Oxygen transport as a structure probe for amorphous polymeric systems

Although permeability of small molecules is often measured as an important performance property, deeper analysis of the transport characteristics provides insight into polymer structure, especially if used in combination with other characterization techniques. Transport of small gas molecules "senses" the permeable amorphous structure and probes the nature of free volume. This work focuses on oxygen transport, supplemented with other methods of physical analysis, as a probe for: (1) the nature of free volume in the oriented glassy state, (2) the role of amorphous phase orientation and strain-induced crystallization on oxygen barrier properties of polyester blends, and (3) the nature of interphase between immiscible amorphous polymers in forced-assemblies.; In the first part, the mechanism of oxygen transport in oriented glassy polyesters is examined. PET, PETBB55, and PEN were oriented by cold-drawing. Densification of the glassy state correlates with conformational transformation of glycol linkages from gauche to trans. Orientation is seen as a process of decreasing the amount of excess-hole free volume and bringing the nonequilibrium polymer glass closer to the equilibrium condition. Further insights into the free volume structure are obtained by exploring the relationships between free volume structure and oxygen transport property using a simple lattice-hole model.; In the second part, oxygen transport through polyester blends is investigated. It is found that cold-drawing the blocky PET/PETBB55 produces highly oriented PETBB55 frustrated LCP microfibrils, which prevent relaxation of the continuous PET phase. On the other hand, careful examination of oxygen barrier for the PET/PEI blends leads to a two-phase model from which the amount of crystallinity and the amorphous phase density are determined.; In the third part, oxygen permeability is utilized as a powerful probe for interphase thickness between immiscible polymers, which is as thin as a few nanometers. We have fabricated a new type of material, interphase material, which is entirely interphase by forced-assembly of two immiscible polymers. The results demonstrate that immiscible polymers can be combined by way of forced-assembly such that the final material behaves like a miscible polymer blend even though they are not thermodynamically miscible. Various interphase structure-property relationships are explicitly demonstrated using conventional polymer analysis including oxygen permeability.