CN114657410B - High-strength high-conductivity copper-iron alloy and preparation method thereof - Google Patents

High-strength high-conductivity copper-iron alloy and preparation method thereof Download PDF

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CN114657410B
CN114657410B CN202210356144.5A CN202210356144A CN114657410B CN 114657410 B CN114657410 B CN 114657410B CN 202210356144 A CN202210356144 A CN 202210356144A CN 114657410 B CN114657410 B CN 114657410B
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CN114657410A (en
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龚深
于翔宇
陶辉锦
李周
邱文婷
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Central South University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B23P15/00Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/0081Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for slabs; for billets
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    • 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
    • C22C9/10Alloys based on copper with silicon as the next major constituent
    • 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

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Abstract

The invention provides a high-strength high-conductivity copper-iron alloy which comprises the following components in percentage by weight: fe: 0.5 to 5.0 wt%, Si: 0.05 to 0.5wt%, Mg: 0.05 to 0.5wt%, Cr: less than or equal to 0.5wt%, Zr: less than or equal to 0.15wt%, Ca: less than or equal to 0.15wt percent, and the balance of Cu; the preparation method of the high-strength high-conductivity copper-iron alloy comprises the following steps: smelting alloy components, and casting to obtain a copper alloy ingot; carrying out homogenization annealing at 920-970 ℃ for 24-48 h; rolling-combined aging heat treatment, after rolling, performing combined aging heat treatment at 300-500 ℃ on the blank, repeating the rolling-aging treatment process for two or more times, and finally performing stress relief annealing on the plate at 200-300 ℃ for 4-5h to prepare the high-strength high-conductivity copper-iron alloy.

Description

High-strength high-conductivity copper-iron alloy and preparation method thereof
Technical Field
The invention relates to the technical field of copper alloy processing, in particular to a high-strength high-conductivity copper-iron alloy and a preparation method thereof.
Background
With the development of science and technology, copper alloy is widely applied to more than two hundred fields due to excellent electric conduction and heat conduction performance, mechanical property and processing performance, and the relevance of the copper alloy industry and other industries is as high as more than 90%. The copper-iron alloy not only has the excellent performances of electric conduction, heat conduction, easy processing, antibiosis and the like of the traditional copper alloy, but also has better electromagnetic shielding performance and more economic price. Therefore, the copper-iron alloy has wide application markets in various fields, and particularly, the Cu-Fe alloy is widely applied to products such as integrated circuit lead frames, connector contacts, contact bridges, vacuum devices and the like. The invention patent CN111424188A discloses that the copper-iron alloy plate is prepared by using a powder metallurgy method, and the mechanical property and the electrical conductivity of the copper-iron alloy plate cannot be optimized due to the interface resistance between the powders and the compactness of the material. The invention patent CN109022896A and the invention patent CN111636010A disclose methods for preparing high-iron content, high-strength and high-conductivity copper-iron alloy by casting, but because of the low solid solubility of iron in copper, the copper-iron alloy produced by smelting is very uneven, and the mechanical properties are deteriorated.
Therefore, the development of the copper-iron alloy with high strength and high conductivity is far from the right.
Disclosure of Invention
The invention aims to solve the technical problem of providing the high-strength high-conductivity copper-iron alloy, wherein the tensile strength can reach 720-740MPa, the electric conductivity can reach 70-72% IACS, and the balance between the alloy strength and the electric conductivity is realized.
In order to solve the problems, the technical scheme of the invention is as follows:
a high-strength high-conductivity copper-iron alloy comprises the following components in percentage by weight:
fe: 0.5 to 5.0 wt%, Si: 0.05 to 0.5wt%, Mg: 0.05 to 0.5wt%, Cr: less than or equal to 0.5wt%, Zr: less than or equal to 0.15wt%, Ca: less than or equal to 0.15wt percent, and the balance of Cu;
the preparation method of the high-strength high-conductivity copper-iron alloy comprises the following steps:
step S1, proportioning elements required by the alloy according to design components, smelting in inert gas, and casting to obtain a copper alloy ingot;
step S2, carrying out homogenization annealing on the copper alloy ingot casting in the step S1, wherein the annealing temperature is 920-970 ℃, the annealing time is 24-48h, and the homogenized ingot casting is cooled to 800-900 ℃;
step S3, rolling-combined aging heat treatment, after rolling, performing combined aging heat treatment at the temperature of 300-;
wherein the total deformation of hot rolling cogging of the rolling process is 70-80%, and the total deformation of cold rolling is 70-90%.
