CN116426789B - Copper-chromium-scandium alloy and preparation method thereof - Google Patents
Copper-chromium-scandium alloy and preparation method thereof Download PDFInfo
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- CN116426789B CN116426789B CN202310481931.7A CN202310481931A CN116426789B CN 116426789 B CN116426789 B CN 116426789B CN 202310481931 A CN202310481931 A CN 202310481931A CN 116426789 B CN116426789 B CN 116426789B
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- 229910000542 Sc alloy Inorganic materials 0.000 title claims abstract description 67
- QHEAZHCOOYEHKX-UHFFFAOYSA-N [Cu].[Cr].[Sc] Chemical compound [Cu].[Cr].[Sc] QHEAZHCOOYEHKX-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000956 alloy Substances 0.000 claims abstract description 52
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 50
- 229910045601 alloy Inorganic materials 0.000 claims description 50
- 229910052802 copper Inorganic materials 0.000 claims description 50
- 239000010949 copper Substances 0.000 claims description 50
- 238000001125 extrusion Methods 0.000 claims description 37
- 238000005242 forging Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 27
- 238000003723 Smelting Methods 0.000 claims description 23
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 23
- 230000032683 aging Effects 0.000 claims description 20
- 229910052706 scandium Inorganic materials 0.000 claims description 18
- 238000000265 homogenisation Methods 0.000 claims description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 abstract description 10
- 230000004927 fusion Effects 0.000 abstract description 5
- 238000010248 power generation Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 35
- 239000007789 gas Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 18
- 238000001816 cooling Methods 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 9
- 238000003754 machining Methods 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000003610 charcoal Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- 239000002893 slag Substances 0.000 description 5
- QZLJNVMRJXHARQ-UHFFFAOYSA-N [Zr].[Cr].[Cu] Chemical compound [Zr].[Cr].[Cu] QZLJNVMRJXHARQ-UHFFFAOYSA-N 0.000 description 4
- ZTXONRUJVYXVTJ-UHFFFAOYSA-N chromium copper Chemical compound [Cr][Cu][Cr] ZTXONRUJVYXVTJ-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000002679 ablation Methods 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000005058 metal casting Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910001093 Zr alloy Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C23/00—Extruding metal; Impact extrusion
- B21C23/001—Extruding metal; Impact extrusion to improve the material properties, e.g. lateral extrusion
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to a copper-chromium-scandium alloy and a preparation method thereof, and belongs to the technical field of copper alloy materials. According to the copper-chromium-scandium alloy, sc is adopted to replace the element Zr easy to burn, so that the copper alloy with excellent mechanical property, electric conduction and heat conduction properties and high-temperature softening resistance is obtained. The conductivity of the copper-chromium-scandium alloy is more than or equal to 82% IACS, the thermal conductivity is more than or equal to 392W (m.K) ‑1, the room-temperature tensile strength is more than or equal to 470MPa, the elongation is more than or equal to 9%, and the copper-chromium-scandium alloy can meet the product requirements of the fields of high-speed railway contact lines, large-scale integrated circuit lead frames, high-pulse electromagnetic coils, nuclear fusion energy power generation and the like.
Description
Technical Field
The invention relates to a copper-chromium-scandium alloy and a preparation method thereof, and belongs to the technical field of copper alloy materials.
Background
The chromium-copper base alloy is used as a typical aging precipitation strengthening copper alloy, has good high-strength and high-conductivity performance, and can be applied to the fields of large-scale integrated circuit lead frames, high-speed railway contact wires, high-end connector connectors and the like. It is also an important candidate material for heat sink components of nuclear fusion reactors. In order to adapt to the high-temperature working environment in the nuclear reactor, the alloy is required to have excellent mechanical properties, high heat resistance and high heat conductivity.
Currently, chromium-zirconium-copper alloy is a typical chromium-copper alloy with excellent combination of properties. For example, chinese patent document CN 109385555A discloses a copper-chromium-zirconium alloy which is prepared from 0.2 to 1.2% of chromium, 0.05 to 0.2% of zirconium, 0.06 to 0.10% of magnesium, 0.05 to 0.5% of scandium and the balance of copper. The copper-chromium-zirconium alloy disclosed in the document has high tensile strength, high conductivity and high elongation, and has higher high-temperature tensile strength and excellent comprehensive performance. However, when the alloy is melted under atmospheric conditions, zirconium (Zr) is liable to burn out and react with the substrate, so that the chromium-zirconium-copper alloy composition is difficult to control, and mass production application cannot be realized. In addition, magnesium is an active metal, and the components are not easily controlled when added.
