WO2023065940A1 - Matériau d'alliage de cuivre cu-sn-p ayant une teneur élevée en étain et son procédé de préparation - Google Patents

Matériau d'alliage de cuivre cu-sn-p ayant une teneur élevée en étain et son procédé de préparation Download PDF

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WO2023065940A1
WO2023065940A1 PCT/CN2022/120144 CN2022120144W WO2023065940A1 WO 2023065940 A1 WO2023065940 A1 WO 2023065940A1 CN 2022120144 W CN2022120144 W CN 2022120144W WO 2023065940 A1 WO2023065940 A1 WO 2023065940A1
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room temperature
copper alloy
rolling
alloy material
annealing
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Chinese (zh)
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王晨
罗诚盛
林晟
周建辉
张云昊
谭文龙
洪都
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福州大学
福建紫金铜业有限公司
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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
    • C22C9/02—Alloys based on copper with tin 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
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon

Definitions

  • the invention belongs to the technical field of copper alloy materials, and in particular relates to a Cu-Sn-P copper alloy material with high tin content and a preparation method thereof.
  • Tin phosphor bronze has good elasticity, diamagnetism, good machinability and weldability. It is often used to make parts such as spring contact pieces, wear-resistant parts and antimagnetic components. It is widely used in electric power, electronics, automobiles, communications, etc. and other related fields.
  • the present invention aims to improve the stress relaxation resistance and corrosion resistance of tin phosphor bronze, on the basis of Cu-Sn-P ternary alloy, by adding scandium, zirconium, nickel, zinc Elements, and innovative preparation process, significantly reduced the element segregation in the alloy, improved the microstructure of the alloy, so as to obtain a high tin content Cu-Sn-P alloy with excellent stress relaxation resistance and corrosion resistance.
  • the present invention provides the following technical solutions:
  • a Cu-Sn-P alloy material with high performance and high tin content which contains the following chemical composition in mass percentage: 10.50-12.50wt% of Sn, 0.30-0.50wt% of P, 0.10-0.35wt% of Sc, 0.05 -0.20wt% Zr, 0.10-0.20wt% Ni, 0.05-0.10wt% Zn, and the rest Cu; the sum of the mass percentages of Sc, Zr and Ni is 0.35-0.70wt%.
  • Tin Due to the large difference in radius between tin atoms and copper atoms, adding tin elements to copper alloys can cause large lattice distortions. Combined with appropriate heat treatment processes, atoms can be aggregated and ordered (that is, ordered domains are formed ), thereby effectively hindering the movement of dislocations and improving the stress relaxation resistance of the alloy. In addition, the tin element can make the copper alloy form a more dense and stable passivation film, thereby improving the corrosion resistance of the alloy.
  • Phosphorus A trace amount of phosphorus can not only remove oxygen, but also form a copper-phosphorus compound with copper to improve the stress relaxation resistance and softening temperature of the alloy.
  • the element content should not exceed 0.50wt%;
  • Scandium According to Miedema’s theoretical calculation, the mixing enthalpy between Sc and Sn is -45kJ/mol. During the annealing process, Sc-Sn precipitates can be formed to play the role of pinning dislocations, thereby improving its stress relaxation resistance. . Moreover, the addition of Sc can reduce the temperature difference between the liquid phase and the solid phase of the alloy, reduce the element segregation in the ingot, eliminate the loose structure defects of casting, and reduce rolling cracking.
  • Nickel element can block the cathodic process of copper alloy in electrochemical corrosion, and form a complete and dense corrosion product film, thereby improving the corrosion resistance of the alloy. At the same time, nickel can refine the grains, which is beneficial to improve the mechanical properties of the alloy.
  • Zinc has the function of degassing during alloy smelting. After adding zinc to copper, the gas dissolved in the high-temperature melt can be taken away by the volatilization of zinc, and the porosity of the ingot can be reduced.
  • a kind of preparation method of high tin content Cu-Sn-P copper alloy material that the present invention relates to comprises the following steps:
  • Alloy melting and casting Put the raw materials into an induction furnace and melt them under the protection of pure argon. After the raw materials are completely melted, keep them warm for 8 to 15 minutes, then cast the alloy melt into a mold and cool it down to room temperature to obtain Copper alloy ingot;
  • Solution treatment Put the copper alloy material rolled at room temperature for the first time into a heat treatment furnace, and carry out solution treatment under the protection of pure argon.
