光谱学研究硅烷钒锆复合钝化膜的结构和成膜机理  

Spectroscopic Study on Film Formation Mechanism and Structure of Composite Silanes-V-Zr Passive Film

作　　者：王雷[1] 刘常升[2] 石磊[2] 安成强[1] 

机构地区：[1]沈阳理工大学环境与化学工程学院,辽宁沈阳110159 [2]东北大学材料各向异性与织构工程教育部重点实验室,辽宁沈阳110004

出　　处：《光谱学与光谱分析》2015年第2期453-456,共4页Spectroscopy and Spectral Analysis

基　　金：国家高技术发展计划(863)项目(2009AA03Z529)资助

摘　　要：在热镀锌钢板表面制备了硅烷钒锆复合钝化膜。用X射线光电子能谱(XPS)、射频辉光放电发射光谱(rf-GD-OES)和傅里叶变换衰减全反射红外光谱(ATR-FTIR)表征了钝化膜的组成结构,分析了硅烷钒锆复合钝化膜的成膜机理。结果表明:硅烷之间互联构成了硅烷钒锆复合钝化膜的主成膜成分,无机缓蚀剂均匀分布在膜层中。钝化膜表面Si2p的XPS窄幅扫描谱100.7eV处的拟合峰和红外光谱在波数1 100cm-1 Si—O吸收峰变宽加强,表明硅烷以Si—O—Zn键的形式化学吸附在锌的表面,硅烷分子之间通过Si—O—Si键相互交联;红外光谱中1 650和1 560cm-1的两个酰胺特征峰,结合910cm-1的环氧特征峰的消失,表明γ-GPT的环氧基团在氨基活性氢的诱导下开环和γ-APT的氨基之间发生聚合反应形成交联的空间网状结构;rf-GD-OES分析发现钝化膜0.3μm处存在一层富氧层,钝化反应生成的ZrF4,ZrO2和钒盐等无机物均匀分布在钝化膜中。分析膜层组成结构和成膜前后的ATR-FTIR光谱,研究了成膜过程中发生的物理过程和化学变化,提出了硅烷钒锆复合钝化膜的成膜机理。A composite silanes-V-Zr passive film was overlayed on hot-dip galvanized steel. Attenuated total reflection Fourier transformed infrared spectroscopy （ATR-FI＇IR）, X-ray photoelectron spectrometer （XPS） and radio frequency glow discharge optical emission spectrometry （rf-GD-OES） were used to characterize the molecular structure of the silanes-V-Zr passive film. The mechanism of film formation was discussed. The results show that the silane molecules are crosslinked as the main film for- mer and inorganic inhibitor is even distributed in the film. The fitting peak of 100. 7 eV in XPS single Si2p energy range spectra of the composite silanes-V-Zr passive film and the widening and strengthening of the Si--O infrared absorption peak at 1 100 cm-1 indicate that the silanes were adsorbed on the surface of zinc with chemical hond of Si--O--Zn, and the silane molecules were connected with each other by bond of Si--O--Si. Two characteristic absorption peaks of amide at 1 650 and 1 560 cm-1 ap- pear in the infrared spectroscopy of the composite silanes-V-Zr passive fihn, and a characteristic absorption peak of epoxy groups at 910 cm 1 disappears in the infrared spectroscopy of the passive film. The results indicate that y-APT can be prepared through nueleophilic ring-opening of ethylene oxide in y-GPT molecule to form C--N covalent bonds. The rf-GD-OES results indicate that there is a oxygen enriched layer in 0.3 μm depth of the composite silanes-V-Zr passive film. Moreover, ZrF4, ZrO2 and some inorganic matter obtained by the reaction during the forming process of the composite silanes-V-Zr passive film are distribu- ted evenly throughout the film. According to the film composition, the physical processes and chemical reactions during the film forming process were studied by using ATR-FTIR. Based on this, the film forming mechanism was proposed.

关 键 词：硅烷钒锆钝化膜 XPS rf-GD-OES FTIR 成膜机理 

分 类 号：TG174[金属学及工艺—金属表面处理]