A micro-nanoparticle hybrid reinforced high-strength high-conductivity Cu-Ni-Si-X alloy and a preparation method thereof

Abstract

This invention provides a micro / nano particle hybrid reinforced high-strength, high-conductivity Cu-Ni-Si-X alloy and its preparation method, belonging to the field of copper alloy preparation technology. The main characteristic of this invention's Cu-Ni-Si-X high-strength, high-conductivity copper alloy is that it contains submicron to micron-sized Ni-Si-X intermetallic compound particles, as well as nano-sized age-hardening phases of Ni-Si-X intermetallic compounds and Ni-Si binary intermetallic compounds. Based on the synergistic effect of the micron-sized Ni-Si-X intermetallic compound particles and the age-precipitated Ni-Si-X intermetallic compounds and Ni-Si binary intermetallic compounds, the Cu-Ni-Si-X alloy of this invention possesses excellent comprehensive properties, including a tensile strength of 450–1150 MPa, a conductivity of 25%–85% IACS, and a high-temperature softening resistance greater than 450℃.

Description

Technical Field

[0001] This invention relates to the field of copper alloy preparation technology, and in particular to a high-strength, high-conductivity Cu-Ni-Si-X alloy reinforced with micro / nano particles and its preparation method. Background Technology

[0002] Copper and its alloys, due to their high electrical and thermal conductivity, high corrosion resistance, ease of processing, and good mechanical properties, are widely used in machinery manufacturing, transportation, electrical and electronic engineering, aerospace, and marine engineering, and are important basic materials for national economic and technological development. High-strength, high-conductivity copper alloys, in particular, possess high strength, high hardness, high elasticity, and high electrical and thermal conductivity, making them key supporting materials for the development of industries such as integrated circuits, network communications, high-speed rail transportation, aerospace, precision instruments, and the military industry.

[0003] For metallic materials, strength and conductivity are a trade-off; increasing strength often comes at the cost of lower conductivity, and vice versa. Therefore, effectively reconciling the contradiction between strength and conductivity is key to developing high-strength, high-conductivity copper alloys.

[0004] Alloying is the main method for improving the mechanical properties of alloys and preparing high-strength, high-conductivity copper alloys. Among them, age hardening is an effective means to achieve high strength while maintaining high conductivity. Aging treatment causes dissolved alloying elements to precipitate and form dispersed age-hardening phases. These phases significantly improve the alloy's strength, and simultaneously, the precipitation of these phases overcomes the adverse effects of dissolved alloying elements on conductivity within the copper alloy matrix, thus effectively improving the alloy's electrical conductivity. Therefore, most high-strength, high-conductivity copper alloys are age-hardening alloys, such as Cu-Cr-Zr, Cu-Ni-Si, Cu-Fe-P, and Cu-Ni-Sn.

[0005] In recent years, with the continuous development of industries such as large-scale integrated circuits and 5G communications, the comprehensive performance requirements for high-strength and high-conductivity copper alloys have become increasingly stringent. For example, as the integration density of large-scale integrated circuits increases, the number of terminals required continues to rise, placing higher demands on the electrical and thermal conductivity of the alloys. Simultaneously, with the increase in the number of terminals, the lead width and spacing of integrated circuits are further reduced, and the lead thickness is further thinned, placing higher demands on the strength of copper alloys used in integrated circuit lead frames. Furthermore, 5G communication base stations generate more heat, thus requiring copper alloys with better thermal conductivity and higher resistance to high-temperature softening.

[0006] Therefore, developing a new high-strength, high-conductivity copper alloy with superior overall performance will be of positive significance to the development of the copper alloy industry and will also provide stronger support for the development of related downstream industries. Summary of the Invention

[0007] To address the above problems, this invention provides a high-strength, high-conductivity Cu-Ni-Si-X alloy reinforced with micro / nano particles and its preparation method.

[0008] The micro / nano particle hybrid reinforced high-strength, high-conductivity Cu-Ni-Si-X alloy of this invention comprises the following elements by weight percentage: Ni 0.5%–10.00%, Si 0.01%–4.00%, X 0.01%–5.00%, with the remainder being Cu and unavoidable impurities; X is one or more of the elements Ti, Zr, V, Nb, Cr, and Hf.

