On the origin of Sanchez-Lacombe equation of state theory in hydrostatic strain energy model for rubber-like materials

Abstract

To capture the volume deformation of rubber-like materials, the strain energy density (SED) function of a compressible hyperelastic model is formulated as the hydrostatic/liquid-like term from interchain interaction changes plus the compressible elastic term owing to elastic deformation of crosslinking network. Notably, the former term dominates volume responses. Although the physics of the hydrostatic term is relatively clear, to our knowledge, few physically-based models are available. However, in our previous work (Liu and Lu, 2023), we constructed a physically-based hydrostatic SED function inspired by the Flory-Orwoll-Vrij equation of state (EOS) theory for pure polymer fluids, and proposed the general strategy for developing hydrostatic functions according to the EOS theories. Sanchez-Lacombe EOS theory (note: a type of lattice-fluid EOS theory) inspired this work. We assume: (i) a rubber-like material consists of polymer segments occupying lattice sites and unoccupied/vacant lattice sites, and the compressibility of the material corresponds to changes in vacant sites fraction; (ii) the hydrostatic strain energy is associated with the interchain interaction energy change and the mixing entropy change between network and vacant sites. According to the Helmholtz free energy in Sanchez-Lacombe EOS theory and limiting our attention to the isothermal condition, another physically-based hydrostatic SED function is constructed; a specific compressible hyperelastic model is provided by further combining compressible 8-chain elastic SED function. The basic framework of this compressible model is inherently consistent with the Flory-Rehner framework for swollen elastomers. Our model provides good predictions for volume deformation data of ten different rubber-like materials in hydrostatic compression (HC), uniaxial tension (UT), and constrained uniaxial compression (CUC). The proposed model reveals that HC, CUC, or uniaxial compression correspond to the entropy-decreasing process and they all are controlled by entropy changes; while for UT, equibiaxial tension, or pure shear, the entropy first increases and then decreases, and the interchain interaction energy and entropy changes control the responses for initial small stretches and remaining large stretches, respectively. This study aims to provide a new physical insight and a valid physically-based hydrostatic SED function for the compressibility of rubber-like materials.