Corrosion-resistant copper slot wire and electrochemical corrosion prevention process thereof

Abstract

The invention discloses a corrosion-resistant copper slot line and an electrochemical corrosion prevention process thereof, and relates to the technical field of copper slot lines, and a nanocrystalline transition layer and a surface protection layer are sequentially arranged from a copper substrate to the outside; the copper base body is prepared from, by mass, 0.1%-0.3% of Ag, 0.01%-0.03% of rare earth elements, 0.01%-0.03% of Ga, 0.1%-0.3% of Mn, 0.05%-0.15% of Si, 0.2%-0.4% of Ni, 0.03%-0.06% of Zr, 0.05%-0.1% of Ti, 0.3%-0.5% of Cr, 0.001%-0.003% of B and the balance Cu and other inevitable impurities. The slot line is excellent in corrosion resistance, fatigue resistance and conductivity and long in service life.

Description

Technical Field

[0001] The present invention relates to the technical field of copper trough wires, in particular to a corrosion-resistant copper trough wire and an anti-electrochemical corrosion process thereof. Background Art

[0002] During the long-term operation of electronic equipment, copper trough cables, as important conductive components, often face complex operating environments. Currently, traditional copper trough cables are susceptible to electrochemical corrosion in humid environments or those containing electrolyte solutions. This can lead to decreased conductivity and even breakage, seriously impacting the normal operation and service life of electronic equipment. Therefore, the development of corrosion-resistant copper trough cables is particularly important.

[0003] Traditional copper trough wires are improved in corrosion resistance by plating or alloying, but a single plating layer such as nickel plating is not very effective in Cl - Microbatteries are easily formed in the environment, accelerating corrosion. Inadequate optimization of the copper alloy composition can lead to uneven passivation films. Some processes also require high-temperature treatment or complex equipment, making large-scale production difficult. Currently, products are available on the market that achieve corrosion resistance by applying a protective coating on the surface of the copper trough wire. However, these protective coatings are prone to shedding and aging during long-term use, greatly reducing their anti-corrosion effectiveness. In addition, traditional coating preparation processes are relatively complex and have high production costs, making them unfavorable for large-scale production and application.

[0004] To address the above problems, a Chinese invention patent with authorization publication number CN103131887B discloses a novel corrosion-resistant boron-copper alloy. The alloy contains, by weight, 37-39% zinc, 0.5-1.5% tin, 0.5-1.0% aluminum, 0.03-0.05% bismuth, 0.005-0.01% boron, 0.4-1.0% iron, 0.01-0.03% selenium, 0.02-0.03% cobalt, and the balance copper. This corrosion-resistant boron-copper alloy has similar physical properties to existing nickel-copper or zinc-copper alloys, but exhibits superior corrosion resistance and reduced cost. However, its electrochemical corrosion resistance, fatigue resistance, and electrical conductivity still need to be further improved.

[0005] It can be seen that the development of a corrosion-resistant copper trough line with excellent corrosion resistance, fatigue resistance and electrical conductivity and long service life and its anti-electrochemical corrosion process meets market demand, has broad market value and application prospects, and is of great significance to promoting the development of the copper trough line field. Summary of the Invention

[0006] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a corrosion-resistant copper trough wire with excellent corrosion resistance, fatigue resistance and electrical conductivity and a long service life and an anti-electrochemical corrosion process thereof.

[0007] To achieve the above-mentioned object, the technical solution adopted by the present invention is: a corrosion-resistant copper trough wire, which comprises, from a copper substrate outward, a nanocrystalline transition layer and a surface protective layer; the copper substrate comprises, by mass percentage, the following components: Ag 0.1-0.3%, rare earth elements 0.01-0.03%, Ga 0.01-0.03%, Mn 0.1-0.3%, Si 0.05-0.15%, Ni 0.2-0.4%, Zr 0.03-0.06%, Ti 0.05-0.1%, Cr 0.3-0.5%, B 0.001-0.003%, and the balance is Cu and other inevitable impurities.

[0008] Preferably, the rare earth elements are Ce, Nd, and Pr mixed in a mass ratio of 2:(1-2):(0.8-1.2).

[0009] Preferably, the thickness of the nanocrystalline transition layer is 5-8 μm.

[0010] Preferably, the thickness of the surface protection layer is 10-15 μm.

