Quenching of lamellar ordering in an n-alkane embedded in nanopores

We present an X-ray diffraction study of the normale alkane nonadecane C_{19}H_{40} embedded in nanoporous Vycor glass. The confined molecular crystal accomplishes a close-packed structure by alignment of the rod-like molecules parallel to the pore axis while sacrificing one basic principle known from the bulk state, i.e. the lamellar ordering of the molecules. Despite this disorder, the phase transitions observed in the confined solid mimic the phase behavior of the 3D unconfined crystal, though enriched by the appearance of a true rotator phase known only from longer alkane chains.Comment: 7 pages, 3 figure

Percolation, depinning, and avalanches in capillary condensation of gases in disordered porous solids

We propose a comprehensive theoretical description of hysteresis in capillary condensation of gases in mesoporous disordered materials. Applying mean-field density functional theory to a coarse-grained lattice-gas model, we show that the morphology of the hysteresis loops is influenced by out-of-equilibrium transitions that are different on filling and on draining. In particular, desorption may be associated to a depinning process and be percolation-like without explicit pore-blocking effects.Comment: 4 pages, 5 figure

Computational study of uniaxial deformations in silica aerogel using a coarse-grained model

Simulations of a flexible coarse-grained model are used to study silica aerogels. This model, introduced in a previous study (J. Phys. Chem. C 2007, 111, 15792), consists of spherical particles which interact through weak nonbonded forces and strong interparticle bonds that may form and break during the simulations. Small-deformation simulations are used to determine the elastic moduli of a wide range of material models, and large-deformation simulations are used to probe structural evolution and plastic deformation. Uniaxial deformation at constant transverse pressure is simulated using two methods: a hybrid Monte Carlo approach combining molecular dynamics for the motion of individual particles and stochastic moves for transverse stress equilibration, and isothermal molecular dynamics simulations at fixed Poisson ratio. Reasonable agreement on elastic moduli is obtained except at very low densities. The model aerogels exhibit Poisson ratios between 0.17 and 0.24, with higher-density gels clustered around 0.20, and Young's moduli that vary with aerogel density according to a power-law dependence with an exponent near 3.0. These results are in agreement with reported experimental values. The models are shown to satisfy the expected homogeneous isotropic linear-elastic relationship between bulk and Young's moduli at higher densities, but there are systematic deviations at the lowest densities. Simulations of large compressive and tensile strains indicate that these materials display a ductile-to-brittle transition as the density is increased, and that the tensile strength varies with density according to a power law, with an exponent in reasonable agreement with experiment. Auxetic behavior is observed at large tensile strains in some models. Finally, at maximum tensile stress very few broken bonds are found in the materials, in accord with the theory that only a small fraction of the material structure is actually load-bearing

Liquid-liquid coexistence in the phase diagram of a fluid confined in fractal porous materials

Multicanonical ensemble sampling simulations have been performed to calculate the phase diagram of a Lennard-Jones fluid embedded in a fractal random matrix generated through diffusion limited cluster aggregation. The study of the system at increasing size and constant porosity shows that the results are independent from the matrix realization but not from the size effects. A gas-liquid transition shifted with respect to bulk is found. On growing the size of the system on the high density side of the gas-liquid coexistence curve it appears a second coexistence region between two liquid phases. These two phases are characterized by a different behaviour of the local density inside the interconnected porous structure at the same temperature and chemical potential.Comment: 5 pages, 4 figures. To be published in Europhys. Letter

Laser driven launch vehicles for continuous access to space

The availability of megawatt laser systems in the next century will make laser launch systems from ground to orbit feasible and useful. Systems studies indicate launch capabilities of 1 ton payload per gigawatt laser power. Recent research in ground to orbit laser propulsion has emphasized laser supported detonation wave thrusters driven by repetitively pulsed infrared lasers. In this propulsion concept each laser repetition cycle consists of two pulses. A lower energy first pulse is used to vaporize a small amount of solid propellant and then after a brief expansion period, a second and higher energy laser pulse is used to drive a detonation wave through the expanded vapor. The results are reported of numerical studies comparing the detonation wave properties of various candidate propellants, and the simulation of thruster performance under realistic conditions. Experimental measurements designed to test the theoretical predictions are also presented. Measurements are discussed of radiance and opacity in absorption waves, and mass loss and momentum transfer. These data are interpreted in terms of specific impulse and energy conversion efficiency

Soft disks in a narrow channel

The pressure components of "soft" disks in a two dimensional narrow channel are analyzed in the dilute gas regime using the Mayer cluster expansion and molecular dynamics. Channels with either periodic or reflecting boundaries are considered. It is found that when the two-body potential, u(r), is singular at some distance r_0, the dependence of the pressure components on the channel width exhibits a singularity at one or more channel widths which are simply related to r_0. In channels with periodic boundary conditions and for potentials which are discontinuous at r_0, the transverse and longitudinal pressure components exhibit a 1/2 and 3/2 singularity, respectively. Continuous potentials with a power law singularity result in weaker singularities of the pressure components. In channels with reflecting boundary conditions the singularities are found to be weaker than those corresponding to periodic boundaries

Does Young's equation hold on the nanoscale? A Monte Carlo test for the binary Lennard-Jones fluid

When a phase-separated binary ($A+B$) mixture is exposed to a wall, that preferentially attracts one of the components, interfaces between A-rich and B-rich domains in general meet the wall making a contact angle $\theta$. Young's equation describes this angle in terms of a balance between the $A-B$ interfacial tension $\gamma_{AB}$ and the surface tensions $\gamma_{wA}$, $\gamma_{wB}$ between, respectively, the $A$- and $B$-rich phases and the wall, $\gamma _{AB} \cos \theta =\gamma_{wA}-\gamma_{wB}$. By Monte Carlo simulations of bridges, formed by one of the components in a binary Lennard-Jones liquid, connecting the two walls of a nanoscopic slit pore, $\theta$ is estimated from the inclination of the interfaces, as a function of the wall-fluid interaction strength. The information on the surface tensions $\gamma_{wA}$, $\gamma_{wB}$ are obtained independently from a new thermodynamic integration method, while $\gamma_{AB}$ is found from the finite-size scaling analysis of the concentration distribution function. We show that Young's equation describes the contact angles of the actual nanoscale interfaces for this model rather accurately and location of the (first order) wetting transition is estimated.Comment: 6 pages, 6 figure

Recovering piecewise smooth functions from nonuniform Fourier measurements

In this paper, we consider the problem of reconstructing piecewise smooth functions to high accuracy from nonuniform samples of their Fourier transform. We use the framework of nonuniform generalized sampling (NUGS) to do this, and to ensure high accuracy we employ reconstruction spaces consisting of splines or (piecewise) polynomials. We analyze the relation between the dimension of the reconstruction space and the bandwidth of the nonuniform samples, and show that it is linear for splines and piecewise polynomials of fixed degree, and quadratic for piecewise polynomials of varying degree