Further, in step S1, electrolytic copper, pure iron, pure silicon, pure chromium, a copper-magnesium intermediate alloy, a copper-zirconium intermediate alloy, and a copper-calcium intermediate alloy are selected as raw materials.
Further, the copper-magnesium intermediate alloy is a Cu-30Mg intermediate alloy, the copper-zirconium intermediate alloy is a Cu-50Zr intermediate alloy, and the copper-calcium intermediate alloy is a Cu-50Ca intermediate alloy.
Further, in step S3, the time of the combined aging heat treatment for the last aging heat treatment is 16-32h, and the time of the rest aging heat treatment is 1-2 h.
Further, in step S1, melting is performed by using a vacuum melting furnace with a vacuum degree of 10 -5 -10 -3 Pa, the inert gas is high-purity argon; in the smelting process, a low-frequency magnetic field generated by an induction smelting furnace is adopted to stir the melt.
The invention also provides a preparation method of the high-strength high-conductivity copper-iron alloy, which comprises the following steps:
step S1, proportioning the elements required by the alloy according to the design components, smelting in inert gas, and casting to obtain a copper alloy ingot;
the alloy comprises the following components in percentage by weight:
fe: 0.5-5.0 wt%, Si: 0.05 to 0.5wt%, Mg: 0.05 to 0.5wt%, Cr: less than or equal to 0.5wt%, Zr: less than or equal to 0.15wt%, Ca: less than or equal to 0.15wt percent, and the balance of Cu;
step S2, carrying out homogenization annealing on the copper alloy ingot casting in the step S1, wherein the annealing temperature is 920-970 ℃, the annealing time is 24-48h, and the homogenized ingot casting is cooled to 800-900 ℃;
step S3, rolling and combined aging heat treatment, after rolling, performing combined aging heat treatment at 200-500 ℃ on the blank, repeating the rolling-aging treatment process for two or more times, and finally performing stress relief annealing on the plate at 200-300 ℃ for 4-5h to prepare the high-strength high-conductivity copper-iron alloy;
wherein the total deformation of hot rolling cogging of the rolling process is 70-80%, and the total deformation of cold rolling is 70-90%.
Further, in step S1, electrolytic copper, pure iron, pure silicon, pure chromium, copper-magnesium intermediate alloy, copper-zirconium intermediate alloy, and copper-calcium intermediate alloy are selected as raw materials; wherein the copper-magnesium intermediate alloy is a Cu-30Mg intermediate alloy, the copper-zirconium intermediate alloy is a Cu-50Zr intermediate alloy, and the copper-calcium intermediate alloy is a Cu-50Ca intermediate alloy.
Furthermore, in step S3, the time of the combined aging heat treatment for the last aging heat treatment is 16-32h, and the time of the rest aging heat treatment is 1-2 h.
Compared with the prior art, the high-strength high-conductivity copper-iron alloy and the preparation method thereof provided by the invention have the beneficial effects that:
according to the high-strength high-conductivity copper-iron alloy and the preparation method thereof, provided by the invention, the grain refinement and the spheroidization of precipitated phases are promoted by utilizing the micro-alloying of Mg, Si, Cr, Zr and Ca, and the FeSi phase, the CuCa phase and the Cr phase precipitated from the alloy are pinned at the grain boundary in the combined aging heat treatment, so that the mechanical property of the alloy is improved. Meanwhile, the addition of microalloying elements promotes the precipitation of a primary iron phase in the casting and solidification process, and a semi-generated CuCa phase beside the primary iron phase inhibits the growth of the primary iron phase. Along with the subsequent cold deformation processing, the micron-sized primary iron phase and the associated CuCa phase are crushed into a submicron-sized second phase, the mechanical property of the alloy is strengthened from multiple scales with the nanoscale iron phase and the nanoscale chromium phase which are separated out by the combined deformation aging heat treatment process, and the separated iron phase promotes the improvement of the electrical conductivity of the alloy. A small amount of Mg element is dissolved in the copper matrix in a solid way, so that the work hardening capacity of the matrix can be greatly improved on the basis of small loss of the conductive capacity. The high-strength high-conductivity copper-iron alloy disclosed by the invention realizes the synergistic improvement of the tensile strength and the electric conductivity by fully utilizing solid solution strengthening, precipitation strengthening, fine grain strengthening and work hardening, the tensile strength can reach 720-750MPa, the electric conductivity can reach 70-72% IACS, and the balance of the alloy strength and the electric conductivity is realized.
