WO2024098749A1 - Anodic oxidation process method for aluminum-based composite material of launch vehicle - Google Patents

Anodic oxidation process method for aluminum-based composite material of launch vehicle Download PDF

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WO2024098749A1
WO2024098749A1 PCT/CN2023/100639 CN2023100639W WO2024098749A1 WO 2024098749 A1 WO2024098749 A1 WO 2024098749A1 CN 2023100639 W CN2023100639 W CN 2023100639W WO 2024098749 A1 WO2024098749 A1 WO 2024098749A1
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solution
aluminum
based composite
concentration
anodic oxidation
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PCT/CN2023/100639
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French (fr)
Chinese (zh)
Inventor
李曼
尚洪帅
王帅东
邹松华
王琳
黄杰
钱伟
朱悦宏
赵彦广
刘静
刘钧
丁艳霞
刘东平
尹禹喆
郭良帅
常保杰
张富
季霖
刘会彬
张昕宇
徐方强
刘铭锦
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天津航天长征火箭制造有限公司
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Publication of WO2024098749A1 publication Critical patent/WO2024098749A1/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/16—Pretreatment, e.g. desmutting
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment

Definitions

  • the invention belongs to the field of aerospace, and in particular relates to an anodizing process method for aluminum-based composite materials for launch vehicles.
  • aluminum-based composite materials Compared with conventional aluminum alloys, aluminum-based composite materials have high specific modulus, good ductility, high specific strength, superior fatigue limit and other good properties, and have been rapidly developed. They are widely used in aerospace, warships, electric vehicles and other fields. Among them, aluminum-based composite materials will be used as tank structural materials in DY, heavy and other types of space launch vehicles due to their better comprehensive performance.
  • aluminum-based composite materials will suffer various forms of damage in corrosive environments, such as pitting, galvanic corrosion between the matrix and the reinforcement phase, etc. These limit its application in environments with higher corrosion resistance. Therefore, it is necessary to propose a method to improve the corrosion resistance of aluminum-based composite materials to further expand its application range.
  • the method for improving the corrosion resistance of aluminum-based composite materials is generally to use anodizing treatment.
  • This process mainly involves anodizing the aluminum-based composite material in an acidic solution to form an oxide film on its surface to improve the corrosion resistance of the aluminum-based composite material.
  • an anodizing method is used to obtain a film layer on the surface of an aluminum-based boron carbide composite material to improve the corrosion resistance.
  • this method can improve the corrosion resistance of aluminum-based boron carbide composite materials, its process is particularly complicated and difficult to be applied industrially.
  • a chemical plating method is used to obtain good wear resistance and corrosion resistance on the surface of aluminum-based composite materials, but the plating solution used is very complex, including nickel sulfate, sodium hypophosphite, rare earth metal salts, citric acid, polyvinyl alcohol, polyethylene glycol, sulfuric acid aqueous solution, tetramethylammonium hydroxide, sodium carboxymethyl cellulose and boron nitride, so the cost is relatively high.
  • the present invention aims to propose an anodizing process method for aluminum-based composite materials for launch vehicles to solve the problems of complex plating solution composition and high cost.
  • a method for anodizing a launch vehicle aluminum-based composite material comprising the following steps: S1: pre-treating the product;
  • step S2 performing anodizing process on the product after being processed in step S1;
  • step S3 The product obtained in step S2 is sealed in a K 2 Cr 2 O 7 solution for the first layer, and the product is placed in a mixed solution containing sodium stearate for the second layer.
  • step S2 includes electrolysis in an anodizing solution for a certain period of time
  • the anodic oxidation solution is a solution containing H 2 SO 4 and Al 3+ , the electrolysis temperature is 13-22° C., the electrolysis voltage is 18-22 V, and the electrolysis time is 30-55 min.
  • the anodizing solution includes sulfuric acid, oxalic acid, malic acid, glycerol, sodium gluconate, sodium dodecylbenzene sulfonate, and salt compounds of Al 3+ ;
  • the concentration of sulfuric acid in the anodic oxidation solution is 160g/L ⁇ 200g/L; the concentration of oxalic acid in the anodic oxidation solution is 5ml/L ⁇ 10ml/L; the concentration of malic acid in the anodic oxidation solution is 7ml/L ⁇ 15ml/L.
  • the concentration of Al3+ in the anodizing solution is 1-3 g/L
  • the concentration of glycerol in the anodizing solution is 2 ml/L-5 ml/L
  • the concentration of sodium gluconate in the anodizing solution is 5 g/L-7 g/L
  • the concentration of sodium dodecylbenzene sulfonate in the anodizing solution is 3 g/L-6 g/L.
  • Aluminum-based composite materials are made by adding TiB2 particles to an aluminum matrix. During the conventional sulfuric acid anodizing process, the particles tend to agglomerate. When the agglomerated particles are large in size, they will fall off, resulting in an uneven surface of the product, pores of varying sizes, uneven pore distribution, and incomplete film layers, which seriously affects the corrosion resistance of the anodized film layer.
  • a buffer film layer that greatly reduces the concentration of hydrogen ions can be formed on the metal surface, resulting in a decrease in the dissolution rate of the film, reducing the agglomeration of TiB 2 particles, increasing the oxide film generation rate, film thickness and hardness, and at the same time, evenly forming holes on the porous layer of the anodized film layer, making the anodized film layer uniform and flat, and effectively improving the compactness of the film layer.
  • the thickness and hardness of the oxide film layer finally obtained are significantly improved, the pore size consistency of the porous layer is increased, the size is reduced, and the pore distribution is more uniform, and the corrosion resistance of the film layer is significantly improved.
  • the first layer sealing in step S3 includes sealing in a K 2 Cr 2 O 7 solution at a certain temperature for a certain period of time;
  • the concentration of K 2 Cr 2 O 7 in the first sealing layer is 70g/L-100g/L;
  • the temperature is 70-90° C. and the sealing time is 30-45 minutes.
  • the second layer of sealing in step S4 includes sealing in a mixed solution containing sodium stearate at a certain temperature for a certain period of time;
  • the temperature is 80-90°C and the time is 45-50 minutes;
  • the mixed solution includes lithium silicate, lithium acetate, sodium stearate, alcohol, potassium sulfate and ammonia water.
  • Lithium silicate is a high-purity stable sol that has many important characteristics of soluble silicates and silica gel. It is a water-based, colorless, odorless, non-flammable, weakly alkaline, transparent, high-temperature resistant inorganic binder. Soluble in water and alkaline solution, insoluble in alcohol and organic solvents. It reacts with acid to form gel. It can self-cure to form a water-insoluble dry film. It can be used in polymer reinforcement materials, coatings and glass surface modification. Due to the unique partial ionization of lithium silicate and the particle size distribution characteristics of partial sol, it can form much better coating and bonding properties than ordinary silica sol. Polylithium silicate has no flash point, and its only volatile matter is water;
  • Lithium silicate aqueous solution is self-drying and can form a dry film that is insoluble in water, and has excellent resistance to alternating wet and dry conditions.
