CN110951990B - Cu-Ni-Co-Fe-Si-Zr-Zn copper alloy material and preparation method thereof - Google Patents
Cu-Ni-Co-Fe-Si-Zr-Zn copper alloy material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 78
- 230000032683 aging Effects 0.000 claims abstract description 43
- 238000005096 rolling process Methods 0.000 claims abstract description 42
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- 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
- C22F1/02—Changing 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
-
- 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
-
- 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
- C22F3/00—Changing the physical structure of non-ferrous metals or alloys by special physical methods, e.g. treatment with neutrons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B2003/005—Copper or its alloys
Abstract
The invention discloses a Cu-Ni-Co-Fe-Si-Zr-Zn copper alloy material and a preparation method thereof. The copper alloy material comprises the following components: 2.0-3.0 wt% of Ni; 0.3-0.8 wt% of Co; 0.3 to 0.8 wt% Fe; 0.5 to 1.1 wt% of Si; 0.1 to 0.2 wt% of Zr; 0.1-0.3 wt% of Zn; the balance being Cu. The preparation method of the copper alloy material comprises the following steps: alloy casting → homogenization treatment → hot rolling → solution treatment → cryogenic rolling → pulsed magnetic field aging treatment. The copper alloy material disclosed by the invention is high in yield strength, tensile strength and conductivity, high in elongation after fracture, and good in comprehensive mechanical property and conductivity. In addition, the copper alloy material disclosed by the invention does not contain toxic elements, is rich in raw material source, does not generate toxic compounds in the preparation process, and is small in harm to human bodies and environment.
Description
Technical Field
The invention belongs to the technical field of copper alloy materials, and particularly relates to a Cu-Ni-Co-Fe-Si-Zr-Zn copper alloy material and a preparation method thereof.
Background
In the electronic industry, conductive elastic elements are developing towards miniaturization and high performance, and the copper alloy materials used are required to have higher strength, better conductivity and good processability. At present, the use amount of age-strengthened copper alloys (such as CuBe, CuNiSi, etc.) is increasing, and solid-solution strengthened copper alloys (such as CuZn, CuSnP, etc.) have been gradually replaced. The aging strengthening type copper alloy is characterized in that one or more other alloy elements are added into a copper matrix, a supersaturated solid solution is formed through solution treatment, solid solution atoms are precipitated from the supersaturated solid solution in the form of intermetallic compounds through aging treatment, and the precipitated phases can block the movement of dislocation and the migration of grain boundaries, so that the strength of the copper alloy is effectively improved. Meanwhile, the electrical conductivity of the copper alloy can be correspondingly improved due to the precipitation of solid solution atoms.
In the aging strengthening type copper alloy, the CuBe alloy has high strength, high elasticity, high wear resistance and good conductivity. However, beryllium and beryllium compounds are toxic to human bodies and can harm the health of workers and destroy the environment during the preparation and processing of the CuBe alloy. Therefore, studies have been made to develop an age-strengthened copper alloy containing no beryllium, such as a CuNiSi alloy and a CuTi alloy. However, the strength and the electrical conductivity of the age-strengthened copper alloy are contradictory, and have such an inverse relationship. In order to improve the strength of copper alloys, alloying elements are often added. However, the addition amount of the alloying elements is too low, and the strength-improving effect is not significant. The addition amount of the alloy elements is too high, the alloy elements cannot be fully precipitated in the aging process, and the conductivity of the alloy elements which are dissolved in the copper matrix can be obviously reduced. If the aging time is prolonged or the aging temperature is raised, although precipitation of alloying elements is facilitated, an overaging phenomenon is caused, which causes a decrease in strength of the material and also causes coarsening of crystal grains, with a consequent deterioration in workability of the material. Therefore, in order to research and develop the aging strengthening type copper alloy material, on one hand, alloy elements need to be reasonably added, and on the other hand, the preparation method of the copper alloy material needs to be improved.