According to the high-strength high-conductivity copper-iron alloy and the preparation method thereof, provided by the invention, the alloy component is designed with low content of iron, so that the production difficulty of preparing the strip foil by using the common smelting process for the copper-iron alloy is greatly reduced, the macroscopic defects of the strip foil of the copper-iron alloy are reduced, and the alloy performance is more stable. The preparation method of the alloy has simple and feasible process and low cost, and is suitable for large-scale industrial production.
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In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a view showing an as-cast microstructure in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of backscattered electrons of the finished sheet of example 1 according to the present invention;
FIG. 3 is a drawing graph of a finished sheet in example 1 of the present invention;
FIG. 4 is a microstructure view of tensile fracture of the product plate in example 1 of the present invention.
Detailed Description
The following description of the present invention is provided to enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention and to make the above objects, features and advantages of the present invention more comprehensible.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The high-strength high-conductivity copper-iron alloy comprises the following components in percentage by weight:
fe: 0.5 to 5.0 wt%, Si: 0.05 to 0.5wt%, Mg: 0.05 to 0.5wt%, Cr: less than or equal to 0.5wt%, Zr: less than or equal to 0.15wt%, Ca: less than or equal to 0.15wt percent, and the balance of Cu;
the components adopt electrolytic copper, pure iron, pure silicon, pure chromium, copper-magnesium intermediate alloy, copper-zirconium intermediate alloy and copper-calcium intermediate alloy as raw materials, wherein the copper-magnesium intermediate alloy is preferably an intermediate alloy of Cu-30Mg, the copper-zirconium intermediate alloy is preferably an intermediate alloy of Cu-50Zr, and the copper-calcium intermediate alloy is preferably an intermediate alloy of Cu-50 Ca.
The preparation method of the high-strength high-conductivity copper-iron alloy comprises the following steps:
step S1, proportioning elements required by the alloy according to design components, smelting in inert gas, and casting to obtain Cu-Fe-Mg-Si-Cr-Zr-Ca copper alloy cast ingots;
specifically, a vacuum melting furnace is adopted for melting, and the vacuum degree is 10 -5 -10 -3 Pa, the inert gas is high-purity argon; in the smelting process, a low-frequency magnetic field generated by an induction smelting furnace is adopted to stir the melt; controlling the furnace temperature at 1450 and 1500 ℃ in the smelting process; wherein the smelting temperature can be 1450 ℃, 1480 ℃ or 1500 ℃, and can also be other temperature values in the range;
after smelting, cooling the molten copper alloy to 1250 ℃ for casting, wherein a graphite mold is used as a casting mold;
step S2, performing homogenization annealing on the copper alloy ingot casting in the step S1, wherein the annealing temperature is 920-970 ℃, the annealing time is 24-48h, and the homogenized ingot casting is cooled to 800-900 ℃;
specifically, the annealing temperature may be 920 ℃, 930 ℃, 940 ℃, 950 ℃, 960 ℃ or 970 ℃, or may be other temperature values within the range;
the annealing time can be 24h, 28h, 32h, 36h, 40h, 44h or 48h, and can also be other time values in the range;
the temperature for cooling the ingot after homogenization can be 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃ or 900 ℃, and can also be other temperature values in the range;
step S3, rolling-combined aging heat treatment, after rolling, performing combined aging heat treatment at the temperature of 300-;
wherein the total deformation of hot rolling cogging of the rolling process is 70-80%, and the total deformation of cold rolling is 70-90%.
