Aluminum alloy coated wire for ship armored cable

Abstract

The invention discloses an aluminum alloy coated wire for a ship armored cable, which comprises a wire cell, the wire cell is made of an aluminum alloy material, and the surface of the wire cell is further subjected to anodic oxidation treatment and hole sealing treatment to form a composite film layer; a hole sealing solution for hole sealing treatment comprises the following components: water, a silane coupling agent, cerous nitrate, lanthanum nitrate, deionized water and a pH regulator; the mass ratio of the silane coupling agent is 2-5 wt%, the mass ratio of the cerous nitrate is 0.15-0.3 wt%, and the mass ratio of the lanthanum nitrate is 0.05-0.1 wt%. The hole sealing liquid comprises the silane coupling agent, the cerous nitrate and the lanthanum nitrate, and micropores of an oxidation film are passivated through hydrolysis cooperation of rare earth ions and siloxane; ce is used for sealing surface point-shaped defects, La is used for strengthening a crystal boundary line-shaped structure, siloxane hydrolysis is used for adding a compact and reinforced composite film layer, point-line-surface all-dimensional protection improvement is achieved, and the corrosion resistance, the adhesive force and the strength of the formed composite film layer are remarkably improved.

Description

Technical Field

[0001] The present application relates to a ship armored cable, and in particular to an aluminum alloy coated conductor for a ship armored cable. Background Art

[0002] In the field of ship armored cables, aluminum alloy conductors are widely used due to their light weight and high conductivity, but their corrosion resistance and mechanical strength need to be improved through surface treatment.

[0003] Traditional processes primarily utilize the following methods: Anodizing: This electrolytic process forms an aluminum oxide (Al2O3) film on the aluminum alloy surface. However, this film contains micropores and cracks, necessitating further sealing with hot water or nickel salts. However, current technologies do not completely seal the micropores of the oxide film, allowing corrosive media such as Cl⁻ to penetrate, leading to intergranular corrosion and pitting. Furthermore, traditional sealing films have low hardness (HV < 300) and poor wear resistance (>20mg / 1,000 revolutions). These films are easily damaged and ineffective under the impact of the constant flow of seawater and collisions with floating ice, sand, and gravel. Summary of the Invention

[0004] In order to improve the protective effect of ship armored cables, an aluminum alloy coated conductor for ship armored cables is provided.

[0005] The above-mentioned object of the present invention is achieved through the following technical solutions: An aluminum alloy coated conductor for ship armored cables, comprising a conductor core made of aluminum alloy. The surface of the conductor core is also subjected to anodizing treatment and sealing treatment to form a composite film layer; The sealing liquid used in the sealing treatment comprises deionized water, a silane coupling agent, cerium nitrate, lanthanum nitrate, deionized water, and a pH regulator; The mass proportion of the silane coupling agent is 2~5wt%, the mass proportion of cerium nitrate is 0.15~0.3wt%, and the mass proportion of lanthanum nitrate is 0.05~0.1wt%.

[0006] By adopting the above technical solution, the sealing liquid in this application includes a silane coupling agent, cerium nitrate, and lanthanum nitrate, and the micropores of the oxide film are passivated by the hydrolysis of rare earth ions and siloxane: Ce³⁺ has a fast hydrolysis rate and is preferentially adsorbed on the pores and cracks on the surface of the oxide film. It hydrolyzes to form Ce(OH)3 colloid, which can quickly seal the macropores. La³⁺ is different from Ce 3+ , it diffuses slowly but has high binding energy. Due to the characteristics of ionic charge, it can penetrate from the defects of the oxide film to the grain boundary of the aluminum alloy, and replace with Al³⁺ at the aluminum alloy crystal to form LaAlO3, which inhibits intergranular corrosion; Ce³⁺ covers the surface defects, and La³⁺ strengthens the grain boundary. The silane coupling agent forms a covalent bond Si-O-Al with the oxide film, then adheres to the oxide film, and then further forms a Si-O-Si cross-linked network through water, which densifies and strengthens the oxide film. In this way, Ce³⁺ is used to seal surface point defects, La³⁺ is used to strengthen the linear structure of grain boundaries, and siloxane is hydrolyzed to add a dense and reinforced composite film layer, thereby achieving all-round protection improvement in "points, lines, and surfaces". The corrosion resistance, adhesion, and strength of the composite film layer are significantly improved.

[0007] Optionally, the sealing liquid further comprises sodium polyacrylate and dispersed hydroxyapatite (HA) nanowires; the mass proportion of sodium polyacrylate is 0.1-0.12 wt%; the mass proportion of hydroxyapatite (HA) nanowires is 1-1.5 wt%.

[0008] By adopting the above technical solution, sodium polyacrylate prevents HA from agglomerating through electrostatic repulsion, keeping the nanowires monodisperse; The evenly dispersed HA nanowires are embedded in the composite film layer during the sealing process, improving the mechanical properties through the "whisker toughening effect". At the same time, the hydroxyl groups (-OH) on the surface of the HA nanowires complex with Ce³⁺ / La³⁺, delaying ion loss and increasing the actual concentration of Ce³⁺ / La³⁺ outside the oxide film during the sealing process, thereby improving the sealing effect, thereby improving the strength, corrosion resistance and wear resistance of the composite film layer, and also improving the utilization of Ce³⁺ / La³⁺ and reducing costs.

[0009] Optionally, the hydroxyapatite (HA) nanowires have a diameter of 45-55 nm and a length of 450-550 nm.

[0010] By adopting the above technical solution, the obtained film layer has better strength performance, film layer adhesion and continuous integrity.

[0011] Optionally, the sealing liquid further comprises dispersed urea-formaldehyde resin microcapsules containing benzotriazole (BTA); the surface of the urea-formaldehyde resin microcapsules is modified with a silane coupling agent; and the mass proportion of the urea-formaldehyde resin microcapsules is 1.5-2 wt%.

