CN114561566B - Preparation method of copper-silver alloy wire - Google Patents

Preparation method of copper-silver alloy wire Download PDF

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CN114561566B
CN114561566B CN202210200827.1A CN202210200827A CN114561566B CN 114561566 B CN114561566 B CN 114561566B CN 202210200827 A CN202210200827 A CN 202210200827A CN 114561566 B CN114561566 B CN 114561566B
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copper
silver alloy
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silver
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CN114561566A (en
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谢伟滨
谢明旺
邓永芳
陈辉明
汪航
杨斌
周鹏飞
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Jiangxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
    • B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/0075—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for rods of limited length
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/0081—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for slabs; for billets
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/525—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods
    • 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
    • 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
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • 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

Abstract

The invention discloses a preparation method of a copper-silver alloy wire, which comprises the following components: 18-26 wt.% of Ag, 0.02-0.25wt.% of La, 0.5-1.5 mass ratio of Sc to La and the balance of Cu; and drawing the wire rod into a wire rod finished product through a plurality of passes. According to the copper-silver alloy wire, only two rare earth elements Sc and La are added, the mass ratio of Sc to La is controlled to be 0.5-1.5, the room-temperature tensile strength can reach 1050-1520MPa, the electric conductivity can reach 75-87% IACS after a strengthening treatment process, and the resistivity is lower than 1.982-2.30 mu omega cm; when the environmental temperature is-196 ℃, the low-temperature tensile strength of the alloy is 1450-1860MPa, the low-temperature resistivity is 0.70-0.87 mu omega-cm, and the comprehensive performance is excellent.

Description

Preparation method of copper-silver alloy wire
Technical Field
The invention belongs to the field of nonferrous metal processing, and relates to a high-strength and high-conductivity copper-silver alloy wire and a preparation method thereof.
Background
The copper-silver alloy has excellent conductivity and mechanical property, is commonly used as a magnet material and an electric contact material for a high-intensity magnetic field, and is widely applied to the fields of high-intensity magnetic fields, electronics and electricity and the like. In order to adapt to the complexity of the service environment, higher requirements are put forward on the strength and the conductivity of the Cu-Ag alloy material. In the field of strong magnetic field, in order to realize the strong magnetic field with the strength of 100T, the tensile strength of the magnetic field magnet material is required to be more than 1 GPa, and the electric conductivity is required to be more than 70% IACS.
In the case of copper-silver alloy, cold deformation, element addition and the like are traditional methods for improving the strength of the alloy, but the traditional strengthening means sacrifice the conductivity of the material, and the strength of the alloy is improved while the conductivity of the alloy is reduced, namely, the strength-conductivity is in an inverse relationship. For example, the addition of alloying elements increases the solute atom content of the copper matrix, thereby reducing the conductivity of the matrix; the deformation can introduce a large amount of dislocation into the alloy and increase the interface density, thereby reducing the conductivity of the material. How to solve the problem that the strength-conductivity is in an inverted relationship is to improve the strength of the material as much as possible on the premise of not losing or losing little conductivity of the material, so that the copper alloy has high strength and high conductivity, and becomes one of the key points of the current research on the high-strength and high-conductivity copper alloy.
By making the microstructure of the copper alloy nano, the alloy can obtain high strength and maintain high conductivity. On one hand, the nano-structure can enhance the alloy interface strengthening effect and improve the alloy strength; on the other hand, the nanostructured copper alloy can still maintain high conductivity due to the small influence of the interface on the conductivity of the alloy. So far, a plurality of scholars apply large-strain deformation technologies such as equal-diameter angular extrusion, high-pressure torsion and the like to the preparation of high-performance copper alloy and realize the nanocrystallization of a microstructure of the copper alloy. A large number of research results prove that alloy microstructure nanometer is an effective mode for improving the strength and the electric conductivity of the alloy.
Based on the above analysis, the main strengthening approaches of the high-strength high-conductivity copper-silver alloy material are as follows: (1) starting from the design of alloy components, the strength of the copper alloy is essentially improved by adding alloy elements which have low solid solubility in the copper matrix and small influence on the conductivity of the copper matrix; (2) the copper alloy tissue structure is nanocrystallized by a large-strain deformation technology such as multi-pass drawing, equal-diameter angular extrusion, high-pressure torsion and the like, so that the copper alloy material obtains high strength and high conductivity; (3) the content of solute atoms in the matrix is controlled through heat treatment, so that the aim of improving the conductivity of the alloy is fulfilled.
Disclosure of Invention
From the above application data of copper-silver alloy, the comprehensive performance of copper-silver alloy needs to be further optimized to meet the increasingly complex service environment. Based on the design, the preparation technology is optimized, the microstructure of the material is regulated and controlled, and the copper-silver alloy material with excellent mechanical property and conductivity is designed and prepared. The developed high-performance copper-silver alloy can solve the key technology and product bottleneck in the fields of super-strong magnetic fields, aerospace and the like in China, and has positive significance for improving the copper processing industrial chain in China.