  • Lithium silicate aqueous solution precipitates when heated, but if the precipitate is not overheated or dehydrated, it can be dissolved again after cooling.
  • Lithium silicate aqueous solution has the characteristic of forming a film by reacting with the surface of glass, steel, aluminum and fiber with hydrophilic surface, which can be carried out above 60°C. The higher the temperature, the faster the reaction.
  • lithium silicate aqueous solution Due to the unique properties of lithium silicate aqueous solution, it has a wide range of uses.
  • a coating base material water can be used as a solvent.
  • the coating film formed has the general properties of inorganic coatings such as heat resistance, non-flammability, radiation resistance, and non-toxicity, and is also self-drying, heat-resistant up to 1000°C, wear resistance, moisture resistance, weather resistance, good resistance to alternating dry and wet conditions, and excellent water resistance. It can be used in offshore engineering, oil pipelines, ships, bridges, and architectural coatings and coatings for building materials, such as bathrooms, kitchens, toilets, buildings, various components, and coatings for cement, concrete, asbestos tiles, aluminum, iron, wood materials, synthetic resins, ceramics, etc. It is especially suitable for humid environments and water-resistant decorative coatings.
  • the mass fraction of lithium silicate in the mixed solution is 7-20%, the mass fraction of lithium acetate in the mixed solution is 5-10%; the concentration of sodium stearate in the mixed solution is 2-5 g/L, the concentration of alcohol in the mixed solution is 10-15 g/L; the concentration of potassium sulfate in the mixed solution is 20-30 g/L, and ammonia water is added to the mixed solution to adjust the pH of the mixed solution to 7.5-9.
  • the pretreatment in step S1 includes: degreasing process, etching process, and polishing process; the degreasing process includes organic degreasing or chemical degreasing, requiring that the metal surface is free of oil stains, dirt and other excess substances, and the surface water film is continuous.
  • the etching process includes treating in a etching solution at a certain temperature for a certain time;
  • the temperature is 40-60°C and the time is 0.5-1 min.
  • the etching solution includes NaOH and NaF.
  • the concentration of NaOH in the etching solution is 30 g/L to 70 g/L.
  • the concentration of NaF in the etching solution is 45 g/L to 70 g/L.
  • the light extraction process includes treating in a light extraction solution at a certain temperature for a certain time;
  • the temperature is room temperature and the treatment time is 0.5 to 3 minutes;
  • the emitting solution is HNO 3 solution, and the concentration of the HNO 3 solution is 150 g/L to 300 g/L.
  • the anodizing process of the aluminum-based composite material for a launch vehicle described in the present invention has the following beneficial effects:
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • a launch vehicle aluminum-based composite material anodizing process method comprises the following steps:
  • step S2 performing anodizing process on the product after being processed in step S1;
  • step S3 The product obtained in step S2 is sealed in a K 2 Cr 2 O 7 solution for the first layer, and the product is placed in a mixed solution containing sodium stearate for the second layer.
  • Clamping parts chemical degreasing - hot water cleaning - cold water cleaning - polishing - cold water cleaning - alkali corrosion - cold water cleaning Washing - polishing - cold water cleaning - pure water cleaning - anodizing - cold water cleaning - first layer sealing - cold water washing - second layer sealing - cold water washing - drying - disassembly of parts - packaging.
  • the anodizing process in step S2 includes electrolyzing in an anodizing solution for a certain period of time;
  • the anodic oxidation solution is a solution containing H 2 SO 4 and Al 3 +, the electrolysis temperature is 13-22°C, the electrolysis voltage is 18-22V, and the electrolysis time is 30-55min.
  • the anodic oxidation solution includes salt compounds of sulfuric acid, oxalic acid, malic acid, glycerol, sodium gluconate, sodium dodecylbenzene sulfonate, and Al3 +;
  • the concentration of sulfuric acid in the anodic oxidation solution is 160g/L to 200g/L; the concentration of oxalic acid in the anodic oxidation solution is 5ml/L to 10ml/L; the concentration of malic acid in the anodic oxidation solution is 7ml/L to 15ml/L, the concentration of Al3+ in the anodic oxidation solution is 1 to 3g/L, the concentration of glycerol in the anodic oxidation solution is 2ml/L to 5ml/L, the concentration of sodium gluconate in the anodic oxidation solution is 5g/L to 7g/L, and the concentration of sodium dodecylbenzene sulfonate in the anodic oxidation solution is 3g/L to 6g/L.
  • Step S3 The first layer of sealing includes sealing in K 2 Cr 2 O 7 solution at a certain temperature for a certain time; the concentration of K 2 Cr 2 O 7 in the first layer of sealing is 70 g/L-100 g/L; preferably, the temperature is 70-90° C., and the sealing time is 30-45 min.
  • the second layer of sealing in step S4 includes sealing in a mixed solution containing sodium stearate at a certain temperature for a certain time; preferably, the temperature is 80-90°C and the time is 45-50 minutes; the mixed solution includes lithium silicate, lithium acetate, sodium stearate, alcohol, potassium sulfate, and ammonia water.
  • the mass fraction of lithium silicate in the mixed solution is 7-20%, the mass fraction of lithium acetate in the mixed solution is 5-10%; the concentration of sodium stearate in the mixed solution is 2-5 g/L, the concentration of alcohol in the mixed solution is 10-15 g/L; the concentration of potassium sulfate in the mixed solution is 20-30 g/L, and ammonia water is added to the mixed solution to adjust the pH of the mixed solution to 7.5-9.
  • the pretreatment in step S1 includes: degreasing process, etching process, and polishing process; the degreasing process includes organic degreasing or chemical degreasing, requiring that the metal surface is free of oil stains, dirt and other excess substances, and the surface water film is continuous.
  • the etching process includes treating a certain temperature in a corrosive solution. Preferably, the temperature is 40-60°C and the time is 0.5-1 min.
  • the etching solution includes NaOH and NaF, the concentration of NaOH in the etching solution is 30 g/L to 70 g/L, and the concentration of NaF in the etching solution is 45 g/L to 70 g/L.
  • the light extraction process includes treating in a light extraction solution for a certain time at a certain temperature; preferably, the temperature is room temperature and the treatment time is 0.5 to 3 minutes; the light extraction solution is HNO3 solution, and the concentration of the HNO3 solution is 150g/L to 300g/L.
  • the remaining conditions are the same as those in Example 1, except that the second layer of blocking solution in step S3 is changed to a stearic acid solution, the solvent of the stearic acid solution is ethanol, the molar concentration of stearic acid is 0.01 mol/L, and the second layer of blocking time in step three is changed to 4 to 4.5 h.
