CN117070867B - Method for improving softening temperature of copper alloy and copper alloy - Google Patents
Method for improving softening temperature of copper alloy and copper alloy Download PDFInfo
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000000956 alloy Substances 0.000 claims abstract description 83
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 78
- 230000032683 aging Effects 0.000 claims abstract description 55
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 33
- 229910017876 Cu—Ni—Si Inorganic materials 0.000 claims abstract description 14
- 229910017824 Cu—Fe—P Inorganic materials 0.000 claims abstract description 12
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 claims abstract description 9
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 claims abstract description 9
- 238000005097 cold rolling Methods 0.000 claims description 28
- 238000005096 rolling process Methods 0.000 claims description 18
- 238000003801 milling Methods 0.000 claims description 13
- 238000005098 hot rolling Methods 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 229910019580 Cr Zr Inorganic materials 0.000 claims description 3
- 229910019817 Cr—Zr Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000005452 bending Methods 0.000 claims description 3
- 238000009749 continuous casting Methods 0.000 claims description 3
- 239000002826 coolant Substances 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 230000035882 stress Effects 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000004804 winding Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 13
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- 238000011161 development Methods 0.000 description 9
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- 239000000243 solution Substances 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910005487 Ni2Si Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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- 229910021484 silicon-nickel alloy Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 239000011573 trace mineral Substances 0.000 description 1
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Classifications
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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
Abstract
The invention belongs to the technical field of copper alloy processing, and particularly relates to a method for improving softening temperature of copper alloy and copper alloy. According to the method for improving the softening temperature of the copper alloy, the pre-ageing and the regression heat treatment are added on the basis of the traditional double-stage ageing heat treatment of the copper alloy, so that the softening temperature of the copper alloy is improved. According to the method disclosed by the invention, the precipitation behavior and the precipitation state of the alloy second-phase particles are optimized, the size of the second-phase particles is greatly reduced, and the particle occupation ratio of the second-phase particles with the size of 2-30 nm is greatly improved. Compared with the prior art, the softening temperature of the Cu-Ni-Si alloy is increased by 50-69 ℃, the softening temperature of the Cu-Cr-Zr alloy is increased by 57-70 ℃, and the softening temperature of the Cu-Fe-P alloy is increased by 53-62 ℃.
Description
Technical Field
The invention belongs to the technical field of copper alloy processing, and particularly relates to a method for improving softening temperature of copper alloy and copper alloy.
Background
The integrated circuit industry has been related to national security and social development, and has progressed rapidly in recent years. With the development of new generation electronic information technology, especially the development of 5G and future 6G technologies, the development of integrated circuits represented by chips is promoted toward high integration and miniaturization. The lead frame plays a key role in bearing chips, transmitting electric signals and radiating heat in an integrated circuit, and is mainly made of copper alloy materials, and particularly takes aging strengthening copper alloy as a main material. Currently, the main lead frame products are C19210 and C19400 alloys of Cu-Fe-P system, and the like, are gradually changed to high-strength medium-conductivity Cu-Ni-Si system alloys, and the future development trend is towards high-strength high-conductivity Cu-Cr-Zr system alloy materials.
With the development of packaging technology and integration technology, lead frames are developed towards light, thin and high definition, and large-scale integrated circuit chips can cause the mechanical performance of lead frame materials to be reduced due to large heat productivity in the operation process. In addition, the lead frame also has a short time high temperature during the existing packaging process. Therefore, the copper alloy material is required to have good mechanical property and electric conductivity, and also is required to have good high-temperature softening resistance. The high-temperature softening resistance of the material can be evaluated by the softening temperature, and the annealing temperature which reduces the hardness by 20% by keeping the material warm for 1h is used as the softening temperature, which is specified in the national standard GB/T33370-2016 method for measuring the softening temperature of copper and copper alloys.
In order to raise the softening temperature of copper alloy, it is common to change the alloy composition and add trace elements even if the hardness of the alloy after 1h annealing is kept high. The content and proportion of the main alloy element have great influence on softening performance, such as a Cu-Ni-Si series representative C70250 alloy, and the prior study proves that the component range of the element Ni is 2.1% -3.2%, the component range of the element Si is 0.5% -0.8%, and the Ni/Si ratio is 3.77% -4.38, so that the sufficient precipitation of Ni and Si in a Ni2Si phase can be ensured. In addition, microalloying elements (such as Mg, fe, zn, ti, P and the like) have certain influence on the strength, conductivity and high-temperature softening resistance of the alloy, wherein Mg and P reduce the vacancy binding energy of the alloy and improve Ni 2 High temperature stability of the Si phase.
