abstract: The exceptional mechanical properties of polymers with heterogeneous structure, such as the high toughness of polyethylene and the excellent blast-protection capability of polyurea, are strongly related to their morphology and nanoscale structure. Different polymer microstructures, such as semicrystalline morphology and segregated nanophases, lead to coordinated molecular motions during deformation in order to preserve compatibility between the different material phases. To study molecular relaxation in polyethylene, a coarse-grained model of polyethylene was calibrated to match the local structural variable distributions sampled from supercooled atomistic melts. The coarse-grained model accurately reproduces structural properties, e.g., the local structure of both the amorphous and crystalline phases, and thermal properties, e.g., glass transition and melt temperatures, and dynamic properties: including the vastly different relaxation time scales of the amorphous and crystalline phases. A hybrid Monte Carlo routine was developed to generate realistic semicrystalline configurations of polyethylene. The generated systems accurately predict the activation energy of the alpha relaxation process within the crystalline phase. Furthermore, the models show that connectivity to long chain segments in the amorphous phase increases the energy barrier for chain slip within crystalline phase. This prediction can guide the development of tougher semicrystalline polymers by providing a fundamental understanding of how nanoscale morphology contributes to chain mobility. In a different study, the macroscopic shock response of polyurea, a phase segregated copolymer, was analyzed using density functional theory (DFT) molecular dynamics (MD) simulations and classical MD simulations. The two models predict the shock response consistently up to shock pressures of 15 GPa, beyond which the DFT-based simulations predict a softer response. From the DFT simulations, an analysis of bond scission was performed as a first step in developing a more fundamental understanding of how shock induced material transformations effect the shock response and pressure dependent strength of polyurea subjected to extreme shocks. / Dissertation/Thesis / Doctoral Dissertation Mechanical Engineering 2017

Dans ce travail, la caractérisation mécanique de l’interphase entre les zones amorphes et cristallines dans le polyéthylène a été abordée. La caractérisation élastique est effectuée en appliquant deux approches micromécaniques à partir des données de la simulation moléculaire pour la zone interlamellaire. Ces approches micromécaniques sont d’une part le modèle étendu d’inclusion composite, et d’autre part la méthode de double inclusion. Les résultats des deux approches s’accordent parfaitement. Il a été mis en évidence que le tenseur de rigidité de l’interphase n’est pas défini positif, l’interphase est donc mécaniquement instable. La comparaison avec les résultats expérimentaux valide la méthodologie proposée. Pour la caractérisation hyperélastique, l’algorithme hybride proposé consiste à appliquer la loi de comportement d’un milieu continu isotrope, compressible et hyperélastique aux résultats de la simulation de la dynamique moléculaire d’un élément unitaire de polyéthylène. La notion d’optimisation d’un ensemble de fonctions coûts non négatives est l’idée clé de cette partie. Les paramètres hyperélastiques identifiés sont en bon accord avec ceux qui ont été estimés expérimentalement. L’évolution des frontières de l’interphase avec la déformation est le second résultat de cette analyse. La fin du travail est dédiée à la simulation numérique de la grande déformation viscoplastique d’un agrégat de polyéthylène. Le modèle de Gent adopté pour la contrainte de rappel, le tenseur de projection proposé pour l’approche modifiée de Taylor, et l’optimisation multiniveau font parties des contributions apportées. / Elastic characterization of the interphase layer in polyethylene is implemented by applying the relationships of two micromechanical approaches, “Extended Composite Inclusion Model” and “Double-Inclusion Method”, to the Monte Carlo molecular simulation data for the interlamellar domain. The results of the two approaches match perfectly. The interphase stiffness lacks the common feature of positive definiteness, which indicates its mechanical instability. Comparison with experimental results endorses the proposed methodology. For the hyperelastic characterization of the interlamellar domain and the interphase layer, the proposed hybrid algorithm consists in applying the constitutive equations of an isotropic, compressible, hyperelastic continuum to the molecular dynamics simulation results of a polyethylene stack. Evolution of the interphase boundaries are introduced as auxiliary variables and the notion of minimizing a set of nonnegative objective functions is employed for parameter identification. The identified hyperelastic parameters for the interlamellar domain arein good agreement with the ones that have been estimated experimentally. Finally, the large, viscoplastic deformation of an aggregate of polyethylene is reexamined. The Gent model adopted for the back stress of the noncrystalline phase, correcting the projection tensor for the modified Taylor approach, and the idea of multilevel optimization are among the contributions made.