A new experimental technique for quantifying the galvanic coupling effects on stainless steel during tribocorrosion under equilibrium conditions

Galvanic coupling during tribocorrosion of passive metals at open circuit potential (OCP) generates a wear-accelerated corrosion process within the depassivated area (worn surface) that is electrically in contact with the still passive one. The galvanic coupling effect at OCP was recently modeled using an electrochemical approach allowing for the theoretical quantification of the wear-accelerated corrosion under equilibrium conditions. Despite the usefulness of this model that mathematically determines the electrochemical conditions inside the wear track in terms of anode potential via the approximation of the net anodic current density, an experimental technique allowing for their experimental determination is essential in the effort to verify the galvanic coupling models and further understand the tribocorrosion mechanisms at OCP. In the present work, a new experimental technique based on galvanic current and potential measurements through a Zero-Resistance Ammeter (ZRA) for quantifying the electrode potential and anodic current inside the wear track during rubbing at OCP has been assessed. This experimental set-up has allowed for the first time to determine the prevailing electrochemical conditions (electrode potential and anodic current) inside the wear track by solely exposing the wear track to the electrolyte and physically separating the cathode from the anode (wear track). The effects of sliding wear at open circuit potential have been investigated for a super duplex stainless steel (UNS S32750) in 3.4 wt% NaCl. The new experimental set-up proposed in this work separates the cathode from the anode and exposes solely the wear track to the electrolyte. Using well-established electrochemical theories, the effect of the extent of the galvanic coupling on wear at the open circuit potential conditions has been quantified.The authors would like to thank the support from the European Union for funding C. Torres through the Leonardo da Vinci Mobility program. C.B. von der Ohe and E. Jensen are also acknowledged for having taken part in the initial phase 1151 of this long project. Dr. N. Papageorgiou (NTNU) is also acknowledged for the input and calculations in the modeling part and for preparing Figs. 6-9 of the paper.Espallargas Álvarez, N.; Johnsen, R.; Torres, C.; Igual Muñoz, AN. (2013). A new experimental technique for quantifying the galvanic coupling effects on stainless steel during tribocorrosion under equilibrium conditions. Wear. 307(1-2):190-197. doi:10.1016/j.wear.2013.08.026S1901973071-

Passivation behaviour of Alloy 31 (UNS N08031) in polluted phosphoric acid at different temperatures

The influence of temperature (20–80 °C) and chloride concentration (0.06–0.42 wt.% KCl) on the electrochemical behaviour of the UNS N08031 was studied in 40 wt.% polluted phosphoric acid solution. Passivation behaviour was investigated by using potentiostatic tests at different potentials. From the linear regions of the log i vs. log t transients, the parameter n was obtained. The results showed that the applied potential hardly affects on the passivation rate n. However, n values decreased when temperature increased. The values of n demonstrated that the passive film formed on Alloy 31 was compact and highly protective.The authors express their gratitude to the MAEC of Spain (PCI Mediterraneo C/8196/07, C/018046/08, D/023608/09 and D/030177/10), to Programa de Apoyo a la Investigacion y Desarrollo de la UPV (PAID-06-09) and to the Generalitat Valenciana (GV/2011/093) for the financial support and to Dr. Asuncion Jaime for her translation assistance.Escrivá Cerdán, C.; Blasco Tamarit, ME.; García García, DM.; García Antón, J.; Guenbour, A. (2012). Passivation behaviour of Alloy 31 (UNS N08031) in polluted phosphoric acid at different temperatures. Corrosion Science. 56:114-122. https://doi.org/10.1016/j.corsci.2011.11.014S1141225

Study of the sensitisation process of a duplex stainless steel (UNS 1.4462) by means of confocal microscopy and localised electrochemical techniques

When duplex stainless steels are heated, they can become sensitised and intermetallic phases can appear. In this work, samples of duplex stainless steel, UNS 1.4462, have been heated (850 degrees C for 1 and 2 h) in a heating unit that can be accommodated to a confocal microscope in order to study the morphological changes in-situ. The electrochemical behaviour of the samples has been analysed by means of conventional and localised electrochemical techniques. According to the results, there is a general decrease in the steel resistance to localised corrosion; this decrease can be related to defects in the formed passive film.We wish to express our gratitude to MICINN (CTQ2009-07518), to Universitat Politecnica de Valencia (CEI-01-11), to the Generalitat Valenciana for its help in the CLSM acquisition (MY08/ISIRM/S/100), to Professor Alda Simoes and Andreia Marques for the help on LEIS measurements and to Dr. Asuncion Jaime for her translation assistance.Leiva García, R.; Fernandes, JS.; Muñoz-Portero, M.; Garcia-Anton, J. (2015). Study of the sensitisation process of a duplex stainless steel (UNS 1.4462) by means of confocal microscopy and localised electrochemical techniques. Corrosion Science. 94:327-341. https://doi.org/10.1016/j.corsci.2015.02.016S3273419

