Electron-beam-induced grafting of hydrophilic polymers was applied to modify PVDF membranes for biomedical applications. Grafting was performed by immersing the membrane in an aqueous solution of different hydrophilic polymers followed by electron-beam irradiation. The two polymer types are able to cross-link by recombination of adjacent radicals formed via the irradiation. Although the untreated membrane was already quite hydrophilic, the modification resulted in even lower water contact angles at the membrane surface indicating improved water wettability. The presence of different functional groups originating from the hydrophilic polymers was detected on the membrane surface by electrokinetic measurements. SEM investigations as well as porosimetry experiments showed that the grafted hydrophilic polymer layer is very thin; therefore, the membrane pore structure is not negatively affected. Soxhlet extraction revealed the stability of the modification for selected polymers: surface contact angles were comparable after extraction, and total organic carbon investigation of the extraction water revealed no significant loss of organic material. Investigated mechanical properties confirmed an increased stability due to cross-linking of the polymers. Undesired hemolysis was not detected with hemocompatibility tests, and coagulation was decreased with selected hydrophilic polymers. Because of the absence of any toxic material during surface modification and the high stability of the product, this method is believed to be suitable for the modification of membranes for medical applications, e.g. for improving the hemo-or biocompatibility.

Abstract:In this work we aim to show that the overall surface potential is a key factor to understand and predict anti-fouling characteristics of a polymer membrane. Therefore, polyvinylidene fluoride membranes were modified by electron beam-induced grafting reactions forming neutral, acidic, alkaline or zwitterionic structures on the membrane surface. The differently charged membranes were investigated regarding their surface properties using diverse analytical methods: zeta potential, static and dynamic water contact angle, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Porosimetry measurements proved that there is no pore blocking due to the modifications. Monodisperse suspensions of differently charged polystyrene beads were synthesized by a radical emulsion polymerization reaction and were used as a model fouling reagent, preventing comparability problems known from current literature. To simulate membrane fouling, different bead suspensions were filtered through the membranes. The fouling characteristics were investigated regarding permeation flux decline and concentration of model fouling reagent in filtrate as well as by SEM. By considering electrostatic interactions equal to hydrophobic interactions we developed a novel fouling test system, which enables the prediction of a membrane's fouling tendency. Electrostatic forces are dominating, especially when charged fouling reagents are present, and can help to explain fouling characteristics that cannot be explained considering the surface wettability.

The zeta potential of membrane surfaces and the resulting electrostatic interactions are determining factors of membrane fouling. This publication presents the impact of salt concentration and pH value on these interactions.

This study presents a new method focussing on electrostatic interactions during fouling of microfiltration membranes.

A new electron beam-based approach for the direct functionalization of polyethersulfone, polyvinylidene fluoride, polysulfone as well as polyacrylonitrile membranes in a one-step procedure is presented. Aqueous solutions of functional molecules were immobilized on the membrane surface by electron beam treatment. The resulting membranes show significantly increased flux and water wettability accompanied by decreased protein adsorption. Stability tests demonstrated the permanence of the modification. This new method neither requires any preceding surface functionalization nor the use of catalysts/photoinitiators or other toxic reagents. In addition, it avoids the synthesis of hydrophilic monomers/polymers, thus avoiding additional synthetic and purification steps as well as the use of organic solvents.

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Abstract:To generate polyethersulfone membranes with a biocatalytically active surface, pancreatin was covalently immobilized. Pancreatin is a mixture of digestive enzymes such as protease, lipase, and amylase. The resulting membranes exhibit self-cleaning properties after "switching on" the respective enzyme by adjusting pH and temperature. Thus, the membrane surface can actively degrade a fouling layer on its surface and regain initial permeability. Fouling tests with solutions of protein, oil, and mixtures of both, were performed, and the membrane's ability to self-clean the fouled surface was characterized. Membrane characterization was conducted by investigation of the immobilized enzyme concentration, enzyme activity, water permeation flux, fouling tests, porosimetry, X-ray photoelectron spectroscopy, and scanning electron microscopy.

Membrane filters are designed for selective separation of components from a mixture. While separation by size might be the most common approach, other characteristics like charge can also be used for separation as presented in this study. Here, a polyether sulfone membrane was modified to create a zwitterionic surface. Depending on the pH value of the surrounding solution the membrane surface will be either negatively or positively charged. Thus, the charged state can be easily adjusted even by small changes of the pH value of the solution. Charged polystyrene beads were used as model reagent to investigate the pH dependent selectivity of the membrane. It was found that electrostatic forces are dominating the interactions between polystyrene beads and membrane surface during the filtration. This enables a complete control of the membrane’s selectivity according to the electrostatic interactions. Furthermore, differently charged beads marked with fluorescent dyes were used to investigate the selectivity of mixtures of charged components. These different components were successfully separated according to their charged state proving the selectivity of the invented membrane.