Disclosure of Invention
The invention aims to provide a Cu-Ni-Co-Fe-Si-Zr-Zn copper alloy material and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a Cu-Ni-Co-Fe-Si-Zr-Zn copper alloy material comprises the following components in percentage by mass: 2.0-3.0 wt% of Ni; 0.3-0.8 wt% of Co; 0.3 to 0.8 wt% Fe; 0.5 to 1.1 wt% of Si; 0.1 to 0.2 wt% of Zr; 0.1-0.3 wt% of Zn; the balance being Cu.
Further, in the Cu-Ni-Co-Fe-Si-Zr-Zn copper alloy material, the total mass percentage of (Ni + Co + Fe + Si) is 3.0-5.0 wt%, the total mass percentage of Ni: Co: Fe = (3-10): 1-2, and the total mass percentage of (Ni + Co + Fe) is 3.5-5.5. The sum of the mass percentages of Ni, Co, Fe and Si is 3.0-5.0 wt%, the mass ratio of Ni, Co and Fe is (3-10): (1-2): 1-2), and the sum of the mass percentages of Ni, Co and Fe is the mass percentage of Si = (3.5-5.5): 1.
A preparation method of a Cu-Ni-Co-Fe-Si-Zr-Zn copper alloy material comprises the following steps:
(1) casting of alloy: according to the mass percentage, the raw materials are put into a crucible of an induction furnace to be smelted under the protection of pure argon (Ar is more than or equal to 99.99 percent), then the alloy melt is cast into a mold, and the mold is opened after cooling to take out the alloy ingot. The raw material used for smelting can be bulk raw material with the purity of more than or equal to 99.9 percent (mass percentage), and can also be bulk Cu-X (X can be one or more of Ni, Co, Fe, Si, Zr and Zn) intermediate alloy.
(2) Homogenizing: placing the alloy cast ingot into a heat treatment furnace for homogenization treatment, wherein the homogenization treatment is carried out under the protection of pure argon (Ar is more than or equal to 99.99 percent), the homogenization temperature is 900-1000 ℃, the heat preservation time is 5-12 hours, and then cooling to room temperature.
(3) Hot rolling: heating the homogenized alloy cast ingot to 800-950 ℃ for hot rolling, wherein the total deformation of the hot rolling is 50-80%, the final rolling temperature is controlled to be above 700 ℃, and the alloy material after the final rolling is immediately subjected to water quenching.
(4) Solution treatment: putting the hot-rolled copper alloy material into a heat treatment furnace, carrying out solid solution treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the solid solution temperature is 800-1000 ℃, the heat preservation time is 1-3 hours, then taking out the heat treatment furnace, and immediately carrying out water quenching.
(5) Deep cooling and rolling: milling the surface of the copper alloy material subjected to solid solution, removing surface oxide skin, and then performing deep cooling rolling deformation, wherein the total deformation of the deep cooling rolling is 60-85%, and the rolling temperature is-125-160 ℃. The cooling medium is liquid nitrogen, and the rolling temperature is adjusted by controlling the flow of the cooling medium.
(6) And (3) aging treatment of a pulse magnetic field: the method comprises the steps of carrying out aging treatment on a copper alloy material subjected to cryogenic rolling under a pulsed magnetic field, wherein the aging temperature is 400-500 ℃, the heat preservation time is 1-5 hours, the adopted pulsed magnetic field parameters are the pulse frequency of 10-300 Hz, the pulse peak magnetic field intensity is 0.3-2T, the pulse width is 100-500 mu s, and the aging is carried out under the protection of pure argon (Ar is more than or equal to 99.99%). And after the aging is finished, cooling the copper alloy material to room temperature under the protection of pure argon (Ar is more than or equal to 99.99 percent) to obtain a final finished product.
THE ADVANTAGES OF THE PRESENT INVENTION
(1) According to the invention, Ni, Co and Fe magnetic elements are added in alloy components, Ni, Co and Fe atoms are easier to diffuse in a Cu matrix under the action of a pulse magnetic field in the aging process, the binding energy with Si, Zr and Zn elements is reduced, the precipitation of solid solution elements is promoted, and a fine and dispersed precipitation phase is formed.