[0011] Another object of the present invention is to provide a process for preventing electrochemical corrosion of the corrosion-resistant copper trough wire, comprising the following steps: Step S1, pretreatment of the copper substrate surface: using 400# sandpaper to polish the copper substrate to a surface roughness of Ra ≤ 1.0 μm to remove the oxide layer; then performing stage-by-stage cleaning and polishing in sequence to obtain a pretreated copper substrate; Step S2, forming a nanocrystalline transition layer: preparing a nanocrystalline transition layer on the surface of the copper substrate by pulse electroplating; Step S2, preparation of a surface protective layer: graphene oxide, hydroxyapatite, and nano-titanium dioxide are uniformly dispersed in an epoxy resin, an appropriate amount of a curing agent is added, and after stirring evenly, the mixture is sprayed on the surface of the transition layer and cured at a temperature of 118-122° C. for 2-3 hours to form a surface protective layer.

[0012] Preferably, the staged cleaning is specifically as follows: first, ultrasonic cleaning with acetone for 10-15 minutes, then rinsing with deionized water, then acid washing for 3-5 minutes, and finally rinsing with deionized water and drying.

[0013] Preferably, the acid used for pickling is a 1-3% sulfuric acid solution, and the pickling temperature is 35-40°C.

[0014] Preferably, the pulse parameters of the pulse electroplating are: forward current density 11-13 A / dm², reverse current density 2-4 A / dm², pulse frequency 1000 Hz, duty cycle 60%, temperature 53-57°C, and deposition time 28-32 min.

[0015] Preferably, the electroplating solution for pulse electroplating comprises components with the following concentrations: nickel sulfate 20-30 g / L, sodium hypophosphite 15-20 g / L, sodium citrate 10-15 g / L, cerium nitrate 3-5 g / L, zwitterionic salt 0.1-0.3 g / L, adenosine 0.1-0.5 g / L, 2,2'-biquinoline-4,4'-dicarboxylate disodium 0.05-0.1 g / L, and its pH is adjusted to 4.8-5.5 with sulfuric acid.

[0016] Preferably, the zwitterionic salt is 1-benzylpyridine-3-carboxylate.

[0017] Preferably, the mass ratio of graphene oxide, hydroxyapatite, nano-titanium dioxide, epoxy resin and curing agent in step S2 is (3-5):(1-3):(4-6):(85-90):(4-6).

[0018] Preferably, the graphene oxide is a single-layer graphene oxide with a sheet diameter of 0.5-5 μm and a thickness of 0.8-1.2 nm.

[0019] Preferably, the average diameter of the hydroxyapatite is 1-5 μm; the average particle size of the nano-titanium dioxide is 10-80 nm.

[0020] Preferably, the epoxy resin is E-51 epoxy resin.

[0021] Preferably, the curing agent is 3,3'-diamino-4,4'-difluorodiphenyl sulfone.

[0022] Due to the application of the above technical solution, the present invention has the following beneficial effects: (1) The electrochemical corrosion prevention process for corrosion-resistant copper trough wire disclosed in the present invention is simple and easy to operate, convenient to operate and control, high in efficiency and qualified rate of finished products, suitable for continuous large-scale production, and has high promotion and application value.

[0023] (2) The corrosion-resistant copper trough wire disclosed in the present invention comprises, from the copper matrix outward, a nanocrystalline transition layer and a surface protective layer; the copper matrix comprises, by mass percentage, the following: Ag 0.1-0.3%, rare earth elements 0.01-0.03%, Ga 0.01-0.03%, Mn 0.1-0.3%, Si 0.05-0.15%, Ni 0.2-0.4%, Zr 0.03-0.06%, Ti 0.05-0.1%, Cr 0.3-0.5%, B 0.001-0.003%, with the remainder being Cu and other inevitable impurities. Through the mutual cooperation and joint action of the various components, the corrosion resistance and fatigue resistance can be effectively improved without significantly reducing the electrical conductivity, thereby effectively extending the service life of the copper trough wire. The rare earth elements are Ce, Nd, and Pr mixed in a mass ratio of 2:(1-2):(0.8-1.2); by adding rare earth elements of this composition and cooperating with other components, they can form high-melting-point compounds with impurities such as oxygen and sulfur, reduce the distortion of the impurities on the crystal lattice, and indirectly improve the conductivity; at the same time, these rare earth elements inhibit grain growth by forming a dispersed phase, thereby improving the strength of the material while having little effect on the conductivity; in addition, these rare earth elements can be adsorbed at the grain boundaries, inhibiting the segregation of impurities at the grain boundaries, reducing the tendency of intergranular corrosion, and improving the corrosion resistance of the material.

