| Small, roughly spherical ceramic particles, approximately 1mm in size are used for a number of applications including casting sands, catalysts, and cement fillers. The oil and natural gas industry utilizes such materials in tonnage quantities yearly as extraction aids. Particles intended for this application are referred to as proppants. Proppants are composed of materials that differ by density, strength and cost, and are selected on a site by site basis. Recently, competing usage and depletion of reserves of one of the most popular category of proppant materials, sintered aluminosilicates (e.g. kaolinite, bauxite) have driven the need for alternative raw materials for proppant manufacturing. Andesite, a by-product of mining operations in the south-west United States was identified as an abundant, readily available, and low cost alternative proppant material that can be fused and net-shaped into a glass which when crystallized results in microstructures which may offer substantial toughening and fracture characteristics which may serve to their advantage for use as proppants that do not decrease the permeability ("blind") the particle bed. This study addressed the devitrification behavior and its role on the mechanical properties of andesite-based glass-ceramic spheres for use as proppants. Timetemperature- transformation studies were performed to evaluate the devitrification behavior of andesite glass. Crystalline phase evolution and microstructural development were evaluated using quantitative x-ray diffraction, scanning electron microscopy, differential thermal analysis, and spectrophotometry. The andesite glass devitrification commenced with the precipitation of iron oxides (magnetite) which served as seeds for the epitaxial growth of dendritic pyroxenes. Mechanical properties, such as diametral compressive strength, fracture toughness, hardness, and fracture morphology were correlated with crystalline phase evolution. Selected heat treatments resulting in the desired combination of high strength, toughness, and coarse fragmentation of crystallized spheres were performed for subsequent evaluation of performance as a proppant using American Petroleum Institute test methodologies. For nominally 1mm diameter devitrified proppants, diametral compressive strengths of 150MPa were observed, while results of indentation fracture resistance measurements showed values of 1.5-2.0MPa˙;m. Combinations of these mechanical properties resulted in nearly 80% incidence of coarse fragmentation compared with 40% incidence in amorphous andesite proppants. Results corroborated the hypothesis that controlled devitrification resulted in substantial improvement in toughness and fracture morphology which in turn contributed to enhanced permeability of packed particle beds relative to state of the art glass proppants, and comparable to the present state of the art sintered bauxite- and kaolinite-based proppants. |