The invention aims to provide a preparation method of a copper-silver alloy wire rod with tensile strength of more than 1 GPa and electric conductivity of more than 70% IACS; the specific technical scheme is as follows:
from the above-mentioned related data of copper-silver alloy, in order to adapt to more severe service conditions, it is necessary to further optimize the alloy components and improve the preparation process of the alloy, so as to prepare the copper-silver alloy material with high strength and high conductivity. In view of the above problems, an object of the present invention is to provide a high-strength and high-conductivity copper-silver alloy and a method for preparing the same, which are suitable for manufacturing electrical contact materials, super-strong magnetic field magnets, and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a copper-silver alloy wire comprises the following components: 18-26 wt.% of Ag, 0.02-0.25wt.% of La, 0.5-1.5 mass ratio of Sc to La and the balance of Cu; the specific process steps comprise:
step one, filling pure copper, pure silver, pure scandium and copper-lanthanum intermediate alloy into a graphite crucible according to the component proportion, and putting the graphite crucible into a vacuum induction melting furnace; first, the degree of vacuum in the vacuum induction melting furnace was controlled to 8.0X 10 -2 Introducing argon or nitrogen into the smelting furnace below Pa; raising the temperature in the furnace to 1100-1250 ℃ under the protection of argon or nitrogen atmosphere, and melting the metal raw material; after the metal is completely melted, preserving the temperature of the metal solution for 10-30 minutes, taking out, pouring into an iron square mould, and preparing a copper-silver alloy casting blank;
step two, after cutting the head and the tail of the copper-silver alloy casting blank and milling the surface, putting the copper-silver alloy casting blank into a heating furnace at the temperature of 680-720 ℃, preserving the heat for 30min-2h, and then hot rolling the copper-silver alloy casting blank into a copper-silver alloy plate, wherein the hot rolling reduction rate is more than 20%;
step three, quenching the copper-silver alloy plate to prepare a quenched copper-silver alloy plate;
fourthly, placing the quenched copper-silver alloy plate in a heating furnace, keeping the temperature within the range of 420-500 ℃ for 20-60 h, and then air-cooling to prepare an annealed copper-silver alloy plate;
step five, cutting the annealed copper-silver alloy plate into rectangular sections, wherein the aspect ratio is between 0.92 and 1, and is greater than or equal to 10;
sixthly, carrying out acid washing treatment on the rectangular section, and removing an oxide layer on the surface of the rectangular section after acid washing, dehydration and drying;
step seven, performing roll forming on the rectangular bar to roll the rectangular bar into a bar with a circular section, wherein the total rolling strain is 2-4;
step eight, drawing the bar material for a plurality of times to form a wire material, wherein the drawing temperature is less than 120 ℃, the drawing speed is 0.05-0.5m/s, and the total drawing strain is 3-6;
step nine, putting the wire into a heating furnace, keeping the temperature within the temperature range of 320-380 ℃ for 8-20 h, and then air-cooling to prepare an annealed copper-silver alloy wire;
step ten, carrying out acid washing treatment on the annealed copper-silver alloy wire, and removing an oxide layer on the surface of the wire after acid washing, dehydration and drying;
step eleven, drawing the wire rod for a plurality of times to obtain a finished wire rod product, wherein the drawing temperature is less than 120 ℃, the drawing speed is 0.5-10m/s, and the total drawing strain is more than 3.
Further, in the step one, the mass purities of the pure copper, the pure silver and the pure scandium are not lower than 99.95%, and the impurity content in the copper-lanthanum intermediate alloy is not more than 0.1%.
Further, the lattice constant of the copper matrix in the alloy of the quenched copper-silver alloy sheet material in the third step is in the range of 0.36291nm to 0.36312 nm.
Further, the lattice constant of the copper matrix in the alloy of the annealed copper-silver alloy sheet in the fourth step is in the range of 0.36178nm to 0.36191 nm.
Further, the lattice constant of the copper matrix in the alloy of the annealed copper-silver alloy wire in the ninth step is in the range of 0.3616nm to 0.36172 nm.
Further, the average diameter of crystal grains of the fibrous Cu phase of the copper matrix in the finished wire rod is within the range of 50nm to 200nm, the average diameter of the Ag phase long fiber with the length-diameter ratio of more than 100 is within the range of 20 nm to 150nm, and the average diameter of the Ag phase short fiber with the length-diameter ratio of less than 100 is within the range of 5 nm to 50 nm.
Further, La is 0.1-0.12wt.%, and the mass ratio of Sc to La is 0.5-0.8.
The strain eta in the invention adopts the formula eta = ln (A) 0 A) is calculated, wherein A 0 Is the area of the cross section before deformation, and A is the area of the cross section after deformation.
The lattice constant of the copper matrix can reflect the solute atom content of the copper matrix in the copper-silver alloy. The larger the lattice constant value of the alloy copper matrix phase, the higher the solute atom content thereof. The lattice constant of the copper matrix in the copper-silver alloy is calculated by adopting a least square method according to diffraction peak data in XRD.
The diameters of the silver phase and the copper phase fibers of the copper-silver alloy are obtained from the measurement statistics in SEM and TEM photographs.
The invention has the following beneficial effects:
1) by adding La and Sc in proportion, solute elements such as O, S, C and the like in the copper-silver alloy are further eliminated, and the alloy matrix is purified, so that the aim of improving the conductivity of the alloy is fulfilled; in addition, the addition of La and Sc can refine the copper phase grains to some extent.