  • the solution temperature is 880-950°C, and the solution time is 0.5 ⁇ 1 hour, then water quenching immediately, and rapidly cooled to room temperature;
  • the second room temperature rolling the copper alloy material after the solution treatment is subjected to the second room temperature rolling, and the total rolling deformation is 65% to 80%;
  • the first intermediate annealing put the copper alloy material rolled at room temperature for the second time into a heat treatment furnace, and perform intermediate annealing under the protection of pure argon. 5 minutes, then cooled to room temperature by air cooling;
  • the third room temperature rolling the copper alloy material after the first intermediate annealing treatment is subjected to room temperature rolling, and the total rolling deformation is 55% to 65%;
  • the second intermediate annealing put the copper alloy material after the third room temperature rolling into a heat treatment furnace, and perform intermediate annealing under the protection of pure argon.
  • the annealing temperature is 650°C to 750°C, and the annealing time is 1 ⁇ 2 minutes, then cooled to room temperature by air cooling;
  • the fourth room temperature rolling the copper alloy material after the second intermediate annealing treatment is subjected to room temperature rolling, and the total rolling deformation is 40% to 50%;
  • Tension annealing Put the copper alloy material after the fourth room temperature rolling into a heat treatment furnace, apply a tension of 300 to 350 MPa to the copper alloy material, and perform tension annealing under the protection of pure argon, and the annealing temperature is 300 ⁇ 350°C, the annealing time is 5-10 minutes, and then cooled to room temperature by means of air cooling to obtain the Cu-Sn-P copper alloy material with high tin content.
  • the raw materials used in step (1) are Cu, Sn, Zn metal blocks with a purity ⁇ 99.9wt%, a Cu-P master alloy containing 15-25wt% P, a Cu-Sc master alloy containing 20-30wt% Sc, Cu-Zr master alloy containing 10-25wt% Zr and Cu-Ni master alloy containing 20-30wt% Ni.
  • volume fraction of Ar in the pure argon used is ⁇ 99.99%.
  • a Cu-Sn-P copper alloy with high tin content of the present invention has the characteristics of high strength, high corrosion resistance, excellent stress relaxation resistance, and good cold working characteristics; the segregation of alloy elements in the ingot is small, and the defects less, which is conducive to industrial production.
  • the preferred alloy composition of the present invention is 10.50 ⁇ 12.50wt% of Sn, 0.30 ⁇ 0.50wt% of P, 0.10 ⁇ 0.35wt% of Sc, 0.05 ⁇ 0.20wt% of Zr, 0.10 ⁇ 0.20wt% of Ni, 0.05-0.10wt% Zn, the rest is Cu; the alloy has a high Sn content, and adding trace amounts of Sc, Zr, Ni, Zn alloy elements can improve the corrosion resistance of the alloy; at the same time reduce the temperature difference between the solid-liquidus line And refine the grain structure, significantly improve the element segregation in the alloy, thereby improving the mechanical properties of the alloy;
  • the material composition of the present invention does not contain toxic elements, and is less harmful to the human body and the environment;
  • Pre-rolling at room temperature can break the dendrites in the alloy ingot, increase the dislocation density at the same time, provide more channels for the diffusion of elements during the homogenization process, improve the diffusion efficiency, and make the distribution of elements more uniform;
  • Low-temperature tension annealing can reduce the residual stress and improve the plate shape on the one hand, and increase the elastic limit value of the material on the other hand, thereby improving the stress relaxation resistance of the material.
  • Fig. 1 is the polarization curve of the copper alloy material obtained in Example 1 in 3.5% NaCl solution.
  • Fig. 2 is a surface corrosion topography diagram of the copper alloy material obtained in Example 1 soaked in 3.5% NaCl solution for 6 hours.
  • Fig. 3 is the bending stress relaxation curve of the copper alloy material obtained in Example 1 after being kept at 150° C. for 200 hours.
  • Fig. 4 is the polarization curve of the copper alloy material obtained in Comparative Example 1 in 3.5% NaCl solution.
  • Fig. 5 is a surface corrosion topography diagram of the copper alloy material obtained in Comparative Example 1 soaked in 3.5% NaCl solution for 6 hours.
  • FIG. 6 is a bending stress relaxation curve of the copper alloy material obtained in Comparative Example 1 after being kept at 150° C. for 200 hours.
  • the present invention will be further described below in conjunction with the examples, but the present invention is not limited thereto.