(2) The invention carries out deep cooling rolling of the copper alloy at-125 ℃ to-160 ℃ so that more twin crystal structures can be formed in the deformation process of the alloy; meanwhile, Zr element is added into the alloy components, so that the stacking fault energy of the alloy is reduced, and more twin crystal structures can be generated in the deformation process of the copper alloy. The twin grain boundary can effectively block dislocation movement, but its scattering ability for electrons is smaller than that of the conventional grain boundary. Therefore, the twin structure is increased, which is beneficial to improving the alloy strength without obviously reducing the conductive performance of the alloy. In addition, the quantity of point defects and dislocation in the alloy can be effectively increased by cryogenic rolling, more precipitation positions can be provided for precipitated phases in the aging process, the precipitation of solid solution elements is promoted, and the formation of the precipitated phases in fine dispersion distribution is facilitated.
(3) According to the invention, Zn element is added into the alloy components, so that the casting performance can be improved, an alloy ingot with good casting structure can be obtained, and excessive growth of crystal grains in the solution treatment process can be prevented.
(4) The copper alloy material disclosed by the invention is high in yield strength, tensile strength and electric conductivity, high in elongation after fracture, and better in comprehensive mechanical property and electric conductivity than the traditional aging-strengthened CuNiSi alloy material.
(5) The copper alloy material disclosed by the invention does not contain toxic elements, is rich in raw material source, does not generate toxic compounds in the preparation process, and is small in harm to human bodies and environment.
Drawings
FIG. 1 is a metallographic structure of a final product of comparative example 1;
FIG. 2 is a scanning electron microscope image of the final product of comparative example 1;
FIG. 3 is a metallographic structure of a final product of example 1;
FIG. 4 is a scanning electron microscope image of the final product of example 1.
Detailed Description
The invention is further illustrated but not limited by the following examples in connection with comparative examples. The related main test methods and standards of the invention are as follows: according to GB/T4340.1-2009 part 1 of Vickers hardness test of metal materials: test method for measuring the hardness of the copper alloy material; according to GB/T228.1-2010 part 1 of the tensile test of metallic materials: the yield strength, the tensile strength and the elongation after fracture of the copper alloy material are measured by a room temperature test method; the electrical conductivity of the Copper alloy material was measured according to GB/T351-2019 "method for measuring resistivity of metallic Material", and the value was compared with the International Annealed Copper Standard (100% IACS, International interconnected coater Standard).
Comparative example 1
The alloy comprises the following components in percentage by mass: 2.5 wt% Ni, 0.8 wt% Si, and the balance Cu. Cu, Ni, Fe and Si used for smelting are bulk raw materials with the purity of more than or equal to 99.9wt percent.
(1) Casting of alloy: putting the raw materials into a crucible of an induction furnace according to the mass percent, and vacuumizing to 10 DEG- 3Pa, then 1.1X 105Pa pure argon (Ar is more than or equal to 99.99 percent), smelting under the protection of the pure argon, keeping for 10 minutes after the solid is completely melted to form alloy melt, then casting the alloy melt into a graphite mold, cooling, opening the mold, taking out the alloy ingot, wherein the thickness of the ingot is 18 mm.
(2) Homogenizing: putting the cast ingot into a heat treatment furnace, carrying out homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the homogenization temperature is 900 ℃, the heat preservation time is 12 hours, and then cooling to room temperature along with the furnace.
(3) Hot rolling treatment: and heating the ingot after the homogenization treatment to 850 ℃, carrying out hot rolling deformation, wherein the final rolling temperature is 730 ℃, and then carrying out water quenching to obtain a hot-rolled sample with the thickness of 3.6 mm.
(4) Solution treatment: putting the hot rolled sample into a heat treatment furnace, carrying out solid solution treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the solid solution temperature is 880 ℃, the heat preservation time is 2 hours, then taking out the heat treatment furnace, and immediately carrying out water quenching.
