Preparation method of anti-corrosion high-thermal-conductivity copper slot wire

Abstract

The application discloses a preparation method of an anti-corrosion high-thermal-conductivity copper slot wire, relates to the technical field of copper slot wires, and adopts a core-transition layer-surface layer three-section gradient structure, wherein the core is selected from superhigh-purity electrolytic copper powder, the transition layer and the surface layer are gradiently added with Ag, Yb, Ir and Os alloy elements; after powder metallurgy cold-pressing sintering, hot extrusion and slot type finishing forming, the core is subjected to laser etching to form a through network micro-thermal-conducting channel, and then surface modification is carried out through plasma bombardment coupling low-temperature oxidation. The anti-corrosion high-thermal-conductivity copper slot wire prepared by the method has excellent thermal conductivity and corrosion resistance without sacrificing the high-purity thermal conductivity of the base body.

Description

Technical Field

[0001] This invention relates to the field of copper channel wire technology, and in particular to a method for preparing corrosion-resistant and high thermal conductivity copper channel wire. Background Technology

[0002] Copper and copper alloys are widely used in various industrial fields due to their excellent thermal and electrical conductivity. Among them, copper channel wire, as a type of copper material with a specific channel structure, is indispensable in products such as superconducting wires, power equipment, and bathroom radiators because it can adapt to special requirements such as wire embedding and heat conduction. However, in practical engineering applications, the traditional manufacturing process of copper channel wire often has many defects, which prevents its thermal conductivity from being fully utilized and its corrosion resistance from being sufficient, seriously affecting its service life.

[0003] To improve the corrosion resistance of copper cable trays, existing technologies often employ surface coating methods such as electroplating and electroless plating. While these methods can improve surface corrosion resistance to some extent, the adhesion between the coating and the copper substrate is weak, leading to problems such as peeling and cracking during long-term use. This not only results in the loss of corrosion resistance but also causes the detached coating to contaminate the service environment and affect the stability of equipment operation. Furthermore, the poor thermal conductivity of the coating itself significantly reduces the overall thermal efficiency of the copper cable tray, contradicting the requirement for high thermal conductivity. In addition, some technologies improve corrosion resistance by adding alloying elements; however, improper selection of the type and amount of alloying elements often leads to a significant decrease in the thermal conductivity of the copper cable tray, failing to achieve a synergistic improvement in both corrosion resistance and high thermal conductivity. Moreover, existing methods for preparing copper cable trays mainly include extrusion, drawing, and rolling. These methods struggle to balance corrosion resistance and thermal conductivity, failing to meet the requirements of some special operating conditions.

[0004] Therefore, developing a method for preparing copper channel wires that can achieve a synergistic improvement in corrosion resistance and high thermal conductivity, and whose preparation process is stable and controllable, has become a technical challenge that urgently needs to be solved in this field. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for preparing corrosion-resistant and high thermal conductivity copper channel wires. This method is simple, can be mass-produced, and produces copper channel wires with excellent corrosion resistance and significant thermal conductivity.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is: a method for preparing corrosion-resistant and high thermal conductivity copper trench wire, comprising the following steps: Step S1, Gradient Structure Batching: A three-stage gradient structure design of core-transition layer-surface layer is adopted. The core raw material is high-purity electrolytic copper powder. The transition layer raw material and the surface layer raw material are both based on high-purity electrolytic copper powder, with different amounts of alloying elements added. The batching results in high-purity copper powder in the core, mixed powder in the transition layer, and mixed powder in the surface layer. Step S2, Preparation of gradient structure billet: Using powder metallurgy, high-purity copper powder in the core is loaded into the core of the mold, the mixed powder in the transition layer is evenly spread on the outside of the core powder, and the mixed powder in the surface layer is evenly spread on the outside of the transition layer powder. After bidirectional cold pressing, it is placed in an atmosphere-protected sintering furnace for green billet sintering, followed by hot extrusion forming and groove finishing. Step S3: Fabrication of microstructured heat conduction channels: Microstructured heat conduction channels are designed and fabricated in the copper groove core using laser etching technology; Step S4, Plasma bombardment + low-temperature oxidation combined treatment: The copper trench wire with the prepared microstructure heat conduction channel is placed in the plasma bombardment equipment and subjected to plasma bombardment and low-temperature oxidation combined treatment in sequence to obtain corrosion-resistant and high thermal conductivity copper trench wire.

[0007] Preferably, the high-purity electrolytic copper powder in step S1 has a purity ≥99.9995%, an oxygen content ≤0.0001%, and an average particle size of 30-50 μm.

[0008] Preferably, the transition layer raw material in step S1 comprises the following components by mass percentage: 0.06-0.08% Ag, 0.014-0.016% Yb, 0.007-0.009% Ir, 0.006-0.008% Os, and the balance being high-purity electrolytic copper powder.

[0009] Preferably, the surface material in step S1 comprises the following components by mass percentage: 0.14-0.16% Ag, 0.024-0.026% Yb, 0.012-0.014% Ir, 0.011-0.013% Os, and the balance being high-purity electrolytic copper powder.

[0010] Preferably, the average particle size of Yb is 10-30 μm, and the average particle size of Ag, Ir, and Os is 40-50 μm.

