CN112322926B - Cu-Ti-Si-Co-La copper alloy material and preparation method thereof - Google Patents
Cu-Ti-Si-Co-La copper alloy material and preparation method thereof Download PDFInfo
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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Abstract
The invention discloses a Cu-Ti-Si-Co-La copper alloy material and a preparation method thereof. The copper alloy material comprises the following components: 0.71-1.35 wt% of Ti, 0.35-0.75 wt% of Si, 0.21-0.61 wt% of Co and 0.02-0.10 wt% of La; the balance being Cu. The preparation method comprises the following steps: alloy casting, homogenization treatment, hot rolling, multi-stage solution treatment, room temperature rolling, aging treatment, regression treatment and magnetic field heat treatment. The components of the copper alloy material obtained by the invention do not contain toxic elements, the harm to human bodies and the environment is small, and the prepared copper alloy material has excellent comprehensive performances such as hardness, strength, conductivity, softening resistance and the like, and can be used for manufacturing conductive elastic elements such as electric connectors and the like required by the electric and electronic industries.
Description
Technical Field
The invention belongs to the technical field of copper alloy materials, and particularly relates to a Cu-Ti-Si-Co-La copper alloy material and a preparation method thereof.
Background
Applications to copper and copper alloys are found in many areas of modern industry. With the development of the times, the requirements of the industries such as electricity, electronics and the like on the performance of copper and copper alloys are continuously improved, and the copper and copper alloys have good electrical conductivity and higher strength and hardness, so people begin to pay attention to the research of high-performance copper alloys. Pure copper has good electrical conductivity but low strength, so it is required to improve the strength by alloying and improving the manufacturing process. The strengthening means of the copper alloy mainly comprises solid solution strengthening, precipitation phase strengthening, deformation strengthening and fine grain strengthening. In recent years, in copper alloy materials for the electrical and electronic industry, the amount of copper alloys (e.g., Cu-Be, Cu-Cr-Zr, etc.) using precipitation phase strengthening as a main strengthening means has increased greatly, and copper alloy materials using solid solution strengthening and strain strengthening as main strengthening means, such as Cu-Zn, Cu-Sn-P, etc., have been replaced.
The Cu-Be alloy is widely applied to the field of conductive elastic materials due to excellent electrical conductivity, thermal conductivity, strength, elastic modulus and the like. After proper solution-aging treatment, the Cu-Be alloy can obtain higher strength and hardness, and has good corrosion resistance and cold-working formability, but the Cu-Be alloy has high production cost, relatively complex process, sensitive performance to heat treatment process parameters and poor high-temperature stress relaxation resistance, and is not suitable for working at high temperature for a long time. In addition, beryllium and compounds thereof are toxic, so that the beryllium and the compounds thereof are harmful to human health and environment, and the application field of the beryllium and the compounds is greatly limited. Although the Cu — Cr — Zr alloy has many advantages such as excellent electrical conductivity, thermal conductivity, and corrosion resistance, it has low strength and a small process window, and has high requirements for production equipment.
The Cu-Ti alloy is similar to the Cu-Be alloy, belongs to precipitation phase reinforced copper-based elastic alloy, has corrosion resistance and wear resistance comparable to the Cu-Be alloy, and is a beryllium bronze substitute material with a very promising prospect. However, Ti atoms are dissolved in the copper matrix, resulting in a low conductivity of the Cu-Ti alloy. For example, the conductivity of the Cu-Ti-Ni-Al alloy prepared in the Chinese patent 'a conductive elastic Cu-Ti-Ni-Al alloy and the preparation method thereof' (patent number: 201810819118.5) is 17.7-19.8% IACS, and the conductivity of the Cu-Ti alloy prepared in the 'high-strength high-elasticity conductive Cu-Ti alloy strip and the preparation method thereof' (patent number: 201911092335. X) is 15.8-19.3% IACS.
In view of the above situation, research and development of new copper alloy components and corresponding preparation processes are urgently needed to adapt to the development of science and technology and society.
Disclosure of Invention
The invention aims to provide a Cu-Ti-Si-Co-La copper alloy material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the Cu-Ti-Si-Co-La copper alloy material comprises the following components in percentage by mass, based on 100% of the sum of the percentages by mass: the copper alloy material comprises 0.71-1.35 wt% of Ti, 0.35-0.75 wt% of Si, 0.21-0.61 wt% of Co, 0.02-0.10 wt% of La and the balance of copper.
The Cu-Ti-Si-Co-La copper alloy material is characterized in that the sum of the mass percentages of Ti and Si is 1.06-2.10 wt%, and the mass ratio of Ti to Si is 1.8: 1-2.2: 1.
The preparation method of the Cu-Ti-Si-Co-La copper alloy material comprises the following steps:
(1) casting of alloy: under the protection of pure argon (Ar is more than or equal to 99.99 percent), putting the raw materials into an induction furnace for smelting, then casting the obtained alloy melt into a mold and cooling to room temperature to obtain an alloy ingot. The raw materials are Cu and Si metal blocks with the purity of more than or equal to 99.9wt% and massive Cu-M (M is Ti, Co and La) intermediate alloy;
(2) homogenizing: placing the obtained alloy ingot into a heat treatment furnace for homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the homogenization treatment temperature is 900-1000 ℃, the heat preservation time is 3-8 hours, and then cooling to room temperature along with the furnace;
(3) hot rolling: heating the sample prepared in the step (2) to 850-950 ℃, taking out the sample and performing hot rolling treatment, wherein the total deformation of the hot rolling is 55-85%, the final rolling temperature is 730-850 ℃, and the alloy material after final rolling is immediately subjected to water quenching treatment;
(4) multi-stage solution treatment: putting the hot-rolled sample into a heat treatment furnace for solution treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the solution treatment process comprises the following steps: the solid solution temperature is 650-700 ℃, the temperature is kept for 0.5-1 h, the temperature is raised to 750-800 ℃, the temperature is kept for 0.5-1 h, then the temperature is raised to 850-900 ℃, the temperature is kept for 0.5-1 h, finally the temperature is raised to 950-980 ℃, the temperature is kept for 0.5-1 h, and the mixture is cooled to the room temperature in a water cooling mode;
(5) rolling at room temperature: milling the surface of the copper alloy material subjected to the multistage solid solution treatment, removing surface oxide skin, and then performing rolling deformation at room temperature, wherein the total rolling deformation is 70-90%;
(6) aging treatment: putting the copper alloy material rolled at room temperature into a heat treatment furnace, and carrying out aging treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the aging temperature is 400-550 ℃, and the heat preservation time is 0.5-2 h; after the aging is finished, cooling to room temperature in an air cooling mode;
(7) and (3) regression treatment: putting the copper alloy material subjected to aging treatment into a heat treatment furnace, performing regression treatment under the protection of pure argon (Ar is more than or equal to 99.99%), wherein the regression temperature is 850-950 ℃, the heat preservation time is 5-15 min, and then taking out the copper alloy material from the heat treatment furnace to perform water quenching treatment immediately;
(8) magnetic field heat treatment: and (3) putting the copper alloy material subjected to the regression treatment into a magnetic field heat treatment furnace, and carrying out magnetic field heat treatment under the protection of pure argon (Ar is more than or equal to 99.99%). The temperature of the magnetic field heat treatment is 400-500 ℃, the heat preservation time is 2-5 h, the peak intensity of the alternating current magnetic field is 5-8 kA/m, and the frequency is 20-50 Hz. And then cooling to room temperature in an air cooling mode to obtain the copper alloy material.
