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Solvent stable UV and EB cross-linked polysulfone-based membranes

Abstract : The importance of membrane technology as a separation technique has increased rapidly over the past decades thanks to its broad range of applications. The expanding market brings along the requirement of advanced polymeric materials, which show resistance towards swelling and plasticization in gas separation (GS) and towards harsh solvents and extreme pH conditions in solvent resistant nanofiltration (SRNF). At this stage, cross-linking has emerged as a promising technology to overcome these issues. Chemical cross- linking is one of the most commonly used techniques and is based on a chemical reaction between a polymer (e.g. polyimide) and a cross-linker (e.g. diamine or diol). However, for polymers which do not contain chemically reactive groups in their backbone, such as polysulfones (PSU), this technique is not feasible. Additionally, chemical cross-linking involves several processing steps and causes harmful waste streams, triggering the quest for a generally applicable, fast and green curing technique. Two new curing techniques, namely ultraviolet (UV) and electron beam (EB) curing, were explored in this thesis, in order to obtain chemically and thermally stable membranes, hence being attractive for SRNF applications. Asymmetric membranes, composed of a semi-interpenetrating polymer network (SIPN), were prepared via non-solvent induced phase separation (NIPS). PSU was chosen as polymer because of its robust thermal and mechanical properties, photosensitivity and lack of reactive groups. Cross-linked membranes with SIPN structure were obtained via UV and EB-curing. In the first part, the influence of cross-linker functionality, radiation energy dose and polymer/crosslinker ratio on the EB-curing efficiency was investigated. Acrylate-based cross-linkers were employed. The obtained membranes were characterized with ATR-FTIR, SEM and filtration experiments, together with stability testing against harsh solvents. The best type of cross-linker and its optimum concentration under optimum EB-dose were then selected for further studies. In the second part, the effects of solvent/co-solvent ratio and the evaporation time before precipitation of UV and EB-cured PSU SRNF-membranes were explored, using tetrahydrofuran (THF) or 1,4-dioxane (DIO) as co-solvent. Both UV and EB-cured PSU membrane morphologies differed as function of the studied phase inversion parameters. Increasing evaporation time reduced macrovoid formation with appearance of spongy structures. The flux generally remained too low for membranes to become really useful in SRNF. A post treatment was performed to increase the flux by immersing UV-cured PSU-based membranes in dimethylformamide (DMF) for 48 h. The resultant membranes showed higher permeances and lower rejections, making them especially useful as potential candidates as stable supports in the preparation of thin film composite membranes. In a third part, the mechanical characteristics, the effect of casting thickness and the surface properties of the membranes cross-linked by both irradiation methods were further studied. Additionally, the swelling behavior of UV-cured thin PSU films as function of different curing parameters (i.e. radiation dose and cross-linker functionality) was analyzed with ellipsometry. In conclusion, solvent stable asymmetric PSU membranes were developed by two simple, environmentally friendly and highly effective methods. The performance and enhanced chemical resistance of the cured membranes show high potential for implementing both cross-linking procedures in adequate industrial applications after further optimization.
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Veysi Altun. Solvent stable UV and EB cross-linked polysulfone-based membranes. Chemical and Process Engineering. Université Paul Sabatier - Toulouse III, 2016. English. ⟨NNT : 2016TOU30393⟩. ⟨tel-01915017⟩

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