2) Through the plastic deformation means such as the roller rolling, the multi-pass drawing and the like, the ultra-fining of the copper-silver alloy structure is realized at the same time, and the Cu phase and the Ag phase which reach the submicron or even nanometer scale in the two-dimensional direction are obtained, thereby improving the mechanical property of the alloy.
3) Ag solute atoms in the matrix are precipitated in a discontinuous desolventizing conversion mode through annealing, a short rod-shaped Ag phase is introduced into the copper matrix, and after deformation, the short rod-shaped Ag phase is elongated into slender short fibers, so that the strength of the copper-silver alloy is further improved.
4) By selecting a proper annealing process, under the premise of avoiding spheroidizing and coarsening of silver phase fibers, the copper phase and the silver phase in the copper-silver alloy are subjected to recovery recrystallization, the work hardening effect is eliminated, and the possibility is provided for subsequent multi-pass drawing of the copper-silver alloy; in addition, Ag phase particles are desolventized and precipitated in a continuous desolventizing transformation mode through annealing, a nano-spherical precipitated phase is introduced into a matrix, and meanwhile, the content of solute atoms in the copper matrix is reduced, so that the strength, the electric conductivity and the elongation of the alloy are improved.
5) By controlling the deformation heat treatment process of the alloy, Ag phase particles in three states are introduced into the copper-silver alloy: one is Ag phase long fiber formed by eutectic Ag phase in the rolling and drawing process; secondly, the short rod-shaped Ag phase separated out in the discontinuous desolvation transformation form is stretched to form Ag phase short fiber in the rolling and drawing process; and the third is spherical nanometer Ag phase particle separated out through continuous desolventizing transformation. The mechanical property of the copper-silver alloy is further enhanced by mixing three states of Ag phases.
6) According to the copper-silver alloy wire, only two rare earth elements Sc and La are added, the mass ratio of Sc to La is controlled to be 0.5-1.5, and after a strengthening treatment process, the structure shown in figure 1 can be obtained, the room-temperature tensile strength reaches 1050-1520MPa, the electric conductivity reaches 79-87% IACS, and the resistivity is lower than 1.982-2.182 mu omega cm; when the environmental temperature is-196 ℃, the low-temperature tensile strength of the alloy is 1450-1860MPa, the low-temperature resistivity is 0.70-0.87 mu omega-cm, and the comprehensive performance is excellent.
Drawings
FIG. 1 is a schematic structural view of an alloy of a Cu-Ag alloy wire according to the present invention;
fig. 2 is an alloy SEM photograph of the copper-silver alloy wire of example 1;
FIG. 3 is the EDS results for the alloy of the copper-silver alloy wire of example 1;
fig. 4 is a TEM photograph of an alloy of the copper-silver alloy wire of example 1.
Detailed Description
In order to further illustrate the present invention, preferred embodiments of the present invention are described below with reference to examples. The description of the embodiments is intended only to further illustrate the features and advantages of the present invention and should not be taken as limiting the invention in any way.
Comparative example
The high-strength high-conductivity copper-silver alloy material comprises Cu, Ag and inevitable impurities, and the components account for the following mass ratio: 18wt.% of Ag element, 0.25wt.% of La element, 0.05wt.% of Sc element, 0.05wt.% of total mass of unavoidable impurities, and the balance copper, wherein the mass ratio of Sc to La is 0.2. The preparation method of the copper-silver alloy comprises the following specific process steps:
step one, filling pure copper and pure silver with the mass purity of 99.95 percent into a graphite crucible, and putting into a vacuum induction melting furnace. First, the degree of vacuum in the vacuum induction melting furnace was controlled to 8.0X 10 -2 Pa below; then argon is introduced into the smelting furnace. The temperature in the furnace is raised to 1120 ℃ under the protection of argon atmosphere, and the metal raw material is melted. After the metal is completely melted, the metal solution is kept for 15 minutes, and a square die made of iron and 40mm multiplied by 100mm multiplied by L (height multiplied by width multiplied by length) is poured to prepare a copper-silver alloy casting blank.
And step two, cutting the head and the tail of the copper-silver alloy cast ingot obtained in the step one, milling the surface to obtain square billets with the length, the width and the height of 38 mm, 95mm and 300 mm respectively, then putting the square billets into a heating furnace with the temperature of 700 ℃ for heat preservation for 2 hours, and then hot rolling the square billets into copper-silver alloy plates with the thickness of 30 mm.
Step three, quenching the hot-rolled copper-silver alloy in the step two, carrying out water quenching on the alloy after keeping the temperature of 700 ℃ for 2h, wherein the lattice constant of a copper phase in the copper-silver alloy after water quenching is 0.36302 nm.
And step four, placing the quenched copper-silver alloy in the step three into a heating furnace, preserving the heat at 470 ℃ for 48 hours, and then air-cooling, wherein the lattice constant of the copper phase in the annealed copper-silver alloy is 0.36187 nm.
Step five, cutting the annealed copper-silver alloy in the step four into rectangular sections of 30mm multiplied by 32 mm multiplied by 340mm, wherein the aspect ratio is 0.9375, and the aspect ratio is 10.