[0024] (3) The corrosion-resistant copper trough disclosed in the present invention has a nanocrystalline transition layer and a surface protective layer from the copper substrate to the outside. Through such a structural design, the copper substrate can obtain "physical + chemical" dual protection, which can not only block Cl - The transition layer exhibits excellent corrosion resistance and strong adhesion to the copper substrate, effectively preventing direct contact between the copper substrate and external corrosive media. The surface protective layer exhibits excellent barrier properties. The lamellar structure of graphene oxide forms a multi-layer barrier within the coating, hindering the penetration of corrosive media. Hydroxyapatite and graphene oxide form a three-dimensional network structure. The nano-titanium dioxide coating exhibits photocatalytic properties, generating active substances such as hydroxyl radicals under light. These active substances decompose organic pollutants and some inorganic corrosive media adsorbed on the coating surface, further enhancing its corrosion protection. Furthermore, the nano-titanium dioxide coating exhibits excellent chemical stability and weather resistance, maintaining its protective properties over long-term use. This multi-layer design not only enhances the corrosion resistance of the copper trough wire, but also ensures excellent electrical conductivity and mechanical properties, meeting the requirements of electronic equipment in various complex environments. Epoxy resin provides excellent adhesion and mechanical properties, allowing the surface protective layer to firmly adhere to the transition layer. The curing agent is 3,3'-diamino-4,4'-difluorodiphenyl sulfone; through curing, a fluorine-containing phenyl sulfone structure is introduced into the protective layer, thereby further improving its corrosion resistance and extending its service life.

[0025] (4) The corrosion-resistant copper trough line disclosed in the present invention adopts pulse electroplating to prepare a nanocrystalline transition layer on the surface of the copper substrate. The pulse electroplating effectively inhibits the continuous growth of grains by periodically switching the current on and off, thereby improving the corrosion resistance; the reverse current of the pulse electroplating has an "etching-activation" effect, which enhances the interface bonding force and improves the anti-stripping performance; the pulse electroplating releases the deposition stress by the reverse current, converts the stress in the coating into compressive stress, thereby improving the toughness of the coating; the plating solution of the pulse electroplating includes the following components in the following concentrations: nickel sulfate 20-30g / L, sodium hypophosphite 15-20g / L, sodium citrate 10-15g / L, cerium nitrate 3-5g / L, zwitterionic salt 0.1-0.3g / L, adenosine 0.1-0.5g / L, 2,2'-biquinoline-4,4'-dicarboxylic acid disodium 0.05-0.1g / L. Cerium nitrate, a rare earth element additive, is incorporated into the formula. It adsorbs onto the grain boundaries of nickel-phosphorus alloys during the electroplating process, inhibiting grain growth through a "poisoning effect." The combined system of adenosine, cerium nitrate, and 2,2'-biquinoline simultaneously achieves grain refinement, stress regulation, and interface strengthening, reducing porosity in the coating and forming a dense structure, thereby improving the coating's corrosion resistance.

[0026] (5) The corrosion-resistant copper trough wire disclosed in the present invention has better corrosion resistance and longer service life through the reasonable selection of anti-electrochemical corrosion process parameters. DETAILED DESCRIPTION

[0027] The following description is intended to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are merely examples, and those skilled in the art may conceive of other obvious variations. Example 1

[0028] A corrosion-resistant copper trough wire comprises, from a copper substrate outward, a nanocrystalline transition layer and a surface protective layer; the copper substrate comprises, by mass percentage, the following components: Ag 0.1%, rare earth elements 0.01%, Ga 0.01%, Mn 0.1%, Si 0.05%, Ni 0.2%, Zr 0.03%, Ti 0.05%, Cr 0.3%, B 0.001%, with the remainder being Cu and other unavoidable impurities; the rare earth elements are Ce, Nd, and Pr mixed in a mass ratio of 2:1:0.8; the nanocrystalline transition layer has a thickness of 5 μm; and the surface protective layer has a thickness of 10 μm.