Electrochemical Quartz Crystal Microbalance and X-Ray Photoelectron Spectroscopy study of cathodic reactions in Bovine Serum Albumin containing solutions on a Physical Vapour Deposition-CoCrMo biomedical alloy

Protein adsorption on biomedical CoCrMo alloys plays a crucial role in biocompatibility, corrosion and wear properties of implants. So far, protein adsorption was studied only on passive CoCrMo alloys above the open circuit potential. In this work the adsorption of Bovine Serum Albumin (BSA) under cathodic conditions was investigated using a combination of Electrochemical Quartz Cristal Microbalance (EQCM) and X-Ray Photoelectron Spectroscopy (XPS) surface analysis. Results show that cathodic polarization yields larger BSA adsorption than what reported at passive potentials. The involved adsorption mechanism is related to the electrochemical controlled reduction of BSA. (C) 2015 Elsevier Ltd. All rights reserved

Effect of the environment on wear ranking and corrosion of biomedical CoCrMo alloys

The corrosion behaviour and the wear ranking of biomedical high carbon (HC) and low carbon (LC) CoCrMo alloys sliding against an alumina ball in four different simulated body fluids [NaCl and phosphate buffered solutions (PBS) with and without albumin] has been analyzed by tribocorrosion and electrochemical techniques. The effects of alloy and of albumin on corrosion depend on the base electrolyte: differences between LC and HC alloy were only observed in NaCl solutions but not in PBS. Albumin increased significantly corrosion of both alloys in PBS solutions while its effect in NaCl was smaller. The wear ranking of the HC and LC alloys also depends on the environment. In the present study, HC CoCrMo alloy had lower wear resistance in NaCl and PBS + albumin than the LC alloy, while no differences between both alloys were found in the other solutions. This was attributed to surface chemical effects affecting third body behaviour

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

Tribological and tribocorrosion behavior of nickel sliding against oxide ceramics

Nickel is widely used as a coating material in electroplating because of its good corrosion and wear resistance even at high temperature. Tribocorrosion has been identified as one of the main degradation mechanisms of nickel. This study evaluated the tribocorrosion behavior of pure nickel in citrate buffer solution (pH 4.5) under controlled mechanical, chemical and electrochemical conditions as well as wear of pure nickel in dry condition sliding against alumina or zirconia balls, respectively. The results showed that the wear of nickel was higher in passive domain due to wear accelerated corrosion compared to that in the cathodic domain. Surprisingly, both alumina and zirconia were worn by nickel in tribocorrosion condition under passive potentials as well as in dry condition. However, in the cathodic domain, negligible wear was observed on the alumina and zirconia balls. The formation of mixed nickel and aluminum/zirconium oxides was proposed as the wear mechanism of alumina and zirconia

Influence of Bovine Serum Albumin (BSA) on the Tribocorrosion Behaviour of a Low Carbon CoCrMo Alloy in Simulated Body Fluids

Tribocorrosion, as the interaction between mechanical wear and electrochemical corrosion, has been found to be the main problem causing the failure and limiting the lifetime of metal-on-metal artificial hip joints. Better understanding of the tribocorrosion mechanisms of CoCrMo alloys is needed in order to reduce the degradation of this alloy, especially in the presence of proteins as one of the organic components present in synovial fluid. In this study, tribocorrosion tests of a low carbon CoCrMo alloy in phosphate buffer solution (PBS) with and without bovine serum albumin (BSA) in two different concentrations at different applied potentials (passive and cathodic) were carried out. The results show that the effect of proteins on wear and friction was concentration and potential dependent. In the cathodic domain (absence of very thin passive film), wear was very low in all solutions and the friction was significantly reduced by the addition of BSA to PBS even at low BSA concentrations. However, in the passive domain, the friction and wear were found not to be affected when the BSA concentration was 0.5 g/L, while they were reduced when increasing the BSA concentration to 36 g/L. The tribocorrosion results were rationalized through an existing tribocorrosion model and the effect of BSA on wear and friction was explained by the consideration of physical factors such as changes in viscosity and double layer structure, because in the present results no tribofilm formation was observed

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