Analysis of Contaminants on Grain-Boundary Fractures

Cracks, with no other damage, were observed in a niobium alloy (Nb-106) part when it was pulled from several months of protective storage for assembly into a rocket nozzle. SEM views showed the cracks to be intergranular, with contaminant particles on a large number of the grain facets. EDX analysis showed they consisted of niobium and fluorine. Plastic replicas, prepared by standard TEM techniques, were analyzed with selected-area electron diffraction, showing a pattern match for niobium tetrafluoride. Auger analyses showed electron spectra containing peaks representing carbon, oxygen, nitrogen, fluorine, and chlorine. Investigation into the processing history of the part showed the tenacious oxide film formed by the affinity of niobium for oxygen - even when heat treated in a vacuum – was removed with a combination of strong acids: nitric, hydrochloric, hydrofluoric, and lactic, resulting in the contaminants found on the surface. Thus, residues of the cleaning acid on the part had caused SCC during storage, with the tensile stresses necessary to generate SCC assumed to have been residual stresses from the heat treatment. Recommendation was made that more stringent cleaning procedures to remove any trace of the cleaning acids be used.