Engineering topics

Almarza, N. G.

Publications and source records attributed to Almarza, N. G..

6 records

DOE OSTI2015

Effects of rigid or adaptive confinement on colloidal self-assembly. Fixed vs. fluctuating number of confined particles

The effects of confinement on colloidal self-assembly in the case of fixed number of confined particles are studied in the one dimensional lattice model solved exactly in the grand canonical ensemble (GCE) in Pȩkalski et al. [J. Chem. Phys. 142, 014903 (2015)]. The model considers a pair interaction defined by a short-range attraction plus a longer-range repulsion. We consider thermodynamic states corresponding to self-assembly into clusters. Both fixed and adaptive boundaries are studied. For fixed boundaries, there are particular states in which, for equal average densities, the number of clusters in the GCE is larger than in the canonical ensemble. The dependence of pressure on density has a different form when the system size changes with fixed number of particles and when the number of particles changes with fixed size of the system. In the former case, the pressure has a nonmonotonic dependence on the system size. The anomalous increase of pressure for expanding system is accompanied by formation of a larger number of smaller clusters. In the case of elastic confining surfaces, we observe a bistability, i.e., two significantly different system sizes occur with almost the same probability. The mechanism of the bistability in the closed system is different to that of the case of permeable walls, where the two equilibrium system sizes correspond to a different number of particles.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2015

Bistability in a self-assembling system confined by elastic walls: Exact results in a one-dimensional lattice model

The impact of confinement on self-assembly of particles interacting with short-range attraction and long-range repulsion potential is studied for thermodynamic states corresponding to local ordering of clusters or layers in the bulk. Exact and asymptotic expressions for the local density and for the effective potential between the confining surfaces are obtained for a one-dimensional lattice model introduced by J. Pȩkalski et al. [J. Chem. Phys. 138, 144903 (2013)]. The simple asymptotic formulas are shown to be in good quantitative agreement with exact results for slits containing at least 5 layers. We observe that the incommensurability of the system size and the average distance between the clusters or layers in the bulk leads to structural deformations that are different for different values of the chemical potential μ. The change of the type of defects is reflected in the dependence of density on μ that has a shape characteristic for phase transitions. Our results may help to avoid misinterpretation of the change of the type of defects as a phase transition in simulations of inhomogeneous systems. Finally, we show that a system confined by soft elastic walls may exhibit bistability such that two system sizes that differ approximately by the average distance between the clusters or layers are almost equally probable. This may happen when the equilibrium separation between the soft boundaries of an empty slit corresponds to the largest stress in the confined self-assembling system.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2014

Adsorption of probe molecules in pillared interlayered clays: Experiment and computer simulation

In this paper we investigate the adsorption of various probe molecules in order to characterize the porous structure of a series of pillared interlayered clays (PILC). To that aim, volumetric and microcalorimetric adsorption experiments were performed on various Zr PILC samples using nitrogen, toluene, and mesitylene as probe molecules. For one of the samples, neutron scattering experiments were also performed using toluene as adsorbate. Various structural models are proposed and tested by means of a comprehensive computer simulation study, using both geometric and percolation analysis in combination with Grand Canonical Monte Carlo simulations in order to model the volumetric and microcalorimetric isotherms. On the basis of this analysis, we propose a series of structural models that aim at accounting for the adsorption experimental behavior, and make possible a microscopic interpretation of the role played by the different interactions and steric effects in the adsorption processes in these rather complex disordered microporous systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

Periodic ordering of clusters and stripes in a two-dimensional lattice model. II. Results of Monte Carlo simulation

The triangular lattice model with nearest-neighbor attraction and third-neighbor repulsion, introduced by Pekalski, Ciach, and Almarza [J. Chem. Phys. 140, 114701 (2014)] is studied by Monte Carlo simulation. Introduction of appropriate order parameters allowed us to construct a phase diagram, where different phases with patterns made of clusters, bubbles or stripes are thermodynamically stable. We observe, in particular, two distinct lamellar phases—the less ordered one with global orientational order and the more ordered one with both orientational and translational order. Our results concern spontaneous pattern formation on solid surfaces, fluid interfaces or membranes that is driven by competing interactions between adsorbing particles or molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

Periodic ordering of clusters and stripes in a two-dimensional lattice model. I. Ground state, mean-field phase diagram and structure of the disordered phases

The short-range attraction and long-range repulsion between nanoparticles or macromolecules can lead to spontaneous pattern formation on solid surfaces, fluid interfaces, or membranes. In order to study the self-assembly in such systems we consider a triangular lattice model with nearest-neighbor attraction and third-neighbor repulsion. At the ground state of the model (T = 0) the lattice is empty for small values of the chemical potential μ, and fully occupied for large μ. For intermediate values of μ periodically distributed clusters, bubbles, or stripes appear if the repulsion is sufficiently strong. At the phase coexistences between the vacuum and the ordered cluster phases and between the cluster and the lamellar (stripe) phases the entropy per site does not vanish. As a consequence of this ground state degeneracy, disordered fluid phases consisting of clusters or stripes are stable, and the surface tension vanishes. For T > 0 we construct the phase diagram in the mean-field approximation and calculate the correlation function in the self-consistent Brazovskii-type field theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

Three-dimensional patchy lattice model: Ring formation and phase separation

We investigate the structural and thermodynamic properties of a model of particles with 2 patches of type A and 10 patches of type B. Particles are placed on the sites of a face centered cubic lattice with the patches oriented along the nearest neighbor directions. The competition between the self-assembly of chains, rings, and networks on the phase diagram is investigated by carrying out a systematic investigation of this class of models, using an extension of Wertheim's theory for associating fluids and Monte Carlo numerical simulations. We varied the ratio r ≡ ε{sub AB}/ε{sub AA} of the interaction between patches A and B, ε{sub AB}, and between A patches, ε{sub AA} (ε{sub BB} is set to 0) as well as the relative position of the A patches, i.e., the angle θ between the (lattice) directions of the A patches. We found that both r and θ (60°, 90°, or 120°) have a profound effect on the phase diagram. In the empty fluid regime (r < 1/2) the phase diagram is reentrant with a closed miscibility loop. The region around the lower critical point exhibits unusual structural and thermodynamic behavior determined by the presence of relatively short rings. The agreement between the results of theory and simulation is excellent for θ = 120° but deteriorates as θ decreases, revealing the need for new theoretical approaches to describe the structure and thermodynamics of systems dominated by small rings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