CN115094266A - High-strength conductive elastic copper alloy and preparation method thereof - Google Patents
High-strength conductive elastic copper alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-strength conductive elastic copper alloy which comprises the following elements: at least one of elements Ni and Co; and the mass content of Ni + Co is 10-20 wt.%; at least one element selected from Si, Sn and Al; the mass ratio of the elements of Ni, Co, Si, Sn and Al also satisfies the following conditions: 6.2: 1 is more than or equal to (Ni + Co)/(Si + Al + Sn) is more than or equal to 9: 1; the balance being Cu and unavoidable impurities. The invention also provides a preparation method of the high-strength conductive elastic copper alloy. The high-strength conductive elastic copper alloy has the advantages of high alloy strength, high elasticity, good conductivity and excellent room temperature and high temperature damping performance.
Description
Technical Field
The invention belongs to the field of alloy materials, and particularly relates to a copper alloy and a preparation method thereof.
Background
The high-strength and high-conductivity copper alloy plays an important role in the fields of aerospace, electronic components, high-speed rails, important parts of automobiles and the like. With continuous iteration of the technology, various fields put higher requirements on the strength and the conductivity of the high-strength and high-conductivity copper alloy. Meanwhile, high-strength and high-conductivity copper alloy is required to meet specific requirements under specific service environments, and as automobile engine parts, besides requirements on strength and conductivity, damping performance is also emphasized. As a reed in a contactor, stress relaxation performance is also one of important performance indexes.
Cu-Ni-Si alloys have recently received much attention as novel high-strength and high-conductivity copper alloys. However, the overall properties of the presently disclosed Cu-Ni-Si alloys need to be enhanced, particularly with respect to damping and stress relaxation properties. In addition, most of the existing Cu-Ni-Si alloy preparation processes have the problems of complex process flow, low working efficiency, high energy consumption and the like. For example, patent CN110195170A discloses a preparation method for improving toughness of Cu-Ni-Si alloy, and the mentioned process flow needs multiple solid solution, cold rolling and annealing treatments, and is relatively complex. For example, patent CN105018871A discloses a CuNiSi lead frame anisotropic tape heat treatment process, which comprises the following steps: annealing: heating at the temperature of 950 ℃ of 800 ℃ for 1 hour, and cooling along with the furnace; hot rolling: hot rolling for five times at 800 ℃, 850 ℃, 900 ℃ and 950 ℃; thirdly, quenching: preserving the heat for 20 minutes at the temperature of 820-; cooling: cooling in air; solution treatment: heating at 600 and 750 ℃ and preserving heat for 40-50 minutes; sixthly, aging: 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ for 2 hours, 3 hours, 4 hours, 5 hours and 6 hours, respectively. The patent needs furnace cooling after annealing, can greatly reduce the work efficiency in the industrial production, and increases the energy consumption in the production process after the solution treatment is cooled.
In general, it is necessary to provide a Cu-Ni-Si alloy with excellent comprehensive performance and a preparation process with short process flow and low energy consumption.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and defects mentioned in the background technology, and provide a high-strength conductive elastic copper alloy with high strength, excellent conductivity, excellent stress relaxation performance and excellent damping performance and a preparation method thereof. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a high-strength conductive elastic copper alloy comprises the following elements:
at least one of elements Ni and Co; and the mass content of Ni + Co is 10-20 wt.%;
at least one element selected from Si, Sn and Al;
the mass ratio of the Ni, Co, Si, Sn and Al elements also satisfies the following conditions: 6.2: 1 is less than or equal to (Ni + Co)/(Si + Al + Sn) is less than or equal to 9: 1;
the balance being Cu and unavoidable impurities. The above (Ni + Co) means the total mass of the element Ni and the element Co.
In the above high-strength conductive elastic copper alloy, preferably, at least one of elements Cr and Mg is further contained; the mass content of the Cr is 0.001-0.15 wt.%, and the mass content of the Mg is 0.001-0.15 wt.%. The comprehensive performance of the material can be further improved by adding Cr and Mg.
As a general technical concept, the present invention also provides a method for preparing the above high-strength conductive elastic copper alloy, comprising the steps of:
(a) batching according to the composition of copper alloy elements, putting copper and other elements into a smelting furnace for smelting, and forming an alloy solution after the solution is uniform;
(b) casting the alloy solution obtained in the step (a) into an ingot to obtain an ingot billet, carrying out homogenization treatment, and then carrying out hot rolling/hot extrusion to obtain a hot rolled plate/hot extrusion rod;
(c) carrying out solution treatment, water quenching and high-temperature aging treatment on the hot-rolled plate/hot extrusion rod obtained in the step (b);
(d) and (c) carrying out cold rolling/drawing deformation treatment on the hot rolled plate/hot extrusion rod subjected to high-temperature aging treatment in the step (c) to obtain the high-strength conductive elastic copper alloy.
In the preparation method, preferably, the temperature of the homogenization treatment is 1000-.
In the above preparation method, preferably, the hot rolling/hot extrusion cogging is directly performed after the homogenization treatment, the initial temperature of the hot rolling/hot extrusion is controlled to be 900-1000 ℃, and the deformation amount of the hot rolling/hot extrusion is 80-95%.
In the preparation method, the temperature of the solution treatment is preferably 950-.
In the preparation method, preferably, online water quenching cooling is carried out after the solution treatment to the temperature of high-temperature aging treatment, the cooling speed of the surface of the sample is more than or equal to 30 ℃/s in the online water quenching cooling process, and the cooling speed of the core of the sample is more than or equal to 10 ℃/s.
In the preparation method, the temperature of the high-temperature aging treatment is preferably 550-700 ℃, and the time is preferably 10-60 minutes.
In the preparation method, preferably, the cold rolling/drawing deformation treatment is carried out in multiple passes, the deformation amount of each pass of cold rolling/drawing is controlled to be less than or equal to 10 percent, and the deformation strain rate is 0.5-10s -1 And the total deformation amount of cold rolling/cold drawing is controlled to be 75-95%.
In the preparation method, preferably, the smelting furnace is protected by using micro reducing gas, the micro reducing gas is formed by mixing nitrogen and reducing gas, the volume content of the nitrogen is not less than 95%, and the reducing gas comprises carbon monoxide, methane and hydrogen.
