LU500862B1 - Copper alloy wire for connector and method for manufacture thereof - Google Patents

Copper alloy wire for connector and method for manufacture thereof Download PDF

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Publication number
LU500862B1
LU500862B1 LU500862A LU500862A LU500862B1 LU 500862 B1 LU500862 B1 LU 500862B1 LU 500862 A LU500862 A LU 500862A LU 500862 A LU500862 A LU 500862A LU 500862 B1 LU500862 B1 LU 500862B1
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Luxembourg
Prior art keywords
copper
copper alloy
alloy wire
alloy
vacuum
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LU500862A
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German (de)
Inventor
Baoan Wu
Huiyi Tang
Zhihong Jia
Yuemin Zhang
Xuefeng Wu
Jun Cao
Xinmin Zhang
Pingmei Ming
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Univ Henan Polytechnic
Chongqing Materials Res Inst Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/03Making non-ferrous alloys by melting using master alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026Alloys based on copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21CMANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/04Manufacture 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/42Wire connectors; Manufacturing methods related thereto
    • H01L24/43Manufacturing methods

Abstract

The present invention provides a copper alloy wire for a connector and a method for manufacturing thereof. vacuum casting is used for the copper alloy wire of the present invention to achieve precise control of the alloy composition and structure; by means of homogenization heat treatment and hot extrusion processing, a high-performance copper alloy material having good consistency and a dense structure is obtained; stabilizing the structure by means of solid solution treatment, further improving the mechanical properties of the alloy material, and finally obtaining a copper alloy wire having high strength, high conductivity, good high temperature stability, good wear resistance, and good processing performance.

Description

BL-5332 COPPER ALLOY WIRE FOR CONNECTOR AND METHOD FOR 999
MANUFACTURE THEREOF
BACKGROUND Field of Invention The present invention belongs to the technical field of alloy material manufacturing, in particular relates to a copper alloy wire for a connector clip (connector) and a method for manufacturing thereof.
Background of the Invention At present, the existing copper alloys for a connector clip of new energy electric vehicles mainly include copper-silver alloys, copper-chromium alloys, copper-beryllium alloys and other materials, but the above series of alloys have the following problems: (1) copper-silver alloys have good electrical conductivity , but its high-temperature strength and hardness are low, and the temperature rise during the current transmission process seriously weakens its mechanical properties, thus it can only be used in small current situations; (2) the alloy materials such as copper-chromium alloys, copper-beryllium alloys have excellent strength and hardness, but their conductivity is too low, and the temperature rises severely during large current transmission. In addition, as the elements such as chromium, beryllium, are highly toxic elements, they cause serious pollution to the environment and human body, and are strictly restricted during use.
Therefore, it is necessary to provide an improved technical solution for the above-mentioned shortcomings of the prior art.
SUMMARY The purpose of the present invention 1s to provide a copper alloy wire for a connector clip and a method for manufacturing thereof, which are used to overcome the above-mentioned problems that copper-silver alloys cannot be used 1
Bd LU500862 in large-current situations in the prior art, and the conductivity of the alloy materials such as copper-chromium alloys, copper-beryllium alloys is too low and the temperature rises severely during large current transmission.
In order to achieve the above purposes, the present invention provides the following technical solutions.
The present invention provides a copper alloy wire for a connector clip, and the copper alloy wire comprises the following components by mass percentage: 5-15% of silver, 0.1-0.9% of zirconium, 0.05-0.2% of rare earth metal, and rest is copper; Preferably, the rare earth metal is one or more selected from the group consisting of cerium, lanthanum, and yttrium. In order to further understand the copper alloy wire for a connector clip of the present invention, the present invention also provides a method for manufacturing a copper alloy wire for a connector clip. The manufacturing method includes the following steps of: S1, weighing silver, copper, copper-zirconium intermediate alloy and rare earth copper intermediate alloy according to a raw material ratio, mixing and adding to a crucible of the vacuum furnace for smelting, wherein the material of the crucible is graphite crucible, completely melting the alloy and the alloy liquid becoming clear, and stirring the alloy liquid by mechanical stirring, and then casting into a mold for molding and cooling to obtain a copper alloy billet.
The method for preparing the copper-zirconium intermediate alloy in step Slis as follows: putting copper and zirconium in a graphite crucible of a vacuum intermediate frequency melting furnace in layers, and vacuumizing the furnace, starting to heat up when the vacuum degree is higher than 1.0x10-1Pa, and raising the temperature to 1800-1900°C, to make the copper-zirconium intermediate alloy completely melt and the copper-zirconium intermediate alloy liquid transparent, standing-preserving heat for 10-20 minutes, then casting the copper-zirconium intermediate alloy liquid into a mold, stopping heating and cooling to obtain a copper-zirconium intermediate alloy, wherein the insulation material in the vacuum intermediate frequency melting furnace is graphite fiber, 2
BL-5332 LU500862 and the temperature is measured by the infrared temperature measurement; Preferably, the mass ratio of copper and zirconium is 3:2.
