Search results for "Polymer melt"
showing 10 items of 14 documents
Small-Angle Excess Scattering: Glassy Freezing or Local Orientational Ordering?
1996
We present Monte Carlo simulations of a dense polymer melt which shows glass-transition-like slowing-down upon cooling, as well as a build up of nematic order. At small wave vectors q this model system shows excess scattering similar to that recently reported for light-scattering experiments on some polymeric and molecular glass-forming liquids. For our model system we can provide clear evidence that this excess scattering is due to the onset of short-range nematic order and not directly related to the glass transition.
Entropy of glassy polymer melts: Comparison between Gibbs-DiMarzio theory and simulation.
1996
We calculate the free energy of a model for a polymer melt in a computer simulation of the bond-fluctuation model and determine the entropy of the melt over a wide range of temperatures, including the region close to the glass transition. The results are compared with the Gibbs-DiMarzio theory, a theory by Flory for semiflexible polymers, and a modification of their theories due to Milchev. We can describe the data within the framework of the Flory theory with Milchev's correction and discuss the consequences for the understanding of the glass transition. \textcopyright{} 1996 The American Physical Society.
Comparing equilibration schemes of high-molecular-weight polymer melts with topological indicators.
2021
Abstract Recent theoretical studies have demonstrated that the behaviour of molecular knots is a sensitive indicator of polymer structure. Here, we use knots to verify the ability of two state-of-the-art algorithms—configuration assembly and hierarchical backmapping—to equilibrate high-molecular-weight (MW) polymer melts. Specifically, we consider melts with MWs equivalent to several tens of entanglement lengths and various chain flexibilities, generated with both strategies. We compare their unknotting probability, unknotting length, knot spectra, and knot length distributions. The excellent agreement between the two independent methods with respect to knotting properties provides an addit…
Some Things We Can Learn from Chemically Realistic Polymer Melt Simulations
2005
We present in this contribution results from Molecular Dynamics (MD) simulations of a chemically realistic model of 1,4-polybutadiene (PB). The work we will discuss exemplifies the physical questions one can address with these types of simulations. We will specifically compare the results of the computer simulations with nuclear magnetic resonance (NMR) experiments, neutron scattering experiments and dielectric data. These comparisons will show how important it is to understand the torsional dynamics of polymers in the melt to be able to explain the experimental findings. We will then introduce a freely rotating chain (FRC) model where all torsion potentials have been switched off and show …
Molecular dynamics of supercooled polymer films
2000
We present results of molecular dynamics simulations for a supercooled polymer melt confined between two smooth and purely repulsive walls. The thickness D of the film is about 7 times the bulk radius of gyration. For all temperatures studied, a significant increase of the monomer and chain mobilities with respect to the bulk is observed. Preliminary results suggest that structural relaxation times exhibit a power-law behavior in the vicinity of a critical temperature T c (D) 0.39 (in Lennard-Jones units). This estimate of T c (D) is about 14% smaller than the corresponding bulk value. Despite this significant decrease the time dependence of various mean-square displacements seems to be una…
Reduction of the glass transition temperature in polymer films: A molecular-dynamics study
2001
We present results of molecular dynamics (MD) simulations for a non-entangled polymer melt confined between two completely smooth and repulsive walls, interacting with inner particles via the potential $U_{\rm wall}\myeq (\sigma/z)^9$, where $z \myeq |z_{\rm particle}-z_{\rm wall}|$ and $\sigma$ is (roughly) the monomer diameter. The influence of this confinement on the dynamic behavior of the melt is studied for various film thicknesses (wall-to-wall separations) $D$, ranging from about 3 to about 14 times the bulk radius of gyration. A comparison of the mean-square displacements in the film and in the bulk shows an acceleration of the dynamics due to the presence of the walls. %Consistent…
Testing of a constitutive equation for entangled networks by elongational and shear data of polymer melts
1973
An entangled network such as a polymer melt or a concentrated solution is here described by a set of two simultaneous equations. One of them is a balance of entanglements, the other gives the stress in the classical form of aMaxwell equation.
The non-isothermal rheological behaviour of molten polymers: Shear and elongational stress growth of polyisobutylene under heating
1981
Data of stress growth under both shear and elongational kinematics have been taken in presence of heating temperature ramps on a commerical polyisobutylene.
Publisher’s Note: “Polymer-specific effects of bulk relaxation and stringlike correlated motion in the dynamics of a supercooled polymer melt” [J. Ch…
2004
a! Present address: Department of Physics, Wesleyan University, Middletown, CT 06459. b!Author to whom correspondence should be addressed. Electronic mail: baschnag@ics.u-strasbg.fr c!Author to whom correspondence should be addressed. Electronic mail: sglotzer@umich.edu FIG. 8. Temperature dependence of the ratio of ^sseg(tstr )& and ^s(tstr )&. tstr max is the peak time of ^sseg& and ^s& at different temperatures. TMCT 50.45. JOURNAL OF CHEMICAL PHYSICS VOLUME 120, NUMBER 14 8 APRIL 2004
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.