[0011] Preferably, the ratio of the thickness of the transition layer mixed powder, the thickness of the surface mixed powder, and the thickness of the core high-purity copper powder in step S2 is 1:1:(6-9).

[0012] Preferably, the cold pressing pressure in step S2 is 300-350 MPa, and the holding time is 5-8 min. Preferably, the green sintering in step S2 specifically involves: introducing high-purity argon gas at a flow rate of 0.6-1.0 L / min, a heating rate of 5-8℃ / min, heating to 880-920℃, and holding at that temperature for 4-5 hours; the hot extrusion molding specifically involves: preheating the billet to 380-420℃, holding at that temperature for 30-40 minutes, extruding at 380-420℃, extrusion speed of 5-8 mm / s, and an extrusion ratio of (12-15):1, followed by online lubrication and extrusion molding; the groove finishing specifically involves: finishing at 200-250℃ and 8-10 MPa for 5-10 minutes, and straightening at 150-200℃ at a speed of 3-5 m / min to ensure straightness ≤0.1 mm / m and dimensional tolerance ≤±0.005 mm.

[0013] Preferably, the specific parameters for preparing the microstructured heat-conducting channels in step S3 are as follows: a pulsed laser etching device is used, with a laser wavelength of 1064nm, a pulse width of 10-20ns, a laser power of 80-100W, and an etching speed of 5-8mm / s; the microstructured heat-conducting channels are designed as a mesh-like interlaced structure, with a channel width of 5-15μm, a channel depth of 20-40μm, and a channel spacing of 80-120μm, uniformly distributed in the core of the copper channel, penetrating the entire length of the copper channel; after etching, the channels are ultrasonically cleaned with anhydrous ethanol for 5-8 minutes to remove residual etching impurities, and then vacuum dried for later use.

[0014] Preferably, the plasma bombardment in step S4 specifically involves: evacuating the vacuum to ≤2×10⁻⁶. -3 Pa, high-purity argon gas with a flow rate of 0.3-0.5 L / min, power of 180-220 W, bombardment for 15-20 min, temperature of 120-150℃.

[0015] Preferably, the low-temperature oxidation in step S4 specifically involves: introducing a mixed gas containing oxygen, maintaining the temperature at 200-250°C for 25-30 minutes, and cooling to room temperature; the mixed gas contains 5-8% oxygen by volume, with the remainder being argon.

[0016] Another object of the present invention is to provide a corrosion-resistant and high thermal conductivity copper channel wire manufactured using the above-described method for preparing corrosion-resistant and high thermal conductivity copper channel wire.

[0017] Due to the application of the above technical solution, the present invention has the following beneficial effects: (1) The method for preparing corrosion-resistant and high thermal conductivity copper trench wire disclosed in this invention adopts a combination of quaternary corrosion-resistant elements Ir-Os-Ag-Yb. Ir and Os work synergistically, and together with Ag and Yb, they form a multi-element corrosion-resistant system. A dense, stable, high-temperature resistant and strong corrosion-resistant passivation film can be formed on the surface of the copper trench wire. Combined with the Cu2O oxide film formed by low-temperature oxidation, a double corrosion-resistant barrier is constructed, which significantly improves the corrosion resistance of the copper trench wire. At the same time, Ir and Os are designed with low dosage and have excellent matching with the copper lattice, without destroying the integrity of the copper lattice. Combined with the high-purity copper in the core and the microstructure heat conduction channel, the thermal conductivity of the copper trench wire is close to the theoretical value of pure copper, realizing the synergistic improvement of corrosion resistance and high thermal conductivity, and solving the technical problem that it is difficult to achieve both in the prior art.

[0018] (2) The method for preparing corrosion-resistant and high thermal conductivity copper channel wire disclosed in this invention adopts a three-stage gradient structure of core-transition layer-surface layer to achieve a continuous gradual change in composition from the surface layer rich in Ir-Os-Ag-Yb combination to the core high-purity copper, avoiding interface defects caused by abrupt changes in composition; through powder metallurgy + hot extrusion process, each layer achieves good metallurgical bonding, the billet has high density, no delamination, pores and other defects, further improving the mechanical properties and service stability of copper channel wire, and adapting to the use requirements of high-end precision electronics, aerospace and other harsh scenarios.

[0019] (3) The method for preparing corrosion-resistant and high thermal conductivity copper trench wire disclosed in this invention adopts a plasma bombardment + low temperature oxidation combined treatment process, which does not require additional coating and avoids the problems of traditional coating peeling and cracking. Plasma bombardment can activate the activity of the surface Ir-Os-Ag-Yb combination, roughen the surface micro morphology, enhance the bonding force between the low temperature oxide film and the copper substrate, and make the oxide film uniform in thickness and dense. It not only improves the corrosion resistance performance, but also does not affect the heat conduction of the heat conduction channel, taking into account both practicality and stability.

