Self-consistent field theory of polymer-ionic molecule complexation

A self-consistent field theory is developed for polymers that are capable of binding small ionic molecules (adsorbates). The polymer-ionic molecule association is described by Ising-like binding variables, C_(i)^(a)(kΔ)(= 0 or 1), whose average determines the number of adsorbed molecules, nBI. Polymer gelation can occur through polymer-ionic molecule complexation in our model. For polymer-polymer cross-links through the ionic molecules, three types of solutions for nBI are obtained, depending on the equilibrium constant of single-ion binding. Spinodal lines calculated from the mean-field free energy exhibit closed-loop regions where the homogeneous phase becomes unstable. This phase instability is driven by the excluded-volume interaction due to the single occupancy of ion-binding sites on the polymers. Moreover, sol-gel transitions are examined using a critical degree of conversion. A gel phase is induced when the concentration of adsorbates is increased. At a higher concentration of the adsorbates, however, a re-entrance from a gel phase into a sol phase arises from the correlation between unoccupied and occupied ion-binding sites. The theory is applied to a model system, poly(vinyl alcohol) and borate ion in aqueous solution with sodium chloride. Good agreement between theory and experiment is obtaine

Phase Separation Induced by Ladder-Like Polymer-Polymer Complexation

Polymer-polymer complexation in solvent is studied using an extension of the self-consistent field theory. The model polymers are capable of forming ladder-like duplex structures. The duplex formation occurs with an abrupt change of entropy, resulting in a first-order transition. Moreover, the complexation can be stabilized by solvent-polymer interactions, instead of the usual specific binding interactions. Various types of unconventional phase diagrams are predicted. For example, phase separation with decreasing χ-parameter between duplex polymer and solvent can be induced, leading to a lower critical solution temperature (LCST) behavior. Multiphase coexistence points at which two, three, or four phases coexist are also obtained. Under certain conditions a homogeneous phase becomes unstable when the polymer chain length is decreased, in contrast to the standard Flory-Huggins theory

Stability of Two-Dimensional Soft Quasicrystals

The relative stability of two-dimensional soft quasicrystals is examined using a recently developed projection method which provides a unified numerical framework to compute the free energy of periodic crystal and quasicrystals. Accurate free energies of numerous ordered phases, including dodecagonal, decagonal and octagonal quasicrystals, are obtained for a simple model, i.e. the Lifshitz-Petrich free energy functional, of soft quasicrystals with two length-scales. The availability of the free energy allows us to construct phase diagrams of the system, demonstrating that, for the Lifshitz-Petrich model, the dodecagonal and decagonal quasicrystals can become stable phases, whereas the octagonal quasicrystal stays as a metastable phase.Comment: 11 pages, 7 figure

Nucleation of stable cylinders from a metastable lamellar phase in a diblock copolymer melt

The nucleation of a droplet of stable cylinder phase from a metastable lamellar phase is examined within the single-mode approximation to the mean-field Landau–Brazovskii model for diblock copolymer melts. By employing a variational ansatz for the droplet interfacial profile, an analytic expression for the interfacial free energy of an interface of arbitrary orientation between cylinders and lamellae is found. The interfacial free energy is anisotropic and is lower when the cylinder axis is perpendicular to the interface than when the cylinders lie along the interface. Consequently, the droplet shape computed via the Wulff construction is lens like, being flattened along the axis of the cylinders. The size of the critical droplet and the nucleation barrier are determined within classical nucleation theory. Near the lamellar–cylinder phase boundary, where classical nucleation theory is applicable, critical droplets of size 30–400 cylinders across with aspect ratios of 4–10 and nucleation barriers of (30–40)kBT are typically found. The general trend is to larger critical droplets, higher aspect ratios, and smaller nucleation barriers as the mean-field critical point is approached