A surface treatment method for an anode plate for electrolytic copper

Abstract

The application relates to the technical field of anode plate surface treatment, and discloses a surface treatment method for an anode plate for electrolytic copper, which comprises the following steps: step S1, pretreating the anode plate; step S2, activating the pretreated anode plate; step S3, ultrasonic-assisted plasma cleaning the activated anode plate; step S4, interlayer bonding transition treatment on the cleaned anode plate; step S5, surface modification treatment on the anode plate after the interlayer bonding transition treatment; step S6, coating a self-repairing nano composite coating on the anode plate after the surface modification treatment; and step S7, post-treatment on the anode plate after the self-repairing nano composite coating is coated. The dual mechanism of ultrasonic cleaning and chemical activation is used to deeply remove micron-level oil stains and oxidized chippings, and the surface active sites are significantly increased.

Description

Technical Field

[0001] This invention relates to the field of anode plate surface treatment technology, and specifically to a surface treatment method for an anode plate used in electrolytic copper. Background Technology

[0002] In the electrolytic copper production process, the anode plate, as the core component of the electrolysis system, is crucial for ensuring electrolysis efficiency and the quality of cathode copper products through its surface treatment technology. Current technologies primarily focus on removing surface impurities, enhancing surface properties, and improving electrolytic stability. Common treatment methods include pretreatment, activation treatment, surface modification, and post-treatment. Pretreatment often involves immersion in alkaline degreasing solutions to remove surface oil, combined with acid washing to remove oxide scale and impurities. Activation treatment typically uses dilute acid immersion to break down the surface passivation layer, providing an active surface for subsequent processing. Surface modification mainly involves chemical conversion film treatment or electroplating to form a dense protective layer, improving the anode plate's corrosion resistance and conductivity. Post-treatment usually includes washing and drying to ensure the anode plate surface is clean and dry, meeting the requirements of electrolysis conditions. These surface treatment technologies, through multi-step synergistic effects, construct a basic protective system for the anode plate surface, optimize the electrochemical performance of the anode plate during electrolysis, reduce impurity precipitation and anode sludge formation, and ensure the stable operation of the electrolysis process.

[0003] However, the existing technology has the following problems:

[0004] Existing anode plate surface treatment processes mostly rely on single acid washing or water washing for surface cleaning, which is difficult to completely remove micron-sized oil stains, oxide debris and carbon residues. This can easily lead to insufficient number of active sites on the anode plate surface, and the subsequent coating may have weak adhesion to the substrate due to impurities. Under the action of thermal and mechanical stress generated during the electrolysis process, delamination and peeling may occur, affecting the integrity and stability of the anode plate. Summary of the Invention

[0005] The purpose of this invention is to provide a surface treatment method for an anode plate used in electrolytic copper in order to solve the above-mentioned problems. This method aims to overcome the shortcomings of existing technologies that rely on a single acid pickling or water washing method for surface cleaning, which makes it difficult to completely remove micron-sized oil stains, oxide debris and carbon residues. Details are described below.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] The present invention provides a surface treatment method for an anode plate used in electrolytic copper, comprising the following steps:

[0008] Step S1: Pre-treat the anode plate to remove oil and oxidation impurities from its surface;

[0009] Step S2: Activate the pretreated anode plate to remove the passivation layer on the surface of the anode plate;

[0010] Step S3: Perform ultrasonic-assisted plasma cleaning on the activated anode plate to deeply remove residual impurities on the surface of the anode plate and improve surface activity;

[0011] Step S4: Perform interlayer bonding transition treatment on the cleaned anode plate to construct an interlayer chemical bonding transition layer;

[0012] Step S5: Perform surface modification treatment on the anode plate after interlayer bonding transition treatment to form a dense transition protective layer;

[0013] Step S6: Apply a self-healing nanocomposite coating to the anode plate after surface modification to give the surface a self-healing function;

[0014] Step S7: Post-process the anode plate coated with the self-healing nanocomposite coating to obtain the finished anode plate.