[0020] (4) The method for preparing corrosion-resistant and high thermal conductivity copper channel wire disclosed in this invention adopts integrated collaborative control in the entire preparation process. From raw material gradient batching, powder metallurgy, hot extrusion molding, to microstructure heat conduction channel preparation and surface modification, the process parameters of each step are precisely controllable, the operation is simple, no complex equipment is required, and continuous production can be realized. The raw materials all meet industry standards, are easy to obtain, and the production cost is controllable, which can meet the needs of large-scale industrial applications. Detailed Implementation

[0021] The following description is intended to disclose the invention and enable those skilled in the art to implement it. The preferred embodiments described below are merely examples, and other obvious variations will occur to those skilled in the art.

[0022] Example 1 A method for preparing a corrosion-resistant, high thermal conductivity copper trench wire includes the following steps: Step S1, Gradient Structure Batching: A three-stage gradient structure design of core-transition layer-surface layer is adopted. The core raw material is high-purity electrolytic copper powder. The transition layer raw material and the surface layer raw material are both based on high-purity electrolytic copper powder, with different amounts of alloying elements added. The batching results in high-purity copper powder in the core, mixed powder in the transition layer, and mixed powder in the surface layer. Step S2, Preparation of gradient structure billet: Using powder metallurgy, high-purity copper powder in the core is loaded into the core of the mold, the mixed powder in the transition layer is evenly spread on the outside of the core powder, and the mixed powder in the surface layer is evenly spread on the outside of the transition layer powder. After bidirectional cold pressing, it is placed in an atmosphere-protected sintering furnace for green billet sintering, followed by hot extrusion forming and groove finishing. Step S3: Fabrication of microstructured heat conduction channels: Microstructured heat conduction channels are designed and fabricated in the copper groove core using laser etching technology; Step S4, Plasma bombardment + low-temperature oxidation combined treatment: The copper trench wire with the prepared microstructure heat conduction channel is placed in the plasma bombardment equipment and subjected to plasma bombardment and low-temperature oxidation combined treatment in sequence to obtain corrosion-resistant and high thermal conductivity copper trench wire.

[0023] The high-purity electrolytic copper powder mentioned in step S1 has a purity ≥99.9995%, an oxygen content ≤0.0001%, and an average particle size of 30 μm; the transition layer raw material mentioned in step S1 includes the following components by mass percentage: 0.06% Ag, 0.014% Yb, 0.007% Ir, 0.006% Os, with the balance being high-purity electrolytic copper powder; the surface layer raw material mentioned in step S1 includes the following components by mass percentage: 0.14% Ag, 0.024% Yb, 0.012% Ir, 0.011% Os, with the balance being high-purity electrolytic copper powder; the average particle size of Yb is 10 μm, and the average particle size of Ag, Ir, and Os is 40 μm.

[0024] In step S2, the ratio of the thickness of the transition layer mixed powder, the thickness of the surface mixed powder, and the thickness of the core high-purity copper powder is 1:1:6; the cold pressing pressure of the bidirectional cold pressing in step S2 is 300MPa, and the holding time is 5min. The green sintering in step S2 specifically involves: introducing high-purity argon gas at a flow rate of 0.6 L / min, a heating rate of 5 °C / min, heating to 880 °C, and holding at that temperature for 4 hours; the hot extrusion molding specifically involves: preheating the billet to 380 °C, holding at that temperature for 30 minutes, extruding at 380 °C, extrusion speed of 5 mm / s, and extrusion ratio of 12:1, and extruding after online lubrication; the groove finishing specifically involves: finishing at 200 °C and 8 MPa for 5 minutes, and straightening at 150 °C at a speed of 3 m / min to ensure straightness ≤ 0.1 mm / m and dimensional tolerance ≤ ±0.005 mm.

[0025] The specific parameters for preparing the microstructured heat-conducting channels in step S3 are as follows: a pulsed laser etching device is used, with a laser wavelength of 1064nm, a pulse width of 10ns, a laser power of 80W, and an etching speed of 5mm / s; the microstructured heat-conducting channels are designed as a mesh-like interlaced structure, with a channel width of 5μm, a channel depth of 20μm, and a channel spacing of 80μm, uniformly distributed in the core of the copper channel, and running through the entire length of the copper channel; after etching, the channels are ultrasonically cleaned with anhydrous ethanol for 5min to remove residual etching impurities, and then vacuum dried for later use.

[0026] The plasma bombardment mentioned in step S4 specifically involves: evacuating the vacuum to ≤2×10⁻⁶. -3 Pa, high-purity argon gas with a flow rate of 0.3 L / min is introduced, power is 180 W, bombardment is carried out for 15 min, and temperature is 120℃; the low-temperature oxidation in step S4 specifically involves: introducing a mixed gas containing oxygen, holding at 200℃ for 25 min, and cooling to room temperature; the mixed gas has an oxygen content of 5% by volume, and the remainder is argon gas.

