CN114645154A - Preparation method of high-hardness copper alloy - Google Patents
Preparation method of high-hardness copper alloy Download PDFInfo
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- CN114645154A CN114645154A CN202011515105.2A CN202011515105A CN114645154A CN 114645154 A CN114645154 A CN 114645154A CN 202011515105 A CN202011515105 A CN 202011515105A CN 114645154 A CN114645154 A CN 114645154A
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 66
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011651 chromium Substances 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 30
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 27
- 238000003723 Smelting Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000032683 aging Effects 0.000 claims abstract description 17
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 16
- 239000010936 titanium Substances 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000005266 casting Methods 0.000 claims abstract description 6
- 238000000265 homogenisation Methods 0.000 claims abstract description 6
- 238000005482 strain hardening Methods 0.000 claims abstract 2
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 17
- 239000002893 slag Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000005242 forging Methods 0.000 claims description 14
- 238000003754 machining Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 7
- OWXLRKWPEIAGAT-UHFFFAOYSA-N [Mg].[Cu] Chemical compound [Mg].[Cu] OWXLRKWPEIAGAT-UHFFFAOYSA-N 0.000 claims description 6
- 239000006104 solid solution Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 230000005540 biological transmission Effects 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000012267 brine Substances 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 238000003466 welding Methods 0.000 abstract description 16
- 229910052790 beryllium Inorganic materials 0.000 abstract description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- 238000005070 sampling Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910000861 Mg alloy Inorganic materials 0.000 description 3
- 241001062472 Stokellia anisodon Species 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 229910019878 Cr3Si Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- PWOSZCQLSAMRQW-UHFFFAOYSA-N beryllium(2+) Chemical compound [Be+2] PWOSZCQLSAMRQW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- 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
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
-
- 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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a preparation method of a high-hardness copper alloy, which comprises the following components in percentage by mass: chromium: 0.3 to 0.6%, silicon: 0.4-0.8%, nickel: 1.6-3.0%, titanium: 0.05 to 0.15%, magnesium: 0.03-0.05%, rare earth: 0.05-0.15% and the balance of copper. The method comprises the steps of 1) material preparation, 2) intermediate frequency smelting, 3) ingot casting, 4) homogenization treatment, 5) hot working, 6) solution treatment, 7) cold working, 8) twice aging treatment, 9) mechanical processing to a finished product and the like. According to the preparation method of the high-hardness copper alloy, the copper alloy with high hardness and high-temperature softening resistance is obtained by optimizing the alloy components, not containing beryllium and adopting a proper production process; can prolong the service life of the welding electrode material, and has no toxicity and low cost.
Description
Technical Field
The invention relates to the technical field of copper alloys, in particular to a preparation method of a high-hardness copper alloy.
Background
The copper alloy electrode of the resistance welding machine is a main easy-damaged part of the resistance welding machine, is required to have good electric and thermal conductivity, wear resistance, high hardness and higher high-temperature softening temperature, is suitable for various resistance welding machines such as butt welding machines, seam welding machines, flash welding machines, projection welding machines and the like, is widely applied to industries such as automobiles, aviation, electronics, electrical appliances and the like, and is an important part for ensuring the welding quality. With the rapid development and application of resistance welding, the consumption of various resistance welding electrode materials is larger and larger, and the performance requirement is higher and higher; the welding process needs heating, works in a high-temperature or high-pressure use environment, and requires that the material has high hardness and high-temperature softening resistance.
The chemical components of the beryllium-cobalt-zirconium-copper alloy material comprise: 0.45-0.75%, cobalt: 2.5-2.7%, after solid solution strengthening treatment, the beryllium-cobalt-zirconium-copper alloy has excellent performance indexes and good comprehensive performance, and is suitable for being used as various electric contact materials, electrodes for resistance welding industry and the like. But because the alloy contains beryllium element, the toxicity of beryllium is higher, and the manufacturing environmental protection pressure is high; meanwhile, the price of beryllium, cobalt and metal is expensive, so that the cost of the beryllium-cobalt-zirconium-copper alloy material is high, and the use price is expensive.
