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.
© 2021 The Authors. Published by American Chemical Society.