(5) Rolling at room temperature: the sample after solid solution treatment is milled to remove a small amount of scale on the surface layer, then rolling deformation is carried out at room temperature (25 ℃), and the thickness of the sample after deep cooling rolling is 0.75 mm.
(6) Aging treatment: and (3) placing the sample rolled at room temperature into a furnace with a heat treatment function, and carrying out aging treatment under the protection of pure argon (Ar is more than or equal to 99.99%). The aging temperature is 450 ℃, and the heat preservation time is 3 hours. And after the aging is finished, cooling the sample to room temperature under the protection of pure argon (Ar is more than or equal to 99.99 percent), and obtaining a final finished product.
The hardness of the final product is 193Hv, the yield strength is 552MPa, the tensile strength is 636MPa, the elongation after fracture is 5 percent, and the conductivity is 39 percent IACS. FIG. 1 is a metallographic photograph showing the structure of the final product of comparative example 1, in which the crystal grains are not uniform in size and a large number of large crystal grains (grain size ≧ 20 μm) are observed. FIG. 2 is a scanning electron micrograph of comparative example 1, from which it can be seen that second-phase precipitates in the copper matrix are flaky, have uneven sizes, and have large second-phase precipitates (the flaky length is not less than 1 μm, and the thickness is not less than 200 nm).
Example 1
The alloy comprises the following components in percentage by mass: 2.5 wt% Ni, 0.5 wt% Co, 0.5 wt% Fe, 0.8 wt% Si, 0.15 wt% Zr, 0.2 wt% Zn, and the balance Cu. Cu, Ni, Fe and Si used for smelting are bulk raw materials with the purity of more than or equal to 99.9wt%, Cu-Zn intermediate alloy containing 20wt% of Zn, Cu-Co intermediate alloy containing 30wt% of Co and Cu-Zr intermediate alloy containing 10wt% of Zr.
(1) Casting of alloy: putting the raw materials into a crucible of an induction furnace according to the mass percent, and vacuumizing to 10 DEG- 3Pa, then 1.1X 105Pa pure argon (Ar is more than or equal to 99.99 percent), smelting under the protection of the pure argon, keeping for 10 minutes after the solid is completely melted to form alloy melt, then casting the alloy melt into a graphite mold, cooling, opening the mold, taking out the alloy ingot, wherein the thickness of the ingot is 18 mm.
(2) Homogenizing: putting the cast ingot into a heat treatment furnace, carrying out homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the homogenization temperature is 900 ℃, the heat preservation time is 12 hours, and then cooling to room temperature along with the furnace.
(3) Hot rolling treatment: and heating the ingot after the homogenization treatment to 850 ℃, carrying out hot rolling deformation, wherein the final rolling temperature is 730 ℃, and then carrying out water quenching to obtain a hot-rolled sample with the thickness of 3.6 mm.
(4) Solution treatment: putting the hot rolled sample into a heat treatment furnace, carrying out solid solution treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the solid solution temperature is 880 ℃, the heat preservation time is 2 hours, then taking out the heat treatment furnace, and immediately carrying out water quenching.
(5) Deep cooling and rolling: and milling the surface of the sample subjected to solid solution to remove a small amount of oxide skin on the surface layer, and then performing deep cold rolling deformation, wherein the rolling temperature is-140 ℃, and the thickness of the sample subjected to deep cold rolling is 0.75 mm.
(6) And (3) aging treatment of a pulse magnetic field: and (3) placing the sample subjected to cryogenic rolling into a heat treatment furnace with a pulsed magnetic field device, and carrying out pulsed magnetic field aging treatment under the protection of pure argon (Ar is more than or equal to 99.99%). The aging temperature is 450 ℃, the heat preservation time is 3 hours, and the adopted pulse magnetic field parameters are pulse frequency of 150Hz, pulse peak magnetic field intensity of 1.5T and pulse width of 300 mus. And after the aging is finished, cooling the sample to room temperature under the protection of pure argon (Ar is more than or equal to 99.99 percent), and obtaining a final finished product.