[0027] Example 2 A method for preparing a corrosion-resistant, high thermal conductivity copper trench wire includes the following steps: Step S1, Gradient Structure Batching: A three-stage gradient structure design of core-transition layer-surface layer is adopted. The core raw material is high-purity electrolytic copper powder. The transition layer raw material and the surface layer raw material are both based on high-purity electrolytic copper powder, with different amounts of alloying elements added. The batching results in high-purity copper powder in the core, mixed powder in the transition layer, and mixed powder in the surface layer. Step S2, Preparation of gradient structure billet: Using powder metallurgy, high-purity copper powder in the core is loaded into the core of the mold, the mixed powder in the transition layer is evenly spread on the outside of the core powder, and the mixed powder in the surface layer is evenly spread on the outside of the transition layer powder. After bidirectional cold pressing, it is placed in an atmosphere-protected sintering furnace for green billet sintering, followed by hot extrusion forming and groove finishing. Step S3: Fabrication of microstructured heat conduction channels: Microstructured heat conduction channels are designed and fabricated in the copper groove core using laser etching technology; Step S4, Plasma bombardment + low-temperature oxidation combined treatment: The copper trench wire with the prepared microstructure heat conduction channel is placed in the plasma bombardment equipment and subjected to plasma bombardment and low-temperature oxidation combined treatment in sequence to obtain corrosion-resistant and high thermal conductivity copper trench wire.

[0028] The high-purity electrolytic copper powder mentioned in step S1 has a purity ≥99.9995%, an oxygen content ≤0.0001%, and an average particle size of 35μm; the transition layer raw material mentioned in step S1 includes the following components by mass percentage: 0.065% Ag, 0.0145% Yb, 0.0075% Ir, 0.0065% Os, with the balance being high-purity electrolytic copper powder; the surface layer raw material mentioned in step S1 includes the following components by mass percentage: 0.145% Ag, 0.0245% Yb, 0.0125% Ir, 0.0115% Os, with the balance being high-purity electrolytic copper powder; the average particle size of Yb is 15μm, and the average particle size of Ag, Ir, and Os is 43μm.

[0029] In step S2, the ratio of the thickness of the transition layer mixed powder, the thickness of the surface mixed powder, and the thickness of the core high-purity copper powder is 1:1:7; the cold pressing pressure of the bidirectional cold pressing in step S2 is 320 MPa, and the holding time is 6 min; the green blank sintering in step S2 specifically involves: introducing high-purity argon gas at a flow rate of 0.7 L / min, a heating rate of 6 °C / min, heating to 890 °C, and holding for 4.3 h; the hot extrusion molding specifically involves: preheating the blank to 390 °C, holding for 33 min, extruding at 390 °C, extruding at a speed of 6 mm / s, and an extrusion ratio of 13:1, followed by online lubrication and extrusion molding; the groove finishing specifically involves: finishing at 220 °C and 8.5 MPa for 6 min, and straightening at 170 °C at a speed of 3.5 m / min to ensure straightness ≤0.1 mm / m and dimensional tolerance ≤±0.005 mm.

[0030] The specific parameters for fabricating the microstructured heat-conducting channels in step S3 are as follows: A pulsed laser etching device is used, with a laser wavelength of 1064 nm, a pulse width of 13 ns, a laser power of 85 W, and an etching speed of 6 mm / s; the microstructured heat-conducting channels are designed as a mesh-like interlaced structure, with a channel width of 8 μm, a channel depth of 25 μm, and a channel spacing of 90 μm, uniformly distributed in the core of the copper channel, penetrating the entire length of the copper channel; after etching, the channels are ultrasonically cleaned with anhydrous ethanol for 6 min to remove residual etching impurities, and then vacuum dried for later use; the plasma bombardment in step S4 specifically involves: evacuating to a vacuum level ≤2 × 10⁻⁶. -3 Pa, high-purity argon gas with a flow rate of 0.35 L / min is introduced, power is 190 W, bombardment is carried out for 17 min, and temperature is 130℃; the low-temperature oxidation in step S4 specifically involves: introducing a mixed gas containing oxygen, holding at 220℃ for 27 min, and cooling to room temperature; the mixed gas has an oxygen content of 6% by volume, and the remainder is argon gas.

[0031] Example 3 A method for preparing a corrosion-resistant, high thermal conductivity copper trench wire includes the following steps: Step S1, Gradient Structure Batching: A three-stage gradient structure design of core-transition layer-surface layer is adopted. The core raw material is high-purity electrolytic copper powder. The transition layer raw material and the surface layer raw material are both based on high-purity electrolytic copper powder, with different amounts of alloying elements added. The batching results in high-purity copper powder in the core, mixed powder in the transition layer, and mixed powder in the surface layer. Step S2, Preparation of gradient structure billet: Using powder metallurgy, high-purity copper powder in the core is loaded into the core of the mold, the mixed powder in the transition layer is evenly spread on the outside of the core powder, and the mixed powder in the surface layer is evenly spread on the outside of the transition layer powder. After bidirectional cold pressing, it is placed in an atmosphere-protected sintering furnace for green billet sintering, followed by hot extrusion forming and groove finishing. Step S3: Fabrication of microstructured heat conduction channels: Microstructured heat conduction channels are designed and fabricated in the copper groove core using laser etching technology; Step S4, Plasma bombardment + low-temperature oxidation combined treatment: The copper trench wire with the prepared microstructure heat conduction channel is placed in the plasma bombardment equipment and subjected to plasma bombardment and low-temperature oxidation combined treatment in sequence to obtain corrosion-resistant and high thermal conductivity copper trench wire.