  • Example 1 Salt spray test was carried out on Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3, and the corrosion resistance thereof is shown in the table.
  • the thickness of the ordinary aluminum alloy anodized film is 15um to 25um, while the thickness of the film produced by the aluminum-based composite material anodizing method in this patent is 22 to 37um, and the film thickness increases by 7um to 12um.
  • the processing tolerance requirement of products using aluminum-based composite materials is ⁇ 200um. Therefore, the growth of the anodized film layer of the launch vehicle aluminum-based composite material parts produced by the aluminum-based composite material anodizing process method in this patent is basically negligible relative to the assembly tolerance requirement.

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Abstract

The present invention provides an anodic oxidation process method for an aluminum-based composite material of a launch vehicle, comprising the following steps: S1: pretreating a product; S2: carrying out an anodic oxidation process on the product treated in step S1; and S3: carrying out first layer sealing on the product obtained in step S2 in a K2Cr2O7 solution, and placing the product in a mixed solution containing sodium stearate for second layer sealing. The anodic oxidation process method for an aluminum-based composite material of a launch vehicle of the present invention solves the problem of corrosion of aluminum-based composite materials in new-generation launch vehicles. When a product produced according to the anodic oxidation process method for an aluminum-based composite material was subjected to performance testing according to QJ 469 (Specifications for sulfuric acid anodized coatings on aluminum and aluminum alloys), it was found that the test piece passed the salt spray test, demonstrating corrosion resistance meeting the requirements of 336 hours of neutral salt spray testing, thereby being capable of effectively ensuring the corrosion resistance and corrosion aging resistance of the anodized film on the product.

Description

一种运载火箭铝基复合材料阳极氧化工艺方法A kind of anodizing process method of aluminum-based composite material for launch vehicle 技术领域Technical Field
本发明属于航空航天领域，尤其是涉及一种运载火箭铝基复合材料阳极氧化工艺方法。The invention belongs to the field of aerospace, and in particular relates to an anodizing process method for aluminum-based composite materials for launch vehicles.
背景技术Background technique
铝基复合材料相对于常规铝合金，具有高比模量、良好的延展性、高比强度、优越的疲劳极限等良好性能得到迅速发展，它广泛应用于航空航天、军舰、电动汽车等领域。其中，铝基复合材料因其综合性能较佳，将作为贮箱结构材料，应用于DY、重型等型号的航天运载火箭中。Compared with conventional aluminum alloys, aluminum-based composite materials have high specific modulus, good ductility, high specific strength, superior fatigue limit and other good properties, and have been rapidly developed. They are widely used in aerospace, warships, electric vehicles and other fields. Among them, aluminum-based composite materials will be used as tank structural materials in DY, heavy and other types of space launch vehicles due to their better comprehensive performance.
但是铝基复合材料由于增强相的加入导致其在腐蚀环境中会遭受各种破坏形式，如点蚀、基体和增强相之间的电偶腐蚀等。这些都限制了其在耐腐蚀性较高的环境下应用，因此，需要提出一种提高铝基复合材料耐腐蚀性的方法，进一步扩展其应用范围。However, due to the addition of reinforcement phase, aluminum-based composite materials will suffer various forms of damage in corrosive environments, such as pitting, galvanic corrosion between the matrix and the reinforcement phase, etc. These limit its application in environments with higher corrosion resistance. Therefore, it is necessary to propose a method to improve the corrosion resistance of aluminum-based composite materials to further expand its application range.
目前，提高铝基复合材料耐腐蚀性的方法是一般采用阳极氧化处理的方法。该工艺主要是在酸性溶液中对铝基复合材料进行阳极氧化，在其表面生成一层氧化膜来提高铝基复合材料的耐腐蚀性。例如：中国发明专利CN108179451A中，采用阳极氧化的方法在铝基碳化硼复合材料表面获得一层膜层来提高耐腐蚀性。这种方法虽然可以提高铝基碳化硼复合材料耐腐蚀性，但其工艺特别复杂，难以进行工业应用。At present, the method for improving the corrosion resistance of aluminum-based composite materials is generally to use anodizing treatment. This process mainly involves anodizing the aluminum-based composite material in an acidic solution to form an oxide film on its surface to improve the corrosion resistance of the aluminum-based composite material. For example: in Chinese invention patent CN108179451A, an anodizing method is used to obtain a film layer on the surface of an aluminum-based boron carbide composite material to improve the corrosion resistance. Although this method can improve the corrosion resistance of aluminum-based boron carbide composite materials, its process is particularly complicated and difficult to be applied industrially.
另外，中国发明专利CN105063715A中，采用化学镀的方法在铝基复合材料表面获得好的耐磨耐腐蚀性，但其使用的镀液成分十分复杂，包括硫酸镍、次磷酸钠、稀土金属盐、柠檬酸，聚乙烯醇、聚乙二醇、硫酸水溶液、四甲基氢氧化铵、羧甲基纤维素钠和氮化硼，因此成本较高。In addition, in Chinese invention patent CN105063715A, a chemical plating method is used to obtain good wear resistance and corrosion resistance on the surface of aluminum-based composite materials, but the plating solution used is very complex, including nickel sulfate, sodium hypophosphite, rare earth metal salts, citric acid, polyvinyl alcohol, polyethylene glycol, sulfuric acid aqueous solution, tetramethylammonium hydroxide, sodium carboxymethyl cellulose and boron nitride, so the cost is relatively high.
所以，针对铝基复合材料腐蚀要求，开发一种工艺简单、成本更低、耐 腐蚀性好的工艺方法具有重要的意义。Therefore, in view of the corrosion requirements of aluminum-based composite materials, a new A process method with good corrosion resistance is of great significance.
针对2A12、2219等常规铝合金的阳极氧化工艺的研究已较为成熟，但按照现有阳极氧化工艺参数对铝基复合材料进行阳极氧化生产，并按照QJ469《铝及铝合金硫酸阳极化膜层技术条件》进行中性盐雾试验测试，时间仅150h左右，不能满足336h的中性盐雾试验测试要求，不具备保障产品阳极氧化膜层耐蚀性及耐蚀时效的功能。The research on the anodizing process for conventional aluminum alloys such as 2A12 and 2219 is relatively mature. However, the anodizing production of aluminum-based composite materials according to the existing anodizing process parameters and the neutral salt spray test according to QJ469 "Technical Conditions for Sulfuric Acid Anodizing Films of Aluminum and Aluminum Alloys" only takes about 150 hours, which cannot meet the 336-hour neutral salt spray test requirement and does not have the function of ensuring the corrosion resistance and corrosion aging of the product's anodized film.
现有铝基复合材料的阳极氧化工艺极少，而且方法特别复杂，不具备型号批量生产要求；化学镀的方法，镀液成分复杂，且成本较高。There are very few existing anodizing processes for aluminum-based composite materials, and the methods are particularly complex and do not meet the requirements for mass production of models; the chemical plating method has complex plating solution components and is relatively costly.