Specifically, the temperature of the combined aging heat treatment can be 300 ℃, 350 ℃, 400 ℃, 450 ℃ or 500 ℃, and can also be other temperature values in the temperature range;
preferably, the final aging heat treatment time is 16 to 32 hours, such as 16 hours, 20 hours, 24 hours, 28 hours, or 32 hours, or other values within this range, with the remaining aging heat treatment time being 1 to 2 hours, such as 1 hour, 1.5 hours, or 2 hours;
the stress relief annealing temperature can be 200 ℃, 220 ℃, 250 ℃, 260 ℃, 280 ℃ or 300 ℃, and can also be other temperature values in the range; the stress relief annealing time may be 4 hours, 4.5 hours, or 5 hours, or may be other time values within this range.
The high-strength high-conductivity copper-iron alloy prepared by the invention is a double 70 series copper alloy with the tensile strength of more than 700MPa and the electric conductivity of more than 70% IACS.
The high-strength high-conductivity copper-iron alloy and the preparation method thereof according to the present invention will be described in detail by specific examples.
Example 1
A high-strength high-conductivity copper-iron alloy comprises the following components in percentage by weight:
fe: 2.5 wt%, Si: 0.2 wt%, Mg: 0.3 wt%, Cr: 0.2 wt%, Zr: 0.1 wt%, Ca: 0.05 wt%, the balance being Cu;
electrolytic copper, pure iron, pure silicon, pure chromium, copper-magnesium intermediate alloy, copper-zirconium intermediate alloy and copper-calcium intermediate alloy are selected as raw materials; preferably, the copper-magnesium intermediate alloy is a Cu-30Mg intermediate alloy, the copper-zirconium intermediate alloy is a Cu-50Zr intermediate alloy, and the copper-calcium intermediate alloy is a Cu-50Ca intermediate alloy.
The preparation method of the high-strength high-conductivity copper-iron alloy of the embodiment comprises the following steps:
(1) vacuum smelting: the preparation method comprises the steps of proportioning according to the alloy components, adding the proportioned raw materials into a graphite crucible, melting the raw materials by using a vacuum induction furnace, using high-purity argon for protection, fully stirring by using a low-frequency magnetic field in the melting process, controlling the furnace temperature at 1450-1500 ℃, and controlling the vacuum degree at 10- -5 -10 -3 Pa;
(2) Cooling the molten copper alloy to 1250 ℃ for casting, wherein a graphite mold is used as a casting mold;
(3) milling a surface: milling oxide layers and casting defects of the head, the tail and the surface of the cast ingot by using a numerical control milling machine;
(4) homogenizing and annealing: placing the cast ingot in a 950 ℃ resistance furnace, and carrying out homogenization annealing treatment for 24 hours;
(5) rolling-combined aging heat treatment: carrying out three times of cold rolling-aging treatment on the cast ingot, wherein the deformation of the three times of cold rolling is more than 80%, the temperature of the first time of aging treatment is 500 ℃, the treatment time is 2 hours, the temperature of the second time of aging treatment is 450 ℃, the treatment time is 1 hour, the temperature of the third time of aging treatment is 350 ℃, the treatment time is 32 hours, further rolling and crushing iron phases through large deformation, accumulating deformation energy for the subsequent aging process, and promoting the precipitation of various precipitated phases; wherein the total deformation of hot rolling cogging of the rolling process is 70-80%, and the total deformation of cold rolling is 70-90%;
(6) finish rolling: cleaning, straightening and trimming a cold-rolled sheet finished product to obtain a sheet, strip and foil finished alloy sheet, wherein the finish rolling deformation is 50%;
(7) annealing: and (3) performing stress relief annealing on the finish-rolled plate for 4 hours at 200 ℃, and obtaining the high-strength high-conductivity copper-iron alloy by adopting gas protection.