[0029] A process for preventing electrochemical corrosion of the corrosion-resistant copper trough line comprises the following steps: Step S1, pretreatment of the copper substrate surface: using 400# sandpaper to polish the copper substrate to a surface roughness of Ra ≤ 1.0 μm to remove the oxide layer; then performing stage-by-stage cleaning and polishing in sequence to obtain a pretreated copper substrate; Step S2, forming a nanocrystalline transition layer: preparing a nanocrystalline transition layer on the surface of the copper substrate by pulse electroplating; Step S2, preparation of a surface protective layer: graphene oxide, hydroxyapatite, and nano-titanium dioxide are uniformly dispersed in an epoxy resin, an appropriate amount of a curing agent is added, and after stirring evenly, the mixture is sprayed on the surface of the transition layer and cured at a temperature of 118° C. for 2 hours to form a surface protective layer.

[0030] The staged cleaning is specifically as follows: first, ultrasonic cleaning with acetone for 10 minutes, then rinsing with deionized water, then acid washing for 3 minutes, and finally rinsing with deionized water and drying; the acid used for the acid washing is a 1% sulfuric acid solution, and the acid washing temperature is 35°C.

[0031] The pulse parameters of the pulse electroplating are: forward current density 11A / dm², reverse current density 2A / dm², pulse frequency 1000Hz, duty cycle 60%, temperature 53°C, and deposition time 28min; the plating solution of the pulse electroplating includes components with the following concentrations: 20g / L nickel sulfate, 15g / L sodium hypophosphite, 10g / L sodium citrate, 3g / L cerium nitrate, 0.1g / L zwitterionic salt, 0.1g / L adenosine, 0.1-0.5g / L, and 0.05-0.1g / L disodium 2,2'-biquinoline-4,4'-dicarboxylate, and the pH is adjusted to 4.8 with sulfuric acid; the zwitterionic salt is 1-benzylpyridine-3-carboxylate.

[0032] In step S2, the mass ratio of graphene oxide, hydroxyapatite, nano-titanium dioxide, epoxy resin, and curing agent is 3:1:4:85:4-6; the graphene oxide is a single-layer graphene oxide with a sheet diameter of 0.5-5 μm and a thickness of 0.8-1.2 nm; the average diameter of the hydroxyapatite is 1 μm; the average particle size of the nano-titanium dioxide is 10 nm; the epoxy resin is E-51 epoxy resin; and the curing agent is 3,3'-diamino-4,4'-difluorodiphenyl sulfone. Example 2

[0033] A corrosion-resistant copper trough wire comprises, from a copper substrate outward, a nanocrystalline transition layer and a surface protective layer. The copper substrate comprises, by mass percentage, the following components: Ag 0.15%, rare earth elements 0.015%, Ga 0.015%, Mn 0.15%, Si 0.07%, Ni 0.25%, Zr 0.04%, Ti 0.06%, Cr 0.35%, and B 0.0015%, with the remainder being Cu and other unavoidable impurities. The rare earth elements are Ce, Nd, and Pr mixed in a mass ratio of 2:1.2:0.9. The nanocrystalline transition layer has a thickness of 5 μm; and the surface protective layer has a thickness of 10 μm.

[0034] A process for preventing electrochemical corrosion of the corrosion-resistant copper trough line comprises the following steps: Step S1, pretreatment of the copper substrate surface: using 400# sandpaper to polish the copper substrate to a surface roughness of Ra ≤ 1.0 μm to remove the oxide layer; then performing stage-by-stage cleaning and polishing in sequence to obtain a pretreated copper substrate; Step S2, forming a nanocrystalline transition layer: preparing a nanocrystalline transition layer on the surface of the copper substrate by pulse electroplating; Step S2, preparation of a surface protective layer: graphene oxide, hydroxyapatite, and nano-titanium dioxide are uniformly dispersed in an epoxy resin, an appropriate amount of a curing agent is added, and after stirring evenly, the mixture is sprayed on the surface of the transition layer and cured at a temperature of 119° C. for 2.3 hours to form a surface protective layer.

[0035] The staged cleaning is specifically as follows: first, ultrasonic cleaning with acetone for 11 minutes, then rinsing with deionized water, then acid washing for 3.5 minutes, and finally rinsing with deionized water and drying; the acid used for the acid washing is a 1.5% sulfuric acid solution, and the acid washing temperature is 36°C.

