School of Civil & Environmental Engineering, Nanyang Technological University, Singapore.
Environ Sci Technol. 2012 Jan 17;46(2):852-9. doi: 10.1021/es203090y. Epub 2012 Jan 5.
The degradation of polyamide (PA) nanofiltration and reverse osmosis membranes by chlorine needs to be understood in order to develop chlorine-resistant membranes. Coated and uncoated fully aromatic (FA) and piperazine (PIP) semi-aromatic PA membranes were treated with hypochlorite solution and analyzed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR). XPS results showed that in chlorine treated FA PA membranes the ratio of bound chlorine to surface nitrogen was 1:1 whereas it was only 1:6 in the case of PIP PA membranes. Surface oxygen of uncoated FA and PIP membranes increased with increasing hypochlorite concentration whereas it decreased for coated FA membranes. High resolution XPS data support that chlorination increased the number of carboxylic groups on the PA surface, which appear to form by hydrolysis of the amide bonds (C(O)-N). FTIR data indicated the disappearance of the amide II band (1541 cm(-1)) and aromatic amide peak (1609 cm(-1)) in both coated and uncoated chlorinated FA membranes, consistent with the N-chlorination suggested by the XPS results. Furthermore, the surface charge of chlorinated membranes at low pH (<6) became negative, consistent with amide-nitrogen chlorination. Chlorination appeared to both increase and decrease membrane hydrophobicity depending on chlorination exposure conditions, which implied that N-chlorination and hydrolysis may be competing processes. The effects of property changes on the membrane performance were also observed for NF90, BW30, and NF270 membranes.
为了开发耐氯膜,需要了解聚酰胺 (PA) 纳滤和反渗透膜被氯降解的情况。用次氯酸盐溶液处理涂覆和未涂覆的全芳香族 (FA) 和哌嗪 (PIP) 半芳香族 PA 膜,并通过 X 射线光电子能谱 (XPS) 和傅里叶变换红外 (FTIR) 进行分析。XPS 结果表明,在处理过的 FA PA 膜中,结合氯与表面氮的比例为 1:1,而在 PIP PA 膜中仅为 1:6。未涂覆的 FA 和 PIP 膜的表面氧随次氯酸盐浓度的增加而增加,而涂覆的 FA 膜则减少。高分辨率 XPS 数据支持氯增加了 PA 表面羧酸基团的数量,这些基团似乎是通过酰胺键 (C(O)-N) 的水解形成的。FTIR 数据表明,在涂覆和未涂覆的氯化 FA 膜中,酰胺 II 带 (1541 cm(-1)) 和芳酰胺峰 (1609 cm(-1)) 都消失了,这与 XPS 结果所表明的 N-氯化一致。此外,在低 pH(<6) 下,氯化膜的表面电荷变为负电荷,与酰胺氮氯化一致。根据氯化暴露条件,氯化似乎会增加和降低膜疏水性,这意味着 N-氯化和水解可能是竞争过程。还观察到 NF90、BW30 和 NF270 膜的性能变化对膜性能的影响。