铝合金表面稀土转化膜的成膜机理及其性能改善研究
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摘要
本文主要针对防锈铝合金(3A21)表面稀土转化膜的沉积过程,探讨了电沉积和化学沉积转化膜的成膜机理和膜层微裂纹的产生机制;并根据膜层的开裂情况进行了后处理工艺的研究,开发了稀土转化膜的磷酸盐后处理工艺,并对后处理的原理进行了研究;最后对电沉积转化溶液的有效利用进行了初步的研究,分析了转化溶液重复利用的可行性。
通过分析电沉积转化膜沉积过程中试片的阴极电压、阴极极化电位、膜层单位面积质量、膜层表面微观形貌和成分随着沉积时间的变化,提出了电沉积过程的三步沉积成膜机理,指出转化膜在沉积过程中首先会在试片表面形成一个铝的氧化膜,然后稀土化合物在试片表面的微观阴极区优先沉积,并向周围延伸直至完全覆盖试片表面,最后是转化膜随着沉积时间的均匀加厚过程。在转化膜沉积完成后,由于膜层的脱水会导致膜层开裂,文章也分析了转化膜表面裂纹源的形成及裂纹扩展的机制。同时,对于化学沉积的转化膜,通过分析膜层形貌组成随沉积时间的变化,以及试片前处理工艺和辅助添加剂对成膜过程的影响,也提出了化学沉积转化膜的成膜机理。
采用正交试验优化了电沉积稀土转化膜的磷酸盐后处理工艺,结果表明,电沉积稀土转化膜在经过磷酸盐后处理后,膜层的开裂得到了有效地抑制,其耐蚀性能也获得了显著的提高,XPS分析发现膜层在后处理过程中脱除了大量的可挥发结晶水,从而减少了膜层的开裂。对化学沉积转化膜也采用了类似的磷酸盐后处理工艺,结果转化膜的抗开裂性和耐蚀性能也获得了很大的提高;另外还试验了电沉积转化膜和化学沉积转化膜的多次沉积成膜处理、波美层工艺、醋酸镍后处理工艺、低温氟化镍处理工艺和溶胶.凝胶膜处理工艺,结果显示醋酸镍后处理和低温氟化镍处理对膜层的耐腐蚀性能有很大提高,波美层工艺也能在一定程度上提高膜层的耐蚀性,而多次沉积成膜处理和溶胶-凝胶膜处理则效果不理想。
为了实现转化溶液的充分利用,文章还研究了电沉积转化溶液中的组分在沉积过程中的变化情况,通过采用紫外吸收的方法来测定溶液中Ce含量。并比较了在不补充组分和适时补充组分的情况下,在电沉积转化溶液中进行连续沉积所的转化膜的性能,结果发现,在不补充组分的情况下,转化溶液连续沉积3次后就已失效,而在适时补充H_2O_2的情况下,转化溶液连续沉积10次后,所得转化膜还能维持一个相当的性能。
This thesis is aimed at the depositing process of Rare Earth (RE) conversion coating on the 3A21 aluminum alloy. The mechanism of the growth of electrolytic and spontaneous deposited conversion coatings and the formation of micro-cracks on the surface of the coatings were discussed. In order to seal the micro-cracks on the conversion coatings and to improve the corrosion resistance of these conversion coatings, some post-treatment methods were carried out. An efficacious phosphate post-treatment was developed, and the theory of this post-treatment was studied. A primary study was carried out to make the electrolytic deposited solution more efficient.
By investigating the relationship between cathodic voltage, cathodic polarization potential, mass per unit area, the appearance, the composition of the coatings and the deposited time, a three-step depositing process theory about the formation of conversion coatings was proposed, which includes: firstly, an aluminum oxide film with several nanometers is formed quickly on the surface of the aluminum alloy; then, the compound containing Ce is precipitated over the micro-cathodes on the surface of matrix and then extends on the whole aluminum alloy untill an integrated film is formed; lastly, the thickness of the film will be uniformly increased with time. After the formation of the conversion coating, some micro-cracks induced by dehydration of the coating will appear. A mechanism about how the cracks arising and expanding was raised. The influence of deposited time on the surface morphology and the composition of the spontaneous deposited film were studied. The effect of pre-treatment and additives on the precipitation process was investigated also. Based on the above study, the theory of the spontaneous deposited conversion coating was proposed.
The phosphate post-treatment of electrolytic deposit Rare Earth (RE) conversion coating was optimized by orthogonal tests. The results showed that after the electrolytic deposit Rare Earth conversion coating was post-treated, the cracking was effectively improved as well as the corrosion resistance. XPS analysis indicated that a mass of volatile crystal water was removed during post-treatment; therefore, the number of cracks in the coating was reduced. The similar phosphate post-treatment was also applied to the spontaneous deposited conversion coating and the number of cracks was reduces and corrosion resistance was improved. Besides Phosphate post-treatment, the Multi-deposited of conversion coating, Boehmite treatment, Nickel acetate post-treatment, Ambient nickel fluoride post-treatment and sol-gel treatment were studied. Nickel acetate post-treatment and ambient nickel fluoride post-treatment showed a great improvement on the corrosion resistance of the conversion coatings. The boehmite treatment also improved the corrosion resistance of the coatings. But the multi-deposited and sol-gel treatment did not displaying a positive effect.