For the alloy material in the invention, the process parameters such as the treatment temperature, the treatment time, the deformation amount and the like can influence the microstructure of the alloy material, thereby showing different performances. Based on the special component design of the invention and the special treatment process, the Cu-Ni-Si alloy with the optimal comprehensive performance can be obtained by controlling the process parameters.
The Cu-Ni-Si alloy is used as a novel high-strength high-conductivity copper alloy, and by reasonably designing the alloy components and contents, Co and Ni can form an infinite solid solution with Cu, so that the strength of the alloy can be greatly improved by solid solution strengthening due to high (Ni + Co) content (10-20 wt%); meanwhile, Si element, Co and Ni element can form Co through aging precipitation 2 Si、Ni 2 Si and Ni 3 The Si strengthening phase particles improve the strength of the alloy. Sn, Al and Ni and Co elements can be formed by forming Ni 3 Sn、Ni 3 Al、Co 3 Sn and Co 2 Al 3 The reinforcing phase particles reinforce the matrix. In addition, the high (Ni + Co) content further promotes the precipitation of Si, Sn, and Al elements, suppresses the influence of the Si, Sn, and Al elements on the decrease in conductivity, and reduces the decrease in conductivity of the alloy.
However, the mass ratio of the elements Ni and Co to the elements Si, Sn and Al needs to be reasonably controlled, the use amount of the elements Ni and Co is too large, and the elements Ni and Co will remain in the copper matrix in the form of solid solution atoms, which can affect the conductivity. The use amount of the elements Ni and Co is too small, so that excessive Si, Al and Sn are left in the alloy, the quantity of the strengthening phases in the material is not enough, and the strength of the material is not high enough.
Furthermore, we have found that the strengthening phase particles during the aging annealing process vary with the aging annealing parameters (including temperature and time), and the strengthening phase particle morphology appears as both continuous precipitates (in the form of plates) and discontinuous precipitates (in the form of platelets). Compared with the continuous phase, the lamellar discontinuous precipitated phase can purify the matrix more effectively, reduce the concentration of solid-solution atoms in the Cu matrix, prevent the conductivity reduction caused by the scattering effect of solute atoms on electrons, and simultaneously, after plastic deformation, the work hardening effect of the discontinuous precipitated phase is better, and the strength of the alloy can be enhanced more effectively. In addition, due to the particularity of the lamellar structure, the discontinuous precipitated phase has more advantages in stress relaxation performance and damping performance than the traditional continuous phase, and can meet the requirements under special environments.
The invention also optimizes the preparation method of the Cu-Ni-Si alloy, optimizes the process steps, particularly adjusts the temperature of high-temperature aging treatment to 550-. Because elements in the supersaturated solid solution form discontinuous precipitation through aging, the matrix can be better purified, the scattering effect of solute atoms on electrons is reduced, and the conductivity of the alloy is improved. Due to the discontinuous precipitated phase lamellar structure, the dislocation motion can be effectively blocked, and the damping performance and the stress relaxation performance are improved.
In addition, the whole process route of the invention adopts ingot casting, homogenization treatment, hot rolling/hot extrusion, solid solution treatment, water quenching, high-temperature aging treatment and cold rolling/drawing deformation treatment, and the mutual synergistic action of a series of process steps is combined with the optimization of process parameters, so that the alloy has good matching relationship with the component design of the alloy, and the advantage of the component design of the alloy is favorably embodied. The ultrahigh-strength conductive elastic copper alloy with high strength, excellent conductivity, stress relaxation performance and damping performance is obtained by adopting the alloy component design of the invention and the process route and process parameters of the invention and matching all factors.
In general, the ultrahigh-strength conductive elastic copper alloy with high strength, excellent conductivity, excellent stress relaxation performance and excellent damping performance is finally obtained by designing the alloy components and combining the preparation method and optimization of process parameters, and the requirements under special environments can be met. In addition, the preparation method has the advantages of simple process, short flow and low energy consumption, and has outstanding advantages compared with the prior art.
Compared with the prior art, the invention has the advantages that:
1. the high-strength conductive elastic copper alloy has high alloy strength, more excellent damping performance and stress relaxation performance, the maximum tensile strength at room temperature is 1300-1500MPa, the yield strength is 1200-1300MPa, the elastic modulus is 140-160GPa, and the electric conductivity is 25-40% IACS; the room temperature loss factor of the damping performance is 0.1-0.2%; the loss factor at 100 ℃ is 0.2-0.32%; the loss factor at 300 ℃ is 1.7-3.2%.
2. The preparation method of the ultrahigh-strength conductive elastic copper alloy has the advantages of short production process flow, low production cost and simple operation, and is applied to industrial production.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an SEM photograph of the ingot obtained after the high strength electrically conductive elastic copper alloy prepared in example 1 is subjected to step (b).
Fig. 2 is an SEM image of the billet obtained after the high strength, electrically conductive and resilient copper alloy prepared in example 1 was subjected to step (c).
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically indicated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a high-strength conductive elastic copper alloy comprises the following components in percentage by mass: ni: 10.0 percent; 0.001% of Co; 1.6 percent of Si; 0.001% of Sn; 0.001% of Al; 0.01 percent of Cr; 0.01 percent of Mg; the balance of Cu and inevitable impurity elements. Wherein the mass content of Ni and Co is 10.0 percent; the mass ratio of (Ni + Co)/(Si + Sn + Al) was 6.25: 1.
the preparation method of the high-strength conductive elastic copper alloy comprises the following steps:
(a) the components are mixed according to the mass percentage of the components, and the mixed gas of nitrogen and carbon monoxide is adopted for protection during smelting. Firstly putting a copper source, a nickel source and a cobalt source into a heating crucible for melting, keeping the temperature of a melt above 1600 ℃, preserving the heat for 3min, then adding a silicon source and a chromium source, finally cooling to 1200 +/-20 ℃, adding a tin source, an aluminum source and a magnesium source, preserving the heat for 10min after all the materials are melted, and casting the melt by adopting a graphite mold.
(b) Homogenizing the obtained cast ingot at 1000 deg.C for 2 h; after homogenization, hot rolling/hot extrusion cogging is directly carried out, wherein the initial temperature of hot rolling/hot extrusion is 900 ℃, and the deformation of hot rolling/hot extrusion is 80%.
