铝管表面复合钝化及防腐性能研究
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摘要
本论文以冰箱、冰柜蒸发器用铝管为研究对象,通过浸渍法在铝管表面进行硅烷稀土铈的复合钝化,论文对其钝化工艺进行了考察和优化,得出最佳的成膜工艺条件：室温下硅烷水解最佳时间为40h,硅烷、稀土铈溶液钝化温度分别为30℃和60℃,钝化时间均为60s,成膜温度均为100℃。论文还通过线性扫描法筛选并确定了用十二烷基磺酸钠(SDS)作为添加剂,并考察了其对耐蚀性的影响。采用硫酸铜点滴、碱浸失重、析氢、中性盐雾试验和电化学手段来考察两种复合膜层的耐蚀性,并分别利用扫描电镜和X射线衍射能谱对钝化膜层表面形貌和成分进行了分析。
耐蚀性测试表明：与空白样和单一沉积膜相比,复合膜层的耐蚀性大幅度提高；其中复合膜耐硫酸铜点滴时间为56"50,碱浸失重速率为0.0006261g/(cm2·h),开始析出氢气的时间为3.5h,耐中性盐雾试验的时间为226h,自腐蚀电流和阻抗值分别为7.2991×10-6A/cm2和12586Ω,其耐蚀性能不如铬酸盐转化膜；而经过表面活性剂SDS协同改性的复合改性膜层,其点滴时间为1'04"48,碱浸失重失重速率为0.0001657g/(cm2·h),开始析出氢气的时间为4.5h,耐中性盐雾试验的时间为252h,自腐蚀电流为4.9582×10-7A/cm2,其耐蚀性优于铬酸盐转化膜。SEM形貌图表明表面钝化膜层较单一沉积膜层均匀致密,但不如经SDS改性复合膜层的形貌；膜层EDX成分分析,结果表明膜层主要由Al、O、Ce、Si和S元素组成,同时由于SDS的加入,使得膜层的S、Si含量有大幅度增加。本论文还对钝化成膜机理和耐蚀机理进行了初步的分析。
SDS改性硅烷稀土铈钝化由于其工艺快速简便、环保和耐蚀性好等优点可望成为一项实用的铝及其合金的防腐钝化技术,是一种较理想的铬酸盐钝化替代工艺,具有广阔的应用前景。
The silane-rare earth cerium composite coatings on the aluminum-tube used in evaporator of refrigerators were prepared by immersion in the workable solution in the paper. The best process conditions of coatings formed that the time of silane hydrolyzing is 40h at room temperature, passivation temperature of silane and rare earth cerium solution are 30℃and 60℃respectively, passivation time and temperature of coatings formed are 60s and 100℃respectively, were obtained by optimizing preparation process. Anionic surfactant sodium dodecyl sulfonate SDS used as additive to prepare modified silane-rare earth cerium composite coatings was selected by means of linear sweep voltammetry. The corrosion resistance of the two coatings was assessed by copper sulfate dropping test, alkaline leaching weight loss, collecting hydrogen experiment, neutral salt spray test and electrochemical methods. Scanning Electron Microscope(SEM) and X-ray Energy Dispersive Spectroscopy(EDX) were used to analysis morphology and composition of the coatings.
The results of testing indicate that corrosion resistance of the composite coatings greatly improved compared with blank sample. The time of copper sulfate dropping is 56"50, loss weight rate is 0.0006261 W/S-h(g/cm2·h), releasing hydrogen's time is 3.5h, the anti-pitting corrosion time is 226h, the self-corrosion current and impedance value are 7.2991E-6A/cm2and 12586Ωrespectively, which show that the composite coatings is less effective than the coatings with Cr. However, the results of corrosion resistance showed that the composite coatings modified with SDS are better than the coatings with Cr, which The time of copper sulfate dropping is 1'04"48, loss weight rate is 0.0001657 W/S·h(g/cm2·h), releasing hydrogen's time is 4.5h, the anti-pitting corrosion time is 252h, the self-corrosion current is 4.9582E-7A/cm2. SEM observation showed that the modified composite conversion coat is much more uniform and dense than the composite coatings; EDX test showed that the complex coat is mainly composed of N, O, Si, Al and Ce and the content of S and Si increased greatly because of SDS adding. The coatings formed and corrosion protection mechanisms of the composite coatings were also analyzed in the paper.