[0012] By adopting the above technical solution, the silane coupling agent modification treatment can ensure that the urea-formaldehyde resin microcapsules are evenly dispersed in the sealing liquid and then evenly embedded in the composite film layer, thereby preventing the urea-formaldehyde resin microcapsules from agglomerating and embedding and reducing the strength and corrosion resistance of the composite film layer; When the film layer is damaged, the stress breaks through the capsule shell, BTA is released and forms an [Al(BTA)3] complex with Al³⁺, which then covers the scratches and inhibits corrosion, thereby further improving the corrosion resistance of the composite film layer in practical applications.

[0013] Optionally, the sealing liquid further comprises 0.05-0.1 wt % of polyoxyethylene sorbitan monooleate.

[0014] By adopting the above technical solution, polyoxyethylene sorbitan monooleate can not only act as a surfactant for the sealing liquid of this application - reducing surface tension, enhancing wettability, and improving the mass transfer efficiency of reactants, but also can reduce Ce³⁺ / La³⁺ by adsorbing on the surface of the oxide film to form a directional hydrophilic-hydrophobic layer, stabilize the reaction intermediate state (such as Ce(OH)3 colloid nucleation) to reduce the activation energy of the hydration reaction, and the polyoxyethylene chain forms a weak coordination with Ce³⁺ / La³⁺, promoting the uniform adsorption of rare earth ions on the surface of the oxide film, reducing local concentration gradients, thereby achieving low-temperature and efficient mass transfer and reducing the temperature requirement for sealing treatment.

[0015] Optionally, after the anodizing treatment, the conductor core is first subjected to a low-temperature plasma treatment in an argon-oxygen atmosphere and then to a sealing treatment.

[0016] By adopting the above technical solution, the surface of the oxide film is activated, the surface wettability is improved, and the bonding force between the oxide film and the sealing agent reaction product is enhanced, thereby improving the adhesion and corrosion resistance of the composite film layer.

[0017] Optionally, the anodizing liquid of the anodizing treatment includes sulfuric acid, citric acid, and polyethylene glycol 2000.

[0018] By adopting the above technical solution, the combination of sulfuric acid and citric acid can broaden the oxidation voltage window, reduce the risk of film ablation, and reduce metallographic defects at the aluminum alloy interface. Polyethylene glycol 2000 is adsorbed on the inner wall of the membrane pore to form a temporary template to guide the growth of the gradient structure, thereby improving the density and bonding strength of the composite film layer, and further improving the corrosion resistance, adhesion and strength of the composite film layer.

[0019] Optionally, the anodizing treatment parameters are: an initial current density of 2±0.05 A / dm², a voltage gradually transitioning to 15 V over 3 to 3.5 minutes, and then maintaining a current density of 1.5±0.05 A / dm².

[0020] By adopting the above technical solution, the initial high current density (2 A / dm²) quickly forms a dense layer, which is reduced in the steady-state stage to maintain uniform deposition, making the composite film dense and with less thickness deviation. The porosity gradient inside the composite film precursor-oxide film is smoother, and the composite film has better corrosion resistance, adhesion and strength.

[0021] In summary, this application has at least the following beneficial effects: This application uses a multi-level collaborative mechanism of chemical passivation, physical enhancement, and self-repair to achieve long-term protection of ship cables and conductors in extreme environments. DETAILED DESCRIPTION

[0022] Polyethylene glycol 2000, molecular weight 2000 ± 200, white waxy solid, purity ≥99 wt%, Maclean catalog number: P816015; Benzotriazole (BTA), white crystalline powder, purity ≥99%, CAS 95-14-7, Anaiji Chemical Product No.: B1028; Tween 20, Anaiji Chemical Product No.: T1023; Urea, purity: ≥99% (analytical grade), Maclean product number: U817980; Liquid paraffin, density 0.84 g / cm³, Maclean product number: L817630; Silane coupling agent, selected from Nanjing Shuguang Chemical KH550, γ-aminopropyltriethoxysilane, CAS number: 919-30-2; Cerium nitrate hexahydrate, purity: ≥99wt%, J&K Technology Catalog Number: J000890; Lanthanum nitrate hexahydrate, purity: ≥99wt%, Anaiji Chemical Product No.: L1012; Sodium polyacrylate, molecular weight 1500 ± 500, Sigma-Aldrich product number: 323667; Hydroxyapatite (HA) nanowires are a product of Xi'an Ruixi Biological. The diameter and aspect ratio specifications are shown in the specific examples. Polyoxyethylene sorbitan monooleate, CAS number: 9005-65-6, Sigma-Aldrich product number: P1754.

[0023] Sulfuric acid, citric acid and ethanol were commercially available analytical grade products.

[0024] Aqueous ammonia, hydrochloric acid, and 10 wt % nitric acid are commercially available products.

[0025] Preparation Example 1 An anodizing treatment solution is prepared from sulfuric acid, citric acid, polyethylene glycol 2000, and deionized water, wherein the concentration of sulfuric acid is 10 g / L, the concentration of citric acid is 4.9 g / L, and the concentration of polyethylene glycol 2000 is 0.1 wt%.

[0026] Preparation Example 2 An anodic oxidation treatment solution is prepared from sulfuric acid, citric acid, and deionized water, wherein the concentration of sulfuric acid is 10 g / L and the concentration of citric acid is 4.9 g / L.