[0032] The high-purity electrolytic copper powder mentioned in step S1 has a purity ≥99.9995%, an oxygen content ≤0.0001%, and an average particle size of 40 μm; the transition layer raw material mentioned in step S1 includes the following components by mass percentage: 0.07% Ag, 0.015% Yb, 0.008% Ir, 0.007% Os, with the balance being high-purity electrolytic copper powder; the surface layer raw material mentioned in step S1 includes the following components by mass percentage: 0.15% Ag, 0.025% Yb, 0.013% Ir, 0.012% Os, with the balance being high-purity electrolytic copper powder; the average particle size of Yb is 20 μm, and the average particle size of Ag, Ir, and Os is 45 μm.

[0033] In step S2, the ratio of the thickness of the transition layer mixed powder, the thickness of the surface mixed powder, and the thickness of the core high-purity copper powder is 1:1:8; the cold pressing pressure of the bidirectional cold pressing in step S2 is 330 MPa, and the holding time is 6.5 min; the green blank sintering in step S2 specifically involves: introducing high-purity argon gas at a flow rate of 0.8 L / min, a heating rate of 6.5 °C / min, heating to 900 °C, and holding for 4.5 h; the hot extrusion forming specifically involves: preheating the blank to 400 °C, holding for 35 min, extruding at 400 °C, extruding at a speed of 6.5 mm / s, and an extrusion ratio of 13.5:1, followed by online lubrication and extrusion forming; the groove finishing specifically involves: finishing at 230 °C and 9 MPa for 7.5 min, and straightening at 180 °C at a speed of 4 m / min to ensure straightness ≤0.1 mm / m and dimensional tolerance ≤±0.005 mm.

[0034] The specific parameters for fabricating the microstructured heat-conducting channels in step S3 are as follows: A pulsed laser etching device is used, with a laser wavelength of 1064 nm, a pulse width of 15 ns, a laser power of 90 W, and an etching speed of 6.5 mm / s; the microstructured heat-conducting channels are designed as a mesh-like interlaced structure, with a channel width of 10 μm, a channel depth of 30 μm, and a channel spacing of 100 μm, uniformly distributed in the core of the copper channel, penetrating the entire length of the copper channel; after etching, the channels are ultrasonically cleaned with anhydrous ethanol for 6.5 min to remove residual etching impurities, and then vacuum dried for later use; the plasma bombardment in step S4 specifically involves: evacuating to a vacuum level ≤2 × 10⁻⁶. -3 Pa, high-purity argon gas with a flow rate of 0.4 L / min is introduced, power is 200 W, bombardment is carried out for 18 min, and temperature is 135℃; the low-temperature oxidation in step S4 specifically involves: introducing a mixed gas containing oxygen, holding at 230℃ for 28 min, and cooling to room temperature; the mixed gas has an oxygen content of 6.5% by volume, with the remainder being argon gas.

[0035] Example 4 A method for preparing a corrosion-resistant, high thermal conductivity copper trench wire includes the following steps: Step S1, Gradient Structure Batching: A three-stage gradient structure design of core-transition layer-surface layer is adopted. The core raw material is high-purity electrolytic copper powder. The transition layer raw material and the surface layer raw material are both based on high-purity electrolytic copper powder, with different amounts of alloying elements added. The batching results in high-purity copper powder in the core, mixed powder in the transition layer, and mixed powder in the surface layer. Step S2, Preparation of gradient structure billet: Using powder metallurgy, high-purity copper powder in the core is loaded into the core of the mold, the mixed powder in the transition layer is evenly spread on the outside of the core powder, and the mixed powder in the surface layer is evenly spread on the outside of the transition layer powder. After bidirectional cold pressing, it is placed in an atmosphere-protected sintering furnace for green billet sintering, followed by hot extrusion forming and groove finishing. Step S3: Fabrication of microstructured heat conduction channels: Microstructured heat conduction channels are designed and fabricated in the copper groove core using laser etching technology; Step S4, Plasma bombardment + low-temperature oxidation combined treatment: The copper trench wire with the prepared microstructure heat conduction channel is placed in the plasma bombardment equipment and subjected to plasma bombardment and low-temperature oxidation combined treatment in sequence to obtain corrosion-resistant and high thermal conductivity copper trench wire.

[0036] The high-purity electrolytic copper powder mentioned in step S1 has a purity ≥99.9995%, an oxygen content ≤0.0001%, and an average particle size of 45 μm; the transition layer raw material mentioned in step S1 includes the following components by mass percentage: 0.075% Ag, 0.0155% Yb, 0.0085% Ir, 0.0075% Os, with the balance being high-purity electrolytic copper powder; the surface layer raw material mentioned in step S1 includes the following components by mass percentage: 0.155% Ag, 0.0255% Yb, 0.0135% Ir, 0.0125% Os, with the balance being high-purity electrolytic copper powder; the average particle size of Yb is 25 μm, and the average particle size of Ag, Ir, and Os is 47 μm.

