Corrosion Behavior and Ion Release of Co–Cr Dental Alloys Fabricated by Casting, CAD/CAM, SLM and DMLS: Influence of Manufacturing Route and Microstructure

The present study demonstrates that the corrosion behavior of dental cobalt–chromium (Co–Cr) alloys is strongly influenced by the interaction between microstructure, manufacturing technique, and oral chemical environment. A comparative investigation was conducted on Co–Cr specimens fabricated using four technological routes: conventional casting, CAD/CAM machining, Selective Laser Melting (SLM), and Direct Metal Laser Sintering (DMLS). The study included microstructural characterization, evaluation of generalized corrosion behavior using the rotating electrode technique, assessment of localized crevice corrosion, and quantitative analysis of the release of twenty metallic cations. Extraction tests were performed for 168 h in two media simulating aggressive oral environments: 0.07 N HCl (acidic medium) and a fluoride-containing electrolyte (0.1% NaF + 0.1% KF). Electrochemical measurements were recorded in the current density range of 10−10 to 10−7 A/cm2, while released cation concentrations were quantified at the µg/L level. All alloys exhibited very low corrosion current densities (icorr in the 10−8 to 10−9 A·cm−2 range), confirming overall good corrosion resistance. Among all manufacturing routes, CAD/CAM specimens demonstrated the highest electrochemical performance, with a wide passivity domain extending up to approximately 740 mV/SCE. A statistical interaction analysis between extraction media and manufacturing techniques was performed using the non-parametric Mann–Whitney (MW) U test. Among the analyzed elements, only chromium showed a statistically significant difference between media (p < 0.05), with an approximately 25-fold-higher release in acidic conditions compared with the fluoride medium, confirming the predominant role of proton-induced destabilization of the protective Cr2O3 passive film. In contrast, fluoride-containing media induced selective release of elements such as Cu (3× higher), W (2.5× higher), and Mo (1.4× higher), associated with complexation phenomena. The manufacturing route significantly influences corrosion behavior. Although additive manufacturing technologies (SLM/DMLS) enable highly accurate and customized prosthetic designs, rapid solidification and microstructural heterogeneities may increase susceptibility to localized corrosion compared with more homogeneous CAD/CAM materials. Clinically, these findings suggest that future restorative strategies should incorporate corrosion-aware material selection within digital workflows. As digital dentistry evolves, predictive models integrating patient-specific oral conditions may assist clinicians in selecting the most appropriate material system for long-term performance. In conclusion, the long-term success of dental Co–Cr prosthetic devices depends not only on mechanical strength and precision of fit, but also on sustained electrochemical stability in the complex oral environment.