Polydispersity Effects in Colloid-Polymer Mixtures

We study phase separation and transient gelation in a mixture consisting of polydisperse colloids and non-adsorbing polymers, where the ratio of the average size of the polymer to that of the colloid is approximately 0.063. Unlike what has been reported previously for mixtures with somewhat lower colloid polydispersity, the addition of polymers does not expand the fluid-solid coexistence region. Instead, we find a region of fluid-solid coexistence which has an approximately constant width but an unexpected re-entrant shape. We detect the presence of a metastable gas-liquid binodal, which gives rise to two-stepped crystallization kinetics that can be rationalized as the effect of fractionation. Finally, we find that the separation into multiple coexisting solid phases at high colloid volume fractions predicted by equilibrium statistical mechanics is kinetically suppressed before the system reaches dynamical arrest.Comment: 11 pages, 5 figure

Projected free energies for polydisperse phase equilibria

A `polydisperse' system has an infinite number of conserved densities. We give a rational procedure for projecting its infinite-dimensional free energy surface onto a subspace comprising a finite number of linear combinations of densities (`moments'), in which the phase behavior is then found as usual. If the excess free energy of the system depends only on the moments used, exact cloud, shadow and spinodal curves result; two- and multi-phase regions are approximate, but refinable indefinitely by adding extra moments. The approach is computationally robust and gives new geometrical insights into the thermodynamics of polydispersity.Comment: 4 pages, REVTeX, uses multicol.sty and epsf.sty, 1 postscript figure include

Spinodal-assisted crystallization in polymer melts

Recent experiments in some polymer melts quenched below the melting temperature have reported spinodal kinetics in small-angle x-ray scattering before the emergence of a crystalline structure. To explain these observations we propose that the coupling between density and chain conformation induces a liquid-liquid binodal within the equilibrium liquid-crystalline solid coexistence region. A simple phenomenological theory is developed to illustrate this idea, and several experimentally testable consequences are discussed. Shear is shown to enhance the kinetic role of the hidden binodal

Solid-state additive manufacturing for metallized optical fiber integration

The formation of smart, Metal Matrix Composite (MMC) structures through the use of solid-state Ultrasonic Additive Manufacturing (UAM) is currently hindered by the fragility of uncoated optical fibers under the required processing conditions. In this work, optical fibers equipped with metallic coatings were fully integrated into solid Aluminum matrices using processing parameter levels not previously possible. The mechanical performance of the resulting manufactured composite structure, as well as the functionality of the integrated fibers, was tested. Optical microscopy, Scanning Electron Microscopy (SEM) and Focused Ion Beam (FIB) analysis were used to characterize the interlaminar and fiber/matrix interfaces whilst mechanical peel testing was used to quantify bond strength. Via the integration of metallized optical fibers it was possible to increase the bond density by 20–22%, increase the composite mechanical strength by 12–29% and create a solid state bond between the metal matrix and fiber coating; whilst maintaining full fiber functionality

Diffusive Evolution of Stable and Metastable Phases II: Theory of Non-Equilibrium Behaviour in Colloid-Polymer Mixtures

By analytically solving some simple models of phase-ordering kinetics, we suggest a mechanism for the onset of non-equilibrium behaviour in colloid-polymer mixtures. These mixtures can function as models of atomic systems; their physics therefore impinges on many areas of thermodynamics and phase-ordering. An exact solution is found for the motion of a single, planar interface separating a growing phase of uniform high density from a supersaturated low density phase, whose diffusive depletion drives the interfacial motion. In addition, an approximate solution is found for the one-dimensional evolution of two interfaces, separated by a slab of a metastable phase at intermediate density. The theory predicts a critical supersaturation of the low-density phase, above which the two interfaces become unbound and the metastable phase grows ad infinitum. The growth of the stable phase is suppressed in this regime.Comment: 27 pages, Latex, eps

The effect of the regular solution model in the condensation of protoplanetary dust

