Search results for "dynamics"

Crystallization of polymer melts under fast cooling. II. High-purity iPP

1992

SYNOPSIS Samples of a high-purity isotactic polypropylene (iPP) were quenched from the melt so as to monitor cooling history. A continuous variation of morphology and crystal structure was obtained with cooling rate. This is discussed in relation to sample thermal history evidencing that cooling history relevant to quenched samples is in the neighborhood of 90°C. In particular the samples are essentially mesomorphic when at this temperature cooling rates larger than 80°C/s were adopted, while below a few tens of °C/s only a­ monocline form is obtained. Densities of quenched samples were compared with predictions of an isokinetic extrapolation of Avrami model of polymer crystallization kinet…

1981

Theoretical predictions from a non-linear model based on the free volume concept, which were previously tested only with a molten polymer, are presented and compared with literature data of solid polyethylene. The agreement is good both when a steady state is reached in the experimentally explored times and when, on the contrary, the data do not show it. Theoretische Berechnungen des elektrischen Verhaltens von Polymeren anhand eines nichtlinearen Modells, die auf dem Konzept des freien Volumens basieren und bisher lediglich an einem geschmolzenen Polymer getestet wurden, werden vorgestellt und mit Literaturdaten von festem Polyethylen verglichen. Die Ubereinstimmung ist gut, wenn in den ex…

Intrinsic viscosities of polyelectrolytes in the absence and in the presence of extra salt: Consequences of the stepwise conversion of dextran into a…

2011

Abstract Viscosities of dilute polymer solutions were measured in capillary viscometers for samples varying in their fraction f of charged units from 0.00 to 0.90. The dependence of the logarithm of the relative viscosity on polymer concentration c is in all cases reproduced quantitatively by three characteristic parameters: [ η ], the intrinsic viscosity; B , a viscometric interaction parameter (related to the Huggins constant); [ η ] , a parameter required only for polyelectrolytes at low concentrations of extra salt. In pure water [ η ] increases more than 80 times as the fraction f rises from zero to 0.90 and [ η ] starts from zero and goes up to ≈71 mL/g. Upon the addition of NaCl [ η …

Osmotic pressure, atomic pressure and the virial equation of state of polymer solutions: Monte Carlo simulations of a bead-spring model

1994

A recently introduced coarse-grained model of polymer chains is studied analyzing various contributions to the pressure as obtained from the virial theorem as a function of chain length N, temperature T and density ϕ. The off-lattice model of the polymer chains has anharmonic springs between the beads, but of finite extensibility, and the Morse-type interaction between beads is repulsive at very short distances and attractive at intermediate distances. Solvent molecules are not explicitly included. It is found that the covalent forces along the chain (modelled by the spring potentials) contribute a negative term to the pressure, irrespective of temperature, which vanishes linearly in ϕ as ϕ…

Glass transition of polymer melts: Test of theoretical concepts by computer simulation.

2003

Abstract Polymers are good glass formers and allow for the study of melts near the glass transition in (meta-)stable equilibrium. Theories of the glass transition imply such an equilibrium and can, hence, be tested by the study of polymer melts. After a brief summary of the basic experimental facts about the glass transition in polymers, the main theoretical concepts are reviewed: mode coupling theory (MCT), entropy theory, free-volume theory, the idea of a growing length describing the size of cooperative regions, etc. Then, two basic coarse-grained models of polymers are described, which have been developed aiming at a test of these concepts. The first model is the bond-fluctuation model …

Adsorption Transition of a Polymer Chain at a Weakly Attractive Surface: Monte Carlo Simulation of Off-Lattice Models

2002

A bead-spring model of a polymer chain with one end attached to a wall is studied by Monte Carlo simulations for chain lengths 16 ≤ N ≤ 256. Two types of adsorption potentials, 9-3 and 10-4 Lennard-Jones (LJ) potentials, between the effective monomers and the wall are assumed. For both cases the adsorption transition where the chain changes its asymptotic statistical properties from a three-dimensional to a two-dimensional configuration is located using a scaling analysis. It is shown that the crossover exponent φ = 0.50 ± 0.02 is the same for both LJ potentials. This value is compatible with recent theoretical predictions and simulation results for lattice models with short-range wall pote…

Molecular dynamics simulations of the glass transition in polymer melts

2004

Computer simulations of polymer models have contributed strongly to our understanding of the glass transition in polymer melts. The ability of the simulation to provide information on experimentally not directly accessible quantities like the detailed spatial arrangement of the particles allows for stringent tests of theoretical concepts about the glass transition and provides additional insight for the interpretation of experimental data. Comparing coarse-grained simulations of a bead-spring model and chemically realistic simulations of 1,4-polybutadiene the importance of dihedral barriers for the glass transition phenomenon can be elucidated.

A procedure for predicting sorption equilibrium in ternary polymer systems from Flory–Huggins binary interaction parameters and the inversion point o…

1989

A procedure has been developed, based on the Flory–Huggins theory as generalized by Pouchlý, which permits the calculation of preferential (λ) and total (Y) sorption coefficients from previous information on the binary interaction parameters, χ, χ, and g12(ϕ10) and on the mixture composition at which the sign of λ inverts. The expressions obtained were applied to 10 cosolvent polymer systems for which experimental values of λ and Y are known. Practically in all the studied systems, the theoretical predictions are in fair accordance with the experimental data.

A Flory–Huggins thermodynamic approach for predicting sorption equilibrium in ternary polymer systems

1989

The Flory–Huggins theory as modified by Pouchlý has been applied to calculate preferential (λ) and total (Y) sorption coefficients for a ternary polymer system. The ternary interaction function (ϕ1ϕ2ϕ3GT(u1, ϕ3)) is described as the product of three independent binary functions. This expression allows prediction of λ and Y from binary interaction parameters χ, χ, g, g, and g12(ϕ10). Three ternary polymer systems are used to check the validity of the expression. Moreover for polymer systems in which the parameters g and/or g are unknown, a procedure to evaluate them has been developed and verified on systems for which sufficient experimental information is available.

Simulation of first- and second-order transitions in asymmetric polymer mixtures

1993

The critical properties of dense asymmetric binary polymer mixtures are studied by grand canonical simulations within the framework of the 3-dimensional bond fluctuation lattice model. The monomers interact with each other via a potential ranging over the entire first peak of the pair distribution. An asymmetry is realized by giving the ratio of interactions λ = ∈AA/∈BB between monomers of the A-species and of the B-species a value different from 1. Using multiple histogram extrapolation techniques for the data analysis, the two phase region, which is a line of first-order transitions driven by the chemical potential difference, and the critical point are determined for a mixture of chains …