Analyzing spinodal decomposition of an anisotropic fluid mixture.

Spinodal decomposition leads to spontaneous fluctuations of the local concentration. In the early stage, the resulting pattern provides explicit information about the material properties of the mixture. In the case of two isotropic fluids, the static structure factor shows the characteristic ring shape. If one component is a liquid crystal, the pattern is typically anisotropic and the structure factor is more complex. Using numerical methods, we investigate how structure factors can be used to extract information about material properties like the diffusion constant or the isotropic and the anisotropic contributions to the interfacial tension. The method is based on momenta taken from structure factors in the early stage of the spinodal demixing. We perform phase field calculations for an isotropic and an anisotropic spinodal decomposition. A comparison of the extracted results with analytic values is made. The calculations show that linear modes dominate in the beginning of the growth process, while non-linear modes grow monotonously in the region of the k-space for which damping is predicted by the linearized theory. As long as non-linear modes are small enough, linearized theory can be applied to extract material properties from the structure factor.

Molecular dynamics study of colloidal quasicrystals.

Colloidal quasicrystals have received increased interest recently due to new insight in exploring their potential for photonic materials as well as for optical devices [Vardeny et al., Nat. Photonics, 2013, 7, 177]. Colloidal quasicrystals in aqueous solutions have been found in systems of micelles with impenetrable cores [Fischer et al., Proc. Natl. Acad. Sci. U. S. A., 2011, 108, 1810]. A simple model potential for micelle-micelle interaction is the step potential, which is infinite for core overlaps and constant for shell overlaps. Dotera et al. performed Monte Carlo simulations of the step potential model and found quasicrystals for specific values of the packing fraction η and the shell-core ratio λ [Dotera et al., Nature, 2014, 506, 208 ]. However, the overlap of real micelles causes repulsive forces, which increase with decreasing core distance. We consider this by introducing a novel model potential with repulsive forces depending on a third parameter α. In a systematic manner we study this more realistic potential with two-dimensional molecular dynamics simulations. For α = 0 the model is similar to the step potential model. For the first time, we provide a comprehensive overview of crystalline, quasicrystalline, and disordered structures as a function of η and λ. Simulations performed with α > 0 show the impact of the repulsive forces. We find that quasicrystalline structures at high densities vanish while new quasicrystalline structures appear at intermediate densities. Our results help to tailor colloidal systems for today's advanced applications in photonics and optical devices.

Solid-liquid surface tensions of critical nuclei and nucleation barriers from a phase-field-crystal study of a model binary alloy using finite system sizes.

Phase-field-crystal (PFC) modeling has emerged as a computationally efficient tool to address crystal growth phenomena on atomistic length and diffusive time scales. We use a two-dimensional phase-field-crystal model for a binary system based on Elder et al. [Phys. Rev. B 75, 064107 (2007)] to study critical nuclei and their liquid-solid phase boundaries, in particular the nucleus size dependence of the liquid-solid interface tension as well as of the nucleation barrier. Critical nuclei are stabilized in finite systems of various sizes, however, the extracted interface tension as function of the nucleus radius r is independent of system size. We suggest a phenomenological expression to describe the dependence of the extracted interface tension on the nucleus radius r for the liquid-solid system. Moreover, the numerical PFC results show that this dependency can not be fully described by the nonclassical Tolman formula.

Mean field theory for a reversibly crosslinked polymer network.

We present a mean field theory for melts and solutions of reversibly crosslinked polymers. In our model, crosslinks are considered as local bonds between two monomers. For a blend of A+B+AB polymers, we assume reversible crosslinks between the copolymers AB with a crosslink strength z and interaction weights ω(A) and ω(B) for monomers of type A and B, respectively. The usual mean field model for polymer blends without reversible crosslinks is recovered if z vanishes. With or without crosslinks, the A+B+AB blend can form a lamellar phase with A and B rich regions. If reversible crosslinks are enabled and ω(A) differs strongly from ω(B), the lamellar nanophase separation of A and B monomers is accompanied by a similar segregation of crosslinked and noncrosslinked polymers. If ω(A) and ω(B) are equal, crosslinked copolymers are well mixed with the homopolymers. For a homopolymer solution with reversible crosslinks between the polymers, our calculations show that polymers and solvent molecules are separated macroscopically if the Flory-Huggins interaction parameter and the crosslink strength are suitably high or if the volume fraction of polymers or the chain length are suitably low.

DDFT calibration and investigation of an anisotropic phase-field crystal model.

The anisotropic phase-field crystal model recently proposed and used by Prieler et al (2009 J. Phys.: Condens. Matter 21 464110) is derived from microscopic density functional theory for anisotropic particles with fixed orientation. Its morphology diagram is also explored. In particular we have investigated the influence of anisotropy and undercooling on the process of nucleation and microstructure formation from the atomic to the microscale. To that end numerical simulations were performed varying those dimensionless parameters which represent anisotropy and undercooling in our anisotropic phase-field crystal model. The results from these numerical simulations are summarized in terms of a morphology diagram of the stable state phases. These stable phases are also investigated with respect to their kinetics and characteristic morphological features.