Effect of the substrate-induced crystalline interphase on the adhesion of polyurethane to metals

Bond strengths of three polyurethane to an aluminum were measured by indentation debonding, and interfacial features between two materials were microscopically investigated. All the polyurethanes crystallized at the Al substrate surface by heterogeneous nucleation, but the spherulitic features varied as a function of OH number. For non-aged samples, crosslinking level determined the adhesion of polyurethane film to aluminum substrate, while number density of spherulites was an important factor for aged samples. There was an optimum OH number to attain the highest bond strength. Hence, it was found that the decrease of OH number below this value, which is usually done by changing blowing gas from CFC-11 to pentane, caused poor adhesion of polyurethane foam to the aluminum. The crystalline interphase formed at the aluminum surface was examined by grazing incidence X-ray diffraction. The crystallinity of non-aged samples varied from air polymer surface to interface. The coherence lengths and interplanar spacings of all the reflections also changes up to interface by the presence of substrate. In particular, the integrated intensity of (100) and (021) reflections is linearly dependent upon X-ray penetration depth. The bond strength was exponentially proportional to the interfacial crystallinity, since stronger interface makes the adhesive force be double or redouble across interface. The preferred polymer molecular ordering in the 100 direction also provided stronger bonding of the polyurethane to the aluminum. From strain induced line broadening estimated by change of interplanar spacing, the polymer films possessing the greater dislocation density at interfacial area showed lower adhesion. It is believed that dislocations as stress concentrator play a part in determining adhesion. The rough zinc phosphated steel was used as a substrate with respect to a HCFC 141b and water co-blown polyurethane foam. Long period dissolution maintained interfacial crystallites, which were appeared by X-ray investigation. There was a complicated bond failure mode. The crystallites, found in the foamed region at the substrate surface, bridged the bulk foam and zinc phosphated substrate.