[0015] Preferably, the pretreatment in step S1 includes degreasing and pickling. The degreasing is performed by immersion in an alkaline degreasing solution, which is prepared by mixing sodium carbonate, sodium hydroxide, sodium pyrophosphate and a nonionic surfactant in a mass ratio of 4:2:1:0.3. The immersion temperature is 45℃-55℃ and the immersion time is 12min-18min. The pickling is performed by a mixed acid solution of dilute sulfuric acid and citric acid, with a mass concentration of 10-14% for dilute sulfuric acid and 1%-3% for citric acid. The pickling temperature is 25℃-30℃ and the pickling time is 6min-9min.

[0016] Preferably, the activation treatment in step S2 is performed by acid immersion. The acid solution is a composite acid solution of dilute hydrochloric acid and fluoroboric acid, with the mass concentration of the dilute hydrochloric acid being 8%-12% and the mass concentration of the fluoroboric acid being 0.5-1.5%. The treatment temperature is 22-28℃ and the time is 3-4 minutes. After immersion in the acid solution, the device is ultrasonically cleaned with deionized water 2-3 times, each time for 2-3 minutes, with the ultrasonic power set to 300W-400W.

[0017] Preferably, the ultrasonic-assisted plasma cleaning process in step S3 includes the following steps:

[0018] Step A1: Place the activated anode plate in the plasma cleaner chamber, introduce a mixture of argon and oxygen, wherein the volume ratio of argon to oxygen is 3:1, and set the vacuum degree of the chamber between 10Pa and 30Pa.

[0019] Step A2: Turn on the plasma generator, set the power to 150W-250W, and simultaneously apply ultrasonic vibration with a power of 200W-300W and a frequency of 40kHz. Clean for 5-8 minutes under the dual action.

[0020] Preferably, the interlayer bonding transition process in step S4 includes the following steps:

[0021] Step B1: Preparation of composite sol. Use ethanol and deionized water mixed at a volume ratio of 4:1 as solvent, add 8%-12% tetrabutyl titanate and 3%-5% silane coupling agent by volume, and adjust the pH of the mixed solution to 3-4 using hydrochloric acid to prepare a uniform composite sol.

[0022] Step B2: Dip coating. Immerse the cleaned anode plate in the composite sol and use the dip coating method to lift it. The lifting speed is controlled at 5mm / s-10mm / s to make the composite sol evenly coated on the surface of the anode plate.

[0023] Step B3: Curing into a film. After the composite sol is coated on the anode plate, it is first pre-cured at 120-150℃ for 10-15 minutes, and then the temperature is raised to 200℃-250℃ for high-temperature curing for 20-30 minutes. Finally, a bridging layer with a thickness of 1μm-3μm is formed on the surface of the anode plate.

[0024] Preferably, the surface modification treatment in step S5 is a chemical conversion film treatment, which specifically includes the following steps:

[0025] Step C1: Preparation of the composite conversion solution. A composite conversion solution is prepared using chromate, phosphate, and titanate, wherein the mass concentration of chromate is 4%-6%, the mass concentration of phosphate is 8%-10%, and the mass concentration of titanate is 1%-2%.

[0026] Step C2: Conversion film formation. The anode plate that has undergone interlayer bonding transition treatment is immersed in the composite conversion solution. The treatment temperature is controlled at 35℃-45℃ and the immersion time is 10min-13min. A dense transition protective layer is formed on the surface of the anode plate. The thickness of the transition protective layer is 3μm-8μm.

[0027] Preferably, the self-healing nanocomposite coating application in step S6 specifically includes the following steps:

[0028] Step D1: Preparation of composite coating. A polyurethane nanocomposite coating containing epoxy resin microcapsules is selected as the coating material. The epoxy resin microcapsules have a particle size of 5μm-10μm and the amount of epoxy resin microcapsules added accounts for 8%-12% of the total mass of the coating. The amount of nano-graphene oxide added accounts for 0.5%-1% of the total mass of the coating. The components are mixed evenly and set aside for later use.