The invention has the advantages that:
(1) according to the invention, Cu, Ti, Si and Co are used as main elements in the alloy components, and the enthalpy of mixing between Ti-Si and Si-Co is larger than that between Cu-Ti, Cu-Si and Cu-Co according to the Miedema mixing enthalpy theory. Therefore, the copper alloy material can form a large amount of fine and dispersed Ti-Si and Ti-Si through a proper heat treatment processSi-Co precipitates, which can block the movement of dislocation and improve the strength and hardness of the alloy. In the invention, the mass ratio of Ti to Si is limited to 1.8: 1-2.2: 1, and TiSi can be generated2、Ti5Si4、TiSi、Ti5Si3And Ti3Ti-Si intermetallic compounds of Si.
(2) According to the invention, the rare earth element La is added into the alloy components, so that the fluidity of the alloy can be improved, the casting defects are reduced, the degassing and impurity removing effects are achieved, the ingot casting structure can be refined, and the hot rolling cracking phenomenon is reduced.
(3) The multi-stage solution treatment can fully dissolve alloy elements in a copper matrix, effectively reduce coarse undissolved crystal phases in the alloy, reduce the heat preservation time of a sample at high temperature (more than or equal to 950 ℃) and improve the cold rolling performance of the alloy.
(4) The invention introduces an alternating magnetic field in the heat treatment process, can promote the diffusion of solute elements (Ti, Si and Co), reduces Gibbs free energy required by precipitated phase nucleation, and is beneficial to obtaining uniform and dispersed precipitated phase particles. The parameters of the alternating magnetic field are required to be adapted to the components of the alloy, and the alloy can obtain good mechanical property and electrical property. If the peak intensity of the alternating magnetic field is too small or the frequency is too low, the introduced magnetic energy is insufficient, and the Gibbs free energy required by nucleation of precipitated phases cannot be effectively reduced. Too high peak intensity or too high frequency of the alternating magnetic field can cause too strong eddy current effect in local areas of the sample, cause large difference in temperature of each part of the sample, and is not beneficial to dispersion distribution of precipitated phase particles.
(5) The copper alloy material disclosed by the invention does not contain toxic elements, is small in harm to human bodies and environment, and has excellent comprehensive mechanical property and conductivity (the hardness is 251-281 HV, the yield strength is 676-755 MPa, the tensile strength is 742-830 MPa, the elongation after fracture is 8-15%, the softening temperature is 570-610 ℃, and the conductivity is 55-65% IACS).
Drawings
FIG. 1 is a metallographic structure diagram of a copper alloy material obtained in example 1;
FIG. 2 is a transmission electron micrograph of the copper alloy material obtained in example 1;
FIG. 3 is a metallographic structure diagram of a copper alloy material obtained in comparative example 1;
FIG. 4 is a transmission electron micrograph of the copper alloy material obtained in comparative example 2.
The present invention will be further illustrated with reference to the following examples, but is not limited thereto. The related main test methods and standards of the invention are as follows: according to GB/T4340.1-2009 part 1 of Vickers hardness test of metal materials: test method for measuring the hardness of the copper alloy material; GB/T34505-2017 'test method for tensile strength at room temperature of copper and copper alloy materials' measures the yield strength, tensile strength and elongation after fracture of the copper alloy materials; the softening temperature of the copper alloy material is measured according to GB/T33370-2016 method for measuring the softening temperature of copper and copper alloy; the conductivity of the Copper alloy material was measured according to GB/T351-2019 "measuring method for resistivity of metallic Material", and the value was compared with the International Annealed Copper Standard (100% IACS, International interconnected coater Standard).
Example 1
The alloy comprises the following components in percentage by mass: 1.00wt% of Ti, 0.55wt% of Si, 0.29wt% of Co, 0.09 wt% of La and the balance of Cu. The sum of the mass percentages of Ti and Si is 1.55wt%, and the mass ratio of Ti to Si is 1.82: 1.
The preparation method comprises the following steps:
(1) casting of alloy: placing the raw materials into a crucible of an induction furnace, and vacuumizing to 3.0 × 10-3Pa, then 1.1X 105Pa pure argon (Ar is more than or equal to 99.99 percent), smelting under the protection of the pure argon, keeping for 10min after the solid is completely melted to form alloy melt, then casting the alloy melt into a graphite mold, cooling, opening the mold, taking out an alloy ingot, wherein the thickness of the ingot is 25 mm; the smelting uses Cu and Si blocks with the purity of more than or equal to 99.9wt%, Cu-Ti intermediate alloy containing 60wt% of Ti, Cu-Co intermediate alloy containing 9wt% of Co and Cu-La intermediate alloy containing 25wt% of La;
(2) homogenizing: placing the alloy cast ingot into a heat treatment furnace, carrying out homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the homogenization treatment temperature is 900 ℃, the heat preservation time is 7 hours, and then cooling to room temperature along with the furnace;
(3) hot rolling: heating the ingot after homogenization treatment to 950 ℃ for hot rolling deformation, wherein the total hot rolling deformation is 85%, the finish rolling temperature is 800 ℃, and then immediately performing water quenching to obtain a hot rolled sample with the thickness of 3.75 mm;
(4) multi-stage solution treatment: putting the hot-rolled sample into a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99%) for solution treatment, wherein the solution temperature is 650 ℃, the heat preservation time is 0.5h, the temperature is increased to 750 ℃, the heat preservation time is 0.5h, the temperature is increased to 850 ℃, the heat preservation time is 0.5h, the temperature is finally increased to 950 ℃, the heat preservation time is 1h, and the sample is cooled to the room temperature in a water cooling mode;
(5) rolling at room temperature: milling the surface of the sample subjected to the multistage solid solution treatment to remove surface oxide skin, and then carrying out rolling deformation at room temperature, wherein the total rolling deformation is 87%, and the thickness of the rolled sample is 0.50 mm;
(6) aging treatment: carrying out aging treatment on the copper alloy material rolled at room temperature in a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the aging temperature is 400 ℃, the heat preservation time is 2 hours, and after the aging treatment is finished, cooling the copper alloy material to the room temperature in an air cooling mode;
(7) and (3) regression treatment: putting the copper alloy material subjected to aging treatment into a heat treatment furnace, performing regression treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the regression temperature is 880 ℃, the heat preservation time is 5min, and then taking out the copper alloy material from the heat treatment furnace to perform water quenching treatment immediately;
(8) magnetic field heat treatment: and (3) putting the copper alloy material subjected to the regression treatment into a magnetic field heat treatment furnace, carrying out magnetic field heat treatment under the protection of pure argon (Ar is more than or equal to 99.99%), wherein the temperature of the magnetic field heat treatment is 400 ℃, the heat preservation time is 5h, the peak intensity of an alternating current magnetic field is 8.0kA/m, the frequency is 20Hz, and then cooling to room temperature in an air cooling mode to obtain the copper alloy material. The detection shows that the hardness of the obtained copper alloy material is 264HV, the yield strength is 724MPa, the tensile strength is 795MPa, the elongation after fracture is 8%, the softening temperature is 590 ℃, and the electric conductivity is 61% IACS.
