Aluminum alloy laminated wire for ship armored cable

Abstract

The application discloses an aluminum alloy film-covered conductor wire for ship armored cable, which comprises a conductor wire core, the conductor wire core is made of aluminum alloy material, and a composite film layer is formed on the surface of the conductor wire core through anodic oxidation treatment and hole sealing treatment; the composition of a hole sealing liquid used for the hole sealing treatment comprises water, a silane coupling agent, cerium nitrate, lanthanum nitrate, deionized water and a pH regulator; the mass percentage of the silane coupling agent is 2-5 wt%, the mass percentage of the cerium nitrate is 0.15-0.3 wt%, and the mass percentage of the lanthanum nitrate is 0.05-0.1 wt%; the hole sealing liquid in the application comprises the silane coupling agent, the cerium nitrate and the lanthanum nitrate, the micropores of the oxide film are passivated through the synergistic effect of rare earth ions and siloxane hydrolysis, the surface point defects are closed by Ce³⁺, the grain boundary linear structure is strengthened by La³⁺, the siloxane hydrolysis adds the dense and reinforced composite film layer, the overall protection is improved in the aspects of points, lines and surfaces, and the corrosion resistance, adhesion and strength of the composite film layer are significantly improved.

Description

Technical Field

[0001] This application relates to armored cables for ships, and more particularly to an aluminum alloy coated conductor for armored cables for ships. Background Technology

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

[0003] Traditional processes mainly employ the following methods: Anodizing: An aluminum oxide (Al2O3) film is generated on the surface of aluminum alloy through electrolysis. However, the film contains micropores and cracks, requiring further sealing treatment, such as hot water sealing or nickel salt sealing. However, current technologies do not completely seal the micropores in the oxide film, allowing corrosive media such as Cl⁻ to easily penetrate, leading to intergranular corrosion and pitting. Furthermore, traditional sealing films have low hardness (HV < 300) and poor wear resistance (> 20 mg / 1000 revolutions), making them prone to damage and failure under the continuous impact of seawater flow and collisions with floating ice / sand. Summary of the Invention

[0004] To improve the protective effect of armored cables for ships, an aluminum alloy coated conductor for armored cables for ships is provided.

[0005] The above-mentioned objective of this invention is achieved through the following technical solutions:

[0006] An aluminum alloy coated conductor for ship armored cables includes a conductor core, wherein the conductor core is made of aluminum alloy.

[0007] The surface of the conductor core is also subjected to anodizing and sealing treatment to form a composite film layer;

[0008] The sealing solution used in the sealing treatment includes deionized water, silane coupling agent, cerium nitrate, lanthanum nitrate, deionized water, and pH adjuster.

[0009] The mass percentage of silane coupling agent is 2-5 wt%, the mass percentage of cerium nitrate is 0.15-0.3 wt%, and the mass percentage of lanthanum nitrate is 0.05-0.1 wt%.

[0010] By adopting the above technical solution, the sealing solution in this application includes silane coupling agent, cerium nitrate, and lanthanum nitrate, which synergistically passivates the micropores of the oxide film through rare earth ions and siloxane hydrolysis:

[0011] Ce³⁺ has a fast hydrolysis rate and preferentially adsorbs onto the pores and cracks on the surface of the oxide film, hydrolyzing to generate Ce(OH)3 colloid, which can quickly seal macropores;

[0012] La³⁺ is different from Ce 3+It diffuses slowly but has a high binding energy. Due to its ionic charge characteristics, it can penetrate from oxide film defects to the aluminum alloy grain boundaries, where it replaces Al³⁺ to form LaAlO3, inhibiting intergranular corrosion; Ce³⁺ covers surface defects, and La³⁺ strengthens grain boundaries.

[0013] The silane coupling agent forms a covalent bond Si-O-Al with the oxide film, and then attaches to the oxide film. Subsequently, it undergoes further hydrobonding to form a Si-O-Si crosslinked network, which densifies and strengthens the oxide film.

[0014] Thus, by sealing surface point defects with Ce³⁺, strengthening grain boundary linear structures with La³⁺, and adding a dense and reinforced composite film layer through siloxane hydrolysis, a comprehensive protection enhancement is achieved in terms of "points, lines, and surfaces." The resulting composite film layer exhibits significantly improved corrosion resistance, adhesion, and strength.

[0015] Optionally, the sealing liquid further includes sodium polyacrylate and dispersed hydroxyapatite (HA) nanowires; the mass percentage of sodium polyacrylate is 0.1~0.12wt%; and the mass percentage of hydroxyapatite (HA) nanowires is 1~1.5wt%.

[0016] By adopting the above technical solution, sodium polyacrylate prevents HA agglomeration through electrostatic repulsion and maintains the monodispersity of nanowires.

[0017] Uniformly dispersed HA nanowires are embedded in the composite film during the sealing process, enhancing mechanical properties through the "whisker toughening effect." Simultaneously, 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. This enhances the strength, corrosion resistance, and wear resistance of the composite film, while also increasing the utilization of Ce³⁺ / La³⁺ and reducing costs.

[0018] Optionally, the hydroxyapatite (HA) nanowires have a diameter of 45-55 nm and a length of 450-550 nm.

