A mass balance analysis of the tribocorrosion process of titanium alloys using a single micro-asperity: Voltage and solution effects on plastic deformation, oxide repassivation, and ion dissolution.

Within modular taper junctions of total hip implants (THA), nominally "smooth" metallic surfaces contain multiple micro-asperities that slide, are plastically deformed, have their oxide film surfaces disrupted and corrode during the fretting corrosion processes. In this work, a mass/volume balance approach is developed and used to assess the contribution of individual components of wear and corrosion to the entirety of the single-asperity tribocorrosion process for the popular THA alloy, Ti-6Al-4V. This analysis measures the total volume change (trough) in the surface due to low cycle single asperity fretting corrosion and compares it to the measured pileup volume which is comprised of plastic deformation, metal particles and oxide particles, plus the fretting current and the concentration of solution-bound species. A simple 17 μm spherical geometry diamond asperity was used and the trough volume, pileup volume, fretting currents and ion concentrations were measured to assess their contribution to the fretting corrosion process. The effects fretting in or out of solution (phosphate buffered saline), and the role of electrode potential, e.g., freely corroding or forced potential (-1.0 V, 0 V, and +1.0 V vs Ag/AgCl) were investigated. Under constant 30 mN loading, 100 cycles duration, 3 Hz cyclic frequency and 80 μm sliding amplitude, the volume abraded, fretting currents, ion release, and pileup volume were all recorded. Damage was analyzed and quantified using digital optical microscopy (DOM), atomic force microscopy (AFM), scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), and inductive coupled plasma mass spectrometry (ICP-MS). The results were analyzed with ANOVA statistics (α = 0.05). The extent of wear damage (asperity trough volume) is as follows: air = E, air > -1.0 V = 0 V = +1.0 V. As the amount of pileup volume decreased between conditions, visible oxide generation increased, with V > 0 V having more oxide debris generation and air fretting resulting in the least oxide (and most plastic deformation). Ions in solution were not significant, accounting for less than 1% of the damage. Volume analysis showed trough volumes and pileup volumes were very close to one another and were dominated by plastic deformation. Synergy between wear and corrosion were not observed in this work.