Synthesis and Polyelectrolyte Functionalization of Hollow Fiber Membranes Formed by Solvent Transfer Induced Phase Separation.

Ultrafiltration membranes are important porous materials to produce freshwater in an increasingly water-scarce world. A recent approach to generate porous membranes is solvent transfer induced phase separation (STrIPS). During STrIPS, the interplay of liquid-liquid phase separation and nanoparticle self-assembly results in hollow fibers with small surface pores, ideal structures for applications as filtration membranes. However, the underlying mechanisms of the membrane formation are still poorly understood, limiting the control over structure and properties. To address this knowledge gap, we study the nonequilibrium dynamics of hollow fiber structure evolution. Confocal microscopy reveals the distribution of nanoparticles and monomers during STrIPS. Diffusion simulations are combined with measurements of the interfacial elasticity to investigate the effect of the solvent concentration on nanoparticle stabilization. Furthermore, we demonstrate the separation performance of the membrane during ultrafiltration. To this end, polyelectrolyte multilayers are deposited on the membrane, leading to tunable pores that enable the removal of dextran molecules of different molecular weights (>360 kDa, >60 kDa, >18 kDa) from a feed water stream. The resulting understanding of STrIPS and the simplicity of the synthesis process open avenues to design novel membranes for advanced separation applications.

Influence of Molecular Weight on the Performance of Polyelectrolyte Multilayer Nanofiltration Membranes.

Polyelectrolyte multilayers (PEMs) are highly promising selective layers for membrane applications, especially because of their versatility. By careful choice of the types of polyelectrolyte and the coating conditions, the PEM material properties can be controlled to achieve desired separations. Less understood, however, is how the molecular weight (Mw) of the chosen polyelectrolytes (PEs) will impact layer build-up and thus separation properties. In this work, we investigate the influence of Mw on the performance of two types of PEM-based membranes. PEM membranes have been fabricated from low (15-20 kDa) and high (150-250 kDa) Mw poly(allylamine hydrochloride) (PAH), poly(sodium-4-styrenesulfonate)(PSS), and poly(acrylic acid) (PAA) to obtain PAH/PSS- and PAH/PAA-based nanofiltration membranes. For the linear growing PSS/PAH system, with low PE mobility, the Mw is found to influence the pore closure of the support membrane during coating but not its subsequent performance. In contrast, for the exponentially growing PAH/PAA system with a high PE mobility, much stronger effects of Mw are observed. For low-Mw PAH/PAA PEM membranes, separation properties are found that would be expected of a negatively charged separation layer, while for high-Mw PAH/PAA PEMs a positive separation layer is found. Moreover, molecular weight cutoff (MWCO) measurements show that the low-Mw PAH/PAA multilayers are much denser than their high-Mw counterparts. Here the higher mobility of the small PE chains is expected to lead to more optimal binding between the oppositely charged PEs, explaining the denser structure. Lastly, we find that PEM pH stability is lowest for low-Mw PAH/PAA multilayers which can again be attributed to their higher mobility. Clearly, the Mw can significantly influence the separation performance of PEM-based membranes, especially for more mobile PEM systems such as PAA/PAH.

Nafion-Based Low-Hydration Polyelectrolyte Multilayer Membranes for Enhanced Water Purification.

The increase of micropollutant concentration in both surface and groundwater is an emerging concern for the environment and human health. Most of such small organic molecules (medicines, hormones, and plasticizers) enter the environment via our wastewater, because they are not sufficiently removed by the current techniques applied in wastewater treatment plants. A possible solution to remove micropollutants is the usage of polyelectrolyte multilayer (PEM) based membranes. PEM membranes have received a growing interest in the past decade due to their high chemical and physical stability and their high permeability and selectivity. A popular polyelectrolyte pair to make dense PEM membranes with high salt retentions is the combination of poly(allylamine hydrochloride) (PAH) and poly(sodium 4-styrenesulfonate) (PSS). Unfortunately, smaller micropollutants (such as bisphenol A, sulfamethoxazole, naproxen, and bezafibrate) still show significant permeation through this membrane. In this study, for the first time, a single final layer of Nafion is applied on the PEM to increase the density of the PEM membrane. It is shown that when terminating with Nafion, the swelling of the multilayer decreases by 50%. These pronounced changes in layer structure are reflected by changes in membrane performance, such as a lower molecular weight cutoff (MWCO) and an increasing hydraulic membrane resistance. Furthermore, we show that the Nafion content of the multilayer can be increased by constructing a Nafion/PAH multilayer on top of the existing PSS/PAH multilayer, thereby lowering the MWCO. Although hydraulic resistance increases, these PSS/PAH/Nafion-based multilayers show excellent performance in rejecting difficult-to-remove micropollutants that have low molecular weight (200-650 Da) and different charges. Overall, a cocktail of eight small micropollutants can be removed up to 97% by these membranes, allowing strongly enhanced water purification.