A novel membrane surface modification approach was proposed to successfully obtain a poly(vinylidene fluoride)-poly(acrylic acid)-ZnO (PVDF-PAA-ZnO) membrane with super-high water permeability and great oil rejection through cold plasma-induced PAA graft-polymerization followed by simple nano-ZnO self-assembly. The experimental parameters of modification were optimized and their optimal combination was identified using Taguchi orthogonal array (OA) design method. The PVDF-PAA-ZnO membrane was comprehensively characterized and the mechanism of nano-ZnO self-assembly was explored by contact angle measurement, scanning electron microscope (SEM) images, elemental analysis, tension test, Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR) and synchrotron-based X-ray analyses. It was revealed that ZnO nanoparticles were immobilized onto membrane surface through the adsorption of PAA layer to form a PAA-ZnO coating without valence change. The carboxyl groups of PAA layer provided complexing ligands to coordinate with Zn2+ and form bidentate species on the nano-ZnO surface. The firm PAA-ZnO coating on PVDF membrane surface converted its hydrophobic nature to hydrophilic, bringing about the dramatically improvement of membrane performance both in water permeation flux and oil rejection rate. The permeation flux of the PVDF-PAA-ZnO membrane was more than 10 times as great as that of the pristine PVDF membrane.

中文翻译：

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用于含油废水处理的等离子体诱导 PAA-ZnO 涂层 PVDF 膜：通过田口 OA 设计和基于同步加速器的 X 射线分析制备、优化和表征

提出了一种新的膜表面改性方法，通过冷等离子体诱导 PAA 接枝成功获得了具有超高透水性和高阻油性的聚（偏二氟乙烯）-聚（丙烯酸）-ZnO（PVDF-PAA-ZnO）膜-聚合，然后是简单的纳米 ZnO 自组装。使用田口正交阵列（OA）设计方法优化修改的实验参数并确定它们的最佳组合。通过接触角测量、扫描电子显微镜（SEM）图像、元素分析、拉伸试验、衰减全反射-傅里叶变换红外光谱等方法，对PVDF-PAA-ZnO膜进行了综合表征，探讨了纳米ZnO自组装的机理。 ATR-FTIR）和基于同步加速器的 X 射线分析。结果表明，ZnO纳米颗粒通过PAA层的吸附固定在膜表面，形成PAA-ZnO涂层而没有价态变化。PAA 层的羧基提供了络合配体以与 Zn2+ 配位并在纳米 ZnO 表面形成双齿物种。PVDF膜表面坚固的PAA-ZnO涂层将其疏水性转化为亲水性，从而显着提高了膜的透水通量和截油率。PVDF-PAA-ZnO 膜的渗透通量是原始 PVDF 膜的 10 倍以上。PAA 层的羧基提供了络合配体以与 Zn2+ 配位并在纳米 ZnO 表面形成双齿物种。PVDF膜表面坚固的PAA-ZnO涂层将其疏水性转化为亲水性，从而显着提高了膜的透水通量和截油率。PVDF-PAA-ZnO 膜的渗透通量是原始 PVDF 膜的 10 倍以上。PAA 层的羧基提供了络合配体以与 Zn2+ 配位并在纳米 ZnO 表面形成双齿物种。PVDF膜表面坚固的PAA-ZnO涂层将其疏水性转化为亲水性，从而显着提高了膜的透水通量和截油率。PVDF-PAA-ZnO 膜的渗透通量是原始 PVDF 膜的 10 倍以上。