  • the main test methods and standards related to the present invention according to GB/T34505-2017 "Room Temperature Tensile Test Method for Copper and Copper Alloy Materials", determine the yield strength, tensile strength and elongation of copper alloy materials; according to GB/T39152- 2020 “Copper and Copper Alloy Bending Stress Relaxation Test Method” to determine the stress relaxation rate of copper alloy materials; according to GB/T 24196-2009 “Metal and Alloy Corrosion Electrochemical Test Methods Constant Potential and Potentiodynamic Polarization Measurement Guidelines”
  • SCE saturated calomel electrode
  • the mass percent of the alloy composition is: 10.50wt% Sn, 0.30wt% P, 0.15wt% Sc, 0.10wt% Zr, 0.10wt% Ni, 0.05wt% Zn, and the rest are Cu, Sc, Zr
  • the sum of the mass percentages of the three alloying elements, Ni and Ni is 0.35wt%.
  • Alloy melting and casting Put the raw materials into an induction furnace and melt them under the protection of pure argon. After the raw materials are completely melted, keep them warm for 10 minutes, then cast the alloy melt into a mold and cool to room temperature to obtain a copper alloy. Ingot;
  • Solution treatment put the copper alloy material rolled at room temperature for the first time into a heat treatment furnace, and carry out solution treatment under the protection of pure argon.
  • the solution temperature is 880° C.
  • the solution time is 0.5 hours. Then immediately carry out water quenching and rapidly cool to room temperature;
  • the first intermediate annealing put the copper alloy material rolled at room temperature for the second time in a heat treatment furnace, and perform intermediate annealing under the protection of pure argon.
  • the annealing temperature is 700 ° C, and the annealing time is 3 minutes, and then Cool to room temperature with air cooling;
  • the third room temperature rolling the copper alloy material after the first intermediate annealing treatment is carried out to room temperature rolling, and the rolling total deformation is 55%;
  • the second intermediate annealing put the copper alloy material rolled at room temperature for the third time in a heat treatment furnace, and perform intermediate annealing under the protection of pure argon, the annealing temperature is 650 ° C, and the annealing time is 2 minutes, and then Cool to room temperature with air cooling;
  • the fourth room temperature rolling the copper alloy material after the second intermediate annealing treatment is carried out at room temperature rolling, and the rolling total deformation is 40%;
  • Tension annealing put the copper alloy material after the fourth room temperature rolling into a heat treatment furnace, apply a tension of 300 MPa to the copper alloy material, and perform tension annealing under the protection of pure argon, the annealing temperature is 300 ° C, The annealing time is 8 minutes, and then cooled to room temperature by air cooling to obtain the Cu—Sn—P copper alloy material with high tin content.
  • the yield strength of the obtained copper alloy material is 670MPa
  • the tensile strength is 690MPa
  • the elongation after fracture is 12%
  • the self-corrosion current density of the sample in 3.5% NaCl solution is 2.779 ⁇ 10-5A cm2
  • 150°C After 192 hours of heat preservation, the stress relaxation rate of the sample is 25.92%.
  • Fig. 1 is the polarization curve of the copper alloy material obtained in Example 1 in 3.5%NaCl solution, according to which the self-corrosion current density of the sample can be obtained;
  • Fig. 2 is the copper alloy material obtained in Example 1 soaked in 3.5%NaCl solution The surface topography after 6 hours shows that the surface corrosion product film is relatively dense and smooth, with few holes;
  • Figure 3 is the bending stress relaxation curve of the copper alloy material obtained in Example 1 after being kept at 150°C for 192 hours.
  • the mass percent of the alloy composition is: the mass percent of the alloy composition is: 11.00wt% of Sn, 0.35wt% of P, 0.20wt% of Sc, 0.15wt% of Zr, 0.10wt% of Ni, 0.05wt% of Zn, The rest is Cu, and the sum of the mass percentages of the three alloying elements Sc, Zr and Ni is 0.45wt%.
  • Alloy melting and casting Put the raw materials into an induction furnace and melt them under the protection of pure argon. After the raw materials are completely melted, keep them warm for 10 minutes, then cast the alloy melt into a mold and cool to room temperature to obtain a copper alloy. Ingot;
  • Solution treatment put the copper alloy material rolled at room temperature for the first time in a heat treatment furnace, and carry out solution treatment under the protection of pure argon.
  • the solution temperature is 880 ° C, and the solution time is 1 hour. Then immediately carry out water quenching and rapidly cool to room temperature;
  • the second room temperature rolling the copper alloy material after solution treatment is subjected to room temperature rolling for the second time, and the total rolling deformation is 80%;
  • the third room temperature rolling the copper alloy material after the first intermediate annealing treatment is carried out to room temperature rolling, and the rolling total deformation is 55%;
  • the second intermediate annealing put the copper alloy material rolled at room temperature for the third time in a heat treatment furnace, and perform intermediate annealing under the protection of pure argon, the annealing temperature is 650 ° C, and the annealing time is 2 minutes, and then Cool to room temperature with air cooling.