The hardness of the final product is 285Hv, the yield strength is 721MPa, the tensile strength is 806MPa, the elongation after fracture is 14%, and the conductivity is 51% IACS. FIG. 3 is a metallographic photograph showing the structure of the final product of example 1, which was fine and uniform in size. FIG. 4 is a SEM photograph of example 1 showing that fine and uniform flaky second phases are dispersedly distributed in the copper matrix. Comparing the microstructures of comparative example 1 and example 1, it can be clearly seen that the crystal grains and the second phase precipitates of example 1 are finer and more uniform, and the excellent microstructure is beneficial to improving various performance indexes of the sample.
Example 2
The alloy comprises the following components in percentage by mass: 2.0 wt% Ni, 0.6 wt% Co, 0.3 wt% Fe, 0.6 wt% Si, 0.2 wt% Zr, 0.3 wt% Zn, and the balance Cu. Cu, Ni, Fe and Si used for smelting are bulk raw materials with the purity of more than or equal to 99.9wt%, Cu-Zn intermediate alloy containing 20wt% of Zn, Cu-Co intermediate alloy containing 30wt% of Co and Cu-Zr intermediate alloy containing 10wt% of Zr.
(1) Casting of alloy: putting the raw materials into a crucible of an induction furnace according to the mass percent, and vacuumizing to 10 DEG- 3Pa, then 1.1X 105Pa pure argon (Ar is more than or equal to 99.99 percent), smelting under the protection of the pure argon, keeping for 10 minutes after the solid is completely melted to form alloy melt, then casting the alloy melt into a graphite mold, cooling, opening the mold, taking out the alloy ingot, wherein the thickness of the ingot is 18 mm.
(2) Homogenizing: putting the cast ingot into a heat treatment furnace, carrying out homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the homogenization temperature is 950 ℃, the heat preservation time is 10 hours, and then cooling to room temperature along with the furnace.
(3) Hot rolling treatment: and heating the ingot after the homogenization treatment to 900 ℃, carrying out hot rolling deformation, wherein the final rolling temperature is 750 ℃, and then carrying out water quenching to obtain a hot-rolled sample with the thickness of 5.4 mm.
(4) Solution treatment: putting the hot rolled sample into a heat treatment furnace, carrying out solid solution treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), keeping the solid solution temperature at 850 ℃ for 3 hours, then taking out the heat treatment furnace, and immediately carrying out water quenching.
(5) Deep cooling and rolling: and milling the surface of the sample subjected to solid solution to remove a small amount of oxide skin on the surface layer, and then performing deep cold rolling deformation, wherein the rolling temperature is-160 ℃, and the thickness of the sample subjected to deep cold rolling is 1.5 mm.
(6) And (3) aging treatment of a pulse magnetic field: and (3) placing the sample subjected to cryogenic rolling into a heat treatment furnace with a pulsed magnetic field device, and carrying out pulsed magnetic field aging treatment under the protection of pure argon (Ar is more than or equal to 99.99%). The aging temperature is 400 ℃, the heat preservation time is 2 hours, and the adopted pulse magnetic field parameters are pulse frequency of 10Hz, pulse peak magnetic field intensity of 1T and pulse width of 500 mus. And after the aging is finished, cooling the sample to room temperature under the protection of pure argon (Ar is more than or equal to 99.99 percent), and obtaining a final finished product.
The hardness of the final product is 278Hv, the yield strength is 682MPa, the tensile strength is 765MPa, the elongation after fracture is 13%, and the conductivity is 50% IACS.
