The Stefan problem with variable thermophysical properties and phase change temperature

In this paper we formulate a Stefan problem appropriate when the thermophysical properties are distinct in each phase and the phase-change temperature is size or velocity dependent. Thermophysical properties invariably take different values in different material phases but this is often ignored for mathematical simplicity. Size and velocity dependent phase change temperatures are often found at very short length scales, such as nanoparticle melting or dendrite formation; velocity dependence occurs in the solidification of supercooled melts. To illustrate the method we show how the governing equations may be applied to a standard one-dimensional problem and also the melting of a spherically symmetric nanoparticle. Errors which have propagated through the literature are highlighted. By writing the system in non-dimensional form we are able to study the large Stefan number formulation and an energy-conserving one-phase reduction. The results from the various simplifications and assumptions are compared with those from a finite difference numerical scheme. Finally, we briefly discuss the failure of Fourier's law at very small length and time-scales and provide an alternative formulation which takes into account the finite time of travel of heat carriers (phonons) and the mean free distance between collisions.Comment: 39 pages, 5 figure

The one-dimensional Stefan problem with non-Fourier heat conduction

We investigate the one-dimensional growth of a solid into a liquid bath, starting from a small crystal, using the Guyer-Krumhansl and Maxwell-Cattaneo models of heat conduction. By breaking the solidification process into the relevant time regimes we are able to reduce the problem to a system of two coupled ordinary differential equations describing the evolution of the solid-liquid interface and the heat flux. The reduced formulation is in good agreement with numerical simulations. In the case of silicon, differences between classical and non-classical solidification kinetics are relatively small, but larger deviations can be observed in the evolution in time of the heat flux through the growing solid. From this study we conclude that the heat flux provides more information about the presence of non-classical modes of heat transport during phase-change processes.Comment: 29 pages, 6 figures, 2 tables + Supplementary Materia

Optimal loading of hydrogel-based drug-delivery systems

Drug-loaded hydrogels provide a means to deliver pharmaceutical agents to specific sites within the body at a controlled rate. The aim of this paper is to understand how controlled drug release can be achieved by tuning the initial distribution of drug molecules in a hydrogel. A mathematical model is presented for a spherical drug-loaded hydrogel. The model captures the nonlinear elasticity of the polymer network and thermodynamics of swelling. By assuming that the drug molecules are dilute, the equations for hydrogel swelling and drug transport partially decouple. A fast optimisation method is developed to accurately compute the optimal initial drug concentration by minimising the error between the numerical drug-release profile and a target profile. By taking the target drug efflux to be piecewise constant, the optimal initial configuration consists of a central drug-loaded core with isolated drug packets near the free boundary of the hydrogel. The optimal initial drug concentration is highly effective at mitigating the burst effect, where a large amount of drug is rapidly released into the environment. The hydrogel stiffness can be used to further tune the rate of drug release. Although stiffer gels lead to less swelling and hence reduce the drug diffusivity, the drug-release kinetics are faster than for soft gels due to the decreased distance that drug molecules must travel to reach the free surface

Security Policies as Membranes in Systems for Global Computing

We propose a simple global computing framework, whose main concern is code migration. Systems are structured in sites, and each site is divided into two parts: a computing body, and a membrane which regulates the interactions between the computing body and the external environment. More precisely, membranes are filters which control access to the associated site, and they also rely on the well-established notion of trust between sites. We develop a basic theory to express and enforce security policies via membranes. Initially, these only control the actions incoming agents intend to perform locally. We then adapt the basic theory to encompass more sophisticated policies, where the number of actions an agent wants to perform, and also their order, are considered

Mathematical Modelling of Tyndall Star Initiation

The superheating that usually occurs when a solid is melted by volumetric heating can produce irregular solid-liquid interfaces. Such interfaces can be visualised in ice, where they are sometimes known as Tyndall stars. This paper describes some of the experimental observations of Tyndall stars and a mathematical model for the early stages of their evolution. The modelling is complicated by the strong crystalline anisotropy, which results in an anisotropic kinetic undercooling at the interface; it leads to an interesting class of free boundary problems that treat the melt region as infinitesimally thin

Controlled topological transitions in thin film phase separation

In this paper the evolution of a binary mixture in a thin-film geometry with a wall at the top and bottom is considered. By bringing the mixture into its miscibility gap so that no spinodal decomposition occurs in the bulk, a slight energetic bias of the walls towards each one of the constituents ensures the nucleation of thin boundary layers that grow until the constituents have moved into one of the two layers. These layers are separated by an interfacial region where the composition changes rapidly. Conditions that ensure the separation into two layers with a thin interfacial region are investigated based on a phase-field model. Using matched asymptotic expansions a corresponding sharp-interface problem for the location of the interface is established. It is then argued that this newly created two-layer system is not at its energetic minimum but destabilizes into a controlled self-replicating pattern of trapezoidal vertical stripes by minimizing the interfacial energy between the phases while conserving their area. A quantitative analysis of this mechanism is carried out via a thin-film model for the free interfaces, which is derived asymptotically from the sharp-interface model.Comment: Submitted 23/12/201

Surface induced phase separation of a swelling hydrogel

We present a formulation of the free boundary problem for a hydrogel that accounts for the interfacial free energy and finite strain due to the large deformation of the polymer network during solvent transport across the free boundary. For the geometry of an initially dry layer fixed at a rigid substrate, our model predicts a phase transition when a critical value of the solvent concentration has been reached near the free boundary. A one-dimensional case study shows that depending on the flux rate at the free boundary an initial saturation front is followed by spinodal decomposition of the hydrogel and the formation of an interfacial front that moves through the layer. Moreover, increasing the shear modulus of the elastic network delays or even suppresses phase separation

Surface induced phase separation of a swelling hydrogel

We present a formulation of the free boundary problem for a hydrogel that accounts for the interfacial free energy and finite strain due to the large deformation of the polymer network during solvent transport across the free boundary. For the geometry of an initially dry layer fixed at a rigid substrate, our model predicts a phase transition when a critical value of the solvent concentration has been reached near the free boundary. A one-dimensional case study shows that depending on the flux rate at the free boundary an initial saturation front is followed by spinodal decomposition of the hydrogel and the formation of an interfacial front that moves through the layer. Moreover, increasing the shear modulus of the elastic network delays or even suppresses phase separation

Fluid-fluid phase separation in a soft porous medium

Various biological and chemical processes lead to the nucleation and growth of non-wetting fluid bubbles within the pore space of a granular medium, such as the formation of gas bubbles in liquid-saturated lake-bed sediments. In sufficiently soft porous materials, the non-wetting nature of these bubbles can result in the formation of open cavities within the granular solid skeleton. Here, we consider this process through the lens of phase separation, where thermomechanics govern the separation of the non-wetting phase from a fluid-fluid-solid mixture. We construct a phase-field model informed by large-deformation poromechanics, in which two immiscible fluids interact with a poroelastic solid skeleton. Our model captures the competing effects of elasticity and fluid-fluid-solid interactions. We use a phase-field damage model to capture the mechanics of the granular solid. As a model problem, we consider an initial distribution of non-wetting fluid in the pore space that separates into multiple cavities. We use simulations and linear-stability analysis to identify the key parameters that control phase separation, the conditions that favour the formation of cavities, and the characteristic size of the resulting cavities