We report dynamic Monte Carlo simulations of immiscible binary polymer blends, which exhibit weakly enhanced crystal nucleation near interfaces between two phase-separated polymers. We found that this enhancement is not accompanied by any preferred crystal orientation, implying its origin is mainly of enthalpic rather than entropic nature. Mean-field theory of polymer blends predicts that for immiscible polymers the melting point of the crystallizable component increases upon dilution in the other component, while it normally decreases for miscible blends. A local dilution is forced to occur at the diffuse interface of immiscible polymers; therefore the melting point of crystallizable polymers rises, which, in turn, enhances the thermodynamic driving force for crystal nucleation near the interface.

Lamellar polymer crystals are metastable due to their limited lamellar thickness. We performed dynamic Monte Carlo simulations of lattice linear polymers to investigate the kinetics of isothermal thickening via chainsliding diffusion in single lamellar crystals of polyethylene and poly(ethylene oxide). We sorted out three typical cases for controversial experimental observations. The basic case is a continuous increase of lamellar thickness for heavily folded long chains, with a logarithmic time dependence typical at the lateral growth front. Its kinetics is dominated by the activation energy barrier for sliding diffusion with higher speeds at higher temperatures. For integerfolded short chains, however, the lamellar thickness increases discontinuously, and its kinetics is dominated by a free energy barrier for surface nucleation. The latter can be further split into two cases: the thickening in the melt is mainly driven by the bulk free energy, with lower speeds at higher temperatures due to a temperature-sensitive barrier; while the thickening on a solid substrate is mainly driven by the surface free energy, with higher speeds at higher temperatures due to a temperature-insensitive barrier. The simulations facilitate our systematic understanding to the case-by-case microscopic mechanisms for the thickening of monolayer lamellar crystals via sliding diffusion of polymers.

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We performed dynamic Monte Carlo simulations of half-half binary blends of symmetric (double and mutual) crystallizable polymers. We separately enhanced the driving forces for polymer-uniform and polymer-staggered crystals. Under parallel enhancements, polymer-uniform crystals exhibit faster nucleation and growth, with more chain folding and less lamellar thickening, than those in polymer-staggered crystals. We attributed the results to intramolecular crystal nucleation, ruined by enhanced polymer-staggered crystallization. Our observations provide direct molecular-level evidence to support the fact that intramolecular crystal nucleation is favored by polymer crystallization in quiescent solutions and melt, which yields chain folding for the characteristic β-sheet or lamellar morphology of macromolecular crystals.

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Polymer membranes with well-controlled and vertically oriented pores are of great importance in the applications for water treatment and tissue engineering. On the basis of two-dimensional solvent freezing, we report environmentally friendly facile fabrication of such membranes from a broad spectrum of polymer resources including poly(vinylidene fluoride), poly(l-lactic acid), polyacrylonitrile, polystyrene, polysulfone and polypropylene. Dimethyl sulfone, diphenyl sulfone, and arachidic acid are selected as green solvents crystallized in the polymer matrices under two-dimensional temperature gradients induced by water at ambient temperature. Parallel Monte Carlo simulations of the lattice polymers demonstrate that the directional process is feasible for each polymer holding suitable interaction with a corresponding solvent. As a typical example of this approach, poly(vinylidene fluoride) membranes exhibit excellent tensile strength, high optical transparence, and outstanding separation performance for the mixtures of yeasts and lactobacilli.

We report dynamic Monte Carlo simulations of polymer crystal nucleation initiated by prior spinodal decomposition in polymer solutions. We observed that the kinetic phase diagrams of homogeneous crystal nucleation appear horizontal in the concentration region below their crossovers with the theoretical liquid-liquid spinodal. When the solution was quenched into the temperature beneath this horizontal boundary, the time evolution of structure factors demonstrated the spinodal decomposition at the early stage of crystal nucleation. In comparison with the case without a prior liquid-liquid demixing, we found that the prior spinodal decomposition can regulate the nanoscale small polymer crystallites toward a larger population, more uniform sizes, and a better spatial homogeneity, whereas chain folding in the crystallites seems little affected.