Example 3
The alloy comprises the following components in percentage by mass: 3.0 wt% Ni, 0.3 wt% Co, 0.6 wt% Fe, 1.1 wt% Si, 0.1 wt% Zr, 0.1 wt% Zn, and the balance Cu. Cu, Fe and Si used for smelting are bulk raw materials with the purity of more than or equal to 99.9wt%, Cu-Ni intermediate alloy containing 50wt% of Ni, Cu-Zn intermediate alloy containing 20wt% of Zn, Cu-Co intermediate alloy containing 30wt% of Co and Cu-Zr intermediate alloy containing 10wt% of Zr.
(1) Casting of alloy: putting the raw materials into a crucible of an induction furnace according to the mass percent, and vacuumizing to 10 DEG- 3Pa, then 1.1X 105Pa pure argon (Ar is more than or equal to 99.99 percent), smelting under the protection of the pure argon, keeping for 10 minutes after the solid is completely melted to form alloy melt, then casting the alloy melt into a graphite mold, cooling, opening the mold, taking out the alloy ingot, wherein the thickness of the ingot is 18 mm.
(2) Homogenizing: putting the cast ingot into a heat treatment furnace, carrying out homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), keeping the temperature for 5 hours at the homogenization temperature of 1000 ℃, and then cooling to room temperature along with the furnace.
(3) Hot rolling treatment: and heating the ingot after the homogenization treatment to 800 ℃, carrying out hot rolling deformation, wherein the final rolling temperature is 710 ℃, and then carrying out water quenching to obtain a hot-rolled sample with the thickness of 8.5 mm.
(4) Solution treatment: putting the hot rolled sample into a heat treatment furnace, carrying out solid solution treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the solid solution temperature is 920 ℃, the heat preservation time is 1.5 hours, then taking out the heat treatment furnace, and immediately carrying out water quenching.
(5) Deep cooling and rolling: and milling the surface of the sample subjected to solid solution to remove a small amount of oxide skin on the surface layer, and then performing deep cold rolling deformation, wherein the rolling temperature is-150 ℃, and the thickness of the sample subjected to deep cold rolling is 3 mm.
(6) And (3) aging treatment of a pulse magnetic field: and (3) placing the sample subjected to cryogenic rolling into a heat treatment furnace with a pulsed magnetic field device, and carrying out pulsed magnetic field aging treatment under the protection of pure argon (Ar is more than or equal to 99.99%). The aging temperature is 500 ℃, the heat preservation time is 1 hour, and the adopted pulse magnetic field parameters are pulse frequency 300Hz, pulse peak magnetic field intensity 0.3T and pulse width 100 mus. And after the aging is finished, cooling the sample to room temperature under the protection of pure argon (Ar is more than or equal to 99.99 percent), and obtaining a final finished product.
The hardness of the final finished product is 316Hv, the yield strength is 808MPa, the tensile strength is 880MPa, the elongation after fracture is 8%, and the conductivity is 45% IACS.
Example 4
The alloy comprises the following components in percentage by mass: 2.3 wt% Ni, 0.8 wt% Co, 0.8 wt% Fe, 0.9 wt% Si, 0.15 wt% Zr, 0.2 wt% Zn, and the balance Cu. Cu, Fe and Si used for smelting are bulk raw materials with the purity of more than or equal to 99.9wt%, Cu-Ni intermediate alloy containing 50wt% of Ni, Cu-Zn intermediate alloy containing 20wt% of Zn, Cu-Co intermediate alloy containing 30wt% of Co and Cu-Zr intermediate alloy containing 10wt% of Zr.
(1) Casting of alloy: putting the raw materials into a crucible of an induction furnace according to the mass percent, and vacuumizing to 10 DEG- 3Pa, then 1.1X 105Pa pure argon (Ar is more than or equal to 99.99 percent), smelting under the protection of the pure argon, keeping for 10 minutes after the solid is completely melted to form alloy melt, then casting the alloy melt into a graphite mold, cooling, opening the mold, taking out the alloy ingot, wherein the thickness of the ingot is 18 mm.
(2) Homogenizing: putting the cast ingot into a heat treatment furnace, carrying out homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), keeping the temperature at 980 ℃ for 9 hours, and then cooling to room temperature along with the furnace.
