Abstract
To evaluate the effect of polymer architecture on surface tension, glass transition, and other thermodynamic properties, we synthesized a series of 4-arm and 11-arm symmetric star polystyrenes. Surface tension was measured as a function of molecular weight of the stars and temperature in the melt using a modified Wilhelmy plate technique. We find that architectural effects play a significant role in determining the molecular weight dependence of polymer melt surface tension. A variable density lattice model that considers effects of entropic attraction of polymer chain ends to surfaces, compressibility and density gradients in the region near the surface is used to determine the origin of this observation. This analysis is complemented with surface tension calculations using more classical thermodynamic models that consider only bulk property changes with polymer architecture and molecular weight. Bulk thermodynamic properties for selected stars were derived from pressure−volume−temperature (PVT) measurem...
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