FIG. 1 is a metallographic structure diagram of a copper alloy material obtained in this example. As can be seen, the crystal grains are fine and uniform, and the average grain size is about 6 to 8 μm.
FIG. 2 is a transmission electron micrograph of the copper alloy material obtained in the present example. Fine, uniform precipitates were observed, dispersed in the copper matrix (precipitates < 10nm were observed in fig. 2). The precipitated phases are mainly spherical in shape, and a small amount of precipitated phases are ellipsoidal in shape. The average size of precipitated phases is about 8-10 nm.
Example 2
The alloy comprises the following components in percentage by mass: 1.17wt% Ti, 0.61wt% Si, 0.35wt% Co, 0.07wt% La, and the balance Cu. The sum of the mass percentages of Ti and Si is 1.78wt%, and the mass ratio of Ti to Si is 1.92: 1.
The preparation method comprises the following steps:
(1) casting of alloy: placing the raw materials into a crucible of an induction furnace, and vacuumizing to 3.0 × 10-3Pa, then 1.1X 105Pa pure argon (Ar is more than or equal to 99.99 percent), smelting under the protection of pure argon (Ar is more than or equal to 99.99 percent), keeping for 10min after the solid is completely melted to form alloy melt, then casting the alloy melt into a graphite mold, cooling, opening the mold, taking out an alloy ingot, wherein the thickness of the ingot is 25 mm; the smelting uses Cu and Si blocks with the purity of more than or equal to 99.9wt%, Cu-Ti intermediate alloy containing 60wt% of Ti, Cu-Co intermediate alloy containing 9wt% of Co and Cu-La intermediate alloy containing 25wt% of La;
(2) homogenizing: placing the alloy cast ingot into a heat treatment furnace, carrying out homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the homogenization treatment temperature is 970 ℃, the heat preservation time is 6 hours, and then cooling to room temperature along with the furnace;
(3) hot rolling: heating the ingot after homogenization treatment to 930 ℃ for hot rolling deformation, wherein the total hot rolling deformation is 60%, the finish rolling temperature is 830 ℃, and then immediately performing water quenching to obtain a hot rolled sample with the thickness of 10.0 mm;
(4) multi-stage solution treatment: putting the hot-rolled sample into a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99%) for solution treatment, wherein the solution temperature is 660 ℃, preserving heat for 0.75h, then heating to 760 ℃, preserving heat for 0.75h, then heating to 860 ℃, preserving heat for 0.5h, finally heating to 960 ℃, preserving heat for 0.75h, and cooling to room temperature in a water cooling manner;
(5) rolling at room temperature: milling the surface of the sample subjected to the multistage solid solution treatment to remove surface oxide skin, and then carrying out rolling deformation at room temperature, wherein the total rolling deformation is 84%, and the thickness of the rolled sample is 1.6 mm;
(6) aging treatment: carrying out aging treatment on the copper alloy material rolled at room temperature in a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the aging temperature is 430 ℃, the heat preservation time is 1.5h, and after the aging treatment is finished, cooling the copper alloy material to room temperature in an air cooling mode;
(7) and (3) regression treatment: putting the copper alloy material subjected to aging treatment into a heat treatment furnace, performing regression treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the regression temperature is 930 ℃, the heat preservation time is 12min, and then taking out the copper alloy material from the heat treatment furnace to perform water quenching treatment immediately;
(8) magnetic field heat treatment: and (3) putting the copper alloy material subjected to the regression treatment into a magnetic field heat treatment furnace, carrying out magnetic field heat treatment under the protection of pure argon (Ar is more than or equal to 99.99%), wherein the temperature of the magnetic field heat treatment is 500 ℃, the heat preservation time is 2h, the peak intensity of an alternating current magnetic field is 7.0kA/m, the frequency is 25Hz, and then cooling to room temperature in an air cooling mode to obtain the copper alloy material. The detection shows that the hardness of the obtained copper alloy material is 273HV, the yield strength is 737MPa, the tensile strength is 810MPa, the elongation after fracture is 8%, the softening temperature is 600 ℃, and the electric conductivity is 57% IACS.
Example 3
The alloy comprises the following components in percentage by mass: 0.97wt% of Ti, 0.53wt% of Si, 0.45wt% of Co, 0.10wt% of La and the balance of Cu. The sum of the mass percentages of Ti and Si is 1.50wt%, and the mass ratio of Ti to Si is 1.83: 1.
The preparation method comprises the following steps:
(1) casting of alloy: placing the raw materials into a crucible of an induction furnace, and vacuumizing to 3.0 × 10-3Pa, then 1.1X 105Pa pure argon (Ar is more than or equal to 99.99 percent), smelting under the protection of pure argon (Ar is more than or equal to 99.99 percent), and melting the solid completelyKeeping for 10min after the alloy melt is formed, then casting the alloy melt into a graphite mold, opening the mold after cooling, and taking out an alloy ingot with the thickness of 25 mm; the smelting uses Cu and Si blocks with the purity of more than or equal to 99.9wt%, Cu-Ti intermediate alloy containing 60wt% of Ti, Cu-Co intermediate alloy containing 9wt% of Co and Cu-La intermediate alloy containing 25wt% of La;
(2) homogenizing: placing the alloy cast ingot into a heat treatment furnace, carrying out homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the homogenization treatment temperature is 920 ℃, the heat preservation time is 8 hours, and then cooling to room temperature along with the furnace;
(3) hot rolling: heating the ingot after homogenization treatment to 900 ℃ for hot rolling deformation, wherein the total hot rolling deformation is 70%, the finish rolling temperature is 770 ℃, and then immediately performing water quenching to obtain a hot rolled sample with the thickness of 7.5 mm;
(4) multi-stage solution treatment: putting the hot-rolled sample into a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99%) for solution treatment, wherein the solution temperature is 670 ℃, preserving heat for 0.5h, then heating to 770 ℃, preserving heat for 0.5h, then heating to 870 ℃, preserving heat for 0.5h, finally heating to 970 ℃, preserving heat for 0.5h, and cooling to room temperature in a water cooling mode;
(5) rolling at room temperature: milling the surface of the sample subjected to the multistage solid solution treatment to remove surface oxide skin, and then performing rolling deformation at room temperature, wherein the thickness of the rolled sample with the total rolling deformation of 77% is 1.7 mm;
(6) aging treatment: carrying out aging treatment on the copper alloy material rolled at room temperature in a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the aging temperature is 460 ℃, the heat preservation time is 1h, and after the aging treatment is finished, cooling the copper alloy material to the room temperature in an air cooling mode;
(7) and (3) regression treatment: putting the copper alloy material subjected to aging treatment into a heat treatment furnace, performing regression treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the regression temperature is 900 ℃, the heat preservation time is 10min, and then taking out the copper alloy material from the heat treatment furnace to perform water quenching treatment immediately;
(8) magnetic field heat treatment: and (3) putting the copper alloy material subjected to the regression treatment into a magnetic field heat treatment furnace, carrying out magnetic field heat treatment under the protection of pure argon (Ar is more than or equal to 99.99%), wherein the temperature of the magnetic field heat treatment is 430 ℃, the heat preservation time is 3h, the peak intensity of an alternating current magnetic field is 6.5kA/m, the frequency is 35Hz, and then cooling to room temperature in an air cooling mode to obtain the copper alloy material. The obtained copper alloy material is detected to have the hardness of 261HV, the yield strength of 705MPa, the tensile strength of 775MPa, the elongation after fracture of 10 percent, the softening temperature of 580 ℃ and the electric conductivity of 61 percent IACS.
