Solvent induced swelling of membranes - measurements and influence in nanofiltration

This paper describes improvements to an apparatus for in-situ determinations of swelling where a linear inductive probe and electronic column gauge with an overall resolution of 0.1 μm was used for measurements of seven variants of polyacrylonitrile (PAN)/polydimethylsiloxane (PDMS) composite nanofiltration membranes in a range of alkane, aromatic and alcohol solvents. The unswollen membranes incorporated PDMS layers between 1 and 10 μm nominal thickness and were manufactured with a radiation and/or thermal crosslinking step. The tested membranes exhibited a range of swelling dependent on the degree of crosslinking, the initial PDMS layer thickness and the type of solvent. With no applied pressure the PDMS layer on some radiation crosslinked membranes swelled as much as ~170% of the initial thickness whilst other membranes were restricted to a maximum swelling of ~80%. When a pressure up to 2000 kPa was applied to a membrane then swelling could be reduced to ~20% of the value obtained at zero applied pressure. By vertically stacking up to 3 membrane samples it was possible to determine the swelling of PDMS layers as thin as 1 μm, although higher imposed pressures rendered some results unreliable as the measurement resolution of the apparatus was approached. The results of the swelling experiments are contrasted with crossflow nanofiltration performance in terms of solvent flux and solute rejection.