Mechanical Properties Of Tetra-Polyethylene And Tetra-Polyethylene Oxide Diamond Networks Via Molecular Dynamics Simulations
The tensile response to uniaxial deformation of polyethylene-based (Tetra-PE) and polyethylene glycol-based (Tetra-PEG) networks of various strand lengths with idealized diamond connectivity have been studied via atomistic molecular dynamics simulations. Tetra-PE and Tetra-PEG diamond networks with the same strand length show comparable maximum extensibility but the Young's moduli and tensile strength of the former are significantly lower than those of the latter, consistent with stronger intersegmental attractions in the amorphous Tetra-PEG networks. The stress-strain curves show that the stress in short-stranded networks increased rapidly and monotonically with strain while for long-stranded networks it increased very little at small strain, in a non-monotonic fashion at intermediate strains, and then very sharply as the limit of extensibility was approached. Spontaneous partial crystallization of a long-stranded Tetra-PE diamond network under supercooling was demonstrated, and the resulting system was used to: (1) Estimate its melting point as the temperature where any crystalline material disappeared abruptly, and (2) show that the presence of crystalline material in the undeformed state leads to higher stress responses upon deformation compared to amorphous samples, a result consistent with experimental observations. The spontaneous crystallization of Tetra-PEG networks at large supercooling was unsuccessful due to the slow motions of the network beads and the prohibitively long crystal nucleation times entailed.
M.S., Chemical Engineering
Master of Science
dissertation or thesis