Example 4
The alloy comprises the following components in percentage by mass: 0.71wt% Ti, 0.35wt% Si, 0.21wt% Co, 0.06wt% La, and the balance Cu. The sum of the mass percentages of Ti and Si is 1.06wt%, and the mass ratio of Ti to Si is 2.03: 1.
The preparation method comprises the following steps:
(1) casting of alloy: placing the raw materials into a crucible of an induction furnace, and vacuumizing to 3.0 × 10-3Pa, then 1.1X 105Pa pure argon (Ar is more than or equal to 99.99 percent), smelting under the protection of the pure argon, keeping for 10min after the solid is completely melted to form alloy melt, then casting the alloy melt into a graphite mold, cooling, opening the mold, taking out an alloy ingot, wherein the thickness of the ingot is 25 mm; the smelting uses Cu and Si blocks with the purity of more than or equal to 99.9wt%, Cu-Ti intermediate alloy containing 60wt% of Ti, Cu-Co intermediate alloy containing 9wt% of Co and Cu-La intermediate alloy containing 25wt% of La;
(2) homogenizing: placing the alloy cast ingot into a heat treatment furnace, carrying out homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the homogenization treatment temperature is 980 ℃, the heat preservation time is 3 hours, and then cooling to room temperature along with the furnace;
(3) hot rolling: heating the ingot after homogenization treatment to 880 ℃ for hot rolling deformation, wherein the total hot rolling deformation is 75%, the finish rolling temperature is 770 ℃, and then immediately performing water quenching to obtain a hot rolled sample with the thickness of 6.25 mm;
(4) multi-stage solution treatment: putting the hot-rolled sample into a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99%) for solution treatment, keeping the solution temperature at 680 ℃, keeping the temperature for 0.5h, then heating to 780 ℃, keeping the temperature for 1h, then heating to 880 ℃, keeping the temperature for 0.5h, finally heating to 980 ℃, keeping the temperature for 1h, and cooling to room temperature in a water cooling manner;
(5) rolling at room temperature: milling the surface of the sample subjected to the multistage solid solution treatment to remove surface oxide skin, and then carrying out rolling deformation at room temperature, wherein the total rolling deformation is 90%, and the thickness of the rolled sample is 0.63 mm;
(6) aging treatment: carrying out aging treatment on the copper alloy material rolled at room temperature in a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the aging temperature is 490 ℃, the heat preservation time is 1h, and after the aging treatment is finished, cooling the copper alloy material to the room temperature in an air cooling mode;
(7) and (3) regression treatment: putting the copper alloy material subjected to aging treatment into a heat treatment furnace, performing regression treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the regression temperature is 850 ℃, the heat preservation time is 15min, and then taking out the copper alloy material from the heat treatment furnace to perform water quenching treatment immediately;
(8) magnetic field heat treatment: and (3) putting the copper alloy material subjected to the regression treatment into a magnetic field heat treatment furnace, carrying out magnetic field heat treatment under the protection of pure argon (Ar is more than or equal to 99.99%), wherein the temperature of the magnetic field heat treatment is 450 ℃, the heat preservation time is 4h, the peak intensity of an alternating current magnetic field is 6.0kA/m, the frequency is 30Hz, and then cooling to room temperature in an air cooling mode to obtain the copper alloy material. The detection shows that the hardness of the obtained copper alloy material is 257HV, the yield strength is 695MPa, the tensile strength is 763MPa, the elongation after fracture is 15%, the softening temperature is 570 ℃, and the electric conductivity is 63% IACS.
Example 5
The alloy comprises the following components in percentage by mass: 1.35wt% Ti, 0.75wt% Si, 0.61wt% Co, 0.02wt% La, and the balance Cu. The sum of the mass percentages of Ti and Si is 2.10wt%, and the mass ratio of Ti to Si is 1.80: 1.
The preparation method comprises the following steps:
(1) casting of alloy: placing the raw materials into a crucible of an induction furnace, and vacuumizing to 3.0 × 10-3Pa, then 1.1X 105Pa pure argon (Ar is more than or equal to 99.99 percent), smelting under the protection of the pure argon, keeping for 10min after the solid is completely melted to form alloy melt, and then casting the alloy melt to a graphite moldCooling, opening the die and taking out an alloy ingot with the thickness of 25 mm; the smelting uses Cu and Si blocks with the purity of more than or equal to 99.9wt%, Cu-Ti intermediate alloy containing 60wt% of Ti, Cu-Co intermediate alloy containing 9wt% of Co and Cu-La intermediate alloy containing 25wt% of La;
(2) homogenizing: placing the alloy cast ingot into a heat treatment furnace, carrying out homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the homogenization treatment temperature is 1000 ℃, the heat preservation time is 5 hours, and then cooling to room temperature along with the furnace;
(3) hot rolling: heating the ingot after homogenization treatment to 950 ℃ for hot rolling deformation, wherein the total hot rolling deformation is 55%, the finish rolling temperature is 850 ℃, and then immediately performing water quenching to obtain a hot rolled sample with the thickness of 11.25 mm;
(4) multi-stage solution treatment: putting the hot-rolled sample into a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99%) for solution treatment, wherein the solution temperature is 690 ℃, preserving heat for 1h, then heating to 790 ℃, preserving heat for 0.5h, then heating to 890 ℃, preserving heat for 0.75h, finally heating to 970 ℃, preserving heat for 1h, and cooling to room temperature in a water cooling manner;
(5) rolling at room temperature: milling the surface of the sample subjected to the multistage solid solution treatment to remove surface oxide skin, and then performing rolling deformation at room temperature, wherein the total rolling deformation is 73%, and the thickness of the rolled sample is 3.0 mm;
(6) aging treatment: carrying out aging treatment on the copper alloy material rolled at room temperature in a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the aging temperature is 520 ℃, the heat preservation time is 1h, and after the aging treatment is finished, cooling the copper alloy material to the room temperature in an air cooling mode;
(7) and (3) regression treatment: putting the copper alloy material subjected to aging treatment into a heat treatment furnace, performing regression treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the regression temperature is 950 ℃, the heat preservation time is 10min, and then taking out the copper alloy material from the heat treatment furnace to perform water quenching treatment immediately;
(8) magnetic field heat treatment: and (3) putting the copper alloy material subjected to the regression treatment into a magnetic field heat treatment furnace, carrying out magnetic field heat treatment under the protection of pure argon (Ar is more than or equal to 99.99%), wherein the temperature of the magnetic field heat treatment is 460 ℃, the heat preservation time is 4h, the peak intensity of an alternating current magnetic field is 5.5kA/m, and the frequency is 40Hz, and then cooling to room temperature in an air cooling mode to obtain the copper alloy material. The hardness of the obtained copper alloy material is 281HV, the yield strength is 755MPa, the tensile strength is 830MPa, the elongation after fracture is 12%, the softening temperature is 610 ℃, and the electric conductivity is 55% IACS.
