Hercílio G. de Melo

Microstructural and electrochemical characterization of environmentally friendly conversion layers on aluminium alloys

Cerium conversion layers (CeCL) have been investigated as a replacement for chromium conversion layers to protect Al alloys against corrosion. In this work the microstructure and the electrochemical behaviour of aluminium alloy 2024 with and without CeCL were investigated using, respectively, SEM-EDX and EIS. EDX results have shown that the presence of dispersed plated Cu particles on the alloy surface enhances the formation of the CeCL increasing the intensity of Ce peaks in the EDX spectra. EIS measurements on conversion-coated samples have shown that the presence of the layer increases the impedance, and that its presence is detected by the presence of a high frequency time constant. Results of potentiodynamic experiments have shown that the corrosion protection afforded by the conversion layer is due to the hindrance of the oxygen reduction reaction and that the pitting potential of the alloy is not changed.

Comparative investigation of the adhesion of Ce conversion layers and silane layers to a AA 2024-T3 substrate through mechanical and electrochemical tests

Cerium conversion layers and silane films are among the potential substitutes for the carcinogenic chromate conversion layers used to protect high-strength Al alloys. In the present work the adhesion of a cerium conversion layer and of a silane film to an aluminium alloy (AA) 2024-T3 substrate was investigated using mechanical and electrochemical tests. Scanning electron microscopy (SEM)- X ray energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FT-IR) and X ray photoelectron spectroscopy (XPS) were used to characterize the layers prior and after the mechanical test consisting of ultrasonic rinse in deionized water during 30 minutes. Mechanically tested and untested layers were also submitted to electrochemical impedance spectroscopy (EIS) and anodic polarization measurements in 0.1 M NaCl solution. The results of the characterization tests have pointed to a stronger adhesion of the Ce layer to the substrate in comparison with the silane film, which was confirmed by the electrochemical tests. The adhesion between the silane film and the Ce conversion layer was also tested, to evaluate the possibility of using the system as a protective bi-layer in accordance with the new trends being developed to substitute chromate conversion layers.

Comparison of the corrosion resistance of DIN W. Nr. 1.4970 (15%Cr-15%Ni-1.2%Mo-Ti) and ASTM F-138 (17%Cr-13%Ni-2.5%Mo) austenitic stainless steels for biomedical applications

The resistance to localised corrosion of the full austenitic 15%Cr-15%Ni-1.2%Mo titanium stabilized stainless steel (DIN W. Nr. 1.4970) was investigated by electrochemical methods including electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and potentiostatic polarization measurements in a phosphate-buffered solution (PBS). The low carbon and non-stabilized austenitic stainless steel, AISI 316L (ASTM F-138), widely used for surgical implants, was also tested for comparison. The tests were conducted at room temperature after a stable potential had been reached. After the electrochemical measurements, the surfaces of the specimens were observed using SEM to evaluate the presence of pits. Potentiodynamic polarization results showed that both steels are prone to localized corrosion. Larger pits were found on the surface of AISI 316L specimens after the electrochemical tests. EIS response has indicated the duplex structure of the passive oxides. The results showed that the electrochemical behaviour of the DIN W. Nr. 1.4970 is better than of AISI 316L steel. Therefore, their application as an implant material may be considered.

Electrochemical Impedance Spectroscopy in a Droplet of Solution for the Investigation of Liquid/Solid Interface

The local electrochemical behavior of a solid-liquid interface can be studied by electrochemical impedance spectroscopy (EIS). The investigated surface area can be delimited by adding a drop of solution, which forms an interface between the liquid drop and the working electrode, and performing the measurements inside. The size of the drop must be sufficiently small for a simultaneous wettability characterization (from the contact angle measurement) and appropriately large so that wettability is not influenced by the presence of the working and the counter electrode inserted in the droplet. In this work, we showed that EIS measurements can be performed in a solution droplet of 2 to 4 μL, although the electrochemical cell lacks the usual geometry. For our measurements, we studied a model system consisting of a KCl aqueous solution of [Fe(CN)6]3-/4- redox couple at a Pt electrode. All the results were compared with those obtained for a bulk configuration. The sessile drop configuration and the EIS response were modeled using finite element method for different electrode sizes and configurations to account for electrochemical kinetics and both current and potential distributions.

EIS investigation of the corrosion resistance of uncoated and coated Nd-Fe-B magnets in PBS solution

The aim of this work is to investigate the corrosion behavior of powder metallurgy produced Nd-Fe-B magnets and to evaluate the corrosion protection afforded by two different surface treatments: a phosphate conversion and a non-functional silane (BTSE) layer. The electrochemical tests were performed in a phosphate buffered solution (PBS) at neutral pH, which ionic concentration coincides with that of the human body. The corrosion behavior was monitored by means of electrochemical impedance spectroscopy (EIS) and anodic potentiodynamic polarization curves, and SEM-EDS analyses were used to monitor coating deposition. EIS response has evidenced a porous electrode behavior for the Nd-Fe-B magnets according to the de Levie theory. The results also indicated a good performance of the phosphate layer, whereas the BTSE layer did not improve the corrosion resistance of the magnets. The good anticorrosion performance of the phosphate layer was explained on the basis of the formation of an insoluble phosphate layer both on the electrode surface (identified by interference colors) and on the pore walls. Precipitation of insoluble Nd phosphate on the Nd-rich phase also contributes to the superior corrosion protection afforded by this coating.