Therefore, the development of the alloy components is relatively easy to control, the chromium-copper alloy with excellent mechanical property, high temperature resistance and heat conductivity can provide a reserve material for the field of nuclear fusion power generation, further promote the development process of nuclear fusion energy, reduce the dependence on fossil energy and have important significance for environmental protection.
Disclosure of Invention
The invention aims to provide a copper-chromium-scandium alloy, which can solve the problems that the alloy composition is difficult to control and the batch production application cannot be realized due to the adoption of zirconium element in the conventional chromium-copper alloy.
The invention further aims at providing a preparation method of the copper-chromium-scandium alloy.
In order to achieve the above purpose, the copper-chromium-scandium alloy of the present invention adopts the following technical scheme:
the copper-chromium-scandium alloy comprises, by mass, 0.16-0.2% of chromium element, 0.08-0.15% of scandium element, and the balance of copper element and unavoidable impurity elements.
According to the copper-chromium-scandium alloy, sc is adopted to replace the element Zr easy to burn, so that the copper alloy with excellent mechanical property, electric conduction and heat conduction properties and high-temperature softening resistance is obtained. The conductivity of the copper-chromium-scandium alloy is more than or equal to 82% IACS, the thermal conductivity is more than or equal to 392W (m.K) -1, the room-temperature tensile strength is more than or equal to 470MPa, the elongation is more than or equal to 9%, and the copper-chromium-scandium alloy can meet the product requirements of the fields of high-speed railway contact lines, large-scale integrated circuit lead frames, high-pulse electromagnetic coils, nuclear fusion energy power generation and the like.
Experiments show that Sc is a typical light rare earth element, and is singly added into pure copper, and the yield strength of the prepared Cu-Sc binary alloy can reach 696MPa and the conductivity can reach 63% IACS by combining a deep cold rolling technology.
Preferably, in the copper-chromium-scandium alloy, the mass percentage of the chromium element is 0.18-0.2%, and the mass percentage of the scandium element is 0.11-0.15%.
Preferably, the impurity element is selected from one or any combination of aluminum element, silicon element, iron element and tin element, and the mass percentage of the impurity element in the copper-chromium-scandium alloy is not more than 0.05%.
The technical scheme adopted by the preparation method of the copper-chromium-scandium alloy is as follows:
Smelting copper, copper-chromium intermediate alloy and scandium, casting and forming to obtain an ingot, and sequentially carrying out homogenization treatment, forging, solution treatment, equal-diameter angular extrusion and aging treatment on the ingot to obtain the copper-chromium scandium alloy.
The preparation method of the copper-chromium-scandium alloy is simple to operate, the component fluctuation rate of the prepared copper-chromium-scandium alloy is within +/-0.02%, the copper-chromium-scandium alloy has good tensile strength and elongation, and high electric conductivity and thermal conductivity, and is suitable for the fields of continuous casting crystallizers, high-end connector connectors and the like. The method comprises the steps of homogenizing treatment for eliminating non-uniform components generated in the casting process, hot forging for eliminating defects generated in the casting process, grain refinement, solution treatment for enabling solute to be fully dissolved into a copper matrix, equal-diameter angular extrusion for obtaining finer micron-sized grains to strengthen the matrix, aging treatment for promoting Cr to be precipitated from supersaturated solid solution to form dispersed nano-sized precipitated phases, further strengthening the matrix, fully playing the synergistic promotion effect of equal-diameter angular extrusion and aging treatment on the mechanical property and the electrical property of the copper-chromium-scandium alloy, and finally obtaining the copper-chromium-scandium alloy with excellent comprehensive performance.
Preferably, the purity of the copper is not less than 99.95%. Further preferably, the purity of the copper is not less than 99.99%. Preferably, the copper is electrolytic copper.
In order to ensure a better melting of scandium, which is homogeneously distributed in the ingot, preferably in the method for producing a copper-chromium-scandium alloy, the scandium is used in the form of scandium powder.
Preferably, the copper-chromium master alloy is a Cu-25Cr master alloy. Because the melting point (1907 ℃) of chromium element is higher and is not easy to melt, the melting temperature is difficult to reach in the smelting process, and the intermediate alloy (Cu-25 Cr intermediate alloy) is convenient to melt into the matrix in the smelting process, so that the components are controlled more accurately, and the melt with evenly distributed chromium alloy elements is obtained. In addition, the use of the master alloy can also shorten the smelting time, reduce the smelting loss and avoid the overheating of the melt.