The method for preparing the rare earth copper intermediate alloy in step S1 is as follows: putting copper in the crucible of the vacuum furnace, and putting the rare earth metal in the feeding box of the vacuum furnace, and vacuumizing the chamber of the vacuum furnace, filling with a protective gas when a vacuum degree is more than 5x10"! Pa, to 0.01-0.05 MPa of the vacuum degree,, and then vacuumizing again until the vacuum degree is higher than 5x10"! Pa, then starting to heat up, stop vacuumizing when the temperature rises to 500-900°C,and filling the vacuum furnace with protective gas until the vacuum degree is 0.2-0.4 MPa, and then continuing to heat up to 1150-1450°C, adding the rare earth metal in the feeding box to the crucible when the copper is completely melted, stirring for 5-10 min under the condition of filling the protective gas in the crucible , cooling to obtain the rare earth copper intermediate alloy.
Preferably, the mass ratio of copper and rare earth metals is 19:1; Preferably, the protective gas is nitrogen or argon.
The smelting in step S1 specifically includes: vacuumizing the vacuum melting furnace, starting to heat up when a vacuum degree is more than 5.0x10"! Pa, and stopping vacuumizing when the temperature rises to 400-600°C, and filling the vacuum melting furnace with protective gas to a vacuum degree of 0.01-0.05 MPa , and then continuing to heat up to 1400 -1750°C, until the alloy 1s completely melted and the alloy liquid becomes clear.
Preferably, the protective gas is argon or nitrogen; More preferably, the vacuum melting furnace is a vacuum intermediate frequency melting furnace; More preferably, the diameter of the copper alloy billet is 120 mm - 200 mm.
S2, placing the copper alloy billet obtained in step S1 in a vacuum heat treatment furnace, performing homogenization heat treatment, and then removing oxides of the surface of copper alloy billet by mechanical processing to obtain a copper alloy ingot; 3
BL-5332 LU500862 The heat treatment in Step S2 is specifically as follows: vacuumizing the vacuum heat treatment furnace, starting to heat up when the vacuum degree 1s higher than 5.0x10"! Pa, and heating to 780-880 °C and preserving heat for 6-9 h, then rapidly cooling; Preferably, the rapid cooling rate is more than 50°C/min; More preferably, the diameter of the copper alloy ingot is 118-200 mm.
S3, performing hot extrusion processing on the copper alloy ingot obtained in step S2 with a large-deformation hot extruderto obtain a copper alloy rod.
In step S3, the copper alloy ingot is subjected to hot extrusion processing, the extrusion temperature of the hot extrusion is 400-700°C, and the diameter of the obtained copper alloy rod is 15-21 mm.
S4, performing multi-pass large-deformation cold drawing on the copper alloy rod obtained in step S3 with a single die wire drawing machine to obtain a large-deformation copper alloy rod.
The single-pass processing rate of the large-deformation cold drawing in step S4 is higher than 25%, and the diameter of the large-deformation copper alloy rod is 8-10 mm.
S5, performing multi-pass small-deformation cold drawing on the large-deformation copper alloy rod obtained in step S4 with a straight single die wire drawing machine to obtain a small-deformation copper alloy rod.
In step S5, the single-pass processing rate of the small-deformation cold drawing is 15% to 25%, and the diameter of the small-deformation copper alloy rod is 2.5-3.5 mm.
S6, placing the small-deformation copper alloy rod obtained in step S5 in a vacuum heat treatment furnace for solution treatment (solid solution treatment), then performing micro drawing with the wire drawing machine, , and then performing annealing treatment with a continuous online annealing equipment to prepare a copper alloy wire.
In step S6, the solution treatment is specifically as follows: the vacuum heat treatment furnace is heated by resistance; vacuumizing the vacuum heat treatment 4
BL-5332 LU500862 furnace, and starting to heat up when the vacuum degree is more than 1.0x10"! Pa, and raising the temperature to 400 - 550 °C, performing preserving heat on the furnace for 20-50 min, and then stopping heating, and then taking it out after cooling with the vacuum heat treatment furnace.
In step S6, the micro drawing is to draw the small-deformation copper alloy rod after solution treatment to a diameter of 0.3-0.8 mm; the cross-section reduction rate during the process of micro-drawing is 8.0-13.0%, and the speed of micro drawing is not more than 400 m/min; preferably, the concentration of the drawing liquid is more than 5%.
In step S6, the annealing treatment temperature is 500-750°C, the length of the annealing tube in the annealing equipment is 4-6 m, and the speed of the annealing treatment 1s 60-210 m/min.
Preferably, a cooling liquid tank is provided at the export of the annealing tube, the cooling liquid tank is used to cool the copper alloy wire after annealing treatment, the cooling medium in the cooling liquid tank is the alcohol solution, and the concentration of the alcohol solution 1s>50 %; More preferably, the posterior segment of the cooling liquid tank is provided with a rubber sheet and an air knife, and the copper alloy wire is passed through the rubber sheet(s), the thickness of the rubber sheet is 2-4 mm, the moisture on the surface of the copper alloy wire is completely removed after the copper alloy wire passes through the rubber sheet(s) and the air knife.
Excellent effects The copper alloy wire for the connector clip of the present invention includes copper, silver, zirconium, and rare earth metals. The copper alloy wire of this composition has the advantages of high strength, high conductivity, good high temperature stability, good wear resistance, good processing performance. The copper can effectively increase the strength of copper alloys in the matrix, and at the same time reduce the conductivity of alloy materials with a limited extent. But for the copper-silver alloy, its high temperature stability and wear resistance are poor, and the mechanical properties are severely reduced under high temperature
BL-5332 LU500862 conditions. The addition of zirconium to the alloy matrix can effectively increase the recrystallization temperature of the alloy, thereby improving the high temperature stability of the copper alloy, and at the same time reducing the alloy conductivity with a limited extent. The addition of trace rare earth metals in the alloy can further refine the alloy grains, and the differences of the size and valence electrons between the rare earth element atoms and copper atoms are greater, which enhances the interaction force between the grain boundaries and the rare earth cerium atoms. In particular, the addition of rare earth metals (especially rare earth cerium) makes the spherical rare earth compounds uniformly distributed in the grain boundaries and within the grains form in the alloy. The spherical rare earth compounds can pin the movement of the grain boundaries at high temperatures and prevent the slippage of the grain boundaries at high temperatures, suppress the merging and growth of sub-grain in the recovery stage, postpone the formation and growth process of the recrystallized nuclei in the subsequent recrystallization process, and further improve the strength and high temperature stability of the alloy materials.