[0019] By adopting the above technical solution, the resulting film has superior strength performance, adhesion, and continuity integrity.

[0020] Optionally, the sealing liquid further includes dispersed urea-formaldehyde resin microcapsules containing benzotriazole (BTA); the surface of the urea-formaldehyde resin microcapsules is modified with a silane coupling agent; the mass percentage of the urea-formaldehyde resin microcapsules is 1.5~2wt%.

[0021] By adopting the above technical solution, the silane coupling agent modification treatment can ensure that the urea-formaldehyde resin microcapsules are uniformly dispersed in the sealing liquid and then uniformly embedded in the composite membrane layer, avoiding the reduction of the composite membrane layer's strength and corrosion resistance due to the agglomeration and embedding of the urea-formaldehyde resin microcapsules.

[0022] When the membrane is damaged, the stress breaks through the capsule shell, BTA is released and forms a [Al(BTA)3] complex with Al³⁺, which in turn covers the scratches and inhibits corrosion, thereby further improving the corrosion resistance of the composite membrane in practical applications.

[0023] Optionally, the sealing solution may further include 0.05-0.1 wt% of polyoxyethylene dehydrated sorbitan monooleate.

[0024] By adopting the above technical solution, polyoxyethylene dehydrated 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 reduce the activation energy of hydration reaction by adsorbing Ce³⁺ / La³⁺ onto the oxide film surface to form a directionally arranged hydrophilic-hydrophobic layer, stabilizing the reaction intermediate state (such as Ce(OH)3 colloidal nucleation), and forming a weak coordination between the polyoxyethylene chain and Ce³⁺ / La³⁺, promoting the uniform adsorption of rare earth ions on the oxide film surface, reducing the local concentration gradient, thereby achieving low-temperature and high-efficiency mass transfer and reducing the temperature requirement for sealing treatment.

[0025] Optionally: The conductor core is subjected to argon-oxygen atmosphere low-temperature plasma treatment after anodizing and then sealed.

[0026] 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.

[0027] Optionally, the anodic oxidation solution used in the anodic oxidation treatment includes sulfuric acid, citric acid, and polyethylene glycol 2000.

[0028] 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, reduce metallographic defects at the aluminum alloy interface, and allow polyethylene glycol 2000 to be adsorbed on the inner wall of the membrane pores, forming a temporary template to guide the growth of the gradient structure, thereby improving the density and bonding of the composite film, and thus improving the corrosion resistance, adhesion and strength of the composite film.

[0029] Optionally, the anodizing treatment parameters are: an initial current density of 2±0.05A / dm², with the voltage gradually transitioning to 15V over 3~3.5 minutes; and then maintaining a current density of 1.5±0.05A / dm².

[0030] By adopting the above technical solution, a dense layer is rapidly formed with an initial high current density (2 A / dm²), and the deposition is reduced in the steady state stage to maintain uniformity, resulting in a dense composite film 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.

[0031] In summary, this application has at least the following beneficial effects:

[0032] This application utilizes a multi-level synergistic mechanism of chemical passivation, physical enhancement, and self-healing to achieve long-term protection of shipboard cables and conductors in extreme environments. Detailed Implementation

[0033] Polyethylene glycol 2000, molecular weight 2000±200, white waxy solid, purity ≥99wt%, Maclean product number: P816015;

[0034] Benzotriazole (BTA), white crystalline powder, purity ≥99%, CAS 95-14-7, Anaiji Chemicals catalog number: B1028;

[0035] Tween 20, Anage Chemicals product number: T1023;

[0036] Urea, purity: ≥99% (analytical grade), Maclean's product number: U817980;

[0037] Liquid paraffin, density 0.84 g / cm³, Maclean product number: L817630;

[0038] The silane coupling agent selected is Nanjing Shuguang Chemical KH550, γ-aminopropyltriethoxysilane, CAS No.: 919-30-2;

[0039] Cerium nitrate, a hexahydrate, purity: ≥99wt%, Bailingwei Technology product number: J000890;

[0040] Lanthanum nitrate, a hexahydrate, purity: ≥99wt%, Anaiji Chemicals product number: L1012;

[0041] Sodium polyacrylate, molecular weight 1500±500, Sigma-Aldrich code: 323667;

[0042] Hydroxyapatite (HA) nanowires are products of Xi'an Ruixi Biotechnology. The diameter and aspect ratio specifications are shown in the specific examples.

[0043] Polyoxyethylene dehydrated sorbitan monooleate, CAS No.: 9005-65-6, Sigma-Aldrich part number: P1754.

[0044] Sulfuric acid, citric acid, and ethanol are commercially available analytical grade products.

[0045] Ammonia, hydrochloric acid, and 10wt% nitric acid are commercially available products.

[0046] Preparation Example 1

[0047] An anodizing solution is prepared from sulfuric acid, citric acid, polyethylene glycol 2000, and deionized water. The sulfuric acid concentration is 10 g / L, the citric acid concentration is 4.9 g / L, and the polyethylene glycol 2000 concentration is 0.1 wt%.

[0048] Preparation Example 2

[0049] An anodizing solution is prepared from sulfuric acid, citric acid, and deionized water. The concentration of sulfuric acid is 10 g / L, and the concentration of citric acid is 4.9 g / L.