发明内容Summary of the invention
有鉴于此，本发明旨在提出一种运载火箭铝基复合材料阳极氧化工艺方法，以解决镀液成分复杂、且成本较高的问题。In view of this, the present invention aims to propose an anodizing process method for aluminum-based composite materials for launch vehicles to solve the problems of complex plating solution composition and high cost.
为达到上述目的，本发明的技术方案是这样实现的：To achieve the above object, the technical solution of the present invention is achieved as follows:
一种运载火箭铝基复合材料阳极氧化工艺方法，包括如下步骤：S1：对产品进行预处理；A method for anodizing a launch vehicle aluminum-based composite material, comprising the following steps: S1: pre-treating the product;
S2：对步骤S1处理后的产品进行阳极氧化工序；S2: performing anodizing process on the product after being processed in step S1;
S3：将步骤S2得到的产品在K2Cr2O7溶液中进行第一层封闭，将产品放在含有硬质酸钠的混合溶液中进行第二层封闭。S3: The product obtained in step S2 is sealed in a K 2 Cr 2 O 7 solution for the first layer, and the product is placed in a mixed solution containing sodium stearate for the second layer.
进一步的，步骤S2中的阳极氧化工序包括在阳极氧化溶液中电解一定的时间；Further, the anodizing process in step S2 includes electrolysis in an anodizing solution for a certain period of time;
优选的，阳极氧化溶液为含有H2SO4和Al3+的溶液，电解温度为13-22℃，电解的电压为18-22V，电解的时间为30-55min。Preferably, the anodic oxidation solution is a solution containing H 2 SO 4 and Al 3+ , the electrolysis temperature is 13-22° C., the electrolysis voltage is 18-22 V, and the electrolysis time is 30-55 min.
进一步的，所述阳极氧化溶液包括硫酸、草酸、苹果酸、甘油、葡萄糖酸钠、十二烷基苯磺酸钠、Al3+的盐类化合物；Further, the anodizing solution includes sulfuric acid, oxalic acid, malic acid, glycerol, sodium gluconate, sodium dodecylbenzene sulfonate, and salt compounds of Al 3+ ;
阳极氧化溶液中硫酸的浓度为160g/L～200g/L；阳极氧化溶液中草酸的浓度为5ml/L～10ml/L；阳极氧化溶液中苹果酸的浓度为7ml/L～15ml/L，阳 极氧化溶液中Al3+的浓度为1～3g/L，阳极氧化溶液中甘油的浓度为2ml/L～5ml/L，阳极氧化溶液中葡萄糖酸钠的浓度为5g/L～7g/L，阳极氧化溶液中十二烷基苯磺酸钠的浓度为3g/L～6g/L。The concentration of sulfuric acid in the anodic oxidation solution is 160g/L~200g/L; the concentration of oxalic acid in the anodic oxidation solution is 5ml/L~10ml/L; the concentration of malic acid in the anodic oxidation solution is 7ml/L~15ml/L. The concentration of Al3+ in the anodizing solution is 1-3 g/L, the concentration of glycerol in the anodizing solution is 2 ml/L-5 ml/L, the concentration of sodium gluconate in the anodizing solution is 5 g/L-7 g/L, and the concentration of sodium dodecylbenzene sulfonate in the anodizing solution is 3 g/L-6 g/L.
铝基复合材料为在铝基体中加入TiB2粒子，其在常规硫酸阳极氧化过程中，粒子容易发生团聚现象，当团聚的粒子尺寸较大时，会发生脱落，致使产品表面凹凸不平，孔隙大小不等，孔隙分布不均、膜层不完整，从而严重影响阳极氧化膜层的耐蚀性。Aluminum-based composite materials are made by adding TiB2 particles to an aluminum matrix. During the conventional sulfuric acid anodizing process, the particles tend to agglomerate. When the agglomerated particles are large in size, they will fall off, resulting in an uneven surface of the product, pores of varying sizes, uneven pore distribution, and incomplete film layers, which seriously affects the corrosion resistance of the anodized film layer.
在特定比例范围的硫酸、草酸和苹果酸溶液中，通过控制Al3+的含量，以及添加一定浓度的甘油、葡萄糖酸钠、十二烷基苯磺酸钠等添加剂，在一定工艺条件下，可以在金属表面形成一层使氢离子浓度大幅度降低的缓冲膜层，致使膜的溶解速度降低，降低TiB2粒子的团聚现象，使氧化膜生成率、膜厚和硬度升高，同时使阳极氧化膜层多孔层上的孔洞均匀形成，使阳极氧化膜层均匀平整，有效改善膜层的致密性。最终得到的氧化膜层的厚度、硬度显著提高，多孔层的孔径一致性增加、尺寸变小，且孔隙分布更加均匀，膜层的耐蚀性得到显著提高。In a solution of sulfuric acid, oxalic acid and malic acid within a specific ratio range, by controlling the content of Al 3+ and adding a certain concentration of glycerol, sodium gluconate, sodium dodecylbenzene sulfonate and other additives, under certain process conditions, a buffer film layer that greatly reduces the concentration of hydrogen ions can be formed on the metal surface, resulting in a decrease in the dissolution rate of the film, reducing the agglomeration of TiB 2 particles, increasing the oxide film generation rate, film thickness and hardness, and at the same time, evenly forming holes on the porous layer of the anodized film layer, making the anodized film layer uniform and flat, and effectively improving the compactness of the film layer. The thickness and hardness of the oxide film layer finally obtained are significantly improved, the pore size consistency of the porous layer is increased, the size is reduced, and the pore distribution is more uniform, and the corrosion resistance of the film layer is significantly improved.
进一步的，所述步骤S3第一层封闭包括在一定温度下，在K2Cr2O7溶液中封闭一定的时间；Furthermore, the first layer sealing in step S3 includes sealing in a K 2 Cr 2 O 7 solution at a certain temperature for a certain period of time;
第一层封闭中K2Cr2O7的浓度为70g/L-100g/L；The concentration of K 2 Cr 2 O 7 in the first sealing layer is 70g/L-100g/L;
优选的，温度为70～90℃，封闭的时间为30～45min。Preferably, the temperature is 70-90° C. and the sealing time is 30-45 minutes.
进一步的，所述步骤S4中第二层封闭包括在一定温度下，在含有硬质酸钠的混合溶液中封闭一定的时间；Furthermore, the second layer of sealing in step S4 includes sealing in a mixed solution containing sodium stearate at a certain temperature for a certain period of time;
优选的，温度为80～90℃，时间为45～50min；Preferably, the temperature is 80-90°C and the time is 45-50 minutes;
混合溶液包括硅酸锂、醋酸锂、硬质酸钠、酒精、硫酸钾、氨水。The mixed solution includes lithium silicate, lithium acetate, sodium stearate, alcohol, potassium sulfate and ammonia water.