On the basis of optimizing and determining the alloy components, regulating and controlling the precipitated phase state through a thermomechanical treatment process is also a way for improving the softening temperature. Firstly, ensuring the sufficient precipitation of main alloy elements is a basic requirement for ensuring the alloy strength and the conductivity, and secondly, regulating the size and the distribution of alloy precipitated phases to be in a better state can obtain better high-temperature softening resistance. The Beijing color institute Huang Guojie et al explored the effect of the aging process on the softening temperature of the C19400 copper alloy, and the results show that the adoption of the graded aging process can obtain a finer and more uniform precipitated phase structure than single-stage aging, and the softening temperature is increased by about 60 ℃. Furthermore, the proportion of the number of fine precipitated phases is also advantageous for increasing the softening temperature. Researches show that particles with the Ni2Si phase size of 2 nm-30 nm in the Cu-Ni-Si alloy and a matrix are in a coherent relation, when the proportion of the particles is more than 90%, the Cu-Ni-Si alloy with good softening performance can be obtained, and meanwhile, the comprehensive performances of strength, conductivity and the like of the alloy are also excellent.
Copper alloy materials undergo work hardening after cold deformation, creating many dislocations and substructures that raise the free energy of the system and enter a metastable state. After the annealing temperature is raised to be higher than the recrystallization temperature, the work hardening is eliminated, recrystallization occurs, the crystal grain grows up, and the high-temperature softening resistance of the alloy is greatly reduced.
In summary, for copper materials for lead frames, such as Cu-Ni-Si-based, cu-Cr-Zr-based and Cu-Fe-P-based alloys, numerous achievements have been obtained in the development of alloy component systems at present, and good matching of strength and conductivity is obtained through a two-stage aging and other thermomechanical treatment processes, so that the softening temperature is increased to a level of 450-500 ℃, and the use requirements of lead frame materials are basically met. However, with the development demands of very large scale and very large scale integrated circuits, how to make copper alloy obtain better high temperature softening resistance and raise the softening temperature to 500 ℃ and above is an urgent problem to be solved.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a method for improving the softening temperature of copper alloy and the copper alloy, which concretely comprise the following contents:
a method of increasing the softening temperature of a copper alloy comprising the steps of:
(1) And (3) hot rolling: heating a copper alloy cast ingot, hot rolling, quenching and rolling;
(2) Milling: milling the surface of the copper alloy after hot rolling, and removing an oxide layer;
(3) And (3) blooming: performing blooming on the copper alloy after milling;
(4) Solution treatment: carrying out solution treatment on the copper alloy after blooming;
(5) Primary cold rolling: carrying out primary cold rolling on the copper alloy subjected to solution treatment;
(6) Pre-ageing: carrying out pre-ageing treatment on the copper alloy subjected to primary cold rolling, wherein the pre-ageing temperature is 490-580 ℃ and the pre-ageing time is 8-20 hours;
(7) Regression heat treatment: carrying out regression heat treatment on the copper alloy after pre-ageing, wherein the regression temperature is 660-820 ℃, and the heat preservation time is 1-10 min;
(8) Cold rolling and aging: and (3) carrying out cold rolling and aging treatment on the copper alloy subjected to the regression heat treatment at least once, and then carrying out final rolling to obtain the copper alloy with the increased softening temperature.
Preferably, the pre-ageing temperature in the step (6) is 510-540 ℃, and the pre-ageing time is 10-15 h.
Preferably, the pre-ageing temperature in the step (6) is 520-530 ℃ and the pre-ageing time is 11-13h.
Preferably, the regression temperature in the step (7) is 720-780 ℃ and the heat preservation time is 2-5 min.
Preferably, the regression temperature in the step (7) is 740-760 ℃, and the heat preservation time is 2-3 min.
Preferably, the copper alloy is one of a Cu-Ni-Si-based alloy, a Cu-Cr-Zr-based alloy and a Cu-Fe-P-based alloy.
