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Using isobaric Monte Carlo simulations, we map out the entire phase diagram of a system of hard cylindrical particles of length $L$ and diameter $D$, using an improved algorithm to identify the overlap condition between two cylinders. Both the prolate $L/D>1$ and the oblate $L/D<1$ phase diagrams are reported with no solution of continuity. In the prolate $L/D>1$ case, we find intermediate nematic textrm{N} and smectic textrm{SmA} phases in addition to a low density isotropic textrm{I} and a high density crystal textrm{X} phase, with textrm{I-N-SmA} and textrm{I-SmA-X} triple points. An apparent columnar phase textrm{C} is shown to be metastable as in the case of spherocylinders. In the oblate $L/D<1$ case, we find stable intermediate cubatic textrm{Cub}, nematic textrm{N}, and columnar textrm{C} phases with textrm{I-N-Cub}, textrm{N-Cub-C}, and textrm{I-Cub-C} triple points. Comparison with previous numerical and analytical studies is discussed. The present study, accounting for the explicit cylindrical shape, paves the way to more sophisticated models with important biological applications, such as viruses and nucleosomes.
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The ion-ion interactions become exponentially screened for ions confined in ultranarrow metallic pores. To study the phase behaviour of an assembly of such ions, called a superionic liquid, we develop a statistical theory formulated on bipartite lattices, which allows an analytical solution within the Bethe-lattice approach. Our solution predicts the existence of ordered and disordered phases in which ions form a crystal-like structure and a homogeneous mixture, respectively. The transition between these two phases can potentially be first or second order, depending on the ion diameter, degree of confinement and pore ionophobicity. We supplement our analytical results by three-dimensional off-lattice Monte Carlo simulations of an ionic liquid in slit nanopores. The simulations predict formation of ionic clusters and ordered snake-like patterns, leading to characteristic close-standing peaks in the cation-cation and anion-anion radial distribution functions.
We extend the Cahn-Landau-de Gennes mean field theory of binary mixtures to understand the wetting thermodynamics of a three phase system, that is in contact with an external surface which prefers one of the phases. We model the system using a phenomenological free energy having three minima corresponding to low, intermediate and high density phases. By systematically varying the textit{(i)} depth of the central minimum, textit{(ii)} the surface interaction parameters, we explore the phase behavior, and wetting characteristics of the system across the triple point corresponding to three phase coexistence. We observe a non-monotonic dependence of the surface tension across the triple point that is associated with a complete to partial wetting transition. The methodology is then applied to study the wetting behaviour of a polymer-liquid crystal mixture in contact with a surface using a renormalised free energy. Our work provides a way to interrogate phase behavior and wetting transitions of biopolymers in cellular environments.
We examined the kinetics of the transformation from the lamellar (LAM) to the hexagonally packed cylinder (HEX) phase for the triblock copolymer, polystyrene-b-poly (ethylene-co-butylene)-b-polystyrene (SEBS) in dibutyl phthalate (DBP), a selective solvent for polystyrene (PS), using time-resolved small angle x-ray scattering (SAXS). We observe the HEX phase with the EB block in the cores at a lower temperature than the LAM phase due to the solvent selectivity of DBP for the PS block. Analysis of the SAXS data for a deep temperature quench well below the LAM-HEX transition shows that the transformation occurs in a one-step process. We calculate the scattering using a geometric model of rippled layers with adjacent layers totally out of phase during the transformation. The agreement of the calculations with the data further supports the continuous transformation mechanism from the LAM to HEX for a deep quench. In contrast, for a shallow quench close to the OOT we find agreement with a two-step nucleation and growth mechanism.
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