Preferably, the scandium has a purity of not less than 99.8%.
Preferably, the smelting temperature is 1150-1250 ℃. Preferably, the smelting time is 30-50 min.
Preferably, the smelting is performed under a micro-oxidizing atmosphere. Preferably, the micro-oxidation atmosphere is formed by covering the molten liquid level with charcoal in the process of heating and melting raw materials, and stirring by a graphite rod during melting, so as to skim slag. Because the graphite rod is high temperature resistant and the graphite rod is adopted for stirring, the introduction of impurities can be avoided.
Preferably, the casting temperature is 1200-1300 ℃. The casting temperature is too high, so that the element ablation is serious, the components of the copper-chromium-scandium alloy are difficult to control, and the casting temperature is too low, so that the solute atoms are unevenly distributed, and the melt fluidity is poor during casting.
Preferably, the homogenization treatment is to keep the ingot at 850-900 ℃. Preferably, the homogenization treatment is not less than 3 hours. For example, the homogenization treatment time is 3 hours. The homogenization treatment temperature is too high, which can cause matrix ablation, and in addition, in the subsequent forging and cooling process, crystal grains can be continuously grown, so that the mechanical property of the ingot is reduced, the ingot plasticity is reduced, the deformation resistance is rapidly increased, and larger residual stress is generated inside the ingot.
Preferably, the forging is performed by forging an ingot subjected to homogenization treatment at a temperature of 850-900 ℃ in air. Preferably, the deformation amount of the forging is 60% -65%. Preferably, the forging is completed within 2 minutes. The forging temperature is too high, which can cause matrix ablation, and in addition, the crystal grains are continuously grown in the cooling process, so that the mechanical property of the forging stock is reduced, the forging temperature is too low, the inside of the forging stock is subjected to work hardening, the plasticity is reduced, the deformation resistance is rapidly increased, larger residual stress is generated in the inside of the forging stock, the forging deformation is too small, the forging cannot meet the performance requirement, and the forging deformation is too large, so that on one hand, the effect of continuously refining the crystal grains is limited, and on the other hand, the anisotropy is caused.
Preferably, the temperature of the solution treatment is 890-970 ℃ and the time is 0.5-2 h. Too high a solution treatment temperature can cause excessive burning of the matrix and coarse structure, too low a solution treatment temperature can prolong the solution time, insufficient solution of solute elements and excessive energy consumption, too short a solution treatment time can cause uneven solute distribution, too long a solution treatment time can cause coarse grains and unnecessary energy consumption.
Preferably, the solution treatment is performed in a shielding gas. Preferably, the shielding gas is nitrogen and/or argon.
Preferably, the solution treatment method comprises the steps of heating the forged cast ingot to 890-970 ℃, preserving heat for 0.5-2 h, and then cooling. Preferably, in the solution treatment method, the cooling is water cooling.
Preferably, the inner angle of the equal diameter angle extrusion channel is 90-110 degrees, and the outer angle is 10-30 degrees. For example, the inside angle of the constant diameter angular extrusion channel is 90 ° and the outside angle is 20 °.
Preferably, the extrusion speed of the constant diameter angle extrusion is 2-10 mm/s.
Preferably, the extrusion pass of the constant diameter angle extrusion is not less than 4 times. The extrusion pass of the equal diameter angle extrusion is too few, which can cause uneven grain refinement degree and poor effect.
Preferably, the constant diameter angular extrusion is performed at room temperature. Compared with the equal diameter angular extrusion at high temperature, the equal diameter angular extrusion at room temperature is adopted, so that energy is saved, and dynamic recovery and recrystallization of grains are reduced.
Preferably, the temperature of the aging treatment is 450-510 ℃ and the time is 0.5-10 h. The aging treatment is too high in temperature, so that a precipitated phase is rapidly precipitated and grown, fine grains are recovered and recrystallized, mechanical properties are reduced, the aging treatment is too low in temperature, the precipitation thermodynamic driving force of the precipitated phase is small, unfavorable solute atoms are precipitated from a supersaturated solid solution, longer aging time is required to be consumed, the aging treatment is too short, solute atoms cannot be completely precipitated from the supersaturated solid solution, the mechanical properties and the electrical properties are not improved, the aging treatment is too long, the precipitated phase is coarsened and grown, and the mechanical properties are reduced.