[0036] The pulse parameters of the pulse electroplating are: forward current density 11.5A / dm², reverse current density 2.5A / dm², pulse frequency 1000Hz, duty cycle 60%, temperature 54°C, and deposition time 29min; the plating solution of the pulse electroplating includes components with the following concentrations: 23g / L nickel sulfate, 17g / L sodium hypophosphite, 12g / L sodium citrate, 3.5g / L cerium nitrate, 0.15g / L zwitterionic salt, 0.2g / L adenosine, and 0.06g / L disodium 2,2'-biquinoline-4,4'-dicarboxylate, and the pH is adjusted to 4.9 with sulfuric acid; the zwitterionic salt is 1-benzylpyridine-3-carboxylate.

[0037] In step S2, the mass ratio of graphene oxide, hydroxyapatite, nano-titanium dioxide, epoxy resin, and curing agent is 3.5:1.5:4.5:86:4.5; the graphene oxide is a single-layer graphene oxide with a sheet diameter of 0.5-5 μm and a thickness of 0.8-1.2 nm; the average diameter of the hydroxyapatite is 2 μm; the average particle size of the nano-titanium dioxide is 30 nm; the epoxy resin is E-51 epoxy resin; and the curing agent is 3,3'-diamino-4,4'-difluorodiphenyl sulfone. Example 3

[0038] A corrosion-resistant copper trough wire comprises, from a copper substrate outward, a nanocrystalline transition layer and a surface protective layer. The copper substrate comprises, by mass percentage, the following components: Ag 0.2%, rare earth elements 0.02%, Ga 0.02%, Mn 0.2%, Si 0.1%, Ni 0.3%, Zr 0.045%, Ti 0.07%, Cr 0.4%, and B 0.002%, with the remainder being Cu and other unavoidable impurities. The rare earth elements are Ce, Nd, and Pr mixed in a mass ratio of 2:1.5:1. The nanocrystalline transition layer has a thickness of 5 μm; and the surface protective layer has a thickness of 10 μm.

[0039] A process for preventing electrochemical corrosion of the corrosion-resistant copper trough line comprises the following steps: Step S1, pretreatment of the copper substrate surface: using 400# sandpaper to polish the copper substrate to a surface roughness of Ra ≤ 1.0 μm to remove the oxide layer; then performing stage-by-stage cleaning and polishing in sequence to obtain a pretreated copper substrate; Step S2, forming a nanocrystalline transition layer: preparing a nanocrystalline transition layer on the surface of the copper substrate by pulse electroplating; Step S2, preparation of a surface protective layer: graphene oxide, hydroxyapatite, and nano-titanium dioxide are uniformly dispersed in an epoxy resin, an appropriate amount of a curing agent is added, and after stirring evenly, the mixture is sprayed on the surface of the transition layer and cured at a temperature of 120° C. for 2.5 hours to form a surface protective layer.

[0040] The staged cleaning is specifically as follows: first, ultrasonic cleaning with acetone for 13 minutes, then rinsing with deionized water, then acid washing for 4 minutes, and finally rinsing with deionized water and drying; the acid used for the acid washing is a 2% sulfuric acid solution, and the acid washing temperature is 38°C.

[0041] The pulse parameters of the pulse electroplating are: forward current density 12A / dm², reverse current density 3A / dm², pulse frequency 1000Hz, duty cycle 60%, temperature 55°C, and deposition time 30min; the electroplating solution of the pulse electroplating comprises the following components in concentrations: nickel sulfate 25g / L, sodium hypophosphite 18g / L, sodium citrate 13g / L, cerium nitrate 4g / L, zwitterionic salt 0.2g / L, adenosine 0.3g / L, 2,2'-biquinoline-4,4'-dicarboxylic acid disodium 0.07g / L, and the pH is adjusted to 5; the zwitterionic salt is 1-benzylpyridine-3-carboxylate; the mass ratio of the graphene oxide, hydroxyapatite, nano-titanium dioxide, epoxy resin, and curing agent in step S2 is 4:2:5:88:5; the graphene oxide is a single-layer graphene oxide with a sheet diameter of 0.5-5 μm and a thickness of 0.8-1.2 nm; the average diameter of the hydroxyapatite is 3 μm; the average particle size of the nano-titanium dioxide is 60 nm; the epoxy resin is E-51 epoxy resin; and the curing agent is 3,3'-diamino-4,4'-difluorodiphenyl sulfone. Example 4

[0042] A corrosion-resistant copper trough wire comprises, from a copper substrate outward, a nanocrystalline transition layer and a surface protective layer. The copper substrate comprises, by mass percentage, the following components: Ag 0.25%, rare earth elements 0.025%, Ga 0.025%, Mn 0.25%, Si 0.13%, Ni 0.35%, Zr 0.055%, Ti 0.09%, Cr 0.45%, and B 0.0025%, with the remainder being Cu and other unavoidable impurities. The rare earth elements are Ce, Nd, and Pr mixed in a mass ratio of 2:1.8:1.1. The nanocrystalline transition layer has a thickness of 5 μm; and the surface protective layer has a thickness of 10 μm.