The manufacturing method of the copper alloy wire for the connector clip in the present invention eliminates the oxidation of alloy elements by adopting vacuum casting, which precisely controls the alloy composition and structure. The manufacturing method of the copper alloy wire for the connector clip in the present invention makes the internal composition of the alloy uniform and the structure of the alloy dense through the homogenization heat treatment and large-deformation hot extrusion processing. The high-performance copper alloy materials with good consistency and dense structure are obtained. The structure is stabilized and the alloy elements are further precipitated by the solution treatment, which further improves the mechanical properties of the alloy materials under the premise of less reduction in electrical conductivity.
DETAILED DESCRIPTION OF THE EMBODYMENTS The high-performance alloy wires for the connector clip in the present 6
BL-5332 LU500862 invention not only has high conductivity, has high strength and wear resistance, and but also has high temperature stability and good processability. The manufacturing method of the high-performance alloy wire for the connector clip of the present invention eliminates the oxidation of alloy elements by vacuum casting, precisely controls the composition of the alloy, and makes the internal composition of the alloy uniform and the structure of the alloy dense through the homogenization heat treatment and large-deformation hot extrusion processing. The solution heat treatment is used to stabilize the structure and further precipitate the alloy elements, which further improves the mechanical properties of the alloy materials under the premise of less reduction in electrical conductivity.
The zirconium raw materials and rare earth metal raw materials used in the following examples and comparative examples need to be prepared in advance into a copper-zirconium intermediate alloy and a rare-earth copper intermediate alloy, specifically including the following.
Preparation of the copper-zirconium intermediate alloy is as follows: according to the mass ratio of 3:2, the copper and zirconium are placed in the graphite crucible of the vacuum intermediate frequency melting furnace in layers, and the furnace is vacuumized; when the vacuum degree is more than 1.0x10 * Pa, it starts to heat up, and the temperature rises to 1850 °C, so that the copper zirconium intermediate alloy is completely melted and the copper zirconium intermediate alloy liquid 1s transparent; after standing -preserving heat for 15 min, the copper zirconium intermediate alloy is cast into a mold, stop heating and cooling to obtain a copper zirconium intermediate alloy.
Preparation of the rare earth copper intermediate alloy is as follows: according to the ratio of copper to rare earth metal of 19 : 1, the copper is put into the crucible of the vacuum furnace, wherein the crucible uses graphite or boron nitride material, and the rare earth metals are put into the feeding box of the vacuum furnace; the chamber of the vacuum furnace is vacuumized, when the vacuum degree is more than 5x10! Pa , nitrogen and argon are filled to the vacuum degree of 0.05 MPa ; and then vacuumizing to the vacuum degree of more than 7
BL-5332 LU500862 5x10" Pa, starting to heat up, after the temperature rises to 800 °C, stop vacuumizing and filling the vacuum furnace with nitrogen until the vacuum degree is 0.3 MPa , then continuing to heat up to 1400 °C, when the copper 1s completely melted and the copper liquid becomes clear, moving the feeding box to add the rare earth metals into the crucible, and stirring for 8 minutes under the condition of filling with nitrogen, and cooling; and the rare earth copper intermediate alloy is obtained.
Example 1 The example provides a copper alloy wire for a connector clip. The copper alloy wire includes the following components by mass percentage: 5% of silver,
0.1% of zirconium, 0.05% of cerium, and the rest (balance) is copper.
This example also provides a method for manufacturing a copper alloy wire for a connector clip, which includes the following steps.
S1, weighing 50 g silver, 2.5 g copper-zirconium intermediate alloy, 10 g cerium-copper intermediate alloy and 937.5 g copper according to the ratio of the raw materials, and then mixing and adding them into the crucible of the vacuum intermediate frequency melting furnace; starting to heat up when the vacuum degree is more than 5.0x10" Pa, and stop vacuumizing when the temperature rises to 500°C; and filling argon gas in the vacuum intermediate frequency melting furnace until the vacuum is 0.03 MPa, and then continuing to heat up to 1600°C until the alloy is completely melted and the alloy liquid becomes clear; stirring the alloy liquid by mechanical agitation, and then casting the alloy liquid into mold for forming; and cooling to obtain the copper alloy billet with a diameter of 120 mm.
S2, placing the copper alloy billet with a diameter of 120 mm obtained in step S1 in a vacuum heat treatment furnace and vacuumizing, starting to heat up when the vacuum degree is more than 5.0x10"! Pa, heating to 850°C and preserving heat for 8 h, and then rapidly cooling at a rate of 60°C/min, and then removing the oxides of the surface of copper alloy billet by mechanical processing to obtain a copper alloy ingot with a diameter of 118 mm; 8
BL-5332 LU500862 S3, performing hot extrusion processing on the copper alloy ingot with a diameter of 118 mm obtained in step S2 with a large-deformation hot extruder to obtain a copper alloy rod with a diameter of 15 mm. The hot extrusion temperature is 500°C.