Preferably, the aging treatment is performed in a protective gas. Preferably, the shielding gas used in the ageing treatment is nitrogen and/or argon.
Preferably, the aging treatment method comprises the following steps of heating an ingot after the extrusion of the constant diameter angle to 450-510 ℃, preserving heat for 0.5-10 h, and then cooling. Preferably, in the aging treatment method, the cooling is air cooling.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
1. Specific examples of the copper-chromium-scandium alloy of the present invention are as follows:
Example 1
The copper-chromium-scandium alloy comprises, by mass, 0.16% of chromium element, 0.08% of scandium element, and the balance of copper element and unavoidable impurity elements, wherein the mass percentage of the impurity elements is not more than 0.05%.
Example 2
The copper-chromium-scandium alloy comprises, by mass, 0.18% of chromium element, 0.11% of scandium element, and the balance of copper element and unavoidable impurity elements, wherein the mass percentage of the impurity elements is not more than 0.05%.
Example 3
The copper-chromium-scandium alloy comprises, by mass, 0.2% of chromium element, 0.15% of scandium element, and the balance of copper element and unavoidable impurity elements, wherein the mass percentage of the impurity elements is not more than 0.05%.
Comparative example 1
The copper-chromium-scandium alloy of this comparative example differs from the copper-chromium-scandium alloy of example 1 only in that the mass fraction of the chromium element in the copper-chromium-scandium alloy of this comparative example is 0.14%.
Comparative example 2
The copper-chromium-scandium alloy of this comparative example differs from the copper-chromium-scandium alloy of example 1 only in that the mass fraction of scandium element in the copper-chromium-scandium alloy of this comparative example is 0.06%.
Comparative example 3
The copper-chromium-scandium alloy of this comparative example differs from the copper-chromium-scandium alloy of example 3 only in that the mass fraction of the chromium element in the copper-chromium-scandium alloy of this comparative example is 0.22%.
Comparative example 4
The copper-chromium-scandium alloy of this comparative example differs from the copper-chromium-scandium alloy of example 3 only in that the mass fraction of scandium element in the copper-chromium-scandium alloy of this comparative example is 0.18%.
Comparative example 5
The copper-based alloy of this comparative example differs from the copper-chromium-scandium alloy of example 3 only in that the scandium element is replaced with the Y element in the copper-based alloy of this comparative example.
Comparative example 6
The copper-based alloy of this comparative example differs from the copper-chromium-scandium alloy of example 3 only in that the scandium element is replaced with the Tm element in the copper-based alloy of this comparative example.
The production methods of the copper-based alloys of comparative examples 1 to 2 were prepared with reference to the production method of the copper-based alloy of example 1.
The copper-based alloy of comparative examples 3 to 6 was prepared with reference to the copper-based alloy of example 3, and the copper-based alloys of comparative examples 5 to 6 were prepared using Y powder and Tm powder having a purity of more than 99.9%, the particle sizes of the Y powder and Tm powder being the same as those of the pure scandium powder used in the copper-based alloy of example 3.
