Fretting and Fretting Corrosion Behavior of Additively Manufactured Ti-6Al-4V and Ti-Nb-Zr Alloys in Air and Physiological Solutions.

Additive manufacturing (AM) of orthopedic implants has increased in recent years, providing benefits to surgeons, patients, and implant companies. Both traditional and new titanium alloys are under consideration for AM-manufactured implants. However, concerns remain about their wear and corrosion (tribocorrosion) performance. In this study, the effects of fretting corrosion were investigated on AM Ti-29Nb-21Zr (pre-alloyed and admixed) and AM Ti-6Al-4V with 1% nano yttria-stabilized zirconia (nYSZ). Low cycle (100 cycles, 3 Hz, 100 mN) fretting and fretting corrosion (potentiostatic, 0 V vs. Ag/AgCl) methods were used to compare these AM alloys to traditionally manufactured AM Ti-6Al-4V. Alloy and admixture surfaces were subjected to (1) fretting in the air (i.e., small-scale reciprocal sliding) and (2) fretting corrosion in phosphate-buffered saline (PBS) using a single diamond asperity (17 µm radius). Wear track depth measurements, fretting currents and scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) analysis of oxide debris revealed that pre-alloyed AM Ti-29Nb-21Zr generally had greater wear depths after 100 cycles (4.67 +/- 0.55 µm dry and 5.78 +/- 0.83 µm in solution) and higher fretting currents (0.58 +/- 0.07 µA). A correlation (R2 = 0.67) was found between wear depth and the average fretting currents with different alloys located in different regions of the relationship. No statistically significant differences were observed in wear depth between in-air and in-PBS tests. However, significantly higher amounts of oxygen (measured by oxygen weight % by EDS analysis of the debris) were embedded within the wear track for tests performed in PBS compared to air for all samples except the ad-mixed Ti-29Nb-21Zr (p = 0.21). For traditional and AM Ti-6Al-4V, the wear track depths (dry fretting: 2.90 +/- 0.32 µm vs. 2.51 +/- 0.51 µm, respectively; fretting corrosion: 2.09 +/- 0.59 µm vs. 1.16 +/- 0.79 µm, respectively) and fretting current measurements (0.37 +/- 0.05 µA vs. 0.34 +/- 0.05 µA, respectively) showed no significant differences. The dominant wear deformation process was plastic deformation followed by cyclic extrusion of plate-like wear debris at the end of the stroke, resulting in ribbon-like extruded material for all alloys. While previous work documented improved corrosion resistance of Ti-29Nb-21Zr in simulated inflammatory solutions over Ti-6Al-4V, this work does not show similar improvements in the relative fretting corrosion resistance of these alloys compared to Ti-6Al-4V.

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.

Low cycle fretting and fretting corrosion properties of low carbon CoCrMo and additively manufactured CoCrMoW alloys for dental and orthopedic applications.

Additive manufacturing (AM) of CoCrMo metallic implants is growing in the orthopedic and dental fields. This is due to the traditional alloy's excellent corrosion resistance and mechanical properties. AM processes like selective laser melting (SLM) require less time, materials, and waste than casting or subtractive manufacturing complex-geometry structures (bridges, partial dentures, etc.). The objective of this work was to investigate the low cycle tribological and tribocorrosion characteristics of AM CoCrMoW alloys compared to wrought LC CoCrMo (ASTM F-1537) to assess this AM alloy's performance. Fretting and tribocorrosion testing was performed in air (wear only), PBS (wear + corrosion), and PBS with 10 mM H2 O2 (wear + corrosion + inflammation) by a single diamond asperity. No variation between alloys in volume of material removed (p = .12), volume of plastic deformation (p = .13), and scratch depth (p = .84) showed that AM was substantially similar in wear resistance to LC in air and PBS. AM exhibited significantly higher fretting currents (p < .01) at loads up to 100 mN ( I AM PBS = 57 nA and I AM H 2 O 2 = 49 nA) than LC CoCrMo ( I LC PBS = 30 nA) and ( I LC H 2 O 2 = 29 nA). In PBS, wear track depth linearly correlates to fretting current, averaged over 100 cycles. Additionally, fretting currents of both alloys were significantly lower in simulated inflammatory conditions compared to PBS alone. AM alloy has generally similar wear and tribocorrosion resistance to wrought LC CoCrMo and would be ideal for patient specific dentistry or orthopedics where precise, complex geometries are required.

