Application of Rotational Isomeric State Theory to Ionic Polymer Stiffness Predictions

Abstract : Presently, rotational Isomeric State (RIS) theory directly addressses polymer chain conformation as it related to mechanical response trends. The primary goal of this work is to explore the adaptation of the methodology to the prediction of material stiffness. This multi-scale modeling approach relies on ionomer chain conformation and polymer morphology and thus has potential as both a predictive modeling tool and a synthesis guide. The Mark-Curro Monte Carlo Methodology is applied to generate a statistically valid number of end-to-end chain lengths via RIS theory for four solvated Nafion cases. For each case, a probability density function for chain length is estimated using various statistical techniques, including the classically applied cubic spline approach. It is found that the stiffness prediction is sensitive to the fitting strategy. The significance of various fitting strategies, as they relate to the physical structure of the polymer, are explored so that a method suitable for stiffness prediction may be identified.