Corrosion Protection of AA2524-T3 Anodized in Tartaric-Sulfuric Acid Bath and Protected with Hybrid Sol-Gel Coating

2xxx Al alloys are particularly sensitive to localized corrosion in chloride environments and in order to maintain their integrity, minimize maintenance needs and repairs, and to maximize component life, protective treatments are required.Anodizing is an electrochemical process based on the growth of the Al oxide layer by applying anodic potentials. One of the alternatives is tartaric/sulphuric acid (TSA) anodizing, which is environmentally compliant and provides corrosion resistance properties, compatible with the requirements of the aerospace industry with appropriate paint adhesion.In this study, AA2524-T3 specimens were anodized in a tartaric-sulfuric acid bath (TSA) and subsequently protected by application of a hybrid sol–gel coating. The sol–gel coating was prepared using a solution with high water content (58 %v/v) and obtained by the hydrolysis and condensation of tetraethoxysilane (TEOS) and 3-glycidoxypropyltrimethoxysilane (GPTMS). The corrosion resistance evaluation of both unsealed and coated samples was carried out in a sodium chloride solution by EIS as a function of immersion time. The results were also fitted using electrical equivalent circuits.

Localized Corrosion Resistance of Dissimilar Aluminum Alloys Joined by Friction Stir Welding (FSW)

2XXX and 7XXX high strength aluminum alloys are the most used materials for structural parts of aircrafts due to their high strength/weight ratio. Their joining procedure is an engineering challenge since they present low weldability. Friction Stir Welding (FSW) is a joining technology developed in the early 90 ́s. It is a solid-state welding process, without the use of fillers or gas shield, that eliminates conventional welding defects and has been considered of great interest for application in the aircraft industry. FSW of aluminum alloys results in four regions of different microstructures, specifically: the base material (BM), the heat affected zone (HAZ), the thermo-mechanically affected zone (TMAZ), and the nugget zone (NZ). The complex microstructure of the weld region leads to higher susceptibility to localized corrosion as compared to the BM even when similar alloys are joined. The welding of dissimilar alloys in its turn results in even more complex microstructures as materials with intrinsically different composition, microstructures and electrochemical properties are put in close contact. Despite the great interest in FSW, up to now, only few corrosion studies have been carried out for characterization of the corrosion resistance of dissimilar Al alloys welded by FSW. The aim of this study is to investigate the corrosion behavior of aluminum alloy 2024-T3 (AA2024-T3) welded to aluminum alloy 7475-T761 (AA7475-T761) by FSW. The evaluation was performed in 0.01 mol.L-1 by means of open circuit potential measurements, polarization techniques and surface observation after corrosion tests.

Study of the Influence of the Rare Earth Elements (Ce3+ and Ce4+) Concentration on the Siloxanes Coating Applied on the Copper Surface

This work studied the influence of the rare earth (Ce3+ and Ce4+) elements concentration in polysiloxane films deposited on copper by dip-coating process, and evaluated their resistance in a 3.5 wt.% NaCl medium. Classical electrochemistry techniques were used as open circuit potential, polarization curves and electrochemical impedance spectroscopy. The results revealed that by adding low concentration of Ce4+ ions, the coating prevents the electrolyte uptake any longer retarding the substrate degradation consequently.

Effect of Intermetallics on the Corrosion of Al 2024-T3 Alloy in Solutions with Different Chloride Concentration

Al 2024-T3 is an important alloy very prone to localized corrosion. In this investigation the effect of chloride concentration on the corrosion resistance of the Al 2024-T3 alloy has been studied, focusing on the dissolution of the intermetallics (IMCs). Sodium chloride solutions of two concentrations, 0.6 M and 0.01mM, were used as test electrolytes. During the investigation selected regions of polished samples had their IMCs analyzed by Scanning Electron Microscopy (SEM) and X-ray Energy Analysis (EDX) prior and after different immersion times in the two test electrolytes. The results showed that even in the lowest chloride concentration the electrolyte was highly corrosive to the Al-Cu-Mg IMCs leading to their partial dissolution and to the attack of the surrounding matrix after only one hour of immersion. On the other hand, the corrosion behavior of the Al-Cu-Mn-Fe IMCs was random, and no correlation could be established between corrosive attack and chloride concentration or time of immersion for this type of particle. Atomic Force Microscopy (AFM) analyses have indicated a stronger dissolution of the matrix in the more concentrated electrolyte. This seems to lead to a milder attack of the IMCs in this solution when compared to the less concentrated one, as indicated in the SEM images.