing speed is 20cm/s, the residence time of the copper wire in an annealing area is 15s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 9 in Table 2.
Example 10
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, pure zinc and copper gadolinium intermediate alloys. The composition of the alloy is shown in Table 1, example 10.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding pure zinc and copper-gadolinium intermediate alloy, raising the temperature to 1350 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1200 ℃, keeping the temperature for 20min, then carrying out up-drawing continuous casting, wherein the pitch is 2mm, the stopping time is 0.15s, the drawing time is 0.05s, the stopping-drawing time ratio is 3, the up-drawing speed is 450mm/min, and casting the copper rod with the diameter of 20 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 450 ℃, the extrusion speed is 10r/min, the extrusion pass is 2 passes, the extrusion ratio is 1, and cooling is carried out by using an alcohol and water mixed solution (the volume ratio of alcohol to water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 90%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell jar type annealing furnace for intermediate annealing, wherein the annealing temperature is 550 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3:1) is cooled.
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 85%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 500 ℃, the annealing speed is 20cm/s, the residence time of the copper wire in an annealing area is 35s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 10 in Table 2.
Example 11
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, copper zirconium intermediate alloy and copper samarium intermediate alloy. The composition of the alloy is shown in Table 1, example 11.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding a copper-zirconium intermediate alloy and a copper-samarium intermediate alloy, raising the temperature to 1350 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1250 ℃, carrying out upward continuous casting after heat preservation for 20min, wherein the pitch is 3mm, the stopping time is 0.15s, the pulling time is 0.05s, the stopping-pulling time ratio is 3, the upward speed is 550mm/min, and casting the copper rod with the diameter of 20 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 400 ℃, the extrusion speed is 5r/min, the extrusion pass is 3, the extrusion ratio is 1, and cooling is carried out by using an alcohol and water mixed solution (the volume ratio of alcohol to water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 90%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell jar type annealing furnace for intermediate annealing, wherein the annealing temperature is 550 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3:1) is cooled.
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 95%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 550 ℃, the annealing speed is 30cm/s, the residence time of the copper wire in an annealing area is 35s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 11 in Table 2.
Example 12
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, copper zirconium master alloy and pure silver. The composition of the alloy is shown in table 1, example 12.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding copper-zirconium intermediate alloy and pure silver, heating to 1300 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1220 ℃, carrying out upward continuous casting after heat preservation for 20min, wherein the pitch is 3mm, the stopping time is 0.15s, the pulling time is 0.1s, the stopping-pulling time ratio is 1.5, the upward speed is 480mm/min, and casting the copper rod with the diameter of 20 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 425 ℃, the extrusion speed is 10r/min, the extrusion pass is 3 passes, the extrusion ratio is 1, and the alloy copper rod is cooled by using an alcohol and water mixed solution (the volume ratio of alcohol to water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 95%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell jar type annealing furnace for intermediate annealing, wherein the annealing temperature is 550 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3:1) is cooled.
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 95%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 525 ℃, the annealing speed is 20cm/s, the residence time of the copper wire in an annealing area is 35s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 12 in Table 2.
Example 13
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, copper zirconium master alloy and pure magnesium. The composition of the alloy is shown in Table 1, example 13.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding a copper-zirconium intermediate alloy and pure magnesium, heating to 1330 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1220 ℃, keeping the temperature for 20min, then carrying out upward continuous casting, wherein the pitch is 4mm, the stopping time is 0.2s, the pulling time is 0.1s, the stopping-pulling time ratio is 2, the upward speed is 500mm/min, and casting the copper rod with the diameter of 20 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 425 ℃, the extrusion speed is 10r/min, the extrusion pass is 2 passes, the extrusion ratio is 5, and cooling is carried out by using an alcohol and water mixed solution (the volume ratio of alcohol to water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 90%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell-type annealing furnace for intermediate annealing, wherein the annealing temperature is 575 ℃, heating for 6 hours, keeping the temperature for 8 hours, and cooling the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3: 1).
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 95%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 425 ℃, the annealing speed is 30cm/s, the residence time of the copper wire in an annealing area is 60s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 13 in Table 2.
