abstract: Polyurea is a highly versatile material used in coatings and armor systems to protect against extreme conditions such as ballistic impact, cavitation erosion, and blast loading. However, the relationships between microstructurally-dependent deformation mechanisms and the mechanical properties of polyurea are not yet fully understood, especially under extreme conditions. In this work, multi-scale coarse-grained models are developed to probe molecular dynamics across the wide range of time and length scales that these fundamental deformation mechanisms operate. In the first of these models, a high-resolution coarse-grained model of polyurea is developed, where similar to united-atom models, hydrogen atoms are modeled implicitly. This model was trained using a modified iterative Boltzmann inversion method that dramatically reduces the number of iterations required. Coarse-grained simulations using this model demonstrate that multiblock systems evolve to form a more interconnected hard phase, compared to the more interrupted hard phase composed of distinct ribbon-shaped domains found in diblock systems. Next, a reactive coarse-grained model is developed to simulate the influence of the difference in time scales for step-growth polymerization and phase segregation in polyurea. Analysis of the simulated cured polyurea systems reveals that more rapid reaction rates produce a smaller diameter ligaments in the gyroidal hard phase as well as increased covalent bonding connecting the hard domain ligaments as evidenced by a larger fraction of bridging segments and larger mean radius of gyration of the copolymer chains. The effect that these processing-induced structural variations have on the mechanical properties of the polymer was tested by simulating uniaxial compression, which revealed that the higher degree of hard domain connectivity leads to a 20% increase in the flow stress. A hierarchical multiresolution framework is proposed to fully link coarse-grained molecular simulations across a broader range of time scales, in which a family of coarse-grained models are developed. The models are connected using an incremental reverse–mapping scheme allowing for long time scale dynamics simulated at a highly coarsened resolution to be passed all the way to an atomistic representation. / Dissertation/Thesis / Doctoral Dissertation Mechanical Engineering 2020

<p>A first-principles theory of plasticity in metals currently does not exist. While many plasticity models make reference to rules based on heuristic arguments regarding dislocations (the fundamental mediators of plastic deformation in crystals), the scientific community still does not have a theory of dislocation dynamics which can recover even basic features of plasticity theory. Discrete dislocation dynamics, though a valuable tool for understanding fundamentals topics in dislocation plasticity, becomes unusable beyond ~1.5\% strain due to the line length multiplication inherent in deformation. As a result, it is necessary to develop continuum theories of dislocation dynamics which treat dislocation densities rather than individual dislocations. This thesis examines the foundations of one such continuum theory: line bundle continuum dislocation dynamics, which assumes that dislocations are roughly parallel at every point. First, this assumption is given definite meaning and it is shown from discrete dislocation dynamics data that to be appropriate when modelling dislocation densities on fine length scales (resolving densities on lengths less than 100 nm). Second, it is found that an additional driving force, the correlation stress, emerges from coarse-graining the line bundle dynamics. This correction to the dislocation interactions is dependent on tensorial dislocation correlation functions describing the short-range errors in the products of dislocation densities lying on two slip systems. The full set of these dislocation correlation functions are evaluated from discrete density data with the aid of a novel left-and-right handed classification of slip system interactions in FCC crystals. Lastly, a study of the correlation stress in a representative dislocation system suggests that these stresses are roughly one tenth the magnitude of the mean-field dislocation interaction stress. Taken together, this thesis bridges discrete and continuum models of dislocation dynamics and provides a foundation for future work on a first-principles theory of metal plasticity. </p>