Preferably, when the copper alloy is a Cu-Ni-Si alloy, the softening temperature of the copper alloy after the softening temperature is increased is 553 ℃ to 572 ℃;
when the copper alloy is a Cu-Cr-Zr alloy, the softening temperature of the copper alloy after the softening temperature is increased is 554-567 ℃;
when the copper alloy is a Cu-Fe-P alloy, the softening temperature of the copper alloy after the softening temperature is increased is 538-547 ℃.
Preferably, the average size of the second phase particles in the copper alloy with the increased softening temperature is 12.1 nm-21.3 nm, wherein the proportion of the second phase particles with the size of 2-30 nm in the total second phase particles is 94.3% -97.3%, and the proportion of the second phase particles with the size of more than 30nm in the total second phase particles is 2.7% -5.7%.
Preferably, step (1): the copper alloy cast ingot is obtained by adopting an intermediate frequency furnace to perform non-vacuum smelting and performing semi-continuous casting; the hot bundling method comprises the following steps: putting the copper alloy cast ingot into a stepping furnace for heating, wherein the furnace temperature is 900-920 ℃, and heating for 3-5h; then hot rolling is started, 9 or 11 passes are adopted, and the final rolling temperature is 780-800 ℃; then spraying and quenching on line; then cooling to 180 ℃ and rolling;
the face milling method in the step (2) comprises the following steps: double-sided milling is carried out on the hot rolled coil obtained by winding, and the upper surface and the lower surface are respectively milled for 0.4-0.6mm;
the blooming method in the step (3) comprises the following steps: performing initial rolling by adopting a four-high mill, and controlling the total deformation to be 85% -90%;
the solution treatment method in the step (4) comprises the following steps: carrying out solution treatment on line at high temperature, wherein the heating temperature is 960-1000 ℃, the passing speed is 3-4 m/min, the cooling medium is nitrogen or ammonia decomposition gas, and the outlet temperature is lower than 80 ℃;
the primary cold rolling method in the step (5) comprises the following steps: cold rolling by using a finishing mill, and controlling the total deformation to be 55-65%;
the cold rolling and aging method in the step (8) comprises the following steps:
a. cold rolling: cold rolling in a finishing mill, wherein the total deformation is controlled to be 55% -60%;
b. primary aging: aging for 5-8 hours at the temperature of 450-480 ℃ in a bell jar furnace for one time;
c. cold rolling: cold rolling in a finishing mill, wherein the total deformation is controlled to be 45% -50%;
d. and (3) secondary aging: performing secondary aging in a bell jar furnace, wherein the aging temperature is 360-420 ℃, and the aging time is 4-6 hours;
e. and (3) final rolling: performing final rolling in a finishing mill, and controlling the total deformation to be 30% -40%; and then carrying out stress relief annealing, stretch bending straightening and slitting to obtain the copper alloy with the increased softening temperature.
The copper alloy treated by the method for improving the softening temperature of the copper alloy.
The invention has the beneficial effects that:
the invention provides a method for improving the softening temperature of a copper alloy, which is characterized in that pre-ageing and regression heat treatment are added on the basis of traditional double-stage ageing heat treatment of the copper alloy, so that the softening temperature of the copper alloy is improved. The regression heat treatment is a process of heating the alloy after the pre-aging strengthening for a short time at a temperature slightly lower than the solid solution temperature to cause the second phase of the alloy to dissolve back and even recover to the solid solution state. The regression heat treatment process has less structural analysis research after the regression heat treatment of the copper alloy, and the relation between the alloy structure and the performance is not clear, so that the influence of the regression heat treatment on the alloy performance and the related mechanism are not clear, and therefore, the performance of the copper alloy is improved by using the regression heat treatment through related patents and technologies at present.
