Rubbery Polymer−Inorganic Nanocomposite Membranes: Free Volume Characteristics on Separation Property

Abstract

The rational design of polymer−inorganic nanocomposite membranes relies heavily on the precise insight and elaborate control of the interface. Presently, the direct exploration of the hierarchical structure of nanocomposite membranes still remains elusive. In the present study, we propose a facile and generic methodology to quantitatively probe the interfacial structure by complementary positron annihilation lifetime spectroscopy (PALS) and molecular dynamics simulation (MDS) techniques. MDS is used to acquire the molecular level information such as the polymer−inorganic interface interaction energy, chain mobility within the nanocomposite membranes, whereas PALS is used to acquire the free volume characteristics of the nanocomposite membranes. As proof-of-principle, we choose anisotropic inorganic nanotube embedded rubbery polymer membrane as a model, which generates the interface between soft polymer and rigid inorganic. PALS reveals that incorporation of titanate nanotubes (TNTs) narrows the free volume pore radius distribution of the membranes. MDS indicates that the segmental chain mobility in the vicinity of the polymer−inorganic interface is substantially restrained, which creates numerous nanosized voids for molecular transport, and dramatically enhances the fractional free volume (FFV) of the membranes. Quite interestingly, it was found that the rubbery membranes can also exhibit simultaneously increased permeability and membrane selectivity, and this unusual phenomenon was tentatively elucidated by relating the separation properties to the free volume characteristics of the membranes.