WO2021097664A1 - Method for preparing citric acid catalyzed rare earth-silane composite conversion film - Google Patents
Method for preparing citric acid catalyzed rare earth-silane composite conversion film Download PDFInfo
- Publication number
- WO2021097664A1 WO2021097664A1 PCT/CN2019/119431 CN2019119431W WO2021097664A1 WO 2021097664 A1 WO2021097664 A1 WO 2021097664A1 CN 2019119431 W CN2019119431 W CN 2019119431W WO 2021097664 A1 WO2021097664 A1 WO 2021097664A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rare earth
- silane
- magnesium
- solution
- citric acid
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/57—Treatment of magnesium or alloys based thereon
Definitions
- the invention relates to the technical field of polymer materials, in particular to a preparation method of a citric acid catalyzed rare earth-silane composite conversion film.
- Magnesium-lithium (Mg-Li) alloy is a kind of ultra-light metal material. It has the advantages of low density, high strength, good ductility and good formability. It has broad applications in the automotive, aerospace, military and nuclear industries. Application prospects.
- magnesium itself is an active metal.
- the addition of higher chemically active lithium makes the alloy more likely to corrode in the use environment and is difficult to protect, which limits its wide application. Therefore, the development of effective Mg-Li alloy protection Corrosion technology is very important.
- the surface film treatment is the simplest and most practical, which is widely used in the field of corrosion protection.
- the traditional surface coating process is chromate treatment. The process is simple, the coating has good bonding force, strong corrosion resistance, and repair ability.
- hexavalent chromium is carcinogenic and can cause serious pollution to the environment.
- the rare earth conversion treatment on the metal surface is mainly formed by the deposition of rare earth compounds on the surface of the base metal.
- the process is simple, non-toxic, non-polluting, and low in cost. It has become a hot spot in the research of chromium-free alternative treatment technology.
- the protective film prepared by the existing technology has problems such as thin film layer, unsatisfactory protective performance, unsatisfactory self-healing ability of silane film, and high cost. Therefore, it is necessary to provide a method for preparing a citric acid-catalyzed rare earth-silane composite conversion film.
- the present invention is realized through the following schemes:
- the immersion temperature of the magnesium-aluminum alloy is Alkaline washing in lye at 50-70°C for 10-20 minutes; then rinse the alkaline-washed magnesium-aluminum alloy surface with deionized water for 20-40 minutes and dry to obtain a magnesium-lithium alloy sample;
- the silane sol and the rare earth salt solution are mixed and shaken for 0.1-0.5h to obtain a mixed conversion solution, and the magnesium-lithium alloy sample is immersed in the mixed conversion solution and converted at a temperature of 20-25°C After the treatment, take it out to dry naturally, put it in a blast drying oven at 70-90°C for curing for 20-40 minutes, to obtain a rare earth-silane composite conversion film.
- step 3 the lye solution is prepared by adding 1-3g sodium phosphate, 2-4g sodium carbonate and 2-4g sodium silicate per liter of solution.
- step 4 the conversion is 1-3 times, 0.5-1min each time.
- step four the number of times of drying and curing is the same as the number of times of conversion.
- the preparation method of the citric acid-catalyzed rare earth-silane composite conversion film of the present invention adds hydrogen peroxide and citric acid to the rare earth salt solution at the same time, and utilizes the oxidation effect of hydrogen peroxide and the coupling effect of citric acid in magnesium-lithium alloy
- a dense cerium conversion film is formed on the surface, which makes the magnesium-lithium alloy have good corrosion resistance; hydrogen peroxide can convert Ce 3+ into Ce 4+ , which shows a close-packed condensed spherical structure in the magnesium-lithium alloy; citric acid can The product deposited on the surface of the magnesium-lithium alloy is coupled to form a dense conversion film with citric acid cross-linked cerium oxide and cerium hydroxide as the main components.
- the preparation method of a citric acid-catalyzed rare earth-silane composite conversion film of the present invention adopts a process of multiple conversions and drying and solidification, so that a multilayer rare earth-silane composite conversion film is formed on the surface of a magnesium-lithium alloy to further improve the corrosion resistance;
- the combination of rare earth and silane further improves the anti-corrosion performance of the conversion film.
- the corrosion current density is reduced and the electrochemical impedance is increased.
- the immersion temperature of the magnesium-aluminum alloy is Alkaline washing in lye at 50-70°C for 10-20 minutes; then rinse the alkaline-washed magnesium-aluminum alloy surface with deionized water for 20-40 minutes and dry to obtain a magnesium-lithium alloy sample;
- the silane sol and the rare earth salt solution are mixed and shaken for 0.1-0.5h to obtain a mixed conversion solution, and the magnesium-lithium alloy sample is immersed in the mixed conversion solution and converted at a temperature of 20-25°C After the treatment, take it out to dry naturally, put it in a blast drying oven at 70-90°C for curing for 20-40 minutes, to obtain a rare earth-silane composite conversion film.