Example 6
The alloy comprises the following components in percentage by mass: 0.86wt% Ti, 0.40wt% Si, 0.55wt% Co, 0.05wt% La, and the balance Cu. The sum of the mass percentages of Ti and Si is 1.26wt%, and the mass ratio of Ti to Si is 2.15: 1.
The preparation method comprises the following steps:
(1) casting of alloy: placing the raw materials into a crucible of an induction furnace, and vacuumizing to 3.0 × 10-3Pa, then 1.1X 105Pa pure argon (Ar is more than or equal to 99.99 percent), smelting under the protection of pure argon (Ar is more than or equal to 99.99 percent), keeping for 10min after the solid is completely melted to form alloy melt, then casting the alloy melt into a graphite mold, cooling, opening the mold, taking out an alloy ingot, wherein the thickness of the ingot is 25 mm; the smelting uses Cu and Si blocks with the purity of more than or equal to 99.9wt%, Cu-Ti intermediate alloy containing 60wt% of Ti, Cu-Co intermediate alloy containing 9wt% of Co and Cu-La intermediate alloy containing 25wt% of La;
(2) homogenizing: placing the alloy cast ingot into a heat treatment furnace, carrying out homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the homogenization treatment temperature is 950 ℃, the heat preservation time is 3 hours, and then cooling to room temperature along with the furnace;
(3) hot rolling: heating the ingot after homogenization treatment to 850 ℃ for hot rolling deformation, wherein the total hot rolling deformation is 80%, the finish rolling temperature is 730 ℃, and then immediately performing water quenching to obtain a hot rolled sample with the thickness of 5.0 mm;
(4) multi-stage solution treatment: putting the hot-rolled sample into a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99%) for solution treatment, wherein the solution temperature is 700 ℃, the temperature is kept for 0.75h, then the temperature is increased to 800 ℃, the temperature is kept for 0.5h, then the temperature is increased to 900 ℃, the temperature is kept for 1h, finally the temperature is increased to 960 ℃, the temperature is kept for 0.5h, and the sample is cooled to the room temperature in a water cooling mode;
(5) rolling at room temperature: milling a sample subjected to multistage solid solution treatment to remove surface oxide skin, and then performing rolling deformation at room temperature, wherein the total rolling deformation is 86%, and the thickness of the rolled sample is 0.66 mm;
(6) aging treatment: carrying out aging treatment on the copper alloy material rolled at room temperature in a heat treatment furnace under the protection of pure argon, wherein the aging temperature is 550 ℃, the heat preservation time is 0.5h, and after the aging treatment is finished, cooling the copper alloy material to the room temperature in an air cooling mode;
(7) and (3) regression treatment: putting the copper alloy material subjected to aging treatment into a heat treatment furnace, performing regression treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the regression temperature is 900 ℃, the heat preservation time is 7min, and then taking out the copper alloy material from the heat treatment furnace to perform water quenching treatment immediately;
(8) magnetic field heat treatment: and (3) putting the copper alloy material subjected to the regression treatment into a magnetic field heat treatment furnace, carrying out magnetic field heat treatment under the protection of pure argon (Ar is more than or equal to 99.99%), wherein the temperature of the magnetic field heat treatment is 480 ℃, the heat preservation time is 3h, the peak intensity of an alternating current magnetic field is 5.0kA/m, the frequency is 50Hz, and then cooling to room temperature in an air cooling mode to obtain the copper alloy material. The detection shows that the hardness of the obtained copper alloy material is 251HV, the yield strength is 676MPa, the tensile strength is 742MPa, the elongation after fracture is 13%, the softening temperature is 570 ℃, and the conductivity is 65% IACS.
Comparative example 1
The alloy comprises the following components in percentage by mass: 0.93wt% Ti, 0.49wt% Si, 0.20wt% Co, 0.04wt% La, and the balance Cu. The sum of the mass percentages of Ti and Si is 1.42wt%, and the mass ratio of Ti to Si is 1.90: 1.
The preparation method comprises the following steps:
(1) casting of alloy: placing the raw materials into a crucible of an induction furnace, and vacuumizing to 3.0 × 10-3Pa, then 1.1X 105Pa pure argon (Ar is more than or equal to 99.99 percent), smelting under the protection of pure argon (Ar is more than or equal to 99.99 percent), keeping for 10min after the solid is completely melted to form alloy melt, then casting the alloy melt into a graphite mold, cooling, opening the mold, taking out the alloy ingot, and castingThe ingot thickness is 25 mm; the smelting uses Cu and Si blocks with the purity of more than or equal to 99.9wt%, Cu-Ti intermediate alloy containing 60wt% of Ti, Cu-Co intermediate alloy containing 9wt% of Co and Cu-La intermediate alloy containing 25wt% of La;
(2) homogenizing: placing the alloy cast ingot into a heat treatment furnace, carrying out homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the homogenization treatment temperature is 900 ℃, the heat preservation time is 5 hours, and then cooling to room temperature along with the furnace;
(3) hot rolling: heating the ingot after homogenization treatment to 960 ℃ for hot rolling deformation, wherein the total hot rolling deformation is 75%, the finish rolling temperature is 800 ℃, and then immediately performing water quenching to obtain a hot rolled sample with the thickness of 6.20 mm;
(4) multi-stage solution treatment: putting the hot-rolled sample into a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99%) for solution treatment, wherein the solution temperature is 650 ℃, the heat preservation time is 0.5h, the temperature is increased to 750 ℃, the heat preservation time is 0.5h, the temperature is increased to 850 ℃, the heat preservation time is 0.5h, the temperature is finally increased to 950 ℃, the heat preservation time is 1h, and the sample is cooled to the room temperature in a water cooling mode;
(5) rolling at room temperature: milling a sample subjected to multistage solid solution treatment to remove surface oxide skin, and then performing rolling deformation at room temperature, wherein the total rolling deformation is 76%, and the thickness of the rolled sample is 1.45 mm;
(6) aging treatment: carrying out aging treatment on the copper alloy material rolled at room temperature in a heat treatment furnace under the protection of pure argon, wherein the aging temperature is 520 ℃, the heat preservation time is 1.5h, and after the aging treatment is finished, cooling the copper alloy material to room temperature in an air cooling mode;
(7) magnetic field heat treatment: and (3) putting the copper alloy material subjected to aging treatment into a magnetic field heat treatment furnace, carrying out magnetic field heat treatment under the protection of pure argon (Ar is more than or equal to 99.99%), wherein the temperature of the magnetic field heat treatment is 430 ℃, the heat preservation time is 3h, the peak intensity of an alternating current magnetic field is 6.5kA/m, the frequency is 35Hz, and then cooling to room temperature in an air cooling mode to obtain the copper alloy material. The detection shows that the hardness of the obtained copper alloy material is 206HV, the yield strength is 632MPa, the tensile strength is 705MPa, the elongation after fracture is 4.3%, the softening temperature is 542 ℃, and the electric conductivity is 31% IACS. Namely, the fact that the mechanical property and the conductivity of the prepared copper alloy material are obviously deteriorated when the regression treatment is lacked in the preparation method is proved.