[0050] Preparation Example 3

[0051] Preparation of urea-formaldehyde resin microcapsules containing benzotriazole (BTA) (hereinafter referred to as BTA microcapsules):

[0052] Add 0.05 kg BTA and 0.03 kg Tween 20 to 0.95 kg of 10 wt% ethanol aqueous solution, stir to dissolve, and obtain the core material solution;

[0053] 1 kg of core material solution was slowly added to 5 kg of liquid paraffin, and homogenized at 10,000 rpm until the droplet size of the dispersed emulsion was 2-5 μm, thus obtaining an water / oil emulsion.

[0054] Urea and 37wt% formaldehyde solution were mixed at a molar ratio of 1:2, stirred in a water bath at 60°C 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.

[0055] 0.75 kg of prepolymer solution was slowly added to 5 kg of water / oil emulsion while maintaining a stirring speed of 700 rpm. The temperature was raised to 55°C and the reaction was carried out for 4 hours. Urea-formaldehyde resin condensed at the oil-water interface to form a wall material.

[0056] The reaction was terminated by adjusting the pH to 7.2 with ammonia. After centrifuging to separate the microcapsules, they were washed three times alternately with ethanol and deionized water to obtain white powdery microcapsules.

[0057] White powdered microcapsules were soaked in an ethanol solution of silane coupling agent (KH550, 1.5wt%). The mass ratio of the white powdered microcapsules to the ethanol solution of silane coupling agent (KH550, 1.5wt%) was 1:8. The soaking time was 30 min. After soaking, the microcapsules were dried at 40℃ to obtain BTA microcapsules.

[0058] Preparation Example 4

[0059] A sealing solution is prepared by mixing a silane coupling agent, cerium nitrate, lanthanum nitrate, a pH adjuster, and deionized water.

[0060] The silane coupling agent is KH550, and the pH adjuster is 10wt% nitric acid.

[0061] The mass percentage of silane coupling agent is 3 wt%, the mass percentage of cerium nitrate is 0.21 wt%, and the mass percentage of lanthanum nitrate is 0.07 wt%.

[0062] The preparation method is as follows:

[0063] Take 70% of the total mass of the pre-prepared sealing solution in deionized water, preheat to 28℃, 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;

[0064] Add silane coupling agent according to the mass ratio, stir continuously at 30°C for 30 minutes, and then let stand for 30 minutes.

[0065] Stir and simultaneously add the remaining deionized water to balance the concentration. During the process, monitor the pH of the solution and add pH adjuster to adjust the pH to 4.2±0.1 if necessary to obtain the sealing solution.

[0066] Preparation Example 5

[0067] A sealing liquid, which differs from Preparation Example 4 in that it uses lanthanum nitrate instead of cerium nitrate in equal molar amounts, i.e., the mass percentage of silane coupling agent is 3 wt% and the mass percentage of lanthanum nitrate is 0.279 wt%.

[0068] Preparation Example 6

[0069] A sealing liquid, which differs from Preparation Example 4 in that it uses cerium nitrate instead of lanthanum nitrate in equal molar amounts, i.e., the mass percentage of silane coupling agent is 3 wt% and the mass percentage of lanthanum nitrate is 0.280 wt%.

[0070] Preparation Example 7

[0071] A sealing solution, which differs from Preparation Example 4, is prepared by mixing cerium nitrate, lanthanum nitrate, pH adjuster and deionized water. That is, no silane coupling agent is added when the sealing solution is prepared. The mass percentage of silane coupling agent in the sealing solution is 0 wt%, the mass percentage of cerium nitrate is 0.21 wt%, and the mass percentage of lanthanum nitrate is 0.07 wt%.

[0072] Preparation Example 8

[0073] A sealing solution is prepared by mixing a silane coupling agent, cerium nitrate, lanthanum nitrate, sodium polyacrylate, HA nanowires, a pH adjuster, and deionized water.

[0074] The silane coupling agent is KH550, and the pH adjuster is 10wt% nitric acid.

[0075] The HA nanowires have a diameter of 50±5 nm and an aspect ratio of 10:1.

[0076] The mass percentage of silane coupling agent is 3 wt%, cerium nitrate is 0.21 wt%, lanthanum nitrate is 0.07 wt%, sodium polyacrylate is 0.11 wt%, and HA nanowires is 1.25 wt%.

[0077] The preparation method is as follows:

[0078] Take 70% of the total mass of the pre-prepared sealing solution in deionized water, preheat to 28℃, 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;

[0079] Add silane coupling agent according to the mass ratio, stir continuously at 30°C for 30 minutes, and then let stand for 30 minutes.

[0080] Add sodium polyacrylate according to the mass ratio, and stir until completely dissolved, resulting in a homogeneous solution without foam.

[0081] Add HA nanowires according to the mass ratio and disperse them under high-speed shearing, then cool to 30°C;

[0082] While stirring, add the remaining deionized water to balance the concentration. During the process, monitor the pH of the solution and add pH adjuster to adjust the pH to 4.2±0.1 if necessary to obtain the sealing solution.