2. The specific examples of the preparation method of the copper-chromium-scandium alloy are as follows:
Example 4
The preparation method of the copper-chromium-scandium alloy of the embodiment is the preparation method of the copper-chromium-scandium alloy of the embodiment 1, and specifically comprises the following steps:
(1) Cutting, drying and surface degreasing an electrolytic copper plate with purity of more than or equal to 99.99 percent and a Cu-25Cr intermediate alloy, adding the treated electrolytic copper plate, the treated Cu-25Cr intermediate alloy and pure scandium powder (Sc of more than or equal to 99.8 percent) into a smelting furnace according to a proportion, melting at 1200 ℃ for 40min, ensuring that the molten liquid level is completely covered by charcoal in the heating and smelting process, isolating most of air by a charcoal covering layer to realize the melting process under a micro-oxidation atmosphere, stirring by a graphite stirring rod in the smelting process, removing slag by a slag removing rod, standing for 1min after the surface of the molten liquid is in a mirror shape, heating the molten liquid to 1250 ℃, pouring the molten liquid with the temperature of 1250 ℃ into a metal casting mold, cooling to room temperature, and taking out to obtain an ingot;
(2) Machining the circumferential and bottom end surfaces of the cast ingot on a common lathe, wherein the machining amount of the circumferential machine is 2mm on one side, and the machining amount of the end surfaces is 2mm;
(3) Placing the cast ingot treated in the step (2) into a box furnace at 850 ℃ for heat preservation for 3 hours to carry out homogenization treatment, then taking the homogenized cast ingot out of the box furnace for hot forging, wherein the forging is completed within 2 minutes, and the forging deformation is 62% (the forging deformation is calculated according to the cross section ratio before and after forging);
Then placing the forged cast ingot into a gas protection tube furnace (the gas in the gas protection tube furnace is mixed gas of nitrogen and argon with the volume ratio of 1:1) at 890 ℃ and preserving heat for 0.5h, then taking out and rapidly placing the cast ingot into flowing tap water for cooling, completing solution treatment, and controlling the total time of taking out the cast ingot from the gas protection tube furnace and placing the cast ingot into the flowing tap water to be not more than 5s;
Then the ingot after solution treatment is extruded at the constant diameter angle under the process conditions that Bc paths are adopted, the extrusion speed is 6mm/s, the extrusion pass is 4 times, the extrusion temperature is room temperature, the inner angle of an equal diameter angle extrusion channel is 90 degrees, and the outer angle is 20 degrees;
And then placing the cast ingot after the constant diameter angle extrusion into a gas protection tube furnace (the gas in the gas protection tube furnace is mixed gas of nitrogen and argon with the volume ratio of 1:1) at the temperature of 450 ℃ for 0.5h, taking out, cooling to room temperature in air, and completing aging treatment to obtain the copper-chromium-scandium alloy.
Example 5
The preparation method of the copper-chromium-scandium alloy of the embodiment is the preparation method of the copper-chromium-scandium alloy of the embodiment 2, and specifically comprises the following steps:
(1) Cutting, drying and surface degreasing an electrolytic copper plate with purity of more than or equal to 99.99 percent and a Cu-25Cr intermediate alloy, adding the treated electrolytic copper plate, the treated Cu-25Cr intermediate alloy and pure scandium powder (Sc of more than or equal to 99.8 percent) into a smelting furnace according to a proportion, melting at 1250 ℃, for 50 minutes, ensuring that the molten liquid level is completely covered by charcoal in the heating and smelting process, isolating most of air by a charcoal covering layer to realize the smelting process under a micro-oxidation atmosphere, stirring by a graphite stirring rod in the smelting process, skimming slag by a skimming rod, standing for 1 minute after the surface of the molten liquid is in a mirror shape, heating the molten liquid to 1300 ℃, pouring the molten liquid with the temperature of 1300 ℃ into a metal casting mold, cooling to room temperature, and taking out to obtain an ingot;
(2) Machining the circumferential and bottom end surfaces of the ingot on a numerical control lathe, wherein the machining amount of the circumferential machine is 2mm on one side, and the machining amount of the end surfaces is 2mm;
(3) Placing the cast ingot treated in the step (2) into a box furnace at 870 ℃ for heat preservation for 3 hours to carry out homogenization treatment, then taking the cast ingot subjected to homogenization treatment out of the box furnace for hot forging, wherein the forging is completed within 2 minutes, and the deformation of the forging is 65% (the deformation of the forging is calculated according to the cross section ratio before and after the forging);
Then placing the forged cast ingot into a gas protection tube furnace (the gas in the gas protection tube furnace is mixed gas of nitrogen and argon with the volume ratio of 1:1) at the temperature of 970 ℃ and preserving heat for 2 hours, then taking out and rapidly placing the cast ingot into flowing tap water for cooling, completing solution treatment, and controlling the total time of taking out the cast ingot from the gas protection tube furnace and placing the cast ingot into the flowing tap water to be not more than 5s;
Then the ingot after solution treatment is extruded at the constant diameter angle under the process conditions that Bc paths are adopted, the extrusion speed is 10mm/s, the extrusion pass is 4 times, the extrusion temperature is room temperature, the inner angle of an equal diameter angle extrusion channel is 90 degrees, and the outer angle is 20 degrees;
And then placing the cast ingot after the constant diameter angle extrusion into a gas protection tube furnace (the gas in the gas protection tube furnace is mixed gas of nitrogen and argon with the volume ratio of 1:1) at the temperature of 510 ℃ and preserving heat for 10 hours, then taking out, placing the cast ingot in air, cooling to room temperature, and completing ageing treatment to obtain the copper-chromium-scandium alloy.