[0029] Step D2: Electrostatic spraying treatment. The prepared composite coating is applied to the surface of the anode plate using electrostatic spraying. The spraying voltage is set to 60kV-80kV and the spraying distance is controlled at 20cm-30cm to ensure uniform coating coverage. The final coating thickness is 5μm-10μm.

[0030] Step D3: Coating curing treatment. Place the sprayed anode plate in a curing device and control the curing temperature at 110℃-130℃. Maintain this temperature for 25-30 minutes to ensure that the coating is firmly bonded to the surface of the anode plate.

[0031] Preferably, the post-processing in step S7 includes water washing, drying, and stress relief treatment, which are performed sequentially.

[0032] Preferably, the post-processing further includes performance testing, which includes appearance testing, adhesion testing, corrosion resistance testing, and electrolytic performance testing.

[0033] The beneficial effects are:

[0034] 1. The surface treatment method for the anode plate of electrolytic copper utilizes a dual mechanism of ultrasonic cleaning and chemical activation to deeply remove micron-level oil stains and oxide debris, significantly increasing surface active sites. This achieves ultra-clean treatment of the substrate surface and construction of a highly active interface, effectively solving the problem of insufficient coating adhesion caused by residual impurities in traditional pickling processes, and laying a solid foundation for the firm adhesion of subsequent multi-layer protective systems.

[0035] 2. The surface treatment method for the anode plate of electrolytic copper constructs a chemical bonding transition layer between layers, creating a stable chemical bonding bridge at the interface of different materials. This molecular-level tight connection significantly improves the interlayer shear strength and effectively buffers the thermal and mechanical stress during the electrolysis process. This solves the problem of delamination and peeling that easily occurs in multilayer coating systems during long-term service, and greatly enhances the integrity of the protective structure.

[0036] 3. The surface treatment method for the anode plate used in electrolytic copper involves coating the anode plate with a self-healing nanocomposite coating. By utilizing the active release and repair mechanism of epoxy resin microcapsules when the coating is damaged, the anode plate surface is endowed with unique damage self-healing ability and excellent corrosion resistance. It can not only quickly restore the protective function after the coating is damaged, but also effectively inhibit the formation of anode mud and improve current efficiency, providing a strong guarantee for the continuity and stability of electrolytic copper production. Attached Figure Description

[0037] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0038] Figure 1 This is a schematic diagram of the overall process flow of the present invention;

[0039] Figure 2 This is a schematic diagram of the interlayer bonding transition process of the present invention;

[0040] Figure 3 This is a schematic diagram of the coating process for the self-healing nanocomposite coating of the present invention. Detailed Implementation

[0041] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be described in detail below. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other implementation methods obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0042] Example 1, please refer to Figure 1 - Figure 3 A surface treatment method for an anode plate used in electrolytic copper includes the following steps:

[0043] Step S1: Pre-treat the anode plate to remove oil and oxide impurities from its surface. The pre-treatment includes degreasing and pickling. Degreasing is performed by immersion in an alkaline degreasing solution, which is prepared by mixing sodium carbonate, sodium hydroxide, sodium pyrophosphate, and a nonionic surfactant in a mass ratio of 4:2:1:0.3. The immersion temperature is 45℃ and the immersion time is 12-18 minutes. Pickling is performed by mixing dilute sulfuric acid and citric acid, with a sulfuric acid mass concentration of 10% and a citric acid mass concentration of 1%. The pickling temperature is 25℃ and the pickling time is 6 minutes.

[0044] Step S2: Activate the pretreated anode plate to remove the passivation layer on the surface of the anode plate. The activation treatment is carried out by acid immersion. The acid solution is a composite acid solution of dilute hydrochloric acid and fluoroboric acid, with a mass concentration of 8% hydrochloric acid and a mass concentration of 0.5% fluoroboric acid. The treatment temperature is 22℃ and the time is 3min. After acid immersion, it is ultrasonically cleaned twice with deionized water for 2min each time, with the ultrasonic power set to 300W.