Therefore, it is necessary to provide a method for preparing a high-hardness copper alloy which does not contain toxic elements and has low cost.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a method for preparing a copper alloy with high hardness and high temperature softening resistance.
To achieve the purpose, the invention provides a preparation method of a high-hardness copper alloy, which comprises the following components in percentage by mass: chromium: 0.3 to 0.6%, silicon: 0.4-0.8%, nickel: 1.6-3.0%, titanium: 0.05 to 0.15%, magnesium: 0.03-0.05%, rare earth: 0.05-0.15% and the balance of copper.
The chromium element is dissolved into a copper matrix through solution treatment to form a solid solution, and is precipitated through aging treatmentAnd a strengthening phase is generated, and the recrystallization temperature and the heat strength of the alloy are improved. Cr element and Si in Cu alloy form Cr3Si high-temperature stable compound phase with strong high-temperature softening resistance. When the chromium content is less, the strengthening effect is not obvious, and the chromium and the silicon are difficult to form Cr3Si compounds, or the formed quantity is small, and the effect is not large; when the content of the added chromium is large, a large amount of chromium is precipitated to cause large amount of chromium accumulated at grain boundaries, so that the plasticity of the material is damaged, and the improvement of the strength is not facilitated.
The silicon element can improve the hardness and the strength of the copper alloy, but has great influence on the conductivity of the copper alloy, and can reduce the conductivity of the copper alloy. Addition of Cr formed in the copper alloy at a lower silicon content3The Si phase is not enough and the effect is not large; addition of Cr which may form at higher silicon contents3The Si phase is more, but the precipitation amount of chromium is reduced at the same time, and the comprehensive performance of the alloy is influenced.
The nickel element can improve the mechanical property of the copper alloy. The copper alloy is subjected to proper heat treatment, silicon and nickel elements can form a compound, and Ni can be precipitated by aging2Si intermetallic compound, and improve strength and thermal stability.
The titanium element can improve the strength and the heat resistance of the copper alloy. However, titanium is sensitive to the influence of the conductivity, and too high titanium causes the conductivity to be reduced.
The magnesium element has a deoxidizing effect and can reduce metal oxides in the copper alloy.
The rare earth elements have the functions of deoxidation and dehydrogenation, impurity removal, grain refinement and impurity form and distribution change; can improve the high-temperature performance and the hot processing performance of the copper alloy, reduce the hot cracking tendency of the copper alloy, and improve the thermoplasticity, the heat resistance, the strength and the hardness. Adding a proper amount of rare earth has good effect on the performance of the copper alloy; however, when the amount of rare earth added is excessive, the rare earth becomes an impurity element, which affects the properties of the copper alloy.
The high-hardness copper alloy takes copper as a base, elements such as chromium, nickel, silicon, titanium, rare earth and the like are added, and the proportion of each component is optimized, so that the elements are mutually supported in function, excellent matching, relevance and interaction are obtained among the elements and the proportion, excellent composition conditions are provided for the formation of the final copper alloy, and the high-hardness and high-temperature softening resistant copper alloy is promoted to be obtained.
A preparation method of a high-hardness copper alloy comprises the following steps:
1) vacuum smelting to obtain copper-chromium intermediate alloy;
2) the raw material electrolytic copper is put into an intermediate frequency smelting furnace, slag removing agent is added, and the raw material electrolytic copper is quickly melted by power transmission;
3) adding plant ash and crystalline flake graphite to cover before the raw material electrolytic copper is completely melted into a melt, then adding the copper-chromium intermediate alloy to melt, and then sequentially adding silicon and nickel to melt;
4) after the raw materials are completely melted, adding magnesium-copper alloy for deoxidation, slag removal treatment by a slag removal agent, and final deoxidation of metal magnesium; then adding titanium and rare earth;
5) casting the alloy melt into an ingot, homogenizing, hot working and carrying out solid solution treatment;
6) carrying out cold processing on the copper alloy material subjected to the solution treatment, and then carrying out aging treatment twice to obtain a copper alloy block material;
7) and (5) machining to obtain a finished product.