- step 3 the lye solution is prepared by adding 1-3g sodium phosphate, 2-4g sodium carbonate and 2-4g sodium silicate per liter of solution.
- step 4 the conversion is 1-3 times, 0.5-1min each time.
- step four the number of times of drying and curing is the same as the number of times of conversion.
- the immersion temperature of the magnesium-aluminum alloy is Alkaline washing in lye at 55°C for 15 minutes; then rinse the alkaline-washed magnesium-aluminum alloy surface with deionized water for 30 minutes and dry to obtain a magnesium-lithium alloy sample;
- the silane sol and the rare earth salt solution were mixed and shaken for 0.2h to obtain a mixed conversion solution, the magnesium-lithium alloy sample was immersed in the mixed conversion solution, and after conversion treatment at a temperature of 20°C, it was taken out Dry naturally, put it in a blast drying oven at 80°C and cure for 35 minutes to obtain a rare earth-silane composite conversion film.
- the lye solution is prepared by adding 2 g of sodium phosphate, 3 g of sodium carbonate and 3 g of sodium silicate per liter of solution.
- step 4 the conversion is 1 time, 1 min each time.
- step four the number of times of drying and curing is the same as the number of times of conversion.
- step 2 6.51g of cerium nitrate, 2mL of hydrogen peroxide and 2mL of hydrogen peroxide are added to each liter of solution. 0.96g citric acid to prepare rare earth salt solution;
- step 4 the conversion is 2 times, 1 min each time.
- step 2 4.34g of cerium nitrate, 2mL of hydrogen peroxide and 2mL of hydrogen peroxide are added to each liter of solution. 1.92g citric acid to prepare rare earth salt solution;
- step 4 the conversion is 3 times, 1 min each time.
- Table 1 List of performance parameters of silane-lanthanum salt composite film on magnesium-lithium alloy surface under different conditions
Abstract
Disclosed is a method for preparing a citric acid catalyzed rare earth-silane composite conversion film, comprising: step 1: preparation of silane sol; step 2: preparation of a rare earth salt solution; step 3: magnesium-lithium alloy surface treatment; and step 4: preparation of a rare earth-silane composite conversion film. The present invention has simple operation, and a uniform and dense cerium conversion film is formed on the surface of a magnesium-lithium alloy, thereby improving the corrosion resistance of the magnesium-lithium alloy.
Description
本发明涉及高分子材料技术领域，尤其是一种柠檬酸催化稀土-硅烷复合转化膜的制备方法。The invention relates to the technical field of polymer materials, in particular to a preparation method of a citric acid catalyzed rare earth-silane composite conversion film.
镁-锂(Mg-Li)合金是一种质量超轻的金属材料，具有密度低、强度高、延展性好和成形性好等优点，在汽车、航空航天、军事及核工业等领域具有广阔的应用前景。然而，镁本身就是一种活泼金属，加入更高化学活性的锂之后，使该合金更易在使用环境中发生腐蚀且难以防护，从而限制了其广泛应用，因此，发展有效的Mg-Li合金防腐蚀技术非常重要。在众多的腐蚀防护方法中，表面膜层处理最为简单实用，广泛应用于防腐蚀领域。传统的表面膜层工艺是铬酸盐处理，其工艺简单，膜层结合力好，耐腐蚀性能强，且具有修复能力，但六价铬具有致癌性，会对环境造成严重污染。金属表面稀土转化处理主要由稀土化合物在基体金属表面沉积而成，工艺简单、无毒、无污染、成本低，已经成为无铬替代处理技术研究的热点。但现有的技术制备的防护膜不同程度的存在膜层薄，防护性能、硅烷膜自愈能力不理想及成本高等问题。因此，需要提供一种柠檬酸催化稀土-硅烷复合转化膜的制备方法。Magnesium-lithium (Mg-Li) alloy is a kind of ultra-light metal material. It has the advantages of low density, high strength, good ductility and good formability. It has broad applications in the automotive, aerospace, military and nuclear industries. Application prospects. However, magnesium itself is an active metal. The addition of higher chemically active lithium makes the alloy more likely to corrode in the use environment and is difficult to protect, which limits its wide application. Therefore, the development of effective Mg-Li alloy protection Corrosion technology is very important. Among the many corrosion protection methods, the surface film treatment is the simplest and most practical, which is widely used in the field of corrosion protection. The traditional surface coating process is chromate treatment. The process is simple, the coating has good bonding force, strong corrosion resistance, and repair ability. However, hexavalent chromium is carcinogenic and can cause serious pollution to the environment. The rare earth conversion treatment on the metal surface is mainly formed by the deposition of rare earth compounds on the surface of the base metal. The process is simple, non-toxic, non-polluting, and low in cost. It has become a hot spot in the research of chromium-free alternative treatment technology. However, the protective film prepared by the existing technology has problems such as thin film layer, unsatisfactory protective performance, unsatisfactory self-healing ability of silane film, and high cost. Therefore, it is necessary to provide a method for preparing a citric acid-catalyzed rare earth-silane composite conversion film.