[0083] Preparation Example 9

[0084] A sealing solution, 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 adjuster, and deionized water. Specifically, sodium polyacrylate is not added during the preparation of the sealing solution. The mass percentage of the silane coupling agent in the sealing solution is 3 wt%, the mass percentage of cerium nitrate is 0.21 wt%, the mass percentage of lanthanum nitrate is 0.07 wt%, the mass percentage of sodium polyacrylate is 0 wt%, and the mass percentage of HA nanowires is 1.25 wt%.

[0085] Preparation Example 10

[0086] A sealing liquid, which differs from Preparation Example 8 in that the HA nanowires have a diameter of 30±5 nm and an aspect ratio of 10:1.

[0087] Preparation Example 11

[0088] A sealing liquid, which differs from Preparation Example 8 in that the HA nanowires have a diameter of 70±5 nm and an aspect ratio of 10:1.

[0089] Preparation Example 12

[0090] A sealing liquid, which differs from Preparation Example 8 in that the HA nanowires have a diameter of 50±5 nm and an aspect ratio of 8:1.

[0091] Preparation Example 13

[0092] A sealing liquid, which differs from Preparation Example 8 in that the HA nanowires have a diameter of 50±5 nm and an aspect ratio of 12:1.

[0093] Preparation Example 14

[0094] A sealing solution is prepared by mixing a silane coupling agent, cerium nitrate, lanthanum nitrate, BTA microcapsules, a pH adjuster, and deionized water.

[0095] The silane coupling agent was KH550, the pH adjuster was 10 wt% nitric acid, and the BTA microcapsules were prepared in Preparation Example 3.

[0096] The mass percentage of the silane coupling agent is 3 wt%, the mass percentage of cerium nitrate is 0.21 wt%, the mass percentage of lanthanum nitrate is 0.07 wt%, and the mass percentage of BTA microcapsules is 1.75 wt%.

[0097] The preparation method is as follows:

[0098] Take 70% of the total mass of the pre-prepared sealing solution in deionized water, preheat to 28℃, 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;

[0099] Add silane coupling agent according to the mass ratio, stir continuously at 30°C for 30 minutes, and then let stand for 30 minutes.

[0100] Add BTA microcapsules according to the mass ratio and disperse ultrasonically for 10 min (40kHz, 300W).

[0101] While stirring, add the remaining deionized water to balance the concentration. During the process, monitor the pH of the solution and add pH adjuster to adjust the pH to 4.2±0.1 if necessary to obtain the sealing solution.

[0102] Preparation Example 15

[0103] A sealing liquid is prepared by mixing a silane coupling agent, cerium nitrate, lanthanum nitrate, polyoxyethylene dehydrated sorbitan monooleate, a pH adjuster, and deionized water.

[0104] The silane coupling agent is KH550, and the pH adjuster is 10wt% nitric acid.

[0105] The silane coupling agent accounts for 3 wt% of the total mass, cerium nitrate accounts for 0.21 wt% of the total mass, lanthanum nitrate accounts for 0.07 wt% of the total mass, and polyoxyethylene dehydrated sorbitan monooleate accounts for 0.08 wt% of the total mass.

[0106] The preparation method is as follows:

[0107] Take 70% of the total mass of the pre-prepared sealing solution in deionized water, preheat to 28℃, 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;

[0108] Add silane coupling agent according to the mass ratio, stir continuously at 30°C for 30 minutes, and then let stand for 30 minutes.

[0109] Add polyoxyethylene dehydrated sorbitan monooleate according to the mass ratio, and mix thoroughly.

[0110] While stirring, add the remaining deionized water to balance the concentration. During the process, monitor the pH of the solution and add pH adjuster to adjust the pH to 4.2±0.1 if necessary to obtain the sealing solution.

[0111] Preparation Example 16

[0112] A sealing liquid is prepared by mixing a silane coupling agent, cerium nitrate, lanthanum nitrate, polyoxyethylene dehydrated sorbitan monooleate, sodium polyacrylate, HA nanowires, a pH adjuster, and deionized water.

[0113] The silane coupling agent was KH550, and the pH adjuster was 10wt% nitric acid. The HA nanowires had a diameter of 50±5 nm and an aspect ratio of 10:1.

[0114] The mass percentage of silane coupling agent is 3 wt%, cerium nitrate is 0.21 wt%, lanthanum nitrate is 0.07 wt%, polyoxyethylene sorbitan monooleate is 0.08 wt%, sodium polyacrylate is 0.11 wt%, and HA nanowires is 1.25 wt%.

[0115] The preparation method is as follows:

[0116] Take 70% of the total mass of the pre-prepared sealing solution in deionized water, preheat to 28℃, 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;

[0117] Add silane coupling agent according to the mass ratio, stir continuously at 30°C for 30 minutes, and then let stand for 30 minutes.

[0118] Add polyoxyethylene dehydrated sorbitan monooleate according to the mass ratio, and mix thoroughly.

[0119] Add sodium polyacrylate according to the mass ratio, and stir until completely dissolved, resulting in a homogeneous solution without foam.

[0120] Add HA nanowires according to the mass ratio and disperse them under high-speed shearing, then cool to 30°C;

[0121] While stirring, add the remaining deionized water to balance the concentration. During the process, monitor the pH of the solution and add pH adjuster to adjust the pH to 4.2±0.1 if necessary to obtain the sealing solution.