Example 14
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, pure tin, pure silicon and copper yttrium master alloys. The composition of the alloy is shown in Table 1, example 14.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding copper-yttrium intermediate alloy, pure tin and pure silicon, raising the temperature to 1350 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature to be 1220 ℃, carrying out upward continuous casting after keeping the temperature for 20min, wherein the pitch is 5mm, the stopping time is 0.2s, the pulling time is 0.1s, the stopping-pulling time ratio is 2, the upward speed is 400mm/min, and casting the copper rod with the diameter of 20 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 425 ℃, the extrusion speed is 5r/min, the extrusion pass is 2 passes, the extrusion ratio is 10, and cooling is carried out by using a mixed solution of alcohol and water (the volume ratio of the alcohol to the water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 85%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell-type annealing furnace for intermediate annealing, wherein the annealing temperature is 575 ℃, heating for 6 hours, keeping the temperature for 8 hours, and cooling the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3: 1).
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 90%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 475 ℃, the annealing speed is 30cm/s, the residence time of the copper wire in an annealing area is 5s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 14 in Table 2.
Example 15
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium and titanium sponge. The composition of the alloy is shown in Table 1, example 15.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding titanium sponge, raising the temperature to 1300 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1200 ℃, carrying out upward continuous casting after heat preservation for 20min, wherein the pitch is 2mm, the stopping time is 0.2s, the pulling time is 0.1s, the stopping-pulling time ratio is 2, the upward speed is 300mm/min, and casting the copper rod with the diameter of 20 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 425 ℃, the extrusion speed is 10r/min, the extrusion pass is 3 passes, the extrusion ratio is 1, and the alloy copper rod is cooled by using an alcohol and water mixed solution (the volume ratio of alcohol to water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 90%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell-type annealing furnace for intermediate annealing, wherein the annealing temperature is 575 ℃, heating for 6 hours, keeping the temperature for 8 hours, and cooling the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3: 1).
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 90%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 500 ℃, the annealing speed is 30cm/s, the residence time of the copper wire in an annealing area is 15s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 15 in Table 2.
Example 16
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, titanium sponge, pure silicon and copper scandium master alloy. The composition of the alloy is shown in Table 1, example 16.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding sponge titanium, pure silicon and copper-scandium intermediate alloy, raising the temperature to 1350 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1200 ℃, carrying out upward continuous casting after heat preservation for 20min, wherein the pitch is 6mm, the stopping time is 0.3s, the pulling time is 0.1s, the stopping-pulling time ratio is 3, the upward speed is 500mm/min, and casting the copper rod with the diameter of 20 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 450 ℃, the extrusion speed is 10r/min, the extrusion pass is 2 passes, the extrusion ratio is 1, and cooling is carried out by using an alcohol and water mixed solution (the volume ratio of alcohol to water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 95%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell jar type annealing furnace for intermediate annealing, wherein the annealing temperature is 600 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3:1) is cooled.
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 99%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 500 ℃, the annealing speed is 20cm/s, the residence time of the copper wire in an annealing area is 25s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 16 in Table 2.
Example 17
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, pure silicon and copper-iron intermediate alloys. The composition of the alloy is shown in Table 1, example 17.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding pure silicon and copper-iron intermediate alloy, raising the temperature to 1350 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1250 ℃, carrying out upward continuous casting after heat preservation for 21min, wherein the pitch is 3mm, the stopping time is 0.3s, the pulling time is 0.05s, the stopping-pulling time ratio is 6, the upward speed is 600mm/min, and casting the copper rod with the diameter of 20 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 450 ℃, the extrusion speed is 10r/min, the extrusion pass is 3 passes, the extrusion ratio is 1, and the alloy copper rod is cooled by using an alcohol and water mixed solution (the volume ratio of alcohol to water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 95%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell jar type annealing furnace for intermediate annealing, wherein the annealing temperature is 500 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3:1) is cooled.
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 90%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 550 ℃, the annealing speed is 30cm/s, the residence time of the copper wire in an annealing area is 35s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 17 in Table 2.
Example 18
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, pure magnesium and copper cerium intermediate alloy. The composition of the alloy is shown in Table 1, example 18.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding pure magnesium and copper-cerium intermediate alloy, raising the temperature to 1300 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1200 ℃, carrying out upward continuous casting after heat preservation for 20min, wherein the pitch is 4mm, the stopping time is 0.3s, the pulling time is 0.05s, the stopping-pulling time ratio is 6, the upward speed is 300mm/min, and casting the copper rod with the diameter of 20 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 450 ℃, the extrusion speed is 5r/min, the extrusion pass is 3 passes, the extrusion ratio is 10, and cooling is carried out by using an alcohol and water mixed solution (the volume ratio of alcohol to water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 95%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell jar type annealing furnace for intermediate annealing, wherein the annealing temperature is 520 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3:1) is cooled.
