The phase behavior of polyethylene ring chains

Abstract

The equilibrium properties of an isolated polyethylene ring chain are studied by using molecular dynamics (MD) simulations. The results of an 80-bond linear chain are also presented, which are in agreement with previous studies of square-well chains and Lennard-Jones (LJ) homopolymers. Mainly, we focus on the collapse of polyethylene ring chains. At high temperatures, a fully oblate structure is observed for the ring chains with different chain lengths. For such an oblate structure, a shape factor of delta(*)=0.25 and a rodlike scaling relation between the radius of gyration and chain lengths could be deduced easily in theory, and the same results are obtained by our MD simulations. Such an oblate structure can be obtained by Monte Carlo simulation only for sufficient stiff ring chains. When the temperature decreases, an internal energy barrier is observed. This induces a strong peak in the heat capacity, denoting a gas-liquid-like transition. This energy barrier comes mainly from the local monomer-monomer interactions, i.e., the bond-stretching, the bond-bending, and the torsion potentials. A low temperature peak is also observed in the same heat capacity curve, representing a liquid-solid-like transition. These numerical simulation results support a two-stage collapse of polyethylene ring chains; however, the nature should be different from the square-well and LJ ring chains.