[0027] Preparation Example 3 Preparation of urea-formaldehyde resin microcapsules containing benzotriazole (BTA) (hereinafter referred to as BTA microcapsules): 0.05 kg BTA and 0.03 kg Tween 20 were added to 0.95 kg 10 wt% ethanol aqueous solution and stirred to dissolve to obtain a core material solution; Slowly add 1 kg of core material solution to 5 kg of liquid paraffin, and homogenize at 10,000 rpm until the droplet size of the dispersed emulsion is 2-5 μm to obtain a water / oil emulsion; Urea and 37 wt% formaldehyde solution were mixed at a urea to formaldehyde molar ratio of 1:2, stirred in a 60°C water bath for 30 min, the pH was adjusted to 2.5 with hydrochloric acid, and the reaction was continued for 1 h to obtain a prepolymer solution; Slowly add 0.75 kg of prepolymer solution to 5 kg of water / oil emulsion, maintain stirring speed at 700 rpm, raise the temperature to 55 ° C, and react for 4 hours. The urea-formaldehyde resin condenses at the oil-water interface to form wall material; Ammonia was added to adjust the pH to 7.2 to terminate the reaction, and the microcapsules were separated by centrifugation and washed alternately with ethanol and deionized water three times to obtain white powder microcapsules; White powder microcapsules were added to an ethanol solution of a silane coupling agent (KH550, 1.5 wt%) and soaked. The mass ratio of the white powder microcapsules to the ethanol solution of the silane coupling agent (KH550, 1.5 wt%) was 1:8. The soaking time was 30 min. After the soaking, the microcapsules were dried at 40° C. to obtain BTA microcapsules.

[0028] Preparation Example 4 A sealing liquid is prepared by mixing a silane coupling agent, cerium nitrate, lanthanum nitrate, a pH regulator and deionized water.

[0029] The silane coupling agent was KH550, and the pH adjuster was 10 wt % nitric acid.

[0030] The mass proportion of the silane coupling agent is 3wt%, the mass proportion of cerium nitrate is 0.21wt%, and the mass proportion of lanthanum nitrate is 0.07wt%.

[0031] The preparation method is as follows: Take 70% of the total mass of the pre-prepared sealing solution in deionized water, preheat it to 28°C, add cerium nitrate and lanthanum nitrate according to the mass ratio, stir to dissolve, and add pH adjuster dropwise to adjust the pH to 4.2±0.1; Add silane coupling agent according to the mass ratio, stir continuously for 30 minutes at 30°C, and then let it stand for 30 minutes; The mixture was stirred and supplemented with excess deionized water to balance the concentration. The pH of the solution was detected during the process. If necessary, a pH regulator was added to adjust the pH to 4.2±0.1 to obtain a sealing solution.

[0032] Preparation Example 5 A sealing liquid is prepared in accordance with Preparation Example 4, wherein the cerium nitrate is replaced by an equal molar amount of lanthanum nitrate, that is, the mass proportion of the silane coupling agent is 3 wt % and the mass proportion of the lanthanum nitrate is 0.279 wt %.

[0033] Preparation Example 6 A sealing liquid is prepared in accordance with Preparation Example 4, wherein lanthanum nitrate is replaced by cerium nitrate in an equal molar amount, that is, the mass proportion of the silane coupling agent is 3 wt %, and the mass proportion of the lanthanum nitrate is 0.280 wt %.

[0034] Preparation Example 7 A sealing liquid, which is different from Preparation Example 4 in that it is prepared by mixing cerium nitrate, lanthanum nitrate, a pH regulator, and deionized water, that is, no silane coupling agent is added during the preparation of the sealing liquid, the mass proportion of the silane coupling agent in the sealing liquid is 0wt%, the mass proportion of cerium nitrate is 0.21wt%, and the mass proportion of lanthanum nitrate is 0.07wt%.

[0035] Preparation Example 8 A sealing liquid is prepared by mixing a silane coupling agent, cerium nitrate, lanthanum nitrate, sodium polyacrylate, HA nanowires, a pH regulator and deionized water.

[0036] The silane coupling agent was KH550, and the pH adjuster was 10 wt % nitric acid.

[0037] The diameter of HA nanowires is 50±5 nm, and the aspect ratio is 10:1.

[0038] The mass proportion of the silane coupling agent is 3wt%, the mass proportion of cerium nitrate is 0.21wt%, the mass proportion of lanthanum nitrate is 0.07wt%, the mass proportion of sodium polyacrylate is 0.11wt%, and the mass proportion of HA nanowires is 1.25wt%.

[0039] The preparation method is as follows: Take 70% of the total mass of the pre-prepared sealing solution in deionized water, preheat it to 28°C, add cerium nitrate and lanthanum nitrate according to the mass ratio, stir to dissolve, and add pH adjuster dropwise to adjust the pH to 4.2±0.1; Add silane coupling agent according to the mass ratio, stir continuously for 30 minutes at 30°C, and then let it stand for 30 minutes; Add sodium polyacrylate according to the mass ratio and stir until it is completely dissolved and the solution is uniform and foam-free; Add HA nanowires according to the mass ratio and disperse by high-speed shearing, and cool to 30°C; While stirring, add the remaining amount of deionized water to balance the concentration. During the process, the pH of the solution is detected and, if necessary, a pH regulator is added to adjust the pH to 4.2±0.1 to obtain a sealing solution.

[0040] Preparation Example 9 A sealing liquid, which differs from Preparation Example 8 in that it is prepared by mixing a silane coupling agent, cerium nitrate, lanthanum nitrate, HA nanowires, a pH regulator, and deionized water, that is, no sodium polyacrylate is added during the preparation of the sealing liquid. The mass proportion of the silane coupling agent in the sealing liquid is 3wt%, the mass proportion of cerium nitrate is 0.21wt%, the mass proportion of lanthanum nitrate is 0.07wt%, the mass proportion of sodium polyacrylate is 0wt%, and the mass proportion of HA nanowires is 1.25wt%.

