Neutron-mapping polymer flow: Scattering, flow visualization, and molecular theory

Flows of complex fluids need to be understood at both macroscopic and molecular scales, because it is the macroscopic response that controls the fluid behavior, but the molecular scale that ultimately gives rise to rheological and solid-state properties. Here the flow field of an entangled polymer melt through an extended contraction, typical of many polymer processes, is imaged optically and by small-angle neutron scattering. The dual-probe technique samples both the macroscopic stress field in the flow and the microscopic configuration of the polymer molecules at selected points. The results are compared with a recent tube model molecular theory of entangled melt flow that is able to calculate both the stress and the single-chain structure factor from first principles. The combined action of the three fundamental entangled processes of reptation, contour length fluctuation, and convective constraint release is essential to account quantitatively for the rich rheological behavior. The multiscale approach unearths a new feature: Orientation at the length scale of the entire chain decays considerably more slowly than at the smaller entanglement length.

Genetic assignment methods for the direct, real-time estimation of migration rate: a simulation-based exploration of accuracy and power

Genetic assignment methods use genotype likelihoods to draw inference about where individuals were or were not born, potentially allowing direct, real-time estimates of dispersal. We used simulated data sets to test the power and accuracy of Monte Carlo resampling methods in generating statistical thresholds for identifying F-0 immigrants in populations with ongoing gene flow, and hence for providing direct, real-time estimates of migration rates. The identification of accurate critical values required that resampling methods preserved the linkage disequilibrium deriving from recent generations of immigrants and reflected the sampling variance present in the data set being analysed. A novel Monte Carlo resampling method taking into account these aspects was proposed and its efficiency was evaluated. Power and error were relatively insensitive to the frequency assumed for missing alleles. Power to identify F-0 immigrants was improved by using large sample size (up to about 50 individuals) and by sampling all populations from which migrants may have originated. A combination of plotting genotype likelihoods and calculating mean genotype likelihood ratios (D-LR) appeared to be an effective way to predict whether F-0 immigrants could be identified for a particular pair of populations using a given set of markers.

Modeling molecular transport in slit pores

We examine the transport of methane in microporous carbon by performing equilibrium and nonequilibrium molecular dynamics simulations over a range of pore sizes, densities, and temperatures. We interpret these simulation results using two models of the transport process. At low densities, we consider a molecular flow model, in which intermolecular interactions are neglected, and find excellent agreement between transport diffusion coefficients determined from simulation, and those predicted by the model. Simulation results indicate that the model can be applied up to fluid densities of the order to 0.1-1 nm(-3). Above these densities, we consider a slip flow model, combining hydrodynamic theory with a slip condition at the solid-fluid interface. As the diffusion coefficient at low densities can be accurately determined by the molecular flow model, we also consider a model where the slip condition is supplied by the molecular flow model. We find that both density-dependent models provide a useful means of estimating the transport coefficient that compares well with simulation. (C) 2004 American Institute of Physics.

Numerical simulation of abrupt contraction flows using the Double Convected Pom-Pom model

The Double Convected Pom-Pom model was recently introduced to circumvent some numerical and theological defects found in other formulations of the Pom-Pom concept. It is used here for the simulation of a benchmark problem: the flow in an abrupt planar contraction. The predictions are compared with birefringence measurements and show reasonable quantitative agreement with experimental data. A parametric study is also carried out with the aim of analysing the effect of the branching parameter on vortex dynamics and extrudate swell. The results show that the Double Convected Pom-Pom model (DCPP) model is able to discriminate between branched and linear macromolecular structures in accordance with experimental observations. In that respect, the role of the extensional properties in determining complex flow behaviour is stressed. Also, the ratio of the first normal stress difference to the shear stress appears to play a major role in die swell observation. For the time being, the role of the second normal stress difference appears to be less obvious to evaluate in this complex flow. (C) 2004 Elsevier B.V. All rights reserved.

Recent development in the mechanics of superplasticity and its applications

This paper reviews the recent developments in the mechanics of superplasticity and its applications in industrial practice. After introducing the phenomena of superplasticity, the basic experiments for determining material deformation behavior and related parameters, and constructing superplastic constitutive equations, are reviewed. Finite element related formulations and techniques for simulating superplastic forming are discussed, together with some practical applications. (C) 2004 Elsevier B.V. All rights reserved.