发明内容Summary of the invention
为了克服现有技术中的缺陷，提供一种柠檬酸催化稀土-硅烷复合转化膜的制备方法。In order to overcome the defects in the prior art, a method for preparing a citric acid-catalyzed rare earth-silane composite conversion film is provided.
本发明通过下述方案实现：The present invention is realized through the following schemes:
一种柠檬酸催化稀土-硅烷复合转化膜的制备方法，A preparation method of citric acid catalyzed rare earth-silane composite conversion film,
步骤一：硅烷溶胶的制备Step 1: Preparation of silane sol
按如下重量份配比称取原料氨基硅烷5-10份，环氧基硅烷15-25份，去离子水10-20份，无水乙醇20-30份；在30-50℃下将氨基硅烷、环氧基硅烷、去离子水和无水乙醇混合配置溶液，用冰醋酸调节溶液的pH为4.55-5.06，搅拌水解7-9h，陈化20-26h，得到硅烷溶胶；Weigh out 5-10 parts of amino silane, 15-25 parts of epoxy silane, 10-20 parts of deionized water, 20-30 parts of anhydrous ethanol according to the following weight parts; , Epoxy silane, deionized water and absolute ethanol mixed to prepare the solution, adjust the pH of the solution to 4.55-5.06 with glacial acetic acid, stir and hydrolyze for 7-9h, and age for 20-26h to obtain a silane sol;
步骤二：稀土盐溶液的制备Step 2: Preparation of rare earth salt solution
按照每升溶液中加入4-10g的硝酸铈、1.5-5mL的过氧化氢和0.9-2g柠檬酸制备稀土盐溶液；Add 4-10g of cerium nitrate, 1.5-5mL of hydrogen peroxide and 0.9-2g of citric acid per liter of solution to prepare a rare earth salt solution;
步骤三：镁锂合金表面处理Step 3: Surface treatment of magnesium-lithium alloy
依次使用240#、800#、1200#和2000#的金相砂纸对镁铝合金表面进行打磨处理，然后抛光处理，得到表面光滑无划痕的镁铝合金；将所述镁铝合金浸入温度为50-70℃的碱液中碱洗10-20min；再用去离子水冲洗碱洗后的镁铝合金表面20-40min，干燥，即得镁锂合金样品；Use 240#, 800#, 1200# and 2000# metallographic sandpaper to polish the surface of magnesium-aluminum alloy, and then polish to obtain a magnesium-aluminum alloy with a smooth surface and no scratches; the immersion temperature of the magnesium-aluminum alloy is Alkaline washing in lye at 50-70°C for 10-20 minutes; then rinse the alkaline-washed magnesium-aluminum alloy surface with deionized water for 20-40 minutes and dry to obtain a magnesium-lithium alloy sample;
步骤四：稀土-硅烷复合转化膜的制备Step 4: Preparation of rare earth-silane composite conversion coating
将所述硅烷溶胶与所述稀土盐溶液混合摇匀0.1-0.5h，得到混合转化液，将 所述镁锂合金样品浸入所述混合转化液中，在温度为20-25℃的条件下转化处理后，取出自然晾干，放入鼓风干燥箱70-90℃固化20-40min，即得稀土-硅烷复合转化膜。The silane sol and the rare earth salt solution are mixed and shaken for 0.1-0.5h to obtain a mixed conversion solution, and the magnesium-lithium alloy sample is immersed in the mixed conversion solution and converted at a temperature of 20-25°C After the treatment, take it out to dry naturally, put it in a blast drying oven at 70-90°C for curing for 20-40 minutes, to obtain a rare earth-silane composite conversion film.
在步骤三中所述碱液按照每升溶液中加入1-3g磷酸钠、2-4g碳酸钠和2-4g硅酸钠制备。In step 3, the lye solution is prepared by adding 1-3g sodium phosphate, 2-4g sodium carbonate and 2-4g sodium silicate per liter of solution.
在步骤四中所述转化为1-3次，每次0.5-1min。In step 4, the conversion is 1-3 times, 0.5-1min each time.
在步骤四中所述干燥固化的次数与所述转化的次数相同。In step four, the number of times of drying and curing is the same as the number of times of conversion.