The method disclosed by the invention is added with regression heat treatment and limits a specific treatment process, so that the precipitated phase and the coarse second phase in the copper alloy are redissolved in the matrix to form solid solution or GP-like area combination again, defects such as dislocation clusters, coarse second phase, vacancies and the like are eliminated, and the structural uniformity is improved. The method has the advantages that the process parameters are specifically limited according to the characteristics of the copper alloy related to the invention through cold deformation and aging treatment after the regression heat treatment, the second phase precipitation is more sufficient, uniform and dispersive, and the size of the precipitated phase is smaller, so that the softening temperature of the copper alloy is improved. According to the method disclosed by the invention, the precipitation behavior and the precipitation state of the alloy second-phase particles are optimized, the size of the second-phase particles is greatly reduced, and the particle occupation ratio of the second-phase particles with the size of 2-30 nm is greatly improved. Compared with the prior art, the softening temperature of the Cu-Ni-Si alloy is increased by 50-69 ℃, the softening temperature of the Cu-Cr-Zr alloy is increased by 57-70 ℃, and the softening temperature of the Cu-Fe-P alloy is increased by 53-62 ℃. The method disclosed by the invention can be used for improving the softening temperature of the copper material of the lead frame and optimizing the comprehensive performance, promotes the progress of new materials and supports the rapid development of the integrated circuit industry.
Drawings
FIG. 1 is a TEM spectrum of an alloy of example 1 of the present invention;
FIG. 2 is a TEM image of the alloy of comparative example 1 of the present invention;
FIG. 3 is a TEM image of the alloy of example 6 of the present invention;
FIG. 4 is a TEM image of the alloy of comparative example 2 of the present invention;
FIG. 5 is a TEM image of the alloy of example 9 of the present invention;
FIG. 6 is a TEM image of the alloy of comparative example 3 of the present invention.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description. The embodiments shown below do not limit the inventive content described in the claims in any way. The whole contents of the constitution shown in the following examples are not limited to the solution of the invention described in the claims.
A method for improving softening temperature of copper alloy, preparation and treatment method of alloy comprises the following steps:
(1) Alloy casting: the ingredients were dosed according to the alloy compositions in table 1, cu-Ni-Si alloy, cu-Cr-Zr alloy and Cu-Fe-P alloy are non-vacuum smelted in intermediate frequency furnace, different covering agents and solution refining agents are selected according to alloy characteristics, alloy ingots are obtained through semi-continuous casting, and the sizes of the ingots are determined according to a crystallizer.
(2) And (3) hot rolling: the ingot is put into a stepping furnace for heating, the furnace temperature is 900-920 ℃ (such as 905 ℃, 910 ℃, 915 ℃, 918 ℃ and the like), heating is carried out for 3-5h (such as 3.2h, 3.5h, 3.8h, 4h, 4.5h and the like), hot rolling is started, 9 passes or 11 passes are adopted, the final rolling temperature is 780-800 ℃ (such as 782 ℃, 784 ℃, 786 ℃, 788 ℃ and the like), then online spray quenching is carried out, the temperature is reduced to 180 ℃ (such as 175 ℃, 165 ℃, 150 ℃, 120 ℃ and the like), and rolling is carried out.
(3) Double-sided milling: milling the surface of the hot rolled coil, and respectively milling the upper surface and the lower surface by 0.4-0.6mm (such as 0.42mm, 0.45mm, 0.5mm, 0.55mm and the like), thereby ensuring that the oxide skin is removed cleanly;
(4) And (3) blooming: and (3) performing initial rolling by adopting a four-high mill, wherein the total deformation is 85% -90% (for example, 86%, 87%, 88%, 89% and the like).
(5) High-temperature online solid solution: carrying out solution treatment on line at high temperature, wherein the heating temperature is 960-1000 ℃ (such as 970 ℃, 975 ℃, 980 ℃, 990 ℃ and the like), the passing speed is 3-4 m/min (such as 3.2m/min, 3.4m/min, 3.6m/min, 3.8m/min and the like), the cooling medium is nitrogen or ammonia decomposition gas, and the outlet temperature is lower than 80 ℃ (such as 15 ℃, 65 ℃, 50 ℃, 20 ℃ and the like).
(6) Cold rolling: cold rolling in a finishing mill with a total deformation of 55-65% (e.g., 56%, 58%, 60%, 62%, etc.).