[0037] In step S2, the ratio of the thickness of the transition layer mixed powder, the thickness of the surface mixed powder, and the thickness of the core high-purity copper powder is 1:1:9; the cold pressing pressure of the bidirectional cold pressing in step S2 is 340 MPa, and the holding time is 7.5 min; the green blank sintering in step S2 specifically involves: introducing high-purity argon gas at a flow rate of 0.9 L / min, a heating rate of 7.5 °C / min, heating to 910 °C, and holding for 4.8 h; the hot extrusion forming specifically involves: preheating the blank to 410 °C, holding for 38 min, extruding at 410 °C, extruding at a speed of 7.5 mm / s, and an extrusion ratio of 14:1, followed by online lubrication and extrusion forming; the groove finishing specifically involves: finishing at 240 °C and 9.5 MPa for 9 min, and straightening at 190 °C at a speed of 4.5 m / min to ensure straightness ≤0.1 mm / m and dimensional tolerance ≤±0.005 mm.

[0038] The specific parameters for fabricating the microstructured heat-conducting channels in step S3 are as follows: A pulsed laser etching device is used, with a laser wavelength of 1064 nm, a pulse width of 18 ns, a laser power of 95 W, and an etching speed of 7.5 mm / s; the microstructured heat-conducting channels are designed as a mesh-like interlaced structure, with a channel width of 13 μm, a channel depth of 35 μm, and a channel spacing of 110 μm, uniformly distributed in the core of the copper channel, penetrating the entire length of the copper channel; after etching, the channels are ultrasonically cleaned with anhydrous ethanol for 7.5 min to remove residual etching impurities, and then vacuum dried for later use; the plasma bombardment in step S4 specifically involves: evacuating to a vacuum level ≤2 × 10⁻⁶. -3 Pa, high-purity argon gas with a flow rate of 0.45 L / min is introduced, power is 210 W, bombardment is carried out for 19 min, and temperature is 145℃; the low-temperature oxidation in step S4 specifically involves: introducing a mixed gas containing oxygen, holding at 240℃ for 29 min, and cooling to room temperature; the mixed gas has an oxygen content of 7.5% by volume percentage, with the remainder being argon gas.

[0039] Example 5 A method for preparing a corrosion-resistant, high thermal conductivity copper trench wire includes the following steps: Step S1, Gradient Structure Batching: A three-stage gradient structure design of core-transition layer-surface layer is adopted. The core raw material is high-purity electrolytic copper powder. The transition layer raw material and the surface layer raw material are both based on high-purity electrolytic copper powder, with different amounts of alloying elements added. The batching results in high-purity copper powder in the core, mixed powder in the transition layer, and mixed powder in the surface layer. Step S2, Preparation of gradient structure billet: Using powder metallurgy, high-purity copper powder in the core is loaded into the core of the mold, the mixed powder in the transition layer is evenly spread on the outside of the core powder, and the mixed powder in the surface layer is evenly spread on the outside of the transition layer powder. After bidirectional cold pressing, it is placed in an atmosphere-protected sintering furnace for green billet sintering, followed by hot extrusion forming and groove finishing. Step S3: Fabrication of microstructured heat conduction channels: Microstructured heat conduction channels are designed and fabricated in the copper groove core using laser etching technology; Step S4, Plasma bombardment + low-temperature oxidation combined treatment: The copper trench wire with the prepared microstructure heat conduction channel is placed in the plasma bombardment equipment and subjected to plasma bombardment and low-temperature oxidation combined treatment in sequence to obtain corrosion-resistant and high thermal conductivity copper trench wire.

[0040] The high-purity electrolytic copper powder mentioned in step S1 has a purity ≥99.9995%, an oxygen content ≤0.0001%, and an average particle size of 50 μm; the transition layer raw material mentioned in step S1 includes the following components by mass percentage: 0.08% Ag, 0.016% Yb, 0.009% Ir, 0.008% Os, with the balance being high-purity electrolytic copper powder; the surface layer raw material mentioned in step S1 includes the following components by mass percentage: 0.16% Ag, 0.026% Yb, 0.014% Ir, 0.013% Os, with the balance being high-purity electrolytic copper powder; the average particle size of Yb is 30 μm, and the average particle size of Ag, Ir, and Os is 50 μm.

[0041] In step S2, the ratio of the thickness of the transition layer mixed powder, the thickness of the surface mixed powder, and the thickness of the core high-purity copper powder is 1:1:6; the cold pressing pressure of the bidirectional cold pressing in step S2 is 350 MPa, and the holding time is 8 min; the green blank sintering in step S2 specifically involves: introducing high-purity argon gas at a flow rate of 1.0 L / min, a heating rate of 8 °C / min, heating to 920 °C, and holding for 5 h; the hot extrusion forming specifically involves: preheating the blank to 420 °C, holding for 40 min, extruding at 420 °C, extruding at a speed of 8 mm / s, and an extrusion ratio of 15:1, followed by online lubrication and extrusion forming; the groove finishing specifically involves: finishing at 250 °C and 10 MPa for 10 min, and straightening at 200 °C at a speed of 5 m / min to ensure straightness ≤0.1 mm / m and dimensional tolerance ≤±0.005 mm.