Example 6
The preparation method of the copper-chromium-scandium alloy of the embodiment is the preparation method of the copper-chromium-scandium alloy of the embodiment 3, and specifically comprises the following steps:
(1) Cutting, drying and surface degreasing an electrolytic copper plate with purity of more than or equal to 99.99 percent and a Cu-25Cr intermediate alloy, adding the treated electrolytic copper plate, the treated Cu-25Cr intermediate alloy and pure scandium powder (Sc of more than or equal to 99.8 percent) into a smelting furnace according to a proportion, melting at 1150 ℃ for 30min, ensuring that the molten liquid level is completely covered by charcoal in the heating and smelting process, isolating most of air by a charcoal covering layer to realize the melting process under a micro-oxidation atmosphere, stirring by a graphite stirring rod in the smelting process, skimming slag by a skimming rod, standing for 1min after the surface of the molten liquid is in a mirror shape, heating the molten liquid to 1200 ℃, pouring the molten liquid with the temperature of 1200 ℃ into a metal casting mold, cooling to room temperature, and taking out to obtain an ingot;
(2) Machining the circumferential and bottom end surfaces of the cast ingot on a common lathe, wherein the machining amount of the circumferential machine is 2mm on one side, and the machining amount of the end surfaces is 2mm;
(3) Placing the cast ingot treated in the step (2) into a box furnace at 900 ℃ for heat preservation for 3 hours to carry out homogenization treatment, then taking the cast ingot subjected to homogenization treatment out of the box furnace for hot forging, wherein the forging is completed within 2 minutes, and the forging deformation is 60% (the forging deformation is calculated according to the cross section ratio before and after forging);
then placing the forged cast ingot into a gas protection tube furnace (the gas in the gas protection tube furnace is mixed gas of nitrogen and argon with the volume ratio of 1:1) at 950 ℃ and preserving heat for 1h, then taking out and rapidly placing the cast ingot into flowing tap water for cooling, completing solution treatment, and controlling the total time of taking out the cast ingot from the gas protection tube furnace and placing the cast ingot into the flowing tap water to be not more than 5s;
then the ingot after solution treatment is extruded at the constant diameter angle under the process conditions that Bc paths are adopted, the extrusion speed is 2mm/s, the extrusion pass is 4 times, the extrusion temperature is room temperature, the inner angle of an equal diameter angle extrusion channel is 90 degrees, and the outer angle is 20 degrees;
And then placing the cast ingot after the constant diameter angle extrusion into a gas protection tube furnace (the gas in the gas protection tube furnace is mixed gas of nitrogen and argon with the volume ratio of 1:1) at the temperature of 480 ℃ and preserving heat for 1h, then taking out, placing the cast ingot in air, cooling to room temperature, and completing ageing treatment to obtain the copper-chromium-scandium alloy.
Experimental example 1
To evaluate the mechanical properties, heat and electrical conductivity of the copper-based alloys of examples 1 to 3 and comparative examples 1 to 6, the copper-based alloys of examples 1 to 3 and comparative examples 1 to 6 were respectively tested for room temperature tensile strength, elongation, electrical conductivity and thermal conductivity, and the test results are shown in table 1. The tensile strength test method is carried out according to the specification in the standard GB/T228.2-2015 metal material tensile test, the elongation test method is carried out according to the specification in the standard GB/T228.2-2015 metal material tensile test, the electric conductivity test method is carried out according to the specification in the standard GB/T32791-2016, and the heat conductivity test method is carried out according to the specification in the standard ASTM E1461.
