Theoretical Evaluation of Polyelectrolyte Layering during Layer-by-Layer Coating of Ultrafiltration Hollow Fiber Membranes.

Layer-by-layer (LbL) modification of porous membranes for water filtration has become an active research field in the past few years. Different mechanisms regarding polyelectrolyte film growth, swelling and smoothing, transport through these films, etc., have been studied. Although there are conjectures, it is not yet fully understood where the polyelectrolyte layering takes place when modifying porous membranes, either within the pores or on top of the porous material. This study presents a theoretical approach to investigate the dominant layer buildup regime between pore-dominated vs. layer-dominated growth of polyelectrolytes on porous membranes without mechanically interfering or damaging the membrane material. For this, fouling mechanism processes are used as an analogy. The presented approach gives a new insight into layering conformation and might be helpful to investigate the interaction between the membrane surface and the PE film. Moreover, the MgSO4 rejection behavior of two types of modified membranes was investigated: one with an initial pore-dominated layer growth followed by a layer-dominated film growth; the other one with a completely layer-dominated film growth. The data confirm that a rejection for MgSO4 could only be achieved in the regime of layer-dominated film growth. Additionally, when layer-dominated film growth prevails from the early stages of the coating process, permeability values are higher at similar MgSO4 rejection rates compared to an initial pore-dominated and then layer-dominated film growth. Accordingly, the interaction between the membrane pore size and molecular weight of the polyelectrolytes in the coating solutions plays an important role during LbL coating.