Further preferably, in the step 1), the copper-chromium intermediate alloy is prepared by a two-step vacuum smelting method, the first vacuum smelting is firstly used for preparing the copper-chromium intermediate alloy with the chromium content of 4-5%, and the second vacuum smelting is carried out on the basis for preparing the copper-chromium intermediate alloy with the chromium content of 8%.
Preferably, in the step 2) and the step 4), the addition amount of the slag remover is 0.2-0.5% of the raw material loading amount.
Further preferably, in the step 4), the magnesium content of the magnesium-copper alloy is 16-20%, and the balance is copper.
Preferably, the temperature of the copper alloy solution is adjusted to be 1300-1360 ℃ after the slag removal treatment in the step 4), and magnesium metal is added for final deoxidation.
Preferably, in the step 5), the homogenization treatment process comprises heating to 840-880 ℃, then preserving heat for 3-5 hours, and cooling to normal temperature in a furnace.
Preferably, the hot working process comprises the steps of heating to 910-950 ℃, preserving heat for 2 hours, and performing hot forging forming, wherein the finish forging temperature is higher than 780 ℃.
Preferably, in the step 5), the solution treatment process includes raising the temperature to 920-970 ℃, then preserving the temperature for 2 hours, and cooling the solution in a saturated brine pool, wherein the brine temperature is not higher than 40 ℃.
More preferably, in the step 6), the deformation amount of the cold machining of the copper alloy material is 35-65%; the two-time aging treatment process comprises the following steps: first time aging treatment: heating to 430-490 ℃, preserving heat for 3-5 hours, and cooling to normal temperature in a furnace; and (3) secondary aging treatment: heating to 420-470 ℃, preserving heat for 2-4 hours, and cooling to normal temperature in the furnace.
Has the advantages that: the preparation method of the high-hardness copper alloy provided by the invention is characterized in that the copper is taken as a base, elements such as chromium, nickel, silicon, titanium, rare earth and the like are added, a proper production process method is adopted, the high-hardness and high-temperature softening resistant copper alloy is prepared, the requirements of resistance welding electrode materials are met, the technical difficulties in the prior art are overcome, the prepared copper alloy has excellent conductivity, high-temperature softening resistance and high hardness, the comprehensive performance is good, the industrial requirements are met, and the practicability is high.
According to the invention, the alloy elements such as chromium, silicon, nickel, titanium, rare earth and the like are added into the alloy material, and beryllium is not contained, so that the copper alloy material has high hardness, good high-temperature softening resistance and conductivity, the service life of the welding material is prolonged, and the welding material is non-toxic and low in cost; chromium is added by adopting a copper-chromium intermediate alloy mode, so that the alloy smelting temperature can be reduced, and the burning loss of the chromium is reduced; the copper-chromium intermediate alloy is prepared by adopting a secondary vacuum smelting mode, so that the uniform and non-segregation components of the copper-chromium intermediate alloy are ensured, and the addition amount is accurately controlled; the heat treatment process of the copper alloy material after hot forging forming adopts a solid solution treatment and two aging treatment modes, so that the comprehensive performance of the alloy is improved; saturated salt water is used as a cooling medium during the solid solution treatment, so that the hardenability can be improved, and the alloy performance is ensured to be uniform.
Detailed Description
The embodiments described below are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one:
putting the raw materials into a vacuum smelting furnace according to a certain proportion to smelt a copper-chromium intermediate alloy, and preparing the copper-chromium intermediate alloy by adopting a secondary vacuum smelting mode; the mass percentage of the copper-chromium intermediate alloy prepared in advance by the first vacuum smelting is 4.6 percent of chromium, and the balance is copper; on the basis, the second vacuum smelting is carried out, and chromium is added, so as to prepare the copper-chromium intermediate alloy, wherein the mass percent of the copper-chromium intermediate alloy is 8 percent, and the balance is copper.