[0043] A process for preventing electrochemical corrosion of the corrosion-resistant copper trough line comprises the following steps: Step S1, pretreatment of the copper substrate surface: using 400# sandpaper to polish the copper substrate to a surface roughness of Ra ≤ 1.0 μm to remove the oxide layer; then performing stage-by-stage cleaning and polishing in sequence to obtain a pretreated copper substrate; Step S2, forming a nanocrystalline transition layer: preparing a nanocrystalline transition layer on the surface of the copper substrate by pulse electroplating; Step S2, preparation of a surface protective layer: graphene oxide, hydroxyapatite, and nano-titanium dioxide are uniformly dispersed in an epoxy resin, an appropriate amount of a curing agent is added, and after stirring evenly, the mixture is sprayed on the surface of the transition layer and cured at a temperature of 121° C. for 2.8 hours to form a surface protective layer.

[0044] The staged cleaning is specifically as follows: first, ultrasonic cleaning with acetone for 14 minutes, then rinsing with deionized water, then pickling with acid for 4.5 minutes, and finally rinsing with deionized water and drying; the acid used for pickling is a 2.5% sulfuric acid solution, and the pickling temperature is 39°C; the pulse parameters of the pulse electroplating are: forward current density 12.5A / dm², reverse current density 3.5A / dm², pulse frequency 1000Hz, duty cycle 60%, temperature 56°C, and deposition time 31 minutes.

[0045] The electroplating solution of the pulse electroplating comprises the following components: nickel sulfate 28 g / L, sodium hypophosphite 19 g / L, sodium citrate 14 g / L, cerium nitrate 4.5 g / L, zwitterion salt 0.25 g / L, adenosine 0.4 g / L, 2,2'-biquinoline-4,4'-dicarboxylate disodium 0.09 g / L, and the pH thereof is adjusted to 5.3 with sulfuric acid; the zwitterion salt is 1-benzylpyridine-3-carboxylate; the graphene oxide and hydroxyphosphine in step S2 are The mass ratio of limestone, nano-titanium dioxide, epoxy resin, and curing agent is 4.5:2.5:5.5:89:5.5; the graphene oxide is a single-layer graphene oxide with a sheet diameter of 0.5-5 μm and a thickness of 0.8-1.2 nm; the average diameter of the hydroxyapatite is 4 μm; the average particle size of the nano-titanium dioxide is 70 nm; the epoxy resin is E-51 epoxy resin; and the curing agent is 3,3'-diamino-4,4'-difluorodiphenyl sulfone. Example 5

[0046] A corrosion-resistant copper trough wire comprises, from a copper substrate outward, a nanocrystalline transition layer and a surface protective layer; the copper substrate comprises, by mass percentage, the following components: Ag 0.3%, rare earth elements 0.03%, Ga 0.03%, Mn 0.3%, Si 0.15%, Ni 0.4%, Zr 0.06%, Ti 0.1%, Cr 0.5%, B 0.003%, with the remainder being Cu and other unavoidable impurities; the rare earth elements are Ce, Nd, and Pr mixed in a mass ratio of 2:2:1.2; the nanocrystalline transition layer has a thickness of 5 μm; and the surface protective layer has a thickness of 10 μm.

[0047] A process for preventing electrochemical corrosion of the corrosion-resistant copper trough line comprises the following steps: Step S1, pretreatment of the copper substrate surface: using 400# sandpaper to polish the copper substrate to a surface roughness of Ra ≤ 1.0 μm to remove the oxide layer; then performing stage-by-stage cleaning and polishing in sequence to obtain a pretreated copper substrate; Step S2, forming a nanocrystalline transition layer: preparing a nanocrystalline transition layer on the surface of the copper substrate by pulse electroplating; Step S2, preparation of a surface protective layer: graphene oxide, hydroxyapatite, and nano-titanium dioxide are uniformly dispersed in an epoxy resin, an appropriate amount of a curing agent is added, and after stirring evenly, the mixture is sprayed on the surface of the transition layer and cured at a temperature of 122° C. for 3 hours to form a surface protective layer.