The alloy ingot prepared in this example was sampled and observed by a metallographic microscope, and a typical as-cast structure photograph of the alloy is shown in fig. 1. As can be seen from figure 1, the crystal grains in the alloy are fine and uniform, and a little dispersed and uniform primary iron-silicon phase and copper-calcium phase exist among the crystal grains.
Referring to fig. 2, a back-scattered electron scanning electron microscope (sem) picture of the sheet material obtained in example 1 of the present invention is shown, and it can be seen from fig. 2 that the primary phase existing in the as-cast state in the alloy is significantly elongated and broken.
Please refer to fig. 3 and fig. 4 in combination, wherein fig. 3 is a drawing graph of the finished plate in example 1 of the present invention; FIG. 4 is a microstructure view of a tensile fracture of the finished sheet in example 1 of the present invention; as can be seen from FIG. 3, the tensile strength of the finished plate of the embodiment is up to 732 MPa; as can be seen from FIG. 4, the fracture mode of the alloy is quasi-cleavage fracture, the fracture surface of the quasi-cleavage fracture is relatively flat, a cleavage step appears, and a large number of large-sized dimples are formed, which means that the elongation of the alloy is relatively good.
Example 2
A high-strength high-conductivity copper-iron alloy comprises the following components in percentage by weight:
fe: 2.0 wt%, Si: 0.2 wt%, Mg: 0.3 wt%, Cr: 0.2 wt%, Zr: 0.05 wt%, Ca: 0.01wt%, the balance being Cu;
the components adopt electrolytic copper, pure iron, pure silicon, pure chromium, copper-magnesium intermediate alloy, copper-zirconium intermediate alloy and copper-calcium intermediate alloy as raw materials.
The preparation process of the high-strength and high-conductivity copper-iron alloy of the present example is the same as that of example 1.
Example 3
A high-strength high-conductivity copper-iron alloy comprises the following components in percentage by weight:
fe: 5wt%, Si: 0.5wt%, Mg: 0.05 wt%, Cr: 0.4 wt%, Zr: 0.04 wt%, Ca: 0.01wt%, the balance being Cu;
electrolytic copper, pure iron, pure silicon, pure chromium, copper-magnesium intermediate alloy, copper-zirconium intermediate alloy and copper-calcium intermediate alloy are selected as raw materials; preferably, the copper-magnesium intermediate alloy is a Cu-30Mg intermediate alloy, the copper-zirconium intermediate alloy is a Cu-50Zr intermediate alloy, and the copper-calcium intermediate alloy is a Cu-50Ca intermediate alloy.
The preparation process of the high-strength and high-conductivity copper-iron alloy of the present example is the same as that of example 1.
Example 4
A high-strength high-conductivity copper-iron alloy comprises the following components in percentage by weight:
fe: 0.5wt%, Si: 0.1 wt%, Mg: 0.5wt%, Cr: 0.5wt%, Zr: 0.15wt%, Ca: 0.15wt%, the balance being Cu;
electrolytic copper, pure iron, pure silicon, pure chromium, copper-magnesium intermediate alloy, copper-zirconium intermediate alloy and copper-calcium intermediate alloy are selected as raw materials; preferably, the copper-magnesium intermediate alloy is a Cu-30Mg intermediate alloy, the copper-zirconium intermediate alloy is a Cu-50Zr intermediate alloy, and the copper-calcium intermediate alloy is a Cu-50Ca intermediate alloy.
The preparation process of the high-strength and high-conductivity copper-iron alloy of the present example is the same as that of example 1.
Example 5
A high-strength high-conductivity copper-iron alloy comprises the following components in percentage by weight:
fe: 1.5 wt%, Si: 0.05 wt%, Mg: 0.2 wt%, Cr: 0.3 wt%, Zr: 0.08 wt%, Ca: 0.04 wt%, the balance being Cu;
electrolytic copper, pure iron, pure silicon, pure chromium, copper-magnesium intermediate alloy, copper-zirconium intermediate alloy and copper-calcium intermediate alloy are selected as raw materials; preferably, the copper-magnesium intermediate alloy is a Cu-30Mg intermediate alloy, the copper-zirconium intermediate alloy is a Cu-50Zr intermediate alloy, and the copper-calcium intermediate alloy is a Cu-50Ca intermediate alloy.