  • Tension annealing put the copper alloy material after the fourth room temperature rolling into a heat treatment furnace, apply a tension of 350 MPa to the copper alloy material, and perform tension annealing under the protection of pure argon, the annealing temperature is 300 ° C, The annealing time is 8 minutes, and then cooled to room temperature by air cooling to obtain the Cu—Sn—P copper alloy material with high tin content.
  • the yield strength of the obtained copper alloy material is 665MPa
  • the tensile strength is 680MPa
  • the elongation after fracture is 12.5%.
  • the self-corrosion current density of the sample in 3.5% NaCl solution is 2.541 ⁇ 10-5A. cm2
  • the stress relaxation rate of the sample after 192 hours at 150°C is 28.88%.
  • the mass percent of the alloy composition is: 11.50wt% of Sn, 0.45wt% of P, 0.30wt% of Sc, 0.15wt% of Zr, 0.15wt% of Ni, 0.05wt% of Zn, and the rest are Cu, Sc, Zr
  • the sum of the mass percentages of the three alloying elements, Ni and Ni is 0.60wt%.
  • Alloy melting and casting Put the raw materials into an induction furnace and melt them under the protection of pure argon. After the raw materials are completely melted, keep them warm for 10 minutes, then cast the alloy melt into a mold and cool to room temperature to obtain a copper alloy. Ingot;
  • Solution treatment put the copper alloy material rolled at room temperature for the first time into a heat treatment furnace, and carry out solution treatment under the protection of pure argon.
  • the solution temperature is 900° C., and the solution time is 0.75 hours. Then immediately carry out water quenching and rapidly cool to room temperature;
  • the first intermediate annealing put the copper alloy material rolled at room temperature for the second time in a heat treatment furnace, and carry out intermediate annealing under the protection of pure argon, the annealing temperature is 700 ° C, the annealing time is 4 minutes, and then Cool to room temperature with air cooling;
  • the third room temperature rolling the copper alloy material after the first intermediate annealing treatment is carried out room temperature rolling, and the rolling total deformation is 60%;
  • the second intermediate annealing put the copper alloy material rolled at room temperature for the third time in a heat treatment furnace, and perform intermediate annealing under the protection of pure argon.
  • the annealing temperature is 700 ° C, and the annealing time is 1.5 minutes, and then Cool to room temperature with air cooling;
  • Tension annealing put the copper alloy material after the fourth room temperature rolling into a heat treatment furnace, apply a tension of 350 MPa to the copper alloy material, and perform tension annealing under the protection of pure argon, the annealing temperature is 350 ° C, The annealing time is 5 minutes, and then cooled to room temperature by air cooling to obtain the Cu—Sn—P copper alloy material with high tin content.
  • the yield strength of the obtained copper alloy material is 680MPa
  • the tensile strength is 695MPa
  • the elongation after fracture is 13%.
  • the self-corrosion current density of the sample in 3.5% NaCl solution is 2.351 ⁇ 10-5A. cm2
  • the stress relaxation rate of the sample after 192 hours at 150°C is 24.57%.
  • the mass percent of the alloy composition is: 12.50wt% of Sn, 0.50wt% of P, 0.35wt% of Sc, 0.20wt% of Zr, 0.15wt% of Ni, 0.10wt% of Zn, and the rest are Cu, Sc, Zr
  • the sum of the mass percentages of the three alloying elements, Ni and Ni is 0.70wt%.
  • Alloy melting and casting Put the raw materials into an induction furnace and melt them under the protection of pure argon. After the raw materials are completely melted, keep them warm for 10 minutes, then cast the alloy melt into a mold and cool to room temperature to obtain a copper alloy. Ingot;
  • Solution treatment put the copper alloy material rolled at room temperature for the first time into a heat treatment furnace, and carry out solution treatment under the protection of pure argon.
  • the solution temperature is 880° C., and the solution time is 1 hour. Then immediately carry out water quenching and rapidly cool to room temperature;
  • the second room temperature rolling the copper alloy material after solution treatment is subjected to room temperature rolling for the second time, and the total rolling deformation is 80%;
  • the third room temperature rolling the copper alloy material after the first intermediate annealing treatment is carried out to room temperature rolling, and the rolling total deformation is 65%;
  • the second intermediate annealing put the copper alloy material rolled at room temperature for the third time in a heat treatment furnace, and carry out intermediate annealing under the protection of pure argon, the annealing temperature is 750 ° C, and the annealing time is 2 minutes, and then Cool to room temperature with air cooling;
  • Tension annealing put the copper alloy material after the fourth room temperature rolling into a heat treatment furnace, apply a tension of 350 MPa to the copper alloy material, and perform tension annealing under the protection of pure argon, the annealing temperature is 350 ° C, The annealing time is 5 minutes, and then cooled to room temperature by air cooling to obtain the Cu—Sn—P copper alloy material with high tin content.
