Role of additives in the water vapor transport through block co-poly(amide/ether) membranes: effects on surface and bulk polymer properties

In the last years there has been a growing industrial interest in modifying the performance of traditional polymers by using additives, working as modifiers for processing, rheological, transport, bonding, and pigmentation properties. This work was focused on the understanding of the relationships between chemical structure and water vapour transport through a polymer matrix modified by different additives regarding hydrophilicity and molecular structure. A screening of the changes in surface energies and bulk morphology, as a function of the chemical nature and weight percent modifier, allowed estimating the effects on the water vapour transport through polymer membranes. Static and dynamic contact angle measurements explained the difference in surface wettability and affinity to polar species such as water molecules. Modifiers having polar groups improved the surface hydrophilicity, enhancing the breathability of the membranes, while hydrophobic components such as aromatic structures led to a reduction of the water vapour mass uptake onto the membrane surface. On the other hand, thermal analyses showed a tendency of the polymer structure to reduce its own mobility with consequent slowdown of the diffusion through polymer matrix. Modification with large and bulky structures disrupted the polymer packing density, but simultaneously increased the stiffness of the polymer chains, inhibiting the penetrant migration. As a result, balancing the effects due to modifier polarity and bulky structure, it is possible to change the performance of a polymer in terms of transport, going from breathable membranes to barrier films.