Search results for "dynamics."
showing 10 items of 9637 documents
Lattice fluid model generalized for specific interactions: An application to ternary polymer solutions
2011
Abstract The phase diagram of the Poly- l -Lactic-Acid (PLLA), dioxane and water system was derived by using the lattice fluid model generalized for specific interactions. A qualitative analysis of Hansen solubility parameters together with empirical observations were adopted to reduce the number of adjustable parameters. The as-selected model parameters were derived by fitting a set of cloud point curves; consequently, the complete phase diagram of the system was computed. The use of specific interactions between species gave out a quantitative agreement with a set of experimental data, whereas changing the polymer polydispersity the agreement is only qualitative. In principle, the present…
The effect of pressure on the liquid–liquid phase equilibrium of two polydisperse polyalkylsiloxane blends
2002
The effect of pressure-induced immiscibility in polymer blends is investigated by experimental and theoretical methods. Experimental data of cloud point curves and critical points are obtained by turbidity measurements. The chosen system is a mixture of polydimethylsiloxane and polyhexylmethylsiloxane which is one of the very few polymer blends exhibiting pressure-induced immiscibility. This unusual behaviour is related to a critical temperature minimum of the critical curve and cloud point isopleths at positive pressure in the temperature–pressure diagram. The effect of the chain length on the critical temperature minimum is investigated here based on theoretical models. The effect of diff…
Shear Effects on the Phase Diagrams of Solutions of Highly Incompatible Polymers in a Common Solvent. 2. Experiment and Theory
1997
Cloud point temperatures (Tcp) were measured at different constant shear rates for three representatives of the ternary system cyclohexanone/polystyrene/poly(n-butyl methacrylate) (CHO/PS/PBMA) by means of a newly constructed rheo-optical apparatus that can be operated in the temperature range from 0 to 100 °C up to maximum shear rates of 1440 s-1 and maximum stresses of 384 Pa. In all cases one observes an extension of the homogeneous region as the shear rate γ is raised. With the system CHO/PS 196w/PBMA 2050 (the figures denote the molar masses of the polymers in kilograms/mole) the effects become maximum for high concentrations of PBMA, where the demixing temperatures increase by more th…
Shear Effects on the Phase Diagrams of Solutions of Highly Incompatible Polymers in a Common Solvent. 1. Equilibrium Behavior and Rheological Propert…
1997
Phase diagrams (cloud points, tie lines, critical compositions) and viscosities of homogeneous solutions were determined at temperatures ranging from 20 to 100 °C for three representatives of the ternary system cyclohexanone/polystyrene/poly(n-butyl methacrylate) [CHO/PS/PBMA] in preparation of a study on shear influences. An only moderate increase of the two-phase region observed upon heating (LCST behavior) witnesses little heat effects upon mixing. Tie lines which are nearly parallel to the PS/PBMA edge of the Gibbs phase triangle indicate comparable solvent quality of CHO for both polymers. The quantitative mathematical description of the equilibrium behavior-required for a theoretical …
Ternary Polymer Solutions with Hydrogen Bonds, 2
2007
Experimental ternary phase diagrams for ternary systems CHL/PS-MAA/PVPy with diverse MAA contents have been determined by GPC. The presence of MAA in the copolymers gives rise to specific interactions, by hydrogen bond formation between both polymeric components, so strong that the isotherm for the system with the highest MAA content so far studied, CHL/PS-MAA(8%)/PVPy, is representative of a complex coacervation situation. By applying the theoretical background deduced by coupling the Flory-Huggins lattice model to the AET developed for ternary polymeric systems SPP with specific intermolecular interactions (via hydrogen bonds), free energy surfaces for the CHL/PS-MAA/PVPy systems are cons…
Optical tweezing electrophoresis of isolated, highly charged colloidal spheres
2001
Abstract We report on a novel optical tweezing experiment measuring the electrophoretic mobility μ of highly charged spherical particles suspended in water at volume fractions Φ≤2×10 −7 . At deionised conditions μ =2.5×10 −8 m 2 V −1 s −1 , it decreases further upon increasing the salt concentration c . We compare our data to measurements at larger Φ, where generally much larger μ and a qualitatively different dependence on the salt concentration are observed. To characterise the dependence on Φ we performed measurements at no added salt. There the mobility increases in the unordered state but stays constant at μ =6.8×10 −8 m 2 V −1 s −1 as the system develops fluid order. In the ordered re…
A slow process in confined polymer melts: layer exchange dynamics at a polymer solid interface
2010
Employing Molecular Dynamics simulations of a chemically realistic model of 1,4-polybutadiene between graphite walls we show that the mass exchange between layers close to the walls is a slow process already in the melt state. For the glass transition of confined polymers this process competes with the slowing down due to packing effects and intramolecular rotation barriers.
On what terms and why the thermodynamic properties of polymer solutions depend on chain length up to the melt
2003
Theoretical considerations based on chain connectivity and conformational variability of polymers have lead to an uncomplicated relation for the dependence of the Flory-Huggins interaction parameter, chi, on the volume fraction of the polymer, phi, and on its number of segments, N. The validity of this expression is being tested extensively by means of vapor pressure measurements and inverse gas chromatography (complemented by osmotic and light scattering data from literature) for solutions of poly(dimethylsiloxane) in the thermodynamically vastly different solvents n-octane (n-C8), toluene (TL), and methylethylketone (MEK) over the entire range of composition for at least six different mol…
Dynamics of confined polymer melts: Recent Monte Carlo simulation results
2000
The dynamic behavior of thin polymer films is studied by Monte Carlo simulations of a simplified lattice model. The film geometry is realized by two opposite hard walls whose distance is varied in the simulations. In the films the dynamics is accelerated with respect to the bulk, leading to a decrease of the extrapolated glass transition temperature with decreasing film thickness.
Glassy dynamics in thin polymer films: recent MD results
2002
The influence of a film geometry on the glass transition is investigated via molecular dynamics (MD) simulations of a (non-entangled) polymer melt. The confinement is realized by two identical potential barriers of the form U wall = z -9 , where z denotes the distance of a particle from the wall. Despite the geometric confinement, basic qualitative features of the system dynamics can be well described in the framework of the mode-coupling theory (MCT). Examples are the two-step relaxation of the incoherent intermediate scattering function, the time-temperature superposition property of the late time α-process and the space-time factorization of the scattering function on the intermediate ti…