And step six, carrying out acid washing treatment on the copper-silver alloy rectangular section bar obtained in the step five, and removing an oxide layer on the surface of the alloy after acid washing, dehydration and drying.
And seventhly, performing roll forming on the copper-silver alloy obtained in the sixth step, namely firstly performing 7 passes of rolling by adopting a box type hole pattern system, then performing 4 passes of rolling by adopting an oval-round hole pattern system, and rolling the copper-silver alloy into a round rod with the diameter of 8mm, wherein the total rolling strain is 2.95.
And step eight, carrying out multi-pass drawing on the copper-silver alloy plate obtained in the step seven, wherein the drawing speed of each pass is 0.1m/s, ensuring that the alloy temperature after each pass of drawing is less than 100 ℃ through air cooling, drawing the copper-silver alloy to a wire rod with the diameter of 1mm, and achieving the total drawing strain of 4.15.
Step nine, keeping the temperature of the drawn copper-silver alloy in the heating furnace at 370 ℃ for 18h, and then air-cooling, wherein the lattice constant of the copper phase in the annealed copper-silver alloy is 0.36170nm, and the elongation is 26%.
And step ten, carrying out acid washing treatment on the copper-silver alloy wire rod obtained in the step nine, and removing an oxide layer on the surface of the alloy after acid washing, dehydration and drying.
Step eleven, performing multi-pass drawing on the copper-silver alloy wire rod obtained in the step ten, wherein the drawing speed of each pass is 1m/s, ensuring that the alloy temperature after each pass of drawing is less than 100 ℃ through air cooling, drawing the copper-silver alloy wire rod to a wire rod with the diameter of 0.1mm, wherein the total drawing strain reaches 4.6, and obtaining a finished product of the copper-silver alloy wire rod with high strength and high conductivity after drawing. In the alloy, the average diameter of fibrous crystal grains of the copper matrix phase is 284nm, the average diameter of the Ag phase long fiber with the length-diameter ratio more than 100 is 142nm, and the average diameter of the Ag phase short fiber with the length-diameter ratio less than 100 is 58 nm; the tensile strength of the copper-silver alloy at room temperature reaches 996MPa, the conductivity reaches 79.6 percent IACS, and the resistivity reaches 2.166 mu omega cm; when the ambient temperature is-196 ℃, the low-temperature strength of the alloy reaches 1240MPa, and the low-temperature resistivity reaches 0.789 mu omega cm.
Example 1
The high-strength high-conductivity copper-silver alloy material comprises Cu, Ag, Sc and La elements and inevitable impurities, wherein the mass ratio of the components is as follows: 20 wt.% of Ag element, 0.02wt.% of La element, 0.03 wt.% of Sc element, 0.05wt.% of total mass of inevitable impurities, and the balance copper, wherein the mass ratio of Sc to La is 1.5. The preparation method of the copper-silver alloy comprises the following specific process steps:
step one, pure copper, pure silver and pure scandium with the mass purity of 99.95 percent and a copper-lanthanum intermediate alloy with the lanthanum mass fraction of 10wt percent are filled into a graphite crucible according to the proportion of the components, and are put into a vacuum induction melting furnace. First, the degree of vacuum in the vacuum induction melting furnace was controlled to 8.0X 10 -2 Pa below; then argon is introduced into the smelting furnace. The temperature in the furnace is raised to 1120 ℃ under the protection of argon atmosphere, and the metal raw material is melted. After the metal is completely melted, the metal solution is kept for 15 minutes, and a square iron mould with the size of 40mm multiplied by 100mm multiplied by L (height multiplied by width multiplied by length) is poured to prepare a copper-silver alloy casting blank.
And step two, cutting the head and the tail of the copper-silver alloy cast ingot obtained in the step one, milling the surface to obtain square billets with the length, the width and the height of 38 mm, 95mm and 300 mm respectively, then putting the square billets into a heating furnace with the temperature of 680 ℃ for heat preservation for 2 hours, and then hot rolling the square billets into copper-silver alloy plates with the thickness of 30 mm.
Step three, quenching the hot-rolled copper-silver alloy obtained in the step two, carrying out water quenching on the alloy after heat preservation for 2 hours at 680 ℃, wherein the lattice constant of a copper phase in the copper-silver alloy after water quenching is 0.36297 nm.
And step four, placing the quenched copper-silver alloy in the step three into a heating furnace, preserving the heat at 420 ℃ for 48 hours, and then air-cooling, wherein the lattice constant of the copper phase in the annealed copper-silver alloy is 0.36178 nm.
Step five, cutting the annealed copper-silver alloy in the step four into rectangular sections of 30mm multiplied by 32 mm multiplied by 340mm, wherein the aspect ratio is 0.9375, and the aspect ratio is 10.
And step six, carrying out acid washing treatment on the copper-silver alloy rectangular section bar obtained in the step five, and removing an oxide layer on the surface of the alloy after acid washing, dehydration and drying.
And step seven, performing roll forming on the copper-silver alloy obtained in the step six, firstly performing 7 passes of rolling by adopting a box type hole pattern system, then performing 4 passes of rolling by adopting an oval-round hole pattern system, and rolling the copper-silver alloy into a round rod with the diameter of 8mm, wherein the total rolling strain is 2.95.
