An investigation of polysulfone-Al/Li alloy interaction involved single lap shear joints and wedge samples following an FPL etch, sulfuric acid anodization (SAA) and phosphoric acid anodization (PAA). The study of the Al/Li surfaces involved the determination of the elemental composition and morphological features of the pretreated adherend before bonding and following failure. When thermoplastic polysulfone (PSF) was either thermally pressed or primed onto the microporous surface, the PSF indeed penetrated into the porous oxide and thereby provided a mechanical means of adhesion. The wedge test results for the adherend pretreated by PAA and SAA were superior to those for the FPL etched adherend. The failure path for the FPL etched samples was at the adhesive/oxide interface whereas the failure path for the SAA and PAA samples was within the adhesive but with occasional divergence of the crack into the oxide. The porous oxides on Al/Li alloy formed after PAA and SAA treatment were shown to undergo dramatic changes in morphology on short term (<90 hrs) exposure to 71 C and 100% R.H. environment. The mechanism of failure was due to moisture which caused slight hydration of the Al/Li oxide and subsequent debonding of the PSF from the oxide layer. Lithium was not concentrated at the surface in the PAA treated Al/Li alloy as shown by AES depth profiling. The effect of lithium on the durability of the bonded alloy is considered minimal. Along these lines, cyclic loading, use of primers, and infrared spectroscopy studies have been carried out. The mode of moisture intrusion into the polysulfone-Al/Li oxide interphase region is discussed. Specifically, water molecules diffuse into the polysulfone rather than transporting along the interface. Moisture then attacks the oxide interface. Thin polysulfone coatings on pretreated aluminum surfaces were characterized utilizing dynamic mechanical thermal analysis (DMTA), and dielectric thermal analysis (DETA) to detect changes in the molecular motions and structural transitions in the polysulfone-aluminum interphase. The order of the loss peak temperature of the polysulfone is, PSF coating on a porous Al > PSF coating on a smooth Al > neat PSF film. The activation energy of relaxation is also lower for neat PSF when compared to the thin film cast onto a smooth Al or a porous PAA Al substrate. The loss peak temperature shift and the higher activation energy associated with the coated films can be explained by the entropy being reduced when the chains are laid down in two dimensions. Thus studies of polymer properties in the interphase region will contribute to the understanding of the adhesive-adherend interaction. / Ph. D.