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Microstructure is key to understanding rheological behaviors of flowing particulate suspensions. During the past decade, Stokesian Dynamics simulations have been the dominant method of determining suspension microstructure. Structure results obtained numerically reveal that an anisotropic structure is formed under high Péclet (Pe) number conditions. Researchers have used various experimental techniques such as small angle neutron scattering (SANS) and light scattering methods to validate microstructure. This work outlines an experimental technique based on confocal microscopy to study microstructure of a colloidal suspension in an index-matched fluid flowing in a microchannel. High resolution scans determining individual particle locations in suspensions 30-50 vol % yield quantitative results of the local microstructure in the form of the pair distribution function, g(r). From these experimentally determined g(r), the effect of shear rate, quantified by the Péclet number as a ratio of shear and Brownian stress, on the suspension viscosity and normal stress follow that seen in macroscopic rheological measurements and simulations.It is generally believed that shear thickening behavior of colloidal suspensions is driven by the formation of hydroclusters. From measurements of particle locations, hydroclusters are identified. The number of hydroclusters grows exponentially with increasing Pe, and the onset of shear thickening is driven by the increase in formation of clusters having 5-8 particles. At higher Pe, we notice the emergence of 12 or more particle clusters. The internal structure of these hydroclusters has been investigated, and there is some evidence that particles internal to hydroclusters preferentially align along the 45° and 135° axis.Beyond observations of bulk suspension behavior, the influence of boundaries on suspension microstructure is also investigated. Experiments were performed for suspensions flowing over smooth walls, made of glass coverslips, and over rough walls having a high density coating of particles. These results show that there is more order in structure near smooth boundaries while near rough boundaries the structure is similar to that found in the bulk. The relative viscosity and normal stress differences also indicate that boundaries have an effect up as far as 6 particle diameters away from the boundary. Finally, we investigate the microstructure evolvement in a model porous medium and notice that such boundary effects come into play in such real process flows.The confocal microscopy technique also provides us with the advantage of measuring structure in real process flows. We have investigated how the microstructure evolves upstream and downstream in a porous medium. We notice more structure in a high volume fraction suspension and notice anisotropic behavior at regions where shear from the wall of the posts dominate. In other cases, a mixed flow behavior is observed due to collisions between pore surfaces and other particles resulting in a deviation from flow streamlines.