(c) Directly transferring a hot rolled plate/hot extrusion rod obtained by hot rolling/hot extrusion into a high-temperature furnace for high-temperature solution treatment, wherein the temperature of the solution treatment is 950 ℃, the heat preservation time is 2h, a sample after the solution treatment is subjected to online water quenching and is cooled to the high-temperature aging temperature, the surface cooling speed of the sample in the online quenching process is 30 ℃/s, and the core cooling speed of the sample is 10 ℃/s; the high-temperature aging temperature is 550 ℃, and the aging treatment time is 60 minutes.
(d) Carrying out large-deformation cold rolling/cold drawing deformation on the hot rolled plate/hot extrusion rod subjected to high-temperature aging treatment, wherein the cold rolling/cold drawing can be carried out in multiple passes, the deformation amount cold rolling/cold drawing deformation amount of each pass is controlled to be 10%, and the deformation strain rate is 10s -1 (ii) a The total cold rolling/cold drawing deformation of the sample was 95%.
Room temperature tensile property, conductivity and damping property tests were performed on the high-strength conductive elastic copper alloy obtained through the above treatment, and the results of the tests on the elastic modulus, yield strength, maximum tensile strength, conductivity and loss factor are shown in table 1.
The SEM photograph of the ingot obtained after step (b) is shown in FIG. 1, and the SEM photograph of the ingot obtained after step (c) is shown in FIG. 2. As can be seen from fig. 1, the grains in the alloy subjected to the homogenization and hot rolling/hot extrusion treatment contain relatively complete grains, and after the microstructure in the alloy is homogenized, most of the as-cast structure is removed, and the grains are equiaxial and contain a certain amount of annealed contracture. Meanwhile, as can be seen from fig. 2, after the high-temperature aging (c) treatment, a discontinuous precipitation structure with a lamellar structure is formed in the alloy, so that a matrix is purified, dislocation movement is hindered, and the conductivity and the yield strength of the alloy are greatly improved.
Example 2:
a high-strength conductive elastic copper alloy comprises the following components in percentage by mass: ni: 10.0 percent; 2.00 percent of Co; 1.60 percent of Si; 0.001% of Sn: 0.001% of Al: 0.01% of Cr: 0.01 percent of Mg; the balance of Cu and inevitable impurity elements. Wherein the mass content of Ni and Co is 12.0 percent; the mass ratio of (Ni + Co)/(Si + Sn + Al) was 7.5: 1.
the preparation method of the high-strength conductive elastic copper alloy comprises the following steps:
(a) the components are mixed according to the mass percentage of the components, and the mixed gas of nitrogen and carbon monoxide is adopted for protection during smelting. Firstly, putting a copper source, a nickel source and a cobalt source into a heating crucible for melting, keeping the temperature of a melt above 1600 ℃, preserving the heat for 3min, then adding a silicon source and a chromium source, finally cooling to 1200 +/-20 ℃, then adding a tin source, an aluminum source and a magnesium source, preserving the heat for 10min after the melts are completely melted, and casting by adopting a graphite mold after the melt is uniform.
(b) Homogenizing the obtained cast ingot, wherein the homogenizing temperature is 1020 ℃, and the heat preservation time is 2 h; and directly performing hot rolling/hot extrusion cogging after homogenization, wherein the initial temperature of the hot rolling/hot extrusion is 920 ℃, and the deformation of the hot rolling/hot extrusion is 80%.
(c) Directly transferring a hot rolled plate/hot extrusion rod obtained by hot rolling/hot extrusion into a high-temperature furnace for high-temperature solution treatment, wherein the temperature of the solution treatment is 960 ℃, the heat preservation time is 2h, a sample after the solution treatment is subjected to online water quenching and is cooled to the high-temperature aging temperature, the surface cooling speed of the sample in the online quenching process is 40 ℃/s, and the core cooling speed of the sample is 20 ℃/s; the high-temperature aging temperature is 580 ℃, and the aging treatment time is 60 minutes.
(d) Carrying out large-deformation cold rolling/cold drawing deformation on the hot rolled plate/hot extrusion rod subjected to high-temperature aging treatment, wherein the cold rolling/cold drawing can be carried out in multiple passes, the deformation amount cold rolling/cold drawing deformation amount of each pass is controlled to be 10%, and the deformation strain rate is 8s -1 (ii) a The total cold rolling/cold drawing deformation of the sample was 95%.
Room temperature tensile property, conductivity and damping property tests were performed on the high-strength conductive elastic copper alloy obtained through the above treatment, and the results of the tests on the elastic modulus, yield strength, maximum tensile strength, conductivity and loss factor are shown in table 1.
Example 3:
a high-strength conductive elastic copper alloy comprises the following components in percentage by mass: ni: 10.0 percent; 4.00 percent of Co; 2.0 percent of Si; 0.001% of Sn: 0.001% of Al: 0.01% of Cr: 0.01 percent of Mg; the balance of Cu and inevitable impurity elements. Wherein the mass content of Ni + Co is 14.0 percent; the mass ratio of (Ni + Co)/(Si + Sn + Al) is 7: 1.
the preparation method of the high-strength conductive elastic copper alloy comprises the following steps:
(a) the components are mixed according to the mass percentage of the components, and the mixed gas of nitrogen and carbon monoxide is adopted for protection during smelting. Firstly putting a copper source, a nickel source and a cobalt source into a heating crucible for melting, keeping the temperature of a melt above 1600 ℃, preserving the heat for 3min, then adding a silicon source and a chromium source, finally cooling to 1200 +/-20 ℃, adding a tin source, an aluminum source and a magnesium source, preserving the heat for 10min after all the materials are melted, and casting the melt by adopting a graphite mold.
(b) Homogenizing the obtained cast ingot, wherein the homogenizing temperature is 1020 ℃, and the heat preservation time is 4 h; after homogenization, hot rolling/hot extrusion cogging is directly carried out, wherein the initial temperature of hot rolling/hot extrusion is 940 ℃, and the deformation of hot rolling/hot extrusion is 85%.