[0122] Preparation Example 17

[0123] A sealing solution is prepared by mixing a silane coupling agent, cerium nitrate, lanthanum nitrate, polyoxyethylene sorbitan monooleate, BTA microcapsules, a pH adjuster, and deionized water.

[0124] The silane coupling agent was KH550, the pH adjuster was 10 wt% nitric acid, and the BTA microcapsules were prepared in Preparation Example 3.

[0125] The mass percentage of silane coupling agent is 3 wt%, cerium nitrate is 0.21 wt%, lanthanum nitrate is 0.07 wt%, polyoxyethylene sorbitan monooleate is 0.08 wt%, and BTA microcapsules are 1.75 wt%.

[0126] The preparation method is as follows:

[0127] Take 70% of the total mass of the pre-prepared sealing solution in deionized water, preheat to 28℃, 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;

[0128] Add silane coupling agent according to the mass ratio, stir continuously at 30°C for 30 minutes, and then let stand for 30 minutes.

[0129] Add polyoxyethylene dehydrated sorbitan monooleate according to the mass ratio, and mix thoroughly.

[0130] Add BTA microcapsules according to the mass ratio and disperse ultrasonically for 10 min (40 kHz, 300 W).

[0131] While stirring, add the remaining deionized water to balance the concentration. During the process, monitor the pH of the solution and add pH adjuster to adjust the pH to 4.2±0.1 if necessary to obtain the sealing solution.

[0132] Preparation Example 18

[0133] A sealing solution is prepared by mixing a silane coupling agent, cerium nitrate, lanthanum nitrate, polyoxyethylene sorbitan monooleate, sodium polyacrylate, HA nanowires, BTA microcapsules, a pH adjuster, and deionized water.

[0134] 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 HA nanowires had a diameter of 50 ± 5 nm and an aspect ratio of 10:1.

[0135] The mass percentage of silane coupling agent is 3 wt%, cerium nitrate is 0.21 wt%, lanthanum nitrate is 0.07 wt%, polyoxyethylene sorbitan monooleate is 0.08 wt%, sodium polyacrylate is 0.11 wt%, HA nanowires are 1.25 wt%, and BTA microcapsules are 1.75 wt%.

[0136] The preparation method is as follows:

[0137] Take 70% of the total mass of the pre-prepared sealing solution in deionized water, preheat to 28℃, 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;

[0138] Add silane coupling agent according to the mass ratio, stir continuously at 30°C for 30 minutes, and then let stand for 30 minutes.

[0139] Add polyoxyethylene dehydrated sorbitan monooleate according to the mass ratio, and mix thoroughly.

[0140] Add sodium polyacrylate according to the mass ratio, and stir until completely dissolved, resulting in a homogeneous solution without foam.

[0141] Add HA nanowires according to the mass ratio and disperse them under high-speed shearing, then cool to 30°C;

[0142] Add BTA microcapsules according to the mass ratio and disperse ultrasonically for 10 min (40 kHz, 300 W).

[0143] While stirring, add the remaining deionized water to balance the concentration. During the process, monitor the pH of the solution and add pH adjuster to adjust the pH to 4.2±0.1 if necessary to obtain the sealing solution.

[0144] Preparation Example 19

[0145] A sealing liquid, which differs from Preparation Example 18 in that the mass percentage of its components is different, specifically, the mass percentage of silane coupling agent is 2 wt%, the mass percentage of cerium nitrate is 0.15 wt%, the mass percentage of lanthanum nitrate is 0.05 wt%, the mass percentage of polyoxyethylene sorbitan monooleate is 0.05 wt%, the mass percentage of sodium polyacrylate is 0.1 wt%, the mass percentage of HA nanowires is 1 wt%, and the mass percentage of BTA microcapsules is 1.5 wt%.

[0146] Preparation Example 20

[0147] A sealing liquid, which differs from Preparation Example 18 in that the mass percentages of its components are different, specifically, the mass percentages of the silane coupling agent are 5 wt%, the mass percentages of cerium nitrate are 0.3 wt%, the mass percentages of lanthanum nitrate are 0.1 wt%, the mass percentages of polyoxyethylene sorbitan monooleate are 0.1 wt%, the mass percentages of sodium polyacrylate are 0.12 wt%, the mass percentages of HA nanowires are 1.5 wt%, and the mass percentages of BTA microcapsules are 2 wt%.

[0148] Example 1

[0149] An aluminum alloy coated conductor for ship armored cables includes a conductor core and a composite film layer outside the conductor core.

[0150] The conductor core is made of aluminum alloy.

[0151] The composite film is formed by anodizing the conductor core, low-temperature plasma treatment, and sealing treatment.

[0152] The preparation method of aluminum alloy coated conductors for ship armored cables is as follows:

[0153] The aluminum alloy wire core is first unwound and then soaked in 5wt% NaOH at 50℃ for 2 minutes, neutralized by water washing, and then soaked in 2wt% nitric acid for 30 seconds to obtain the pretreated core material.

[0154] The pretreated core material was immersed in anodizing solution for anodizing treatment. The anodizing solution was prepared in Preparation Example 1. The anodizing treatment parameters were as follows: the initial current density was 2±0.05A / dm², the voltage was gradually increased to 15V over 3 minutes, and the current density was reduced to 1.5±0.05A / dm². Anodizing was maintained for 50 minutes to form an oxide film on the surface of the conductor core. After drying, the oxide core material was obtained.

