脉冲电场作用下铈盐对铝阳极氧化膜的封闭作用
摘要
为了提高铝的耐蚀性，需要对铝进行阳极氧化和后续的封闭处理。传统的封闭工艺如重铬酸钾封闭和氟化镍封闭对环境具有较高的污染，并且对人体有害，而沸水封闭能耗很大。稀土封闭是一种绿色环保的封闭工艺，国内外有许多专家对其进行了研究。本文对一种脉冲电场下的铈盐封闭工艺的封闭机理进行研究，讨论了各参数对封闭效果的影响，并且研究了几种封闭工艺后氧化膜的时效性。主要的研究结果有：
（1）铈盐双向脉冲封闭的封闭效果要好于铈盐的浸泡封闭、无氧脉冲封闭和单负向脉冲封闭的封闭效果。铈盐双向脉冲封闭后，阳极氧化膜表面已经基本封闭完全，并且发现有颗粒状物填充多孔层的孔洞。铈盐双向脉冲封闭工艺的封闭效果与外加电流、氧气和正向电流密切相关，其中的机理可能是负向电流的通入促进了负电荷在氧化膜端部积累，进而产生了OH-，并且负向电流促进了溶液中Ce3+向氧化膜表面迁移，而氧气的存在是溶液中产生OH-的根本原因，正向电流的通入则有利于溶液中产生的OH-向氧化膜及其多孔层孔中迁移。
（2）铈盐双向脉冲封闭后氧化膜表面有明显的铈元素存在，氧化膜表面的铈元素主要以三价形式存在，也有少部分的四价铈的存在。表面的氧元素主要存在于铈的氧化物和氢氧化物中，其中三价铈主要以氢氧化亚铈和氧化亚铈的形式存在，四价铈存在形式是氧化铈，四价铈的形成是由三价铈在空气中氧化而成。
（3）本文所研究影响铈盐双向脉冲封闭的参数有：封闭时间、温度、外加电压、电源脉冲频率、负向占空比、正向占空比、铈离子添加量等。它们都对封闭后阳极氧化膜的耐蚀性有一定的影响，其中封闭时间、脉冲频率以及负向占空比对氧化膜耐蚀性的影响更为明显。首次在稀土封闭中引入氟离子，得到氟离子的添加对加快封闭进程有利。
（4）经过铈盐脉冲封闭的阳极氧化膜耐蚀性相比未封闭之前得到了很大提高，并且其耐蚀性要好于沸水封闭得到的阳极氧化膜，其耐蚀性与重铬酸钾封闭的阳极氧化膜具有可比性。但是在30g/L的NaCl溶液中浸泡180天后，铈盐脉冲封闭得到的阳极氧化膜耐蚀性要好于重铬酸钾封闭和沸水封闭得到的阳极氧化膜。
In order to improve the corrosion resistance of aluminum, it is necessaryto take the anodizing and subsequent sealing processing on aluminum. Thetraditional sealing such as potassium dichromate sealing and nickel fluoridesealing are harmful to the environment and the healthy, and the boilingwater sealing is high energy consumption.Rare earth sealing isenvironmentally-friendly, and there are many scholars at home and abroadtaking on the research.In this paper, the mechanism of the sealing of ceriumsalt on anodic film of aluminum under pulse electric filed was Put forward.The parameters which effected the sealing were discussed. The aging ofanodic film under rare earth sealing and some other sealings was alsoconsidered. The main research conclusions are as follows:
(1) The sealing quality of cerium salt bi-directional pulse sealing is betterthan that of soaking sealing, anaerobic pulse sealing and single negative pulsesealing. The anodic film is almost sealed after the cerium salt pulse sealing. Itwas found that there were particles sealing the hole. The sealing quality ofcerium salt bi-directional pulse sealing is closely related to the impressed current, oxygen and the positive current. We assume the mechanism is that theproviding of the negative current not only promotes the accumulation ofnegative charge on the boundary of the oxidation film which creates OH-, butalso promotes the migration of Ce3+to the surface of the oxidation film. Thepresence of oxygen is the root cause of producing OH-. The providing of thepositive current promotes the migration of OH-to the pore and the suface ofthe oxidation film.
(2) It is obvious that there is cerium existed on the surface of anodic filmwhich is sealed by bi-directional pulse power. The cerium that existes on theoxidation film is mainly in trivalence and the rest is in quadrivalence. Theoxide and hydrogen chloride were found on the surface of the sealed film. Thecerium is existed in the form of oxide and hydrogen chloride. The cerium oftrivalence is in oxide and hydrogen chloride, and that of quadrivalence is inoxide which is the oxidization product of trivalence cerium compound due tothe exposure to the air.
(3) It was proposed some influencing factors that effected the sealingquality, They were sealing time, sealing temperature, valtage, pulse frequency,negative duty cycle, positive duty cycle, the amout that cerium added, theadding of the fluorin ion and so on. All of them effect the corrosion resistanceof the anodic film under the sealing more or less. The corrosion resistance isaffected mostly by sealing time, pulse frequency and negative duty cycle.Fluorine ion was first introduced to rare earth sealing, and it is beneficial to speed up the closed process.