[0042] The specific parameters for fabricating the microstructured heat-conducting channels in step S3 are as follows: A pulsed laser etching device is used, with a laser wavelength of 1064 nm, a pulse width of 20 ns, a laser power of 100 W, and an etching speed of 8 mm / s; the microstructured heat-conducting channels are designed as a mesh-like interlaced structure, with a channel width of 15 μm, a channel depth of 40 μm, and a channel spacing of 120 μm, uniformly distributed in the core of the copper channel, penetrating the entire length of the copper channel; after etching, the channels are ultrasonically cleaned with anhydrous ethanol for 8 min to remove residual impurities, and then vacuum dried for later use; the plasma bombardment in step S4 specifically involves: evacuating to a vacuum level ≤2 × 10⁻⁶. -3 Pa, high-purity argon gas with a flow rate of 0.5 L / min is introduced, power is 220 W, bombardment is carried out for 20 min, and temperature is 150℃; the low-temperature oxidation in step S4 specifically involves: introducing a mixed gas containing oxygen, holding at 250℃ for 30 min, and cooling to room temperature; the mixed gas has an oxygen content of 8% by volume percentage, with the remainder being argon gas.

[0043] Comparative Example 1 A method for preparing a corrosion-resistant, high thermal conductivity copper trench wire is basically the same as that in Example 5, except that an equal amount of Ir is used instead of Os.

[0044] Comparative Example 2 A method for preparing a corrosion-resistant, high thermal conductivity copper trench wire is basically the same as that in Example 5, except that an equal amount of Os is used instead of Ir.

[0045] Comparative Example 3 A method for preparing corrosion-resistant, high thermal conductivity copper trench wire is basically the same as that in Example 5, except that there is no preparation step for microstructured heat conduction channels.

[0046] Comparative Example 4 A method for preparing corrosion-resistant, high thermal conductivity copper trench wire is basically the same as that in Example 5, except that the plasma bombardment + low-temperature oxidation combined treatment step is omitted.

[0047] Comparative Example 5 A method for preparing a corrosion-resistant, high thermal conductivity copper trench wire is basically the same as in Example 5, except that the composition of the transition layer material and the surface material is the same, including the following components by mass percentage: 0.08% Ag, 0.016% Yb, 0.009% Ir, 0.008% Os, with the balance being high-purity electrolytic copper powder.

[0048] To further illustrate the unexpected positive technical effects achieved by the corrosion-resistant, high thermal conductivity copper trench wires manufactured in the embodiments of the present invention, relevant performance tests were conducted on the corrosion-resistant, high thermal conductivity copper trench wires of Example 5 and Comparative Examples 1-5. The test results are shown in Table 1, and the test methods are as follows: (1) Thermal conductivity test: The test was conducted in accordance with the national standard GB / T 22588-2008 "Measuring thermal diffusivity or thermal conductivity by flash method". The sample was cut into a circular piece with a diameter of 10 mm and a thickness of 2 mm, and the surface was polished to a smooth finish. The sample was placed in a laser flash thermal conductivity meter, the test temperature was set to 25℃, and nitrogen protection was used. Each sample was tested 3 times, and the average value was taken as the final thermal conductivity, in W / (m·K). (2) Corrosion resistance test: Neutral salt spray test (5% NaCl solution, 35℃, continuous spraying for 1300 hours, spray volume 2mL / 80 (cm)) was conducted in accordance with GB / T 10125-2021. 2 •h), observe the corrosion on the sample surface.

[0049] As can be seen from the test results in Table 1, Example 5 of the present invention adopts a three-stage stepped alloy ratio of high-purity copper in the core, transition layer, and surface layer, laser etching of a through-mesh micro-thermal conductive channel in the core, and a synergistic process of plasma bombardment and low-temperature oxidation modification. Under a 1300-hour neutral salt spray test, the surface showed no rust or pitting corrosion, and the thermal conductivity reached 401.2 W / (m·K), demonstrating the best overall performance. Comparative Examples 1 and 2, due to the lack of the synergistic effect of Ir and Os compounding, both experienced a simultaneous decline in corrosion resistance and thermal conductivity. Comparative Example 3, lacking microstructured thermal conductive channels, resulted in a significant decrease in thermal conductivity, but the decrease in corrosion resistance was relatively small. Comparative Example 4, omitting plasma and low-temperature oxidation treatment, showed a significant deterioration in corrosion resistance. Comparative Example 5, by eliminating the component gradient design and having the same formulation for the transition layer and surface layer, exhibited uniform slight pitting corrosion, and the interface stress concentration resulted in a thermal conductivity lower than that of Example 5. This fully demonstrates that the gradient component ratio, Ir-Os compounding, microstructured thermal conductive channels, and plasma surface modification are key to achieving both high thermal conductivity and strong corrosion resistance in copper trench lines.