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 90%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 550 ℃, the annealing speed is 20cm/s, the residence time of the copper wire in an annealing area is 45s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 18 in Table 2.
Example 19
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium, pure tin and copper gadolinium intermediate alloys. The composition of the alloy is shown in Table 1, example 19.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding pure tin and copper gadolinium intermediate alloy, raising the temperature to 1300 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature at 1250 ℃, carrying out up-drawing continuous casting after heat preservation for 22min, wherein the pitch is 5mm, the stopping time is 0.2s, the drawing time is 0.05s, the stopping-drawing time ratio is 4, the up-drawing speed is 500mm/min, and casting the copper rod with the diameter of 20 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 450 ℃, the extrusion speed is 5r/min, the number of extrusion passes is 2, the extrusion ratio is 25, and cooling is carried out by using alcohol (and water mixed solution (the volume ratio of the alcohol to the water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 90%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell jar type annealing furnace for intermediate annealing, wherein the annealing temperature is 520 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3:1) is cooled.
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 90%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 550 ℃, the annealing speed is 10cm/s, the residence time of the copper wire in an annealing area is 35s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 19 in Table 2.
Example 20
The alloy of the invention is smelted by adopting the following raw materials: electrolytic copper, pure chromium and copper-iron intermediate alloys. The composition of the alloy is shown in table 1, example 20.
1. Smelting and casting: adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, introducing high-purity argon for protection after the materials are all melted, adding a copper-iron intermediate alloy, raising the temperature to 1350 ℃, uniformly stirring after the melt is completely melted, controlling the casting temperature to 1250 ℃, carrying out upward continuous casting after heat preservation for 25min, wherein the pitch is 2mm, the stopping time is 0.2s, the pulling time is 0.05s, the stopping-pulling time ratio is 4, the upward speed is 600mm/min, and casting the copper rod with the diameter of 20 mm.
2. Continuous extrusion: and (2) carrying out multi-pass continuous extrusion on the alloy copper rod on a Conform continuous extruder, wherein the heating temperature of an extrusion wheel is 450 ℃, the extrusion speed is 5r/min, the extrusion pass is 3 passes, the extrusion ratio is 1, and the alloy copper rod is cooled by using an alcohol and water mixed solution (the volume ratio of alcohol to water is 1: 4).
3. Drawing: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass extrusion, wherein the processing rate is 90%.
4. Bell jar annealing: and (3) placing the cold-drawn copper wire in a bell jar type annealing furnace for intermediate annealing, wherein the annealing temperature is 520 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen (the volume ratio of the nitrogen to the hydrogen is 3:1) is cooled.
5. Drawing: and (3) carrying out multi-pass cold drawing on the annealed copper wire, wherein the processing rate is 99%.
6. And (3) online annealing treatment: and carrying out on-line annealing treatment on the copper wire subjected to cold drawing, wherein the annealing temperature is 550 ℃, the annealing speed is 20cm/s, the residence time of the copper wire in an annealing area is 35s, the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
After the above melting and casting, continuous extrusion, drawing, bell annealing, drawing, and in-line annealing treatments, the microstructure and properties were as shown in example 20 in Table 2.
Figure BDA0002166755240000181
Figure BDA0002166755240000191
Figure BDA0002166755240000201
The alloy material system of the invention can observe the precipitation density of the bean petal-shaped Cr phase with the grain diameter of 10 nm-30 nm on the copper alloy to be 1 x 10 after the short-flow preparation processing technology20～4×1023m-3The precipitation density of the body-centered cubic structure Moire fringe-like Cr phase with the grain diameter of 10nm to 15nm is 1 x 1021～5×1022m-3The alloy has tensile strength of 400-600 MPa, yield strength of 300-500 MPa, elongation of 6-20% and electric conductivity of 80-95% IACS, softening temperature of 500-600 ℃, and repeated bending times of 1 × 106～1×109Next, the process is carried out. Meanwhile, the invention omits the high-temperature solution treatment and multiple aging treatment processes in the traditional process, is easy to realize the short-flow continuous preparation of the copper alloy wire rod, can meet the requirement of high-end precise cables on the large length of the wire rod, shortens the production process flow and improves the production efficiency of alloy materials.