(c) Directly transferring a hot rolled plate/hot extrusion rod obtained by hot rolling/hot extrusion into a high-temperature furnace for high-temperature solution treatment, wherein the temperature of the solution treatment is 960 ℃, the heat preservation time is 4h, a sample after the solution treatment is subjected to online water quenching and is cooled to the high-temperature aging temperature, the surface cooling speed of the sample in the online quenching process is 30 ℃/s, and the core cooling speed of the sample is 20 ℃/s; the high-temperature aging temperature is 600 ℃, and the aging treatment time is 30 minutes.
(d) The hot rolled plate/hot extrusion bar after high-temperature aging treatment is subjected to large-deformation cold rolling/cold drawing deformation, the cold rolling/cold drawing can be carried out in multiple passes, and the deformation of each pass is controlled by the cold rolling/cold drawing deformationThe strain rate of deformation is 0.5s at 10% -1 (ii) a The total cold rolling/cold drawing deformation of the sample was 90%.
Room temperature tensile property, conductivity and damping property tests were performed on the high-strength conductive elastic copper alloy obtained through the above treatment, and the results of the tests on the elastic modulus, yield strength, maximum tensile strength, conductivity and loss factor are shown in table 1.
Example 4:
a high-strength conductive elastic copper alloy comprises the following components in percentage by mass: ni: 13.0 percent; 2.00 percent of Co; 2.10 percent of Si; 0.001% of Sn: 0.001% of Al: 0.01% of Cr: 0.01 percent of Mg; the balance of Cu and inevitable impurity elements. Wherein the mass content of Ni and Co is 15.0 percent; the mass ratio of (Ni + Co)/(Si + Sn + Al) was 7.14: 1.
the preparation method of the high-strength conductive elastic copper alloy comprises the following steps:
(a) the components are mixed according to the mass percentage of the components, and the mixed gas of nitrogen and carbon monoxide is adopted for protection during smelting. Firstly, putting a copper source, a nickel source and a cobalt source into a heating crucible for melting, keeping the temperature of a melt above 1600 ℃, preserving the heat for 3min, then adding a silicon source and a chromium source, finally cooling to 1200 +/-20 ℃, then adding a tin source, an aluminum source and a magnesium source, preserving the heat for 10min after the melts are completely melted, and casting by adopting a graphite mold after the melt is uniform.
(b) Homogenizing the obtained cast ingot at 1040 ℃ for 2 h; after homogenization, hot rolling/hot extrusion cogging is directly carried out, wherein the initial temperature of hot rolling/hot extrusion is 940 ℃, and the deformation of hot rolling/hot extrusion is 85%.
(c) Directly transferring a hot rolled plate/hot extrusion rod obtained by hot rolling/hot extrusion into a high-temperature furnace for high-temperature solution treatment, wherein the temperature of the solution treatment is 960 ℃, the heat preservation time is 2h, a sample after the solution treatment is subjected to online water quenching and is cooled to the high-temperature aging temperature, the surface cooling speed of the sample in the online quenching process is 50 ℃/s, and the core cooling speed of the sample is 20 ℃/s; the high-temperature aging temperature is 580 ℃, and the aging treatment time is 60 minutes.
(d) For the high temperature aging treatmentThe hot rolled plate/hot extrusion rod is subjected to large-deformation cold rolling/cold drawing deformation, the cold rolling/cold drawing can be carried out by multiple passes, the deformation cold rolling/cold drawing deformation amount of each pass is controlled to be 10%, and the deformation strain rate is 8s -1 (ii) a The total cold rolling/cold drawing deformation of the sample was 90%.
Room-temperature tensile property, conductivity and damping property tests are carried out on the high-strength conductive elastic copper alloy obtained through the treatment, and the results of the tests on the elastic modulus, the yield strength, the maximum tensile strength, the conductivity and the loss factor are shown in table 1.
Example 5:
a high-strength conductive elastic copper alloy comprises the following components in percentage by mass: ni: 16.0 percent; 0.001% of Co; 0.001% of Si; 1.000% of Sn; 1.000% of Al; 0.01 percent of Cr; 0.01 percent of Mg; the balance of Cu and inevitable impurity elements. Wherein the mass content of Ni + Co is about 16.0%; the mass ratio of (Ni + Co)/(Si + Sn + Al) is 8: 1.
the preparation method of the high-strength conductive elastic copper alloy comprises the following steps:
(a) the components are mixed according to the mass percentage of the components, and the mixed gas of nitrogen and carbon monoxide is adopted for protection during smelting. Firstly, putting a copper source, a nickel source and a cobalt source into a heating crucible for melting, keeping the temperature of a melt above 1600 ℃, preserving the heat for 3min, then adding a silicon source and a chromium source, finally cooling to 1200 +/-20 ℃, then adding a tin source, an aluminum source and a magnesium source, preserving the heat for 10min after the melts are completely melted, and casting by adopting a graphite mold after the melt is uniform.
(b) Homogenizing the obtained cast ingot, wherein the homogenizing temperature is 1040 ℃, and the heat preservation time is 2 h; and directly performing hot rolling/hot extrusion cogging after homogenization, wherein the initial temperature of the hot rolling/hot extrusion is 950 ℃, and the deformation of the hot rolling/hot extrusion is 90%.
(c) Directly transferring a hot rolled plate/hot extrusion rod obtained by hot rolling/hot extrusion into a high-temperature furnace for high-temperature solution treatment, wherein the temperature of the solution treatment is 970 ℃, the heat preservation time is 2h, a sample after the solution treatment is subjected to online water quenching and is cooled to the high-temperature aging temperature, the surface cooling speed of the sample in the online quenching process is 30 ℃/s, and the core cooling speed of the sample is 25 ℃/s; the high-temperature aging temperature is 600 ℃, and the aging treatment time is 60 minutes.
(d) Carrying out large-deformation cold rolling/cold drawing deformation on the hot-rolled plate/hot extrusion rod subjected to high-temperature aging treatment, wherein the cold rolling/cold drawing can be carried out in multiple passes, the deformation amount of the cold rolling/cold drawing deformation in each pass is controlled to be 10%, and the deformation strain rate is 6s -1 (ii) a The total cold rolling/cold drawing deformation of the sample was 90%.
Room temperature tensile property, conductivity and damping property tests were performed on the high-strength conductive elastic copper alloy obtained through the above treatment, and the results of the tests on the elastic modulus, yield strength, maximum tensile strength, conductivity and loss factor are shown in table 1.