  • the yield strength of the obtained copper alloy material is 650MPa
  • the tensile strength is 670MPa
  • the elongation after fracture is 11%.
  • the self-corrosion current density of the sample in 3.5% NaCl solution is 1.484 ⁇ 10-5A cm2, and it is kept at 150°C.
  • the stress relaxation rate of the sample after 192 hours was 26.40%.
  • the mass percent of the alloy composition is: 12.50wt% Sn, 0.40wt% P, 0.1wt% Sc, 0.05wt% Zr, 0.20wt% Ni, 0.08wt% Zn, and the rest are Cu, Sc, Zr
  • the sum of the mass percentages of the three alloying elements, Ni and Ni is 0.35wt%.
  • Alloy melting and casting Put the raw materials into an induction furnace and melt them under the protection of pure argon. After the raw materials are completely melted, keep them warm for 10 minutes, then cast the alloy melt into a mold and cool it to room temperature to obtain a copper alloy. Ingot;
  • Solution treatment put the copper alloy material rolled at room temperature for the first time into a heat treatment furnace, and carry out solution treatment under the protection of pure argon gas.
  • the solution temperature is 950° C.
  • the solution time is 0.5 hours. Then immediately carry out water quenching and rapidly cool to room temperature;
  • the first intermediate annealing put the copper alloy material after the second room temperature rolling into a heat treatment furnace, and perform intermediate annealing under the protection of pure argon, the annealing temperature is 750 ° C, the annealing time is 2 minutes, and then Cool to room temperature with air cooling;
  • the third room temperature rolling the copper alloy material after the first intermediate annealing treatment is carried out to room temperature rolling, and the rolling total deformation is 65%;
  • the second intermediate annealing put the copper alloy material rolled at room temperature for the third time in a heat treatment furnace, and perform intermediate annealing under the protection of pure argon, the annealing temperature is 700 ° C, the annealing time is 1 minute, and then Cool to room temperature with air cooling;
  • Tension annealing put the copper alloy material after the fourth room temperature rolling into a heat treatment furnace, apply a tension of 350 MPa to the copper alloy material, and perform tension annealing under the protection of pure argon, the annealing temperature is 300 ° C, The annealing time is 10 minutes, and then cooled to room temperature by air cooling to obtain the Cu—Sn—P copper alloy material with high tin content.
  • the yield strength of the obtained copper alloy material is 660MPa
  • the tensile strength is 680MPa
  • the elongation after fracture is 11.5%.
  • the self-corrosion current density of the sample in 3.5% NaCl solution is 1.780 ⁇ 10-5A cm2, and it is kept at 150°C
  • the stress relaxation rate of the sample after 192 hours was 27.51%.
  • the mass percent of the alloy composition is: 10.50wt% Sn, 0.30wt% P, 0.15wt% Sc, 0.10wt% Zr, 0.10wt% Ni, 0.05wt% Zn, and the rest are Cu, Sc, Zr
  • the sum of the mass percentages of the three alloying elements, Ni and Ni is 0.35wt%.
  • Alloy melting and casting Put the raw materials into an induction furnace and melt them under the protection of pure argon. After the raw materials are completely melted, keep them warm for 10 minutes, then cast the alloy melt into a mold and cool to room temperature to obtain a copper alloy. Ingot;
  • the second intermediate annealing put the copper alloy material rolled at room temperature for the second time in a heat treatment furnace, and carry out intermediate annealing under the protection of pure argon, the annealing temperature is 650 ° C, and the annealing time is 2 minutes, and then Cool to room temperature with air cooling;
  • the third room temperature rolling the copper alloy material after the second intermediate annealing treatment is carried out room temperature rolling, and the rolling total deformation is 40%;
  • Tension annealing Put the copper alloy material after the third room temperature rolling into a heat treatment furnace, apply a tension of 300 to 350 MPa to the copper alloy material, and perform tension annealing under the protection of pure argon.
  • the annealing temperature is 300 °C
  • the annealing time is 8 minutes, and then cooled to room temperature by air cooling to obtain the Cu-Sn-P copper alloy material with high tin content.
  • the yield strength of the obtained copper alloy material is 585MPa
  • the tensile strength is 620MPa
  • the elongation after fracture is 8.5%.
