Undirected graphical model of adjacency matrix for dynamic elasticity in polyelectrolyte hydrogels

Abstract

Molecular network plays a critical role in determining dynamic elasticity of soft condensed polymers, e.g., their varied cross-linking densities and end-to-end distances with changed Young's moduli. Although it has been studied for decades, the coupling relationship between vertices and edges of molecular networks is not well understood, mainly because the degree of the crosslinking points and asymmetry molecular networks have not been considered in the previously models. In this study, a graph theory was employed to formulate an undirected graphical model and describe the coupling between vertices and edges in molecular networks, based on which the dynamic elasticity of polyelectrolyte hydrogel was modeled. From the Kirchhoff graph theory and bead-spring model, the coupling relationship between vertices and edges was obtained using end-to-end distance and viscosity parameters. Combining the Watts–Strogatz model and kinetic probability, the coupling between vertices and edges for the polyelectrolyte network was studied. Furthermore, an adjacency matrix with eigenvalue, number of vertices and mean degree was proposed to formulate constitutive relationships including dynamic elasticity and stress-strain, according to rubber elasticity theory and Mooney-Rivlin model, respectively. The linking between the vertices and edges determines the network structure and dynamic elasticity of the polyelectrolyte hydrogel. Based on the graph theory, the vertices and edges are encoded by adjacency matrix, which is proposed to describe the dynamic elasticity of symmetric and asymmetric network structures using the crosslinking density and end-to-end distance. Finally, effectiveness of the undirected graphical model was verified using both finite element analysis and experimental results of polyelectrolyte hydrogels reported in literature.