[0041] Preparation Example 10 A sealing liquid, which differs from Preparation Example 8 in that the diameter of the HA nanowire is 30±5 nm and the aspect ratio is 10:1.

[0042] Preparation Example 11 A sealing liquid, which differs from Preparation Example 8 in that the diameter of the HA nanowire is 70±5 nm and the aspect ratio is 10:1.

[0043] Preparation Example 12 A sealing liquid, which differs from Preparation Example 8 in that the diameter of the HA nanowire is 50±5 nm and the aspect ratio is 8:1.

[0044] Preparation Example 13 A sealing liquid, which differs from Preparation Example 8 in that the diameter of the HA nanowire is 50±5 nm and the aspect ratio is 12:1.

[0045] Preparation Example 14 A sealing liquid is prepared by mixing a silane coupling agent, cerium nitrate, lanthanum nitrate, BTA microcapsules, a pH regulator and deionized water.

[0046] The silane coupling agent is KH550, the pH adjuster is 10 wt % nitric acid, and the BTA microcapsules are prepared in Preparation Example 3.

[0047] The mass proportion of the silane coupling agent is 3wt%, the mass proportion of cerium nitrate is 0.21wt%, the mass proportion of lanthanum nitrate is 0.07wt%, and the mass proportion of BTA microcapsules is 1.75wt%.

[0048] The preparation method is as follows: Take 70% of the total mass of the pre-prepared sealing solution in deionized water, preheat it to 28°C, add cerium nitrate and lanthanum nitrate according to the mass ratio, stir to dissolve, and add pH adjuster dropwise to adjust the pH to 4.2±0.1; Add silane coupling agent according to the mass ratio, stir continuously for 30 minutes at 30°C, and then let it stand for 30 minutes; Add BTA microcapsules according to the mass ratio and disperse them ultrasonically for 10 min (40 kHz, power 300 W); While stirring, add the remaining amount of deionized water to balance the concentration. During the process, the pH of the solution is detected and, if necessary, a pH regulator is added to adjust the pH to 4.2±0.1 to obtain a sealing solution.

[0049] Preparation Example 15 A sealing liquid is prepared by mixing a silane coupling agent, cerium nitrate, lanthanum nitrate, polyoxyethylene sorbitan monooleate, a pH regulator and deionized water.

[0050] The silane coupling agent was KH550, and the pH adjuster was 10 wt % nitric acid.

[0051] The mass proportion of the silane coupling agent is 3 wt %, the mass proportion of cerium nitrate is 0.21 wt %, the mass proportion of lanthanum nitrate is 0.07 wt %, and the mass proportion of polyoxyethylene sorbitan monooleate is 0.08 wt %.

[0052] The preparation method is as follows: Take 70% of the total mass of the pre-prepared sealing solution in deionized water, preheat it to 28°C, add cerium nitrate and lanthanum nitrate according to the mass ratio, stir to dissolve, and add pH adjuster dropwise to adjust the pH to 4.2±0.1; Add silane coupling agent according to the mass ratio, stir continuously for 30 minutes at 30°C, and then let it stand for 30 minutes; Add polyoxyethylene sorbitan monooleate according to the mass ratio and mix well; While stirring, add the remaining amount of deionized water to balance the concentration. During the process, the pH of the solution is detected and, if necessary, a pH regulator is added to adjust the pH to 4.2±0.1 to obtain a sealing solution.

[0053] Preparation Example 16 A sealing liquid is prepared by mixing a silane coupling agent, cerium nitrate, lanthanum nitrate, polyoxyethylene sorbitan monooleate, sodium polyacrylate, HA nanowires, a pH regulator and deionized water.

[0054] The silane coupling agent was KH550, and the pH adjuster was 10 wt% nitric acid. The diameter of the HA nanowires was 50 ± 5 nm, and the aspect ratio was 10:1.

[0055] The mass proportion of silane coupling agent is 3wt%, the mass proportion of cerium nitrate is 0.21wt%, the mass proportion of lanthanum nitrate is 0.07wt%, the mass proportion of polyoxyethylene sorbitan monooleate is 0.08wt%, the mass proportion of sodium polyacrylate is 0.11wt%, and the mass proportion of HA nanowires is 1.25wt%.

[0056] The preparation method is as follows: Take 70% of the total mass of the pre-prepared sealing solution in deionized water, preheat it to 28°C, add cerium nitrate and lanthanum nitrate according to the mass ratio, stir to dissolve, and add pH adjuster dropwise to adjust the pH to 4.2±0.1; Add silane coupling agent according to the mass ratio, stir continuously for 30 minutes at 30°C, and then let it stand for 30 minutes; Add polyoxyethylene sorbitan monooleate according to the mass ratio and mix well; Add sodium polyacrylate according to the mass ratio and stir until it is completely dissolved and the solution is uniform and foam-free; Add HA nanowires according to the mass ratio and disperse by high-speed shearing, and cool to 30°C; While stirring, add the remaining amount of deionized water to balance the concentration. During the process, the pH of the solution is detected and, if necessary, a pH regulator is added to adjust the pH to 4.2±0.1 to obtain a sealing solution.

[0057] Preparation Example 17 A sealing liquid is prepared by mixing a silane coupling agent, cerium nitrate, lanthanum nitrate, polyoxyethylene sorbitan monooleate, BTA microcapsules, a pH regulator and deionized water.

[0058] The silane coupling agent is KH550, the pH adjuster is 10 wt % nitric acid, and the BTA microcapsules are prepared in Preparation Example 3.

[0059] The mass proportion of the silane coupling agent is 3wt%, the mass proportion of cerium nitrate is 0.21wt%, the mass proportion of lanthanum nitrate is 0.07wt%, the mass proportion of polyoxyethylene sorbitan monooleate is 0.08wt%, and the mass proportion of BTA microcapsules is 1.75wt%.

