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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Quasi-one-dimensional fibril crystal growth of diblock copolymers is a fundamental issue in the investigation of nanotechnology and neurodegenerative diseases. We performed dynamic Monte Carlo simulations of lattice polymers to study the crystallization-driven fibril crystal growth of diblock copolymers under two circumstances of solutions: sporadic crystals with the feeding mode of constant polymer concentrations, and massive crystals with the depleting mode of decaying polymer concentrations. We confirmed anisotropic driving forces as a prerequisite of steady growth of fibril crystals. The lamellar crystal width is confined by the noncrystalline block below a critical concentration that shifts down with the decrease of the noncrystallizable block fractions. In the depleting mode, the long-axis sizes at the early stage of fibril crystal growth can be fitted well by an exponential-decay function of time, and the growth rates decrease linearly with polymer concentrations by following the growth rates in the feeding mode, appearing as consistent with our previous simulation results of homopolymer solutions.

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.