TABLE 1 room temperature tensile Strength, elongation, electrical conductivity and thermal conductivity of copper-based alloys of examples 1-3 and comparative examples 1-6
| Copper base alloy | Tensile strength (MPa) | Elongation (%) | Conductivity (IACS) | Thermal conductivity (W.m.K) -1 |
| Example 1 | 470.2 | 11.1 | 87.6% | 393.8 |
| Example 2 | 500.8 | 10.0 | 85.1% | 393.1 |
| Example 3 | 541.6 | 9.4 | 82.5% | 392.5 |
| Comparative example 1 | 445.5 | 12.0 | 88.1% | 394.1 |
| Comparative example 2 | 430.8 | 13.2 | 89.2% | 395.7 |
| Comparative example 3 | 542.8 | 8.2 | 80.3% | 378.6 |
| Comparative example 4 | 545.5 | 7.6 | 79.1% | 375.3 |
| Comparative example 5 | 513.2 | 7.0 | 78.5% | 373.6 |
| Comparative example 6 | 510.9 | 6.9 | 77.3% | 369.5 |
Experimental example 2
To evaluate the composition fluctuation of the copper-based alloys of examples 1 to 3 and comparative examples 1 to 6, experiments were repeated 3 times (the difference percentage of the mass of the same raw material used in the 3 repeated experiments was not more than 0.002% for the same copper-based alloy) according to the preparation methods of the copper-based alloys of examples 1 to 3 and comparative examples 1 to 6, respectively, and then the composition fluctuation rate of each batch of the prepared copper-based alloy was tested to reduce the composition fluctuation rate due to the instability of the raw material addition, and the test results showed that the composition fluctuation rate of the copper-based alloy of examples 1 to 3 was within.+ -. 0.02%. The maximum value of the absolute value of the component fluctuation ratio of the copper-based alloys of comparative examples 1 to 6 was 0.05%. In this experimental example, the component fluctuation ratio of the copper-based alloy refers to the difference percentage of the mass fractions of the same element in 3 copper-based alloy samples prepared in a certain example or comparative example, for example, taking 3 copper-based alloy samples prepared in example 1 as examples, the fluctuation ratio of the copper element in the copper-based alloy of example 1 is (a-B)/a×100, (a-C)/a×100, (B-C)/b×100, and then the fluctuation ratio of the chromium element and the fluctuation ratio of the scandium element in the copper-based alloy of example 1 are collectively referred to as the component fluctuation ratio of the copper-based alloy of example 1. As can be seen from the results of the component fluctuation ratios of the copper-based alloys of examples 1 to 3 and comparative examples 1 to 6, the component fluctuation ratios of the copper-based alloys of examples 1 to 3 are smaller, which means that the components of the copper-based alloys of examples 1 to 3 are more stable and are advantageous for mass production.
Claims (10)
1. The preparation method of the copper-chromium-scandium alloy comprises the following steps of smelting copper, copper-chromium intermediate alloy and scandium, casting and forming to obtain an ingot, and sequentially carrying out homogenization treatment, forging, solution treatment, constant diameter angle extrusion and aging treatment on the ingot to obtain the copper-chromium-scandium alloy.
2. The copper-chromium-scandium alloy according to claim 1, wherein in said copper-chromium-scandium alloy, the mass percentage of said chromium element is 0.18 to 0.2%, the mass percentage of said scandium element is 0.11 to 0.15%, and in said copper-chromium-scandium alloy, the mass percentage of said impurity element is not more than 0.05%.
3. A method for preparing the copper-chromium-scandium alloy according to claim 1 or 2, comprising the steps of smelting copper, a copper-chromium intermediate alloy and scandium, casting and forming to obtain an ingot, and sequentially carrying out homogenization treatment, forging, solution treatment, equal-diameter angular extrusion and aging treatment on the ingot to obtain the copper-chromium-scandium alloy.
4. The method for preparing the copper-chromium scandium alloy according to claim 3, wherein the copper-chromium intermediate alloy is a Cu-25Cr intermediate alloy, the smelting temperature is 1150-1250 ℃, the smelting time is 30-50 min, and the smelting is performed in a micro-oxidation atmosphere.
5. The method for preparing a copper-chromium-scandium alloy according to claim 3, wherein the casting temperature is 1200-1300 ℃.
6. The method for preparing the copper-chromium-scandium alloy according to claim 3, wherein the homogenizing treatment is to keep the ingot at 850 ℃ to 900 ℃ for at least 3 hours.
7. The method for producing a copper-chromium-scandium alloy according to claim 3 or 6, wherein the forging deformation amount is 60% to 65%.
8. The method for producing a copper-chromium-scandium alloy according to claim 3, wherein the solution treatment is carried out in a protective gas at 890 to 970 ℃ for 0.5 to 2 hours.
9. The method for preparing the copper-chromium-scandium alloy according to claim 3, wherein the inner angle of the equal diameter angle extrusion channel is 90-110 degrees, the outer angle is 10-30 degrees, the extrusion speed of the equal diameter angle extrusion is 2-10 mm/s, and the extrusion pass of the equal diameter angle extrusion is not less than 4 times.
10. The method for preparing the copper-chromium-scandium alloy according to claim 3, wherein the temperature of the ageing treatment is 450-510 ℃ and the time is 0.5-10 h.
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