FIG. 3 is a photograph showing the metallographic structure of the copper alloy material obtained in the comparative example, which was relatively coarse, and a large number of coarse grains (grain size. gtoreq.35 μm) were observed, and the grain sizes were very uneven.
Comparative example 2
The alloy comprises the following components in percentage by mass: 0.97wt% of Ti, 0.53wt% of Si, 0.20wt% of Co, 0.06wt% of La and the balance of Cu. The sum of the mass percentages of Ti and Si is 1.50wt%, and the mass ratio of Ti to Si is 1.83: 1.
The preparation method comprises the following steps:
(1) casting of alloy: placing the raw materials into a crucible of an induction furnace, and vacuumizing to 3.0 × 10-3Pa, then 1.1X 105Pa pure argon (Ar is more than or equal to 99.99 percent), smelting under the protection of the pure argon, keeping for 10min after the solid is completely melted to form alloy melt, then casting the alloy melt into a graphite mold, cooling, opening the mold, taking out an alloy ingot, wherein the thickness of the ingot is 25 mm; the smelting uses Cu and Si blocks with the purity of more than or equal to 99.9wt%, Cu-Ti intermediate alloy containing 60wt% of Ti, Cu-Co intermediate alloy containing 9wt% of Co and Cu-La intermediate alloy containing 25wt% of La;
(2) homogenizing: placing the alloy cast ingot into a heat treatment furnace, carrying out homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the homogenization treatment temperature is 920 ℃, the heat preservation time is 8 hours, and then cooling to room temperature along with the furnace;
(3) hot rolling: heating the ingot after homogenization treatment to 900 ℃ for hot rolling deformation, wherein the total hot rolling deformation is 70%, the finish rolling temperature is 800 ℃, and then immediately performing water quenching to obtain a hot rolled sample with the thickness of 7.5 mm;
(4) multi-stage solution treatment: putting the hot-rolled sample into a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99%) for solution treatment, wherein the solution temperature is 660 ℃, preserving heat for 0.75h, then heating to 760 ℃, preserving heat for 0.75h, then heating to 860 ℃, preserving heat for 0.5h, finally heating to 960 ℃, preserving heat for 0.75h, and cooling to room temperature in a water cooling manner;
(5) rolling at room temperature: milling the surface of the sample subjected to the multistage solid solution treatment to remove surface oxide skin, and then carrying out rolling deformation at room temperature, wherein the total rolling deformation is 77%, and the thickness of the rolled sample is 1.7 mm;
(6) aging treatment: carrying out aging treatment on the copper alloy material rolled at room temperature in a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the aging temperature is 460 ℃, the heat preservation time is 3h, and after the aging treatment is finished, cooling the copper alloy material to the room temperature in an air cooling mode;
(7) and (3) regression treatment: putting the copper alloy material subjected to aging treatment into a heat treatment furnace, performing regression treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the regression temperature is 900 ℃, the heat preservation time is 10min, and then taking out the copper alloy material from the heat treatment furnace to perform water quenching treatment immediately;
(8) magnetic field-free heat treatment: and (3) putting the copper alloy material subjected to the regression treatment into a magnetic field-free heat treatment furnace, carrying out heat treatment under the protection of pure argon (Ar is more than or equal to 99.99%), wherein the heat treatment temperature is 460 ℃, the heat preservation time is 3 hours, and then cooling to room temperature in an air cooling mode to obtain the copper alloy material.
The detection shows that the hardness of the obtained copper alloy material is 192HV, the yield strength is 524MPa, the tensile strength is 573MPa, the elongation after fracture is 6%, the softening temperature is 530 ℃, and the electric conductivity is 42% IACS. Namely, the fact that the mechanical property and the conductivity of the prepared copper alloy material are obviously deteriorated due to the lack of magnetic field assistance in the heat treatment process after the regression treatment is proved.
FIG. 4 is a transmission electron micrograph of the copper alloy material obtained in the present comparative example, which shows that the precipitation phase in the copper matrix is relatively rare. The average size of precipitated phase particles is about 30-35 nm.
Comparative example 3
The alloy comprises the following components in percentage by mass: 0.95wt% of Ti, 0.52wt% of Si, 0.20wt% of Co, 0.06wt% of La and the balance of Cu, wherein the sum of the mass percentages of Ti and Si is 1.47wt%, and the mass ratio of Ti to Si is 1.83: 1.
