Chromic acid anodizing has been used for almost a century to enhance corrosion protection of aerospace alloys. For some applications, hydrothermal sealing in hexavalent chromium-containing solution is required to enhance further the corrosion resistance but, due to environmental concerns, the use of hexavalent chromium must be discontinued. Good progress has been made to replace chromates during anodizing but comparatively less effort has focused on the sealing process. In this work, for the first time, electrochemical impedance spectroscopy (EIS) has been used to characterize in-situ the sealing processes occurring during hot water sealing, sodium chromate sealing and cerium sealing. The results suggest that the processes occurring during sodium chromate sealing are significantly different compared to hot water and cerium sealing. In particular, during chromate sealing, the porous skeleton is significantly attacked, suggesting that the anticorrosion performance is likely to arise from the residuals of chromate rather than from the improvement of the barrier properties. In contrast, during hot water sealing, little attack occurs on the porous skeleton, and the improved corrosion protection is due to the enhanced barrier effect. During cerium sealing, precipitation of cerium products occurs, providing an inhibitor reservoir, and little, if any, attack occurs on the pre-existing oxide. Chromic acid anodizing (CAA) is widely used in the aeronautic industry to improve corrosion resistance of aluminum alloys.1 Since the beginning of the 1990s, however, the high toxicity associated with Cr (VI) has imposed restrictions on their use in industrial applications. As a consequence, numerous attempts have been made to find less toxic alternatives. 2,3Anodizing with dilute sulfuric acid (DSA) has been used to obtain thin anodic films (1-5 μm) that provide some protection without excessive deterioration of the fatigue life for specific aerospace alloys. Although the fatigue performance of DSA is acceptable, the corrosion resistance is lower than that of parts anodized in chromic acid (CAA). More recently, a new anodizing procedure, involving the addition of tartaric acid in dilute sulfuric acid electrolyte and called tartaric-sulfuric acid anodizing (TSA), was introduced.4-6 The addition of tartaric acid to sulfuric acid baths improves significantly the anticorrosive properties of the anodic layers compared to those obtained by sulfuric acid anodizing.7 Recent work, 7 however, indicates that the mechanism of porous film growth is not significantly affected by tartaric acid additions and that tartaric acid is not incorporated in significant amounts into the oxide material. Thus the corrosion resistance provided by TSA is likely to be associated with residuals of tartaric acid adsorbed on the porous skeleton. Tartaric acid concentration in the order of ppm, has been proved to be effective in reducing both the oxide dissolution rate in acidic environments and the anodic reaction rate. The effect of tartaric acid on the anodic fi...

In this work, porous anodic oxides were produced by traditional and modified tartaric sulfuric anodizing (TSA) processes and sealed in hot water, chromate and cerium based solutions. The sealing behavior of a film with relatively coarse porosity, generated at high voltage (traditional TSA), was compared to the sealing behavior of a film with finer porosity and generated at reduced potential (modified TSA). After sodium chromate sealing, the two anodizing cycles produced film with similar anticorrosion performance. Conversely, after hot water or cerium sealing, the finer oxides generated at low voltage (modified TSA) provided much better corrosion resistance. EIS performed in-situ during sealing revealed that chromate sealing is very aggressive to the porous skeleton compared to the other sealing treatments. Therefore, the original morphology has little effect on the final performance, since both fine and coarse oxides are substantially attacked. In contrast, the oxide morphology has a substantial effect when sealing is performed in hot water or cerium-based solution. Overall, it is possible to obtain films with anticorrosion performance equivalent or improved compared to that obtained by traditional TSA anodizing cycle sealed with chromate by combining the low voltage anodizing cycle with the cerium-based sealing. Aerospace aluminum alloys display outstanding mechanical properties but require specific protection measures in order to meet the requirements of durability and corrosion resistance. Anodizing in acidic electrolytes is one of the methods that are most widely employed for this purpose, since it produces porous oxides that improve corrosion resistance and adhesion with organic coatings.The porous anodic oxide morphology generated on high copper alloys is significantly different from that generated on high purity aluminium.1-3 Specifically, on aluminum, anodizing in phosphoric, sulfuric, or oxalic acid, results in the generation of a well-ordered oxide morphology, comprising closely-packed hexagonal cells with a central cylindrical pore, and having a diameter that is proportional to the applied potential.4-10 Under these conditions, the pore walls are generally straight and uniform (provided that anodizing is conducted under steady applied potential or current). At the bottom of the pores, close to the metal, a barrier layer is observed with thickness proportional to the applied potential. On the other hand, the thickness of the porous oxide is proportional to the charge passed. Due to the dependence of barrier layer thickness and pore diameter on the applied potential, and to the dependence of the film thickness on charge, porous morphologies can be tailored by controlling the electrical regime (potential-time or current-time), and complex morphologies can be achieved to enhance specific properties.11-14 It has been shown that fine pores and thick films are beneficial for corrosion protection.13 However fatigue life can be an issue for aerospace alloys 15 and therefore film thickness should be limited to...

Anodic oxidation is an easy and cheap surface treatment to form nanostructures on the surface of titanium items for improving the interaction between metallic implants and the biological environment. The long-term success of the devices is related to their stability. In this work, titanium nanotubes were formed on a dental screw, made of titanium CP2, through an anodization process using an "organic" solution based on ethylene glycol containing ammonium fluoride and water. Then, the electrochemical stability in the Hank's solution of these "organic" nanotubes has been investigated for 15 days and compared to that of titanium nanotubes on a similar type of sample grown in an inorganic solution, containing phosphoric and hydrofluoridric acids. Morphological and crystallographic analysis were performed by using scanning electron microscopy (SEM) and X-Ray diffractometry (XRD) tests. Electrochemical measurements were carried out to study the stability of the nanotubes when are in contact with the biological environment. The morphological measurements revealed long nanotubes, small diameters, smooth side walls, and a high density of "organic" nanotubes if compared to the "inorganic" ones. XRD analysis demonstrated the presence of rutile form. An appreciable electrochemical stability has been revealed by Electrochemical Impedance Spectroscopy (EIS) analysis, suggesting that the "organic" nanotubes are more suitable for biomedical devices.

Magnesium alloys are candidates to be used as biodegradable biomaterials for producing medical device. Their use is restricted due to the high degradation rate in physiological media. To contribute to solving this problem, a polydopamine (PDOPA) layer could be used to increase adhesion between the metallic substrate and external organic coating. In this paper, the corrosion behaviour of samples was investigated to determine their performance during the long-term exposure in simulated body fluid. Electrochemical methods including Open Circuit Potential (OCP) and Electrochemical Impedance Spectroscopy (EIS) were used to investigate the corrosion resistance of samples. The results demonstrated a decreasing of the substrate degradation rate when PDOPA was used as interlayer supposing a synergistic effect when it was used together with the organic coating.

No abstract