(3) Hot rolling treatment: and heating the ingot after the homogenization treatment to 950 ℃, carrying out hot rolling deformation, wherein the final rolling temperature is 760 ℃, and then carrying out water quenching to obtain a hot-rolled sample with the thickness of 5.5 mm.
(4) Solution treatment: putting the hot rolled sample into a heat treatment furnace, carrying out solid solution treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the solid solution temperature is 980 ℃, the heat preservation time is 1 hour, then taking out the heat treatment furnace, and immediately carrying out water quenching.
(5) Deep cooling and rolling: and milling the surface of the sample subjected to solid solution to remove a small amount of scale cinder, and then performing deep cold rolling deformation, wherein the rolling temperature is-145 ℃, and the thickness of the sample subjected to deep cold rolling is 1 mm.
(6) And (3) aging treatment of a pulse magnetic field: and (3) placing the sample subjected to cryogenic rolling into a heat treatment furnace with a pulsed magnetic field device, and carrying out pulsed magnetic field aging treatment under the protection of pure argon (Ar is more than or equal to 99.99%). The aging temperature is 480 ℃, the heat preservation time is 1.5 hours, the adopted pulse magnetic field parameters are pulse frequency 200Hz, the pulse peak magnetic field intensity is 0.6T, and the pulse width is 400 mus. And after the aging is finished, cooling the sample to room temperature under the protection of pure argon (Ar is more than or equal to 99.99 percent), and obtaining a final finished product.
The hardness of the final finished product is 302Hv, the yield strength is 761MPa, the tensile strength is 840MPa, the elongation after fracture is 10%, and the conductivity is 48% IACS.
Example 5
The alloy comprises the following components in percentage by mass: 2.0 wt% Ni, 0.4 wt% Co, 0.3 wt% Fe, 0.5 wt% Si, 0.2 wt% Zr, 0.3 wt% Zn, and the balance Cu. Cu, Ni, Fe and Si used for smelting are bulk raw materials with the purity of more than or equal to 99.9wt%, Cu-Zn intermediate alloy containing 20wt% of Zn, Cu-Co intermediate alloy containing 30wt% of Co and Cu-Zr intermediate alloy containing 10wt% of Zr.
(1) Casting of alloy: putting the raw materials into a crucible of an induction furnace according to the mass percent, and vacuumizing to 10 DEG- 3Pa, then 1.1X 105Pa pure argon (Ar is more than or equal to 99.99 percent), smelting under the protection of the pure argon, keeping for 10 minutes after the solid is completely melted to form alloy melt, then casting the alloy melt into a graphite mold, cooling, opening the mold, taking out the alloy ingot, wherein the thickness of the ingot is 18 mm.
(2) Homogenizing: putting the cast ingot into a heat treatment furnace, carrying out homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), keeping the temperature for 8 hours at the homogenization temperature of 920 ℃, and then cooling to room temperature along with the furnace.
(3) Hot rolling treatment: and heating the ingot after the homogenization treatment to 930 ℃, carrying out hot rolling deformation, wherein the final rolling temperature is 755 ℃, and then carrying out water quenching to obtain a hot-rolled sample with the thickness of 4.8 mm.
(4) Solution treatment: putting the hot rolled sample into a heat treatment furnace, carrying out solid solution treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the solid solution temperature is 800 ℃, the heat preservation time is 3 hours, then taking out the heat treatment furnace, and immediately carrying out water quenching.
(5) Deep cooling and rolling: and milling the surface of the sample subjected to solid solution to remove a small amount of oxide skin on the surface layer, and then performing deep cold rolling deformation, wherein the rolling temperature is-135 ℃, and the thickness of the sample subjected to deep cold rolling is 1.1 mm.