Example 6:
a high-strength conductive elastic copper alloy comprises the following components in percentage by mass: ni: 15.0 percent; 3.00 percent of Co; 0.001% of Si; 1.000% of Sn; 1.000 percent of Al; 0.01 percent of Cr; 0.01 percent of Mg; the balance of Cu and inevitable impurity elements. Wherein the mass content of Ni and Co is 18.0 percent; the mass ratio of (Ni + Co)/(Si + Sn + Al) is 9: 1.
the preparation method of the high-strength conductive elastic copper alloy comprises the following steps:
(a) the components are mixed according to the mass percentage of the components, and the mixed gas of nitrogen and carbon monoxide is adopted for protection during smelting. Firstly, putting a copper source, a nickel source and a cobalt source into a heating crucible for melting, keeping the temperature of a melt above 1600 ℃, preserving the heat for 3min, then adding a silicon source and a chromium source, finally cooling to 1200 +/-20 ℃, then adding a tin source, an aluminum source and a magnesium source, preserving the heat for 10min after the melts are completely melted, and casting by adopting a graphite mold after the melt is uniform.
(b) Homogenizing the obtained cast ingot, wherein the homogenizing temperature is 1050 ℃, and the heat preservation time is 2 h; after homogenization, hot rolling/hot extrusion cogging is directly carried out, wherein the initial temperature of hot rolling/hot extrusion is 960 ℃, and the deformation of hot rolling/hot extrusion is 80%.
(c) Directly transferring a hot rolled plate/hot extrusion rod obtained by hot rolling/hot extrusion into a high-temperature furnace for high-temperature solution treatment, wherein the temperature of the solution treatment is 960 ℃, the heat preservation time is 2h, a sample after the solution treatment is subjected to online water quenching and is cooled to the high-temperature aging temperature, the surface cooling speed of the sample in the online quenching process is 40 ℃/s, and the core cooling speed of the sample is 20 ℃/s; the high-temperature aging temperature is 600 ℃, and the aging treatment time is 60 minutes.
(d) Carrying out large-deformation cold rolling/cold drawing deformation on the hot rolled plate/hot extrusion rod subjected to high-temperature aging treatment, wherein the cold rolling/cold drawing can be carried out in multiple passes, the deformation amount cold rolling/cold drawing deformation amount of each pass is controlled to be 10%, and the deformation strain rate is 4s -1 (ii) a The total cold rolling/cold drawing deformation of the sample was 75%.
Room temperature tensile property, conductivity and damping property tests were performed on the high-strength conductive elastic copper alloy obtained through the above treatment, and the results of the tests on the elastic modulus, yield strength, maximum tensile strength, conductivity and loss factor are shown in table 1.
Example 7:
a high-strength conductive elastic copper alloy comprises the following components in percentage by mass: ni: 13.0 percent; 6.00 percent of Co; 3.0 percent of Si; 0.001% of Sn; 0.001% of Al; 0.01 percent of Cr; 0.01 percent of Mg; the balance of Cu and inevitable impurity elements. Wherein the mass content of Ni and Co is 19.0 percent; the mass ratio of (Ni + Co)/(Si + Sn + Al) was 6.33: 1.
the preparation method of the high-strength conductive elastic copper alloy comprises the following steps:
(a) the components are mixed according to the mass percentage of the components, and the mixed gas of nitrogen and carbon monoxide is adopted for protection during smelting. Firstly putting a copper source, a nickel source and a cobalt source into a heating crucible for melting, keeping the temperature of a melt above 1600 ℃, preserving the heat for 3min, then adding a silicon source and a chromium source, finally cooling to 1200 +/-20 ℃, adding a tin source, an aluminum source and a magnesium source, preserving the heat for 10min after all the materials are melted, and casting the melt by adopting a graphite mold.
(b) Homogenizing the obtained cast ingot, wherein the homogenizing temperature is 1050 ℃, and the heat preservation time is 4 h; and directly carrying out hot rolling/hot extrusion cogging after homogenization, wherein the initial temperature of the hot rolling/hot extrusion is 980 ℃, and the deformation of the hot rolling/hot extrusion is 80%.
(c) Directly transferring a hot rolled plate/hot extrusion rod obtained by hot rolling/hot extrusion into a high-temperature furnace for high-temperature solution treatment, wherein the temperature of the solution treatment is 1000 ℃, the heat preservation time is 2h, a sample after the solution treatment is subjected to online water quenching and is cooled to the high-temperature aging temperature, the surface cooling speed of the sample in the online quenching process is 50 ℃/s, and the core cooling speed of the sample is 25 ℃/s; the high-temperature aging temperature is 600 ℃, and the aging treatment time is 60 minutes.
(d) Carrying out large-deformation cold rolling/cold drawing deformation on a hot-rolled plate/hot extrusion rod subjected to high-temperature aging treatment, wherein the cold rolling/cold drawing can be carried out in multiple passes, the deformation amount of the cold rolling/cold drawing deformation in each pass is controlled to be 10%, and the deformation strain rate is 1s -1 (ii) a The total cold rolling/cold drawing deformation of the sample was 85%.
Room temperature tensile property, conductivity and damping property tests were performed on the high-strength conductive elastic copper alloy obtained through the above treatment, and the results of the tests on the elastic modulus, yield strength, maximum tensile strength, conductivity and loss factor are shown in table 1.
Example 8:
a high-strength conductive elastic copper alloy comprises the following components in percentage by mass: ni: 14.0 percent; 6.00 percent of Co; 1.60 percent of Si; 0.7 percent of Sn; 0.001% of Al; 0.01 percent of Cr; 0.01 percent of Mg; the balance of Cu and inevitable impurity elements. Wherein the mass content of Ni and Co is 20.0 percent; the mass ratio of (Ni + Co)/(Si + Sn + Al) was 8.7: 1.
the preparation method of the high-strength conductive elastic copper alloy comprises the following steps:
(a) the components are mixed according to the mass percentage of the components, and the mixed gas of nitrogen and carbon monoxide is adopted for protection during smelting. Firstly, putting a copper source, a nickel source and a cobalt source into a heating crucible for melting, keeping the temperature of a melt above 1600 ℃, preserving the heat for 3min, then adding a silicon source and a chromium source, finally cooling to 1200 +/-20 ℃, then adding a tin source, an aluminum source and a magnesium source, preserving the heat for 10min after the melts are completely melted, and casting by adopting a graphite mold after the melt is uniform.
