Influence of Different Sterilization Methods on the Surface Chemistry and Electrochemical Behavior of Biomedical Alloys.

Sterilization is a prerequisite for biomedical devices before contacting the human body. It guarantees the lack of infection by eliminating microorganisms (i.e., bacteria, spores and fungi). It constitutes the last fabrication process of a biomedical device. The aim of this paper is to understand the effect of different sterilization methods (ethanol-EtOH, autoclave-AC, autoclave + ultraviolet radiation-ACUV and gamma irradiation-G) on the surface chemistry and electrochemical reactivity (with special attention on the kinetics of the oxygen reduction reaction) of CoCrMo and titanium biomedical alloys used as prosthetic materials. To do that, electrochemical measurements (open circuit potential, polarization resistance, cathodic potentiodynamic polarization and electrochemical impedance spectroscopy) and surface analyses (Auger Electron Spectroscopy) of the sterilized surfaces were carried out. The obtained results show that the effect of sterilization on the corrosion behavior of biomedical alloys is material-dependent: for CoCrMo alloys, autoclave treatment increases the thickness and the chromium content of the passive film increasing its corrosion resistance compared to simple sterilization in EtOH, while in titanium and its alloys, autoclave and UV-light accelerates its corrosion rate by accelerating the kinetics of oxygen reduction.

The Electrochemical Behavior of Ti in Human Synovial Fluids.

In this study, we report results of the interaction of titanium (Ti) with human synovial fluids. A wide palette of electrochemical techniques was used, including open circuit potential, potentiodynamic methods, and electrochemical impedance. After the electrochemical testing, selected surfaces were analyzed using Auger Electron Spectroscopy to provide laterally resolved information on surface chemistry. For comparison purposes, similar tests were conducted in a series of simulated body fluids. This study shows that compared to the tested simulated body fluids, synovial liquids show a large patient variability up to one order of magnitude for some crucial electrochemical parameters such as corrosion current density. The electrochemical behavior of Ti exposed to human synovial fluids seems to be controlled by the interaction with organic molecules rather than with reactive oxygen species.

Adsorption of organic matter on titanium surfaces with nano- and micro-scale roughness studied with the electrochemical quartz crystal microbalance dissipation technique.

Adsorption of calf serum organic matter from a phosphate-buffered solution was studied using the electrochemical quartz crystal microbalance with additional dissipation measurements. Two types of crystal surfaces were used: one rough with micrometer-range surface features and one with roughness in the low nanometer range. The results showed that the adsorption of the organic material was about 1.5 orders of magnitude larger on the rough surface and almost independent of serum concentration in the electrolyte. The adsorption rates were found to increase with increasing serum concentration. For rough crystals, the adsorption kinetics were interpreted with the Johnson-Mehl-Avrami-Kolmogorov model, indicating an initial growth phase according to the tn-law, followed by a slower growth as the nucleation sites fill up. This study suggests that specific surface sites are critical to promote adsorption of proteins on a titanium surface.

A Crevice Corrosion Model for Biomedical Trunnion Geometries and Surfaces Feature.

Modular hip joint implants were introduced in arthroplasty medical procedures because they facilitate the tailoring of patients' anatomy, the use of different materials in one single configuration, as well as medical revision. However, in certain cases, such prostheses may undergo deterioration at the head-neck junctions with negative clinical consequences. Crevice-corrosion is commonly invoked as one of the degradation mechanisms acting at those junctions despite biomedical alloys such as Ti6Al4V and CoCr being considered generally resistant to this form of corrosion. To verify the occurrence of crevice corrosion in modular hip joint junctions, laboratory crevice-corrosion tests were conducted in this work under hip joint-relevant conditions, i.e., using similar convergent crevice geometries, materials (Ti6Al4V and CoCr alloys vs. ceramic), surface finish, NaCl solution pHs (5.6 and 2.3), and electrochemical conditions. A theoretical model was also developed to describe crevice-corrosion considering relevant geometrical and electrochemical parameters. To verify the model, a FeCr alloy, known to be sensitive to this phenomenon, was subjected to the crevice-corrosion test in sulfuric acid. The experiments and the model predictions clearly showed that, in principle, crevice corrosion of Ti6Al4V or CoCr is not supposed to occur in typical crevices formed at the stem-neck junction of hip implants.

An Overview of Serum Albumin Interactions with Biomedical Alloys.