[0045] Step S3: The activated anode plate is subjected to ultrasonic-assisted plasma cleaning to deeply remove residual impurities on the surface of the anode plate and enhance surface activity. By utilizing the dual mechanism of ultrasonic cleaning and chemical activation, micron-sized oil stains and oxide debris are deeply removed, significantly increasing the surface active sites. This achieves ultra-clean treatment of the substrate surface and construction of a highly active interface, thereby effectively solving the problem of insufficient coating adhesion caused by residual impurities in traditional pickling processes, and laying a solid foundation for the firm adhesion of the subsequent multi-layer protection system.

[0046] Step S4: Perform interlayer bonding transition treatment on the cleaned anode plate to construct an interlayer chemical bonding transition layer. This builds a stable chemical bonding bridge at the interface of different materials. This molecular-level tight connection significantly improves the interlayer shear strength and effectively buffers the thermal and mechanical stress during the electrolysis process. This solves the delamination and peeling problem that is prone to occur in multilayer coating systems during long-term service and greatly enhances the integrity of the protective structure.

[0047] Step S5: The anode plate after interlayer bonding transition treatment is subjected to surface modification treatment to form a dense transition protective layer. The transition protective layer further strengthens the shielding protection of the substrate, effectively blocks the penetration of corrosive media, and provides an excellent support skeleton for subsequent coatings. It significantly improves the corrosion resistance and structural stability of the overall protection system and extends the effective protection life of the anode plate in harsh electrolytic environments.

[0048] Step S6: Apply a self-healing nanocomposite coating to the anode plate after surface modification to give the surface a self-healing function. A polyurethane nanocomposite coating containing epoxy resin microcapsules is selected as the coating material. By utilizing the active release and repair mechanism of epoxy resin microcapsules when the coating is damaged, the anode plate surface is endowed with unique damage self-healing ability and excellent corrosion resistance. It can not only quickly restore the protective function after the coating is damaged, but also effectively inhibit the formation of anode mud and improve current efficiency, providing a strong guarantee for the continuity and stability of electrolytic copper production.

[0049] Step S7: Post-process the anode plate coated with the self-healing nanocomposite coating to obtain the finished anode plate. The post-processing includes sequential water washing, drying, and stress release treatment. First, the anode plate surface is rinsed with deionized water at 25℃-30℃ for 4 minutes, then dried at 70℃ for 12 minutes to ensure the surface moisture content is reduced to below 0.3%. Finally, low-temperature annealing stress release is performed at 150℃, held for 30 minutes, and then cooled to room temperature in the furnace. The post-processing also includes performance testing, including appearance testing. The testing process includes adhesion testing, corrosion resistance testing, and electrolytic performance testing. Visual inspection requires the surface to be free of cracks, peeling, and other defects. Adhesion testing uses a cross-cut test with a 1mm spacing between the cuts; after three applications of adhesive tape, the coating should not peel off. Corrosion resistance testing is conducted through a neutral salt spray test; after 72 hours of continuous spraying, the surface corrosion area should not exceed 1%. Electrolytic performance testing requires that the amount of anode mud generated be reduced by more than 50% compared to traditional treatment methods, and that current efficiency be increased by 8%. Furthermore, after 10 cycles of self-healing damage testing, the coating's corrosion resistance retention rate should not be less than 90%.

[0050] Furthermore, the specific process of ultrasonic-assisted plasma cleaning in step S3 includes the following steps:

[0051] Step A1: Place the activated anode plate in the plasma cleaner chamber, introduce a mixture of argon and oxygen with a volume ratio of 3:1, and set the chamber vacuum to 10 Pa.

[0052] Step A2: Turn on the plasma generator, set the power to 150W, and simultaneously apply ultrasonic vibration with a power of 200W and a frequency of 40kHz. Clean for 5 minutes under the dual action.

