Increasing temperature accelerates Ti-6Al-4V oxide degradation and selective dissolution: An Arrhenius-based analysis.

Ti-6Al-4V selective dissolution occurs in vivo on orthopedic implants as the leading edge of a pitting corrosion attack. A gap persists in our fundamental understanding of selective dissolution and pre-clinical tests fail to reproduce this damage. While CoCrMo clinical use decreases, Ti-6Al-4V and the crevice geometries where corrosion can occur remain ubiquitous in implant design. Additionally, most additively manufactured devices cleared by the FDA use Ti-6Al-4V. Accelerated preclinical testing, therefore, would aid in the evaluation of new titanium devices and biomaterials. In this study, using temperature, we (1) developed an accelerated pre-clinical methodology to rapidly induce dissolution and (2) investigated the structure-property relationship between the dissolving surface and the oxide layer. We hypothesized that solution temperature and H2O2 concentration would accelerate oxide degradation, increase corrosion kinetics and decrease experimental times. To assess this effect, we selected temperatures above (45 °C), below (24 °C), and at (37 °C) physiological levels. Then, we acquired electrochemical impedance spectra during active ß dissolution, showing significant decreases in oxide polarization resistance (Rp) both over time (p = 0.000) and as temperature increased (p = 0.000). Next, using the impedance response as a guide, we quantified the extent of selective dissolution in scanning electron micrographs. As the temperature increased, the corrosion rate increased in an Arrhenius-dependent manner. Last, we identified three surface classes as the oxide properties changed: undissolved, transition and dissolved. These results indicate a concentration and temperature dependent structure-property relationship between the solution, the protective oxide film, and the substrate alloy. Additionally, we show how supraphysiological temperatures induce structurally similar dissolution to tests run at 37 °C in less experimental time. STATEMENT OF SIGNIFICANCE: Within modular taper junctions of total hip replacement systems, retrieval studies document severe corrosion including Ti-6AL-4V selective dissolution. Current pre-clinical tests and ASTM standards fail to reproduce this damage, preventing accurate screening of titanium-based biomaterials and implant designs. In this study, we induce selective dissolution using accelerated temperatures. Building off previous work, we use electrochemical impedance spectroscopy to rapidly monitor the oxide film during dissolution. We elucidate components of the dissolution mechanism, where oxide degradation precedes pit nucleation within the ß phase. Using an Arrhenius approach, we relate these accelerated testing conditions to more physiologically relevant solution concentrations. In total, this study shows the importance of including adverse electrochemical events like cathodic activation and inflammatory species in pre-clinical testing.

Oxide degradation precedes additively manufactured Ti-6Al-4V selective dissolution: An unsupervised machine learning correlation of impedance and dissolution compared to Ti-29Nb-21Zr.

Additively manufactured (AM) Ti-6Al-4V devices are implanted with increasing frequency. While registry data report short-term success, a gap persists in our understanding of long-term AM Ti-6Al-4V corrosion behavior. Retrieval studies document ß phase selective dissolution on conventionally manufactured Ti-6Al-4V devices. Researchers reproduce this damage in vitro by combining negative potentials (cathodic activation) and inflammatory simulating solutions (H2 O2 -phosphate buffered saline). In this study, we investigate the effects of these adverse electrochemical conditions on AM Ti-6Al-4V impedance and selective dissolution. We hypothesize that cathodic activation and H2 O2 solution will degrade the oxide, promoting corrosion. First, we characterized AM Ti-6Al-4V samples before and after a 48 h -0.4 V hold in 0.1 M H2 O2 /phosphate buffered saline. Next, we acquired nearfield electrochemical impedance spectroscopy (EIS) data. Finally, we captured micrographs and EIS during dissolution. Throughout, we used AM Ti-29Nb-21Zr as a comparison. After 48 h, AM Ti-6Al-4V selectively dissolved. Ti-29Nb-21Zr visually corroded less. Structural changes at the AM Ti-6Al-4V oxide interface manifested as property changes to the impedance. After dissolution, the log-adjusted constant phase element (CPE) parameter, Q, significantly increased from -4.75 to -3.84 (Scm-2 (s)α ) (p = .000). The CPE exponent, α, significantly decreased from .90 to .84 (p = .000). Next, we documented a systematic decrease in oxide polarization resistance before pit nucleation and growth. Last, using k-means clustering, we established a structure-property relationship between impedance and the surface's dissolution state. These results suggest that AM Ti-6Al-4V may be susceptible to in vivo crevice corrosion within modular taper junctions.

Additively manufactured Ti-29Nb-21Zr shows improved oxide polarization resistance versus Ti-6Al-4V in inflammatory simulating solution.

Retrieval studies in the past two decades show severe corrosion of titanium and its alloys in orthopedic implants. This damage is promoted by mechanically assisted crevice corrosion (MACC), particularly within modular titanium-titanium junctions. During MACC, titanium interfaces may be subject to negative potentials and reactive oxygen species (ROS), generated from cathodic activation and/or inflammation. Additive manufacturing (AM) may be able to produce new, corrosion-resistant titanium alloys and admixtures that are less susceptible to these adverse electrochemical events. In this study, we characterize the impedance and corrosion properties of three new AM titanium materials, including Ti-6Al-4V with added 1% nano-yttria stabilized ZrO2 , admixed Ti-29Nb-21Zr, and pre-alloyed Ti-29Nb-21Zr. We aim to elucidate how these materials perform when subjected to high ROS solutions. We include conventionally and additively manufactured Ti-6Al-4V in our study as comparison groups. A 0.1 M H2 O2 phosphate-buffered saline (PBS) solution, simulating inflammatory conditions, significantly increased biomaterial OCP (-0.14 V vs. Ag/AgCl) compared to PBS only (-0.38 V, p = .000). During anodic polarization, Ti-6Al-4V passive current density more than doubled from 1.28 × 10-7 to 3.81 × 10-7 A/cm2 when exposed to 0.1 M H2 O2 . In contrast, Ti-29Nb-21Zr passive current density remained relatively unchanged, slightly increasing from 7.49 × 10-8 in PBS to 9.31 × 10-8 in 0.1 M H2 O2 . Ti-29Nb-21Zr oxide polarization resistance (Rp ) was not affected by 0.1 M H2 O2 , maintaining a high value (1.09 × 106 vs. 1.89 × 106 Ω cm2 ), while Ti-6Al-4V in 0.1 M H2 O2 solution had significantly diminished Rp (4.38 × 106 in PBS vs. 7.24 × 104 Ω cm2 in H2 O2 ). These results indicate that Ti-29Nb-21Zr has improved corrosion resistance in ROS containing solutions when compared with Ti-6Al-4V based biomaterials.