(b) Homogenizing the obtained cast ingot, wherein the homogenizing temperature is 1050 ℃, and the heat preservation time is 4 h; after homogenization, hot rolling/hot extrusion cogging is directly carried out, wherein the initial temperature of hot rolling/hot extrusion is 1000 ℃, and the deformation of hot rolling/hot extrusion is 80%.
(c) Directly transferring a hot rolled plate/hot extrusion rod obtained by hot rolling/hot extrusion into a high-temperature furnace for high-temperature solution treatment, wherein the temperature of the solution treatment is 1050 ℃, the heat preservation time is 8h, a sample after the solution treatment is subjected to online water quenching and is cooled to the high-temperature aging temperature, the surface cooling speed of the sample in the online quenching process is 50 ℃/s, and the core cooling speed of the sample is 25 ℃/s; the high-temperature aging temperature is 700 ℃, and the aging treatment time is 60 minutes.
(d) The hot rolled plate/hot extrusion bar subjected to high-temperature aging treatment is subjected to large-deformation cold rolling/cold drawing deformation, the cold rolling/cold drawing can be carried out in multiple passes, the deformation amount of the cold rolling/cold drawing deformation in each pass is controlled to be 10%, and the deformation strain rate is 0.5s -1 (ii) a The total cold rolling/cold drawing deformation of the sample was 80%.
Room-temperature tensile property, conductivity and damping property tests are carried out on the high-strength conductive elastic copper alloy obtained through the treatment, and the results of the tests on the elastic modulus, the yield strength, the maximum tensile strength, the conductivity and the loss factor are shown in table 1.
Comparative example 1:
a copper alloy comprises the following components in percentage by mass: ni: 10.0 percent; 0.001% of Co; 2.0 percent of Si; 0.001% of Sn; 0.001% of Al; 0.01 percent of Cr; 0.01 percent of Mg; the balance of Cu and inevitable impurity elements. Wherein the mass content of Ni + Co is about 10.0%; the mass ratio of (Ni + Co)/(Si + Sn + Al) is 5: 1.
the method for producing the copper alloy of the present comparative example includes the steps of:
(a) the components are mixed according to the mass percentage of the components, and the mixed gas of nitrogen and carbon monoxide is adopted for protection during smelting. Firstly, putting a copper source, a nickel source and a cobalt source into a heating crucible for melting, keeping the temperature of a melt above 1600 ℃, preserving the heat for 3min, then adding a silicon source and a chromium source, finally cooling to 1200 +/-20 ℃, then adding a tin source, an aluminum source and a magnesium source, preserving the heat for 10min after the melts are completely melted, and casting by adopting a graphite mold after the melt is uniform.
(b) Homogenizing the obtained cast ingot, wherein the homogenizing temperature is 1000 ℃, and the heat preservation time is 2 h; after homogenization, hot rolling/hot extrusion cogging is directly carried out, wherein the initial temperature of hot rolling/hot extrusion is 900 ℃, and the deformation of hot rolling/hot extrusion is 80%.
(c) Directly transferring a hot rolled plate/hot extrusion rod obtained by hot rolling/hot extrusion into a high-temperature furnace for high-temperature solution treatment, wherein the temperature of the solution treatment is 950 ℃, the heat preservation time is 2h, a sample after the solution treatment is subjected to online water quenching and is cooled to the high-temperature aging temperature, the surface cooling speed of the sample in the online quenching process is 30 ℃/s, and the core cooling speed of the sample is 10 ℃/s; the high-temperature aging temperature is 550 ℃, and the aging treatment time is 60 minutes.
(d) Carrying out large-deformation cold rolling/cold drawing deformation on the hot-rolled plate/hot extrusion rod subjected to high-temperature aging treatment, wherein the cold rolling/cold drawing can be carried out in multiple passes, the deformation amount of the cold rolling/cold drawing deformation in each pass is controlled to be 10%, and the deformation strain rate is 10s -1 (ii) a The total cold rolling/cold drawing deformation of the sample was 95%.
Room temperature tensile property, conductivity and damping property tests were performed on the copper alloy obtained through the above treatment, and the results of the tests on the elastic modulus, yield strength, maximum tensile strength, conductivity and loss factor are shown in table 1.
Comparative example 2:
a copper alloy comprises the following components in percentage by mass: ni: 16.0 percent; 0.001% of Co; 0.001% of Si; 1.000% of Sn; 1.000% of Al; 0.01 percent of Cr; 0.01 percent of Mg; the balance of Cu and inevitable impurity elements. Wherein the mass content of Ni + Co is about 16.0%; the mass ratio of (Ni + Co)/(Si + Sn + Al) is 8: 1.
the method for producing the copper alloy of the present comparative example includes the steps of:
(a) the components are mixed according to the mass percentage of the components, and the mixed gas of nitrogen and carbon monoxide is adopted for protection during smelting. Firstly, putting a copper source, a nickel source and a cobalt source into a heating crucible for melting, keeping the temperature of a melt above 1600 ℃, preserving the heat for 3min, then adding a silicon source and a chromium source, finally cooling to 1200 +/-20 ℃, then adding a tin source, an aluminum source and a magnesium source, preserving the heat for 10min after the melts are completely melted, and casting by adopting a graphite mold after the melt is uniform.
(b) Homogenizing the obtained cast ingot at 850 deg.C for 2 h; after homogenization, hot rolling/hot extrusion cogging is directly carried out, wherein the initial temperature of hot rolling/hot extrusion is 950 ℃, and the deformation of hot rolling/hot extrusion is 90%.
(c) Directly transferring a hot rolled plate/hot extrusion rod obtained by hot rolling/hot extrusion into a high-temperature furnace for high-temperature solid solution treatment, wherein the temperature of the solid solution treatment is 970 ℃, the heat preservation time is 2h, the sample after the solid solution treatment is subjected to on-line water quenching and cooled to the high-temperature aging temperature, the surface cooling speed of the sample in the on-line quenching process is 30 ℃/s, and the core cooling speed of the sample is 25 ℃/s; the high-temperature aging temperature is 600 ℃, and the aging treatment time is 60 minutes.
