abstract: Ultra High Performance (UHP) cementitious binders are a class of cement-based materials with high strength and ductility, designed for use in precast bridge connections, bridge superstructures, high load-bearing structural members like columns, and in structural repair and strengthening. This dissertation aims to elucidate the chemo-mechanical relationships in complex UHP binders to facilitate better microstructure-based design of these materials and develop machine learning (ML) models to predict their scale-relevant properties from microstructural information.To establish the connection between micromechanical properties and constitutive materials, nanoindentation and scanning electron microscopy experiments are performed on several cementitious pastes. Following Bayesian statistical clustering, mixed reaction products with scattered nanomechanical properties are observed, attributable to the low degree of reaction of the constituent particles, enhanced particle packing, and very low water-to-binder ratio of UHP binders. Relating the phase chemistry to the micromechanical properties, the chemical intensity ratios of Ca/Si and Al/Si are found to be important parameters influencing the incorporation of Al into the C-S-H gel. ML algorithms for classification of cementitious phases are found to require only the intensities of Ca, Si, and Al as inputs to generate accurate predictions for more homogeneous cement pastes. When applied to more complex UHP systems, the overlapping chemical intensities in the three dominant phases – Ultra High Stiffness (UHS), unreacted cementitious replacements, and clinker – led to ML models misidentifying these three phases. Similarly, a reduced amount of data available on the hard and stiff UHS phases prevents accurate ML regression predictions of the microstructural phase stiffness using only chemical information. The use of generic virtual two-phase microstructures coupled with finite element analysis is also adopted to train MLs to predict composite mechanical properties. This approach applied to three different representations of composite materials produces accurate predictions, thus providing an avenue for image-based microstructural characterization of multi-phase composites such UHP binders. This thesis provides insights into the microstructure of the complex, heterogeneous UHP binders and the utilization of big-data methods such as ML to predict their properties. These results are expected to provide means for rational, first-principles design of UHP mixtures. / Dissertation/Thesis / Doctoral Dissertation Engineering 2020