RESUMEN

Corrosion processes at cut edges of galvanized steels proceed as highly localized electrochemical reactions between the exposed bulk steel matrix and the protective thin metallic coating of a more electrochemically active material. Scanning microelectrochemical techniques can thus provide the spatially resolved information needed to assess the corrosion initiation and propagation phenomena, yet most methods scan cut edge sections as embedded in insulating resin to achieve a flat surface for scanning purposes. In this work, the galvanized coatings on both sides of the material were concomitantly exposed to simulated acid rain while characterizing the cut edge response using SECM and SVET techniques, thereby maintaining the coupled effects through the exposure of the whole system as rather realistic operation conditions. The cut edges were shown to strongly promote oxygen consumption and subsequent alkalization to pH 10-11 over the iron, while diffusion phenomena eventually yielded the complete depletion of oxygen and pH neutralization of the nearby electrolyte. In addition, the cathodic activation of the exposed iron was intensified with a thinner coating despite the lower presence of sacrificial anode, and preferential sites of the attack in the corners revealed highly localized acidification below pH 4, which sustained hydrogen evolution at spots of the steel-coating interface.

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Amperometric and potentiometric probes were employed for the detection and characterization of reactive sites on the 2098-T351 Al-alloy (AA2098-T351) using scanning electrochemical microscopy (SECM). Firstly, the probe of concept was performed on a model Mg-Al galvanic pair system using SECM in the amperometric and potentiometric operation modes, in order to address the responsiveness of the probes for the characterization of this galvanic pair system. Next, these sensing probes were employed to characterize the 2098-T351 alloy surface immersed in a saline aqueous solution at ambient temperature. The distribution of reactive sites and the local pH changes associated with severe localized corrosion (SLC) on the alloy surface were imaged and subsequently studied. Higher hydrogen evolution, lower oxygen depletion and acidification occurred at the SLC sites developed on the 2098-T351 Al-alloy.

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Material characterization is essential to the provenance of graphic arts. Non-destructive analytical techniques are increasingly required in the authentication process of cultural heritage. This work presents a suite of portable, non-destructive, and complementary analytical techniques, energy dispersive x-ray fluorescence (EDXRF), Fourier transform infrared (FTIR) spectroscopies, and brightfield microscopy, applied to the analysis of historical photographs depicting São Paulo city architecture, whose registration date and process of fabrication are unknown. The EDXRF analysis emphasizes the use of typical POP (printing-out paper) photograph with baryta (BaSO4 ) coated paper substrate while the FTIR and microscopy analyses confirm the presence of collodion and a gelatin-based baryta layer. This photographic process was widely employed by professional photographers from 1889 to 1930, when it was gradually abandoned in commercial use. This time interval (1889-1930) is consistent with the information surveyed on the photographic collection. In conclusion, employing complementary techniques (elemental and molecular spectroscopies and image magnification) is essential in identifying the manufacturing materials of cultural heritage material, which is the basis of contemporary authentication procedures. These data provide to curators and historians fundamental information for cataloging, adding subsidies for the correct storage and preservation ("heritage appreciation"). Still, for professional photographers, they present information on the manufacturing processes of historical photographs. The data from the present study also emphasize its perspective of use in graphic arts to aid connoisseurship in identifying forgeries during provenance and authentication studies.

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BACKGROUND: Titanium (Ti) and its alloys possess high biocompatibility and corrosion resistance due to Ti ability to form a passive oxide film, i.e. TiO2, immediately after contact with oxygen. This passive layer is considered stable during function in the oral cavity, however, emerging information associate inflammatory peri-implantitis to vast increases in Ti corrosion products around diseased implants as compared to healthy ones. Thus, it is imperative to identify which factors in the peri-implant micro-environment may reduce Ti corrosion resistance. METHODS: The aim of this work is to simulate peri-implant inflammatory conditions in vitro to determine which factors affect corrosion susceptibility of Ti-6Al-4V dental implants. The effects of hydrogen peroxide (surrogate for reactive oxygen species, ROS, found during inflammation), albumin (a protein typical of physiological fluids), deaeration (to simulate reduced pO2 conditions during inflammation), in an acidic environment (pH 3), which is typical of inflammation condition, were investigated. Corrosion resistance of Ti-6Al-4V clinically-relevant acid etched surfaces was investigated by electrochemical techniques: Open Circuit Potential; Electrochemical Impedance Spectroscopy; and Anodic Polarization. RESULTS: Electrochemical tests confirmed that most aggressive conditions to the Ti-6Al-4V alloy were those typical of occluded cells, i.e. oxidizing conditions (H2O2), in the presence of protein and deaeration of the physiological medium. CONCLUSIONS: Our results provide evidence that titanium's corrosion resistance can be reduced by intense inflammatory conditions. This observation indicates that the micro-environment to which the implant is exposed during peri-implant inflammation is highly aggressive and may lead to TiO2 passive layer attack. Further investigation of the effect of these aggressive conditions on titanium dissolution is warranted.

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Titanium is one of the most used materials in implants and changes in its surface can modify the cellular functional response to better implant fixation. An argon plasma treatment generates a surface with improved mechanical proprieties without modifying its chemical composition. Oxidative stress induced by biomaterials is considered one of the major causes of implant failure and studies in this field are fundamental to evaluate the biocompatibility of a new material. Therefore, in this work, induction of oxidative stress by titanium surfaces subjected to plasma treatment (PTTS) was evaluated. The viability of CHO-k1 cells was higher on PTTS discs. Cells grown on titanium surfaces are subjected to intracellular oxidative stress. Titanium discs subjected to the plasma treatment induced less oxidative stress than the untreated ones, which resulted in improved cellular survival. These were associated with improved cellular antioxidant response in Plasma Treated Titanium Surface (PTTS). Furthermore, a decrease in protein and DNA oxidative damage was observed on cells grown on the roughed surface when compared to the smooth one. In conclusion, our data suggest that the treatment of titanium with argon plasma may improve its biocompatible, thus improving its performance as implants or as a scaffold in tissue engineering.

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The corrosion stability of a W-DLC coated surgical AISI 316L stainless steel in Hanks' solution has been evaluated. Particle induced X-ray emission (PIXE) measurements were performed to evaluate the incorporation of potentially bioactive elements from the physiological solution. The film structure was analyzed by X-ray diffractometry and micro-Raman spectroscopy. The wear behavior was assessed using the sphere-on-disc geometry. The in vitro biocompatibility of the W-DLC film was evaluated by cytotoxicity tests. The corrosion resistance of the stainless steel substrate decreased in the presence of the PVD layer. EIS measurements suggest that this behavior was closely related to the corrosion attack through the coating pores. PIXE measurements revealed the presence of Ca and P in the W-DLC film after immersion in Hanks' solution. This result shows that the PIXE technique can be applied to identify and evaluate the incorporation of bioactive elements by W-DLC films. The film showed good wear resistance and biocompatibility.

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