本发明的有益效果为：The beneficial effects of the present invention are:
1.本发明一种柠檬酸催化稀土-硅烷复合转化膜的制备方法在稀土盐溶液中同时加入过氧化氢和柠檬酸，利用过氧化氢的氧化作用和柠檬酸的偶联作用在镁锂合金表面形成了致密铈转化膜，使得镁锂合金具有良好的防腐蚀性能；过氧化氢可以使Ce
3+转化为Ce
4+，在镁锂合金表现为紧密堆积的凝聚态球形结构；柠檬酸可以偶联在镁锂合金表面沉积的产物，形成以柠檬酸交联的氧化铈和氢氧化铈为主要成分的致密的转化膜。
1. The preparation method of the citric acid-catalyzed rare earth-silane composite conversion film of the present invention adds hydrogen peroxide and citric acid to the rare earth salt solution at the same time, and utilizes the oxidation effect of hydrogen peroxide and the coupling effect of citric acid in magnesium-lithium alloy A dense cerium conversion film is formed on the surface, which makes the magnesium-lithium alloy have good corrosion resistance; hydrogen peroxide can convert Ce 3+ into Ce 4+ , which shows a close-packed condensed spherical structure in the magnesium-lithium alloy; citric acid can The product deposited on the surface of the magnesium-lithium alloy is coupled to form a dense conversion film with citric acid cross-linked cerium oxide and cerium hydroxide as the main components.
2.本发明一种柠檬酸催化稀土-硅烷复合转化膜的制备方法采用多次转化和干燥固化的工艺，使得镁锂合金表面形成多层稀土-硅烷复合转化膜，进一步提高防腐蚀性能；并且稀土和硅烷的复合进一步提高了转化膜的防腐蚀性能，相相比现有的单一硅烷膜，其腐蚀电流密度降低，电化学阻抗升高。2. The preparation method of a citric acid-catalyzed rare earth-silane composite conversion film of the present invention adopts a process of multiple conversions and drying and solidification, so that a multilayer rare earth-silane composite conversion film is formed on the surface of a magnesium-lithium alloy to further improve the corrosion resistance; The combination of rare earth and silane further improves the anti-corrosion performance of the conversion film. Compared with the existing single silane film, the corrosion current density is reduced and the electrochemical impedance is increased.
下面结合具体实施例对本发明进一步说明：The present invention will be further described below in conjunction with specific embodiments:
一种柠檬酸催化稀土-硅烷复合转化膜的制备方法，A preparation method of citric acid catalyzed rare earth-silane composite conversion film,
步骤一：硅烷溶胶的制备Step 1: Preparation of silane sol
按如下重量份配比称取原料氨基硅烷5-10份，环氧基硅烷15-25份，去离子水10-20份，无水乙醇20-30份；在30-50℃下将氨基硅烷、环氧基硅烷、去离子水和无水乙醇混合配置溶液，用冰醋酸调节溶液的pH为4.55-5.06，搅拌水解7-9h，陈化20-26h，得到硅烷溶胶；Weigh out 5-10 parts of amino silane, 15-25 parts of epoxy silane, 10-20 parts of deionized water, 20-30 parts of anhydrous ethanol according to the following weight parts; , Epoxy silane, deionized water and absolute ethanol mixed to prepare the solution, adjust the pH of the solution to 4.55-5.06 with glacial acetic acid, stir and hydrolyze for 7-9h, and age for 20-26h to obtain a silane sol;
步骤二：稀土盐溶液的制备Step 2: Preparation of rare earth salt solution
按照每升溶液中加入4-10g的硝酸铈、1.5-5mL的过氧化氢和0.9-2g柠檬酸制备稀土盐溶液；Add 4-10g of cerium nitrate, 1.5-5mL of hydrogen peroxide and 0.9-2g of citric acid per liter of solution to prepare a rare earth salt solution;
步骤三：镁锂合金表面处理Step 3: Surface treatment of magnesium-lithium alloy
依次使用240#、800#、1200#和2000#的金相砂纸对镁铝合金表面进行打磨处理，然后抛光处理，得到表面光滑无划痕的镁铝合金；将所述镁铝合金浸入温度为50-70℃的碱液中碱洗10-20min；再用去离子水冲洗碱洗后的镁铝合金表面20-40min，干燥，即得镁锂合金样品；Use 240#, 800#, 1200# and 2000# metallographic sandpaper to polish the surface of magnesium-aluminum alloy, and then polish to obtain a magnesium-aluminum alloy with a smooth surface and no scratches; the immersion temperature of the magnesium-aluminum alloy is Alkaline washing in lye at 50-70°C for 10-20 minutes; then rinse the alkaline-washed magnesium-aluminum alloy surface with deionized water for 20-40 minutes and dry to obtain a magnesium-lithium alloy sample;
步骤四：稀土-硅烷复合转化膜的制备Step 4: Preparation of rare earth-silane composite conversion coating
将所述硅烷溶胶与所述稀土盐溶液混合摇匀0.1-0.5h，得到混合转化液，将所述镁锂合金样品浸入所述混合转化液中，在温度为20-25℃的条件下转化处理后，取出自然晾干，放入鼓风干燥箱70-90℃固化20-40min，即得稀土-硅烷复合转化膜。The silane sol and the rare earth salt solution are mixed and shaken for 0.1-0.5h to obtain a mixed conversion solution, and the magnesium-lithium alloy sample is immersed in the mixed conversion solution and converted at a temperature of 20-25°C After the treatment, take it out to dry naturally, put it in a blast drying oven at 70-90°C for curing for 20-40 minutes, to obtain a rare earth-silane composite conversion film.