Understanding the interactions between biomedical alloys and body fluids is of importance for the successful and safe performance of implanted devices. Albumin, as the first protein that comes in contact with an implant surface, can determine the biocompatibility of biomedical alloys. The interaction of albumin with biomedical alloys is a complex process influenced by numerous factors. This literature overview aims at presenting the current understanding of the mechanisms of serum albumin (both Bovine Serum Albumin, BSA, and Human Serum Albumin, HSA) interactions with biomedical alloys, considering only those research works that present a mechanistic description of the involved phenomena. Widely used biomedical alloys, such as 316L steel, CoCrMo and Titanium alloys are specifically addressed in this overview. Considering the literature analysis, four albumin-related phenomena can be distinguished: adsorption, reduction, precipitation, and protein-metal binding. The experimental techniques used to understand and quantify those phenomena are described together with the studied parameters influencing them. The crucial effect of the electrochemical potential on those phenomena is highlighted. The effect of the albumin-related phenomena on corrosion behavior of biomedical materials also is discussed.

'Green' Cr(iii)-glycine electrolyte for the production of FeCrNi coatings: electrodeposition mechanisms and role of by-products in terms of coating composition and microstructure.

The electrodeposition of stainless steel-like FeCrNi alloys for miniaturised devices is appealing as it would allow combining excellent material properties (e.g. corrosion resistance, hardness, biocompatibility) at low-cost. However, conventional baths often contain hazardous hexavalent chromium. Cr-based alloys electrodeposited from environmentally friendly trivalent chromium electrolytes are crucial for industrial application for facilitating the transition towards sustainable and ecological production and processing. Nevertheless, this process has not been comprehensively studied or understood in depth: especially the role of organic agents (common additives for improving Cr(iii)-based plating; e.g. glycine) in terms of material properties of the electrodeposits. The aim of this work was to investigate the electrodeposition of FeCrNi coatings from a 'green' Cr(iii)-glycine electrolyte. Novel information was attained by analysing films developed under various conditions and characterising them using a combination of advanced techniques. The evolution of microstructure (from amorphous to nanocrystalline) in correlation with film composition (i.e. metals ratio and presence of impurities) and elemental 3D spatial distribution was achieved for coatings produced from different anode materials and thermal post-treatment. The influence of Cr(iii) and glycine in terms of coating atomic contents (i.e. Fe-Cr-Ni-O-C-N-H) was evaluated for films in which both the applied current density and electrolyte composition were varied. These results, together with a thorough analysis on metals speciation/complexation allowed us to propose various Cr(iii)-based electroreduction mechanisms, and to observe, upon annealing, segregation and distribution of impurities, as well as of oxides and metals with respect to microstructure variation, providing an explanation for the amorphisation process.

Micromechanics of Amorphous Metal/Polymer Hybrid Structures with 3D Cellular Architectures: Size Effects, Buckling Behavior, and Energy Absorption Capability.

By designing advantageous cellular geometries and combining the material size effects at the nanometer scale, lightweight hybrid microarchitectured materials with tailored structural properties are achieved. Prior studies reported the mechanical properties of high strength cellular ceramic composites, obtained by atomic layer deposition. However, few studies have examined the properties of similar structures with metal coatings. To determine the mechanical performance of polymer cellular structures reinforced with a metal coating, 3D laser lithography and electroless deposition of an amorphous layer of nickel-boron (NiB) is used for the first time to produce metal/polymer hybrid structures. In this work, the mechanical response of microarchitectured structures is investigated with an emphasis on the effects of the architecture and the amorphous NiB thickness on their deformation mechanisms and energy absorption capability. Microcompression experiments show an enhancement of the mechanical properties with the NiB thickness, suggesting that the deformation mechanism and the buckling behavior are controlled by the brittle-to-ductile transition in the NiB layer. In addition, the energy absorption properties demonstrate the possibility of tuning the energy absorption efficiency with adequate designs. These findings suggest that microarchitectured metal/polymer hybrid structures are effective in producing materials with unique property combinations.

Orientation-dependent mechanical behaviour of electrodeposited copper with nanoscale twins.

The mechanical properties of electrodeposited copper with highly-oriented nanoscale twins were investigated by micropillar compression. Uniform nanotwinned copper films with preferred twin orientations, either vertical or horizontal, were obtained by controlling the plating conditions. In addition, an ultrafine grained copper film was synthesized to be used as a reference sample. The mechanical properties were assessed by in situ SEM microcompression of micropillars fabricated with a focused ion beam. Results show that the mechanical properties are highly sensitive to the twin orientation. When compared to the ultrafine grained sample, an increase of 44% and 130% in stress at 5% offset strain was observed in quasi-static tests for vertically and horizontally aligned twins, respectively. Inversely strain rate jump microcompression testing reveals higher strain sensitivity for vertical twins. These observations are attributed to a change in deformation mechanism from dislocation pile-ups at the twin boundary for horizontal twins to dislocations threading inside the twin lamella for vertical twins.