The glass transition temperature (T g) is a key property that dictates the applicability of conjugated polymers. The T g demarks the transition into a brittle glassy state, making its accurate prediction for conjugated polymers crucial for the design of soft, stretchable, or flexible electronics. Here we show that a single adjustable parameter can be used to build a relationship between the T g and the molecular structure of 32 semiflexible (mostly conjugated) polymers that differ drastically in aromatic backbone and alkyl side chain chemistry. An effective mobility value, ζ, is calculated using an assigned atomic mobility value within each repeat unit. The only adjustable parameter in the calculation of ζ is the ratio of mobility between conjugated and non-conjugated atoms. We show that ζ correlates strongly to the T g , and that this simple method predicts the T g with a root-mean-square error of 13°C for conjugated polymers with alkyl side chains.

The stiff backbones of conjugated polymers can lead to a rich phase behavior that includes both crystalline and liquid crystalline phases, making measurements of the glass transition challenging. In this work, the glass transitions of regioregular poly(3-hexylthiophene-2,5-diyl) (RR P3HT), regiorandom (RRa) P3HT, and poly((9,9-bis(2-octyl)-fluorene-2,7-diyl)-alt-(4,7-di(thiophene-2-yl)-2,1,3benzothiadiazole)-5′,5″-diyl) (PFTBT) are probed by linear viscoelastic measurements as a function of molecular weight. We find two glass transition temperatures (T g 's) for both RR and RRa P3HT and one for PFTBT. The higher T g , T α , is associated with the backbone segmental motion and depends on the molecular weight, such that the Flory−Fox model yields T α = 22 and 6 °C in the long chain limit for RR and RRa P3HT, respectively. For RR P3HT, a different molecular weight dependence of T α is seen below M n = 14 kg/mol, suggesting this is the typical molecular weight of intercrystal tie chains. The lower T g (T αPE ≈ −100 °C) is associated with the side chains and is independent of molecular weight. RRa P3HT exhibits a lower T α and higher T αPE than RR P3HT, possibly due to a different degree of nanophase separation between the side chains and the backbones. In contrast, PFTBT only exhibits one T g above −120 °C, at 144 °C in the long chain limit.

Biological membranes can achieve remarkably high permeabilities, while maintaining ideal selectivities, by relying on well-defined internal nanoscale structures in the form of membrane proteins. Here, we apply such design strategies to desalination membranes. A series of polyamide desalination membranes—which were synthesized in an industrial-scale manufacturing line and varied in processing conditions but retained similar chemical compositions—show increasing water permeability and active layer thickness with constant sodium chloride selectivity. Transmission electron microscopy measurements enabled us to determine nanoscale three-dimensional polyamide density maps and predict water permeability with zero adjustable parameters. Density fluctuations are detrimental to water transport, which makes systematic control over nanoscale polyamide inhomogeneity a key route to maximizing water permeability without sacrificing salt selectivity in desalination membranes.