And step eight, carrying out multi-pass drawing on the copper-silver alloy plate obtained in the step seven, wherein the drawing speed of each pass is 0.1m/s, ensuring that the alloy temperature after each pass of drawing is less than 100 ℃ through air cooling, drawing the copper-silver alloy to a wire rod with the diameter of 1mm, and achieving the total drawing strain of 4.15.
Step nine, keeping the temperature of the drawn copper-silver alloy in the heating furnace at 370 ℃ for 18h, and then air-cooling, wherein the lattice constant of the copper phase in the annealed copper-silver alloy is 0.36170nm, and the elongation is 28.5%.
And step ten, carrying out acid washing treatment on the copper-silver alloy wire rod obtained in the step nine, and removing an oxide layer on the surface of the alloy after acid washing, dehydration and drying.
Step eleven, performing multi-pass drawing on the copper-silver alloy wire rod obtained in the step ten, wherein the drawing speed of each pass is 1m/s, ensuring that the alloy temperature after each pass of drawing is less than 100 ℃ through air cooling, drawing the copper-silver alloy wire rod to a wire rod with the diameter of 0.1mm, wherein the total drawing strain reaches 4.6, and obtaining a finished product of the copper-silver alloy wire rod with high strength and high conductivity after drawing. In the process, when the alloy is drawn to the diameter of 0.417mm, the SEM photograph and the EDS analysis result of the alloy structure are respectively shown in figure 2 and figure 3; drawing to a diameter of 0.1mm, and a TEM photograph of the alloy structure is shown in FIG. 4. In the alloy, the average diameter of fibrous crystal grains of the copper matrix phase is 172nm, the average diameter of the Ag phase long fiber with the length-diameter ratio more than 100 is 98nm, and the average diameter of the Ag phase short fiber with the length-diameter ratio less than 100 is 42 nm; the tensile strength of the copper-silver alloy at room temperature reaches 1116MPa, the conductivity reaches 85.2 percent IACS, and the resistivity reaches 2.038 mu omega cm; when the environmental temperature is-196 ℃, the low-temperature strength of the alloy reaches 1580MPa, and the low-temperature resistivity reaches 0.742 mu omega cm.
Example 2
The high-strength high-conductivity copper-silver alloy material comprises Cu, Ag, Sc and La elements and inevitable impurities, wherein the mass ratio of the components is as follows: 24 wt.% of Ag element, 0.12wt.% of La element, 0.1wt.% of Sc element, 0.05wt.% of total mass of inevitable impurities, and the balance copper, wherein the mass ratio of Sc to La is 0.83. The preparation method of the copper-silver alloy comprises the following specific process steps:
step one, pure copper, pure silver and pure scandium with the mass purity of 99.95 percent and a copper-lanthanum intermediate alloy with the lanthanum mass fraction of 10wt percent are filled into a graphite crucible according to the proportion of the components, and are put into a vacuum induction melting furnace. First, the degree of vacuum in the vacuum induction melting furnace was controlled to 8.0X 10 -2 Pa below; then argon is introduced into the smelting furnace. The temperature in the furnace is raised to 1120 ℃ under the protection of argon atmosphere, and the metal raw material is melted. After the metal is completely melted, the metal solution is kept for 15 minutes, and a square die made of iron and 40mm multiplied by 100mm multiplied by L (height multiplied by width multiplied by length) is poured to prepare a copper-silver alloy casting blank.
And step two, cutting the head and the tail of the copper-silver alloy cast ingot obtained in the step one, milling the surface to obtain square billets with the length, the width and the height of 38 mm, 95mm and 300 mm respectively, then putting the square billets into a heating furnace with the temperature of 700 ℃ for heat preservation for 2 hours, and then hot rolling the square billets into copper-silver alloy plates with the thickness of 28 mm.
Step three, quenching the hot-rolled copper-silver alloy obtained in the step two, carrying out water quenching on the alloy after the alloy is kept at 720 ℃ for 2h, wherein the lattice constant of a copper phase in the copper-silver alloy after water quenching is 0.36312 nm.
And step four, placing the quenched copper-silver alloy in the step three into a heating furnace, preserving the heat at 450 ℃ for 48 hours, and then air-cooling, wherein the lattice constant of the copper phase in the annealed copper-silver alloy is 0.36182 nm.
Step five, cutting the annealed copper-silver alloy in the step four into rectangular sections with the length-width ratio of 28mm multiplied by 340mm, wherein the height-width ratio is 1, and the length-width ratio is 12.1.
And step six, carrying out acid washing treatment on the copper-silver alloy rectangular section bar obtained in the step five, and removing an oxide layer on the surface of the alloy after acid washing, dehydration and drying.
And step seven, performing roll forming on the copper-silver alloy obtained in the step six, firstly performing 7 passes of rolling by adopting a box type hole pattern system, then performing 4 passes of rolling by adopting an oval-round hole pattern system, and rolling the copper-silver alloy into a round bar with the diameter of 8mm, wherein the total rolling strain is 2.75.
And step eight, carrying out multi-pass drawing on the copper-silver alloy plate obtained in the step seven, wherein the drawing speed of each pass is 0.1m/s, ensuring that the alloy temperature after each pass of drawing is less than 100 ℃ through air cooling, drawing the copper-silver alloy to a wire rod with the diameter of 1mm, and achieving the total drawing strain of 4.15.
