Effect of branching and confinement on star-branched polymeric systems.
The effect of confinement, number of branches (functionality), and size of the molecules on various properties as a function of temperature of star-branched polymers confined between two walls was studied using Monte Carlo simulations with the parallel tempering technique. The coil-to-globule transition and the liquidlike to solidlike transition, similar to those observed for linear chains, were characterized in all systems by changes in the heat capacity, internal energy, and radius of gyration. The transitions were also characterized by the most probable isomeric structure at a given temperature. The radius of gyration of the star polymers was smaller than the values of linear chains when the number of arms f increased. For star chains with more than f=5 arms the values of the radius of gyration, and therefore the size of the molecules, were similar for every condition of confinement studied, especially at higher temperatures. As confinement was increased, the difference in the radius of gyration of linear chains and star polymers became even larger. The coil-to-globule transition temperatures shifted to higher temperatures as the size of the chains and the number of arms in a molecule were increased. Effects of confinement were higher on the properties of the system at the smallest separations (less than twice the monomer diameter), where the coil-to-globule transition shifted to lower temperatures. The liquidlike to solidlike transition was present at almost the same temperature for different conditions of confinement, chain size, and number of arms. The behavior of the systems for separations between the walls greater than five bead diameters was similar to the behavior in the unconfined case. Hence, no considerable effect of confinement was found above this separation.
Maury-Evertsz
Johnny R
JR
Department of Chemical Engineering, University of Puerto Rico, Mayagüez, P.O. Box 9046, Puerto Rico 00681-9046.
Estévez
L Antonio
LA
López
Gustavo E
GE
D002627:Chemistry, Physical / Q000379:methods*; D003198:Computer Simulation; D006358:Hot Temperature; D046911:Macromolecular Substances / Q000737:chemistry; D008958:Models, Molecular; D015233:Models, Statistical; D008968:Molecular Conformation; D009010:Monte Carlo Method; D011108:Polymers / Q000737:chemistry; D013499:Surface Properties; D013696:Temperature; D013816:Thermodynamics
D046911:Macromolecular Substances; D011108:Polymers