含氟电解质中镁阳极膜的微观结构和电压电流特性:先进镁合金平台科学与技术专刊,2

S. Ono, Hideo Kijima, N. Masuko
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引用次数: 28

摘要

研究了镁在含氟电解质中阳极氧化膜的形成行为,并考察了阳极氧化电压、pH和铝含量的影响。在形成电压2V ~ 100V范围内,在碱性氟溶液中形成多孔膜,在5 V左右和击穿电压下具有较高的电流密度。允许最大电流流过的击穿临界电压约为60V,相对独立于衬底纯度。在其他电压下形成由水合外层和内层组成的势垒型或半势垒型薄膜。在Dow 17和氟化铵等酸性氟化溶液中阳极氧化未观察到5 V左右高电流密度的特殊现象,这可能是由交换被动态引起的。AZ91D的临界电压增加到70 V,在5 V时没有观察到特殊现象,只有在低于临界击穿电压时才形成势垒膜。当电解质中加入AlO - 2离子时,随着AlO - 2含量的增加,临界电压显著升高,电流密度有效降低。在电解液中添加铝的钝化效果比在镁基体中添加铝的钝化效果更显著。组成元素的深度分布表明,铝迁移到氧化膜中,到达氧化物/衬底界面附近。铝与镁的原子比随着电压的增加而增加,在80 V时达到0.42,薄膜中存在结晶mgal2o4和MgO。
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Microstructure and voltage-current characteristics of anodic films formed on magnesium in electrolytes containing fluoride : Special issue on platform science and technology for advanced magnesium alloys, II
Formation behavior of anodic oxide films on magnesium in various electrolytes including fluoride was investigated with attention to the effects of anodizing voltage, pH and aluminum content. In the range of formation voltage between 2V and 100V, porous film was formed in alkaline fluoride solution associated with high current density at around 5 V and at breakdown voltage. The critical voltage of breakdown to allow maximum current flow was approximately 60V and relatively independent on substrate purity. Barrier type films or semi-barrier type films, which were composed of hydrated outer layer and inner layer, were formed at the other voltages. A peculiar phenomenon of high current density at around 5 V, which may be caused by trans-passive state, was not observed for anodizing in acidic fluoride solutions such as Dow 17 and ammonium fluoride. In the case of AZ91D, the critical voltage increased to 70 V and peculiar phenomenon at 5 V was not observed, so that only barrier films were formed at less than the critical breakdown voltage. When AlO - 2 ion was added in the electrolytes, the critical voltage remarkably increased and current density effectively decreased with increasing AlO - 2 content. The passivation effect of aluminum addition in the electrolytes is more remarkable than the addition in magnesium substrates. The depth profiles of constituent elements showed that aluminum migrated into oxide film to reach near oxide/substrate interface. Atomic ratio of aluminum to magnesium increased with increasing voltage to attain 0.42 at 80 V and crystalline MgAl 2 O 4 and MgO were found in the film.
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