Monte Carlo simulations on the effects of nanoparticles on chain deformations and reinforcement in amorphous polyethylene networks

Reinforcing effects in an amorphous polyethylene matrix were estimated for spherical filler particles arranged either on a cubic lattice or randomly in space. Attention was first focused on the effects of the type of arrangement of the particles on the microscopic properties of the polymer chains. Specifically, Monte Carlo rotational isomeric state (MC-RIS) simulations were carried out to predict the effects of the volumes excluded by the filler particles on the configurational distribution functions of the chains, and from these distributions the elastomeric properties of the composites. The calculations were carried out for a range of particle sizes and particle volume fractions. As expected, filler inclusions are found to increase the non-Gaussian behavior of the chains. The results were compared with those from small-angle neutron scattering (SANS) experiments. In the case of arrangement on a cubic lattice, chains dimensions were always found to decrease. In the randomly-dispersed filler arrangements, there were significant increases in chain dimensions relative to the unfilled system in some instances, and the changes were in excellent agreement with the SANS results. The present simulations thus give further encouragement to interpretations of chain deformations in filled systems in terms of volume exclusion effects from the nanoparticle inclusions, including their dispersions and arrangements within polymer matrices.