(6) And (3) aging treatment of a pulse magnetic field: and (3) placing the sample subjected to cryogenic rolling into a heat treatment furnace with a pulsed magnetic field device, and carrying out pulsed magnetic field aging treatment under the protection of pure argon (Ar is more than or equal to 99.99%). The aging temperature is 420 ℃, the heat preservation time is 2 hours, and the adopted pulse magnetic field parameters are pulse frequency of 80Hz, pulse peak magnetic field intensity of 2T and pulse width of 200 mus. And after the aging is finished, cooling the sample to room temperature under the protection of pure argon (Ar is more than or equal to 99.99 percent), and obtaining a final finished product.
The hardness of the final product is 270Hv, the yield strength is 660MPa, the tensile strength is 745MPa, the elongation after fracture is 15%, and the electrical conductivity is 53% IACS.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (4)
1. The Cu-Ni-Co-Fe-Si-Zr-Zn copper alloy material is characterized by comprising the following components in percentage by mass: 2.0-3.0 wt% of Ni; 0.3-0.8 wt% of Co; 0.3 to 0.8 wt% Fe; 0.5 to 1.1 wt% of Si; 0.1 to 0.2 wt% of Zr; 0.1-0.3 wt% of Zn; the balance being Cu;
the sum of the mass percentages of Ni, Co, Fe and Si is 3.0-5.0 wt%, the mass ratio of Ni, Co and Fe is (3-10): (1-2): 1-2), and the sum of the mass percentages of Ni, Co and Fe is that the mass percentage of Si is = (3.5-5.5): 1;
the preparation method of the Cu-Ni-Co-Fe-Si-Zr-Zn copper alloy material comprises the following steps:
(1) casting of alloy: putting the raw materials into a crucible of an induction furnace, smelting under the protection of pure argon, then casting the alloy melt into a mold, cooling, opening the mold and taking out an alloy ingot;
(2) homogenizing: placing the alloy cast ingot into a heat treatment furnace for homogenization treatment under the protection of pure argon, and then cooling to room temperature;
(3) hot rolling: heating the homogenized alloy cast ingot to 800-950 ℃ for hot rolling, wherein the total deformation of the hot rolling is 50-80%, the final rolling temperature is controlled to be above 700 ℃, and the alloy material after the final rolling is immediately subjected to water quenching;
(4) solution treatment: putting the hot-rolled copper alloy material into a heat treatment furnace, carrying out solid solution treatment under the protection of pure argon, taking out the heat treatment furnace, and immediately carrying out water quenching;
(5) deep cooling and rolling: milling the surface of the copper alloy material subjected to solid solution, removing surface oxide skin, and then performing deep cooling rolling deformation;
(6) and (3) aging treatment of a pulse magnetic field: carrying out aging treatment on the copper alloy material subjected to cryogenic rolling under a pulsed magnetic field, and cooling the copper alloy material to room temperature under the protection of pure argon after the aging treatment is finished to obtain a Cu-Ni-Co-Fe-Si-Zr-Zn copper alloy material;
in the step (5), the total deformation of the deep cooling rolling is 60-85%, and the rolling temperature is-125 ℃ to-160 ℃; the aging treatment in the step (6) is carried out at the temperature of 400-500 ℃ for 1-5 hours; the parameters of the pulse magnetic field adopted in the step (6) are as follows: the pulse frequency is 10-300 Hz, the pulse peak magnetic field intensity is 0.3-2T, and the pulse width is 100-500 mu s.
2. The Cu-Ni-Co-Fe-Si-Zr-Zn copper alloy material according to claim 1, wherein the raw material used for the smelting in the step (1) is a bulk raw material with a purity of 99.9% or more or an intermediate alloy of bulk Cu-X, and X is one or more of Ni, Co, Fe, Si, Zr and Zn.
3. The Cu-Ni-Co-Fe-Si-Zr-Zn copper alloy material according to claim 1, wherein the homogenization temperature in the step (2) is 900 ℃ to 1000 ℃ for 5 to 12 hours.
4. The Cu-Ni-Co-Fe-Si-Zr-Zn copper alloy material according to claim 1, wherein the solid solution temperature in the step (4) is 800 ℃ to 1000 ℃ for 1 to 3 hours.
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