S4, performing multi-pass large-deformation cold drawing on the copper alloy rod with a diameter of 15 mm obtained in step S3 by a single die wire drawing machine with a single pass processing rate of 30%, to obtain a large-deformation copper alloy rod with a diameter of 8 mm.
S5, performing multi-pass small-deformation cold drawing on the large-deformation copper alloy rod with a diameter of 8 mm obtained in step S4 by a straight single die wire drawing machine with a single-pass processing rate of 20%, to obtain a small-deformation copper alloy rod with a diameter of 2.5 mm.
S6, placing the small-deformation copper alloy rod with a diameter of 2.5 mm obtained in step S5 in a vacuum heat treatment furnace, and vacuumizing the heat treatment furnace, starting to heat up when the vacuum degree is more than
1.0x10 Pa, and raising the temperature to 500°C, and performing heat preservation on the furnace body for 30 minutes, stop heating, then cooling in a vacuum heat treatment furnace, and then performing micro drawing on the small-deformation copper alloy rod after solution treatment. The cross-section reduction rate in the micro drawing process is 10%, the concentration of the drawing liquid is more than 5%, and the micro drawing speed is 300 m/min. The drawn copper alloy wire with a diameter of 0.3 mm is obtained, and then the annealing treatment is carried out in the continuous online annealing equipment. The annealing treatment temperature is 600°C, the length of the annealing tube in the annealing equipment is 5 m, and the annealing treatment speed is 150 m/min. The export of the annealing tube is equipped with a cooling liquid tank, and the posterior segment of the cooling liquid tank is equipped with a rubber sheet(s) and an air knife. The copper alloy wire passes through the rubber sheet(s), and the thickness of the rubber sheet is 3 mm. When the copper alloy wire passes through the rubber sheet(s) and the air knife, the moisture on the surface of the copper alloy 9
BL-5332 LU500862 wire 1s completely removed, and a copper alloy wire with a diameter of 0.3 mm 1s prepared.
Performance testing The copper alloy wire(s) prepared in the example of the present invention is tested for mechanical properties, electrical conductivity, hardness and softening temperature. The strength test refers to the GB-T 3048.2-2007 test methods for electrical properties of electric wires and cables, using the electronic strength tester for testing. The electrical conductivity test refers to GB-T 3048.2-2007 test methods for electrical properties of electric wires and cables, using the double-arm electric bridge for testing. The hardness test refers to GB/T 230.1-2018 Metallic materials-Rockwell hardness test, Part 1 , using a hardness tester for testing. The softening temperature test refers to the GB/T 33370-2016 measuring method for soften temperature of copper and copper alloys , using the Vickers hardness tester for testing.
By testing the mechanical properties, electrical conductivity, hardness and softening temperature of the prepared copper alloy wire for a connector clip, the strength of the copper alloy wire prepared in this example is 420 MPa, and the elongation rate 1s 11%, the conductivity is 83% IACS, the hardness is 132 HV, and the softening temperature 1s 380°C, as shown in Table 1.
Example 2 In this example, a copper alloy wire for a connector clip is provided. The copper alloy wire includes the following components by mass percentage: 5% of silver, 0.5% of zirconium, 0.05% of cerium, and the balance is copper.
In the method for manufacturing a copper alloy wire for a connector clip provided in this example, in step S1, 50 g silver, 12.5 g copper-zirconium intermediate alloy, 10 g cerium-copper intermediate alloy and 927.5g copper are weighed according to the raw material ratio. The other methods and steps are the same as in Example 1, and will not be repeated here.
The mechanical properties, electrical conductivity, hardness, and softening
BL53323 0000000000 LU500862 temperature of the copper alloy wire for the connector clip prepared in this example are tested. The test standards and methods are the same as those in Example 1.
It is measured that the strength is 470 MPa, the elongation is 11%, the conductivity 1s 76% IACS, the hardness 1s 149 HV, and the softening temperature 1s 460°C, of the copper alloy wire prepared in this example, as shown in Table 1.
Example 3 In this example, a copper alloy wire for a connector clip is provided, which includes the following components by mass percentage: 5% of silver, 0.9% of zirconium, 0.05% of lanthanum, and the balance is copper.
In the method for manufacturing a copper alloy wire for a connector clip provided in this example, in step S1, 50 g silver, 22.5 g copper-zirconium intermediate alloy, 10 g lanthanum-copper intermediate alloy and 917.5 g copper are weighed according to the raw material ratio. The other methods and steps are the same as in Example 1, and will not be repeated here.
The mechanical properties, electrical conductivity, hardness, and softening temperature of the copper alloy wire for the connector clip prepared in this example are tested. The test standards and methods are the same as those in Example 1.
It is measured that the strength is 490 MPa, the elongation rate is 11%, the conductivity 1s 76% IACS, the hardness 1s 154 HV, and the softening temperature 1s 530°C, of the copper alloy wire prepared in this example, as shown in Table 1.
Example 4 In this example, a copper alloy wire for a connector clip is provided. The copper alloy wire includes the following components by mass percentage: 10% of silver, 0.1% of zirconium, 0.05% of lanthanum, and the balance is copper.