硅酸锂是一种高纯度的稳定溶胶，兼具可溶硅酸盐和硅胶的许多重要的特点。是一种水性，无色，无味，不燃，弱碱性，透明的耐高温无机粘结剂。 溶于水及碱性溶液，不溶于醇及有机溶剂。与酸作用游离出凝胶。能自固化，生成一种不溶于水的干膜。可用于聚合物增强材料，涂料和玻璃表面改性等方面。由于硅酸锂独特的部分离子化，部分溶胶的粒子尺寸分布特性，跟普通的硅溶胶相比，能形成好得多的涂膜和粘结性能。多聚硅酸锂没有闪点，而且其挥发物只有水；Lithium silicate is a high-purity stable sol that has many important characteristics of soluble silicates and silica gel. It is a water-based, colorless, odorless, non-flammable, weakly alkaline, transparent, high-temperature resistant inorganic binder. Soluble in water and alkaline solution, insoluble in alcohol and organic solvents. It reacts with acid to form gel. It can self-cure to form a water-insoluble dry film. It can be used in polymer reinforcement materials, coatings and glass surface modification. Due to the unique partial ionization of lithium silicate and the particle size distribution characteristics of partial sol, it can form much better coating and bonding properties than ordinary silica sol. Polylithium silicate has no flash point, and its only volatile matter is water;
1、硅酸锂水溶液具有自干性，且能生成不溶于水的干膜，耐干湿交替性极好。2、硅酸锂水溶液在受热时析出沉淀，但如沉淀不过热、不脱水，则在冷却后还能重新溶解。3、硅酸锂水溶液有和具有亲水表面的玻璃、钢铁、铝及纤维等的表面反应成膜的特性，60℃以上即可进行，温度愈高，反应愈快。1. Lithium silicate aqueous solution is self-drying and can form a dry film that is insoluble in water, and has excellent resistance to alternating wet and dry conditions. 2. Lithium silicate aqueous solution precipitates when heated, but if the precipitate is not overheated or dehydrated, it can be dissolved again after cooling. 3. Lithium silicate aqueous solution has the characteristic of forming a film by reacting with the surface of glass, steel, aluminum and fiber with hydrophilic surface, which can be carried out above 60°C. The higher the temperature, the faster the reaction.
由于硅酸锂水溶液的独特性能，因而有其广泛的用途。作为涂料基料，可用水作溶剂，形成的涂膜，除具有无机涂料的耐热、不燃、耐辐射、无毒等一般性能外，还具有自干，耐热可达1000℃，耐磨性、耐湿性、耐侯性、耐干湿交替性佳，耐水性优异等特点。可用于海上工程、石油管道、船舶、桥梁以及建筑涂料和建筑材料用涂料，如浴室、厨房、卫生间、大厦、各种构件，以及水泥、混凝土、石棉瓦、铝、铁、木质材料、合成树脂、陶瓷等的涂装，尤其适宜用于潮湿环境和耐水性装饰涂料。Due to the unique properties of lithium silicate aqueous solution, it has a wide range of uses. As a coating base material, water can be used as a solvent. The coating film formed has the general properties of inorganic coatings such as heat resistance, non-flammability, radiation resistance, and non-toxicity, and is also self-drying, heat-resistant up to 1000°C, wear resistance, moisture resistance, weather resistance, good resistance to alternating dry and wet conditions, and excellent water resistance. It can be used in offshore engineering, oil pipelines, ships, bridges, and architectural coatings and coatings for building materials, such as bathrooms, kitchens, toilets, buildings, various components, and coatings for cement, concrete, asbestos tiles, aluminum, iron, wood materials, synthetic resins, ceramics, etc. It is especially suitable for humid environments and water-resistant decorative coatings.
进一步的，混合溶液中硅酸锂的质量分数为7～20％，混合溶液中醋酸锂的质量分数为5～10％；混合溶液中硬质酸钠的浓度为2～5g/L，混合溶液中酒精的浓度为10～15g/L；混合溶液中硫酸钾的浓度为20～30g/L，混合溶液的氨水，调节混合溶液的pH至7.5～9。Furthermore, the mass fraction of lithium silicate in the mixed solution is 7-20%, the mass fraction of lithium acetate in the mixed solution is 5-10%; the concentration of sodium stearate in the mixed solution is 2-5 g/L, the concentration of alcohol in the mixed solution is 10-15 g/L; the concentration of potassium sulfate in the mixed solution is 20-30 g/L, and ammonia water is added to the mixed solution to adjust the pH of the mixed solution to 7.5-9.
进一步的，所述步骤S1中的预处理包括：除油工序、腐蚀工序、出光工序；除油工序包括采用有机除油或者化学除油，要求金属表面无油迹、污物和其他多余物，表面水膜呈连续状即可。Furthermore, the pretreatment in step S1 includes: degreasing process, etching process, and polishing process; the degreasing process includes organic degreasing or chemical degreasing, requiring that the metal surface is free of oil stains, dirt and other excess substances, and the surface water film is continuous.
进一步的，腐蚀工序包括在一定温度下，在腐蚀溶液中处理一定的时间； Further, the etching process includes treating in a etching solution at a certain temperature for a certain time;
优选的，温度为40-60℃，时间为0.5-1min。Preferably, the temperature is 40-60°C and the time is 0.5-1 min.
腐蚀溶液包括NaOH、NaF，腐蚀溶液中的NaOH的浓度为30g/L～70g/L，腐蚀溶液中NaF的浓度为45g/L～70g/L。The etching solution includes NaOH and NaF. The concentration of NaOH in the etching solution is 30 g/L to 70 g/L. The concentration of NaF in the etching solution is 45 g/L to 70 g/L.
进一步的，所述出光工序包括，在一定温度下，在出光溶液中处理一定的时间；Furthermore, the light extraction process includes treating in a light extraction solution at a certain temperature for a certain time;
优选的，温度为室温，处理的时间为0.5～3min；Preferably, the temperature is room temperature and the treatment time is 0.5 to 3 minutes;
出光溶液为HNO3溶液，HNO3溶液的浓度为150g/L～300g/L。The emitting solution is HNO 3 solution, and the concentration of the HNO 3 solution is 150 g/L to 300 g/L.
