Aromatic polyimides have found widespread applicability which can be partially attributed to their thermal stability, chemical resistance, and high glass transition temperature. However, deficiencies in their processability, solubility, transparency, and relatively high dielectric constants do not always provide the optimum properties for many specialty microelectronics applications. The incorporation of aliphatic segments to form partially aliphatic polyimides, has been used to counteract these shortcomings. Many of the potential uses of partially aliphatic polyimides require them to adhere to ceramic substrates, a main topic of this research. Polyimides and copolyimides that varied in chemical composition by their aliphatic content were characterized by their molecular weight, glass transition temperature, thermal stability, coefficient of thermal expansion, refractive index, dielectric behavior, and mechanical properties. Structure-property relationships were established. The gamma and beta sub-Tg viscoelastic relaxations were investigated to understand their molecular origins. The adhesion performance of a selected series of partially aliphatic polyimides to SiO2/Si was examined using a shaft loaded blister test, which was designed and instrumented for use in a dynamic mechanical analysis instrument. The adhesion was studied at high and low percent relative humidities and for several temperatures to examine if adhesion strength is influenced by polymer chemical composition. The adhesion energy could not be quantified for the entire series of polyimides. It was possible to interpret the quantitative adhesive fracture energies along with the qualitative adhesion strength behaviors, the failure surface analyses, and to offer an understanding of the adhesive chemical structure-physical property relationships. These understandings provide a conclusion that the incorporation of aliphatic segments into the polyimide chemical structure improves the durability of the adhesive bond to SiO2/Si under high percent relative humidities. / Ph. D.

Environmental stresses arising from temperature and moisture changes, and/or other aggressive fluid ingressions can degrade the mechanical properties of the adhesive, as well as the integrity of an adhesive interface with a substrate. Therefore such disruptions can significantly reduce the lifetime and durability of an adhesive joint.1-4 In this research, the durability of certain epoxy adhesive joints and coatings were characterized using a fracture mechanics approach and also by constant frequency impedance spectroscopy. The shaft-loaded blister test (SLBT) was utilized to measure the strain energy release rate (G) or adhesive fracture energy of a pressure sensitive adhesive tape. In this study, support for the value of the SLBT fracture mechanics approach was obtained. The SLBT was then used to investigate the effects of relative humidity on a model epoxy bonded to silicon oxide. Lastly, the effects of water and temperature on the adhesion of a commercial filled epoxy bonded to silicon oxide was characterized and interpreted. A novel impedance sensor for investigating adhesion was developed in a collaborative effort between Virginia Tech and Hewlett-Packard. Utilizing the technique of constant frequency impedance spectroscopy, the distribution and transport of fluids at the interface of adhesive joints was measured. A broad spectrum of adhesives was tested. In addition, the effects of hygroscopic cycling on the durability of adhesive coatings were measured for the commercial filled epoxy using the device. Lastly, recommended modifications of the experimental set-up with the new sensor are proposed to improve the technique. / Ph. D.