[0060] The preparation method is as follows: Take 70% of the total mass of the pre-prepared sealing solution in deionized water, preheat it to 28°C, add cerium nitrate and lanthanum nitrate according to the mass ratio, stir to dissolve, and add pH adjuster dropwise to adjust the pH to 4.2±0.1; Add silane coupling agent according to the mass ratio, stir continuously for 30 minutes at 30°C, and then let it stand for 30 minutes; Add polyoxyethylene sorbitan monooleate according to the mass ratio and mix well; BTA microcapsules were added according to the mass ratio and ultrasonically dispersed for 10 min (40 kHz, power 300 W); While stirring, add the remaining amount of deionized water to balance the concentration. During the process, the pH of the solution is detected and, if necessary, a pH regulator is added to adjust the pH to 4.2±0.1 to obtain a sealing solution.

[0061] Preparation Example 18 A sealing liquid is prepared by mixing a silane coupling agent, cerium nitrate, lanthanum nitrate, polyoxyethylene sorbitan monooleate, sodium polyacrylate, HA nanowires, BTA microcapsules, a pH regulator and deionized water.

[0062] The silane coupling agent was KH550, the pH adjuster was 10 wt % nitric acid, and the BTA microcapsules were prepared in Preparation Example 3. The diameter of the HA nanowires was 50±5 nm, and the aspect ratio was 10:1.

[0063] The mass proportion of silane coupling agent is 3wt%, the mass proportion of cerium nitrate is 0.21wt%, the mass proportion of lanthanum nitrate is 0.07wt%, the mass proportion of polyoxyethylene sorbitan monooleate is 0.08wt%, the mass proportion of sodium polyacrylate is 0.11wt%, the mass proportion of HA nanowires is 1.25wt%, and the mass proportion of BTA microcapsules is 1.75wt%.

[0064] The preparation method is as follows: Take 70% of the total mass of the pre-prepared sealing solution in deionized water, preheat it to 28°C, add cerium nitrate and lanthanum nitrate according to the mass ratio, stir to dissolve, and add pH adjuster dropwise to adjust the pH to 4.2±0.1; Add silane coupling agent according to the mass ratio, stir continuously for 30 minutes at 30°C, and then let it stand for 30 minutes; Add polyoxyethylene sorbitan monooleate according to the mass ratio and mix well; Add sodium polyacrylate according to the mass ratio and stir until it is completely dissolved and the solution is uniform and foam-free; Add HA nanowires according to the mass ratio and disperse by high-speed shearing, and cool to 30°C; BTA microcapsules were added according to the mass ratio and ultrasonically dispersed for 10 min (40 kHz, power 300 W); While stirring, add the remaining amount of deionized water to balance the concentration. During the process, the pH of the solution is detected and, if necessary, a pH regulator is added to adjust the pH to 4.2±0.1 to obtain a sealing solution.

[0065] Preparation Example 19 A sealing liquid, the difference from Preparation Example 18 is that the mass proportions of the components are different, specifically, the mass proportion of the silane coupling agent is 2 wt%, the mass proportion of cerium nitrate is 0.15 wt%, the mass proportion of lanthanum nitrate is 0.05 wt%, the mass proportion of polyoxyethylene sorbitan monooleate is 0.05 wt%, the mass proportion of sodium polyacrylate is 0.1 wt%, the mass proportion of HA nanowires is 1 wt%, and the mass proportion of BTA microcapsules is 1.5 wt%.

[0066] Preparation Example 20 A sealing liquid, the difference from Preparation Example 18 is that the mass proportions of the components are different, specifically, the mass proportion of the silane coupling agent is 5wt%, the mass proportion of cerium nitrate is 0.3wt%, the mass proportion of lanthanum nitrate is 0.1wt%, the mass proportion of polyoxyethylene sorbitan monooleate is 0.1wt%, the mass proportion of sodium polyacrylate is 0.12wt%, the mass proportion of HA nanowires is 1.5wt%, and the mass proportion of BTA microcapsules is 2wt%.

[0067] Example 1 An aluminum alloy coated conductor for ship armored cables comprises a conductor core and a composite film layer outside the conductor core.

[0068] The conductor core is made of aluminum alloy.

[0069] The composite film layer is formed after the conductor core is subjected to anodizing treatment, low-temperature plasma treatment, and pore sealing treatment.

[0070] The preparation method of aluminum alloy coated conductor for ship armored cable is as follows: The aluminum alloy wire core was unwound and first soaked and washed in 5wt% NaOH at 50°C for 2 minutes, washed and neutralized with water, and then soaked in 2wt% nitric acid for 30 seconds to obtain a pretreated core material; The pretreated core material was immersed in an anodic oxidation solution for anodizing treatment. The anodic oxidation solution was prepared in Preparation Example 1. The anodizing treatment parameters were as follows: an initial current density of 2±0.05A / dm², a voltage gradually increased to 15V over 3 minutes, and the current density was reduced to 1.5±0.05A / dm². The anodizing was continued for 50 minutes to form an oxide film on the surface of the conductor core. After drying, an oxidized core material was obtained. The oxidized core material was placed into a plasma reaction chamber, vacuumed to 10⁻³Pa, and a mixed gas (50 sccm of argon and 2.5 sccm of oxygen) was introduced. The oxidized core material was treated with a 13.56 MHz RF power supply at 300 W for 3 minutes. After the treatment, nitrogen was purged for 8 minutes to obtain the core material to be sealed. The core to be sealed was unwound and immersed in a sealing liquid for sealing treatment. The sealing temperature was 60° C. and the sealing time was 20 min. The sealing liquid was the sealing liquid prepared in Preparation Example 4. After the sealing treatment, the product was rinsed with pure water and dried at 80°C for 30 minutes to obtain an aluminum alloy coated conductor for ship armored cables.