[0009] The matrix of the micro / nano particle hybrid reinforced high-strength and high-conductivity Cu-Ni-Si-X alloy of the present invention simultaneously contains: submicron to micron-sized Ni-Si-X intermetallic compound particles, and nano-sized aging-strengthening phase, wherein the aging-strengthening phase comprises Ni-Si-X intermetallic compounds and / or Ni-Si binary intermetallic compounds.

[0010] This invention does not limit the source of Ni, Si, X, and Cu, but preferably uses pure Cu, pure Ni, pure Si, and pure Ti as raw materials for alloy preparation.

[0011] This invention also provides a preparation process for high-strength, high-conductivity Cu-Ni-Si-X alloys reinforced with micro / nano particles, specifically including the following steps: S1. Raw material preparation: Weigh the raw materials according to the mass percentage; S2. Preparation of as-cast Cu-Ni-Si-X alloy: Pure copper is placed in a melting furnace to melt and form a copper-based melt. Then other raw materials are added to form a Cu-Ni-Si-X alloy melt. After holding at the temperature, it is cast to obtain the as-cast Cu-AM-Si-X alloy. S3, Heat treatment of Cu-Ni-Si-X alloy: Heat treatment is performed on the as-cast Cu-Ni-Si-X alloy to induce the precipitation of strengthening phases in the matrix during aging, resulting in a high-strength and high-conductivity Cu-Ni-Si-X alloy reinforced by micro-nano particles.

[0012] Furthermore, the melting temperature is 1150℃~1250℃. This invention does not limit the melting conditions. In the actual preparation process, vacuum melting, adding a covering agent, or filling with inert gas can be used to protect the melt as needed.

[0013] Furthermore, the molten metal is purified after being kept at a constant temperature.

[0014] Furthermore, solution treatment and aging heat treatment are performed before, during, or after alloy deformation.

[0015] Furthermore, the alloy deformation process is one or both of rolling and drawing.

[0016] Furthermore, the alloy is subjected to homogenization annealing treatment before deformation, with an annealing temperature of 850℃~1000℃ and a holding time of 4~8h.

[0017] Furthermore, the heat treatment is one or both of solution treatment and aging treatment.

[0018] Furthermore, the solution treatment temperature is 850℃~950℃, and the holding time is 2~4h.

[0019] Furthermore, the aging temperature treatment is 425℃-525℃, and the holding time is 0.5-6h.

[0020] The Cu-Ni-Si-X alloy of this invention can form submicron to micron-sized Ni-Si-X intermetallic compound particles during solidification and rolling. Simultaneously, after solution treatment and aging heat treatment, nanoscale age-hardening phases precipitate, primarily Ni-Si-X intermetallic compounds and Ni-Si binary intermetallic compounds. The synergistic effect of the micron-sized Ni-Si-X intermetallic compound particles in the Cu-Ni-Si-X alloy, along with the age-precipitated Ni-Si-X intermetallic compounds and Ni-Si binary intermetallic compounds, gives the Cu-Ni-Si-X alloy of this invention excellent comprehensive properties, including a tensile strength of 450–1150 MPa, an electrical conductivity of 25%–85% IACS, and a high-temperature softening resistance greater than 450℃. Attached Figure Description

[0021] Figure 1 This is a scanning electron microscope image of the as-cast microstructure of the Cu-Ni-Si-Ti high-strength and high-conductivity copper alloy prepared in Example 1 of this invention; Figure 2 This is a scanning electron microscope image of the as-cast microstructure of the Cu-Ni-Si-Ti high-strength and high-conductivity copper alloy prepared in Example 2 of the present invention. Detailed Implementation

[0022] The present invention will be further described below with reference to the embodiments.

[0023] Example 1 A method for preparing a Cu-Ni-Si-Ti high-strength and high-conductivity copper alloy, comprising the following steps: (1) Raw material preparation: Weigh pure Cu, pure Ni, pure Si and pure Ti as raw materials according to the weight ratio of Cu:Ni:Si:Ti of 95.15:3.20:0.67:0.98; (2) Preparation of as-cast Cu-Ni-Si-Ti alloy: Pure copper is placed in a smelting furnace and smelted under Ar atmosphere by adding charcoal to cover it, forming a copper-based melt. When the melt temperature reaches 1200℃, other raw materials are added to form a Cu-Ni-Si-Ti alloy melt. After holding the temperature for 10 minutes and adding cryolite for slag removal, the as-cast Cu-Ni-Si-Ti alloy is obtained by casting. (3) Deformation of Cu-Ni-Si-Ti alloy: The alloy ingot is heated to the homogenization annealing temperature and held for heat treatment, then hot rolled and quenched online, then the hot rolled product is milled, and finally cold rolled to obtain rolled Cu-Ni-Si-Ti alloy. The homogenization annealing temperature is 900℃, and the holding time is 4h; the initial rolling temperature of hot rolling is 900℃, the final rolling temperature of hot rolling is 750℃, the pass rate of hot rolling is 20-30%, and the total processing rate is 80%; the cooling method of quenching is water cooling; the single-sided milling amount of milling is 0.5mm; the pass rate of cold rolling is 20-30%, and the total processing rate is 60%. (4) Heat treatment of Cu-Ni-Si-Ti alloy: The rolled Cu-Ni-Si-Ti alloy was aged at 450℃ for 4 hours. After aging, it was air-cooled to room temperature to obtain a high-strength and high-conductivity Cu-Ni-Si-Ti alloy.