[0053] Step A3: The carbon residue on the surface of the anode plate is reduced to below 0.05%, and the number of surface active sites is increased by more than 50% compared with traditional cleaning methods.

[0054] In addition, the specific process of interlayer bonding transition processing in step S4 includes the following steps:

[0055] Step B1: Preparation of composite sol. Ethanol and deionized water are mixed at a volume ratio of 4:1 as solvent. 8% tetrabutyl titanate and 3% silane coupling agent are added. The pH of the mixed solution is adjusted to 3 using hydrochloric acid to prepare a uniform composite sol.

[0056] Step B2: Dip coating. Immerse the cleaned anode plate in the composite sol and use a dip coating method to lift it. Control the lifting speed at 5mm / s to ensure that the composite sol is evenly coated on the surface of the anode plate.

[0057] Step B3: Curing into a film. After the composite sol is coated on the anode plate, it is first pre-cured at 120-150℃ for 10 minutes, and then the temperature is raised to 200℃ for high-temperature curing for 20 minutes. Finally, a bridging layer with a thickness of 1μm is formed on the surface of the anode plate. The interfacial shear strength of the bridging layer is ≥15MPa.

[0058] It is worth mentioning that the surface modification treatment in step S5 is a chemical conversion film treatment, which specifically includes the following steps:

[0059] Step C1: Preparation of the composite conversion solution. A composite conversion solution is prepared using chromate, phosphate, and titanate, wherein the mass concentration of chromate is 4%, the mass concentration of phosphate is 8%, and the mass concentration of titanate is 1%.

[0060] Step C2: Conversion film formation. The anode plate that has undergone interlayer bonding transition treatment is immersed in the composite conversion solution. The treatment temperature is controlled at 35℃ and the immersion time is 10min. A dense transition protective layer is formed on the surface of the anode plate with a thickness of 3μm.

[0061] It is worth noting that the self-healing nanocomposite coating application in step S6 specifically includes the following steps:

[0062] Step D1: Preparation of composite coating. Polyurethane nanocomposite coating containing epoxy resin microcapsules is selected as coating material. The epoxy resin microcapsules have a particle size of 5μm and are added at 8% of the total mass of the coating. The amount of nano-graphene oxide added is 0.5% of the total mass of the coating. Mix all components evenly and set aside.

[0063] Step D2: Electrostatic spraying treatment. The prepared composite coating is applied to the surface of the anode plate using electrostatic spraying. The spraying voltage is set to 60kV and the spraying distance is controlled at 20cm to ensure uniform coating coverage. The final coating thickness is 5μm.

[0064] Step D3: Coating curing treatment. Place the sprayed anode plate in a curing device and control the curing temperature at 110℃. Maintain this temperature for 25 minutes to ensure that the coating is firmly bonded to the surface of the anode plate. The resulting self-healing nanocomposite coating can achieve a self-healing rate of over 78% within 24 hours when the damaged width does not exceed 50μm. At the same time, it increases the overall service life of the anode plate by more than 29% compared with traditional treatment methods.

[0065] Example 2, please refer to Figure 1 - Figure 3 A surface treatment method for an anode plate used in electrolytic copper includes the following steps:

[0066] Step S1: Pre-treat the anode plate to remove oil and oxide impurities from its surface. The pre-treatment includes degreasing and pickling. Degreasing is performed by immersion in an alkaline degreasing solution, which is prepared by mixing sodium carbonate, sodium hydroxide, sodium pyrophosphate, and a nonionic surfactant in a mass ratio of 4:2:1:0.3. The immersion temperature is 55℃ and the immersion time is 18 minutes. Pickling is performed by mixing dilute sulfuric acid and citric acid, with a sulfuric acid mass concentration of 14% and a citric acid mass concentration of 3%. The pickling temperature is 30℃ and the pickling time is 9 minutes.