在步骤三中所述碱液按照每升溶液中加入1-3g磷酸钠、2-4g碳酸钠和2-4g 硅酸钠制备。In step 3, the lye solution is prepared by adding 1-3g sodium phosphate, 2-4g sodium carbonate and 2-4g sodium silicate per liter of solution.
在步骤四中所述转化为1-3次，每次0.5-1min。In step 4, the conversion is 1-3 times, 0.5-1min each time.
在步骤四中所述干燥固化的次数与所述转化的次数相同。In step four, the number of times of drying and curing is the same as the number of times of conversion.
下面结合具体实施例对本申请做进一步阐述。The application will be further elaborated below in conjunction with specific embodiments.
实施例一Example one
一种柠檬酸催化稀土-硅烷复合转化膜的制备方法，A preparation method of citric acid catalyzed rare earth-silane composite conversion film,
步骤一：硅烷溶胶的制备Step 1: Preparation of silane sol
按如下重量份配比称取原料氨基硅烷7份，环氧基硅烷20份，去离子水12份，无水乙醇24份；在35℃下将氨基硅烷、环氧基硅烷、去离子水和无水乙醇混合配置溶液，用冰醋酸调节溶液的pH为4.87，搅拌水解8h，陈化20h，得到硅烷溶胶；Weigh 7 parts of raw amino silane, 20 parts of epoxy silane, 12 parts of deionized water, and 24 parts of anhydrous ethanol according to the following proportions by weight; combine amino silane, epoxy silane, deionized water and Mix the solution with absolute ethanol, adjust the pH of the solution to 4.87 with glacial acetic acid, stir and hydrolyze for 8 hours, and age for 20 hours to obtain a silane sol;
步骤二：稀土盐溶液的制备Step 2: Preparation of rare earth salt solution
按照每升溶液中加入4.34g的硝酸铈、2mL的过氧化氢和0.96g柠檬酸制备稀土盐溶液；Add 4.34g of cerium nitrate, 2mL of hydrogen peroxide and 0.96g of citric acid to each liter of solution to prepare a rare earth salt solution;
步骤三：镁锂合金表面处理Step 3: Surface treatment of magnesium-lithium alloy
依次使用240#、800#、1200#和2000#的金相砂纸对镁铝合金表面进行打磨处理，然后抛光处理，得到表面光滑无划痕的镁铝合金；将所述镁铝合金浸入温度为55℃的碱液中碱洗15min；再用去离子水冲洗碱洗后的镁铝合金表面30min，干燥，即得镁锂合金样品；Use 240#, 800#, 1200#, and 2000# metallographic sandpaper to polish the surface of magnesium-aluminum alloy, and then polish to obtain a magnesium-aluminum alloy with a smooth surface and no scratches; the immersion temperature of the magnesium-aluminum alloy is Alkaline washing in lye at 55°C for 15 minutes; then rinse the alkaline-washed magnesium-aluminum alloy surface with deionized water for 30 minutes and dry to obtain a magnesium-lithium alloy sample;
步骤四：稀土-硅烷复合转化膜的制备Step 4: Preparation of rare earth-silane composite conversion coating
将所述硅烷溶胶与所述稀土盐溶液混合摇匀0.2h，得到混合转化液，将所述镁锂合金样品浸入所述混合转化液中，在温度为20℃的条件下转化处理后，取出自然晾干，放入鼓风干燥箱80℃固化35min，即得稀土-硅烷复合转化膜。The silane sol and the rare earth salt solution were mixed and shaken for 0.2h to obtain a mixed conversion solution, the magnesium-lithium alloy sample was immersed in the mixed conversion solution, and after conversion treatment at a temperature of 20°C, it was taken out Dry naturally, put it in a blast drying oven at 80°C and cure for 35 minutes to obtain a rare earth-silane composite conversion film.