In the method for manufacturing a copper alloy wire for a connector clip provided in this example,, in step S1, 100 g silver, 2.5 g copper-zirconium intermediate alloy, 10 g lanthanum-copper intermediate alloy and 887.5 g copper are weighed according to the raw material ratio. In step S4, the single-pass 11
BL53323 0000000000 LU500862 processing rate is 40%, and the multi-pass large-deformation cold drawing is performed to obtain a large-deformation copper alloy rod with a diameter of 9.0 mm. In step S5, the single-pass processing rate is 15%, and the small-deformation copper alloy rod with a diameter of 3.0 mm is obtained. The other methods and steps are the same as in Example 1, and will not be repeated here.
The mechanical properties, electrical conductivity, hardness, and softening temperature of the copper alloy wire for the connector clip prepared in this example are tested. The test standards and methods are the same as those in Example 1.
It is measured that the strength is 470 MPa, the elongation rate is 11%, the conductivity 1s 72% IACS, the hardness 1s 138 HV, and the softening temperature 1s 410°C, of the copper alloy wire prepared in this example, as shown in Table 1.
Example 5 In this example, a copper alloy wire for a connector clip is provided. The copper alloy wire includes the following components by mass percentage: 10% of silver, 0.5% of zirconium, 0.05% of lanthanum, and the balance is copper.
In the method for manufacturing a copper alloy wire for a connector clip provided in this example, in step SI, 100 g silver, 12.5 g copper-zirconium intermediate alloy, 10 g lanthanum-copper intermediate alloy and 877.5 g copper are weighed according to the raw material ratio. The other methods and steps are the same as in Example 4, and will not be repeated here.
The mechanical properties, electrical conductivity, hardness, and softening temperature of the copper alloy wire for the connector clip prepared in this example are tested. The test standards and methods are the same as those in Example 1.
It is measured that the strength is 511 MPa, the elongation is 11%, the conductivity 1s 70% IACS, the hardness 1s 162 HV, and the softening temperature 1s 510°C, of the copper alloy wire prepared in this example, as shown in Table 1.
Example 6 In this example, a copper alloy wire for a connector clip is provided. The 12
BL-5332 LU500862 copper alloy wire includes the following components by mass percentage: 10% of silver, 0.9% of zirconium, 0.08% of yttrium, and the balance is copper.
In the method for manufacturing a copper alloy wire for a connector clip provided in this example, in step SI, 100 g silver, 22.5 g copper-zirconium intermediate alloy, 16 g yttrium-copper intermediate alloy and 861.5 g copper are weighed according to the raw material ratio. The other methods and steps are the same as in Example 4, and will not be repeated here.
The mechanical properties, electrical conductivity, hardness, and softening temperature of the copper alloy wire for the connector clip prepared in this example are tested. The test standards and methods are the same as those in Example 1.
It is measured that the strength is 521 MPa, the elongation rate is 11%, the conductivity 1s 67% IACS, the hardness is 164 HV, and the softening temperature 1s 570°C, of the copper alloy wire prepared in this example, as shown in Table 1.
Example 7 In this example, a copper alloy wire for a connector clip is provided. The copper alloy wire includes the following components by mass percentage: 15% of silver, 0.1% of zirconium, 0.05% of yttrium, and the balance is copper.
In the method for manufacturing a copper alloy wire for a connector clip provided in this example, in step S1, 150 g of silver, 2.5 g of copper-zirconium intermediate alloy, 10 g of yttrium-copper intermediate alloy and 837.5 g of copper are weighed according to the raw material ratio. In step S6, placing the small-deformation copper alloy rod in the vacuum heat treatment furnace, vacuumizing the vacuum heat treatment furnace; starting to heat up when the vacuum degree is more than 1.0x10"! Pa; and raising the temperature to 400°C, performing heat preservation on the furnace body for 50 minutes, stop heating, and then cooling in the vacuum heat treatment furnace; and then performing micro drawing on the small-deformation copper alloy rod after solution treatment, wherein the cross-section reduction rate in the micro drawing process is 8%, the concentration of the drawing liquid is more than 5%, the micro drawing speed 1s 13
BL-5332 LU500862 200 m/min; and obtaining the drawn copper alloy wire with a diameter of 0.5 mm; and then performing the annealing treatment in the continuous online annealing equipment, wherein the annealing temperature is 750°C, the length of the annealing tube on the annealing equipment is 5 m, the annealing treatment speed is 60 m/min; and preparing a copper alloy wire with a diameter of 0.5 mm. The other methods and steps are the same as in Example 1, and will not be repeated here.
The mechanical properties, electrical conductivity, hardness, and softening temperature of the copper alloy wire for the connector clip prepared in this example are tested. The test standards and methods are the same as those in Example 1.
It is measured that the strength is 480 MPa, the elongation is 11.5%, the conductivity 1s 70% IACS, the hardness 1s 148 HV, and the softening temperature 1s 415°C, of the copper alloy wire prepared in this example, as shown in Table 1.
Example 8 In this example, a copper alloy wire for a connector clip is provided. The copper alloy wire includes the following components by mass percentage: 15% of silver, 0.5% of zirconium, 0.08% of yttrium, and the balance is copper.
In the method for manufacturing a copper alloy wire for a connector clip provided in this example, in step S1, 150 g of silver, 12.5 g of copper-zirconium intermediate alloy, 16 g of yttrium-copper intermediate alloy and 821.5 g of copper are weighed according to the raw material ratio. The other methods and steps are the same as in Example 7, and will not be repeated here.