[0067] Step S2: Activate the pretreated anode plate to remove the passivation layer on the surface of the anode plate. The activation treatment is carried out by acid immersion. The acid solution is a composite acid solution of dilute hydrochloric acid and fluoroboric acid, with a mass concentration of 12% for dilute hydrochloric acid and 1.5% for fluoroboric acid. The treatment temperature is 28℃ and the time is 4min. After acid immersion, ultrasonically clean it three times with deionized water for 3min each time, with the ultrasonic power set to 400W.

[0068] Step S3: Perform ultrasonic-assisted plasma cleaning on the activated anode plate to deeply remove residual impurities on the surface of the anode plate and improve surface activity;

[0069] Step S4: Perform interlayer bonding transition treatment on the cleaned anode plate to construct an interlayer chemical bonding transition layer;

[0070] Step S5: Perform surface modification treatment on the anode plate after interlayer bonding transition treatment to form a dense transition protective layer;

[0071] Step S6: Apply a self-healing nanocomposite coating to the anode plate after surface modification to give the surface a self-healing function;

[0072] Step S7: Post-process the anode plate coated with the self-healing nanocomposite coating to obtain the finished anode plate. The post-processing includes sequential water washing, drying, and stress release treatment. First, the anode plate surface is rinsed with deionized water at 25℃-30℃ for 6 minutes, then dried at 80℃ for 15 minutes to ensure the surface moisture content is reduced to below 0.3%. Finally, low-temperature annealing stress release is performed at 200℃, held for 45 minutes, and then cooled to room temperature in the furnace. The post-processing also includes performance testing, including appearance testing. The testing process includes adhesion testing, corrosion resistance testing, and electrolytic performance testing. Visual inspection requires the surface to be free of cracks, peeling, and other defects. Adhesion testing uses a cross-cut test with a 1mm spacing between the cuts; after three applications of adhesive tape, the coating should not peel off. Corrosion resistance testing is conducted through a neutral salt spray test; after 72 hours of continuous spraying, the surface corrosion area should not exceed 1%. Electrolytic performance testing requires that the amount of anode mud generated be reduced by more than 50% compared to traditional treatment methods, and that current efficiency be increased by 12%. Furthermore, after 10 cycles of self-healing damage testing, the coating's corrosion resistance retention rate should not be less than 90%.

[0073] Furthermore, the specific process of ultrasonic-assisted plasma cleaning in step S3 includes the following steps:

[0074] Step A1: Place the activated anode plate in the plasma cleaner chamber, introduce a mixture of argon and oxygen with a volume ratio of 3:1, and set the chamber vacuum to 30 Pa.

[0075] Step A2: Turn on the plasma generator, set the power to 250W, and simultaneously apply ultrasonic vibration with a power of 300W and a frequency of 40kHz. Clean for 8 minutes under the dual action. After cleaning, the carbon residue on the surface of the anode plate is reduced to below 0.05%, and the number of surface active sites is increased by more than 50% compared with the traditional cleaning method.

[0076] In addition, the specific process of interlayer bonding transition processing in step S4 includes the following steps:

[0077] Step B1: Preparation of composite sol. Ethanol and deionized water are mixed at a volume ratio of 4:1 as solvent. 12% tetrabutyl titanate and 5% silane coupling agent are added. The pH of the mixed solution is adjusted to 4 using hydrochloric acid to prepare a uniform composite sol.

[0078] Step B2: Dip coating. Immerse the cleaned anode plate in the composite sol and use a dip coating method to lift it. The lifting speed is controlled at 10mm / s to ensure that the composite sol is evenly coated on the surface of the anode plate.

[0079] Step B3: Curing into a film. After the composite sol is coated on the anode plate, it is first pre-cured at 150°C for 15 minutes, and then the temperature is raised to 250°C for high-temperature curing for 30 minutes. Finally, a bridging layer with a thickness of 3 μm is formed on the surface of the anode plate. The interfacial shear strength of the bridging layer is ≥15 MPa.

