Condensed Matter Theory

Abstract:

We present a combined experimental and numerical investigation of the coiling of a liquid "rope" falling on a solid surface, focusing on three little-explored aspects of the phenomenon: The time dependence of "inertio-gravitational" coiling, the systematic dependence of the radii of the coil and the rope on the experimental parameters, and the "secondary buckling" of the columnar structure generated by high-frequency coiling. Inertio-gravitational coiling is characterized by oscillations between states with different frequencies, and we present experimental observations of four distinct branches of such states in the frequency-fall height space. The transitions between coexisting states have no characteristic period, may take place with or without a change in the sense of rotation, and usually (but not always) occur via an intermediate "figure of eight" state. We present extensive laboratory measurements of the radii of the coil and of the rope within it, and show that they agree well with the predictions of a "slender-rope" numerical model. Finally, we use dimensional analysis to reveal a systematic variation of the critical column height for secondary buckling as a function of (dimensionless) flow rate and surface tension parameters.

Abstract:

We present an investigation of the phase diagram of cholesteric liquid crystals within the framework of Landau-de Gennes theory. The free energy is modified to incorporate all three Frank elastic constants and to allow for a temperature dependent pitch in the cholesteric phase. It is found that the region of stability of the cubic blue phases depends significantly on the value of the elastic constants, being reduced when the bend elastic constant is larger than splay and when twist is smaller than the other two. Most dramatically we find a large increase in the region of stability of blue phase I, and a qualitative change in the phase diagram, in a system where the cholesteric phase displays helix inversion.

Abstract:

We use bead-spring models for a polymer coupled to a solvent described by multiparticle collision dynamics to investigate shear thinning effects in dilute polymer solutions. First, we consider the polymer motion and configuration in a shear flow. For flexible polymer models we find a sharp increase in the polymer radius of gyration and the fluctuations in the radius of gyration at a Weissenberg number approximately 1. We then consider the polymer viscosity and the effect of solvent quality, excluded volume, hydrodynamic coupling between the beads, and finite extensibility of the polymer bonds. We conclude that the excluded volume effect is the major cause of shear thinning in polymer solutions. Comparing the behavior of semiflexible chains, we find that the fluctuations in the radius of gyration are suppressed when compared to the flexible case. The shear thinning is greater and, as the rigidity is increased, the viscosity measurements tend to those for a multibead rod.

Abstract:

We have used neutron reflectometry to characterize the swelling behaviour of brushes of poly[2-(diethyl amino)ethyl methacrylate], a polybase, as a function of pH. The brushes, synthesized by the "grafting from" method of atom transfer radical polymerization, were observed to approximately double their thickness in low pH solutions, although the pKa is shifted to a lower pH than in dilute solution. The composition-depth profile obtained from the reflectometry experiments for the swollen brushes reveals a region depleted in polymer between the substrate and the extended part of the brush. © The Royal Society of Chemistry.