[0048] The staged cleaning is specifically as follows: first, ultrasonic cleaning with acetone for 15 minutes, then rinsing with deionized water, then acid washing for 5 minutes, and finally rinsing with deionized water and drying; the acid used for the acid washing is a 3% sulfuric acid solution, and the acid washing temperature is 40°C.

[0049] The pulse plating parameters are as follows: forward current density 13A / dm², reverse current density 4A / dm², pulse frequency 1000Hz, duty cycle 60%, temperature 57°C, and deposition time 32min. The plating solution for the pulse plating comprises the following components in the following concentrations: nickel sulfate 30g / L, sodium hypophosphite 20g / L, sodium citrate 15g / L, cerium nitrate 5g / L, zwitterion salt 0.3g / L, adenosine 0.5g / L, and disodium 2,2'-biquinoline-4,4'-dicarboxylate 0.1g / L, and the pH is adjusted to 5. 5; the zwitterionic salt is 1-benzylpyridine-3-carboxylate; the mass ratio of the graphene oxide, hydroxyapatite, nano-titanium dioxide, epoxy resin, and curing agent in step S2 is 5:3:6:90:6; the graphene oxide is a single-layer graphene oxide with a sheet diameter of 0.5-5 μm and a thickness of 0.8-1.2 nm; the average diameter of the hydroxyapatite is 5 μm; the average particle size of the nano-titanium dioxide is 80 nm; the epoxy resin is E-51 epoxy resin; and the curing agent is 3,3'-diamino-4,4'-difluorodiphenyl sulfone.

[0050] Comparative Example 1 This example provides a corrosion-resistant copper trough line and an electrochemical corrosion protection process thereof, which is basically the same as Example 1, except that Ga, Si and disodium 2,2'-biquinoline-4,4'-dicarboxylate are not added.

[0051] Comparative Example 2 This example provides a corrosion-resistant copper slot line and an anti-electrochemical corrosion process thereof, which is basically the same as Example 1, except that Nd, Zr and adenosine are not added.

[0052] Comparative Example 3 This example provides a corrosion-resistant copper slot line and an electrochemical corrosion protection process thereof, which is basically the same as Example 1, except that hydroxyapatite, B and zwitterionic salt are not added.

[0053] In order to further illustrate the beneficial technical effects of the corrosion-resistant copper trough wires involved in various embodiments of the present invention, relevant performance tests were conducted on the corrosion-resistant copper trough wires involved in various examples. The test results are shown in Table 1. The test method is as follows: (1) Conductivity test: Refer to GB / T 351-2019 for testing; (2) Corrosion resistance test: Conduct a neutral salt spray test (5% NaCl solution, 35°C, continuous spraying for 1200 hours, spray volume 2 mL / 80 cm²·h) in accordance with GB / T 10125-2021, and observe the corrosion condition of the sample surface.

[0054] (3) Electrochemical impedance: With reference to GB / T 24196-2009 “Method for testing electrochemical impedance spectroscopy of metals and alloys”, a three-electrode system was used for testing in 3.5% NaCl solution (25°C). The working electrode was the copper slot wire (exposed area 1 cm²) of each embodiment of the present invention, the reference electrode was a saturated calomel electrode (SCE), and the auxiliary electrode was a platinum sheet electrode (area 5 cm²). The frequency range was 10²-10 6 Hz.

[0055] (4) Fatigue life: With reference to the fatigue test of JISZ 2273-1978, the number of repetitions until the test piece breaks when the load stress is 500 MPa is calculated; the wire diameter of the test piece is 0.5 mm; in each case, three wires are used to conduct the above test, and the average number of repetitions until the groove wire breaks is calculated.

[0056] As can be seen from Table 1, the corrosion-resistant copper slot lines involved in various embodiments of the present invention have better conductivity, fatigue resistance and corrosion resistance than the comparative example products. The combined addition of Ga, Si, disodium 2,2'-biquinoline-4,4'-dicarboxylate, Nd, Zr, adenosine, hydroxyapatite, B and zwitterionic salts is beneficial to improving the above properties.

[0057] Table 1 Corrosion-resistant copper trough performance test results

[0058] The above embodiments are only for illustrating the technical concept and features of the present invention. Their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it accordingly. They are not intended to limit the scope of protection of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of protection of the present invention.

