There is notable discrepancy between experiments and coarse-grained model studies regarding the thermodynamic driving force in polyelectrolyte complex coacervation: experiments find the free energy change to be dominated by entropy, while simulations using coarse-grained models with implicit solvent usually report a large, even dominant energetic contribution in systems with weak to intermediate electrostatic strength. Here, using coarse-grained, implicit-solvent molecular dynamics simulation combined with thermodynamic analysis, we study the potential of mean force (PMF) in the two key stages on the coacervation pathway for symmetric polyelectrolyte mixtures: polycation–polyanion complexation and polyion pair–pair condensation. We show that the temperature dependence in the dielectric constant of water gives rise to a substantial entropic contribution in the electrostatic interaction. By accounting for this electrostatic entropy, which is due to solvent reorganization, we find that under common conditions (monovalent ions, room temperature) for aqueous systems, both stages are strongly entropy-driven with negligible or even unfavorable energetic contributions, consistent with experimental results. Furthermore, for weak to intermediate electrostatic strengths, this electrostatic entropy, rather than the counterion-release entropy, is the primary entropy contribution. From the calculated PMF, we find that the supernatant phase consists predominantly of polyion pairs with vanishingly small concentration of bare polyelectrolytes, and we provide an estimate of the spinodal of the supernatant phase. Finally, we show that prior to contact, two neutral polyion pairs weakly attract each other by mutually induced polarization, providing the initial driving force for the fusion of the pairs.

The morphology of coatings created by electrostatic deposition can be generally divided into three categories: wire mats, particles, and films. At intermediate regimes, there should exist nanowire forests as a...

Emulsion polymerization is a versatile approach to produce different polymeric nanoparticle morphologies, which can be useful in a variety of applications. However, the detailed mechanism of the morphology formation is not entirely clear. We study the kinetics of nanoparticle morphology evolution during a seeded emulsion polymerization using both experimental and computational tools. Lightly crosslinked polystyrene seeds were first synthesized using dispersion polymerization. Then the seed particles were swollen in tert-butyl acrylate and styrene monomers, and subsequently polymerized into nanoparticles of dumbbell and multilobe morphologies. It was discovered that both the seed and final particle morphology were affected by the methanol concentration during the seed synthesis.Systematically adjusting the methanol amount will not only yield spherical seed particles of different size, but also dumbbell particles even without the second monomer polymerization. In addition to methanol concentration, morphology can be controlled by crosslinking density. The kinetics studies revealed an

Nanoparticle aggregation in a nanocomposite can be physically modulated by the polymer conformational change into open fractal structures.