CN112251627A - High-strength high-conductivity Cu-Sc alloy and preparation method thereof - Google Patents
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- 229910000542 Sc alloy Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000005096 rolling process Methods 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 37
- 230000032683 aging Effects 0.000 claims abstract description 33
- 239000000956 alloy Substances 0.000 claims abstract description 32
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 31
- 239000010949 copper Substances 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005266 casting Methods 0.000 claims abstract description 11
- 238000013461 design Methods 0.000 claims abstract description 8
- 238000003723 Smelting Methods 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000005098 hot rolling Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 3
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- 238000005728 strengthening Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
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- 238000005097 cold rolling Methods 0.000 description 4
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- 229910017985 Cu—Zr Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 2
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- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 2
- 229910017818 Cu—Mg Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
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- 229910000838 Al alloy Inorganic materials 0.000 description 1
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- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017770 Cu—Ag Inorganic materials 0.000 description 1
- 229910017767 Cu—Al Inorganic materials 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
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- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
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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
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- 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
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- 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
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Abstract
The invention belongs to the field of copper alloy preparation, and particularly relates to a high-strength high-conductivity Cu-Sc alloy and a preparation method thereof. The high-strength high-conductivity Cu-Sc alloy comprises the following components in percentage by mass: sc0.1-0.4 wt.%, and the balance copper. The preparation method comprises the following steps: the method sequentially comprises the following steps: the method comprises the following steps of component design, smelting and casting, homogenization treatment, thermal deformation treatment, solid solution treatment, low-temperature rolling and aging treatment. The method of the invention obtains the nanometer precipitated phase to strengthen the alloy through the combination process of low-temperature rolling and aging treatment, thereby obtaining the binary copper alloy Cu-Sc with higher mechanical property and electrical property, and the ideal combination of yield strength not lower than 695MPa and electric conductivity not lower than 62% IACS can be realized through the process of low-temperature rolling and subsequent aging for 4 hours at 400 ℃.
Description
Technical Field
The invention belongs to the field of copper alloy preparation, and particularly relates to a high-strength high-conductivity Cu-Sc alloy and a preparation method thereof.
Background
The copper alloy is widely applied to the fields of aerospace, navigation, electric power and the like by virtue of excellent performances such as electrical conductivity, thermal conductivity, wear resistance, corrosion resistance, non-magnetism, high strength and the like. With the development and demand of modern science and technology, more rigorous requirements are put on the performance of copper alloy, wherein the most important requirement is that high conductivity and high strength are simultaneously provided.
Currently, the research and development of high-performance copper alloys are mainly carried out by two means. One method is to add alloying elements meeting the precipitation dispersion strengthening condition into a copper matrix through solution treatment to obtain a supersaturated solid solution, wherein the strength of the alloy is improved due to the solution strengthening effect, but the conductivity of the alloy is greatly reduced due to the scattering effect of the alloying elements on electrons. The dispersed second phase particles can also play a role in precipitation strengthening, so that the strength of the alloy is improved to a great extent.
There has also been a related study on the addition of rare earth elements to copper alloys. The addition of low content of Y element in copper alloy can change its internal structure obviously, raise recrystallization temperature and change its plastic deformation mechanism. The addition of trace rare earth elements can obviously improve the mechanical properties of the alloy. In addition, the addition of the mixed rare earth elements in the Cu-Zn-Al alloy can also obviously improve the fracture strength. Sc is a rare earth element having the same period as the transition element. Sc is also reported to be one of the best modifiers for aluminum alloys and steel. The introduction of Sc element into Al-Cu alloy can promote the precipitation of theta' phase and enhance precipitation strengthening effect. The result shows that the addition of Sc element in the Cu-Zn-Al shape memory alloy can effectively refine grains and generate fine and dispersed precipitates, thereby improving the hardness of the alloy. It is reported that the addition of very low Sc elements to Cu-Ag alloys suppresses the formation of discontinuous Ag precipitates, thus maintaining the high conductivity of the alloy with a hardness increase of up to 41.5%. However, the specific role of Sc as a single additive element in copper alloys is not yet clear.