Putting 45.31Kg of raw electrolytic copper into an intermediate frequency furnace, and quickly melting by power transmission; adding plant ash and flake graphite covering agent into the solution before the electrolytic copper is completely melted into the solution, wherein the thickness of the covering agent is about 25 mm; then adding 2.85Kg of baked copper-chromium intermediate alloy, after the copper-chromium intermediate alloy is completely melted, then adding 0.36Kg of silicon, and then adding 1.3Kg of nickel; after the raw materials are completely melted, 0.13Kg of copper-magnesium alloy is added for deoxidation, and after the deoxidation, 0.25Kg of slag removing agent is added for slag removing treatment; adjusting the temperature of the copper alloy melt at 1300 ℃, adding 0.024Kg of magnesium metal for final deoxidation, and then adding titanium and rare earth; finally, pouring the alloy melt into an ingot casting mold, and adding plant ash to cover the top of the cap opening after pouring; after the ingot is cooled and demoulded, carrying out homogenization treatment: raising the temperature to 840 ℃, preserving the temperature for 5 hours, and cooling to the normal temperature in the furnace.
Ingot sampling analysis the mass percentage of the components of the copper alloy content is chromium: 0.44%, silicon: 0.69%, nickel: 2.59%, titanium: 0.06%, magnesium: 0.03%, rare earth: 0.13 percent, and the balance being copper.
Carrying out hot working on the homogenized copper alloy ingot: heating to 910 ℃, preserving heat for 2 hours, and performing hot forging molding, wherein the final forging temperature is higher than 780 ℃; then carrying out solution treatment on the copper alloy material after hot forging forming: heating to 930 deg.C, maintaining for 2 hr, cooling in saturated brine tank with water temperature not higher than 40 deg.C; carrying out cold machining on the copper alloy material subjected to the solution treatment, wherein the machining deformation is 40%; carrying out primary aging treatment on the cold-processed copper alloy material: heating to 460 ℃, preserving heat for 5 hours, and cooling to normal temperature in the furnace; and then carrying out secondary aging treatment: heating to 440 ℃, and preserving the heat for 3 hours; cooling to normal temperature in a furnace; and (4) sampling and detecting the performance of the treated copper alloy, and finally machining the copper alloy into a product.
The copper alloy sampling test performance results are that the Hardness (HRB) is 98, the conductivity (Ms/m) is 25 and the softening resistance temperature is more than 600 ℃.
Example two:
putting the raw materials into a vacuum smelting furnace according to a proportion to smelt a copper-chromium intermediate alloy, and adopting a secondary vacuum smelting mode to prepare the copper-chromium intermediate alloy: the mass percent of the copper-chromium intermediate alloy prepared in advance by the first vacuum smelting is 4 percent of chromium, and the balance is copper; on the basis, the second vacuum smelting is carried out, and chromium is added, so as to prepare the copper-chromium intermediate alloy, wherein the mass percent of the copper-chromium intermediate alloy is 8 percent, and the balance is copper.
Putting 45.45Kg of raw electrolytic copper into an intermediate frequency furnace, and quickly melting by electrifying; adding plant ash and flake graphite covering agent into the molten copper before the electrolytic copper is completely melted, wherein the thickness of the covering agent is about 25 mm; then adding 2.56Kg of baked copper-chromium intermediate alloy, after the copper-chromium intermediate alloy is completely melted, then adding 0.32Kg of silicon, and then adding 1.5Kg of nickel; after the raw materials are completely melted, 0.2Kg of copper-magnesium alloy is added for deoxidation, and after the deoxidation, 0.1Kg of slag removing agent is added for slag removing treatment; adjusting the temperature of the copper alloy melt to 1360 ℃, adding 0.023Kg of magnesium metal for final deoxidation, and then adding titanium and rare earth; finally, pouring the alloy melt into an ingot casting mold, and adding plant ash to cover the upper surface of the cap opening after pouring; after the cast ingot is cooled and demoulded, carrying out homogenization treatment: raising the temperature to 860 ℃, preserving the heat for 4 hours, and cooling to the normal temperature in the furnace.