在步骤三中所述碱液按照每升溶液中加入2g磷酸钠、3g碳酸钠和3g硅酸钠制备。In step 3, the lye solution is prepared by adding 2 g of sodium phosphate, 3 g of sodium carbonate and 3 g of sodium silicate per liter of solution.
在步骤四中所述转化为1次，每次1min。在步骤四中所述干燥固化的次数与所述转化的次数相同。In step 4, the conversion is 1 time, 1 min each time. In step four, the number of times of drying and curing is the same as the number of times of conversion.
实施例2Example 2
本实施例与实施例一存在诸多相同之处，其相同之处不再赘述，将不同之处简述如下：步骤二中按照每升溶液中加入6.51g的硝酸铈、2mL的过氧化氢和0.96g柠檬酸制备稀土盐溶液；There are many similarities between this embodiment and the first embodiment, and the similarities will not be repeated, and the differences will be briefly described as follows: In step 2, 6.51g of cerium nitrate, 2mL of hydrogen peroxide and 2mL of hydrogen peroxide are added to each liter of solution. 0.96g citric acid to prepare rare earth salt solution;
在步骤四中所述转化为2次，每次1min。In step 4, the conversion is 2 times, 1 min each time.
实施例3Example 3
本实施例与实施例一存在诸多相同之处，其相同之处不再赘述，将不同之处简述如下：步骤二中按照每升溶液中加入4.34g的硝酸铈、2mL的过氧化氢和1.92g柠檬酸制备稀土盐溶液；There are many similarities between this embodiment and the first embodiment, and the similarities will not be repeated, and the differences will be briefly described as follows: In step 2, 4.34g of cerium nitrate, 2mL of hydrogen peroxide and 2mL of hydrogen peroxide are added to each liter of solution. 1.92g citric acid to prepare rare earth salt solution;
在步骤四中所述转化为3次，每次1min。In step 4, the conversion is 3 times, 1 min each time.
对实施例1～实施例3制备的镁锂合金表面稀土-硅烷复合转化膜进行耐腐蚀性测试，结果如表1所示。The corrosion resistance test of the rare earth-silane composite conversion film on the surface of the magnesium-lithium alloy prepared in Example 1 to Example 3 was carried out, and the results are shown in Table 1.
表1 不同情况下镁锂合金表面硅烷-镧盐复合膜性能参数一览表Table 1 List of performance parameters of silane-lanthanum salt composite film on magnesium-lithium alloy surface under different conditions
| 样品编号Sample serial number | 涂层附着力Coating adhesion | 涂层电阻Ω..cm 2 Coating resistance Ω..cm 2 | 腐蚀电流A/cm 2 Corrosion current A/cm 2 |
| 单一硅烷膜Single silane film | 良good | 2.48×10 2 2.48×10 2 | 1.14×10 -5 1.14×10 -5 |
| 实施例1Example 1 | 良good | 3.56×10 3 3.56×10 3 | 7.54×10 -5 7.54×10 -5 |
| 实施例2Example 2 | 优excellent | 1.33×10 4 1.33×10 4 | 3.24×10 -6 3.24×10 -6 |
| 实施例3Example 3 | 良good | 3.04×10 4 3.04×10 4 | 1.13×10 -6 1.13×10 -6 |
从表1可以看出，采用本发明方法制备的镁锂合金表面稀土-硅烷复合转化膜的各项性能均优于单一硅烷膜的性能，具有良好的防腐蚀性能。It can be seen from Table 1 that the performance of the rare earth-silane composite conversion film on the surface of the magnesium-lithium alloy prepared by the method of the present invention is better than that of a single silane film, and has good corrosion resistance.
尽管已经对本发明的技术方案做了较为详细的阐述和列举，应当理解，对于本领域技术人员来说，对上述实施例做出修改或者采用等同的替代方案，这对本领域的技术人员而言是显而易见，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。Although the technical solutions of the present invention have been described and enumerated in more detail, it should be understood that for those skilled in the art, it is important for those skilled in the art to modify the above-mentioned embodiments or adopt equivalent alternatives. Obviously, these modifications or improvements made without departing from the spirit of the present invention all belong to the scope of the present invention.