Step nine, keeping the temperature of the drawn copper-silver alloy in the heating furnace at 340 ℃ for 18h, and then air-cooling, wherein the lattice constant of the copper phase in the annealed copper-silver alloy is 0.36162nm, and the elongation is 25%.
And step ten, carrying out acid washing treatment on the copper-silver alloy wire rod obtained in the step nine, and removing an oxide layer on the surface of the alloy after acid washing, dehydration and drying.
Step eleven, performing multi-pass drawing on the copper-silver alloy wire rod obtained in the step ten, wherein the drawing speed of each pass is 1m/s, ensuring that the alloy temperature after each pass of drawing is less than 100 ℃ through air cooling, drawing the copper-silver alloy wire rod to a wire rod with the diameter of 0.073mm, wherein the total drawing strain reaches 5.23, and obtaining a finished product of the copper-silver alloy wire rod with high strength and high conductivity after drawing. In the alloy, the average diameter of fibrous crystal grains of the copper matrix phase is 106nm, the average diameter of the Ag phase long fiber with the length-diameter ratio more than 100 is 58nm, and the average diameter of the Ag phase short fiber with the length-diameter ratio less than 100 is 18 nm; the tensile strength of the copper-silver alloy at room temperature reaches 1342MPa, the conductivity reaches 80.8 percent IACS, and the resistivity reaches 2.133 mu omega cm; when the environmental temperature is-196 ℃, the low-temperature tensile strength of the alloy reaches 1764MPa, and the low-temperature resistivity reaches 0.772 mu omega cm.
Example 3
The high-strength high-conductivity copper-silver alloy material comprises Cu, Ag, Sc and La elements and inevitable impurities, wherein the mass ratio of the components is as follows: 25wt.% of Ag element, 0.1wt.% of La element, 0.05wt.% of Sc element, 0.05wt.% of total mass of inevitable impurities, and the balance copper, wherein the mass ratio of Sc to La is 0.5. The preparation method of the copper-silver alloy comprises the following specific process steps:
step one, mixing the components according to the proportionPure copper with the mass purity of 99.95%, pure silver, pure scandium and a copper-lanthanum intermediate alloy with the mass fraction of lanthanum of 10wt.% are filled into a graphite crucible and are put into a vacuum induction melting furnace. First, the degree of vacuum in the vacuum induction melting furnace was controlled to 8.0X 10 -2 Pa below; then argon is introduced into the smelting furnace. The temperature in the furnace is raised to 1120 ℃ under the protection of argon atmosphere, and the metal raw material is melted. After the metal is completely melted, the metal solution is kept warm for 10 minutes, and a square die made of iron with the thickness of 40mm multiplied by 100mm multiplied by L (height multiplied by width multiplied by length) is poured to prepare a copper-silver alloy casting blank.
And step two, cutting the head and the tail of the copper-silver alloy cast ingot obtained in the step one, milling the surface to obtain square billets with the length, the width and the height of 38 mm, 95mm and 300 mm respectively, then putting the square billets into a heating furnace with the temperature of 700 ℃ for heat preservation for 2 hours, and then hot rolling the square billets into copper-silver alloy plates with the thickness of 30 mm.
Step three, quenching the hot-rolled copper-silver alloy in the step two, carrying out water quenching on the alloy after keeping the temperature of 700 ℃ for 4h, wherein the lattice constant of a copper phase in the copper-silver alloy after water quenching is 0.36302 nm.
And step four, placing the quenched copper-silver alloy in the step three into a heating furnace, preserving the heat at 480 ℃ for 48 hours, and then air-cooling, wherein the lattice constant of the copper phase in the annealed copper-silver alloy is 0.36188 nm.
Step five, cutting the annealed copper-silver alloy in the step four into rectangular sections of 30mm multiplied by 32 mm multiplied by 340mm, wherein the aspect ratio is 0.9375, and the aspect ratio is 10.
And step six, carrying out acid washing treatment on the copper-silver alloy rectangular section bar obtained in the step five, and removing an oxide layer on the surface of the alloy after acid washing, dehydration and drying.
And step seven, performing roll forming on the copper-silver alloy obtained in the step six, firstly performing 7 passes of rolling by adopting a box type hole pattern system, then performing 4 passes of rolling by adopting an oval-round hole pattern system, and rolling the copper-silver alloy into a round rod with the diameter of 8mm, wherein the total rolling strain is 2.95.
And step eight, carrying out multi-pass drawing on the copper-silver alloy plate obtained in the step seven, wherein the drawing speed of each pass is 0.1m/s, ensuring that the alloy temperature after each pass of drawing is less than 100 ℃ through air cooling, drawing the copper-silver alloy to a wire rod with the diameter of 1mm, and achieving the total drawing strain of 4.15.
Step nine, keeping the temperature of the drawn copper-silver alloy in the step eight in a heating furnace at 350 ℃ for 16h, and then air-cooling, wherein the lattice constant of the copper phase in the annealed copper-silver alloy is 0.36164nm, and the elongation is 24%.
And step ten, carrying out acid washing treatment on the copper-silver alloy wire rod obtained in the step nine, and removing an oxide layer on the surface of the alloy after acid washing, dehydration and drying.