The mechanical properties, electrical conductivity, hardness, and softening temperature of the copper alloy wire for the connector clip prepared in this example are tested. The test standards and methods are the same as those in Example 1.
It is measured that the strength is 531 MPa, the elongation is 10.5%, the conductivity 1s 68% IACS, the hardness 1s 166 HV, and the softening temperature 1s 530°C, of the copper alloy wire prepared in this example, as shown in Table 1.
Example 9 14
BL-5332 LU500862 In this example, a copper alloy wire for a connector clip is provided, and the copper alloy wire includes the following components by mass percentage: 15% of silver, 0.9% of zirconium, 0.1% of cerium, and the balance is copper.
In the method for manufacturing a copper alloy wire for a connector clip provided in this example, in step S1, 150 g of silver, 22.5 g of copper-zirconium intermediate alloy, 20 g of cerium-copper intermediate alloy and 807.5g of copper are weighed according to the raw material ratio. The other methods and steps are the same as in Example 7, and will not be repeated here.
The mechanical properties, electrical conductivity, hardness, and softening temperature of the copper alloy wire for the connector clip prepared in this example are tested. The test standards and methods are the same as those in Example 1.
It is measured that the strength is 542 MPa, the elongation rate is 11%, the conductivity 1s 65% IACS, the hardness is 170 HV, and the softening temperature 1s 585°C, of the copper alloy wire prepared in this example, as shown in Table 1.
Example 10 In this example, a copper alloy wire for a connector clip is provided, and the copper alloy wire includes the following components by mass percentage: 5% of silver, 0.1% of zirconium, 0.1% of cerium, and the balance is copper.
In the method for manufacturing a copper alloy wire for a connector clip provided in this example, in step S1, 50 g silver, 2.5 g copper-zirconium intermediate alloy, 20 g cerium-copper intermediate alloy and 927.5g copper are weighed according to the raw material ratio. The other methods and steps are the same as in Example 1, and will not be repeated here.
The mechanical properties, electrical conductivity, hardness, and softening temperature of the copper alloy wire for the connector clip prepared in this example are tested. The test standards and methods are the same as those in Example 1.
It is measured that the strength is 425 MPa, the elongation is 11%, the conductivity 1s 80% IACS, the hardness 1s 138 HV, and the softening temperature 1s 380°C, of the copper alloy wire prepared in this example, as shown in Table 1.
BL53323 0000000000 LU500862 Example 11 In this example, a copper alloy wire for a connector clip is provided, and the copper alloy wire includes the following components by mass percentage: 10% of silver, 0.5% of zirconium, 0.1% of lanthanum, and the balance is copper.
In the method for manufacturing a copper alloy wire for a connector clip provided in this example, in step SI, 100 g silver, 12.5 g copper-zirconium intermediate alloy, 20 g lanthanum-copper intermediate alloy and 867.5 g copper are weighed according to the raw material ratio. The other methods and steps are the same as in Example 5, and will not be repeated here.
The mechanical properties, electrical conductivity, hardness, and softening temperature of the copper alloy wire for the connector clip prepared in this example are tested. The test standards and methods are the same as those in Example 1.
It is measured that the strength is 519 MPa, the elongation is 11%, the conductivity 1s 69% IACS, the hardness is 164 HV, and the softening temperature 1s 510°C, of the copper alloy wire prepared in this example, as shown in Table 1.
Example 12 In this example, a copper alloy wire for a connector clip is provided. The copper alloy wire includes the following components by mass percentage: 15% of silver, 0.9% of zirconium, 0.1% of cerium, and the balance is copper.
In the method for manufacturing a copper alloy wire for a connector clip provided in this example, in step S1, 150 g of silver, 22.5 g of copper-zirconium intermediate alloy, 20 g of certum-copper intermediate alloy and 807.5 g of copper are weighed according to the raw material ratio. The other methods and steps are the same as in Example 9, and will not be repeated here.
The mechanical properties, electrical conductivity, hardness, and softening temperature of the copper alloy wire for the connector clip prepared in this example are tested. The test standards and methods are the same as those in Example 1.
It is measured that the strength is 550 MPa, the elongation is 11%, the 16
BL53323 0000000000 LU500862 conductivity 1s 63% IACS, the hardness 1s 175 HV, and the softening temperature 1s 595 °C, of the copper alloy wire prepared in this example, as shown in Table 1.
Example 13 In this example, a copper alloy wire for a connector clip is provided. The copper alloy wire includes the following components by mass percentage: 5% of silver, 0.1% of zirconium, 0.05% of cerium, and the balance is copper.
In the method for manufacturing a copper alloy wire for a connector clip also provided in this example, the homogenization post-treatment temperature in step S2 1s as follows: heating to 800° C and preserving heat for 7 hours. The other methods and steps are the same as in Example 1, and will not be repeated here.
The mechanical properties, electrical conductivity, hardness, and softening temperature of the copper alloy wire for the connector clip prepared in this example are tested. The test standards and methods are the same as those in Example 1.
It is measured that the strength is 416 MPa, the elongation is 11%, the conductivity 1s 81% IACS, the hardness 1s 130 HV, and the softening temperature 1s 375°C, of the copper alloy wire prepared in this example, as shown in Table 1.
Example 14 In this example, a copper alloy wire for a connector clip is provided, and the copper alloy wire includes the following components by mass percentage: 5% of silver, 0.1% of zirconium, 0.05% of cerium, and the balance is copper.