(7) Pre-ageing: the pre-aging is performed in a bell jar furnace at 490 to 580 ℃ (e.g., 500 ℃, 520 ℃, 540 ℃, 560 ℃, etc.), 8 to 20 hours (e.g., 9 hours, 10 hours, 12 hours, 15 hours, 18 hours, etc.), preferably 510 to 540 ℃ (e.g., 515 ℃, 520 ℃, 530 ℃, 535 ℃, etc.), 10 to 15 hours (e.g., 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, etc.), and more preferably 520 to 530 ℃ (e.g., 522 ℃, 524 ℃, 526 ℃, 528 ℃, etc.), and 12 hours.
(8) Regression heat treatment: the heat preservation is carried out in an air cushion furnace, the regression temperature is 660-820 ℃ (such as 680 ℃, 700 ℃, 740 ℃, 780 ℃, 800 ℃ and the like), the heat preservation time is 1-10 min (such as 2min, 4min, 6min, 8min and the like), the regression temperature is 720-780 ℃ (such as 730 ℃, 735 ℃, 740 ℃, 750 ℃, 760 ℃ and the like), the heat preservation time is 2-5 min (such as 2.5min, 3min, 3.5min, 4min and the like), the regression temperature is 740-760 ℃ (such as 745 ℃, 748 ℃, 750 ℃, 752 ℃, 755 ℃, 758 ℃ and the like), and the heat preservation time is 2-3 min (such as 2.2min, 2.4min, 2.6min, 2.8min and the like).
(9) Cold rolling: the cold rolling is performed in a finishing mill, and the total deformation amount is 55% -60% (for example, 56%, 57%, 58%, 59%, etc.).
(10) Primary aging: aging for 5-8 h (e.g. 5.5h, 6h, 6.5h, 7h, 7.5h, etc.) in a bell jar furnace at 450-480 ℃ (e.g. 455 ℃, 460 ℃, 465 ℃, 470 ℃, 475 ℃), etc.).
(11) Cold rolling: cold rolling is performed in a finishing mill, and the total deformation is 45% -50% (for example, 46%, 47%, 48%, 49%, etc.).
(12) And (3) secondary aging: and (3) performing secondary aging in a bell jar furnace, wherein the aging temperature is 360-420 ℃ (such as 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃ and the like), and the aging time is 4-6 hours (such as 4.2 hours, 4.5 hours, 4.8 hours, 5 hours, 5.5 hours and the like).
(13) And (3) final rolling: and (3) final rolling is carried out in a finishing mill, the total deformation is 30% -40% (such as 32%, 34%, 36%, 38%, and the like), and then the strip is subjected to processes of stress relief annealing, stretch bending straightening, slitting and the like.
For a better understanding of the present invention, the following description will provide further explanation of the present invention with reference to specific examples.
Microhardness test in examples microhardness test according to the national standard GB/T4340.1-2009 section 1 of Vickers hardness test of metallic materials: the test method prescribed in test method is measured; conductivity test the conductivity of the alloy was tested according to the method specified in the national standard GB/T32791-2016 copper and copper alloy conductivity vortex test method; the softening temperature test is measured according to a test method specified in national standard GB/T33370-2016 copper and copper alloy softening temperature determination method; the sizes and distribution states of the second phase particles are counted according to a TEM image of the strip sample, wherein the TEM image is not less than 10 pieces, and the total number of the counted second phase particles is not less than 500.
Examples 1 to 3
Examples 1 to 3 involved alloys of Cu-Ni-Si type, with Cu-2.6Ni-0.6Si as the alloy components, were processed according to the processes shown in Table 1, and the properties and second phase particle characteristics of the alloys are shown in Table 2.
Comparative example 1
In comparative example 1, the alloy involved was the same as examples 1-3, the composition was Cu-2.6Ni-0.6Si, as shown in Table 1, the preparation process was not subjected to pre-aging and regression heat treatment, the rest of the processing techniques were the same, and the properties and second phase particle characteristics of the alloy were as shown in Table 2.
Examples 4 to 6
Examples 4 to 6 involved alloys of Cu-Cr-Zr system, with Cu-0.6Cr-0.1Zr as the alloy components, were processed according to the processes shown in Table 1, and the properties and second phase particle characteristics of the alloys are shown in Table 2.
Comparative example 2
In comparative example 2, the alloy involved was the same as in examples 4-6, the composition was Cu-0.6Cr-0.1Zr, as shown in Table 1, the preparation process was not subjected to pre-aging and regression heat treatment, the rest of the processing techniques were the same, and the properties and second phase particle characteristics of the alloy were as shown in Table 2.