[0050] Table 1. Performance test results of corrosion-resistant and high thermal conductivity copper tubing

[0051] The above embodiments are only for illustrating the technical concept and features of the present invention. Their purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be used to limit the scope of protection of the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a corrosion-resistant, high thermal conductivity copper trench wire, characterized in that, Includes the following steps: Step S1, Gradient Structure Batching: A three-stage gradient structure design of core-transition layer-surface layer is adopted. The core raw material is high-purity electrolytic copper powder. The transition layer raw material and the surface layer raw material are both based on high-purity electrolytic copper powder, with different amounts of alloying elements added. The batching results in high-purity copper powder in the core, mixed powder in the transition layer, and mixed powder in the surface layer. Step S2, Preparation of gradient structure billet: Using powder metallurgy, high-purity copper powder in the core is loaded into the core of the mold, the mixed powder in the transition layer is evenly spread on the outside of the core powder, and the mixed powder in the surface layer is evenly spread on the outside of the transition layer powder. After bidirectional cold pressing, it is placed in an atmosphere-protected sintering furnace for green billet sintering, followed by hot extrusion forming and groove finishing. Step S3: Fabrication of microstructured heat conduction channels: Microstructured heat conduction channels are designed and fabricated in the copper groove core using laser etching technology; Step S4, Plasma bombardment + low-temperature oxidation combined treatment: The copper trench wire with the prepared microstructure heat conduction channel is placed in the plasma bombardment equipment and subjected to plasma bombardment and low-temperature oxidation combined treatment in sequence to obtain corrosion-resistant and high thermal conductivity copper trench wire.

2. The method for preparing corrosion-resistant, high thermal conductivity copper trench wire according to claim 1, characterized in that, The high-purity electrolytic copper powder mentioned in step S1 has a purity of ≥99.9995%, an oxygen content of ≤0.0001%, and an average particle size of 30-50μm.

3. The method for preparing corrosion-resistant, high thermal conductivity copper trench wire according to claim 1, characterized in that, The transition layer raw material in step S1 comprises the following components by mass percentage: 0.06-0.08% Ag, 0.014-0.016% Yb, 0.007-0.009% Ir, 0.006-0.008% Os, with the balance being high-purity electrolytic copper powder; the surface layer raw material in step S1 comprises the following components by mass percentage: 0.14-0.16% Ag, 0.024-0.026% Yb, 0.012-0.014% Ir, 0.011-0.013% Os, with the balance being high-purity electrolytic copper powder; the average particle size of Yb is 10-30 μm, and the average particle size of Ag, Ir, and Os is 40-50 μm.

4. The method for preparing corrosion-resistant, high thermal conductivity copper trench wire according to claim 1, characterized in that, The ratio of the thickness of the transition layer mixed powder, the thickness of the surface mixed powder, and the thickness of the core high-purity copper powder in step S2 is 1:1:(6-9).

5. The method for preparing corrosion-resistant, high thermal conductivity copper trench wire according to claim 1, characterized in that, The cold pressing pressure for bidirectional cold pressing in step S2 is 300-350 MPa, and the holding time is 5-8 min.

6. The method for preparing corrosion-resistant, high thermal conductivity copper trench wire according to claim 1, characterized in that, The green sintering in step S2 specifically involves: introducing high-purity argon gas at a flow rate of 0.6-1.0 L / min, a heating rate of 5-8℃ / min, heating to 880-920℃, and holding at that temperature for 4-5 hours; the hot extrusion molding specifically involves: preheating the billet to 380-420℃, holding at that temperature for 30-40 minutes, extruding at 380-420℃, extrusion speed of 5-8 mm / s, and an extrusion ratio of (12-15):1, followed by online lubrication and extrusion molding; the groove finishing specifically involves: finishing at 200-250℃ and 8-10 MPa for 5-10 minutes, and straightening at 150-200℃ at a speed of 3-5 m / min to ensure straightness ≤0.1 mm / m and dimensional tolerance ≤±0.005 mm.

7. The method for preparing corrosion-resistant, high thermal conductivity copper trench wire according to claim 1, characterized in that, The specific parameters for preparing the microstructured heat-conducting channels in step S3 are as follows: a pulsed laser etching device is used, with a laser wavelength of 1064nm, a pulse width of 10-20ns, a laser power of 80-100W, and an etching speed of 5-8mm / s; the microstructured heat-conducting channels are designed as a mesh-like interlaced structure, with a channel width of 5-15μm, a channel depth of 20-40μm, and a channel spacing of 80-120μm, uniformly distributed in the core of the copper channel, penetrating the entire length of the copper channel; after etching, the channels are ultrasonically cleaned with anhydrous ethanol for 5-8 minutes to remove residual etching impurities, and then vacuum dried for later use.

8. The method for preparing corrosion-resistant, high thermal conductivity copper trench wire according to claim 1, characterized in that, The plasma bombardment mentioned in step S4 specifically involves: evacuating the vacuum to ≤2×10⁻⁶. -3 Pa, high-purity argon gas with a flow rate of 0.3-0.5 L / min, power of 180-220 W, bombardment for 15-20 min, temperature of 120-150℃.

9. The method for preparing corrosion-resistant, high thermal conductivity copper trench wire according to claim 1, characterized in that, The low-temperature oxidation in step S4 specifically involves: introducing a mixed gas containing oxygen, holding at 200-250°C for 25-30 minutes, and cooling to room temperature; the mixed gas contains 5-8% oxygen by volume, with the remainder being argon.

10. A corrosion-resistant, high thermal conductivity copper channel wire manufactured using the preparation method of the corrosion-resistant, high thermal conductivity copper channel wire according to any one of claims 1-9.

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