Fretting corrosion testing of acetabular modular tapers for total hip replacements: A comparison of two designs.

Acetabular components (DePuy Pinnacle (A) and Stryker Trident (B), Ti-6Al-4V shells and CoCrMo liners) with varying geometries were assembled under a 4 kN seating load. Liner-displacement was recorded. Cyclic compression to 4 kN, R = 0.01, 9 Hz was applied for three million cycles to evaluate fretting corrosion currents (n = 5). Fretting currents, load-displacement, ion dissolution, and disassembly loads were used to compare device performance. Data were analyzed using ANOVA with Tukey post hoc comparisons (p < 0.05). Liner seating displacements were not significantly different between groups. Fretting currents averaged over the initial 10 h and over three million cycles were 0.17 µA (A) and 0.55 µA (B) and 0.05 µA (A) and 0.17 µA (B), respectively (p = 0.19). No variation in ion averages between A and B (0.23 and 0.45 ppm for Ti [p = 0.21], 0.63 and 0.85 ppm for Co [p = 0.47]) existed. Average push-out forces, -2.41 (A) and -2.42 kN (B), were not significantly different (p = 0.97). SEM and EDS showed some titanium and metal oxide transfer from the shell to the liner in both designs. Overall, both implant designs exhibited very minor MACC in these experiments. This study demonstrates quantitative measures of in vitro fretting corrosion over the course of three million cycles and the minimal degree of acetabular taper damage. Clinical Significance: Retrieval studies show dual mobility acetabular shell-liner tapers with metal-on-metal contacts are susceptible to fretting corrosion in vivo.

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 = Ecorr, 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.

Corrosion properties of low carbon CoCrMo and additively manufactured CoCr alloys for dental applications.

OBJECTIVES: Additive manufacturing (AM) is being applied to metallic biomaterials and dental alloys, including CoCrMo. CoCrMo mechanical properties and corrosion resistance are vital to the structural integrity of implants and dental appliances. The goal of this work is to assess the resistivity of AM cobalt chromium alloys by comparing them with traditional CoCrMo, regarding electrochemical properties resulting from microstructural and oxide film differences. METHODS: In this work, selective laser melting (SLM), was used to manufacture CoCrMoW. The corrosion characteristics of AM alloy were compared to that of wrought LC CoCrMo (ASTM F-1537) in both phosphate buffered saline (PBS) and PBS with 10 mM H2O2 to simulate increased inflammatory conditions. Anodic polarization and electrochemical impedance spectroscopy (EIS) were performed. RESULTS: Both alloys were substantially similar in corrosion behavior in both solutions. They exhibited changes with the different solutions. Polarization resistances were statistically lower (RpAM = 1.4 MΩcm2 (PBS) vs. 0.72 MΩcm2 (H2O2), RpLC = 1.86 MΩcm2 (PBS) vs. 0.55 MΩcm2 (H2O2)), and open circuit potentials (OCP's) were statistically higher in 10 mM H2O2 for both alloys (0.20 V (in H2O2) vs. - 0.09 V in PBS). Chemistry variations were revealed by the corrosion tests indicating that wrought LC CoCrMo retained its casting-based chemical heterogeneity, while AM CoCrMoW had sub-cell structures within the solidified grains. SIGNIFICANCE: As novel production methods like AM arise, it is necessary to understand any microstructural differences that may diminish the corrosion resistance properties. AM CoCrMoW alloys hold significant promise for use in dentistry where complex geometries are required.

Nanostructured porous graphene and its composites for energy storage applications.

Graphene, 2D atomic-layer of sp2 carbon, has attracted a great deal of interest for use in solar cells, LEDs, electronic skin, touchscreens, energy storage devices, and microelectronics. This is due to excellent properties of graphene, such as a high theoretical surface area, electrical conductivity, and mechanical strength. The fundamental structure of graphene is also manipulatable, allowing for the formation of an even more extraordinary material, porous graphene. Porous graphene structures can be categorized as microporous, mesoporous, or macroporous depending on the pore size, all with their own unique advantages. These characteristics of graphene, which are further explained in this paper, may be the key to greatly improving a wide range of applications in energy storage systems.