[0080] It is worth mentioning that the surface modification treatment in step S5 is a chemical conversion film treatment, which specifically includes the following steps:

[0081] Step C1: Preparation of the composite conversion solution. A composite conversion solution is prepared using chromate, phosphate, and titanate, wherein the mass concentration of chromate is 6%, the mass concentration of phosphate is 10%, and the mass concentration of titanate is 2%.

[0082] Step C2: Conversion film formation. The anode plate that has undergone interlayer bonding transition treatment is immersed in the composite conversion solution. The treatment temperature is controlled at 45℃ and the immersion time is 13min. A dense transition protective layer is formed on the surface of the anode plate with a thickness of 8μm.

[0083] It is worth noting that the self-healing nanocomposite coating application in step S6 specifically includes the following steps:

[0084] Step D1: Preparation of composite coating. Polyurethane nanocomposite coating containing epoxy resin microcapsules is selected as coating material. The epoxy resin microcapsules have a particle size of 10μm and the amount added accounts for 12% of the total mass of the coating. The amount added of nano graphene oxide accounts for 1% of the total mass of the coating. Mix all components evenly and set aside.

[0085] Step D2: Electrostatic spraying treatment. The prepared composite coating is applied to the surface of the anode plate using electrostatic spraying. The spraying voltage is set to 80kV and the spraying distance is controlled at 30cm to ensure uniform coating coverage. The final coating thickness is 10μm.

[0086] Step D3: Coating curing treatment. Place the sprayed anode plate in a curing device and control the curing temperature at 130℃. Maintain this temperature for 30 minutes to ensure that the coating is firmly bonded to the surface of the anode plate. The resulting self-healing nanocomposite coating can achieve a self-healing rate of over 79% within 24 hours when the damaged width does not exceed 50μm. At the same time, it increases the overall service life of the anode plate by more than 30% compared with traditional treatment methods.

[0087] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A surface treatment method for an anode plate used in electrolytic copper, characterized in that, Includes the following steps: Step S1: Pre-treat the anode plate to remove oil and oxidation impurities from its surface; Step S2: Activate the pretreated anode plate to remove the passivation layer on the surface of the anode plate; Step S3: Perform ultrasonic-assisted plasma cleaning on the activated anode plate to deeply remove residual impurities on the surface of the anode plate and improve surface activity; Step S4: Perform interlayer bonding transition treatment on the cleaned anode plate to construct an interlayer chemical bonding transition layer; Step S5: Perform surface modification treatment on the anode plate after interlayer bonding transition treatment to form a dense transition protective layer; Step S6: Apply a self-healing nanocomposite coating to the anode plate after surface modification to give the surface a self-healing function; Step S7: Post-process the anode plate coated with the self-healing nanocomposite coating to obtain the finished anode plate.

2. The surface treatment method for an anode plate for electrolytic copper according to claim 1, characterized in that: The pretreatment in step S1 includes degreasing and pickling. The degreasing is performed by immersion in an alkaline degreasing solution, which is prepared by mixing sodium carbonate, sodium hydroxide, sodium pyrophosphate, and a nonionic surfactant in a mass ratio of 4:2:1:0.

3. The immersion temperature is 45℃-55℃ and the immersion time is 12min-18min. The pickling is performed by using a mixed acid solution of dilute sulfuric acid and citric acid, with a mass concentration of 10%-14% for dilute sulfuric acid and 1%-3% for citric acid. The pickling temperature is 25℃-30℃ and the pickling time is 6min-9min.

3. The surface treatment method for an anode plate for electrolytic copper according to claim 1, characterized in that: The activation treatment in step S2 is performed by acid immersion. The acid solution is a composite acid solution of dilute hydrochloric acid and fluoroboric acid. The mass concentration of the dilute hydrochloric acid is 8-12%, and the mass concentration of the fluoroboric acid is 0.5-1.5%. The treatment temperature is 22-28℃, and the time is 3-4 minutes. After acid immersion, the solution is ultrasonically cleaned with deionized water 2-3 times, each time for 2-3 minutes, with the ultrasonic power set to 300W-400W.