The preparation process of the high-strength and high-conductivity copper-iron alloy of the present example is the same as that of example 1.
Comparative example 1
A copper alloy comprises the following components in percentage by weight:
fe: 2.5 wt%, Si: 0.2 wt%, and the balance being Cu; the components are electrolytic copper, pure iron and pure silicon in proportion.
The copper alloy of this example was prepared by the same process as in example 1.
Comparative example 2
A copper alloy comprises the following components in percentage by weight:
fe: 2.5 wt%, Si: 0.2 wt%, Cr: 0.2 wt%, Zr: 0.08 wt%, the balance being Cu; the components are selected from electrolytic copper, pure iron, pure silicon, pure chromium and copper-zirconium intermediate alloy.
The copper alloy of this example was prepared by the same process as in example 1.
The high-strength and high-conductivity CuFeMgSiCrZrCa alloy of examples 1-5 and the copper alloy prepared in comparative examples 1-2 were subjected to performance tests, and the test results are shown in Table 1:
table 1: performance Table of copper alloy obtained in each embodiment
Figure BDA0003583003150000081
Figure BDA0003583003150000091
As can be seen from Table 1, the addition of Mg and Ca can greatly improve the strength of the alloy on the basis of small reduction of the conductivity, so that the conductivity and the strength performance of the alloy are improved in a relatively balanced manner, and the comprehensive performance of the copper-iron alloy is improved.
Compared with the prior art, the high-strength high-conductivity copper-iron alloy and the preparation method thereof have the beneficial effects that:
according to the high-strength high-conductivity copper-iron alloy and the preparation method thereof, provided by the invention, the grain refinement and the spheroidization of precipitated phases are promoted by utilizing the micro-alloying of Mg, Si, Cr, Zr and Ca, and the FeSi phase, the CuCa phase and the Cr phase precipitated from the alloy are pinned at the grain boundary in the combined aging heat treatment, so that the mechanical property of the alloy is improved. Meanwhile, the addition of microalloying elements promotes the precipitation of a primary iron phase during casting and solidification, and a semi-grown CuCa phase beside the primary iron phase inhibits the growth of the primary iron phase. Along with the subsequent cold deformation processing, the micron-sized primary iron phase and the associated CuCa phase are crushed into a submicron-sized second phase, and the mechanical property of the alloy is strengthened from multiple scales with the nanoscale iron phase and the nanoscale chromium phase separated out in the combined deformation aging heat treatment process, and the separated-out iron phase promotes the improvement of the electrical conductivity of the alloy. A small amount of Mg element is dissolved in the copper matrix in a solid way, so that the work hardening capacity of the matrix can be greatly improved on the basis of small loss of the conductive capacity. The high-strength high-conductivity copper-iron alloy disclosed by the invention realizes the synergistic improvement of the tensile strength and the electric conductivity by fully utilizing solid solution strengthening, precipitation strengthening, fine grain strengthening and work hardening, the tensile strength can reach 720-750MPa, the electric conductivity can reach 70-72% IACS, and the balance of the alloy strength and the electric conductivity is realized.
According to the high-strength high-conductivity copper-iron alloy and the preparation method thereof, provided by the invention, the alloy component is designed with low content of iron, so that the production difficulty of preparing the strip foil by using the common smelting process for the copper-iron alloy is greatly reduced, the macroscopic defects of the strip foil of the copper-iron alloy are reduced, and the alloy performance is more stable. The preparation method of the alloy has simple and feasible process and low cost, and is suitable for large-scale industrial production.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and these embodiments are therefore considered to be within the scope of the invention.