  • the self-corrosion current density of the sample in 3.5% NaCl solution is 3.779 ⁇ 10-5A cm2, and it is kept at 150°C
  • the stress relaxation rate of the sample after 192 hours was 60.30%.
  • Fig. 4 is the polarization curve of the copper alloy material obtained in Comparative Example 1 in 3.5%NaCl solution
  • Fig. 5 is the surface corrosion morphology figure of the copper alloy material obtained in Comparative Example 1 soaked in 3.5%NaCl solution for 6 hours, and the surface corrosion The product film layer is relatively loose and rough, and there are many corrosion holes
  • Figure 6 shows the bending stress relaxation curve of the copper alloy material obtained in the comparative example after being kept at 150°C for 192 hours.
  • the mass percent of the alloy composition is: 10.50wt% Sn, 0.30wt% P, 0.15wt% Sc, 0.10wt% Zr, 0.10wt% Ni, 0.05wt% Zn, and the rest is Cu.
  • the sum of the mass percentages of the three alloying elements Sc, Zr and Ni is 0.35 wt%.
  • Alloy melting and casting Put the raw materials into an induction furnace and melt them under the protection of pure argon. After the raw materials are completely melted, keep them warm for 10 minutes, then cast the alloy melt into a mold and cool to room temperature to obtain a copper alloy. Ingot;
  • Solution treatment put the copper alloy material rolled at room temperature for the first time into a heat treatment furnace, and carry out solution treatment under the protection of pure argon.
  • the solution temperature is 880° C.
  • the solution time is 0.5 hours. Then immediately carry out water quenching and rapidly cool to room temperature;
  • the first intermediate annealing put the copper alloy material rolled at room temperature for the second time in a heat treatment furnace, and perform intermediate annealing under the protection of pure argon.
  • the annealing temperature is 700 ° C, and the annealing time is 3 minutes, and then Cool to room temperature with air cooling;
  • the third room temperature rolling the copper alloy material after the first intermediate annealing treatment is carried out to room temperature rolling, and the rolling total deformation is 55%;
  • the second intermediate annealing put the copper alloy material rolled at room temperature for the third time in a heat treatment furnace, and perform intermediate annealing under the protection of pure argon, the annealing temperature is 650 ° C, and the annealing time is 2 minutes, and then Cool to room temperature by air cooling to obtain the Cu-Sn-P copper alloy material with high tin content.
  • the yield strength of the obtained copper alloy material is 580MPa
  • the tensile strength is 610MPa
  • the elongation after fracture is 7.2%.
  • the self-corrosion current density of the sample in 3.5% NaCl solution is 3.541 ⁇ 10-5A cm2, and it is kept at 150°C After 192 hours, the stress relaxation rate of the sample was 66.23%.
  • the mass percent of the alloy composition is: 10.50wt% Sn, 0.30wt% P, 0.15wt% Sc, 0.10wt% Zr, 0.10wt% Ni, 0.05wt% Zn, and the rest are Cu, Sc, Zr
  • the sum of the mass percentages of the three alloying elements, Ni and Ni is 0.35wt%.
  • Alloy melting and casting Put the raw materials into an induction furnace and melt them under the protection of pure argon. After the raw materials are completely melted, keep them warm for 10 minutes, then cast the alloy melt into a mold and cool to room temperature to obtain a copper alloy. Ingot;
  • Solution treatment put the copper alloy material rolled at room temperature for the first time into a heat treatment furnace, and carry out solution treatment under the protection of pure argon.
  • the solution temperature is 880° C.
  • the solution time is 0.5 hours. Then immediately carry out water quenching and rapidly cool to room temperature;
  • the first intermediate annealing put the copper alloy material rolled at room temperature for the second time in a heat treatment furnace, and perform intermediate annealing under the protection of pure argon.
  • the annealing temperature is 700 ° C, and the annealing time is 3 minutes, and then Cool to room temperature with air cooling;
  • the third room temperature rolling the copper alloy material after the first intermediate annealing treatment is carried out to room temperature rolling, and the rolling total deformation is 55%;
  • the yield strength of the obtained copper alloy material is 615MPa
  • the tensile strength is 645MPa
  • the elongation after fracture is 8.8%.
  • the self-corrosion current density of the sample in 3.5% NaCl solution is 4.298 ⁇ 10-5A cm2, and it is kept at 150°C
  • the stress relaxation rate of the sample after 192 hours was 59.88%.
  • the mass percentage of the alloy composition is: 10wt% of Sn, 0.15wt% of P, 0.10wt% of Sc, 0.05wt% of Zr, 0.10wt% of Ni, 0.05wt% of Zn, and the rest are Cu, Sc, Zr, The sum of the mass percentages of the three alloying elements of Ni is 0.25wt%.
