镀锌板绿色钝化及其耐蚀性能研究
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摘要
为了消除六价铬对人体和环境的危害,必须寻求能替代六价铬钝化镀锌层的绿色钝化工艺。本论文从无机稀土钝化和有机硅烷钝化两个方面研究了镀锌层表面无铬钝化的工艺,并对耐蚀性能和机理进行了探讨。
通过正交实验确定了单一稀土膜的最优工艺为:稀土铈盐25g/L,双氧水20ml/L,硼酸2.0 g/L,钝化时间3min,钝化温度45℃,pH为3。利用醋酸铅点滴实验和表面形貌观察,研究了铈盐的浓度、H_2O_2的含量、pH值、温度及处理时间等因素对成膜的影响。将铈盐与常用的有机硅烷KH-570复配使用应用于锌的无铬钝化处理。扫描电镜显示试样表面形成了带有微裂纹的稀土钝化膜。极化曲线、交流阻抗等电化学测试结果表明改性稀土膜的耐蚀性比单一稀土钝化膜以及镀锌层的好。利用X射线衍射、X光电子能谱对稀土钝化膜的成分及结构等进行了分析。结果表明膜层主要成分为铈
和锌的氧化物及氢氧化物。利用Tafel极化曲线确定了单一的双-(γ-(三乙氧基硅烷)-丙基)-四硫化物硅烷(BTESPT)钝化液的最佳配方为:V(BTESPT):V(乙醇):V(水)=4.5:5.5:90。研究了无机缓蚀剂Ce(NO)_3和纳米SiO_2粒子对BTESPT有机膜改性的效果,Tafel极化曲线表明Ce(NO)_3和纳米SiO_2粒子的最佳使用量分别为5.5×10~(-5)M、15ppm,Ce(NO)_3改性的效果较纳米SiO_2粒子的好。本论文还研究了KH-550表面预处理对两种改性膜的成膜影响,电化学阻抗测试表明,由于KH-550表面预处理增大了改性膜的厚度,对BTESPT在镀锌层表面成膜有一定的促进作用,所以比未经表面预处理的改性膜的耐蚀性能好。
In order to eliminate hazards of hexavalent chromium to humans and the environment, it was necessary to find new passivation process to replace chromate passivation. This paper studied two methods of chromium-free passivation, i.e, inorganic rare earth passivation film and organic silane passivation film, used for the galvanized layer.
The single rare-earth films optimum process determined by orthogonal experiments was that Ce (NO)_3:25g/L, H_2O_2 20ml/L, H_3BO_3: 2.0 g/L, processing time: 3min, temperature: 45℃, pH:3. It studied the effect of cerium salt concentration, pH, temperature, H_2O_2 content and processing time on the film-forming by Pb (AC)_2·9H_2O drop test and scanning electron microscopy. A kind of new passivation on the galvanized layer was formed by the cerium salt complexed with KH-570. Scanning electron microscopy showed the complexed passivation film some micro-cracks. Electrochemical tests of polarization curves and AC impedance show that the corrosion resistance of modified rare earth film was better than a single rare earth passive film as well as galvanized layer. X-ray diffraction analysis (XRD) and X-ray photon (XPS) spectroscopy analyzed the composition and structure of rare earth passive film. The results showed that the coating mainly was composed of oxides and hydroxides of cerium and zinc.
Tafel polarization curves determined the optimum formula for the passivation solution was V (BTESPT): V (ethanol): V (H_2O) = 4.5: 5.5: 90. It Studied the modified effect of inorganic inhibitor Ce(NO)_3 and nano-SiO_2 particles on BTESPT film, Tafel polarization curves showed that optimum amount of the Ce(NO)_3 and nano-SiO_2 particles were 5.5×10-5M and 15ppm, and that the modified effect of Ce(NO)_3 was better than that of nano-SiO_2 particles. Besides, it also studied that the role of KH-550 surface pretreatment in two kinds of modified passive film. Electrochemical impedance tests show that the corrosion resistance of modified films pretreated by KH-550 was better than that of modified film because KH-550 made the modified films thicker and promoted the BTESPT film forming on the galvanized sheet.