Claims (6)

1. The high-strength high-conductivity copper-iron alloy is characterized by comprising the following components in percentage by weight:
fe: 0.5 to 5.0 wt%, Si: 0.05 to 0.5wt%, Mg: 0.05 to 0.5 weight percent, more than or equal to 0.2 weight percent and less than or equal to 0.5 weight percent of Cr, more than or equal to 0.04 weight percent and less than or equal to 0.15 weight percent of Zr, more than or equal to 0.01 weight percent and less than or equal to 0.15 weight percent of Ca, and the balance of Cu;
the preparation method of the high-strength high-conductivity copper-iron alloy comprises the following steps:
step S1, proportioning the elements required by the alloy according to the design components, smelting in inert gas, and casting to obtain a copper alloy ingot;
step S2, carrying out homogenization annealing on the copper alloy ingot casting in the step S1, wherein the annealing temperature is 920-970 ℃, the annealing time is 24-48h, and the homogenized ingot casting is cooled to 800-900 ℃;
step S3, the total deformation of hot rolling cogging of the rolling process is 70-80%, and the total deformation of cold rolling is 70-90%; after cold rolling, the blank is subjected to aging heat treatment at the temperature of 300-500 ℃, and the cold rolling-aging treatment process is repeated for two or more times; cleaning, straightening and trimming a cold-rolled sheet finished product to obtain a sheet, strip and foil finished alloy sheet, wherein the finish rolling deformation is 50%; finally, the plate is subjected to stress relief annealing at the temperature of 200-300 ℃ for 4-5h to prepare the high-strength high-conductivity copper-iron alloy;
the final aging heat treatment time is 16-32h, and the rest aging heat treatment time is 1-2 h.
2. The high-strength high-conductivity copper-iron alloy according to claim 1, wherein in step S1, electrolytic copper, pure iron, pure silicon, pure chromium, copper-magnesium intermediate alloy, copper-zirconium intermediate alloy, and copper-calcium intermediate alloy are selected as raw materials.
3. The high-strength high-conductivity copper-iron alloy according to claim 2, wherein the copper-magnesium master alloy is a Cu-30Mg master alloy, the copper-zirconium master alloy is a Cu-50Zr master alloy, and the copper-calcium master alloy is a Cu-50Ca master alloy.
4. The high-strength high-conductivity copper-iron alloy according to claim 1, wherein in step S1, melting is performed by using a vacuum melting furnace with a vacuum degree of 10 -5 -10 -3 Pa, the inert gas is high-purity argon; in the smelting process, a low-frequency magnetic field generated by an induction smelting furnace is adopted to stir the melt.
5. A preparation method of a high-strength high-conductivity copper-iron alloy is characterized by comprising the following steps:
step S1, proportioning the elements required by the alloy according to the design components, smelting in inert gas, and casting to obtain a copper alloy ingot;
the alloy comprises the following components in percentage by weight:
fe: 0.5 to 5.0 wt%, Si: 0.05 to 0.5wt%, Mg: 0.05 to 0.5 weight percent, more than or equal to 0.2 weight percent and less than or equal to 0.5 weight percent of Cr, more than or equal to 0.04 weight percent and less than or equal to 0.15 weight percent of Zr, more than or equal to 0.01 weight percent and less than or equal to 0.15 weight percent of Ca, and the balance of Cu;
step S2, carrying out homogenization annealing on the copper alloy ingot casting in the step S1, wherein the annealing temperature is 920-970 ℃, the annealing time is 24-48h, and the homogenized ingot casting is cooled to 800-900 ℃;
step S3, the total deformation of hot rolling cogging of the rolling process is 70-80%, and the total deformation of cold rolling is 70-90%; after cold rolling, the blank is subjected to aging heat treatment at the temperature of 300-500 ℃, and the cold rolling-aging treatment process is repeated for two or more times; cleaning, straightening and trimming a cold-rolled sheet finished product to obtain a sheet, strip and foil finished alloy sheet, wherein the finish rolling deformation is 50%; finally, the plate is subjected to stress relief annealing at the temperature of 200-300 ℃ for 4-5h to prepare the high-strength high-conductivity copper-iron alloy;
the final aging heat treatment time is 16-32h, and the rest aging heat treatment time is 1-2 h.