[0155] The oxide core material was sent into the plasma reaction chamber, evacuated to 10⁻³Pa, and a mixed gas (argon 50 sccm, oxygen 2.5 sccm) was introduced. It was then treated with a 13.56 MHz radio frequency power supply at 300W for 3 minutes. After the treatment, nitrogen was purged for 8 minutes to obtain the core material to be sealed.

[0156] The core to be sealed was unwound and immersed in the sealing solution for sealing treatment. The sealing treatment temperature was 60°C and the sealing treatment time was 20 min. The sealing solution was the sealing solution prepared in Preparation Example 4.

[0157] After sealing, the wire is rinsed with pure water and then dried at 80°C for 30 minutes to obtain aluminum alloy coated conductors for ship armored cables.

[0158] Comparative Example 1

[0159] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing liquid was prepared in Preparation Example 5.

[0160] Comparative Example 2

[0161] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing liquid was prepared in Preparation Example 6.

[0162] Comparative Example 3

[0163] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing liquid was prepared in Preparation Example 7.

[0164] Example 2

[0165] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing liquid was prepared in Preparation Example 8.

[0166] Comparative Example 4

[0167] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing liquid was prepared in Preparation Example 9.

[0168] Example 3

[0169] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing liquid was prepared in Preparation Example 10.

[0170] Example 4

[0171] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing liquid was prepared in Preparation Example 11.

[0172] Example 5

[0173] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing liquid was prepared in Preparation Example 12.

[0174] Example 6

[0175] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing liquid was prepared in Preparation Example 13.

[0176] Example 7

[0177] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing liquid was prepared in Preparation Example 14.

[0178] Example 8

[0179] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing liquid was prepared in Preparation Example 15, and the sealing treatment temperature was 40°C and the sealing treatment time was 20 min.

[0180] Comparative Example 5

[0181] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing temperature is 40°C and the sealing time is 20 minutes.

[0182] Example 9

[0183] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the anodizing solution was prepared in Example 2.

[0184] Example 10

[0185] 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, maintaining anodizing for 50 minutes to form an oxide film on the surface of the conductor core. After drying, an oxide core material is obtained.

[0186] Example 11

[0187] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing liquid was prepared in Preparation Example 16, and the sealing treatment temperature was 40°C and the sealing treatment time was 20 min.

[0188] Example 12

[0189] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing liquid was prepared in Preparation Example 17, and the sealing treatment temperature is 40°C and the sealing treatment time is 20 min.

[0190] Example 13

[0191] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing liquid was prepared in Preparation Example 18, and the sealing treatment temperature is 40°C and the sealing treatment time is 20 min.

[0192] Example 14

[0193] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing liquid was prepared in Preparation Example 19, and the sealing treatment temperature was 40°C and the sealing treatment time was 20 min.

[0194] Example 15

[0195] An aluminum alloy coated conductor for ship armored cables differs from Example 1 in that the sealing liquid was prepared in Preparation Example 20, and the sealing treatment temperature was 40°C and the sealing treatment time was 20 min.

[0196] The corrosion resistance, adhesion grade, abrasion resistance, film hardness, and self-healing efficiency of Examples 1-15 and Comparative Examples 1-4 were tested.

[0197] Corrosion resistance: Salt spray corrosion test was conducted according to ASTM B117, using 5wt% NaCl solution, neutral salt spray, and 35℃. The surface corrosion condition (such as rust spots, blistering, and peeling) was observed regularly, and the time of the first corrosion was recorded. The longer the time of the first corrosion, the better the corrosion resistance.

[0198] Adhesion: Tested using the cross-cut adhesion test in ASTM D3359. The coating is rated according to the percentage of peeling area, from 0 to 10B, where 10B is no peeling. The less peeling, the better the adhesion.

[0199] Abrasion resistance: According to ASTM D4060, the sample surface was subjected to rotational friction with a 1kg load and a CS-10 grinding wheel using a Taber abrasion tester. The mass loss (mg) of the film layer after every 1000 revolutions was recorded as the result. The less the mass loss, the better the abrasion resistance.

[0200] Film hardness: According to ASTM E384, use a micro Vickers hardness tester (load 0.05kg, HV 0.05) to measure the diagonal length of the indentation and calculate the hardness value (HV). The higher the hardness value, the higher the hardness.

[0201] Self-healing efficiency: The scratch exposure method was used. A standard scratch (50 μm wide) was created on the film surface using a diamond scratcher. The film was then exposed to a 3.5% NaCl solution for 12 hours. The self-healing efficiency was calculated by observing the change in corrosion area of ​​the scratched region under an optical microscope. Self-healing efficiency = (1 − scratch corrosion area / initial scratch area) × 100%. The higher the self-healing efficiency, the better the self-healing performance.

[0202] The test results are shown in Table 1 below.