SDS modified silane-rare earth cerium composite coatings, which can be well used to replace the chromate treatment, is expected to be a practical passivation technology of the aluminum and aluminum alloy because of simple process, environmental friendly and excellent corrosion resistance.
耐蚀性测试表明：与空白样和单一沉积膜相比,复合膜层的耐蚀性大幅度提高；其中复合膜耐硫酸铜点滴时间为56"50,碱浸失重速率为0.0006261g/(cm2·h),开始析出氢气的时间为3.5h,耐中性盐雾试验的时间为226h,自腐蚀电流和阻抗值分别为7.2991×10-6A/cm2和12586Ω,其耐蚀性能不如铬酸盐转化膜；而经过表面活性剂SDS协同改性的复合改性膜层,其点滴时间为1'04"48,碱浸失重失重速率为0.0001657g/(cm2·h),开始析出氢气的时间为4.5h,耐中性盐雾试验的时间为252h,自腐蚀电流为4.9582×10-7A/cm2,其耐蚀性优于铬酸盐转化膜。SEM形貌图表明表面钝化膜层较单一沉积膜层均匀致密,但不如经SDS改性复合膜层的形貌；膜层EDX成分分析,结果表明膜层主要由Al、O、Ce、Si和S元素组成,同时由于SDS的加入,使得膜层的S、Si含量有大幅度增加。本论文还对钝化成膜机理和耐蚀机理进行了初步的分析。
SDS改性硅烷稀土铈钝化由于其工艺快速简便、环保和耐蚀性好等优点可望成为一项实用的铝及其合金的防腐钝化技术,是一种较理想的铬酸盐钝化替代工艺,具有广阔的应用前景。
The silane-rare earth cerium composite coatings on the aluminum-tube used in evaporator of refrigerators were prepared by immersion in the workable solution in the paper. The best process conditions of coatings formed that the time of silane hydrolyzing is 40h at room temperature, passivation temperature of silane and rare earth cerium solution are 30℃and 60℃respectively, passivation time and temperature of coatings formed are 60s and 100℃respectively, were obtained by optimizing preparation process. Anionic surfactant sodium dodecyl sulfonate SDS used as additive to prepare modified silane-rare earth cerium composite coatings was selected by means of linear sweep voltammetry. The corrosion resistance of the two coatings was assessed by copper sulfate dropping test, alkaline leaching weight loss, collecting hydrogen experiment, neutral salt spray test and electrochemical methods. Scanning Electron Microscope(SEM) and X-ray Energy Dispersive Spectroscopy(EDX) were used to analysis morphology and composition of the coatings.
The results of testing indicate that corrosion resistance of the composite coatings greatly improved compared with blank sample. The time of copper sulfate dropping is 56"50, loss weight rate is 0.0006261 W/S-h(g/cm2·h), releasing hydrogen's time is 3.5h, the anti-pitting corrosion time is 226h, the self-corrosion current and impedance value are 7.2991E-6A/cm2and 12586Ωrespectively, which show that the composite coatings is less effective than the coatings with Cr. However, the results of corrosion resistance showed that the composite coatings modified with SDS are better than the coatings with Cr, which The time of copper sulfate dropping is 1'04"48, loss weight rate is 0.0001657 W/S·h(g/cm2·h), releasing hydrogen's time is 4.5h, the anti-pitting corrosion time is 252h, the self-corrosion current is 4.9582E-7A/cm2. SEM observation showed that the modified composite conversion coat is much more uniform and dense than the composite coatings; EDX test showed that the complex coat is mainly composed of N, O, Si, Al and Ce and the content of S and Si increased greatly because of SDS adding. The coatings formed and corrosion protection mechanisms of the composite coatings were also analyzed in the paper.
SDS modified silane-rare earth cerium composite coatings, which can be well used to replace the chromate treatment, is expected to be a practical passivation technology of the aluminum and aluminum alloy because of simple process, environmental friendly and excellent corrosion resistance.
引文
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