Fluctuations and Pattern Formation in Fluids with Competing Interactions

One of the most interesting phenomena in the soft-matter realm consists in the spontaneous formation of super-molecular structures (microphases) in condition of thermodynamic equilibrium. A simple mechanism responsible for this self-organization or pattern formation is based on the competition between attractive and repulsive forces with different length scales in the microscopic potential, typically, a short-range attraction against a longer-range repulsion. We analyse this problem by simulations in 2D fluids. We find that, as the temperature is lowered, liquid-vapor phase separation is inhibited by the competition between attraction and repulsion, and replaced by a transition to non-homogeneous phases. The structure of the fluid shows well defined signatures of the presence of both intra- and inter-cluster correlations. Even when the competition between attraction and repulsion is not so strong as to cause microphase formation, it still induces large density fluctuations in a wide region of the temperature-density plane. In this large-fluctuation regime, pattern formation can be triggered by a weak external modulating field.Comment: To appear in the proceedings of the "International workshop on collective phenomena in macroscopic systems", 2006 Villa Olmo (Como), Ital

Phase diagram of symmetric binary mixtures at equimolar and non-equimolar concentrations: a systematic investigation

We consider symmetric binary mixtures consisting of spherical particles with equal diameters interacting via a hard-core plus attractive tail potential with strengths epsilon_{ij}, i,j=1,2, such that epsilon_{11} = epsilon_{22} > epsilon_{12}. The phase diagram of the system at all densities and concentrations is investigated as a function of the unlike-to-like interaction ratio delta = epsilon_{12}/epsilon_{11} by means of the hierarchical reference theory (HRT). The results are related to those of previous investigations performed at equimolar concentration, as well as to the topology of the mean-field critical lines. As delta is increased in the interval 0 < delta < 1, we find first a regime where the phase diagram at equal species concentration displays a tricritical point, then one where both a tricritical and a liquid-vapor critical point are present. We did not find any clear evidence of the critical endpoint topology predicted by mean-field theory as delta approaches 1, at least up to delta=0.8, which is the largest value of delta investigated here. Particular attention was paid to the description of the critical-plus-tricritical point regime in the whole density-concentration plane. In this situation, the phase diagram shows, in a certain temperature interval, a coexistence region that encloses an island of homogeneous, one-phase fluid.Comment: 27 pages + 20 figure

Anisotropy effects on the magnetic excitations of a ferromagnetic monolayer below and above the Curie temperature

The field-driven reorientation transition of an anisotropic ferromagnetic monolayer is studied within the context of a finite-temperature Green's function theory. The equilibrium state and the field dependence of the magnon energy gap $E_0$ are calculated for static magnetic field $H$ applied in plane along an easy or a hard axis. In the latter case, the in-plane reorientation of the magnetization is shown to be continuous at T=0, in agreement with free spin wave theory, and discontinuous at finite temperature $T>0$, in contrast with the prediction of mean field theory. The discontinuity in the orientation angle creates a jump in the magnon energy gap, and it is the reason why, for $T>0$, the energy does not go to zero at the reorientation field. Above the Curie temperature $T_C$, the magnon energy gap $E_0(H)$ vanishes for H=0 both in the easy and in the hard case. As $H$ is increased, the gap is found to increase almost linearly with $H$, but with different slopes depending on the field orientation. In particular, the slope is smaller when $H$ is along the hard axis. Such a magnetic anisotropy of the spin-wave energies is shown to persist well above $T_C$ ($T \approx 1.2 T_C$).Comment: Final version accepted for publication in Physical Review B (with three figures

Phase transitions in simple and not so simple binary fluids

Compared to pure fluids, binary mixtures display a very diverse phase behavior, which depends sensitively on the parameters of the microscopic potential. Here we investigate the phase diagrams of simple model mixtures by use of a microscopic implementation of the renormalization group technique. First, we consider a symmetric mixture with attractive interactions, possibly relevant for describing fluids of molecules with internal degrees of freedom. Despite the simplicity of the model, slightly tuning the strength of the interactions between unlike species drastically changes the topology of the phase boundary, forcing or inhibiting demixing, and brings about several interesting features such as double critical points, tricritical points, and coexistence domains enclosing `islands' of homogeneous, mixed fluid. Homogeneous phase separation in mixtures can be driven also by purely repulsive interactions. As an example, we consider a model of soft particles which has been adopted to describe binary polymer solutions. This is shown to display demixing (fluid-fluid) transition at sufficiently high density. The nature and the physical properties of the corresponding phase transition are investigated.Comment: 6 pages + 3 figures, presented at the 5th EPS Liquid Matter Conference, Konstanz, 14-18 September 200