[0071] Comparative Example 1 An aluminum alloy coated conductor for ship armored cables is different from Example 1 in that the sealing liquid is prepared according to Preparation Example 5.

[0072] Comparative Example 2 An aluminum alloy coated conductor for ship armored cables is different from Example 1 in that the sealing liquid is prepared according to Preparation Example 6.

[0073] Comparative Example 3 An aluminum alloy coated conductor for ship armored cables is different from Example 1 in that the sealing liquid is prepared according to Preparation Example 7.

[0074] Example 2 An aluminum alloy coated conductor for ship armored cables is different from Example 1 in that the sealing liquid is prepared according to Preparation Example 8.

[0075] Comparative Example 4 An aluminum alloy coated conductor for ship armored cables is different from Example 1 in that the sealing liquid is prepared according to Preparation Example 9.

[0076] Example 3 An aluminum alloy coated conductor for ship armored cables is different from Example 1 in that the sealing liquid is prepared according to Preparation Example 10.

[0077] Example 4 An aluminum alloy coated conductor for ship armored cables is different from Example 1 in that the sealing liquid is prepared according to Preparation Example 11.

[0078] Example 5 An aluminum alloy coated conductor for ship armored cables is different from Example 1 in that the sealing liquid is prepared according to Preparation Example 12.

[0079] Example 6 An aluminum alloy coated conductor for ship armored cables is different from Example 1 in that the sealing liquid is prepared according to Preparation Example 13.

[0080] Example 7 An aluminum alloy coated conductor for ship armored cables is different from Example 1 in that the sealing liquid is prepared according to Preparation Example 14.

[0081] Example 8 An aluminum alloy coated conductor for ship armored cables is different from Example 1 in that the sealing liquid is prepared according to Preparation Example 15, the sealing treatment temperature is 40° C., and the sealing treatment time is 20 minutes.

[0082] Comparative Example 5 An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing treatment temperature is 40° C. and the sealing treatment time is 20 minutes.

[0083] Example 9 An aluminum alloy coated conductor for ship armored cables is different from Example 1 in that the anodizing liquid is prepared according to Preparation Example 2.

[0084] Example 10 An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the anodizing treatment parameters are as follows: the initial current density is 2±0.05A / dm², the voltage gradually transitions to 15V over 3 minutes, and then the current density is maintained at 2±0.05A / dm². The anodizing is continued for 50 minutes to form an oxide film on the surface of the conductor core, and the oxidized core material is obtained after drying.

[0085] Example 11 An aluminum alloy coated conductor for ship armored cables is different from Example 1 in that the sealing liquid is prepared according to Preparation Example 16, the sealing treatment temperature is 40° C., and the sealing treatment time is 20 minutes.

[0086] Example 12 An aluminum alloy coated conductor for ship armored cables is different from Example 1 in that the sealing liquid is prepared according to Preparation Example 17, the sealing treatment temperature is 40° C., and the sealing treatment time is 20 minutes.

[0087] Example 13 An aluminum alloy coated conductor for ship armored cables is different from Example 1 in that the sealing liquid is prepared according to Preparation Example 18, the sealing treatment temperature is 40° C., and the sealing treatment time is 20 minutes.

[0088] Example 14 An aluminum alloy coated conductor for ship armored cables is different from Example 1 in that the sealing liquid is prepared according to Preparation Example 19, the sealing treatment temperature is 40° C., and the sealing treatment time is 20 minutes.

[0089] Example 15 An aluminum alloy coated conductor for ship armored cables is different from Example 1 in that the sealing liquid is prepared according to Preparation Example 20, the sealing treatment temperature is 40° C., and the sealing treatment time is 20 minutes.

[0090] The corrosion resistance, adhesion level, wear resistance, film hardness and self-repair efficiency of Examples 1 to 15 and Comparative Examples 1 to 4 were tested.

[0091] Corrosion resistance: Salt spray corrosion testing was conducted according to ASTM B117, using a 5wt% NaCl solution, neutral salt spray, and 35°C. Surface corrosion (such as rust, blistering, and flaking) was regularly observed, and the time of first corrosion was recorded. The longer the time to first corrosion, the better the corrosion resistance.

[0092] Adhesion: Adopting the 100-grid method in ASTM D3359 to test, the film is graded based on the percentage of film shedding area, with a rating of 0 to 10B, where 10B means no shedding. The less shedding, the better the adhesion.

[0093] Wear resistance: According to ASTM D4060, a Taber abrasion tester was used to rotate the sample surface with a 1 kg load and a CS-10 grinding wheel. The mass loss (mg) of the film layer after every 1000 revolutions was recorded as the result. The smaller the mass loss, the better the wear resistance.

[0094] Film hardness: According to ASTM E384, use a micro Vickers hardness tester (load 0.05 kg, HV 0.05) to measure the diagonal length of the indentation and calculate the hardness value (HV). The larger the hardness value, the higher the hardness.

[0095] Self-repair efficiency: A standard scratch (50 μm width) was created on the film surface using a diamond scratch tester. The film was then exposed to a 3.5% NaCl solution for 12 h. The change in corrosion area in the scratched area was observed using an optical microscope to calculate the self-repair efficiency. Self-repair efficiency = (1 − scratch corrosion area / initial scratch area) × 100%. A higher self-repair efficiency indicates better self-repairability.

[0096] The test results are shown in Table 1 below.