We utilize a chemical equilibrium code in order to study the condensation process which occurs in protoplanetary discs during the formation of the first solids. The model specifically focuses on the thermodynamic behaviour on the solid species assuming the regular solution model. For each solution, we establish the relationship between the activity of the species, the composition and the temperature using experimental data from the literature. We then apply the Gibbs free energy minimization method and study the resulting condensation sequence for a range of temperatures and pressures within a protoplanetary disc. Our results using the regular solution model show that grains condense over a large temperature range and therefore throughout a large portion of the disc. In the high temperature region (T > 1400 K) Ca-Al compounds dominate and the formation of corundum is sensitive to the pressure. The mid-temperature region is dominated by Fe(s) and silicates such as Mg2SiO4 and MgSiO3 . The chemistry of forsterite and enstatite are strictly related, and our simulations show a sequence of forsterite-enstatite-forsterite with decreasing temperature. In the low temperature regions (T < 600 K) a range of iron compounds and sulfides form. We also run simulations using the ideal solution model and see clear differences in the resulting condensation sequences with changing solution model In particular, we find that the turning point in which forsterite replaces enstatite in the low temperature region is sensitive to the solution model. Our results show that the ideal solution model is often a poor approximation to experimental data at most temperatures important in protoplanetary discs. We find some important differences in the resulting condensation sequences when using the regular solution model, and suggest that this model should provide a more realistic condensation sequence.Comment: MNRAS: Accepted 2011 February 16. Received 2011 February 14; in original form 2010 July 2

Predicting phase equilibria in polydisperse systems

Many materials containing colloids or polymers are polydisperse: They comprise particles with properties (such as particle diameter, charge, or polymer chain length) that depend continuously on one or several parameters. This review focusses on the theoretical prediction of phase equilibria in polydisperse systems; the presence of an effectively infinite number of distinguishable particle species makes this a highly nontrivial task. I first describe qualitatively some of the novel features of polydisperse phase behaviour, and outline a theoretical framework within which they can be explored. Current techniques for predicting polydisperse phase equilibria are then reviewed. I also discuss applications to some simple model systems including homopolymers and random copolymers, spherical colloids and colloid-polymer mixtures, and liquid crystals formed from rod- and plate-like colloidal particles; the results surveyed give an idea of the rich phenomenology of polydisperse phase behaviour. Extensions to the study of polydispersity effects on interfacial behaviour and phase separation kinetics are outlined briefly.Comment: 48 pages, invited topical review for Journal of Physics: Condensed Matter; uses Institute of Physics style file iopart.cls (included

Genotype-Guided Hydralazine Therapy

Background: Despite its approval in 1953, hydralazine hydrochloride continues to be used in the management of resistant hypertension, a condition frequently managed by nephrologists and other clinicians. Hydralazine hydrochloride undergoes metabolism by the N-acetyltransferase 2 (NAT2) enzyme. NAT2 is highly polymorphic as approximately 50% of the general population are slow acetylators. In this review, we first evaluate the link between NAT2 genotype and phenotype. We then assess the evidence available for genotype-guided therapy of hydralazine, specifically addressing associations of NAT2 acetylator status with hydralazine pharmacokinetics, antihypertensive efficacy, and toxicity. Summary: There is a critical need to use hydralazine in some patients with resistant hypertension. Available evidence supports a significant link between genotype and NAT2 enzyme activity as 29 studies were identified with an overall concordance between genotype and phenotype of 92%. The literature also supports an association between acetylator status and hydralazine concentration, as fourteen of fifteen identified studies revealed significant relationships with a consistent direction of effect. Although fewer studies are available to directly link acetylator status with hydralazine antihypertensive efficacy, the evidence from this smaller set of studies is significant in 7 of 9 studies identified. Finally, 5 studies were identified which support the association of acetylator status with hydralazine-induced lupus. Clinicians should maintain vigilance when prescribing maximum doses of hydralazine. Key Messages: NAT2 slow acetylator status predicts increased hydralazine levels, which may lead to increased efficacy and adverse effects. Caution should be exercised in slow acetylators with total daily hydralazine doses of 200 mg or more. Fast acetylators are at risk for inefficacy at lower doses of hydralazine. With appropriate guidance on the usage of NAT2 genotype, clinicians can adopt a personalized approach to hydralazine dosing and prescription, enabling more efficient and safe treatment of resistant hypertension