Surface analysis of tarnished dental alloys

Six crown and bridge alloys ranging in nobility between 25-63 wt % (18-45 at %) were analyzed by optical microscopy, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and secondary ion mass spectroscopy (SIMS), as well as by L*a*b* colorimetry before and after in vitro tarnishing in artificial saliva with and without additions of 0.00016, 0.016, and 1.6 % Na2S with a rotating wheel apparatus. All alloys except the lowest of 18 at % changed colors to about the same degree after 72 h of tarnishing. All alloys decreased in L*, while increased in both a* and b*, thus appearing darker and with increased redness and yellowness. This was due to localized darkening and to other products. For all alloys except one, saliva without sulfide promoted color changes more severe than for saliva with 0.016 % Na2S. For the most part, analysis by EDS was unable to detect differences between the tarnished films and the as-polished surfaces. SIMS analysis, however, showed changes in the substrate ion (Cu, Ag, Pd, and In) peak intensities. In most cases the intensities decreased and with the decrease greater with the sulfide-free saliva than with sulfide-containing. This indicated that sulfide promoted insoluble deposition of products. Changes in the Ag, Pd, and In peak intensities followed much the same pattern as with Cu. The as-polished surfaces, even though carefully prepared, showed much contamination in the form of organics, namely C, CH, N, NH, O, CHN, CN, as well as from Na, K, Ca, Si, S, Cl, and others. Most tarnished surfaces showed large increases in Na, K, and Ca, and with the sulfide-free saliva being more severe in this regard. The mass spectrum also showed peaks with atomic mass units in the range 55-58 related to only some of the tarnished surfaces.