[0097] Table 1. Test results of Examples 1 to 15 and Comparative Examples 1 to 4

[0098] Comparing Example 1 with Comparative Examples 1 to 3, the sealing liquid of Example 1 of the present application contains a silane coupling agent, cerium nitrate, and lanthanum nitrate. The three sealing liquids of Comparative Example 1 contain only a silane coupling agent and lanthanum nitrate. The three sealing liquids of Comparative Example 2 contain only a silane coupling agent and cerium nitrate. The three sealing liquids of Comparative Example 3 contain only cerium nitrate and lanthanum nitrate. From the test results, it can be seen that the corrosion resistance, adhesion, wear resistance and hardness of Example 1 are significantly greater than those of Comparative Examples 1 to 3.

[0099] The reason is that the silane coupling agent, cerium nitrate, and lanthanum nitrate in Example 1 passivate the micropores of the oxide film through the synergistic passivation of rare earth ions and silane, achieving all-round protection improvement of "points, lines, and surfaces": Ce3⁺ has a fast hydrolysis rate and is preferentially adsorbed on the pores and cracks on the surface of the oxide film, hydrolyzing to form Ce(OH)3 colloid, which can quickly close the macropores; La³⁺ is different from Ce 3+, it diffuses slowly but has high binding energy. Due to the characteristics of ionic charge, it can penetrate from the defects of the oxide film to the aluminum alloy grain boundary, and replace with Al³⁺ at the aluminum alloy crystal to form LaAlO3, which inhibits intergranular corrosion; Ce³⁺ covers the surface defects, and La³⁺ strengthens the grain boundary; the silane coupling agent forms a covalent bond Si-O-Al with the oxide film, and then adheres to the oxide film, and then further hydrates to form a Si-O-Si cross-linked network, which densifies and strengthens the oxide film; Therefore, Ce³⁺ seals surface point defects, La³⁺ strengthens the linear structure of grain boundaries, and siloxane hydrolysis adds a dense and strengthened composite film layer, and the corrosion resistance, adhesion and strength of the composite film layer are significantly improved.

[0100] Comparing Example 1, Example 2 and Comparative Example 4, Example 2 further improves Example 1 by adding HA nanowires, and uses sodium polyacrylate to stably and evenly disperse the HA nanowires in the sealing liquid. During the sealing process, the HA nanowires will be embedded in the composite membrane layer; Comparative Example 4 adds HA nanowires on the basis of Example 1, but does not add sodium polyacrylate for auxiliary dispersion.

[0101] The test results show that the corrosion resistance, wear resistance, and film hardness of Example 2 are all improved compared with Example 1. However, the corrosion resistance, adhesion, wear resistance, and film hardness of Comparative Example 4 are decreased compared with Example 1. This is because the HA nanowires agglomerate and embed into the composite film layer, which significantly reduces the density and integrity during the sealing process.

[0102] Therefore, the HA nanowires uniformly embedded in the composite film layer in this application can improve the mechanical properties through the "whisker toughening effect". At the same time, the hydroxyl groups (-OH) on the surface of the HA nanowires complex with Ce³⁺ / La³⁺, delaying ion loss and increasing the actual concentration of Ce³⁺ / La³⁺ outside the oxide film during the sealing process, thereby improving the sealing effect, thereby improving the strength, corrosion resistance and wear resistance of the composite film layer, and also improving the utilization of Ce³⁺ / La³⁺ and reducing costs.

[0103] Combined with Examples 3 to 6, the particle size / aspect ratio of the HA nanowires used in Examples 3 to 6 is different from that in Example 2, wherein the corrosion resistance is from high to low as follows: Example 2, Example 6, Example 4, Example 3, and Example 5; the adhesion of Example 2 and Examples 3 to 6 is equal; the wear resistance is from high to low as follows: Example 2, Example 6, Example 4, Example 3, and Example 5; the film hardness is from high to low as follows: Example 2, Example 6, Example 4, Example 3, and Example 5. It can be seen that considering the performance comprehensively, Example 2 is the best, followed by Example 6. Therefore, in this application, the diameter of the HA nanowire is 50±5nm, and the aspect ratio is 10:1, which is better.

[0104] Comparing Example 1 and Example 7, Example 7 further adds silane surface-modified BTA microcapsules on the basis of Example 1. The test results show that the corrosion resistance, adhesion level, wear resistance and film hardness of Example 7 are similar to those of Example 1. Therefore, in this application, the BTA microcapsules are added after being modified with a silane coupling agent, which reduces the strength and corrosion resistance of the composite film layer less. In addition, this application also tests the self-repair efficiency of Example 1 and Example 7. Example 1 does not have self-repair performance, while Example 7 has self-repair performance. Therefore, in this application, BTA microcapsules are introduced into the composite film layer through BTA microcapsules, which is adaptively released when the composite film layer is damaged by mechanical external force, and can cover scratches and inhibit corrosion, thereby further improving the corrosion resistance of the composite film layer in actual application.

[0105] By comparing Example 1, Example 8, and Comparative Example 5, it can be seen that the sealing liquid of Example 8 further contains polyoxyethylene sorbitan monooleate compared with Example 1, and the sealing treatment temperature of Example 8 is lower than that of Example 1; compared with Example 1, polyoxyethylene sorbitan monooleate is not added to Comparative Example 5, and the sealing treatment temperature of Comparative Example 5 is lower than that of Example 1.

[0106] In the test results, the corrosion resistance, adhesion, wear resistance and film hardness of Example 8 are similar to those of Example 1, while the corrosion resistance, adhesion, wear resistance and film hardness of Comparative Example 5 are significantly lower than those of Example 1. Therefore, in the present application, polyoxyethylene dehydrated sorbitan monooleate can target Ce³⁺ / La³⁺ and can also reduce the formation of a directional hydrophilic-hydrophobic layer by adsorbing on the surface of the oxide film, stabilizing the reaction intermediate state (such as Ce(OH)3 colloid nucleation) to reduce the activation energy of the hydration reaction, and the polyethylene oxide chain forms a weak coordination with Ce³⁺ / La³⁺, thereby promoting the uniform adsorption of rare earth ions on the surface of the oxide film and reducing the local concentration gradient, thereby achieving low-temperature and efficient mass transfer and reducing the sealing treatment temperature requirement.