  • Alloy melting and casting Put the raw materials into an induction furnace and melt them under the protection of pure argon. After the raw materials are completely melted, keep them warm for 10 minutes, then cast the alloy melt into a mold and cool to room temperature to obtain a copper alloy. Ingot;
  • Solution treatment put the copper alloy material rolled at room temperature for the first time into a heat treatment furnace, and carry out solution treatment under the protection of pure argon.
  • the solution temperature is 880° C.
  • the solution time is 0.5 hours. Then immediately carry out water quenching and rapidly cool to room temperature;
  • the first intermediate annealing put the copper alloy material rolled at room temperature for the second time in a heat treatment furnace, and perform intermediate annealing under the protection of pure argon.
  • the annealing temperature is 700 ° C, and the annealing time is 3 minutes, and then Cool to room temperature with air cooling;
  • the third room temperature rolling the copper alloy material after the first intermediate annealing treatment is carried out to room temperature rolling, and the rolling total deformation is 55%;
  • the second intermediate annealing put the copper alloy material rolled at room temperature for the third time in a heat treatment furnace, and perform intermediate annealing under the protection of pure argon, the annealing temperature is 650 ° C, and the annealing time is 2 minutes, and then Cool to room temperature with air cooling;
  • the fourth room temperature rolling the copper alloy material after the second intermediate annealing treatment is carried out at room temperature rolling, and the rolling total deformation is 40%;
  • Tension annealing put the copper alloy material after the fourth room temperature rolling into a heat treatment furnace, apply a tension of 300 MPa to the copper alloy material, and perform tension annealing under the protection of pure argon, the annealing temperature is 300 ° C, The annealing time is 8 minutes, and then cooled to room temperature by air cooling to obtain the Cu—Sn—P copper alloy material with high tin content.
  • the yield strength of the obtained copper alloy material is 615MPa
  • the tensile strength is 655MPa
  • the elongation after fracture is 9.3%.
  • the self-corrosion current density of the sample in 3.5% NaCl solution is 4.298 ⁇ 10-6A cm2, and the temperature is kept at 150°C. After 192 hours, the stress relaxation rate of the sample was 56.25%
  • the mass percentage of the alloy composition is: 13wt% of Sn, 0.60wt% of P, 0.45wt% of Sc, 0.20wt% of Zr, 0.20wt% of Ni, 0.15wt% of Zn, and the rest are Cu, Sc, Zr, The sum of the mass percentages of the three alloying elements of Ni is 0.85wt%.
  • Alloy melting and casting Put the raw materials into an induction furnace and melt them under the protection of pure argon. After the raw materials are completely melted, keep them warm for 10 minutes, then cast the alloy melt into a mold and cool to room temperature to obtain a copper alloy. Ingot;
  • Solution treatment put the copper alloy material rolled at room temperature for the first time into a heat treatment furnace, and carry out solution treatment under the protection of pure argon.
  • the solution temperature is 880° C.
  • the solution time is 0.5 hours. Then immediately carry out water quenching and rapidly cool to room temperature;
  • the first intermediate annealing put the copper alloy material rolled at room temperature for the second time in a heat treatment furnace, and perform intermediate annealing under the protection of pure argon.
  • the annealing temperature is 700 ° C, and the annealing time is 3 minutes, and then Cool to room temperature with air cooling;
  • the third room temperature rolling the copper alloy material after the first intermediate annealing treatment is carried out to room temperature rolling, and the rolling total deformation is 55%;
  • the second intermediate annealing put the copper alloy material rolled at room temperature for the third time in a heat treatment furnace, and perform intermediate annealing under the protection of pure argon, the annealing temperature is 650 ° C, and the annealing time is 2 minutes, and then Cool to room temperature with air cooling;
  • the fourth room temperature rolling the copper alloy material after the second intermediate annealing treatment is carried out at room temperature rolling, and the rolling total deformation is 40%;
  • Tension annealing put the copper alloy material after the fourth room temperature rolling into a heat treatment furnace, apply a tension of 300 MPa to the copper alloy material, and perform tension annealing under the protection of pure argon, the annealing temperature is 300 ° C, The annealing time is 8 minutes, and then cooled to room temperature by air cooling to obtain the Cu—Sn—P copper alloy material with high tin content.
  • the yield strength of the obtained copper alloy material is 610MPa
  • the tensile strength is 645MPa
  • the elongation after fracture is 9.1%.