[0203] Table 1. Detection results of Examples 1-15 and Comparative Examples 1-4

[0204]

[0205] Compared with Comparative Examples 1 and 3, the sealing liquid of Example 1 contains silane coupling agent, cerium nitrate, and lanthanum nitrate. The sealing liquid of Comparative Example 1 contains only silane coupling agent and lanthanum nitrate. The sealing liquid of Comparative Example 2 contains only silane coupling agent and cerium nitrate. The sealing liquid of Comparative Example 3 contains only cerium nitrate and lanthanum nitrate. The test results show that the corrosion resistance, adhesion, wear resistance and hardness of Example 1 are significantly greater than those of Comparative Examples 1 and 3.

[0206] The reason lies in the silane coupling agent, cerium nitrate, and lanthanum nitrate in Example 1, which, through the synergistic passivation of rare earth ions and silanes, passivate the micropores of the oxide film, achieving comprehensive protection enhancement at "points, lines, and surfaces": Ce3⁺ has a fast hydrolysis rate and preferentially adsorbs onto the pores and cracks on the oxide film surface, hydrolyzing to generate Ce(OH)3 colloid, which can quickly seal macropores; La³⁺ is different from Ce 3+ It diffuses slowly but has a high binding energy. Due to its ionic charge characteristics, it can penetrate from the defects in the oxide film to the grain boundaries of the aluminum alloy and replace Al³⁺ at the aluminum alloy grain boundaries to form LaAlO3, which inhibits intergranular corrosion. Ce³⁺ covers surface defects, and La³⁺ strengthens the grain boundaries. The silane coupling agent forms covalent bonds Si-O-Al with the oxide film and then attaches to the oxide film. Subsequently, it undergoes further hydrobonding to form a Si-O-Si crosslinked network, which densifies and strengthens the oxide film.

[0207] Therefore, Ce³⁺ seals surface point defects, La³⁺ strengthens grain boundary linear structures, and siloxane hydrolysis adds a dense and reinforced composite film layer, resulting in a composite film layer with significantly improved corrosion resistance, adhesion, and strength.

[0208] Comparing Example 1, Example 2 and Comparative Example 4, Example 2 further improved upon Example 1 by adding HA nanowires and using sodium polyacrylate to stably and uniformly disperse the HA nanowires in the sealing liquid. During the sealing process, the HA nanowires will be embedded in the composite film layer. Comparative Example 4 added HA nanowires to Example 1, but did not add sodium polyacrylate for auxiliary dispersion.

[0209] In the test results, the corrosion resistance, wear resistance, and film hardness of Example 2 were all improved compared to Example 1. However, the corrosion resistance, adhesion, wear resistance, and film hardness of Comparative Example 4 decreased compared to Example 1. This was because the agglomeration and embedding of HA nanowires into the composite film significantly reduced the density and integrity during the sealing process.

[0210] Therefore, the HA nanowires uniformly embedded in the composite film layer in this application can improve 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. This improves the strength, corrosion resistance and wear resistance of the composite film layer, and also increases the utilization of Ce³⁺ / La³⁺, reducing costs.

[0211] Furthermore, considering Examples 3-6, the particle size / length-to-diameter ratio of the HA nanowires used in Examples 3-6 differs from that in Example 2. The corrosion resistance, from highest to lowest, is as follows: Example 2, Example 6, Example 4, Example 3, Example 5. The adhesion is equal in Examples 2 and 3-6. The wear resistance, from highest to lowest, is as follows: Example 2, Example 6, Example 4, Example 3, Example 5. The film hardness, from highest to lowest, is as follows: Example 2, Example 6, Example 4, Example 3, Example 5. Therefore, considering all performance factors, Example 2 is the best, followed by Example 6. Thus, in this application, a diameter of 50±5nm and a length-to-diameter ratio of 10:1 for the HA nanowires are preferred.

[0212] Comparing Examples 1 and 7, Example 7, based on Example 1, further incorporates silane-modified BTA microcapsules. The test results show that the corrosion resistance, adhesion grade, abrasion resistance, and film hardness of Example 7 are similar to those of Example 1. Therefore, the addition of BTA microcapsules modified with a silane coupling agent in this application results in minimal reduction of the composite film's strength and corrosion resistance. Furthermore, this application also tested the self-healing efficiency of Examples 1 and 7. Example 1 lacked self-healing properties, while Example 7 possessed them. Therefore, this application introduces BTA microcapsules into the composite film, which adaptively releases BTA when the composite film is damaged by mechanical forces. This can cover scratches and inhibit corrosion, thereby further improving the corrosion resistance of the composite film in practical applications.

[0213] Comparing Example 1, Example 8, and Comparative Example 5, it can be seen that the sealing liquid of Example 8 contains polyoxyethylene dehydrated sorbitan monooleate, which is different from that of Example 1, and the sealing treatment temperature of Example 8 is lower than that of Example 1; compared with Example 1, Comparative Example 5 does not contain polyoxyethylene dehydrated sorbitan monooleate, and the sealing treatment temperature of Comparative Example 5 is lower than that of Example 1.