[0107] Comparing Example 1 and Example 9, the difference between the two is whether polyethylene glycol 4000 is added to the anodizing liquid. The corrosion resistance, adhesion, wear resistance and film hardness of Example 1 are all better than those of Example 9. Therefore, polyethylene glycol 2000 is added in this application to be adsorbed on the inner wall of the membrane pore to form a temporary template to guide the growth of the gradient structure, thereby improving the density and bonding force of the composite film layer, and further improving the corrosion resistance, adhesion and strength of the composite film layer.

[0108] Comparing Example 1 and Example 10, Example 1 adopts high current density first and then low current density for anodization compared to Example 10. The corrosion resistance, adhesion, wear resistance and film hardness of Example 1 are all better than those of Example 10. Therefore, in this application, an initial high current density is adopted to quickly form a dense layer, and the steady-state stage is reduced to maintain uniform deposition, so that the composite film layer is dense and has less thickness deviation, the porosity gradient of the composite film precursor-oxide film is smoother, and the composite film layer has better corrosion resistance, adhesion and strength.

[0109] Comparing Examples 2 and 11, Example 11 incorporates not only HA nanowires and sodium polyacrylate but also polyoxyethylene sorbitan monooleate, and achieves a lower sealing temperature. The corrosion resistance, wear resistance, and film hardness of Example 11 are all improved compared to the already superior performance of Example 2. Therefore, polyoxyethylene sorbitan monooleate can be used synergistically with HA nanowires and sodium polyacrylate in this application.

[0110] Comparing Examples 7 and 12, Example 12 not only incorporates BTA microcapsules but also polyoxyethylene sorbitan monooleate, and the sealing temperature is lower. Example 12 exhibits improved corrosion resistance compared to Example 7, and also exhibits enhanced self-healing efficiency. Therefore, polyoxyethylene sorbitan monooleate can be used together with BTA microcapsules in this application, achieving a synergistic effect.

[0111] Combined with Example 13, it can be seen that HA nanowires, sodium polyacrylate, polyoxyethylene sorbitan monooleate, and BTA microcapsules are added to the sealing liquid of Example 13 at the same time, and the sealing temperature is low. The corrosion resistance, wear resistance, and film hardness of Example 13 are all improved. Therefore, the HA nanowires, sodium polyacrylate, polyoxyethylene sorbitan monooleate, and BTA microcapsules of the present application can be used in combination. During use, polyoxyethylene sorbitan monooleate can also act as a surfactant to stabilize the dispersion of HA nanowires and BTA microcapsules, so that the effects of both can be exerted.

[0112] In this regard, there are also Examples 14 to 15, which are based on the superiority of Example 13 during the research process. Compared with Comparative Examples 1 to 3, their corrosion resistance, adhesion, wear resistance, and film hardness are significantly improved.

[0113] This specific embodiment is merely an explanation of the present invention and is not a limitation of the present invention. After reading this specification, those skilled in the art may make non-creative modifications to this embodiment as needed. However, as long as the modifications are within the scope of protection required by the present invention, they will be protected by patent law.

Claims

1. An aluminum alloy coated conductor for ship armored cables, characterized in that: It includes a wire core, and the wire core is made of aluminum alloy. The surface of the conductor core is also subjected to anodizing and sealing treatments to form a composite film layer; The sealing liquid used in the sealing treatment comprises deionized water, a silane coupling agent, cerium nitrate, lanthanum nitrate, deionized water, and a pH regulator; The mass proportion of the silane coupling agent is 2~5wt%, the mass proportion of cerium nitrate is 0.15~0.3wt%, and the mass proportion of lanthanum nitrate is 0.05~0.1wt%.

2. The aluminum alloy coated conductor for ship armored cables according to claim 1, characterized in that: The sealing liquid further comprises sodium polyacrylate and dispersed hydroxyapatite (HA) nanowires; the mass proportion of sodium polyacrylate is 0.1-0.12 wt%; the mass proportion of hydroxyapatite (HA) nanowires is 1-1.5 wt%.

3. The aluminum alloy coated conductor for ship armored cables according to claim 2, characterized in that: The hydroxyapatite (HA) nanowire has a diameter of 45-55 nm and a length of 450-550 nm.

4. The aluminum alloy coated conductor for ship armored cables according to claim 1, characterized in that: The sealing liquid further comprises dispersed urea-formaldehyde resin microcapsules containing benzotriazole (BTA); the surface of the urea-formaldehyde resin microcapsules is modified with a silane coupling agent; and the mass proportion of the urea-formaldehyde resin microcapsules is 1.5-2 wt%.

5. The aluminum alloy coated conductor for ship armored cables according to claim 1, 2 or 4, characterized in that: The sealing liquid further comprises 0.05-0.1 wt % of polyoxyethylene sorbitan monooleate.

6. The aluminum alloy coated conductor for ship armored cables according to claim 1, characterized in that: After the anodizing treatment, the conductor core is first subjected to an argon-oxygen atmosphere low-temperature plasma treatment and then to a sealing treatment.

7. The aluminum alloy coated conductor for ship armored cables according to claim 1, characterized in that: The anodizing solution for the anodizing treatment includes sulfuric acid, citric acid, and polyethylene glycol 2000.

8. The aluminum alloy coated conductor for ship armored cables according to claim 7, characterized in that: The anodizing treatment parameters are as follows: an initial current density of 2±0.05A / dm², a voltage gradually transitioning to 15V over 3-3.5 minutes, and then maintaining a current density of 1.5±0.05A / dm².

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