  • the self-corrosion current density of the sample in 3.5% NaCl solution is 3.816 ⁇ 10-6A cm2, and it is kept at 150°C. After 192 hours, the stress relaxation rate of the sample was 58.63%.

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Abstract

La divulgation concerne un matériau d'alliage de cuivre Cu-Sn-P ayant une teneur élevée en étain et son procédé de préparation. Le matériau d'alliage de cuivre est composé de Cu ainsi que de 10,50 à 12,50 % en poids de Sn, de 0,30 à 0,50 % en poids de P, de 0,10 à 0,35 % en poids de Sc, de 0,05 à 0,20 % en poids de Zr, de 0,10 à 0,20 % en poids de Ni et de 0,05 à 0,10 % en poids de Zn. Le procédé de préparation comprend les étapes de fusion et de coulée de l'alliage, de pré-laminage à température ambiante, de traitement d'homogénéisation, de traitement en solution solide, de laminage à température ambiante, de recuit intermédiaire, de recuit de tension, etc. Le matériau d'alliage de cuivre obtenu par la présente invention ne contient pas d'éléments toxiques, et ne produit pas de substances toxiques pendant le processus de préparation, et ne cause ainsi que peu de dommages au corps humain et à l'environnement. Le matériau d'alliage de cuivre préparé présente des propriétés satisfaisantes, telles qu'une résistance, une résistance à la relaxation de contrainte et une résistance à la corrosion élevées, et peut être appliqué pour fabriquer divers composants électroniques, instruments et compteurs à hautes performances.
PCT/CN2022/120144 2021-10-23 2022-09-21 Matériau d'alliage de cuivre cu-sn-p ayant une teneur élevée en étain et son procédé de préparation WO2023065940A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5789449A (en) * 1980-11-21 1982-06-03 Sumitomo Electric Ind Ltd Method of manufacture of copper alloy for conducting electricity
CN101074461A (zh) * 2006-09-30 2007-11-21 阳西县电梯配件有限公司 一种锡磷青铜合金铸件及其制作方法
CN103088229A (zh) * 2012-11-06 2013-05-08 北京有色金属研究总院 一种低成本接插件用铜合金及其加工方法
CN105803249A (zh) * 2016-05-09 2016-07-27 安徽鑫科新材料股份有限公司 一种高性能锡磷青铜带及其生产方法
CN107904436A (zh) * 2017-12-13 2018-04-13 浙江灿根智能科技有限公司 用于制造快速冲床导套的铜合金及制备方法
CN108300894A (zh) * 2018-03-21 2018-07-20 温州市赢创新材料技术有限公司 一种耐腐蚀耐磨铜合金及其制备方法
CN113943875A (zh) * 2021-10-23 2022-01-18 福州大学 一种高锡含量的Cu-Sn-P铜合金材料及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002302721A (ja) * 2001-01-31 2002-10-18 Nippon Mining & Metals Co Ltd りん青銅条およびこれを用いた端子・コネクタ
CN102259252B (zh) * 2011-06-14 2015-08-05 福建紫金铜业有限公司 一种高弹性锡磷青铜合金箔材的制备方法
CN109266877B (zh) * 2018-11-01 2019-11-08 福建紫金铜业有限公司 一种高性能铜合金的制备方法
CN111235426B (zh) * 2020-03-23 2021-12-14 河北励恩新材料科技有限公司 一种多元铜合金及其制备方法和在增材制造中的应用
CN112251627A (zh) * 2020-09-27 2021-01-22 北京科技大学 一种高强高导Cu-Sc合金及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5789449A (en) * 1980-11-21 1982-06-03 Sumitomo Electric Ind Ltd Method of manufacture of copper alloy for conducting electricity
CN101074461A (zh) * 2006-09-30 2007-11-21 阳西县电梯配件有限公司 一种锡磷青铜合金铸件及其制作方法
CN103088229A (zh) * 2012-11-06 2013-05-08 北京有色金属研究总院 一种低成本接插件用铜合金及其加工方法
CN105803249A (zh) * 2016-05-09 2016-07-27 安徽鑫科新材料股份有限公司 一种高性能锡磷青铜带及其生产方法
CN107904436A (zh) * 2017-12-13 2018-04-13 浙江灿根智能科技有限公司 用于制造快速冲床导套的铜合金及制备方法
CN108300894A (zh) * 2018-03-21 2018-07-20 温州市赢创新材料技术有限公司 一种耐腐蚀耐磨铜合金及其制备方法
CN113943875A (zh) * 2021-10-23 2022-01-18 福州大学 一种高锡含量的Cu-Sn-P铜合金材料及其制备方法

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