The preparation method comprises the following steps:
(1) casting of alloy: will be originalPlacing the material in a crucible of an induction furnace, and vacuumizing to 3.0 × 10-3Pa, then 1.1X 105Pa pure argon (Ar is more than or equal to 99.99 percent), smelting under the protection of the pure argon, keeping for 10min after the solid is completely melted to form alloy melt, then casting the alloy melt into a graphite mold, cooling, opening the mold, taking out an alloy ingot, wherein the thickness of the ingot is 25 mm; the smelting uses Cu and Si blocks with the purity of more than or equal to 99.9wt%, Cu-Ti intermediate alloy containing 60wt% of Ti, Cu-Co intermediate alloy containing 9wt% of Co and Cu-La intermediate alloy containing 25wt% of La;
(2) homogenizing: placing the alloy cast ingot into a heat treatment furnace, carrying out homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the homogenization treatment temperature is 950 ℃, the heat preservation time is 5 hours, and then cooling to room temperature along with the furnace;
(3) hot rolling: heating the ingot after homogenization treatment to 950 ℃ for hot rolling deformation, wherein the total deformation amount of hot rolling is 80%, the finish rolling temperature is 790 ℃, and then immediately performing water quenching to obtain a hot rolled sample with the thickness of 5.0 mm;
(4) rolling at room temperature: milling a sample subjected to hot rolling to remove surface oxide skin, and then performing rolling deformation at room temperature, wherein the total rolling deformation is 81%, and the thickness of the sample subjected to rolling is 0.92 mm;
(5) aging treatment: carrying out aging treatment on the copper alloy material rolled at room temperature in a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the aging temperature is 460 ℃, the heat preservation time is 3h, and after the aging treatment is finished, cooling the copper alloy material to the room temperature in an air cooling mode;
(6) and (3) regression treatment: putting the copper alloy material subjected to aging treatment into a heat treatment furnace, performing regression treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the regression temperature is 950 ℃, the heat preservation time is 15min, and then taking out the copper alloy material from the heat treatment furnace to perform water quenching treatment immediately;
(7) magnetic field heat treatment: and (3) putting the copper alloy material subjected to the regression treatment into a magnetic field heat treatment furnace, carrying out magnetic field heat treatment under the protection of pure argon (Ar is more than or equal to 99.99%), wherein the temperature of the magnetic field heat treatment is 450 ℃, the heat preservation time is 3h, the peak intensity of an alternating current magnetic field is 6.5kA/m, the frequency is 35Hz, and then cooling to room temperature in an air cooling mode to obtain the copper alloy material. The detection shows that the hardness of the obtained copper alloy material is 214HV, the yield strength is 582MPa, the tensile strength is 637MPa, the elongation after fracture is 9.3%, the softening temperature is 524 ℃, and the conductivity is 39% IACS. Namely, the fact that the mechanical property and softening temperature of the prepared copper alloy material are obviously deteriorated and the conductivity is reduced to a certain degree when the preparation method is lack of multi-stage solution treatment is proved.
Comparative example 4
The alloy comprises the following components in percentage by mass: 0.45wt% of Ti, 0.16wt% of Si, 0.20wt% of Co, 0.01wt% of La and the balance of Cu, wherein the sum of the mass percentages of Ti and Si is 0.61wt%, and the mass ratio of Ti to Si is 2.81: 1.
The preparation method comprises the following steps:
(1) casting of alloy: placing the raw materials into a crucible of an induction furnace, and vacuumizing to 3.0 × 10-3Pa, then 1.1X 105Pa pure argon (Ar is more than or equal to 99.99 percent), smelting under the protection of the pure argon, keeping for 10min after the solid is completely melted to form alloy melt, then casting the alloy melt into a graphite mold, cooling, opening the mold, taking out an alloy ingot, wherein the thickness of the ingot is 25 mm; the smelting uses Cu and Si blocks with the purity of more than or equal to 99.9wt%, Cu-Ti intermediate alloy containing 60wt% of Ti, Cu-Co intermediate alloy containing 9wt% of Co and Cu-La intermediate alloy containing 25wt% of La;
(2) homogenizing: placing the alloy cast ingot into a heat treatment furnace, carrying out homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the homogenization treatment temperature is 950 ℃, the heat preservation time is 5 hours, and then cooling to room temperature along with the furnace;
(3) hot rolling: heating the ingot after homogenization treatment to 950 ℃ for hot rolling deformation, wherein the total deformation amount of hot rolling is 80%, the finish rolling temperature is 790 ℃, and then immediately performing water quenching to obtain a hot rolled sample with the thickness of 5.0 mm;
(4) multi-stage solution treatment: putting the hot-rolled sample into a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99%) for solution treatment, wherein the solution temperature is 700 ℃, the temperature is kept for 0.75h, then the temperature is increased to 800 ℃, the temperature is kept for 0.5h, then the temperature is increased to 900 ℃, the temperature is kept for 1h, finally the temperature is increased to 960 ℃, the temperature is kept for 0.5h, and the sample is cooled to the room temperature in a water cooling mode;
(5) rolling at room temperature: milling a sample subjected to multistage solid solution treatment to remove surface oxide skin, and then performing rolling deformation at room temperature, wherein the total rolling deformation is 81%, and the thickness of the rolled sample is 0.92 mm;
(6) aging treatment: carrying out aging treatment on the copper alloy material rolled at room temperature in a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the aging temperature is 460 ℃, the heat preservation time is 3h, and after the aging treatment is finished, cooling the copper alloy material to the room temperature in an air cooling mode;
(7) and (3) regression treatment: putting the copper alloy material subjected to aging treatment into a heat treatment furnace, performing regression treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the regression temperature is 950 ℃, the heat preservation time is 15min, and then taking out the copper alloy material from the heat treatment furnace to perform water quenching treatment immediately;
(8) magnetic field heat treatment: : and (3) putting the copper alloy material subjected to the regression treatment into a magnetic field heat treatment furnace, carrying out magnetic field heat treatment under the protection of pure argon (Ar is more than or equal to 99.99%), wherein the temperature of the magnetic field heat treatment is 460 ℃, the heat preservation time is 4h, the peak intensity of an alternating current magnetic field is 5.5kA/m, and the frequency is 40Hz, and then cooling to room temperature in an air cooling mode to obtain the copper alloy material. The obtained copper alloy material has the hardness of 193HV, the yield strength of 618MPa, the tensile strength of 669MPa, the elongation after fracture of 9.3 percent, the softening temperature of 524 ℃ and the conductivity of 44 percent IACS through detection. Namely, the contents of the alloy components (Ti, Si, Co and La) are lower than the limited range, the mechanical property and the softening temperature of the prepared copper alloy material are obviously deteriorated, and the electrical conductivity is also reduced to a certain degree.
Comparative example 5
The alloy comprises the following components in percentage by mass: 2.50wt% Ti, 1.30wt% Si, 0.40wt% Co, 0.05wt% La, and the balance Cu. The sum of the mass percentages of Ti and Si is 3.80wt%, and the mass ratio of Ti to Si is 1.92: 1.