Ingot sampling analysis the copper alloy content components are chromium in mass percent: 0.39%, silicon: 0.6%, nickel: 2.99%, titanium: 0.1%, magnesium: 0.037%, rare earth: 0.094 percent and the balance of copper.
Carrying out hot working on the homogenized copper alloy ingot: heating to 950 ℃, preserving heat for 2 hours, and performing hot forging molding, wherein the final forging temperature is higher than 780 ℃; carrying out solution treatment on the copper alloy material after hot forging forming: heating to 960 deg.C, keeping the temperature for 2 hr, and cooling in a saturated brine pool with water temperature not higher than 40 deg.C; carrying out cold processing on the copper alloy material after the solution treatment, wherein the processing deformation is 55%; carrying out primary aging treatment on the cold-processed copper alloy material: heating to 465 ℃, preserving heat for 3 hours, and cooling to normal temperature in a furnace; and then carrying out secondary aging treatment: heating to 450 ℃, and preserving the heat for 2.5 hours; cooling to normal temperature in a furnace; and (4) sampling and detecting the performance of the treated copper alloy, and finally machining the copper alloy into a product.
The copper alloy sampling test performance results are that the Hardness (HRB) is 97, the conductivity (Ms/m) is 26 and the softening resistance temperature is more than 600 ℃.
Example three:
putting the raw materials into a vacuum smelting furnace according to a proportion to smelt a copper-chromium intermediate alloy, and adopting a secondary vacuum smelting mode to prepare the copper-chromium intermediate alloy: the mass percent of the copper-chromium intermediate alloy prepared in advance by the first vacuum smelting is 5 percent of chromium, and the balance is copper; on the basis, the second vacuum smelting is carried out, and chromium is added, so as to prepare the copper-chromium intermediate alloy, wherein the mass percent of the copper-chromium intermediate alloy is 8 percent, and the balance is copper.
45.22Kg of raw material electrolytic copper is put into an intermediate frequency furnace, and is quickly melted by power transmission; adding plant ash and flake graphite covering agent into the molten copper before the electrolytic copper is completely melted, wherein the thickness of the covering agent is about 25 mm; then adding 3.2Kg of baked copper-chromium intermediate alloy, after the copper-chromium intermediate alloy is completely melted, then adding 0.8Kg of silicon, and then adding 1Kg of nickel; after the raw materials are completely melted, 0.22Kg of copper-magnesium alloy is added for deoxidation, and after the deoxidation, 0.1Kg of slag removing agent is added for slag removing treatment; adjusting the temperature of the copper alloy melt to 1330 ℃, adding 0.035Kg of metal magnesium for final deoxidation, and then adding titanium and rare earth; finally, pouring the alloy melt into an ingot casting mold, and adding plant ash to cover the upper surface of the cap opening after pouring; after the cast ingot is cooled and demoulded, carrying out homogenization treatment: heating to 880 ℃, preserving heat for 3 hours, and cooling to normal temperature in the furnace.
Ingot sampling analysis the copper alloy content components are chromium in mass percent: 0.51%, silicon: 0.77%, nickel: 2.0%, titanium: 0.14%, magnesium: 0.032%, rare earth: 0.063%, the rest is copper.
Heating the homogenized copper alloy ingot to 930 ℃, preserving heat for 2 hours, and performing hot forging molding, wherein the finish forging temperature is higher than 780 ℃; carrying out solution treatment on the copper alloy material after hot forging forming: heating to 940 deg.C, keeping the temperature for 2 hr, and cooling in a saturated brine pool with water temperature not higher than 40 deg.C; carrying out cold machining on the copper alloy material subjected to the solution treatment, wherein the machining deformation is 65%; carrying out primary aging treatment on the cold-pressed copper alloy material: heating to 455 ℃, preserving heat for 4 hours, and cooling to normal temperature in a furnace; and then carrying out secondary aging treatment: heating to 440 ℃, and preserving heat for 3 hours; cooling to normal temperature in a furnace; and (4) sampling and detecting the performance of the treated copper alloy, and finally machining to obtain the product.