Low temperature rolling is an effective pretreatment method for obtaining Ultra Fine Grain (UFG) copper-based alloys with excellent mechanical properties, which has been proven to be suitable for Cu-Zn alloys, Cu-Al alloys, and Cu-Zr alloys. The low-temperature rolling process can inhibit dynamic recovery and recrystallization, thereby improving the efficiency of plastic deformation. In addition, before the aging process, the low-temperature rolling process can obtain higher distortion strain energy and high dislocation density, and promote the precipitation process in the subsequent aging treatment, thereby improving the mechanical properties of the alloy. The low-temperature rolling in Cu-Mg and Cu-Cr-Zr alloy can not only inhibit dislocation activity, but also is beneficial to introducing deformation twin crystal. Research shows that the lamellar structure of the Cu-Mg alloy can be refined by low-temperature rolling compared with room-temperature rolling. Therefore, the low temperature rolling process and subsequent aging treatment are a promising method for preparing high-strength and high-conductivity binary copper alloy.
Disclosure of Invention
The invention aims to provide a comprehensive preparation method of the composition design, low-temperature rolling and aging treatment of a high-strength high-conductivity Cu-Sc alloy, so that the prepared material has higher comprehensive performance than other Cu-Cr series and Cu-Zr series copper alloy materials prepared by common cold rolling.
In order to achieve the purpose, the invention adopts the technical scheme that:
a treatment process integrating component design, low-temperature rolling and aging treatment of a high-strength high-conductivity Cu-Sc alloy comprises the following steps:
step 1, component design and smelting casting. Adding 0.1-0.4 wt.% of Sc element into a copper matrix, preparing Cu-Sc alloy in a vacuum induction furnace, and finally casting into an ingot. The basis of component design is as follows: grain refinement can be caused by the addition of Sc, and the grain refinement of the Sc microalloyed copper alloy is more uniform than that of the common copper alloy. The phase diagrams of Cu-Sc and Cu-Zr have similar solid solution and precipitation change trends, and the Cu-Sc alloy can be regarded as another promising high-conductivity material. The maximum solubility of Sc and Zr in the copper matrix at the eutectic temperature is 0.4 wt.% and 0.15 wt.%, respectively, and greater hardening effects may result after aging due to the higher solubility of Sc than Zr in the copper matrix.
And 2, homogenizing. And transferring the cast ingot into a resistance furnace for heating and heat preservation, so that the alloy elements are uniformly dissolved in the copper matrix. Heating at 820-870 deg.C for 6-8h, and quenching with water.
And 3, performing thermal deformation treatment. Rolling the cast ingot into a plate with the thickness of 8-12mm, and performing multi-pass rolling on the cast ingot, wherein the hot rolling temperature is 820-870 ℃.
And 4, carrying out solution treatment. And carrying out solution treatment on the rolled Cu-Sc alloy, wherein the solution temperature is 860-880 ℃, the heat preservation time is 1-2h, and then carrying out water quenching to room temperature.
And 5, rolling at low temperature. And immersing the Cu-Sc alloy subjected to the solution treatment in liquid nitrogen for heat preservation and cooling, and performing multi-pass rolling on the Cu-Sc alloy cooled by the liquid nitrogen, wherein the thickness of the Cu-Sc alloy is 0.8-1.2mm after each pass of liquid nitrogen cooling. The low-temperature rolling temperature is controlled below 160 ℃ below zero by liquid nitrogen, and the deformation is 80-90%.
And 6, aging treatment. And carrying out aging treatment on the Cu-Sc alloy after low-temperature rolling to obtain a high-strength high-conductivity Cu-Sc alloy sample. Controlling the aging treatment temperature at 400-600 ℃, keeping the temperature for 0.5-16h, and cooling in air to room temperature.
The invention technically designs a binary copper alloy added with Sc element, and adjusts the structure of a sample by combining the low-temperature rolling and aging treatment processes, so that the sample can obtain higher performance. The strength of the sample after low-temperature rolling and aging treatment is improved to a certain extent compared with the strength of the sample after conventional treatment. The strength of the Cu-Sc alloy sample obtained by the method exceeds that of a cold-rolled Cu-Cr-Zr alloy sample, the surface hardness of the Cu-Sc alloy sample reaches 200-240 HV, and the Cu-Sc alloy can obtain good matching of the yield strength not lower than 695.8MPa and the electric conductivity not lower than 62.8% IACS after low-temperature rolling and subsequent aging treatment for 4 hours at 400 ℃.
