One of the important parameters in water management of proton exchange membranes is the electro-osmotic drag (EOD) coefficient of water. The value of the EOD coefficient is difficult to justify, and available literature data on this for Nafion membranes show scattering from in experiments and simulations. Here, we use a classical all-atom model to compute the EOD coefficient and thermodynamic properties of water from molecular dynamics simulations for temperatures between 330 and 420 K, and for different water contents between λ = 5 and λ = 20. λ is the ratio between the moles of water molecules to the moles of sulfonic acid sites. This classical model does not capture the Grotthuss mechanism; however, it is shown that it can predict the EOD coefficient within the range of experimental values for λ = 5 where the vehicular mechanism dominates proton transfer. For λ > 5, the Grotthuss mechanism becomes dominant. To obtain the EOD coefficient, average velocities of water and ions are computed by imposing different electric fields to the system. Our results show that the velocities of water and hydronium scale linearly with the electric field, resulting in a constant ratio of ca. 0.4 within the error bars. We find that the EOD coefficient of water linearly increases from 2 at λ = 5 to 8 at λ = 20 and the results are not sensitive to temperature. The EOD coefficient at λ = 5 is within the range of experimental values, confirming that the model can capture the vehicular transport of protons well. At λ = 20, due to the absence of proton hopping in the model, the EOD coefficient is overestimated by a factor of 3 compared to experimental values. To analyze the interactions between water and Nafion, the partial molar enthalpies and partial molar volumes of water are computed from molecular dynamics simulations. At different water uptakes, multiple linear regression is used on raw simulation data within a narrow composition range of water inside the Nafion membrane. The partial molar volumes and partial molar excess enthalpies of water asymptotically approach the molar volumes and molar excess enthalpies of pure water for water uptakes above 5. This confirms the model can capture the bulklike behavior of water in the Nafion at high water uptakes.

This reactive molecular dynamics study explores the salt concentration dependence of the viscoelastic and mechanical failure properties of a poly(propylene glycol)/LiPF₆-based solid polymer electrolyte (SPE) at a graphitic carbon electrode interface. To account for the finite-size effect of interface-confined SPE films, the properties of two distinct film thicknesses are compared with the respective bulk properties. Additionally, the effect of uniaxial compression in the interface-normal direction on free energy profiles of Li-ion SPE-desolvation is studied.

We propose a computational procedure to assess size effects in nonfunctionalized single-walled carbon nanotube (CNT)-polymer composites. The procedure upscales results obtained with atomistic simulations on a composite unit cell with one CNT to an equivalent continuum composite model with a large number of CNTs. Molecular dynamics simulations demonstrate the formation of an ordered layer of polymer matrix surrounding the nanotube. This layer, known as the interphase, plays a central role in the overall mechanical response of the composite. Due to poor load transfer from the matrix to the CNT, the reinforcement effect attributed to the CNT is negligible; hence the interphase is regarded as the only reinforcement phase in the composite. Consequently, the mechanical properties of the interface and the CNT are not derived since their contribution to the elastic response of the composite is negligible. To derive the elastic properties of the interphase, we employ an intermediate continuum micromechanical model consisting of only the polymer matrix and a three-dimensional fiber representing the interphase. The Young's modulus and Poisson's ratio of the equivalent fiber, and therefore of the interphase, are identified through an optimization procedure based on the comparison between results from atomistic simulations and those obtained from an isogeometric analysis of the intermediate micromechanical model. Finally, the embedded reinforcement method is employed to determine the macroscopic elastic properties of a representative volume element of a composite with various fiber volume fractions and distributions. We then investigate the role of the CNT diameter on the elastic response of a CNT-polymer composite; our simulations predict a size effect on the composite elastic properties, clearly related to the interphase volume fraction.

Molecular-dynamics simulations of single-walled carbon nanotubes (CNTs) embedded in a coarse-grained amorphous monodisperse polyethylene-like model system have been carried out. The roles of nanotube diameter and chirality on the physical and structural properties of the composite are thoroughly discussed for several CNTs with different diameter and chirality. It is shown that the glass-transition temperature of the polymer matrix increases with the diameter of the CNT while chirality effects are negligible. A denser and ordered layered region of polymer matrix is found in the vicinity of the nanotube surface. The density and ordering of this layer increases with the CNT diameter. All simulations indicate that chirality does not affect the atomic structure of the highly ordered layer surrounding the CNTs. Despite the simplicity of the polymer model, results of this study are qualitatively comparable with those obtained from experiments and numerical simulations that consider a chemically specific polymer matrix.