相对于现有技术，本发明所述的一种运载火箭铝基复合材料阳极氧化工艺方法具有以下有益效果：Compared with the prior art, the anodizing process of the aluminum-based composite material for a launch vehicle described in the present invention has the following beneficial effects:
解决了新一代运载火箭中铝基复合材料防腐问题。根据铝基复合材料阳极氧化工艺方法生产的产品，按照QJ469《铝及铝合金硫酸阳极化膜层技术条件》进行性能检测，发现试验件通过盐雾试验检测，其耐蚀性满足336h中性盐雾试验要求，能够有效保障产品阳极氧化膜层耐蚀性及耐蚀时效。The corrosion protection problem of aluminum-based composite materials in the new generation of launch vehicles has been solved. The products produced according to the anodizing process of aluminum-based composite materials were tested for performance in accordance with QJ469 "Technical Conditions for Aluminum and Aluminum Alloy Sulfuric Acid Anodizing Film". It was found that the test pieces passed the salt spray test and their corrosion resistance met the requirements of the 336h neutral salt spray test, which can effectively guarantee the corrosion resistance and corrosion resistance time of the product anodized film.
具体实施方式Detailed ways
需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments may be combined with each other.
下面将参考实施例来详细说明本发明。The present invention will be described in detail below with reference to examples.
实施例1：Embodiment 1:
一种运载火箭铝基复合材料阳极氧化工艺方法，包括如下步骤：A launch vehicle aluminum-based composite material anodizing process method comprises the following steps:
S1：对产品进行预处理；S1: Pre-treat the product;
S2：对步骤S1处理后的产品进行阳极氧化工序；S2: performing anodizing process on the product after being processed in step S1;
S3：将步骤S2得到的产品在K2Cr2O7溶液中进行第一层封闭，将产品放在含有硬质酸钠的混合溶液中进行第二层封闭。S3: The product obtained in step S2 is sealed in a K 2 Cr 2 O 7 solution for the first layer, and the product is placed in a mixed solution containing sodium stearate for the second layer.
具体包括：Specifically include:
装卡零件-化学除油-热水清洗-冷水清洗-出光-冷水清洗-碱腐蚀-冷水清 洗-出光-冷水清洗-纯水清洗-阳极氧化-冷水清洗-第一层封闭-冷水洗-第二层封闭-冷水洗-烘干-拆卸零件-包装。Clamping parts - chemical degreasing - hot water cleaning - cold water cleaning - polishing - cold water cleaning - alkali corrosion - cold water cleaning Washing - polishing - cold water cleaning - pure water cleaning - anodizing - cold water cleaning - first layer sealing - cold water washing - second layer sealing - cold water washing - drying - disassembly of parts - packaging.
步骤S2中的阳极氧化工序包括在阳极氧化溶液中电解一定的时间；The anodizing process in step S2 includes electrolyzing in an anodizing solution for a certain period of time;
优选的，阳极氧化溶液为含有H2SO4和Al3+的溶液，电解温度为13-22℃，电解的电压为18-22V，电解的时间为30-55min。阳极氧化溶液包括硫酸、草酸、苹果酸、甘油、葡萄糖酸钠、十二烷基苯磺酸钠、Al3+的盐类化合物；Preferably, the anodic oxidation solution is a solution containing H 2 SO 4 and Al 3 +, the electrolysis temperature is 13-22°C, the electrolysis voltage is 18-22V, and the electrolysis time is 30-55min. The anodic oxidation solution includes salt compounds of sulfuric acid, oxalic acid, malic acid, glycerol, sodium gluconate, sodium dodecylbenzene sulfonate, and Al3 +;
阳极氧化溶液中硫酸的浓度为160g/L～200g/L；阳极氧化溶液中草酸的浓度为5ml/L～10ml/L；阳极氧化溶液中苹果酸的浓度为7ml/L～15ml/L，阳极氧化溶液中Al3+的浓度为1～3g/L，阳极氧化溶液中甘油的浓度为2ml/L～5ml/L，阳极氧化溶液中葡萄糖酸钠的浓度为5g/L～7g/L，阳极氧化溶液中十二烷基苯磺酸钠的浓度为3g/L～6g/L。The concentration of sulfuric acid in the anodic oxidation solution is 160g/L to 200g/L; the concentration of oxalic acid in the anodic oxidation solution is 5ml/L to 10ml/L; the concentration of malic acid in the anodic oxidation solution is 7ml/L to 15ml/L, the concentration of Al3+ in the anodic oxidation solution is 1 to 3g/L, the concentration of glycerol in the anodic oxidation solution is 2ml/L to 5ml/L, the concentration of sodium gluconate in the anodic oxidation solution is 5g/L to 7g/L, and the concentration of sodium dodecylbenzene sulfonate in the anodic oxidation solution is 3g/L to 6g/L.
步骤S3第一层封闭包括在一定温度下，在K2Cr2O7溶液中封闭一定的时间；第一层封闭中K2Cr2O7的浓度为70g/L-100g/L；优选的，温度为70～90℃，封闭的时间为30～45min。Step S3: The first layer of sealing includes sealing in K 2 Cr 2 O 7 solution at a certain temperature for a certain time; the concentration of K 2 Cr 2 O 7 in the first layer of sealing is 70 g/L-100 g/L; preferably, the temperature is 70-90° C., and the sealing time is 30-45 min.
步骤S4中第二层封闭包括在一定温度下，在含有硬质酸钠的混合溶液中封闭一定的时间；优选的，温度为80～90℃，时间为45～50min；混合溶液包括硅酸锂、醋酸锂、硬质酸钠、酒精、硫酸钾、氨水。The second layer of sealing in step S4 includes sealing in a mixed solution containing sodium stearate at a certain temperature for a certain time; preferably, the temperature is 80-90°C and the time is 45-50 minutes; the mixed solution includes lithium silicate, lithium acetate, sodium stearate, alcohol, potassium sulfate, and ammonia water.
混合溶液中硅酸锂的质量分数为7～20％，混合溶液中醋酸锂的质量分数为5～10％；混合溶液中硬质酸钠的浓度为2～5g/L，混合溶液中酒精的浓度为10～15g/L；混合溶液中硫酸钾的浓度为20～30g/L，混合溶液的氨水，调节混合溶液的pH至7.5～9。The mass fraction of lithium silicate in the mixed solution is 7-20%, the mass fraction of lithium acetate in the mixed solution is 5-10%; the concentration of sodium stearate in the mixed solution is 2-5 g/L, the concentration of alcohol in the mixed solution is 10-15 g/L; the concentration of potassium sulfate in the mixed solution is 20-30 g/L, and ammonia water is added to the mixed solution to adjust the pH of the mixed solution to 7.5-9.
步骤S1中的预处理包括：除油工序、腐蚀工序、出光工序；除油工序包括采用有机除油或者化学除油，要求金属表面无油迹、污物和其他多余物，表面水膜呈连续状即可。腐蚀工序包括在一定温度下，在腐蚀溶液中处理一 定的时间；优选的，温度为40-60℃，时间为0.5-1min。腐蚀溶液包括NaOH、NaF，腐蚀溶液中的NaOH的浓度为30g/L～70g/L，腐蚀溶液中NaF的浓度为45g/L～70g/L。The pretreatment in step S1 includes: degreasing process, etching process, and polishing process; the degreasing process includes organic degreasing or chemical degreasing, requiring that the metal surface is free of oil stains, dirt and other excess substances, and the surface water film is continuous. The etching process includes treating a certain temperature in a corrosive solution. Preferably, the temperature is 40-60°C and the time is 0.5-1 min. The etching solution includes NaOH and NaF, the concentration of NaOH in the etching solution is 30 g/L to 70 g/L, and the concentration of NaF in the etching solution is 45 g/L to 70 g/L.