Compared with the existing copper alloy and treatment process, the invention has the following beneficial effects:
the method adopts a mode of combining low-temperature rolling and subsequent aging treatment to replace the traditional solid solution aging after cold rolling, forms a large amount of fine dispersed strengthening phases, not only has higher strengthening effect, but also can improve the plasticity by the evenly distributed strengthening phases; the dislocation distribution is improved by low-temperature rolling, which is beneficial to refining crystal grains and greatly improving plasticity. The method utilizes the combination of pre-aging before low-temperature rolling and warm rolling after low-temperature rolling to replace the long-time aging after the traditional cold rolling, thereby greatly shortening the process period, being simple to operate and improving the production efficiency. The Cu-Sc alloy prepared by the thermomechanical treatment method has excellent comprehensive mechanical properties, and has wide application prospect as a substitute material of some high-performance copper alloys.
It should be understood that all combinations of the foregoing concepts and additional concepts described in greater detail below can be considered as part of the inventive subject matter of this disclosure unless such concepts are mutually inconsistent. In addition, all combinations of claimed subject matter are considered a part of the presently disclosed subject matter.
The foregoing and other aspects, embodiments and features of the present teachings can be more fully understood from the following description taken in conjunction with the accompanying drawings. Additional aspects of the present invention, such as features and advantages of exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of specific embodiments in accordance with the teachings of the present invention.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of a high-strength high-conductivity Cu-Sc alloy of the invention.
FIG. 2 is a microstructure diagram of a Cu-Sc alloy after medium and low temperature rolling by the method.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific embodiments.
As shown in fig. 1, the method for preparing the high-strength and high-conductivity Cu-Sc alloy of the present invention specifically includes the following steps:
s1) weighing the raw materials according to the design components, preparing Cu-Sc alloy in a vacuum induction furnace, and finally casting into cast ingots;
s2) transferring the cast ingot obtained in the step S1) into a resistance furnace for heating and heat preservation, so that the alloy elements are uniformly dissolved in the copper matrix;
s3) carrying out multi-pass rolling on the cast ingot treated by the S2) at a set temperature, and rolling into a plate;
s4) carrying out solution treatment on the plate obtained in the S3);
s5) carrying out low-temperature rolling on the plate processed by the S4);
s6) carrying out aging treatment on the alloy treated by the S5) to obtain a high-strength high-conductivity Cu-Sc alloy sample.
The high-strength high-conductivity Cu-Sc alloy comprises the following components in percentage by mass: 0.1-0.4 wt.% of Sc, and the balance copper.
The melting temperature in the S1) is 1200-1250 ℃, and argon is introduced to be used as protective gas.
The heating temperature in the S2) is 820-870 ℃, the heat preservation time is 6-8h, and then quenching and cooling are carried out to the room temperature by water.
And the hot rolling temperature in the S3) is 820-870 ℃, the rolling reduction of each pass is controlled to be 6-12%, and the plate with the thickness of 8-12mm is rolled.
The heating temperature of the solution treatment in the S4) is 860-880 ℃, the temperature is kept for 1-2h, and the water is cooled to the room temperature.
And the low-temperature rolling process in the step S5) comprises the steps of placing the alloy processed in the step S4) in liquid nitrogen, taking the alloy out of the liquid nitrogen, immediately carrying out multi-pass rolling at room temperature, controlling the reduction amount of each pass to be 8-15%, and immersing the alloy into the liquid nitrogen for heat preservation for 5-8min during each pass.
And (4) controlling the effective treatment temperature in the S6) to be 400-600 ℃, keeping the temperature for 0.5-16h, and cooling in air to room temperature.
The yield strength of the high-strength high-conductivity Cu-Sc alloy is not lower than 695.8MPa, and the conductivity of the high-strength high-conductivity Cu-Sc alloy is not lower than 62.8% IACS.