The above embodiments are only used for illustrating but not limiting the technical solutions of the present invention, and although the above embodiments describe the present invention in detail, those skilled in the art should understand that: modifications and equivalents may be made thereto without departing from the spirit and scope of the invention and any modifications and equivalents may fall within the scope of the claims.

Claims (9)

1. A short-flow continuous preparation and processing method of a high-performance copper-chromium wire rod comprises the following steps: a. the method comprises the following steps of proportioning, feeding, smelting and casting according to the mass percentage of the copper-chromium alloy, and carrying out continuous upward casting by adopting a non-vacuum power frequency induction furnace, wherein the pitch is 1-6 mm, the stopping time is 0.15-0.30 s, the pulling time is 0.05-0.20 s, the stopping-pulling time ratio is 1.5-6, and the upward casting speed is 300-600 mm/min; the copper-chromium alloy comprises the following components in percentage by weight: 0.1-0.6% of Cr, one or two of Zr, Ti, Ag, Mg, Sn, Fe, Si and Zn, the total content of alloy elements is 0.08-0.4%, the content of each alloy element is 0.05-0.2%, and the balance is Cu; b. continuous extrusion; c. drawing; d. performing bell-type intermediate annealing; e. drawing; f. and (4) carrying out online annealing treatment.
2. The short-flow continuous preparation and processing method of the high-performance copper-chromium wire rod according to claim 1, characterized in that: the copper-chromium alloy also comprises one of La, Ce, Y, Sc, Gd and Sm rare earth elements, and the mass percentage content is 0.005-0.01%.
3. The short-flow continuous production and processing method of the high-performance copper-chromium wire rod according to claim 1 or 2, characterized in that: before smelting, adding electrolytic copper and pure chromium into a non-vacuum power frequency induction furnace, after melting, introducing argon for protection, adding one or two of copper-zirconium intermediate alloy, pure silicon, sponge titanium, pure magnesium, copper-iron intermediate alloy, pure zinc, pure silver and pure tin, adding or not adding one of copper-lanthanum, copper-cerium, copper-yttrium, copper-scandium, copper-gadolinium and copper-samarium intermediate alloy, raising the temperature to 1300-1350 ℃, after completely melting, uniformly stirring, keeping the casting temperature at 1200-1250 ℃, keeping the temperature for 20-25 min, then carrying out up-drawing continuous casting, and casting into a copper rod with the diameter of 18-20 mm.
4. The short-flow continuous preparation and processing method of the high-performance copper-chromium wire rod according to claim 1, characterized in that: and (2) carrying out multi-pass continuous extrusion on the prepared alloy copper rod on a continuous extruder, wherein the heating temperature of an extrusion wheel is 400-450 ℃, the extrusion speed is 5-10 r/min, the extrusion pass is 1-3, the extrusion ratio is 1-25, and cooling is carried out by using an alcohol and water mixed solution.
5. The short-flow continuous preparation and processing method of the high-performance copper-chromium wire rod according to claim 4, characterized in that: and (3) carrying out multi-pass drawing on the copper rod subjected to multi-pass continuous extrusion, wherein the processing rate is 85-99%.
6. The short-flow continuous preparation and processing method of the high-performance copper-chromium wire rod according to claim 5, characterized in that: and (3) placing the cold-drawn copper wire in a bell jar type annealing furnace for intermediate annealing, wherein the annealing temperature is 500-600 ℃, the temperature is raised for 6 hours, the temperature is kept for 8 hours, and the mixed gas of nitrogen and hydrogen is cooled.
7. The short-flow continuous preparation and processing method of the high-performance copper-chromium wire rod according to claim 6, characterized in that: the volume ratio of nitrogen to hydrogen in the mixed gas was 3: 1.
8. The short-flow continuous preparation and processing method of the high-performance copper-chromium wire rod according to claim 6, characterized in that: and (3) carrying out multi-pass cold drawing on the copper wire subjected to intermediate annealing, wherein the processing rate is 85-99%.
9. The short-flow continuous preparation and processing method of the high-performance copper-chromium wire rod according to claim 8, characterized in that: carrying out online annealing treatment on the copper wire subjected to secondary cold drawing, wherein the annealing temperature is 400-550 ℃, the annealing speed is 5-30 cm/s, and the residence time of the copper wire in an annealing area is 5-60 s; the cooling mode is room temperature cooling, and the protective gas is pure hydrogen gas.
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