The copper alloy sampling test performance results are that the Hardness (HRB) is 99, the conductivity (Ms/m) is 24 and the softening resistance temperature is more than 600 ℃.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention.
Claims (8)
1. The preparation method of the high-hardness copper alloy comprises the following components in percentage by mass: chromium: 0.3 to 0.6%, silicon: 0.4-0.8%, nickel: 1.6-3.0%, titanium: 0.05 to 0.15%, magnesium: 0.03-0.05%, rare earth: 0.05-0.15% and the balance of copper; the preparation method is characterized by comprising the following steps:
1) vacuum smelting to obtain copper-chromium intermediate alloy;
2) the raw material electrolytic copper is put into an intermediate frequency smelting furnace, slag removing agent is added, and the raw material electrolytic copper is quickly melted by power transmission;
3) adding plant ash and crystalline flake graphite to cover before the raw material electrolytic copper is completely melted into a melt, then adding the copper-chromium intermediate alloy to melt, and then sequentially adding silicon and nickel to melt;
4) after the raw materials are completely melted, adding magnesium-copper alloy for deoxidation, slag removal treatment by a slag removal agent, and final deoxidation of metal magnesium; then adding titanium and rare earth;
5) casting the alloy melt into an ingot, homogenizing, hot working and carrying out solid solution treatment;
6) carrying out cold processing on the copper alloy material after the solution treatment, and then carrying out aging treatment twice to obtain a copper alloy lump material;
7) and (5) machining to obtain a finished product.
2. The preparation method of the high-hardness copper alloy according to claim 1, wherein in the step 1), the copper-chromium intermediate alloy is prepared by a two-time vacuum smelting method, the first vacuum smelting method is firstly used for preparing the copper-chromium intermediate alloy with the chromium content of 4-5%, and the second vacuum smelting method is carried out on the basis of the first vacuum smelting method for preparing the copper-chromium intermediate alloy with the chromium content of 8-10%.
3. The method for preparing the high-hardness copper alloy according to claim 1, wherein in the step 2) and the step 4), the addition amount of the slag removing agent is 0.2-0.5% of the raw material loading amount.
4. The high-hardness copper alloy according to claim 1, wherein after the slag removal treatment in step 4), the temperature of the copper alloy solution is adjusted to 1300-1360 ℃, and magnesium metal is added for final deoxidation.
5. The method for preparing the high-hardness copper alloy according to claim 1, wherein in the step 5), the homogenization treatment process comprises the steps of heating to 840-880 ℃, preserving heat for 3-5 hours, and cooling to normal temperature in a furnace.
6. The method for preparing the high-hardness copper alloy according to claim 1, wherein in the step 5), the hot working process comprises heating to 910-950 ℃, keeping the temperature for 2 hours, and performing hot forging forming, wherein the finish forging temperature is greater than 780 ℃.
7. The method for preparing a high-hardness copper alloy according to claim 1, wherein in the step 5), the solution treatment process comprises raising the temperature to 920-970 ℃, then preserving the temperature for 2 hours, and cooling the alloy in a saturated brine pool, wherein the brine temperature is not higher than 40 ℃.
8. The method for preparing a high-hardness copper alloy according to claim 1, wherein in the step 6), the cold-working deformation amount of the copper alloy material is 35-65%; the two-time aging treatment process comprises the following steps: first time aging treatment: heating to 430-490 ℃, preserving heat for 3-5 hours, and cooling to normal temperature in a furnace; and (3) secondary aging treatment: heating to 420-470 ℃, preserving heat for 2-4 hours, and cooling to normal temperature in the furnace.
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