Example 1:
the alloy comprises the following components in percentage by mass: and (C) Sc: 0.35 wt.%, with the balance being Cu.
Homogenizing the Cu-Sc alloy after smelting and casting at 860 ℃, and carrying out hot rolling treatment after ingot casting homogenization, wherein the hot rolling temperature is 860 ℃. And (3) carrying out solution treatment on the hot-rolled sample, wherein the solution treatment process is 870 ℃ for 2h, and quenching and cooling by adopting water. And immersing the sample obtained after the solution treatment in liquid nitrogen, cooling, taking out the plate, rolling at room temperature, wherein the total deformation is 90%, immersing the plate in the liquid nitrogen every time, and keeping the temperature for 6 min. And (3) carrying out aging treatment on the sample after low-temperature rolling, wherein the specific aging treatment process comprises the following steps: the heating temperature is 400 ℃, and the air cooling is carried out to the room temperature after the heat preservation is carried out for 2 hours. The samples were tested for hardness, tensile properties and conductivity and the results are shown in table 1.
Example 2:
the alloy comprises the following components in percentage by mass: and (C) Sc: 0.40 wt.%, with the balance being Cu.
Homogenizing the Cu-Sc alloy after smelting and casting at 850 ℃, and carrying out hot rolling treatment after ingot casting homogenization, wherein the hot rolling temperature is 850 ℃. And (3) carrying out solid solution treatment on the hot-rolled sample, wherein the solid solution process is carried out at 880 ℃ for 2h, and quenching and cooling are carried out by adopting water. And immersing the sample obtained after the solution treatment in liquid nitrogen, cooling, taking out the plate, rolling at room temperature, wherein the total deformation is 90%, immersing the plate in the liquid nitrogen every time, and keeping the temperature for 7 min. And (3) carrying out aging treatment on the sample after low-temperature rolling, wherein the specific aging treatment process comprises the following steps: the heating temperature is 400 ℃, the temperature is kept for 4 hours, and then the air cooling is carried out to the room temperature. The samples were tested for hardness, tensile properties and conductivity and the results are shown in table 1.
Example 3
The alloy comprises the following components in percentage by mass: and (C) Sc: 0.30 wt.%, with the balance being Cu.
Homogenizing the smelted and cast Cu-Sc alloy at 870 ℃, homogenizing the cast ingot, and then carrying out hot rolling treatment at the hot rolling temperature of 840 ℃. And (3) carrying out solid solution treatment on the hot-rolled sample, wherein the solid solution process is carried out at 880 ℃ for 1.5h, and quenching and cooling are carried out by adopting water. And immersing the sample obtained after the solution treatment in liquid nitrogen, cooling, taking out the plate, rolling at room temperature, wherein the total deformation is 90%, immersing the plate in the liquid nitrogen every time, and keeping the temperature for 8 min. And (3) carrying out aging treatment on the sample after low-temperature rolling, wherein the specific aging treatment process comprises the following steps: the heating temperature is 450 ℃, the temperature is kept for 0.5h, and then the air cooling is carried out to the room temperature. The samples were tested for hardness, tensile properties and conductivity and the results are shown in table 1.
Comparative example
The alloy comprises the following components in percentage by mass: and (C) Sc: 0.4 wt.%, with the balance being Cu.
Homogenizing the Cu-Sc alloy after smelting and casting at 850 ℃, and carrying out hot rolling treatment after ingot casting homogenization, wherein the hot rolling temperature is 840 ℃. And (3) carrying out solution treatment on the hot-rolled sample, wherein the solution treatment process is 870 ℃ for 2h, and quenching and cooling by adopting water. The sample obtained after the solution treatment was rolled at room temperature, and the total deformation was 90%. And (3) carrying out aging treatment on the rolled sample, wherein the specific aging treatment process comprises the following steps: the heating temperature is 400 ℃, and the air cooling is carried out to the room temperature after the heat preservation is carried out for 2 hours. The samples were tested for hardness, tensile properties and conductivity and the results are shown in table 1.