(4) Compared to the unsealed anodic film, the corrosion resistance of theanodic film under cerium salt sealing largely increased. The results show thatrare earth sealing for anodized film is comparable to that of chromate sealing,and is better than boiling water sealing. The aluminum sheets are put in thesolution including NaCl of30g/L for180days, the corrosion resistance of theanodic film under cerium salt sealing is hither than that of potassiumdichromate sealing and boiling water sealing.
（1）铈盐双向脉冲封闭的封闭效果要好于铈盐的浸泡封闭、无氧脉冲封闭和单负向脉冲封闭的封闭效果。铈盐双向脉冲封闭后，阳极氧化膜表面已经基本封闭完全，并且发现有颗粒状物填充多孔层的孔洞。铈盐双向脉冲封闭工艺的封闭效果与外加电流、氧气和正向电流密切相关，其中的机理可能是负向电流的通入促进了负电荷在氧化膜端部积累，进而产生了OH-，并且负向电流促进了溶液中Ce3+向氧化膜表面迁移，而氧气的存在是溶液中产生OH-的根本原因，正向电流的通入则有利于溶液中产生的OH-向氧化膜及其多孔层孔中迁移。
（2）铈盐双向脉冲封闭后氧化膜表面有明显的铈元素存在，氧化膜表面的铈元素主要以三价形式存在，也有少部分的四价铈的存在。表面的氧元素主要存在于铈的氧化物和氢氧化物中，其中三价铈主要以氢氧化亚铈和氧化亚铈的形式存在，四价铈存在形式是氧化铈，四价铈的形成是由三价铈在空气中氧化而成。
（3）本文所研究影响铈盐双向脉冲封闭的参数有：封闭时间、温度、外加电压、电源脉冲频率、负向占空比、正向占空比、铈离子添加量等。它们都对封闭后阳极氧化膜的耐蚀性有一定的影响，其中封闭时间、脉冲频率以及负向占空比对氧化膜耐蚀性的影响更为明显。首次在稀土封闭中引入氟离子，得到氟离子的添加对加快封闭进程有利。
（4）经过铈盐脉冲封闭的阳极氧化膜耐蚀性相比未封闭之前得到了很大提高，并且其耐蚀性要好于沸水封闭得到的阳极氧化膜，其耐蚀性与重铬酸钾封闭的阳极氧化膜具有可比性。但是在30g/L的NaCl溶液中浸泡180天后，铈盐脉冲封闭得到的阳极氧化膜耐蚀性要好于重铬酸钾封闭和沸水封闭得到的阳极氧化膜。
In order to improve the corrosion resistance of aluminum, it is necessaryto take the anodizing and subsequent sealing processing on aluminum. Thetraditional sealing such as potassium dichromate sealing and nickel fluoridesealing are harmful to the environment and the healthy, and the boilingwater sealing is high energy consumption.Rare earth sealing isenvironmentally-friendly, and there are many scholars at home and abroadtaking on the research.In this paper, the mechanism of the sealing of ceriumsalt on anodic film of aluminum under pulse electric filed was Put forward.The parameters which effected the sealing were discussed. The aging ofanodic film under rare earth sealing and some other sealings was alsoconsidered. The main research conclusions are as follows:
(1) The sealing quality of cerium salt bi-directional pulse sealing is betterthan that of soaking sealing, anaerobic pulse sealing and single negative pulsesealing. The anodic film is almost sealed after the cerium salt pulse sealing. Itwas found that there were particles sealing the hole. The sealing quality ofcerium salt bi-directional pulse sealing is closely related to the impressed current, oxygen and the positive current. We assume the mechanism is that theproviding of the negative current not only promotes the accumulation ofnegative charge on the boundary of the oxidation film which creates OH-, butalso promotes the migration of Ce3+to the surface of the oxidation film. Thepresence of oxygen is the root cause of producing OH-. The providing of thepositive current promotes the migration of OH-to the pore and the suface ofthe oxidation film.
(2) It is obvious that there is cerium existed on the surface of anodic filmwhich is sealed by bi-directional pulse power. The cerium that existes on theoxidation film is mainly in trivalence and the rest is in quadrivalence. Theoxide and hydrogen chloride were found on the surface of the sealed film. Thecerium is existed in the form of oxide and hydrogen chloride. The cerium oftrivalence is in oxide and hydrogen chloride, and that of quadrivalence is inoxide which is the oxidization product of trivalence cerium compound due tothe exposure to the air.
(3) It was proposed some influencing factors that effected the sealingquality, They were sealing time, sealing temperature, valtage, pulse frequency,negative duty cycle, positive duty cycle, the amout that cerium added, theadding of the fluorin ion and so on. All of them effect the corrosion resistanceof the anodic film under the sealing more or less. The corrosion resistance isaffected mostly by sealing time, pulse frequency and negative duty cycle.Fluorine ion was first introduced to rare earth sealing, and it is beneficial to speed up the closed process.
(4) Compared to the unsealed anodic film, the corrosion resistance of theanodic film under cerium salt sealing largely increased. The results show thatrare earth sealing for anodized film is comparable to that of chromate sealing,and is better than boiling water sealing. The aluminum sheets are put in thesolution including NaCl of30g/L for180days, the corrosion resistance of theanodic film under cerium salt sealing is hither than that of potassiumdichromate sealing and boiling water sealing.
引文
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