(d) Carrying out large-deformation cold rolling/cold drawing deformation on the hot rolled plate/hot extrusion rod subjected to high-temperature aging treatment, wherein the cold rolling/cold drawing can be carried out in multiple passes, the deformation amount cold rolling/cold drawing deformation amount of each pass is controlled to be 10%, and the deformation strain rate is 6s -1 (ii) a The total cold rolling/cold drawing deformation of the sample was 90%.
Room temperature tensile property, conductivity and damping property tests were performed on the copper alloy obtained through the above treatment, and the results of the tests on the elastic modulus, yield strength, maximum tensile strength, conductivity and loss factor are shown in table 1.
Comparative example 3:
a copper alloy comprises the following components in percentage by mass: ni: 14.0 percent; 6.00 percent of Co; 1.60 percent of Si; 0.7 percent of Sn; 0.001% of Al; 0.01 percent of Cr; 0.01 percent of Mg; the balance of Cu and inevitable impurity elements. Wherein the mass content of Ni and Co is 20.0 percent; the mass ratio of (Ni + Co)/(Si + Sn + Al) was 8.7: 1.
the method for producing a copper alloy of this comparative example includes the steps of:
(a) the components are mixed according to the mass percentage of the components, and the mixed gas of nitrogen and carbon monoxide is adopted for protection during smelting. Firstly, putting a copper source, a nickel source and a cobalt source into a heating crucible for melting, keeping the temperature of a melt above 1600 ℃, preserving the heat for 3min, then adding a silicon source and a chromium source, finally cooling to 1200 +/-20 ℃, then adding a tin source, an aluminum source and a magnesium source, preserving the heat for 10min after the melts are completely melted, and casting by adopting a graphite mold after the melt is uniform.
(b) Homogenizing the obtained cast ingot, wherein the homogenizing temperature is 1050 ℃, and the heat preservation time is 4 h; after homogenization, hot rolling/hot extrusion cogging is directly carried out, wherein the initial temperature of hot rolling/hot extrusion is 1000 ℃, and the deformation of hot rolling/hot extrusion is 80%.
(c) Directly transferring a hot rolled plate/hot extrusion rod obtained by hot rolling/hot extrusion into high-temperature aging treatment, wherein the cooling speed of the surface of a sample is 50 ℃/s and the cooling speed of the core of the sample is 25 ℃/s in the online quenching process; the high-temperature aging temperature is 700 ℃, and the aging treatment time is 60 minutes.
(d) Carrying out large-deformation cold rolling/cold drawing deformation on the hot rolled plate/hot extrusion rod subjected to high-temperature aging treatment, wherein the cold rolling/cold drawing can be carried out in multiple passes, the deformation amount cold rolling/cold drawing deformation amount of each pass is controlled to be 10%, and the deformation strain rate is 0.5s -1 (ii) a The total cold rolling/cold drawing deformation of the sample was 80%.
Room temperature tensile property, conductivity and damping property tests were performed on the copper alloy obtained through the above treatment, and the results of the tests on the elastic modulus, yield strength, maximum tensile strength, conductivity and loss factor are shown in table 1.
Comparative example 4:
a copper alloy comprises the following components in percentage by mass: ni: 15.0 percent; 3.00 percent of Co; 0.001% of Si; 1.000% of Sn; 1.000% of Al; 0.01 percent of Cr; 0.01 percent of Mg; the balance of Cu and inevitable impurity elements. Wherein the mass content of Ni and Co is 18.0 percent; the mass ratio of (Ni + Co)/(Si + Sn + Al) is 9: 1.
the method for producing a copper alloy of this comparative example includes the steps of:
(a) the components are mixed according to the mass percentage of the components, and the mixed gas of nitrogen and carbon monoxide is adopted for protection during smelting. Firstly putting a copper source, a nickel source and a cobalt source into a heating crucible for melting, keeping the temperature of a melt above 1600 ℃, preserving the heat for 3min, then adding a silicon source and a chromium source, finally cooling to 1200 +/-20 ℃, adding a tin source, an aluminum source and a magnesium source, preserving the heat for 10min after all the materials are melted, and casting the melt by adopting a graphite mold.
(b) Homogenizing the obtained cast ingot, wherein the homogenizing temperature is 1050 ℃, and the heat preservation time is 2 h; after homogenization, hot rolling/hot extrusion cogging is directly carried out, wherein the initial temperature of hot rolling/hot extrusion is 960 ℃, and the deformation of hot rolling/hot extrusion is 80%.
(c) Directly transferring a hot rolled plate/hot extrusion rod obtained by hot rolling/hot extrusion into a high-temperature furnace for high-temperature solution treatment, wherein the solution treatment temperature is 960 ℃, the heat preservation time is 2h, the sample after the solution treatment is subjected to online water quenching and cooling to the high-temperature aging temperature, the surface cooling speed of the sample in the online quenching process is 40 ℃/s, and the core cooling speed of the sample is 20 ℃/s; the high temperature aging temperature is 450 ℃, and the aging treatment time is 60 minutes.
(d) Carrying out large-deformation cold rolling/cold drawing deformation on the hot rolled plate/hot extrusion rod subjected to high-temperature aging treatment, wherein the cold rolling/cold drawing can be carried out in multiple passes, the deformation amount cold rolling/cold drawing deformation amount of each pass is controlled to be 10%, and the deformation strain rate is 4s -1 (ii) a The total cold rolling/cold drawing deformation of the sample was 75%.
Room temperature tensile property, conductivity and damping property tests were performed on the copper alloy obtained through the above treatment, and the results of the tests on the elastic modulus, yield strength, maximum tensile strength, conductivity and loss factor are shown in table 1.
Comparative example 5:
a copper alloy comprises the following components in percentage by mass: ni: 15.0 percent; 3.00 percent of Co; 0.001% of Si; 1.000% of Sn; 1.000 percent of Al; 0.01 percent of Cr; 0.01 percent of Mg; the balance of Cu and inevitable impurity elements. Wherein the mass content of Ni and Co is 18.0 percent; the mass ratio of (Ni + Co)/(Si + Sn + Al) is 9: 1.
the method for producing the copper alloy of the present comparative example includes the steps of:
(a) the components are mixed according to the mass percentage of the components, and the mixed gas of nitrogen and carbon monoxide is adopted for protection during smelting. Adding a copper source, a nickel source, a cobalt source, a silicon source, a chromium source, a tin source, an aluminum source and a magnesium source together, preserving heat for 10min after the materials are completely melted, and casting by adopting a graphite mold after the melt is uniform.