According to the experimental results in the table 1, the strength of the Cu-Sc alloy treated by the low-temperature rolling and aging process is improved by 111MPa and the hardness is improved by 28HV compared with the conventional room-temperature cold rolling process under the same aging time. Over longer aging times, the conductivity increases while still maintaining higher strength and hardness. Therefore, the Cu-Sc alloy sample has higher conductivity and higher strength and hardness. The Cu-Sc alloy can achieve the ideal combination of yield strength (695MPa) and electrical conductivity (62% IACS) by a process of low temperature rolling and subsequent aging at 400 ℃ for 4 h.
TABLE 1 mechanical and electrical test Performance data for the samples of examples 1, 2, 3 and comparative example 1
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.
Claims (9)
1. The high-strength high-conductivity Cu-Sc alloy is characterized by comprising the following components in percentage by mass: sc0.1-0.4 wt.%, and the balance copper.
2. A method for preparing the high-strength high-conductivity Cu-Sc alloy according to claim 1, characterized in that the method comprises the following steps:
s1) weighing Cu and Sc metal powder according to the design components, preparing Cu-Sc alloy in a vacuum induction furnace, and finally casting into an ingot;
s2) transferring the cast ingot obtained in the step S1) into a resistance furnace for heating and heat preservation, so that the alloy elements are uniformly dissolved in the copper matrix;
s3) carrying out multi-pass rolling on the cast ingot treated by the S2) at a set temperature, and rolling into a plate;
s4) carrying out solution treatment on the plate obtained in the S3);
s5) carrying out low-temperature rolling on the plate processed by the S4);
s6) carrying out aging treatment on the alloy treated by the S5) to obtain a high-strength high-conductivity Cu-Sc alloy sample.
3. The method as claimed in claim 2, wherein the smelting temperature in S1) is 1200-1250 ℃, and argon is introduced as protective gas.
4. The method as claimed in claim 2, wherein the heating temperature in S2) is 820-870 ℃, the holding time is 6-8h, and then quenching cooling is carried out to room temperature by water.
5. The method as claimed in claim 2, wherein the hot rolling temperature in S3) is 820-870 ℃, the rolling reduction per pass is controlled to be 6-12%, and the plate with the thickness of 8-12mm is rolled.
6. The method as claimed in claim 2, wherein the heating temperature of the solution treatment in S4) is 860-880 ℃, the temperature is kept for 1-2h, and the water is cooled to room temperature.
7. The method as claimed in claim 2, wherein the low temperature rolling in S5) is carried out by placing the alloy processed in S4) in liquid nitrogen, taking out the material from the liquid nitrogen, immediately carrying out multi-pass rolling at room temperature, wherein the rolling reduction of each pass is controlled to be 8-15%, and each pass is immersed in the liquid nitrogen for 5-8 min.
8. The method as claimed in claim 2, wherein the treatment temperature in S6) is controlled at 400-600 deg.C, the holding time is 0.5-16h, and the air cooling is carried out to room temperature.
9. The method of claims 2-8, wherein the high strength and conductivity Cu-Sc alloy has a yield strength of not less than 695.8MPa and an electrical conductivity of not less than 62.8% IACS.
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CN113943875A (en) * | 2021-10-23 | 2022-01-18 | 福州大学 | A kind of Cu-Sn-P copper alloy material with high tin content and preparation method thereof |
CN114959350A (en) * | 2022-05-31 | 2022-08-30 | 西安理工大学 | High-performance Cu-Hf-RE alloy and preparation method thereof |
CN115466865A (en) * | 2022-08-15 | 2022-12-13 | 宁波康强电子股份有限公司 | Method for preparing high-strength and high-conductivity Cu-Cr-Sn alloy based on low-temperature plastic deformation and graded aging |
CN116240423A (en) * | 2023-02-22 | 2023-06-09 | 河南科技大学 | Copper alloy with high-density twins and low-mismatch precipitated phase and preparation method thereof |
CN116377280A (en) * | 2023-02-22 | 2023-07-04 | 河南科技大学 | Copper-nickel-silicon alloy with internal multi-orientation twins and precipitated phase coexistence and preparation method thereof |
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