Step eleven, performing multi-pass drawing on the copper-silver alloy wire rod obtained in the step ten, wherein the drawing speed of each pass is 1m/s, ensuring that the alloy temperature after each pass of drawing is less than 100 ℃ through air cooling, drawing the copper-silver alloy wire rod to a wire rod with the diameter of 0.071mm, and obtaining a finished product of the copper-silver alloy wire rod with high strength and high conductivity after drawing, wherein the total drawing strain reaches 5.29. In the alloy, the average diameter of fibrous crystal grains of the copper matrix phase is 116nm, the average diameter of the Ag phase long fiber with the length-diameter ratio more than 100 is 64nm, and the average diameter of the Ag phase short fiber with the length-diameter ratio less than 100 is 21 nm; the tensile strength of the copper-silver alloy at room temperature reaches 1326MPa, the conductivity reaches 79.5 percent IACS, and the resistivity reaches 2.169 mu omega cm; when the environment temperature is-196 ℃, the low-temperature strength of the alloy reaches 1742MPa, and the low-temperature resistivity reaches 0.791 mu omega cm.
Example 4
The high-strength high-conductivity copper-silver alloy material comprises Cu, Ag, Sc and La elements and inevitable impurities, wherein the mass ratio of the components is as follows: 18.5 wt.% of Ag element, 0.05wt.% of La element, 0.05wt.% of Sc element, 0.05wt.% of the total mass of unavoidable impurities, and the balance copper, wherein the mass ratio of Sc to La is 1. The preparation method of the copper-silver alloy comprises the following specific process steps:
step one, pure copper, pure silver and pure scandium with the mass purity of 99.95 percent and a copper-lanthanum intermediate alloy with the lanthanum mass fraction of 10wt percent are filled into a graphite crucible according to the proportion of the components, and are put into a vacuum induction melting furnace. First, the degree of vacuum in the vacuum induction melting furnace was controlled to 8.0X 10 -2 Pa below; subsequently in the meltingArgon is introduced into the smelting furnace. The temperature in the furnace is raised to 1120 ℃ under the protection of argon atmosphere, and the metal raw material is melted. After the metal is completely melted, the metal solution is kept warm for 10 minutes, and a square die made of iron with the thickness of 40mm multiplied by 100mm multiplied by L (height multiplied by width multiplied by length) is poured to prepare a copper-silver alloy casting blank.
And step two, cutting the head and the tail of the copper-silver alloy cast ingot obtained in the step one, milling the surface to obtain square billets with the length, the width and the height of 38 mm, 95mm and 300 mm respectively, then putting the square billets into a heating furnace with the temperature of 720 ℃ for heat preservation for 2 hours, and then hot rolling the square billets into copper-silver alloy plates with the thickness of 30 mm.
Step three, quenching the hot-rolled copper-silver alloy obtained in the step two, carrying out water quenching on the alloy after keeping the temperature of 720 ℃ for 4h, wherein the lattice constant of a copper phase in the copper-silver alloy after water quenching is 0.36312 nm.
And step four, placing the quenched copper-silver alloy in the step three into a heating furnace, preserving the heat at 480 ℃ for 48 hours, and then air-cooling, wherein the lattice constant of the copper phase in the annealed copper-silver alloy is 0.36188 nm.
Step five, cutting the annealed copper-silver alloy in the step four into rectangular sections of 30mm multiplied by 32 mm multiplied by 340mm, wherein the aspect ratio is 0.9375, and the aspect ratio is 10.
And step six, carrying out acid washing treatment on the copper-silver alloy rectangular section bar obtained in the step five, and removing an oxide layer on the surface of the alloy after acid washing, dehydration and drying.
And step seven, performing roll forming on the copper-silver alloy obtained in the step six, firstly performing 7 passes of rolling by adopting a box type hole pattern system, then performing 4 passes of rolling by adopting an oval-round hole pattern system, and rolling the copper-silver alloy into a round rod with the diameter of 8mm, wherein the total rolling strain is 2.95.
And step eight, carrying out multi-pass drawing on the copper-silver alloy plate obtained in the step seven, wherein the drawing speed of each pass is 0.1m/s, ensuring that the alloy temperature after each pass of drawing is less than 100 ℃ through air cooling, drawing the copper-silver alloy to a wire rod with the diameter of 1mm, and achieving the total drawing strain of 4.15.
Step nine, keeping the temperature of the drawn copper-silver alloy in the heating furnace at 320 ℃ for 16h, and then cooling in air, wherein the lattice constant of the copper phase in the annealed copper-silver alloy is 0.36162nm, and the elongation is 21.5%.
And step ten, carrying out acid washing treatment on the copper-silver alloy wire rod obtained in the step nine, and removing an oxide layer on the surface of the alloy after acid washing, dehydration and drying.