Adsorption of ethylene on graphitized thermal carbon black and in slit pores: A computer simulation study

In this paper, we studied vapor-liquid equilibria (VLE) and adsorption of ethylene on graphitized thermal carbon black and in slit pores whose walls are composed of graphene layers. Simple models of a one-center Lennard-Jones (LJ) potential and a two-center united atom (UA)-LJ potential are investigated to study the impact of the choice of potential models in the description of VLE and adsorption behavior. Here, we used a Monte Carlo simulation method with grand canonical Monte Carlo (GCMC) and Gibbs ensemble Monte Carlo ensembles. The one-center potential model cannot describe adequately the VLE over the practical range of temperature from the triple point to the critical point. On the other hand, the two-center potential model (Wick et al. J. Phys. Chem. B 2000, 104, 8008-8016) performs well in the description of VLE (saturated vapor and liquid densities and vapor pressure) over the wide range of temperature. This UA-LJ model is then used in the study of adsorption of ethylene on graphitized thermal carbon black and in slit pores. Agreement between the GCMC simulation results and the experimental data on graphitized thermal carbon black for moderate temperatures is excellent, demonstrating that the potential of the GCMC method and the proper choice of potential model are essential to investigate adsorption. For slit pores of various sizes, we have found that the behavior of ethylene exhibits a number of features that are not manifested in the study of spherical LJ particles. In particular, the singlet density distribution versus distance across the pore and the angle between the molecular axis and the z direction provide rich information about the way molecules arrange themselves when the pore width is varied. Such an arrangement has been found to be very sensitive to the pore width.

Fast simulation of a quantum phase transition in an ion-trap realizable unitary map

We show that a specific implementation of a unitary map on multiple qubits in an ion trap is physically equivalent to a Hamiltonian evolution that belongs to the same universality class as the transverse Ising Hamiltonian. We suggest experimental signatures, and present numerical simulations for the case of four qubits.

Adsorbate transport in nanopores

We present a tractable theory of transport of simple fluids in cylindrical nanopores, considering trajectories of molecules between diffuse wall collisions at low-density, and including viscous flow contributions at higher densities. The model is validated through molecular dynamics simulations of supercritical methane transport, over a wide range of conditions. We find excellent agreement between model and simulation at low to medium densities. However, at high densities the model tends to over-predict the transport behaviour, due to a large decrease in surface slip that is not well represented by the model. It is also seen that the concept of activated diffusion, commonly associated with diffusion in small pores, is fundamentally invalid for smooth pores.

Three-dimensional simulation of the rolling of a saturated fibro-porous media

This paper describes recent advances made in computational modelling of the sugar cane liquid extraction process. The saturated fibro-porous material is rolled between circumferentially grooved rolls, which enhance frictional grip and provide a low-resistance path for liquid flow during the extraction process. Previously reported two-dimensional (2D) computational models, account for the large deformation of the porous material by solving the fully coupled governing fibre stress and fluid-flow equations using finite element techniques. While the 2D simulations provide much insight into the overarching cause-effect relationships, predictions of mechanical quantities such as roll separating force and particularly torque as a function of roll speed and degree of compression are not satisfactory for industrial use. It is considered that the unsatisfactory response in roll torque prediction may be due to the stress levels that exist between the groove tips and roots which have been largely neglected in the geometrically simplified 2D model. This paper gives results for both two- and three-dimensional finite element models and highlights their strengths and weaknesses in predicting key milling parameters. (c) 2005 Elsevier B.V. All rights reserved.

Adsorption of N-2, Ar, acetone, chloroform and acetone-chloroform mixture on carbon black in the framework of molecular layer structure theory (MLST)

Adsorption of pure nitrogen, argon, acetone, chloroform and acetone-chloroform mixture on graphitized thermal carbon black is considered at sub-critical conditions by means of molecular layer structure theory (MLST). In the present version of the MLST an adsorbed fluid is considered as a sequence of 2D molecular layers, whose Helmholtz free energies are obtained directly from the analysis of experimental adsorption isotherm of pure components. The interaction of the nearest layers is accounted for in the framework of mean field approximation. This approach allows quantitative correlating of experimental nitrogen and argon adsorption isotherm both in the monolayer region and in the range of multi-layer coverage up to 10 molecular layers. In the case of acetone and chloroform the approach also leads to excellent quantitative correlation of adsorption isotherms, while molecular approaches such as the non-local density functional theory (NLDFT) fail to describe those isotherms. We extend our new method to calculate the Helmholtz free energy of an adsorbed mixture using a simple mixing rule, and this allows us to predict mixture adsorption isotherms from pure component adsorption isotherms. The approach, which accounts for the difference in composition in different molecular layers, is tested against the experimental data of acetone-chloroform mixture (non-ideal mixture) adsorption on graphitized thermal carbon black at 50 degrees C. (C) 2005 Elsevier Ltd. All rights reserved.

Adsorption of argon from sub- to supercritical conditions on graphitized thermal carbon black and in graphitic slit pores: A grand canonical Monte Carlo simulation study

In this paper we consider the adsorption of argon on the surface of graphitized thermal carbon black and in slit pores at temperatures ranging from subcritical to supercritical conditions by the method of grand canonical Monte Carlo simulation. Attention is paid to the variation of the adsorbed density when the temperature crosses the critical point. The behavior of the adsorbed density versus pressure (bulk density) shows interesting behavior at temperatures in the vicinity of and those above the critical point and also at extremely high pressures. Isotherms at temperatures greater than the critical temperature exhibit a clear maximum, and near the critical temperature this maximum is a very sharp spike. Under the supercritical conditions and very high pressure the excess of adsorbed density decreases towards zero value for a graphite surface, while for slit pores negative excess density is possible at extremely high pressures. For imperfect pores (defined as pores that cannot accommodate an integral number of parallel layers under moderate conditions) the pressure at which the excess pore density becomes negative is less than that for perfect pores, and this is due to the packing effect in those imperfect pores. However, at extremely high pressure molecules can be packed in parallel layers once chemical potential is great enough to overcome the repulsions among adsorbed molecules. (c) 2005 American Institute of Physics.