Examples 7 to 9
Examples 7 to 9 involved alloys of Cu-Fe-P system, with Cu-2.5Fe-0.1P as the alloy component, were processed according to the process shown in Table 1, and the properties and second phase particle characteristics of the alloys are shown in Table 2.
Comparative example 3
In comparative example 3, the alloy involved was the same as in examples 7 to 9, the composition was Cu-2.5Fe-0.1P, as shown in Table 1, the preparation process was not subjected to pre-aging and regression heat treatment, the rest of the processing techniques were the same, and the properties and second phase particle characteristics of the alloy were as shown in Table 2.
Table 1 alloy composition and processing parameters
Table 2 properties and second phase particle characteristics of alloys in examples and comparative examples
As can be seen from Table 2, the softening temperatures of the three copper alloys are greatly increased after the pre-aging and the regression heat treatment, as compared with the comparative example 1, the softening temperatures of the Cu-Ni-Si alloy are increased by 50 ℃ to 69 ℃, the softening temperatures of the Cu-Cr-Zr alloy are increased by 57 ℃ to 70 ℃, and the softening temperatures of the Cu-Fe-P alloy are increased by 53 ℃ to 62 ℃ in comparison with the comparative example 1, the examples 4 to 6 and the comparative example 3. Through analyzing the characteristics of the second phase particles of the alloy material, the sizes of the second phase particles are greatly reduced after the pre-ageing and regression heat treatment, the proportion of the particles with the sizes of 2-30 nm is greatly improved, that is, the precipitation behavior and the precipitation state of the second phase particles of the alloy are optimized, so that the effect of improving the comprehensive performance of the copper alloy is realized.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for increasing the softening temperature of a copper alloy comprising the steps of:
(1) And (3) hot rolling: heating a copper alloy cast ingot, hot rolling, quenching and rolling; the copper alloy is Cu-Ni-Si alloy, cu-Cr-Zr alloy or Cu-Fe-P alloy;
(2) Milling: milling the surface of the copper alloy after hot rolling, and removing an oxide layer;
(3) And (3) blooming: performing blooming on the copper alloy after milling;
(4) Solution treatment: carrying out solution treatment on the copper alloy after blooming;
(5) Primary cold rolling: carrying out primary cold rolling on the copper alloy subjected to solution treatment;
(6) Pre-ageing: carrying out pre-ageing treatment on the copper alloy subjected to primary cold rolling, wherein the pre-ageing temperature is 490-580 ℃ and the pre-ageing time is 8-20 hours;
(7) Regression heat treatment: carrying out regression heat treatment on the copper alloy after pre-ageing, wherein the regression temperature is 660-820 ℃, and the heat preservation time is 1-10 min;
(8) Cold rolling and aging:
a. cold rolling: cold rolling in a finishing mill, wherein the total deformation is controlled to be 55% -60%;
b. primary aging: aging for 5-8 hours at the temperature of 450-480 ℃ in a bell jar furnace for one time;
c. cold rolling: cold rolling in a finishing mill, wherein the total deformation is controlled to be 45% -50%;
d. and (3) secondary aging: performing secondary aging in a bell jar furnace, wherein the aging temperature is 360-420 ℃, and the aging time is 4-6 hours;
e. and (3) final rolling: performing final rolling in a finishing mill, and controlling the total deformation to be 30% -40%; and then carrying out stress relief annealing, stretch bending straightening and slitting to obtain the copper alloy with the increased softening temperature.
2. The method for increasing the softening temperature of a copper alloy according to claim 1, wherein the pre-ageing temperature in the step (6) is 510-540 ℃ and the pre-ageing time is 10-15 h.
3. The method for increasing the softening temperature of a copper alloy according to claim 1, wherein the pre-ageing temperature in the step (6) is 520-530 ℃ and the pre-ageing time is 11-13h.
4. The method for increasing the softening temperature of a copper alloy according to any one of claims 1 to 3, wherein the regression temperature in the step (7) is 720 to 780 ℃ and the holding time is 2 to 5 minutes.
5. The method for increasing the softening temperature of a copper alloy according to any one of claims 1 to 3, wherein the regression temperature in the step (7) is 740 to 760 ℃ and the holding time is 2 to 3min.