[0024] Performance tests showed that the prepared Cu-Ni-Si-Ti alloy had a hardness of 165.5 HV, a tensile strength of 480.6 MPa, and a conductivity of 52% IACS.

[0025] Example 2 A method for preparing a Cu-Ni-Si-Ti high-strength and high-conductivity copper alloy, comprising the following steps: (1) Raw material preparation: Weigh pure Cu, pure Ni, pure Si and pure Ti as raw materials according to the weight ratio of Cu:Ni:Si:Ti of 95.15:3.20:0.67:0.98; (2) Preparation of as-cast Cu-Ni-Si-Ti alloy: Pure copper is placed in a smelting furnace and smelted under Ar atmosphere by adding charcoal to cover it, forming a copper-based melt. When the melt temperature reaches 1200℃, other raw materials are added to form a Cu-Ni-Si-Ti alloy melt. After holding the temperature for 10 minutes and adding cryolite for slag removal, the as-cast Cu-Ni-Si-Ti alloy is obtained by casting. (3) Deformation of Cu-Ni-Si-Ti alloy: The alloy ingot is heated to the homogenization annealing temperature and held for heat treatment, then hot rolled and quenched online, then the hot rolled product is milled, and finally cold rolled to obtain rolled Cu-Ni-Si-Ti alloy. The homogenization annealing temperature is 975℃, and the holding time is 4h; the initial rolling temperature of hot rolling is 975℃, the final rolling temperature of hot rolling is 800℃, the pass rate of hot rolling is 20-30%, and the total processing rate is 80%; the cooling method of quenching is water cooling; the single-sided milling amount of milling is 0.5mm; the pass rate of cold rolling is 20-30%, and the total processing rate is 60%. (4) Heat treatment of Cu-Ni-Si-Ti alloy: The rolled Cu-Ni-Si-Ti alloy was aged at 450℃ for 16 hours. After aging, it was air-cooled to room temperature to obtain a high-strength and high-conductivity Cu-Ni-Si-Ti alloy.

[0026] Performance tests showed that the prepared Cu-Ni-Si-Ti alloy achieved a hardness of 185.6 HV, a tensile strength of 536.3 MPa, and a conductivity of 54% IACS.

[0027] Example 3 A method for preparing a Cu-Ni-Si-Ti high-strength and high-conductivity copper alloy, comprising the following steps: (1) Raw material preparation: Weigh pure Cu, pure Ni, pure Si and pure Ti in a weight ratio of Cu:Ni:Si:Ti of 95.59:3.20:0.71:0.50 as raw materials for later use; (2) Preparation of as-cast Cu-Ni-Si-Ti alloy: Pure copper is placed in a smelting furnace and smelted under Ar atmosphere by adding charcoal to cover it, forming a copper-based melt. When the melt temperature reaches 1200℃, other raw materials are added to form a Cu-Ni-Si-Ti alloy melt. After holding the temperature for 10 minutes and adding cryolite for slag removal, the as-cast Cu-Ni-Si-Ti alloy is obtained by casting. (3) Deformation of Cu-Ni-Si-Ti alloy: The alloy ingot is heated to the homogenization annealing temperature and held for heat treatment, then hot rolled and quenched online, then the hot rolled product is milled, and finally cold rolled to obtain rolled Cu-Ni-Si-Ti alloy. The homogenization annealing temperature is 975℃, and the holding time is 4h; the initial rolling temperature of hot rolling is 975℃, the final rolling temperature of hot rolling is 800℃, the pass rate of hot rolling is 20-30%, and the total processing rate is 80%; the cooling method of quenching is water cooling; the single-sided milling amount of milling is 0.5mm; the pass rate of cold rolling is 20-30%, and the total processing rate is 60%. (4) Heat treatment of Cu-Ni-Si-Ti alloy: The rolled Cu-Ni-Si-Ti alloy was aged at 450℃ for 1 hour. After aging, it was air-cooled to room temperature to obtain a high-strength and high-conductivity Cu-Ni-Si-Ti alloy.