出光工序包括，在一定温度下，在出光溶液中处理一定的时间；优选的，温度为室温，处理的时间为0.5～3min；出光溶液为HNO3溶液，HNO3溶液的浓度为150g/L～300g/L。The light extraction process includes treating in a light extraction solution for a certain time at a certain temperature; preferably, the temperature is room temperature and the treatment time is 0.5 to 3 minutes; the light extraction solution is HNO3 solution, and the concentration of the HNO3 solution is 150g/L to 300g/L.
对比例1：Comparative Example 1:
与实施例1其余条件相同，但未进行步骤S3中的第二层封闭步骤。The remaining conditions were the same as those in Example 1, but the second layer sealing step in step S3 was not performed.
对比例2：Comparative Example 2:
与实施例1其余条件相同，将步骤S3中的第二层封闭液修改为硬脂酸溶液，硬脂酸溶液的溶剂为乙醇，硬脂酸摩尔浓度0.01mol/L，步骤三中二层封闭的时间改为4～4.5h。The remaining conditions are the same as those in Example 1, except that the second layer of blocking solution in step S3 is changed to a stearic acid solution, the solvent of the stearic acid solution is ethanol, the molar concentration of stearic acid is 0.01 mol/L, and the second layer of blocking time in step three is changed to 4 to 4.5 h.
对比例3：Comparative Example 3:
与实施例1其余条件相同，将步骤S3中的第二层封闭液中不含有硅酸锂。The remaining conditions are the same as those in Example 1, except that the second layer of sealing liquid in step S3 does not contain lithium silicate.
对实施例1、对比例1、对比例2、对比例3进行盐雾实验，其耐蚀性如表所示。

Salt spray test was carried out on Example 1, Comparative Example 1, Comparative Example 2 and Comparative Example 3, and the corrosion resistance thereof is shown in the table.

由于铝基复合材料为新研制材料，结构复杂，性能特殊，市场上暂无成熟的封闭工艺。Since aluminum-based composite materials are newly developed materials with complex structures and special properties, there is currently no mature sealing process on the market.
经过调研，采用针对常规铝合金的前沿双层封闭体系，对铝基复合材料进行封闭验证，发现耐蚀性提升效果不明显，难以满足使用要求。After investigation, we used the cutting-edge double-layer sealing system for conventional aluminum alloys to verify the sealing of aluminum-based composite materials, and found that the corrosion resistance improvement effect was not obvious and it was difficult to meet the use requirements.
阳极氧化膜层厚度及封闭层厚度：Anodized film thickness and sealing layer thickness:
在运载火箭零件加工中，普通铝合金阳极氧化膜层厚度15um～25um，而采用本专利中铝基复合材料阳极氧化方法生产的膜层厚度为22～37um，膜层厚度增加7um～12um。根据运载火箭产品装配技术要求可知，采用铝基复合材料的产品其加工公差要求为±200um，所以，采用本专利中铝基复合材料阳极氧化工艺方法生产的运载火箭铝基复合材料零件，阳极氧化膜层的增长量相对装配公差要求，基本可忽略不计。In the processing of launch vehicle parts, the thickness of the ordinary aluminum alloy anodized film is 15um to 25um, while the thickness of the film produced by the aluminum-based composite material anodizing method in this patent is 22 to 37um, and the film thickness increases by 7um to 12um. According to the technical requirements for the assembly of launch vehicle products, it is known that the processing tolerance requirement of products using aluminum-based composite materials is ±200um. Therefore, the growth of the anodized film layer of the launch vehicle aluminum-based composite material parts produced by the aluminum-based composite material anodizing process method in this patent is basically negligible relative to the assembly tolerance requirement.
解决了新一代运载火箭中铝基复合材料防腐问题。根据铝基复合材料阳极氧化工艺方法生产的产品，按照QJ469《铝及铝合金硫酸阳极化膜层技术条件》进行性能检测，发现试验件通过盐雾试验检测，其耐蚀性满足336h中性盐雾试验要求，能够有效保障产品阳极氧化膜层耐蚀性及耐蚀时效。 The corrosion protection problem of aluminum-based composite materials in the new generation of launch vehicles has been solved. The products produced according to the anodizing process of aluminum-based composite materials were tested for performance in accordance with QJ469 "Technical Conditions for Aluminum and Aluminum Alloy Sulfuric Acid Anodizing Film". It was found that the test pieces passed the salt spray test and their corrosion resistance met the requirements of the 336h neutral salt spray test, which can effectively guarantee the corrosion resistance and corrosion resistance time of the product anodized film.

Claims (10)

  1. 一种运载火箭铝基复合材料阳极氧化工艺方法，其特征在于：包括如下步骤：S1：对产品进行预处理；A method for anodizing a launch vehicle aluminum-based composite material, characterized in that it comprises the following steps: S1: pre-treating the product;
    S2：对步骤S1处理后的产品进行阳极氧化工序；S2: performing anodizing process on the product after being processed in step S1;
    S3：将步骤S2得到的产品在K2Cr2O7溶液中进行第一层封闭，将产品放在含有硬质酸钠的混合溶液中进行第二层封闭。S3: The product obtained in step S2 is sealed in a K 2 Cr 2 O 7 solution for the first layer, and the product is placed in a mixed solution containing sodium stearate for the second layer.
  2. 根据权利要求1所述的一种运载火箭铝基复合材料阳极氧化工艺方法，其特征在于：步骤S2中的阳极氧化工序包括在阳极氧化溶液中电解一定的时间；The anodizing process for aluminum-based composite materials for launch vehicles according to claim 1 is characterized in that: the anodizing process in step S2 includes electrolyzing in an anodizing solution for a certain period of time;
    优选的，阳极氧化溶液为含有H2SO4和Al3+的溶液，电解温度为13-22℃，电解的电压为18-22V，电解的时间为30-55min。Preferably, the anodic oxidation solution is a solution containing H 2 SO 4 and Al 3+ , the electrolysis temperature is 13-22° C., the electrolysis voltage is 18-22 V, and the electrolysis time is 30-55 min.