Claims (4)
- 一种柠檬酸催化稀土-硅烷复合转化膜的制备方法，其特征在于：A preparation method of citric acid catalyzed rare earth-silane composite conversion film, which is characterized in that:步骤一：硅烷溶胶的制备Step 1: Preparation of silane sol按如下重量份配比称取原料氨基硅烷5-10份，环氧基硅烷15-25份，去离子水10-20份，无水乙醇20-30份；在30-50℃下将氨基硅烷、环氧基硅烷、去离子水和无水乙醇混合配置溶液，用冰醋酸调节溶液的pH为4.55-5.06，搅拌水解7-9h，陈化20-26h，得到硅烷溶胶；Weigh out 5-10 parts of amino silane, 15-25 parts of epoxy silane, 10-20 parts of deionized water, 20-30 parts of anhydrous ethanol according to the following weight parts; , Epoxy silane, deionized water and absolute ethanol mixed to prepare the solution, adjust the pH of the solution to 4.55-5.06 with glacial acetic acid, stir and hydrolyze for 7-9h, and age for 20-26h to obtain a silane sol;步骤二：稀土盐溶液的制备Step 2: Preparation of rare earth salt solution按照每升溶液中加入4-10g的硝酸铈、1.5-5mL的过氧化氢和0.9-2g柠檬酸制备稀土盐溶液；Add 4-10g of cerium nitrate, 1.5-5mL of hydrogen peroxide and 0.9-2g of citric acid per liter of solution to prepare a rare earth salt solution;步骤三：镁锂合金表面处理Step 3: Surface treatment of magnesium-lithium alloy依次使用240#、800#、1200#和2000#的金相砂纸对镁铝合金表面进行打磨处理，然后抛光处理，得到表面光滑无划痕的镁铝合金；将所述镁铝合金浸入温度为50-70℃的碱液中碱洗10-20min；再用去离子水冲洗碱洗后的镁铝合金表面20-40min，干燥，即得镁锂合金样品；Use 240#, 800#, 1200# and 2000# metallographic sandpaper to polish the surface of magnesium-aluminum alloy, and then polish to obtain a magnesium-aluminum alloy with a smooth surface and no scratches; the immersion temperature of the magnesium-aluminum alloy is Alkaline washing in lye at 50-70°C for 10-20 minutes; then rinse the alkaline-washed magnesium-aluminum alloy surface with deionized water for 20-40 minutes and dry to obtain a magnesium-lithium alloy sample;步骤四：稀土-硅烷复合转化膜的制备Step 4: Preparation of rare earth-silane composite conversion coating将所述硅烷溶胶与所述稀土盐溶液混合摇匀0.1-0.5h，得到混合转化液，将所述镁锂合金样品浸入所述混合转化液中，在温度为20-25℃的条件下转化处理后，取出自然晾干，放入鼓风干燥箱70-90℃固化20-40min，即得稀土-硅烷复合转化膜。The silane sol and the rare earth salt solution are mixed and shaken for 0.1-0.5h to obtain a mixed conversion solution, and the magnesium-lithium alloy sample is immersed in the mixed conversion solution and converted at a temperature of 20-25°C After the treatment, take it out to dry naturally, put it in a blast drying oven at 70-90°C for curing for 20-40 minutes, to obtain a rare earth-silane composite conversion film.
- 根据权利要求1所述的一种柠檬酸催化稀土-硅烷复合转化膜的制备方法， 其特征在于：在步骤三中所述碱液按照每升溶液中加入1-3g磷酸钠、2-4g碳酸钠和2-4g硅酸钠制备。The method for preparing a citric acid-catalyzed rare earth-silane composite conversion film according to claim 1, characterized in that: in step 3, the alkali solution is added with 1-3g sodium phosphate and 2-4g carbonic acid per liter of solution. Sodium and 2-4g sodium silicate preparation.
- 根据权利要求1所述的一种柠檬酸催化稀土-硅烷复合转化膜的制备方法，其特征在于：在步骤四中所述转化为1-3次，每次0.5-1min。The method for preparing a citric acid-catalyzed rare earth-silane composite conversion film according to claim 1, characterized in that: in step 4, the conversion is 1-3 times, each time is 0.5-1 min.