6. The method for preparing the high-strength high-conductivity copper-iron alloy according to claim 5, wherein in step S1, electrolytic copper, pure iron, pure silicon, pure chromium, a copper-magnesium intermediate alloy, a copper-zirconium intermediate alloy and a copper-calcium intermediate alloy are selected as raw materials; wherein the copper-magnesium intermediate alloy is an intermediate alloy of Cu-30Mg, the copper-zirconium intermediate alloy is an intermediate alloy of Cu-50Zr, and the copper-calcium intermediate alloy is an intermediate alloy of Cu-50 Ca.
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CN115870665B (en) * 2022-12-21 2024-09-17 宁波鑫悦合金材料有限公司 Copper-iron welding wire and preparation method and application thereof
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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54101712A (en) * 1978-01-27 1979-08-10 Furukawa Electric Co Ltd:The Manufacture of high tensile, highly electrically conductive copper alloy
CN1626692A (en) * 2003-12-12 2005-06-15 中国科学院金属研究所 Copper, iron and chrome ternary copper base alloy
JP2012188709A (en) * 2011-03-11 2012-10-04 Japan Steel Works Ltd:The High-strength and high-conductivity two-phase copper alloy and method for manufacturing the same
JP2012207246A (en) * 2011-03-29 2012-10-25 Kobe Steel Ltd Copper alloy for electromagnetic shielding material and method for producing the same
CN102782168A (en) * 2010-02-08 2012-11-14 株式会社豊山 Copper alloy having high strength and high conductivity, and preparation method thereof
CN105102157A (en) * 2013-03-25 2015-11-25 新日铁住金株式会社 Copper alloy powder, sintered copper alloy body and brake lining for use in high-speed railway
CN105518164A (en) * 2013-08-30 2016-04-20 同和金属技术有限公司 Copper alloy sheet material and method for producing same, and current-carrying component
JP2016079472A (en) * 2014-10-17 2016-05-16 Dowaメタルテック株式会社 Manufacturing method of copper alloy sheet material, copper alloy sheet material, and electrification component
CN109777994A (en) * 2019-04-01 2019-05-21 宁波金田铜业(集团)股份有限公司 A kind of electronic shield copper alloy wire and its preparation method and application
CN111593227A (en) * 2020-07-07 2020-08-28 中南大学 High-conductivity high-strength copper-iron-calcium alloy and preparation method thereof
CN111876626A (en) * 2020-07-16 2020-11-03 中南大学 High-electromagnetic-shielding high-strength high-conductivity CuFeSiCr alloy and preparation method thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54101712A (en) * 1978-01-27 1979-08-10 Furukawa Electric Co Ltd:The Manufacture of high tensile, highly electrically conductive copper alloy
CN1626692A (en) * 2003-12-12 2005-06-15 中国科学院金属研究所 Copper, iron and chrome ternary copper base alloy
CN102782168A (en) * 2010-02-08 2012-11-14 株式会社豊山 Copper alloy having high strength and high conductivity, and preparation method thereof
JP2012188709A (en) * 2011-03-11 2012-10-04 Japan Steel Works Ltd:The High-strength and high-conductivity two-phase copper alloy and method for manufacturing the same
JP2012207246A (en) * 2011-03-29 2012-10-25 Kobe Steel Ltd Copper alloy for electromagnetic shielding material and method for producing the same
CN105102157A (en) * 2013-03-25 2015-11-25 新日铁住金株式会社 Copper alloy powder, sintered copper alloy body and brake lining for use in high-speed railway
CN105518164A (en) * 2013-08-30 2016-04-20 同和金属技术有限公司 Copper alloy sheet material and method for producing same, and current-carrying component
JP2016079472A (en) * 2014-10-17 2016-05-16 Dowaメタルテック株式会社 Manufacturing method of copper alloy sheet material, copper alloy sheet material, and electrification component
CN109777994A (en) * 2019-04-01 2019-05-21 宁波金田铜业(集团)股份有限公司 A kind of electronic shield copper alloy wire and its preparation method and application
CN111593227A (en) * 2020-07-07 2020-08-28 中南大学 High-conductivity high-strength copper-iron-calcium alloy and preparation method thereof
CN111876626A (en) * 2020-07-16 2020-11-03 中南大学 High-electromagnetic-shielding high-strength high-conductivity CuFeSiCr alloy and preparation method thereof

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