In the method for manufacturing a copper alloy wire for a connector clip also provided in this example, in step S4, the single-pass processing rate of the cold-processing is changed, and the single-pass processing rate is 45%. The other methods and steps are the same as in Example 1, and will not be repeated here.
The mechanical properties, electrical conductivity, hardness, and softening temperature of the copper alloy wire for the connector clip prepared in this example are tested. The test standards and methods are the same as those in Example 1.
It is measured that the strength is 425 MPa, the elongation rate is 11%, the 17
BL-5332 LU500862 conductivity 1s 83% IACS, the hardness 1s 134 HV, and the softening temperature 1s 385°C, of the copper alloy wire prepared in this example, as shown in Table 1.
Control (comparative example) 1 This comparative example provides a copper alloy wire for a connector clip, and the copper alloy wire includes the following components by mass percentage: 5% of silver, 0.05% of cerium, and the balance is copper.
In the method for manufacturing a copper alloy wire for a connector clip provided in this comparative example, in step S1, 50 g silver, 10 g cerium-copper intermediate alloy and 940 g copper are weighed according to the raw material ratio. The other methods and steps are the same as in example 1, and will not be repeated here.
The mechanical properties, electrical conductivity, hardness, and softening temperature of the copper alloy wire for the connector clip prepared in this comparative example were tested. The testing standards and methods are the same as those in Example 1.
It is measured that the strength is 380 MPa, the elongation is 11%, the conductivity is 83% IACS, the hardness is 110 HV, and the softening temperature 1s 320°C, of the copper alloy wire prepared in this comparative example, as shown in Table 1.
Control 2 This comparative example provides a copper alloy wire for a connector clip, and the copper alloy wire includes the following components by mass percentage: 15% of silver, 0.05% of yttrium, and the balance is copper.
In the method for manufacturing a copper alloy wire for a connector clip provided in this comparative example, in step SI, 150 g of silver, 10 g of yttrium-copper intermediate alloy and 840 g of copper are weighed according to the raw material ratio. The other methods and steps are the same as in Example 1, and will not be repeated here.
18
BL-5332 LU500862 The mechanical properties, electrical conductivity, hardness, and softening temperature of the copper alloy wire for the connector clip prepared in this comparative example were tested. The testing standards and methods are the same as those in Example 1.
It is measured that the strength is 450 MPa, the elongation is 11%, the conductivity 1s 71% IACS, the hardness 1s 124 HV, and the softening temperature 1s 380°C, of the copper alloy wire prepared in this comparative example, as shown in Table 1.
Control 3 This comparative example provides a copper alloy wire for a connector clip, and the copper alloy wire includes the following components by mass percentage:
0.9% of zirconium, 0.1% of cerium, and the balance 1s copper.
In the method for manufacturing a copper alloy wire for a connector clip provided in this comparative example, in step SI, 22.5 g copper-zirconium intermediate alloy, 20 g cerium-copper intermediate alloy and 957.5g copper are weighed according to the raw material ratio. The other methods and steps are the same as in Example 1, and will not be repeated here.
The mechanical properties, electrical conductivity, hardness, and softening temperature of the copper alloy wire for the connector clip prepared in this comparative example were tested. The test standards and methods are the same as those in Example 1.
It is measured that the strength is 460 MPa, the elongation is 11%, the conductivity 1s 68% IACS, the hardness is 148 HV, and the softening temperature is 505°C, of the copper alloy wire prepared in this comparative example, as shown in Table 1.
Control 4 This comparative example provides a copper alloy wire for a connector clip, and the copper alloy wire includes the following components by mass percentage: 19
BES LU500862 10% of silver, and the balance is copper.
In the method for manufacturing a copper alloy wire for a connector clip provided in this comparative example, in step S1, 100 g of silver and 900 g of copper are weighed according to the raw material ratio. The other methods and steps are the same as in Example 1, and will not be repeated here.
The mechanical properties, electrical conductivity, hardness, and softening temperature of the copper alloy wire for the connector clip prepared in this comparative example were tested. The testing standards and methods are the same as those in Example 1.
It is measured that the strength is 435 MPa, the elongation is 11%, the conductivity is 74% IACS, the hardness is 118 HV, and the softening temperature 1s 340°C, of the copper alloy wire prepared in this comparative example, as shown in Table 1.
Table 1 below shows the performance data of the copper alloy wires prepared in each example and comparative example.
Table 1. Properties of the copper alloy wires prepared in each example and comparative example Item Strength Elongation | Conductivity hardness Softening /MPa /% /%IACS /HV temperature / °C | Examples [sos ls wee 830 | pamper [425 nls es fs
BL-5332 5500862 _Example 1519 |) | le (so | Conrols Jao nu Je jus ss 21

Claims (8)

BL-5332 CLAIMS. LU500862
1. A method for manufacturing a copper alloy wire for a connector clip, characterized in that the manufacturing method includes the following steps of: S1, weighing silver, copper, copper-zirconium intermediate alloy and rare earth copper intermediate alloy according to a raw material ratio, mixing and adding to a vacuum furnace for smelting, completely melting the alloy and then stirring alloy liquid, then casting-molding and cooling to obtain a copper alloy billet; S2, placing the copper alloy billet obtained in step SI in a vacuum heat treatment furnace, performing homogenization heat treatment, and then removing oxides of surface of the copper alloy billet by mechanical processing to obtain a copper alloy ingot; S3, performing hot extrusion processing on the copper alloy ingot obtained in step S2, wherein a extrusion temperature of the hot extrusion is 400-700°C, and a diameter of a copper alloy rod obtained is 15-21 mm; S4, performing multi-pass large-deformation cold drawing on the copper alloy rod obtained in step S3with a wire drawing machine to obtain a large-deformation copper alloy rod with a diameter of 8-10 mm; S5, performing multi-pass small-deformation cold drawing on the large-deformation copper alloy rod obtained in step S4 with the wire drawing machine to obtain a small-deformation copper alloy rod with a diameter of 2.5-3.5 mm; S6, placing the small-deformation copper alloy rod obtained in step S5 in a vacuum heat treatment furnace for solution treatment, then performing micro drawing with the wire drawing machine, and then performing annealing treatment with an annealing equipment to prepare a copper alloy wire.