Measuring and modelling supercritical adsorption of CO2 and CH4 on montmorillonite source clay

The porosity of clay minerals is dominated by nanoscale pores that provide a large surface area for physical and chemical interactions with the surrounding fluids, including gas adsorption. Measuring gas adsorption at subsurface conditions is difficult, because elevated pressures are required and the interactions between the supercritical gas and the clay are relatively weak. Here, we report on the measurement of adsorption isotherms of CO2 and CH4 on the source clay Na-montmorillonite (SWy-2) at different temperatures (25–115°C) over a wide range of pressures (0.02–25 MPa). The experimental observations are thoroughly analysed by considering both net and excess adsorbed amounts, and by extracting adsorption metrics, such as the Henry's constants and enthalpy of adsorption. The results consistently indicate that SWy-2 favours adsorption of CO2 over CH4 with selectivity, . The experimental data are successfully described using a Lattice Density Functional Theory (LDFT) model. The adsorption energetics estimated by the model compare well with the experimentally obtained enthalpy of adsorption. It is further shown that even at the highest pressure the pore space of the clay is only partially filled and that the degree of saturation increases upon approaching the critical temperature of the gas. The ability of the LDFT model to reveal pore-dependent adsorption behaviours demonstrates its potential against empirical models, such as the Langmuir equation, which fail at capturing the complexities of supercritical gas adsorption at subsurface conditions

Formation of cluster crystals in an ultra-soft potential model on a spherical surface

We investigate the formation of cluster crystals with multiply occupied lattice sites on a spherical surface in systems of ultra-soft particles interacting via repulsive, bounded pair potentials. Not all interactions of this kind lead to clustering: we generalize the criterion devised in C. N. Likos et al., Phys. Rev. E, 2001, 63, 031206 to spherical systems in order to distinguish between cluster-forming systems and fluids which display reentrant melting. We use both DFT and Monte Carlo simulations to characterize the behavior of the system, and obtain semi-quantitative agreement between the two. We find that the number of clusters is determined by the ratio between the size s of the ultra-soft particles and the radius R of the sphere in such a way that each stable configuration spans a certain interval of s/R. Furthermore, we study the effect of topological frustration on the system due to the sphere curvature by comparing the properties of disclinations, i.e., clusters with fewer than six neighbors, and non-defective clusters. Disclinations are shown to be less stable, contain fewer particles, and be closer to their neighbors than other lattice points: these properties are explained on the basis of geometric and energetic considerations

A model colloidal fluid with competing interactions: bulk and interfacial properties

Using a simple mean-field density functional theory theory (DFT), we investigate the structure and phase behaviour of a model colloidal fluid composed of particles interacting via a pair potential which has a hard core of diameter $\sigma$, is attractive Yukawa at intermediate separations and repulsive Yukawa at large separations. We analyse the form of the asymptotic decay of the bulk fluid correlation functions, comparing results from our DFT with those from the self consistent Ornstein-Zernike approximation (SCOZA). In both theories we find rich crossover behaviour, whereby the ultimate decay of correlation functions changes from monotonic to long-wavelength damped oscillatory decay on crossing certain lines in the phase diagram, or sometimes from oscillatory to oscillatory with a longer wavelength. For some choices of potential parameters we find, within the DFT, a $\lambda$-line at which the fluid becomes unstable with respect to periodic density fluctuations. SCOZA fails to yield solutions for state points near such a $\lambda$-line. The propensity to clustering of particles, which is reflected by the presence of a long wavelength $\gg \sigma$, slowly decaying oscillatory pair correlation function, and a structure factor that exhibits a very sharp maximum at small but non zero wavenumbers, is enhanced in states near the $\lambda$-line. We present density profiles for the planar liquid-gas interface and for fluids adsorbed at a planar hard wall. The presence of a nearby $\lambda$-transition gives rise to pronounced long-wavelength oscillations in the one-body densities at both types of interface.Comment: 14 pages, 11 figure

Quantitative imaging of gas adsorption equilibrium and dynamics by X-ray Computed Tomography

We present the development and application of X-ray Computed Tomography (CT) for the determination of the adsorption properties of microporous adsorbents and the study of breakthrough experiments in a laboratory fixed-bed adsorption column. Using the model system CO2/helium on activated carbon, equilibrium and dynamic adsorption/desorption measurements by X-ray CT are described, and the results are successfully compared to those obtained from conventional methods, including the application of a one-dimensional dynamic column breakthrough model. The study demonstrates the practical feasibility of applying X-ray CT to measure internal and transient concentration profiles in adsorbent systems on the length-scales from a single adsorbent pellet to a packed column