[0214] In the test results, the corrosion resistance, adhesion, wear resistance, and film hardness of Example 8 were similar to those of Example 1, while the corrosion resistance, adhesion, wear resistance, and film hardness of Comparative Example 5 were significantly lower than those of Example 1. Therefore, the polyoxyethylene dehydrated sorbitan monooleate in this application can reduce the hydration reaction activation energy by adsorbing onto the oxide film surface to form a directional hydrophilic-hydrophobic layer, stabilizing the intermediate state of the reaction (such as the nucleation of Ce(OH)3 colloids), and forming a weak coordination between the polyoxyethylene chain and Ce³⁺ / La³⁺, promoting the uniform adsorption of rare earth ions on the oxide film surface, reducing the local concentration gradient, thereby achieving low-temperature and efficient mass transfer and reducing the temperature requirement for sealing treatment.

[0215] Comparing Example 1 and Example 9, the difference lies in whether or not polyethylene glycol 4000 is added to the anodic oxidation solution. The corrosion resistance, adhesion, wear resistance, and film hardness of Example 1 are all better than those of Example 9. Therefore, in this application, polyethylene glycol 2000 is added and adsorbed on the inner wall of the membrane pores to form a temporary template to guide the growth of the gradient structure, thereby improving the density and bonding of the composite film, and thus improving the corrosion resistance, adhesion, and strength of the composite film.

[0216] Comparing Example 1 and Example 10, Example 1 uses a high current density followed by a low current density for anodizing, resulting in better corrosion resistance, adhesion, wear resistance, and film hardness than Example 10. Therefore, in this application, an initial high current density is used to quickly form a dense layer, and the current density is reduced in the steady-state stage to maintain uniform deposition, making the composite film dense with less thickness deviation. The porosity gradient between the precursor and oxide film of the composite film is smoother, and the composite film has better corrosion resistance, adhesion, and strength.

[0217] Compared with Examples 2 and 11, Example 11 not only added HA nanowires and sodium polyacrylate, but also polyoxyethylene dehydrated sorbitan monooleate, and the sealing temperature was lower. The corrosion resistance, wear resistance, and film hardness of Example 11 were all improved compared to the already superior performance of Example 2. Therefore, in this application, polyoxyethylene dehydrated sorbitan monooleate can be used together with HA nanowires and sodium polyacrylate and has a synergistic effect.

[0218] Comparing Examples 7 and 12, Example 12 not only incorporated BTA microcapsules but also polyoxyethylene sorbitan monooleate, and the sealing temperature was lower. Example 12 showed improved corrosion resistance and self-healing efficiency compared to Example 7. Therefore, in this application, polyoxyethylene sorbitan monooleate can be used in conjunction with BTA microcapsules and has a synergistic effect.

[0219] Furthermore, in conjunction with Example 13, it can be seen that the sealing solution of Example 13 simultaneously contains HA nanowires, sodium polyacrylate, polyoxyethylene sorbitan monooleate, and BTA microcapsules, and the sealing temperature is relatively 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 this 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 brought into play.

[0220] Examples 14-15 are also provided, which are superior examples based on the research process of Example 13. Compared with Comparative Examples 1-3, their corrosion resistance, adhesion, wear resistance and film hardness are significantly improved.

[0221] This specific embodiment is merely an explanation of the present invention and is not intended to limit the present invention. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but as long as they are within the scope of protection claimed by the present invention, they are protected by patent law.

Claims

1. An aluminum alloy coated conductor for ship armored cables, characterized in that, Includes a wire core, wherein the wire core is made of aluminum alloy. The surface of the conductor core is also subjected to anodic oxidation treatment, argon-oxygen atmosphere low-temperature plasma treatment, and sealing treatment in sequence to form a composite film layer. The sealing solution used in the sealing treatment includes deionized water, silane coupling agent, cerium nitrate, lanthanum nitrate, deionized water, and pH adjuster. The mass percentage of silane coupling agent is 2-5 wt%, the mass percentage of cerium nitrate is 0.15-0.3 wt%, and the mass percentage of lanthanum nitrate is 0.05-0.1 wt%.

2. The aluminum alloy coated conductor for ship armored cables according to claim 1, characterized in that, The sealing liquid also includes sodium polyacrylate and dispersed hydroxyapatite nanowires; the mass percentage of sodium polyacrylate is 0.1~0.12wt%; and the mass percentage of hydroxyapatite nanowires is 1~1.5wt%.

3. The aluminum alloy coated conductor for ship armored cables according to claim 2, characterized in that, The hydroxyapatite nanowires have 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 also includes dispersed urea-formaldehyde resin microcapsules containing benzotriazole; the surface of the urea-formaldehyde resin microcapsules is modified with a silane coupling agent; the mass percentage of the urea-formaldehyde resin microcapsules is 1.5~2wt%.

5. The aluminum alloy coated conductor for ship armored cables according to claim 1, 2, or 4, characterized in that, The sealing solution also includes 0.05~0.1wt% of polyoxyethylene dehydrated sorbitan monooleate.

6. The aluminum alloy coated conductor for ship armored cables according to claim 1, characterized in that, The anodic oxidation solution used in the anodic oxidation process includes sulfuric acid, citric acid, and polyethylene glycol 2000.

7. The aluminum alloy coated conductor for ship armored cables according to claim 6, characterized in that, The anodizing parameters are as follows: the initial current density is 2±0.05A / dm², the voltage gradually transitions to 15V over 3~3.5 minutes, and then the current density is maintained at 1.5±0.05A / dm².

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