2. The method for manufacturing a copper alloy wire for a connector clip according to claim 1, characterized in that a method for preparing the 22
BL-5332 copper-zirconium intermediate alloy in step S1: putting copper and zirconium LE a vacuum melting furnace in layers and vacuumizing, starting to heat up when a vacuum degree is higher than 1.0x10" Pa, and raising temperature to 1800-1900 °C to make the copper-zirconium intermediate alloy completely melt and copper-zirconium intermediate alloy liquid transparent, standing-preserving heat for 10-20 minutes, then casting the copper-zirconium intermediate alloy liquid into a mold, stoppingheating and cooling to obtain a copper-zirconium intermediate alloy.
3. The method for manufacturing a copper alloy wire for a connector clip according to claim 1, characterized in that a method for preparing the rare earth copper intermediate alloy in step S1: putting copper in a crucible of a vacuum furnace, and putting rare earth metal in a feeding box of the vacuum furnace, and vacuumizing a chamber of the vacuum furnace, filling with a protective gas when a vacuum degree is more than 5x10"! Pa, to 0.01-0.05 MPa of the vacuum degree, and vacuumizing again until the vacuum degree is more than 5x10! Pa, starting to heat up, stop vacuumizing when the temperature rises to 500-900 °C, and filling the vacuum furnace with protective gas until the vacuum degree is 0.2-0.4MPa, and then continuing to heat up to 1150-1450°C, adding the rare earth metal in the feeding box to the crucible when the copper is completely melted, stirring for 5-10 min under a condition of filling the protective gas in the crucible, cooling to obtain a rare earth copper intermediate alloy.
4. The method for manufacturing a copper alloy wire for a connector clip according to claim 1, characterized in that the smelting in step S1 specifically includes: vacuumizing the vacuum furnace, starting to heat up when a vacuum degree is more than 5.0x10"! Pa, and stopping vacuumizing when temperature rises to 400-600°C, and filling the vacuum furnace with protective gas to a vacuum degree of 0.01-0.05 MPa , and then continuing to heat up to 1400 -1750°C, until the alloy 1s completely melted and the alloy liquid becomes clear.
23
BL-5332 LU500862
5. The method for manufacturing a copper alloy wire for a connector clip according to claim 1, characterized in that the solution treatment in step S6 specifically includes: vacuumizing the vacuum heat treatment furnace, starting to heat up when a vacuum degree is more than 1.0x10"! Pa, raising temperature to 400-550°C and preserving heat for 20-50 min, and then stopping heating, and then taking out after cooling with the furnace.
6. The method for manufacturing a copper alloy wire for a connector clip according to claim 5, characterized in that the micro drawing in step S6 1s to draw the small-deformation copper alloy rod after solution treatment to a diameter of
0.3-0.8 mm; a cross-section reduction rate during a process of the micro drawing is
8.0-13.0%, and a speed of the micro drawing is not more than 400 m/min.
7. The method for manufacturing a copper alloy wire for a connector clip according to claim 6, characterized in that an annealing treatment temperature in step S6 1s 500-750°C, and a length of an annealing tube in the annealing equipment 1S 4-6 m, a speed of the annealing treatment 1s 60-210 m/min.
8. A copper alloy wire for a connecter clip as claimed in any one of claims 1 to 7, characterized in that the copper alloy wire comprises the following components by mass percentage: 5-15% of silver, 0.1-0.9% of zirconium, 0.05- 0.2% of rare earth metal, and rest is copper; the rare earth metal is one or more selected from the group consisting of cerium, lanthanum, and yttrium.
24
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CN111363937B (en) * 2020-03-19 2021-09-21 河南理工大学 Copper alloy wire for plug connector and manufacturing method thereof
CN113560365B (en) * 2021-07-22 2023-08-15 诺克威新材料(江苏)有限公司 Processing method for improving wiredrawing strength of copper alloy
CN113976656A (en) * 2021-10-26 2022-01-28 江西云泰铜业有限公司 Preparation method of high-strength bending-resistant copper wire
CN114345973A (en) * 2021-12-24 2022-04-15 通鼎互联信息股份有限公司 Method for cleaning oxidized finished copper wire
CN114472578A (en) * 2022-01-13 2022-05-13 武汉正威新材料科技有限公司 Re-doped copper-tin alloy contact wire and preparation method thereof
CN114649109B (en) * 2022-04-24 2023-12-29 福建南新电缆有限公司 High-conductivity antioxidant cable and manufacturing method thereof

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CN105088010B (en) * 2015-08-31 2017-08-25 河南科技大学 A kind of high-strength highly-conductive rare earth copper zirconium alloy and preparation method thereof
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