The preparation method comprises the following steps:
(1) casting of alloy: putting raw materials into a crucible of an induction furnace, vacuumizing to 3.0 a10-3Pa, then 1.1X 105Pa pure argon (Ar is more than or equal to 99.99 percent), smelting under the protection of the pure argon, keeping for 10min after the solid is completely melted to form alloy melt, then casting the alloy melt into a graphite mold, cooling, opening the mold, taking out an alloy ingot, wherein the thickness of the ingot is 25 mm; the smelting uses Cu and Si blocks with the purity of more than or equal to 99.9wt%, Cu-Ti intermediate alloy containing 60wt% of Ti, Cu-Co intermediate alloy containing 9wt% of Co and Cu-La intermediate alloy containing 25wt% of La;
(2) homogenizing: placing the alloy cast ingot into a heat treatment furnace, carrying out homogenization treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the homogenization treatment temperature is 960 ℃, the heat preservation time is 8 hours, and then cooling to room temperature along with the furnace;
(3) hot rolling: heating the ingot after homogenization treatment to 880 ℃ for hot rolling deformation, wherein the total hot rolling deformation is 70%, the finish rolling temperature is 770 ℃, and then immediately performing water quenching to obtain a hot rolled sample with the thickness of 7.5 mm;
(4) multi-stage solution treatment: putting the hot-rolled sample into a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99%) for solution treatment, wherein the solution temperature is 700 ℃, the temperature is kept for 0.75h, then the temperature is increased to 800 ℃, the temperature is kept for 0.5h, then the temperature is increased to 900 ℃, the temperature is kept for 1h, finally the temperature is increased to 960 ℃, the temperature is kept for 0.5h, and the sample is cooled to the room temperature in a water cooling mode;
(5) rolling at room temperature: milling the surface of the sample subjected to the multistage solid solution treatment to remove surface oxide skin, and then carrying out rolling deformation at room temperature, wherein the total rolling deformation is 72%, and the thickness of the rolled sample is 2.1 mm;
(6) aging treatment: carrying out aging treatment on the copper alloy material rolled at room temperature in a heat treatment furnace under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the aging temperature is 460 ℃, and the heat preservation time is 3 h; after the aging is finished, cooling to room temperature in an air cooling mode;
(7) and (3) regression treatment: putting the copper alloy material subjected to aging treatment into a heat treatment furnace, performing regression treatment under the protection of pure argon (Ar is more than or equal to 99.99 percent), wherein the regression temperature is 860 ℃, the heat preservation time is 15min, and then taking out the copper alloy material from the heat treatment furnace to perform water quenching treatment immediately;
(8) magnetic field heat treatment: : and (3) putting the copper alloy material subjected to the regression treatment into a magnetic field heat treatment furnace, carrying out magnetic field heat treatment under the protection of pure argon (Ar is more than or equal to 99.99%), wherein the temperature of the magnetic field heat treatment is 480 ℃, the heat preservation time is 3h, the peak intensity of an alternating current magnetic field is 5.0kA/m, the frequency is 50Hz, and then cooling to room temperature in an air cooling mode to obtain the copper alloy material. The detection shows that the hardness of the obtained copper alloy material is 222HV, the yield strength is 603MPa, the tensile strength is 660MPa, the elongation after fracture is 3.5%, the softening temperature is 562 ℃, and the conductivity is 21% IACS. Namely, the contents of the alloy components (Ti, Si, Co and La) exceed the limited range, the mechanical property and the softening temperature of the prepared copper alloy material are obviously deteriorated, and the electrical conductivity is also reduced to a certain degree.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (3)
1. The preparation method of the Cu-Ti-Si-Co-La copper alloy material is characterized in that the Cu-Ti-Si-Co-La copper alloy material comprises the following components in percentage by mass according to the sum of 100 percent by mass: 0.71-1.35 wt% of Ti, 0.35-0.75 wt% of Si, 0.21-0.61 wt% of Co, 0.02-0.10 wt% of La and the balance of copper; the sum of the mass percentages of Ti and Si is 1.06-2.10 wt%, and the mass ratio of Ti to Si is 1.8: 1-2.2: 1;
the preparation method of the Cu-Ti-Si-Co-La copper alloy material comprises the following steps:
(1) casting of alloy: under the protection of pure argon, putting the raw materials into an induction furnace for smelting, then casting the obtained alloy melt into a mold and cooling to room temperature to obtain an alloy ingot;
(2) homogenizing: placing the obtained alloy ingot into a heat treatment furnace under the protection of pure argon for homogenization treatment, wherein the homogenization treatment temperature is 900-1000 ℃, the heat preservation time is 3-8 h, and then cooling to room temperature along with the furnace;
(3) hot rolling: heating the sample prepared in the step (2) to 850-950 ℃, taking out the sample and performing hot rolling treatment, wherein the total deformation of the hot rolling is 55-85%, the final rolling temperature is 730-850 ℃, and the alloy material after final rolling is immediately subjected to water quenching treatment;
(4) multi-stage solution treatment: putting the hot-rolled sample into a heat treatment furnace under the protection of pure argon gas for solution treatment, wherein the solution treatment process comprises the following steps: the temperature is 650-700 ℃, the temperature is kept for 0.5-1 h, the temperature is raised to 750-800 ℃, the temperature is kept for 0.5-1 h, then the temperature is raised to 850-900 ℃, the temperature is kept for 0.5-1 h, finally the temperature is raised to 950-980 ℃, the temperature is kept for 0.5-1 h, and the temperature is cooled to the room temperature in a water cooling mode;
(5) rolling at room temperature: milling the surface of the copper alloy material subjected to the multistage solid solution treatment, removing surface oxide skin, and then performing rolling deformation at room temperature, wherein the total rolling deformation is 70-90%;
(6) aging treatment: placing the copper alloy material rolled at room temperature into a heat treatment furnace, and carrying out aging treatment under the protection of pure argon, wherein the aging temperature is 400-550 ℃, and the heat preservation time is 0.5-2 h; after the aging is finished, cooling to room temperature in an air cooling mode;
(7) and (3) regression treatment: putting the copper alloy material subjected to aging treatment into a heat treatment furnace, performing regression treatment under the protection of pure argon, wherein the regression temperature is 850-950 ℃, the heat preservation time is 5-15 min, and then taking out the copper alloy material from the heat treatment furnace to perform water quenching treatment immediately;
(8) magnetic field heat treatment: and (3) putting the regressed copper alloy material into a magnetic field heat treatment furnace, carrying out magnetic field heat treatment under the protection of pure argon, wherein the temperature of the magnetic field heat treatment is 400-500 ℃, the heat preservation time is 2-5 h, the peak intensity of an alternating current magnetic field is 5-8 kA/m, and the frequency is 20-50 Hz, and then cooling to room temperature in an air cooling mode to obtain the copper alloy material.
2. The method for preparing Cu-Ti-Si-Co-La copper alloy material according to claim 1, wherein the raw material is Cu, Si metal block with purity not less than 99.9wt%, bulk Cu-M intermediate alloy, M is Ti, Co, La.
3. The method for preparing a Cu-Ti-Si-Co-La copper alloy material according to claim 1, wherein the volume fraction of Ar in the pure argon gas used is not less than 99.99%.
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| CN115927986A (en) * | 2022-12-28 | 2023-04-07 | 北冶功能材料(江苏)有限公司 | Hot processing method of homogeneous high-strength copper-nickel-tin alloy section |
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| JPH02170934A (en) * | 1988-12-24 | 1990-07-02 | Nippon Mining Co Ltd | Copper alloy having superior direct bonding property |
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| JP2009242814A (en) * | 2008-03-28 | 2009-10-22 | Furukawa Electric Co Ltd:The | Copper alloy material and producing method thereof |
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| KR20160117210A (en) * | 2015-03-30 | 2016-10-10 | 제이엑스금속주식회사 | Cu-Ni-Si BASED ROLLED COPPER ALLOY AND METHOD FOR MANUFACTURING THE SAME |
| CN106987738B (en) * | 2017-03-31 | 2018-11-09 | 江西理工大学 | A kind of Cu-Ni-Si-Co-Ti-RE copper alloys and preparation method thereof |
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| CN110951990B (en) * | 2019-11-22 | 2021-12-31 | 福州大学 | Cu-Ni-Co-Fe-Si-Zr-Zn copper alloy material and preparation method thereof |
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