Search results for "dynamics"
showing 10 items of 9782 documents
A thermodynamic analysis on the coincidence of extrema conditions in the sorption equilibrium for ternary polymer systems
1993
Flory-Huggins theory of polymer solutions has been used to express the condition of extrema values in the total sorption, as well as the inversion point in the preferential adsorption parameters for termary polymer systems. Two approaches have been followed, the first considers the binary and ternary interaction parameters independent of polymer concentration and solvent composition. In the second one, this dependence has been introduced. Our attention is focused on the volume fraction of solvent mixture dependence of the above parameters, in order to confirm or not the coincidence between the extrema values and the inversion point. Several cosolvent and cononsolvent ternary polymer systems…
Prediction of maxima and minima in the curve of total sorption parameter in ternary polymer systems. Influence of ternary interaction parameter
1993
Flory-Huggins theory modified by Pouchly has been applied to predict maxima and minima in the curve of total sorption in ternary polymer systems formed by a polymer and two liquids. In this work, different diagrams based on experimental magnitudes easily obtained such as the difference in affinities of liquids, solvents and non solvents, and the solvent molar volume ratio. Total sorption parameter has been considered to be the decisive magnitude to define extrema conditions in both cosolvent and cononsolvent ternary polymer systems. The theoretical prediction is not altered by the inclusion of ternary interactions. Different examples of ternary systems dealing with vinyl polymers and polydi…
A comparative study between cosolvent and cononsolvent ternary polymer systems through the preferential adsorption coefficient
1993
Sorption equilibrium of polystyrene and poly (dimethyl siloxane) in mixed solvents has been monitored by means of the preferential adsorption coefficient experimentally determined from intensity light scattering measurements. The pairs of solvents used to dissolve each polymer sample have been selected for the purpose to perform cosolvent and cononsolvent ternary polymer systems. Flory-Huggins formalism including ternary interactions has been used to predict the sorption equilibrium for the cosolvent system and, for the first time, for cononsolvent ones. Moreover, the proportionality between binary and ternary interactions, recognized by Pouchly, is also corroborated for both ternary polyme…
Polymer brushes in solvents of variable quality: Molecular dynamics simulations using explicit solvent
2007
The structure and thermodynamic properties of a system of end-grafted flexible polymer chains grafted to a flat substrate and exposed to a solvent of variable quality are studied by molecular dynamics methods. The macromolecules are described by a coarse-grained bead-spring model, and the solvent molecules by pointlike particles, assuming Lennard-Jones-type interactions between pairs of monomers (epsilon(pp)), solvent molecules (epsilon(ss)), and solvent monomer (epsilon(ps)), respectively. Varying the grafting density sigma(g) and some of these energy parameters, we obtain density profiles of solvent particles and monomers, study structural properties of the chain (gyration radius componen…
Atomistic Molecular Dynamics Simulations of the Static and Dynamic Properties of a Polyethylene Melt
1999
I will discuss in this work the atomistic modelling of polymer melts using Molecular Dynamics (MD) simulations. After a general introduction into the problems one faces in the computer simulation of polymers in general and the atomistic simulations in particular, I will present some recent work on the atomistic modelling of an — C 100 H 202 melt,i.e. short chain polyethylene (PE). The aim of this work is to establish a quantitatively validated atomistic model which then can be used in two directions. One direction is the generation of input for the calibration of parameters in coarse-grained models, which in turn can be used to simulate the polymer under investigation over a much broader te…
Entropy theory and glass transition: A test by Monte Carlo simulation
1997
This article reviews the results of a test of the Gibbs-DiMarzio theory by Monte Carlo Simulation. The simulation employed the bond-fluctuation model on a simple cubic lattice. This model incorporates two kinds of interactions: the excluded volume interaction among all monomers of the melt and an internal energy of the chains, which favors large bonds and makes the chains stiffen with decreasing temperature. The stiffening of the chains leads to an increase of their volume requirements, which competes with the packing constraints at low temperatures. This competition strongly slows down the structural relaxation of the melt and induces the glassy behavior. The model therefore takes into acc…
Hydrodynamic mechanisms of spinodal decomposition in confined colloid-polymer mixtures: A multiparticle collision dynamics study
2013
A multiscale model for a colloid-polymer mixture is developed. The colloids are described as point particles interacting with each other and with the polymers with strongly repulsive potentials, while polymers interact with each other with a softer potential. The fluid in the suspension is taken into account by the multiparticle collision dynamics method (MPC). Considering a slit geometry where the suspension is confined between parallel repulsive walls, different possibilities for the hydrodynamic boundary conditions (b.c.) at the walls (slip versus stick) are treated. Quenching experiments are considered, where the system volume is suddenly reduced (keeping the density of the solvent flui…
Investigation of the glass transition and melting of polymers by nuclear magnetic resonance
2007
Investigations of the glass transition and melting of partially crystalline polymers by nuclear magnetic resonance provide valuable information on the nature of noncrystalline regions. The broad line NMR signal was separated into a narrow component and a broad component by using a new method which does not imply the ambiguity usually present. From the intensity of the narrow component the mobile fraction was determined. This fraction was extrapolated to “infinite” temperature. By subtracting the mobile fraction from the noncrystalline fraction, the noncrystalline rigid fraction was obtained. Comparison of the measured second moments of the two components of the NMR line with calculated seco…
On the tribology and rheology of polymer brushes in good solvent conditions: a molecular dynamics study
2003
Tribological and rheological properties of two polymer brushes in relative sliding motion and good solvent conditions are investigated by means of molecular dynamics (MD) simulations. The lateral forces between the brushes are found to decrease logarithmically with increasing relative sliding velocity v0 over a range of more than one decade in v0. We also observe an almost logarithmic relaxation of the end-to-end distance vector that occurs after sliding is stopped. The coincidence of these logarithmic dependencies support the picture that friction between polymer brushes is small due to the retraction of the polymers from the interpenetration zone. The shear stress relaxes almost instantly…
Interfacial properties of glassy polymer melts: A Monte Carlo study
1996
The properties of the interface between a polymer melt and a solid wall are studied over a wide range of temperatures by dynamic Monte Carlo simulations. It is shown that in the supercooled state near the glass transition of the melt an “interphase” forms, the structure of which is influenced by the wall. The thickness of this interphase is determined from the monomer density profile near the surface and is strongly temperature dependent. At low glass-like temperatures it is larger than the bulk radius of gyration of the chains.