In order to make the conversion solution more efficient, the changes of components of electrolytic depositon solution were studied. UV absorbance spectrum was used to determine the concentration of Ce in solution. While the components of electrolytic deposited solution were supplied periodically or not, the performances of sequential deposited conversion coatings were checked. The results showed that the solution without supplementaries became invalid after 3 times deposited, but the solution would keep its efficacity until the tenth deposited while the H_2O_2 was supplied periodically.
通过分析电沉积转化膜沉积过程中试片的阴极电压、阴极极化电位、膜层单位面积质量、膜层表面微观形貌和成分随着沉积时间的变化,提出了电沉积过程的三步沉积成膜机理,指出转化膜在沉积过程中首先会在试片表面形成一个铝的氧化膜,然后稀土化合物在试片表面的微观阴极区优先沉积,并向周围延伸直至完全覆盖试片表面,最后是转化膜随着沉积时间的均匀加厚过程。在转化膜沉积完成后,由于膜层的脱水会导致膜层开裂,文章也分析了转化膜表面裂纹源的形成及裂纹扩展的机制。同时,对于化学沉积的转化膜,通过分析膜层形貌组成随沉积时间的变化,以及试片前处理工艺和辅助添加剂对成膜过程的影响,也提出了化学沉积转化膜的成膜机理。
采用正交试验优化了电沉积稀土转化膜的磷酸盐后处理工艺,结果表明,电沉积稀土转化膜在经过磷酸盐后处理后,膜层的开裂得到了有效地抑制,其耐蚀性能也获得了显著的提高,XPS分析发现膜层在后处理过程中脱除了大量的可挥发结晶水,从而减少了膜层的开裂。对化学沉积转化膜也采用了类似的磷酸盐后处理工艺,结果转化膜的抗开裂性和耐蚀性能也获得了很大的提高;另外还试验了电沉积转化膜和化学沉积转化膜的多次沉积成膜处理、波美层工艺、醋酸镍后处理工艺、低温氟化镍处理工艺和溶胶.凝胶膜处理工艺,结果显示醋酸镍后处理和低温氟化镍处理对膜层的耐腐蚀性能有很大提高,波美层工艺也能在一定程度上提高膜层的耐蚀性,而多次沉积成膜处理和溶胶-凝胶膜处理则效果不理想。
为了实现转化溶液的充分利用,文章还研究了电沉积转化溶液中的组分在沉积过程中的变化情况,通过采用紫外吸收的方法来测定溶液中Ce含量。并比较了在不补充组分和适时补充组分的情况下,在电沉积转化溶液中进行连续沉积所的转化膜的性能,结果发现,在不补充组分的情况下,转化溶液连续沉积3次后就已失效,而在适时补充H_2O_2的情况下,转化溶液连续沉积10次后,所得转化膜还能维持一个相当的性能。
This thesis is aimed at the depositing process of Rare Earth (RE) conversion coating on the 3A21 aluminum alloy. The mechanism of the growth of electrolytic and spontaneous deposited conversion coatings and the formation of micro-cracks on the surface of the coatings were discussed. In order to seal the micro-cracks on the conversion coatings and to improve the corrosion resistance of these conversion coatings, some post-treatment methods were carried out. An efficacious phosphate post-treatment was developed, and the theory of this post-treatment was studied. A primary study was carried out to make the electrolytic deposited solution more efficient.
By investigating the relationship between cathodic voltage, cathodic polarization potential, mass per unit area, the appearance, the composition of the coatings and the deposited time, a three-step depositing process theory about the formation of conversion coatings was proposed, which includes: firstly, an aluminum oxide film with several nanometers is formed quickly on the surface of the aluminum alloy; then, the compound containing Ce is precipitated over the micro-cathodes on the surface of matrix and then extends on the whole aluminum alloy untill an integrated film is formed; lastly, the thickness of the film will be uniformly increased with time. After the formation of the conversion coating, some micro-cracks induced by dehydration of the coating will appear. A mechanism about how the cracks arising and expanding was raised. The influence of deposited time on the surface morphology and the composition of the spontaneous deposited film were studied. The effect of pre-treatment and additives on the precipitation process was investigated also. Based on the above study, the theory of the spontaneous deposited conversion coating was proposed.
The phosphate post-treatment of electrolytic deposit Rare Earth (RE) conversion coating was optimized by orthogonal tests. The results showed that after the electrolytic deposit Rare Earth conversion coating was post-treated, the cracking was effectively improved as well as the corrosion resistance. XPS analysis indicated that a mass of volatile crystal water was removed during post-treatment; therefore, the number of cracks in the coating was reduced. The similar phosphate post-treatment was also applied to the spontaneous deposited conversion coating and the number of cracks was reduces and corrosion resistance was improved. Besides Phosphate post-treatment, the Multi-deposited of conversion coating, Boehmite treatment, Nickel acetate post-treatment, Ambient nickel fluoride post-treatment and sol-gel treatment were studied. Nickel acetate post-treatment and ambient nickel fluoride post-treatment showed a great improvement on the corrosion resistance of the conversion coatings. The boehmite treatment also improved the corrosion resistance of the coatings. But the multi-deposited and sol-gel treatment did not displaying a positive effect.
In order to make the conversion solution more efficient, the changes of components of electrolytic depositon solution were studied. UV absorbance spectrum was used to determine the concentration of Ce in solution. While the components of electrolytic deposited solution were supplied periodically or not, the performances of sequential deposited conversion coatings were checked. The results showed that the solution without supplementaries became invalid after 3 times deposited, but the solution would keep its efficacity until the tenth deposited while the H_2O_2 was supplied periodically.
引文
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