Grand canonical Monte Carlo simulation study of methane adsorption at an open graphite surface and in slitlike carbon pores at 273 K

Grand canonical Monte Carlo (GCMC) simulation was used for the systematic investigation of the supercritical methane adsorption at 273 K on an open graphite surface and in slitlike micropores of different sizes. For both considered adsorption systems the calculated excess adsorption isotherms exhibit a maximum. The effect of the pore size on the maximum surface excess and isosteric enthalpy of adsorption for methane storage at 273 K is discussed. The microscopic detailed picture of methane densification near the homogeneous graphite wall and in slitlike pores at 273 K is presented with selected local density profiles and snapshots. Finally, the reliable pore size distributions, obtained in the range of the microporosity, for two pitch-based microporous activated carbon fibers are calculated from the local excess adsorption isotherms obtained via the GCMC simulation. The current systematic study of supercritical methane adsorption both on an open graphite surface and in slitlike micropores performed by the GCMC summarizes recent investigations performed at slightly different temperatures and usually a lower pressure range by advanced methods based on the statistical thermodynamics.

Constriction flows of monodisperse linear entangled polymers: Multiscale modeling and flow visualization

We explore both the rheology and complex flow behavior of monodisperse polymer melts. Adequate quantities of monodisperse polymer were synthesized in order that both the materials rheology and microprocessing behavior could be established. In parallel, we employ a molecular theory for the polymer rheology that is suitable for comparison with experimental rheometric data and numerical simulation for microprocessing flows. The model is capable of matching both shear and extensional data with minimal parameter fitting. Experimental data for the processing behavior of monodisperse polymers are presented for the first time as flow birefringence and pressure difference data obtained using a Multipass Rheometer with an 11:1 constriction entry and exit flow. Matching of experimental processing data was obtained using the constitutive equation with the Lagrangian numerical solver, FLOWSOLVE. The results show the direct coupling between molecular constitutive response and macroscopic processing behavior, and differentiate flow effects that arise separately from orientation and stretch. (c) 2005 The Society of Rheology.

Adsorption of flexible n-alkane on graphitized thermal carbon black: analysis of adsorption isotherm by means of GCMC simulation

In this paper, we investigate the suitability of the grand canonical Monte Carlo in the description of adsorption equilibria of flexible n-alkane (butane, pentane and hexane) on graphitized thermal carbon black. Potential model of n-alkane of Martin and Siepmann (J. Phys. Chem. 102 (1998) 2569) is employed in the simulation, and we consider the flexibility of molecule in the simulation. By this we study two models, one is the fully flexible molecular model in which n-alkane is subject to bending and torsion, while the other is the rigid molecular model in which all carbon atoms reside on the same plane. It is found that (i) the adsorption isotherm results of these two models are close to each other, suggesting that n-alkane model behaves mostly as rigid molecules with respect to adsorption although the isotherm for longer chain n-hexane is better described by the flexible molecular model (ii) the isotherms agree very well with the experimental data at least up to two layers on the surface.

Comparative adsorption of spherical argon and flexible n-butane in carbon slit pores - a GCMC computer simulation study

In this paper we investigate the difference between the adsorption of spherical molecule argon (at 87.3 K) and the flexible normal butane (at an equivalent temperature of 150 K) in carbon slit pores. These temperatures are equivalent in the sense that they have the same relative distances between their respective triple points and critical points. Higher equivalent temperatures are also studied (122.67 K for argon and 303 K for n-butane) to investigate the effects of temperature on the 2D-transition in adsorbed density. The Grand Canonical Monte Carlo simulation is used to study the adsorption of these two model adsorbates. Beside the longer computation times involved in the computation of n-butane adsorption, n-butane exhibits many interesting behaviors such as: (i) the onset of adsorption occurs sooner (in terms of relative pressure), (ii) the hysteresis for 2D- and 3D-transitions is larger, (iii) liquid-solid transition is not possible, (iv) 2D-transition occurs for n-butane at 150 K while it does not happen for argon except for pores that accommodate two layers of molecules, (v) the maximum pore density is about four times less than that of argon and (vi) the sieving pore width is slightly larger than that for argon. Finally another feature obtained from the Grand Canonical Monte Carlo (GCMC) simulation is the configurational arrangement of molecules in pores. For spherical argon, the arrangement is rather well structured, while for n-butane the arrangement depends very much on the pore size. (C) 2004 Elsevier B.V. All rights reserved.