Step eleven, performing multi-pass drawing on the copper-silver alloy wire rod obtained in the step ten, wherein the drawing speed of each pass is 1m/s, ensuring that the alloy temperature after each pass of drawing is less than 100 ℃ through air cooling, drawing the copper-silver alloy wire rod to a wire rod with the diameter of 0.068mm, and obtaining a finished product of the copper-silver alloy wire rod with high strength and high conductivity after drawing, wherein the total drawing strain reaches 5.38. In the alloy, the average diameter of fibrous crystal grains of the copper matrix phase is 102nm, the average diameter of the Ag phase long fiber with the length-diameter ratio more than 100 is 56nm, and the average diameter of the Ag phase short fiber with the length-diameter ratio less than 100 is 18 nm; the tensile strength of the copper-silver alloy at room temperature reaches 1264MPa, the conductivity reaches 80.4 percent IACS, and the resistivity reaches 2.144 mu omega cm; when the ambient temperature is-196 ℃, the low-temperature strength of the alloy reaches 1674MPa, and the low-temperature resistivity reaches 0.778 mu omega cm.
Table 1 shows the chemical compositions, structural characteristics and performance indexes of the copper-silver alloys of the examples and the comparative examples
Figure 526715DEST_PATH_IMAGE001
The above examples are only for illustrating the present invention, and besides, there are many different embodiments, which can be conceived by those skilled in the art after understanding the idea of the present invention, and therefore, they are not listed here.

Claims (6)

1. The preparation method of the copper-silver alloy wire is characterized in that the copper-silver alloy comprises the following components: 18-26 wt.% of Ag, 0.02-0.25wt.% of La, 0.5-1.5 mass ratio of Sc to La and the balance of Cu; the specific process steps comprise:
step one, filling pure copper, pure silver, pure scandium and copper-lanthanum intermediate alloy into a graphite crucible according to the component proportion, and putting the graphite crucible into a vacuum induction melting furnace; firstly, the methodControlling the vacuum degree in the vacuum induction melting furnace to be 8.0 multiplied by 10 -2 Introducing argon or nitrogen into the smelting furnace below Pa; raising the temperature in the furnace to 1100-1250 ℃ under the protection of argon or nitrogen atmosphere, and melting the metal raw material; after the metal is completely melted, preserving the temperature of the metal solution for 10-30 minutes, taking out, pouring into an iron square mould, and preparing a copper-silver alloy casting blank;
step two, cutting the head and the tail of the copper-silver alloy casting blank, milling the surface of the copper-silver alloy casting blank, putting the copper-silver alloy casting blank into a heating furnace at the temperature of 680-720 ℃, preserving the heat for 30min-2h, and hot rolling the copper-silver alloy casting blank into a copper-silver alloy plate, wherein the hot rolling reduction rate is more than 20%;
step three, quenching the copper-silver alloy plate to prepare a quenched copper-silver alloy plate;
fourthly, placing the quenched copper-silver alloy plate in a heating furnace, keeping the temperature within the range of 420-500 ℃ for 20-60 h, and then air-cooling to prepare an annealed copper-silver alloy plate;
step five, cutting the annealed copper-silver alloy plate into rectangular sections, wherein the aspect ratio is between 0.92 and 1, and is greater than or equal to 10;
sixthly, carrying out acid washing treatment on the rectangular section, and removing an oxide layer on the surface of the rectangular section after acid washing, dehydration and drying;
step seven, performing roll forming on the rectangular bar to roll the rectangular bar into a bar with a circular section, wherein the total rolling strain is 2-4;
step eight, drawing the bar material for a plurality of times to form a wire material, wherein the drawing temperature is less than 120 ℃, the drawing speed is 0.05-0.5m/s, and the total drawing strain is 3-6;
step nine, putting the wire into a heating furnace, keeping the temperature within the temperature range of 320-380 ℃ for 8-20 h, and then air-cooling to prepare an annealed copper-silver alloy wire;
step ten, carrying out acid washing treatment on the annealed copper-silver alloy wire, and removing an oxide layer on the surface of the wire after acid washing, dehydration and drying;
step eleven, drawing the wire rod for a plurality of times to obtain a finished wire rod product, wherein the drawing temperature is less than 120 ℃, the drawing speed is 0.5-10m/s, and the total drawing strain is more than 3.
2. The method for preparing the copper-silver alloy wire rod according to claim 1, wherein the mass purities of the pure copper, the pure silver and the pure scandium in the step one are not less than 99.95%, and the impurity content in the copper-lanthanum intermediate alloy is not more than 0.1%.
3. The method of manufacturing the copper-silver alloy wire according to claim 1, wherein the lattice constant of the copper matrix in the alloy of the quenched copper-silver alloy sheet in step three is in the range of 0.36291nm to 0.36312 nm.
4. The method of manufacturing the copper-silver alloy wire according to claim 1, wherein the lattice constant of the copper matrix in the alloy of the annealed copper-silver alloy sheet in the fourth step is in the range of 0.36178nm to 0.36191 nm.
5. The method of making a copper-silver alloy wire according to claim 1, wherein the annealed copper-silver alloy wire in step nine has a lattice constant of a copper matrix in a range of 0.3616nm to 0.36172 nm.
6. The method of producing a copper-silver alloy wire according to claim 1, wherein the average diameter of the crystal grains of the fibrous Cu phase of the copper matrix in the finished wire is in the range of 50nm to 200nm, the average diameter of the long Ag phase fibers having an aspect ratio of more than 100 is in the range of 20 to 150nm, and the average diameter of the short Ag phase fibers having an aspect ratio of less than 100 is in the range of 5 to 50 nm.
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