- 根据权利要求1所述的一种柠檬酸催化稀土-硅烷复合转化膜的制备方法，其特征在于：在步骤四中所述干燥固化的次数与所述转化的次数相同。The method for preparing a citric acid-catalyzed rare earth-silane composite conversion film according to claim 1, wherein the number of times of drying and curing in step 4 is the same as the number of times of conversion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2019/119431 WO2021097664A1 (en) | 2019-11-19 | 2019-11-19 | Method for preparing citric acid catalyzed rare earth-silane composite conversion film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2019/119431 WO2021097664A1 (en) | 2019-11-19 | 2019-11-19 | Method for preparing citric acid catalyzed rare earth-silane composite conversion film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2021097664A1 true WO2021097664A1 (en) | 2021-05-27 |
Family
ID=75981106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2019/119431 WO2021097664A1 (en) | 2019-11-19 | 2019-11-19 | Method for preparing citric acid catalyzed rare earth-silane composite conversion film |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2021097664A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003213446A (en) * | 2002-01-22 | 2003-07-30 | Nippon Hyomen Kagaku Kk | Black film formation treatment agent for metallic surface and treatment method therefor |
| CN1549873A (en) * | 2001-06-28 | 2004-11-24 | �������ء���³̩�����¶����������� | Treatment for improved magnesium surface corrosion-resistance |
| CN102409325A (en) * | 2011-12-06 | 2012-04-11 | 中国科学院金属研究所 | Environmentally-friendly corrosion-resistant chromium-free chemical conversion liquid and method for preparing chemical conversion film |
| CN105483684A (en) * | 2015-11-27 | 2016-04-13 | 贵州航天风华精密设备有限公司 | Corrosion resistance processing method for surface of magnesium alloy or aluminum alloy |
| WO2019157612A1 (en) * | 2018-02-13 | 2019-08-22 | Henkel Ag & Co. Kgaa | Surface treatment composition for light metallic material |
-
2019
- 2019-11-19 WO PCT/CN2019/119431 patent/WO2021097664A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1549873A (en) * | 2001-06-28 | 2004-11-24 | �������ء���³̩�����¶����������� | Treatment for improved magnesium surface corrosion-resistance |
| JP2003213446A (en) * | 2002-01-22 | 2003-07-30 | Nippon Hyomen Kagaku Kk | Black film formation treatment agent for metallic surface and treatment method therefor |
| CN102409325A (en) * | 2011-12-06 | 2012-04-11 | 中国科学院金属研究所 | Environmentally-friendly corrosion-resistant chromium-free chemical conversion liquid and method for preparing chemical conversion film |
| CN105483684A (en) * | 2015-11-27 | 2016-04-13 | 贵州航天风华精密设备有限公司 | Corrosion resistance processing method for surface of magnesium alloy or aluminum alloy |
| WO2019157612A1 (en) * | 2018-02-13 | 2019-08-22 | Henkel Ag & Co. Kgaa | Surface treatment composition for light metallic material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020000559A1 (en) | Silane/graphene oxide composite passivation solution and preparation method therefor and application thereof | |
| WO2021139227A1 (en) | Bionic sandwich corrosion-resistant coating, preparation method therefor, and use thereof | |
| CN102766862B (en) | Treating fluid and method for preparing vanadium-zirconium composite conversion coatings with self-repairing performance on aluminum alloy surfaces through same | |
| CN104988485A (en) | Environment-friendly universal metal surface pretreatment liquid and use method | |
| CN111235620B (en) | Electrophoresis coating process for vehicle frame | |
| CN102653643A (en) | Zinc-based composite coating for improving corrosion resistance of neodymium-iron-boron magnet | |
| CN112251744B (en) | Metal plate coating pretreatment process | |
| US20150284869A1 (en) | Pretreatment Process for Magnesium Alloy Wheel | |
| CN104141138A (en) | Preparation method of micro-arc oxidation-composite chemical nickel plating coating layer on surface of magnesium alloy | |
| WO2024056109A1 (en) | "brick-mortar" layered structure corrosion-resistant phosphate composite coating, and preparation method and use therefor | |
| CN108149232B (en) | Environment-friendly passivation solution for aluminum or seven-series aluminum alloy and preparation method and treatment process thereof | |
| CN113737246A (en) | Micro-arc oxidation treatment process for aluminum alloy surface | |
| CN108642502B (en) | Corrosion-resistant pretreatment method of aluminum alloy | |
| WO2021097664A1 (en) | Method for preparing citric acid catalyzed rare earth-silane composite conversion film | |
| CN101914743A (en) | Magnesium alloy surface treatment method | |
| CN109385628A (en) | A kind of aluminum alloy nickel plated technique of high-efficiency environment friendly | |
| CN103695905A (en) | Method for preparing composite nickel coating on surface of magnesium alloy micro-arc oxidation film | |
| CN103242736B (en) | Electric arc spraying zinc-aluminium alloy coating sealant with high corrosion resistance, preparation process and application of sealant | |
| CN102181851B (en) | Anhydrous pretreatment method for coating surfaces of magnesium alloys | |
| CN114032547B (en) | Alloy surface composite coating and preparation method thereof | |
| CN113174150B (en) | Aluminum zinc phosphate coating and use method thereof | |
| CN114921782A (en) | Composite treating agent for surface pretreatment of neodymium iron boron magnet and preparation method and application thereof | |
| CN109913862B (en) | Treatment method of aluminum foil for aluminum-plastic composite film | |
| CN109355651B (en) | Chemical conversion coating on surface of magnesium alloy and preparation method thereof | |
| CN106893485A (en) | Relatively low chromium-free zinc aluminum coating of a kind of sintering temperature and its production and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19953290 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 19953290 Country of ref document: EP Kind code of ref document: A1 |