通过正交实验确定了单一稀土膜的最优工艺为:稀土铈盐25g/L,双氧水20ml/L,硼酸2.0 g/L,钝化时间3min,钝化温度45℃,pH为3。利用醋酸铅点滴实验和表面形貌观察,研究了铈盐的浓度、H_2O_2的含量、pH值、温度及处理时间等因素对成膜的影响。将铈盐与常用的有机硅烷KH-570复配使用应用于锌的无铬钝化处理。扫描电镜显示试样表面形成了带有微裂纹的稀土钝化膜。极化曲线、交流阻抗等电化学测试结果表明改性稀土膜的耐蚀性比单一稀土钝化膜以及镀锌层的好。利用X射线衍射、X光电子能谱对稀土钝化膜的成分及结构等进行了分析。结果表明膜层主要成分为铈
和锌的氧化物及氢氧化物。利用Tafel极化曲线确定了单一的双-(γ-(三乙氧基硅烷)-丙基)-四硫化物硅烷(BTESPT)钝化液的最佳配方为:V(BTESPT):V(乙醇):V(水)=4.5:5.5:90。研究了无机缓蚀剂Ce(NO)_3和纳米SiO_2粒子对BTESPT有机膜改性的效果,Tafel极化曲线表明Ce(NO)_3和纳米SiO_2粒子的最佳使用量分别为5.5×10~(-5)M、15ppm,Ce(NO)_3改性的效果较纳米SiO_2粒子的好。本论文还研究了KH-550表面预处理对两种改性膜的成膜影响,电化学阻抗测试表明,由于KH-550表面预处理增大了改性膜的厚度,对BTESPT在镀锌层表面成膜有一定的促进作用,所以比未经表面预处理的改性膜的耐蚀性能好。
In order to eliminate hazards of hexavalent chromium to humans and the environment, it was necessary to find new passivation process to replace chromate passivation. This paper studied two methods of chromium-free passivation, i.e, inorganic rare earth passivation film and organic silane passivation film, used for the galvanized layer.
The single rare-earth films optimum process determined by orthogonal experiments was that Ce (NO)_3:25g/L, H_2O_2 20ml/L, H_3BO_3: 2.0 g/L, processing time: 3min, temperature: 45℃, pH:3. It studied the effect of cerium salt concentration, pH, temperature, H_2O_2 content and processing time on the film-forming by Pb (AC)_2·9H_2O drop test and scanning electron microscopy. A kind of new passivation on the galvanized layer was formed by the cerium salt complexed with KH-570. Scanning electron microscopy showed the complexed passivation film some micro-cracks. Electrochemical tests of polarization curves and AC impedance show that the corrosion resistance of modified rare earth film was better than a single rare earth passive film as well as galvanized layer. X-ray diffraction analysis (XRD) and X-ray photon (XPS) spectroscopy analyzed the composition and structure of rare earth passive film. The results showed that the coating mainly was composed of oxides and hydroxides of cerium and zinc.
Tafel polarization curves determined the optimum formula for the passivation solution was V (BTESPT): V (ethanol): V (H_2O) = 4.5: 5.5: 90. It Studied the modified effect of inorganic inhibitor Ce(NO)_3 and nano-SiO_2 particles on BTESPT film, Tafel polarization curves showed that optimum amount of the Ce(NO)_3 and nano-SiO_2 particles were 5.5×10-5M and 15ppm, and that the modified effect of Ce(NO)_3 was better than that of nano-SiO_2 particles. Besides, it also studied that the role of KH-550 surface pretreatment in two kinds of modified passive film. Electrochemical impedance tests show that the corrosion resistance of modified films pretreated by KH-550 was better than that of modified film because KH-550 made the modified films thicker and promoted the BTESPT film forming on the galvanized sheet.
引文
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