4. The surface treatment method for an anode plate for electrolytic copper according to claim 1, characterized in that: The specific process of ultrasonic-assisted plasma cleaning in step S3 includes the following steps: Step A1: Place the activated anode plate in the plasma cleaner chamber, introduce a mixture of argon and oxygen, wherein the volume ratio of argon to oxygen is 3:1, and set the vacuum degree of the chamber between 10Pa and 30Pa. Step A2: Turn on the plasma generator and set the power to 150W-250W. At the same time, apply ultrasonic vibration with a power of 200W-300W and a frequency of 40kHz. Clean for 5-8 minutes under the dual action.

5. The surface treatment method for an anode plate for electrolytic copper according to claim 1, characterized in that: The specific process of interlayer bonding transition processing in step S4 includes the following steps: Step B1: Preparation of composite sol. Use ethanol and deionized water mixed at a volume ratio of 4:1 as solvent, add 8%-12% tetrabutyl titanate and 3%-5% silane coupling agent by volume, and adjust the pH of the mixed solution to 3-4 using hydrochloric acid to prepare a uniform composite sol. Step B2: Dip coating. Immerse the cleaned anode plate in the composite sol and use the dip coating method to lift it. The lifting speed is controlled at 5mm / s-10mm / s to make the composite sol evenly coated on the surface of the anode plate. Step B3: Curing into a film. After the composite sol is coated on the anode plate, it is first pre-cured at 120-150℃ for 10-15 minutes, and then the temperature is raised to 200℃-250℃ for high-temperature curing for 20-30 minutes. Finally, a bridging layer with a thickness of 1μm-3μm is formed on the surface of the anode plate.

6. The surface treatment method for an anode plate for electrolytic copper according to claim 1, characterized in that: The surface modification treatment in step S5 is a chemical conversion film treatment, which specifically includes the following steps: Step C1: Preparation of the composite conversion solution. A composite conversion solution is prepared using chromate, phosphate, and titanate, wherein the mass concentration of chromate is 4%-6%, the mass concentration of phosphate is 8%-10%, and the mass concentration of titanate is 1%-2%. Step C2: Conversion film formation. The anode plate that has undergone interlayer bonding transition treatment is immersed in the composite conversion solution. The treatment temperature is controlled at 35℃-45℃ and the immersion time is 10min-13min. A dense transition protective layer is formed on the surface of the anode plate. The thickness of the transition protective layer is 3μm-8μm.

7. The surface treatment method for an anode plate for electrolytic copper according to claim 1, characterized in that: The self-healing nanocomposite coating application in step S6 specifically includes the following steps: Step D1: Preparation of composite coating. A polyurethane nanocomposite coating containing epoxy resin microcapsules is selected as the coating material. The epoxy resin microcapsules have a particle size of 5μm-10μm and the amount of epoxy resin microcapsules added accounts for 8%-12% of the total mass of the coating. The amount of nano-graphene oxide added accounts for 0.5%-1% of the total mass of the coating. The components are mixed evenly and set aside for later use. Step D2: Electrostatic spraying treatment. The prepared composite coating is applied to the surface of the anode plate using electrostatic spraying. The spraying voltage is set to 60kV-80kV and the spraying distance is controlled at 20cm-30cm to ensure uniform coating coverage. The final coating thickness is 5μm-10μm. Step D3: Coating curing treatment. Place the sprayed anode plate in a curing device and control the curing temperature at 110℃-130℃. Maintain this temperature for 25-30 minutes to ensure that the coating is firmly bonded to the surface of the anode plate.

8. The surface treatment method for an anode plate for electrolytic copper according to claim 1, characterized in that: The post-processing in step S7 includes water washing, drying, and stress relief treatment, which are performed sequentially.

9. The surface treatment method for an anode plate for electrolytic copper according to claim 8, characterized in that: The post-processing also includes performance testing, which includes appearance testing, adhesion testing, corrosion resistance testing, and electrolytic performance testing.

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