Search results for "Thermodynamics"

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…

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…

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 …

Influence of Molar Mass Distribution on the Compatibility of Polymers

1996

Abstract Phase equilibria were calculated by means of a new method (direct minimization of the Gibbs energy of mixing) for polymer blends consisting of monodisperse polymer A and polydisperse polymer B. The results obtained for a Schulz-Flory distribution of B (molecular nonuniformity U = (M w/M n) −1 = 1 and 100 components of model B) agree quantitatively with that of computations on the basis of continuous thermodynamics. The influence of U B on the miscibility of A and B in 1:1 mixtures was studied for constant M w of B, quantifying the incompatibility of the polymers by the length of the tie lines. The outcome of these calculations demonstrates that the typical effect of an augmentation…

An Alternate Interpretation of Polymer/Solvent Jump Size Units for Free-Volume Diffusion Models

1996

Polystyrene/toluene mutual-diffusion coefficients have been measured as a function of temperature in the limit of infinite solvent dilution. The solvent to polymer jump size unit ratio (ξ) was determined from the Vrentas−Duda free-volume diffusion model for polymer self-diffusion and is in excellent agreement with values evaluated from solvent self- and binary mutual-diffusion coefficient data. Comparison of the free-volume model to a version of the Kirkwood−Riseman theory, modified for diffusion at infinite dilution under non-ϑ conditions, suggests that ξ follows the temperature dependence of the root-mean-squared end-to-end distance of the polystyrene and can be estimated without the use …