[0028] Performance tests showed that the prepared Cu-Ni-Si-Ti alloy achieved a hardness of 226.1 HV, a tensile strength of 632.8 MPa, and a conductivity of 40% IACS.

[0029] Example 4 A method for preparing a Cu-Ni-Si-Ti high-strength and high-conductivity copper alloy, comprising the following steps: (1) Raw material preparation: Weigh pure Cu, pure Ni, pure Si and pure Ti in the weight ratio of Cu:Ni:Si:Ti of 95.95:3.20:0.75:0.10 as raw materials for later use; (2) Preparation of as-cast Cu-Ni-Si-Ti alloy: Pure copper is placed in a smelting furnace and smelted under Ar atmosphere by adding charcoal to cover it, forming a copper-based melt. When the melt temperature reaches 1200℃, other raw materials are added to form a Cu-Ni-Si-Ti alloy melt. After holding the temperature for 10 minutes and adding cryolite for slag removal, the as-cast Cu-Ni-Si-Ti alloy is obtained by casting. (3) Deformation of Cu-Ni-Si-Ti alloy: The alloy ingot is heated to the homogenization annealing temperature and held for heat treatment, then hot rolled and quenched online, then the hot rolled product is milled, and finally cold rolled to obtain rolled Cu-Ni-Si-Ti alloy. The homogenization annealing temperature is 900℃, and the holding time is 4h; the initial rolling temperature of hot rolling is 900℃, the final rolling temperature of hot rolling is 750℃, the pass rate of hot rolling is 20-30%, and the total processing rate is 80%; the cooling method of quenching is water cooling; the single-sided milling amount of milling is 0.5mm; the pass rate of cold rolling is 20-30%, and the total processing rate is 60%. (4) Heat treatment of Cu-Ni-Si-Ti alloy: The rolled Cu-Ni-Si-Ti alloy was aged at 450℃ for 2 hours. After aging, it was air-cooled to room temperature to obtain a high-strength and high-conductivity Cu-Ni-Si-Ti alloy.

[0030] Performance tests showed that the prepared Cu-Ni-Si-Ti alloy had a hardness of 261.8 HV, a tensile strength of 761.5 MPa, and a conductivity of 40% IACS.

[0031] Example 5 A method for preparing a Cu-Ni-Si-Zr high-strength and high-conductivity copper alloy, comprising the following steps: (1) Raw material preparation: Weigh pure Cu, pure Ni, pure Si, and Cu-40Zr master alloy in a weight ratio of Cu:Ni:Si:Zr of 95.72:3.20:0.70:0.38 as raw materials for later use; (2) Preparation of as-cast Cu-Ni-Si-Zr alloy: Pure copper is placed in a melting furnace and charcoal is added under Ar atmosphere to cover and melt to form a copper-based melt. When the melt temperature reaches 1200℃, other raw materials are added to form a Cu-Ni-Si-Zr alloy melt. After holding at the temperature for 10 minutes, the as-cast Cu-Ni-Si-Zr alloy is obtained. (3) Heat treatment of Cu-Ni-Si-Zr alloy: The as-cast Cu-Ni-Si-Zr alloy is subjected to solution treatment and aging treatment; The solution treatment temperature was 950℃, and the solution was held for 2 hours, followed by water quenching. The aging temperature was 475℃, and the solution was held for 8 hours. After aging, the solution was air-cooled to room temperature to obtain a high-strength and high-conductivity Cu-Ni-Si-Zr alloy.

[0032] Performance tests showed that the prepared Cu-Ni-Si-Ti alloy had a hardness of 234.7 HV, a tensile strength of 700.5 MPa, and a conductivity of 41% IACS.