(b) Homogenizing the obtained cast ingot, wherein the homogenizing temperature is 1050 ℃, and the heat preservation time is 2 h; after homogenization, hot rolling/hot extrusion cogging is directly carried out, wherein the initial temperature of hot rolling/hot extrusion is 960 ℃, and the deformation of hot rolling/hot extrusion is 80%.
(c) Directly transferring a hot rolled plate/hot extrusion rod obtained by hot rolling/hot extrusion into a high-temperature furnace for high-temperature solution treatment, wherein the solution treatment temperature is 960 ℃, the heat preservation time is 2 hours, and the high-temperature aging temperature of a sample after the solution treatment is 600 ℃, and the aging treatment time is 60 minutes.
(d) And (3) carrying out large-deformation cold rolling/cold drawing deformation on the hot rolled plate/hot extrusion rod subjected to high-temperature aging treatment, wherein the total deformation of the cold rolling/cold drawing of the sample is 75%.
Room temperature tensile property, conductivity and damping property tests were performed on the copper alloy obtained through the above treatment, and the results of the tests on the elastic modulus, yield strength, maximum tensile strength, conductivity and loss factor are shown in table 1.
In the following table 1, the testing instrument for the elastic modulus, the yield strength and the tensile strength is a universal tensile testing machine, the testing instrument for the conductivity is a double-bridge testing instrument, and the testing instrument for the loss factor is a damping performance testing instrument.
Table 1: performance data for alloys of examples 1-8 and comparative examples 1-5
Claims (10)
1. A high-strength conductive elastic copper alloy is characterized by comprising the following elements:
at least one of elements Ni and Co; and the mass content of Ni + Co is 10-20 wt.%;
at least one element selected from Si, Sn and Al;
the mass ratio of the elements of Ni, Co, Si, Sn and Al also satisfies the following conditions: 6.2: 1 is less than or equal to (Ni + Co)/(Si + Al + Sn) is less than or equal to 9: 1;
the balance being Cu and unavoidable impurities.
2. The high strength, electrically conductive, resilient copper alloy of claim 1, further comprising at least one of the elements Cr, Mg; the mass content of the Cr is 0.001-0.15 wt.%, and the mass content of the Mg is 0.001-0.15 wt.%.
3. A method for producing a high strength, electrically conductive, resilient copper alloy as claimed in claim 1 or 2, comprising the steps of:
(a) batching according to the composition of copper alloy elements, putting copper and other elements into a smelting furnace for smelting, and forming an alloy solution after the solution is uniform;
(b) casting the alloy solution obtained in the step (a) into an ingot to obtain an ingot billet, carrying out homogenization treatment, and then carrying out hot rolling/hot extrusion to obtain a hot rolled plate/hot extrusion rod;
(c) carrying out solution treatment, water quenching and high-temperature aging treatment on the hot-rolled plate/hot extrusion rod obtained in the step (b);
(d) and (c) carrying out cold rolling/drawing deformation treatment on the hot rolled plate/hot extrusion rod subjected to high-temperature aging treatment in the step (c) to obtain the high-strength conductive elastic copper alloy.
4. The method as claimed in claim 3, wherein the homogenization treatment is carried out at a temperature of 1000-1050 ℃ and a holding time of 2-4 h.
5. The method as claimed in claim 3, wherein the homogenization treatment is followed by hot rolling/hot extrusion cogging, wherein the initial temperature of hot rolling/hot extrusion is controlled to be 900-1000 ℃, and the deformation of hot rolling/hot extrusion is controlled to be 80-95%.
6. The preparation method as claimed in claim 3, wherein the temperature of the solution treatment is 950-1050 ℃, and the holding time is 2-8 h.
7. The preparation method of claim 3, wherein the solution treatment is followed by on-line water quenching and cooling to the temperature of high-temperature aging treatment, the cooling speed of the sample surface is not less than 30 ℃/s during on-line water quenching and cooling, and the cooling speed of the sample core is not less than 10 ℃/s during on-line water quenching and cooling.
8. The method as claimed in claim 3, wherein the temperature of the high temperature aging treatment is 550-700 ℃ for 10-60 minutes.
9. The method according to claim 3, wherein the cold rolling/drawing deformation process is performed in a plurality of passes, the amount of deformation in each pass is controlled to be 10% or less, and the strain rate is 0.5 to 10s -1 And controlling the total deformation amount of cold rolling/cold drawing to be 75-95%.
10. The preparation method of any one of claims 3 to 9, characterized in that the smelting furnace is protected by using a micro reducing gas, the micro reducing gas is mixed with a reducing gas by using nitrogen, the volume content of the nitrogen is not less than 95%, and the reducing gas comprises carbon monoxide, methane and hydrogen.
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| WO2009123136A1 (en) * | 2008-03-31 | 2009-10-08 | 日鉱金属株式会社 | Cu-ni-si alloy for electronic materials |
| CN103328665A (en) * | 2010-12-13 | 2013-09-25 | 日本精线株式会社 | Copper alloy and method for producing copper alloy |
| US20140366604A1 (en) * | 2012-03-27 | 2014-12-18 | Ngk, Insulators, Ltd. | Forging method and forging die |
| CN114196851A (en) * | 2021-12-20 | 2022-03-18 | 有研工程技术研究院有限公司 | High-strength conductive copper alloy material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009123136A1 (en) * | 2008-03-31 | 2009-10-08 | 日鉱金属株式会社 | Cu-ni-si alloy for electronic materials |
| CN103328665A (en) * | 2010-12-13 | 2013-09-25 | 日本精线株式会社 | Copper alloy and method for producing copper alloy |
| US20140366604A1 (en) * | 2012-03-27 | 2014-12-18 | Ngk, Insulators, Ltd. | Forging method and forging die |
| CN114196851A (en) * | 2021-12-20 | 2022-03-18 | 有研工程技术研究院有限公司 | High-strength conductive copper alloy material and preparation method thereof |
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