Claims

1. A corrosion-resistant copper trough wire, characterized in that: From the copper matrix outward, there are a nanocrystalline transition layer and a surface protective layer. The copper matrix comprises, by mass percentage, the following components: Ag 0.1-0.3%, rare earth elements 0.01-0.03%, Ga 0.01-0.03%, Mn 0.1-0.3%, Si 0.05-0.15%, Ni 0.2-0.4%, Zr 0.03-0.06%, Ti 0.05-0.1%, Cr 0.3-0.5%, B 0.001-0.003%, and the balance is Cu and other inevitable impurities.

2. The corrosion-resistant copper trough wire according to claim 1, characterized in that: The rare earth elements are Ce, Nd and Pr mixed in a mass ratio of 2:(1-2):(0.8-1.2).

3. The corrosion-resistant copper trough wire according to claim 1, characterized in that: The thickness of the nanocrystalline transition layer is 5-8 μm; the thickness of the surface protection layer is 10-15 μm.

4. An electrochemical corrosion protection process for corrosion-resistant copper trough wire according to any one of claims 1 to 3, characterized in that: The steps include: Step S1, pretreatment of the copper substrate surface: using 400# sandpaper to polish the copper substrate to a surface roughness of Ra ≤ 1.0 μm to remove the oxide layer; then performing stage-by-stage cleaning and polishing in sequence to obtain a pretreated copper substrate; Step S2, forming a nanocrystalline transition layer: preparing a nanocrystalline transition layer on the surface of the copper substrate by pulse electroplating; Step S2, preparation of a surface protective layer: graphene oxide, hydroxyapatite, and nano-titanium dioxide are uniformly dispersed in an epoxy resin, an appropriate amount of a curing agent is added, and after stirring evenly, the mixture is sprayed on the surface of the transition layer and cured at a temperature of 118-122° C. for 2-3 hours to form a surface protective layer.

5. The electrochemical corrosion prevention process for corrosion-resistant copper trough wire according to claim 4, characterized in that: The staged cleaning is specifically as follows: first, ultrasonic cleaning with acetone for 10-15 minutes, then rinsing with deionized water, then acid washing for 3-5 minutes, and finally rinsing with deionized water and drying; the acid used for the acid washing is a 1-3% sulfuric acid solution, and the acid washing temperature is 35-40°C.

6. The electrochemical corrosion prevention process for corrosion-resistant copper trough wire according to claim 4, characterized in that: The pulse parameters of the pulse electroplating are: forward current density 11-13 A / dm², reverse current density 2-4 A / dm², pulse frequency 1000 Hz, duty cycle 60%, temperature 53-57°C, and deposition time 28-32 min.

7. The electrochemical corrosion prevention process for corrosion-resistant copper trough wire according to claim 4, characterized in that: The pulse electroplating electroplating solution comprises components with the following concentrations: 20-30 g / L nickel sulfate, 15-20 g / L sodium hypophosphite, 10-15 g / L sodium citrate, 3-5 g / L cerium nitrate, 0.1-0.3 g / L zwitterionic salt, 0.1-0.5 g / L adenosine, and 0.05-0.1 g / L disodium 2,2'-biquinoline-4,4'-dicarboxylate. The pH is adjusted to 4.8-5.5 with sulfuric acid. The zwitterionic salt is 1-benzylpyridine-3-carboxylate.

8. The electrochemical corrosion prevention process for corrosion-resistant copper trough wire according to claim 4, characterized in that: The mass ratio of graphene oxide, hydroxyapatite, nano-titanium dioxide, epoxy resin and curing agent in step S2 is (3-5):(1-3):(4-6):(85-90):(4-6).

9. The electrochemical corrosion prevention process for corrosion-resistant copper trough wire according to claim 4, characterized in that: The graphene oxide is a single-layer graphene oxide with a sheet diameter of 0.5-5 μm and a thickness of 0.8-1.2 nm; the average diameter of the hydroxyapatite is 20-30 μm; and the average particle size of the nano-titanium dioxide is 10-80 nm.

10. The electrochemical corrosion prevention process for corrosion-resistant copper trough wire according to claim 4, characterized in that: The epoxy resin is E-51 epoxy resin; the curing agent is 3,3'-diamino-4,4'-difluorodiphenyl sulfone.

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