Structural adhesive bonding offers several advantages over other types of joining. These include improved stress distribution and increased design flexibility. Adhesive bonding is important in aerospace, automotive, and packaging applications. However, the full potential of the technology has not been exploited because the understanding of the basic mechanisms of adhesion and adhesion failure is incomplete. This investigation elucidates the chemical and mechanical mechanisms responsible for durable adhesion of epoxy resins to phosphorus oxo acid treated aluminum alloys. By systematically altering the adherend surface chemistry, surface topography, and adhesive formulation, combined with accelerated testing, the chemical and mechanical factors that influence the properties of adhesively bonded aluminum are isolated and assessed. It is postulated that a combination of two factors determines the strength and environmental durability of epoxy-bonded aluminum. One is the formation of hydrolytically stable, primary bonds between the adhesive and the adherend, and the second is the hydrolytic stability of the surface oxide, which is always present on the surface of aluminum and aluminum alloys. These conditions can best be met by chemical pretreatment of the oxide surface, which renders the oxide insoluble and creates, at the same time, functional surface sites. These sites can form chemical bonds with reactive components of the adhesive. Morphological and mechanical alteration of the metal surface oxide through hydroxide formation requires liquid water. Liquid water can only form by capillary condensation in interfacial gaps from molecularly diffusing water. A hydrolytically stable oxide will prevent bond failure due to mechanical weakening of the substrate surface, while a high density of hydrolytically stable surface bonding sites will minimize the occurrence of capillary gaps at the interface, thus decreasing the formation of liquid water. It is shown that highly chemically active, although not inherently stable, oxide surfaces can provide environmentally stable adhesive bonds. Conversely, certain highly stable oxide surfaces with few chemically active sites provide no environmental stability to adhesive joints, regardless of the topography of the surface. / Ph. D.