Systematic characterization of thermodynamic and dynamical phase behavior in systems with short-ranged attraction

In this paper we demonstrate the feasibility and utility of an augmented version of the Gibbs ensemble Monte Carlo method for computing the phase behavior of systems with strong, extremely short-ranged attractions. For generic potential shapes, this approach allows for the investigation of narrower attractive widths than those previously reported. Direct comparison to previous self-consistent Ornstein-Zernike approximation calculations is made. A preliminary investigation of out-of-equilibrium behavior is also performed. Our results suggest that the recent observations of stable cluster phases in systems without long-ranged repulsions are intimately related to gas-crystal and metastable gas-liquid phase separation.

Design of Latent Thermal Energy Storage Systems

This dissertation documents the results of a theoretical and numerical study of time dependent storage of energy by melting a phase change material. The heating is provided along invading lines, which change from single-line invasion to tree-shaped invasion. Chapter 2 identifies the special design feature of distributing energy storage in time-dependent fashion on a territory, when the energy flows by fluid flow from a concentrated source to points (users) distributed equidistantly on the area. The challenge in this chapter is to determine the architecture of distributed energy storage. The chief conclusion is that the finite amount of storage material should be distributed proportionally with the distribution of the flow rate of heating agent arriving on the area. The total time needed by the source stream to ‘invade’ the area is cumulative (the sum of the storage times required at each storage site), and depends on the energy distribution paths and the sequence in which the users are served by the source stream. Chapter 3 shows theoretically that the melting process consists of two phases: “invasion” thermal diffusion along the invading line, which is followed by “consolidation” as heat diffuses perpendicularly to the invading line. This chapter also reports the duration of both phases and the evolution of the melt layer around the invading line during the two-dimensional and three-dimensional invasion. It also shows that the amount of melted material increases in time according to a curve shaped as an S. These theoretical predictions are validated by means of numerical simulations in chapter 4. This chapter also shows that the heat transfer rate density increases (i.e., the S curve becomes steeper) as the complexity and number of degrees of freedom of the structure are increased, in accord with the constructal law. The optimal geometric features of the tree structure are detailed in this chapter. Chapter 5 documents a numerical study of time-dependent melting where the heat transfer is convection dominated, unlike in chapter 3 and 4 where the melting is ruled by pure conduction. In accord with constructal design, the search is for effective heat-flow architectures. The volume-constrained improvement of the designs for heat flow begins with assuming the simplest structure, where a single line serves as heat source. Next, the heat source is endowed with freedom to change its shape as it grows. The objective of the numerical simulations is to discover the geometric features that lead to the fastest melting process. The results show that the heat transfer rate density increases as the complexity and number of degrees of freedom of the structure are increased. Furthermore, the angles between heat invasion lines have a minor effect on the global performance compared to other degrees of freedom: number of branching levels, stem length, and branch lengths. The effect of natural convection in the melt zone is documented.

Phase behavior and far-from-equilibrium gelation in charged attractive colloids

In this Rapid Communication we demonstrate the applicability of an augmented Gibbs ensemble Monte Carlo approach for the phase behavior determination of model colloidal systems with short-ranged depletion attraction and long-ranged repulsion. This technique allows for a quantitative determination of the phase boundaries and ground states in such systems. We demonstrate that gelation may occur in systems of this type as the result of arrested microphase separation, even when the equilibrium state of the system is characterized by compact microphase structures.