6. The method of increasing the softening temperature of a copper alloy according to claim 1, wherein the copper alloy is one of a Cu-Ni-Si based, a Cu-Cr-Zr based, and a Cu-Fe-P based alloy.
7. A method for increasing the softening temperature of a copper alloy in accordance with claim 6,
when the copper alloy is a Cu-Ni-Si alloy, the softening temperature of the copper alloy after the softening temperature is increased is 553-572 ℃;
when the copper alloy is a Cu-Cr-Zr alloy, the softening temperature of the copper alloy after the softening temperature is increased is 554-567 ℃;
when the copper alloy is a Cu-Fe-P alloy, the softening temperature of the copper alloy after the softening temperature is increased is 538-547 ℃.
8. The method for increasing the softening temperature of a copper alloy according to claim 1, wherein the average size of second phase particles in the copper alloy after the softening temperature is increased is 12.1nm to 21.3nm, the proportion of the second phase particles with the size of 2 to 30nm in the total second phase particles is 94.3 to 97.3%, and the proportion of the second phase particles with the size of more than 30nm in the total second phase particles is 2.7 to 5.7%.
9. A method for increasing the softening temperature of a copper alloy according to claim 1,
the copper alloy cast ingot is obtained by adopting an intermediate frequency furnace to perform non-vacuum smelting and performing semi-continuous casting; the hot rolling method comprises the following steps: putting the copper alloy cast ingot into a stepping furnace for heating, wherein the furnace temperature is 900-920 ℃, and heating for 3-5h; then hot rolling is started, 9 or 11 passes are adopted, and the final rolling temperature is 780-800 ℃; then spraying and quenching on line; then cooling to 180 ℃ and rolling;
the face milling method comprises the following steps: double-sided milling is carried out on the hot rolled coil obtained by winding, and the upper surface and the lower surface are respectively milled for 0.4-0.6mm;
the blooming method comprises the following steps: performing initial rolling by adopting a four-high mill, and controlling the total deformation to be 85% -90%;
the solution treatment method comprises the following steps: carrying out solution treatment on line at high temperature, wherein the heating temperature is 960-1000 ℃, the passing speed is 3-4 m/min, the cooling medium is nitrogen or ammonia decomposition gas, and the outlet temperature is lower than 80 ℃;
the primary cold rolling method comprises the following steps: cold rolling with finishing mill with total deformation controlled to 55-65%.
10. A copper alloy treated by the method for increasing the softening temperature of a copper alloy according to claim 1.
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| CN107267802A (en) * | 2016-03-31 | 2017-10-20 | Ｊｘ金属株式会社 | The manufacture method of copper alloy plate and copper alloy plate |
| JP2020079436A (en) * | 2018-11-13 | 2020-05-28 | Ｄｏｗａメタルテック株式会社 | HIGH YOUNG Cu-Ni-Al-BASED COPPER ALLOY SHEET, METHOD FOR PRODUCING THE SAME, AND CONDUCTIVE SPRING MEMBER |
| CN112375939A (en) * | 2020-11-16 | 2021-02-19 | 福州大学 | Cu-Ni-Zr-V-B copper alloy material and preparation method thereof |
| CN116815008A (en) * | 2023-07-10 | 2023-09-29 | 中南大学 | Fine-grain high-performance Cu-Ni-Si alloy material and preparation method thereof |
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| CN107267802A (en) * | 2016-03-31 | 2017-10-20 | Ｊｘ金属株式会社 | The manufacture method of copper alloy plate and copper alloy plate |
| JP2020079436A (en) * | 2018-11-13 | 2020-05-28 | Ｄｏｗａメタルテック株式会社 | HIGH YOUNG Cu-Ni-Al-BASED COPPER ALLOY SHEET, METHOD FOR PRODUCING THE SAME, AND CONDUCTIVE SPRING MEMBER |
| CN112375939A (en) * | 2020-11-16 | 2021-02-19 | 福州大学 | Cu-Ni-Zr-V-B copper alloy material and preparation method thereof |
| CN116815008A (en) * | 2023-07-10 | 2023-09-29 | 中南大学 | Fine-grain high-performance Cu-Ni-Si alloy material and preparation method thereof |
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