[0033] Example 5 A method for preparing a Cu-Ni-Si-V high-strength and high-conductivity copper alloy, comprising the following steps: (1) Raw material preparation: Weigh pure Cu, pure Ni, pure Si and Cu-20V master alloy in the weight ratio of Cu:Ni:Si:V 95.00:4.00:0.95:0.05 as raw materials for later use; (2) Preparation of as-cast Cu-Ni-Si-V alloy: Pure copper is placed in a melting furnace and charcoal is added under Ar atmosphere to cover and melt to form a copper-based melt. When the melt temperature reaches 1200℃, other raw materials are added to form a Cu-Ni-Si-V alloy melt. After holding at the temperature for 10 minutes, the as-cast Cu-Ni-Si-V alloy is obtained by casting. (3) Heat treatment of Cu-Ni-Si-V alloy: The as-cast Cu-Ni-Si-V alloy is subjected to solution treatment and aging treatment; The solution treatment temperature was 950℃, and the solution was held for 2 hours, followed by water quenching. The aging temperature was 475℃, and the solution was held for 1 hour. After aging, the solution was air-cooled to room temperature to obtain a high-strength and high-conductivity Cu-Ni-Si-V alloy.

[0034] Performance tests showed that the prepared Cu-Ni-Si-V alloy had a hardness of 261.5 HV, a tensile strength of 807.5 MPa, and a conductivity of 34% IACS.

[0035] The above are merely preferred embodiments of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A high-strength, high-conductivity Cu-Ni-Si-X alloy reinforced with micro / nano particle hybridization, characterized in that, Includes elements with the following weight percentages: Ni 0.5%–10.00%, Si 0.01%–4.00%, X 0.01%–5.00%, with the remainder being Cu and unavoidable impurities; X is one or more of the elements Ti, Zr, V, Nb, Cr and Hf.

2. The high-strength, high-conductivity Cu-Ni-Si-X alloy reinforced with micro / nano particle hybridization according to claim 1, characterized in that, Its matrix simultaneously contains: submicron to micron-sized Ni-Si-X intermetallic compound particles, and nanoscale aging-strengthening phase, wherein the aging-strengthening phase comprises Ni-Si-X intermetallic compounds and / or Ni-Si binary intermetallic compounds.

3. A method for preparing a Cu-Ni-Si-X alloy reinforced with micro / nano particles, comprising the following steps: S1. Raw material preparation: Weigh the raw materials according to the mass percentage; S2. Preparation of as-cast Cu-Ni-Si-X alloy: Pure copper is placed in a melting furnace to melt and form a copper-based melt. Then other raw materials are added to form a Cu-Ni-Si-X alloy melt. After holding at the temperature, it is cast to obtain the as-cast Cu-AM-Si-X alloy. S3. Heat treatment of Cu-Ni-Si-X alloy: The as-cast Cu-Ni-Si-X alloy is heat-treated to obtain a high-strength and high-conductivity Cu-Ni-Si-X alloy reinforced with micro-nano particles.

4. The preparation process of the micro / nano particle hybrid reinforced high-strength and high-conductivity Cu-Ni-Si-X alloy according to claim 3, characterized in that, The melting temperature is 1150℃~1250℃, and the molten metal is purified after being kept at the temperature.

5. The preparation process of the micro / nano particle hybrid reinforced high-strength and high-conductivity Cu-Ni-Si-X alloy according to claim 3, characterized in that, The heat treatment process is carried out before, during, or after alloy deformation.

6. The preparation process of the micro / nano particle hybrid reinforced high-strength and high-conductivity Cu-Ni-Si-X alloy according to claim 5, characterized in that, The alloy deformation process is one or both of rolling and drawing.

7. The preparation process of the micro / nano particle hybrid reinforced high-strength and high-conductivity Cu-Ni-Si-X alloy according to claim 5, characterized in that, Before deformation, the alloy is subjected to homogenization annealing treatment at a temperature of 850℃ to 1000℃ and a holding time of 4 to 8 hours.

8. The preparation process of the micro / nano particle hybrid reinforced high-strength and high-conductivity Cu-Ni-Si-X alloy according to claim 3, characterized in that, The heat treatment is one or both of solution treatment and aging treatment.

9. The preparation process of the micro / nano particle hybrid reinforced high-strength and high-conductivity Cu-Ni-Si-X alloy according to claim 3, characterized in that, The solution treatment temperature is 850℃~950℃, and the holding time is 2~4h.

10. The preparation process of the micro / nano particle hybrid reinforced high-strength and high-conductivity Cu-Ni-Si-X alloy according to claim 3, characterized in that, The aging temperature treatment is 425℃-525℃, and the holding time is 0.5-6h.

Images