  3. 根据权利要求2所述的一种运载火箭铝基复合材料阳极氧化工艺方法，其特征在于：所述阳极氧化溶液包括硫酸、草酸、苹果酸、甘油、葡萄糖酸钠、十二烷基苯磺酸钠、Al3+的盐类化合物；The anodizing process for aluminum-based composite materials for launch vehicles according to claim 2 is characterized in that: the anodizing solution comprises sulfuric acid, oxalic acid, malic acid, glycerol, sodium gluconate, sodium dodecylbenzene sulfonate, and salt compounds of Al 3+ ;
    阳极氧化溶液中硫酸的浓度为160g/L～200g/L；阳极氧化溶液中草酸的浓度为5ml/L～10ml/L；阳极氧化溶液中苹果酸的浓度为7ml/L～15ml/L，阳极氧化溶液中Al3+的浓度为1～3g/L，阳极氧化溶液中甘油的浓度为2ml/L～5ml/L，阳极氧化溶液中葡萄糖酸钠的浓度为5g/L～7g/L，阳极氧化溶液中十二烷基苯磺酸钠的浓度为3g/L～6g/L。The concentration of sulfuric acid in the anodic oxidation solution is 160g/L to 200g/L; the concentration of oxalic acid in the anodic oxidation solution is 5ml/L to 10ml/L; the concentration of malic acid in the anodic oxidation solution is 7ml/L to 15ml/L, the concentration of Al3+ in the anodic oxidation solution is 1 to 3g/L, the concentration of glycerol in the anodic oxidation solution is 2ml/L to 5ml/L, the concentration of sodium gluconate in the anodic oxidation solution is 5g/L to 7g/L, and the concentration of sodium dodecylbenzene sulfonate in the anodic oxidation solution is 3g/L to 6g/L.
  4. 根据权利要求1所述的一种运载火箭铝基复合材料阳极氧化工艺方法，其特征在于：所述步骤S3第一层封闭包括在一定温度下，在K2Cr2O7溶液中封闭一定的时间；The anodizing process of aluminum-based composite materials for launch vehicles according to claim 1 is characterized in that: the first layer sealing in step S3 includes sealing in a K 2 Cr 2 O 7 solution at a certain temperature for a certain period of time;
    第一层封闭中K2Cr2O7的浓度为70g/L-100g/L；The concentration of K 2 Cr 2 O 7 in the first sealing layer is 70g/L-100g/L;
    优选的，温度为70～90℃，封闭的时间为30～45min。Preferably, the temperature is 70-90° C. and the sealing time is 30-45 minutes.
  5. 根据权利要求1所述的一种运载火箭铝基复合材料阳极氧化工艺方法，其特征在于：所述步骤S4中第二层封闭包括在一定温度下，在含有硬 质酸钠的混合溶液中封闭一定的时间；The anodizing process of aluminum-based composite materials for launch vehicles according to claim 1 is characterized in that: the second layer of sealing in step S4 includes heating the aluminum-based composite materials in a certain temperature in a vessel containing hard The mixture is sealed in a sodium hyaluronic acid solution for a certain period of time;
    优选的，温度为80～90℃，时间为45～50min；Preferably, the temperature is 80-90°C and the time is 45-50 minutes;
    混合溶液包括硅酸锂、醋酸锂、硬质酸钠、酒精、硫酸钾、氨水。The mixed solution includes lithium silicate, lithium acetate, sodium stearate, alcohol, potassium sulfate and ammonia water.
  6. 根据权利要求5所述的一种运载火箭铝基复合材料阳极氧化工艺方法，其特征在于：混合溶液中硅酸锂的质量分数为7～20％，混合溶液中醋酸锂的质量分数为5～10％；混合溶液中硬质酸钠的浓度为2～5g/L，混合溶液中酒精的浓度为10～15g/L；混合溶液中硫酸钾的浓度为20～30g/L，混合溶液的氨水，调节混合溶液的pH至7.5～9。The anodizing process for aluminum-based composite materials for launch vehicles according to claim 5 is characterized in that: the mass fraction of lithium silicate in the mixed solution is 7-20%, the mass fraction of lithium acetate in the mixed solution is 5-10%; the concentration of sodium stearate in the mixed solution is 2-5 g/L, the concentration of alcohol in the mixed solution is 10-15 g/L; the concentration of potassium sulfate in the mixed solution is 20-30 g/L, and ammonia water in the mixed solution is added to adjust the pH of the mixed solution to 7.5-9.
  7. 根据权利要求1所述的一种运载火箭铝基复合材料阳极氧化工艺方法，其特征在于：所述步骤S1中的预处理包括：除油工序、腐蚀工序、出光工序；除油工序包括采用有机除油或者化学除油，要求金属表面无油迹、污物和其他多余物，表面水膜呈连续状即可。According to the anodizing process method for aluminum-based composite materials for launch vehicles as described in claim 1, it is characterized in that the pretreatment in step S1 includes: an oil removal process, an etching process, and a light-emitting process; the oil removal process includes the use of organic oil removal or chemical oil removal, and the metal surface is required to be free of oil stains, dirt and other excess materials, and the surface water film is continuous.
  8. 根据权利要求7所述的一种运载火箭铝基复合材料阳极氧化工艺方法，其特征在于：腐蚀工序包括在一定温度下，在腐蚀溶液中处理一定的时间；The anodizing process for aluminum-based composite materials for launch vehicles according to claim 7 is characterized in that: the corrosion process includes treating in a corrosion solution at a certain temperature for a certain time;
    优选的，温度为40-60℃，时间为0.5-1min。Preferably, the temperature is 40-60°C and the time is 0.5-1 min.
  9. 根据权利要求8所述的一种运载火箭铝基复合材料阳极氧化工艺方法，其特征在于：腐蚀溶液包括NaOH、NaF，腐蚀溶液中的NaOH的浓度为30g/L～70g/L，腐蚀溶液中NaF的浓度为45g/L～70g/L。The anodizing process for aluminum-based composite materials for launch vehicles according to claim 8 is characterized in that the corrosion solution includes NaOH and NaF, the concentration of NaOH in the corrosion solution is 30g/L to 70g/L, and the concentration of NaF in the corrosion solution is 45g/L to 70g/L.
  10. 根据权利要求7所述的一种运载火箭铝基复合材料阳极氧化工艺方法，其特征在于：所述出光工序包括，在一定温度下，在出光溶液中处理一定的时间；The anodizing process for aluminum-based composite materials for launch vehicles according to claim 7 is characterized in that: the light emitting step includes treating in a light emitting solution at a certain temperature for a certain time;
    优选的，温度为室温，处理的时间为0.5～3min；Preferably, the temperature is room temperature and the treatment time is 0.5 to 3 minutes;
    出光溶液为HNO3溶液，HNO3溶液的浓度为150g/L～300g/L。 The emitting solution is HNO 3 solution, and the concentration of the HNO 3 solution is 150 g/L to 300 g/L.
PCT/CN2023/100639 2022-11-11 2023-06-16 Anodic oxidation process method for aluminum-based composite material of launch vehicle WO2024098749A1 (en)

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