REJANE MARIA PEREIRA DA SILVA

REJANE MARIA PEREIRA DA SILVA

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Investigating local corrosion processes of magnesium alloys with scanning probe electrochemical techniques
2022 - OLIVEIRA, MARA C.L. de; SILVA, REJANE M.P. da; SOUTO, RICARDO M.; ANTUNES, RENATO A.
The study of corrosion of magnesium and its alloys has emerged a hot topic in the applications of lightweight structural materials. The inherently high electrochemical activity of bare magnesium surfaces still lacks a convincing mechanism to describe the observed experimental characteristics, and it has prompted the development of various types of protective coatings with the aim of slowing metal dissolution. In recent years, new instruments and techniques have been developed to study with spatial resolution the local corrosion processes that occur in metallic materials in general, and for magnesium and its alloys in particular, both for bare surfaces and coated. Scanning microelectrochemical techniques, such as local electrochemical impedance spectroscopy (LEIS), scanning electrochemical microscopy (SECM), scanning vibrating electrode technique (SVET), scanning ion-selective electrode technique (SIET) and scanning Kelvin probe (SKP) can provide information about the local electrochemical activity of metallic surfaces. In the present work, the applications of these techniques in corrosion studies of magnesium and its alloys are reviewed. Assessment of corrosion mechanisms, barrier properties of conventional coatings and active corrosion behavior of self-healing coatings are examined. Limitations and future developments in this area are discussed.
Surface finishing effects on the corrosion behavior and electrochemical activity of 2098-T351 aluminum alloy investigated using scanning microelectrochemical techniques
2022 - SILVA, REJANE M.P. da; MILAGRE, MARIANA X.; IZQUIERDO, JAVIER; BETANCOR-ABREU, ABENCHARA M.; OLIVEIRA, LEANDRO A. de; ARAUJO, JOAO V. de S.; ANTUNES, RENATO A.; SOUTO, RICARDO M.; COSTA, ISOLDA
The effects of surface finishing on the corrosion behavior and electrochemical activity of AA2098-T351 (Al–Cu–Li alloy) were investigated on the basis of the correlation between surface chemistry, microstructure and electrochemical activity. The alloy was evaluated in the as-received and polished conditions. The morphology of the two types of surfaces was investigated using confocal laser scanning microscopy (CLSM), optical microscopy and optical 3D profilometry. The surface chemistry was analyzed by X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX). Scanning microelectrochemical techniques (namely, localized electrochemical impedance spectroscopy (LEIS), the scanning vibrating electrode technique (SVET) and scanning electrochemical microscopy (SECM) in potentiometric mode) were used to examine the electrochemical activity of the surfaces. The results showed that on the as-received surface, the near surface deformed layer (NSDL), which is composed of Mg-rich bands, influenced the corrosion activity of the alloy. Higher electrochemical activity and greater susceptibility to severe localized corrosion were related to the polished surface condition compared to the as-received one.
Compreendendo os mecanismos de corrosão de ligas de Al-Cu-Li
2022 - ARAUJO, JOAO V. de S.; SILVA, REJANE M.P. da; VIVEIROS, BARBARA V.; MILAGRE, MARIANA X.; MACHADO, CARULINE de S.C.; COSTA, ISOLDA
In this study, the corrosion mechanism of an Al-Cu-Li alloy manufactured by two different treatment routes (T3 and T851) was evaluated by immersion and electrochemical tests in solutions containing chloride ions (Cl-). For both alloys, the formation of cavities on the surface was associated with micrometer-sized intermetallics (IM’s), however, in addition to this attack, the alloy submitted to T851 treatment also presented an attack called severe localized corrosion (SLC), caused by the preferential attack to the nanometric T1 (Al2CuLi) phase. The electrochemical concepts involved in these two types of attacks were discussed. During the IM’s corrosive process, whereas the O2 reduction occurred over the IM’s, the Al dissolution is favored around the particle, forming trenching and cavities (with 2 and 6 mm of depth). On the other hand, the mechanism associated with the SLC is related to the formation of a differential aeration cell followed by the evolution of H2, with greater depth of attack penetration (8 and 35 mm). Additionally, by the use of the Scanning Vibrating Electrode Technique (SVET), it was concluded that the higher anodic currents observed for the T851 temper were related to the relation between the anodic area (Aa) and the cathodic area (Ac).
Development of an Al3+ ion-selective microelectrode for the potentiometric microelectrochemical monitoring of corrosion sites on 2098-T351 aluminum alloy surfaces
2022 - SILVA, REJANE M.P. da; IZQUIERDO, JAVIER; MILAGRE, MARIANA X.; ANTUNES, RENATO A.; SOUTO, RICARDO M.; COSTA, ISOLDA
A novel potentiometric Al3+−ion selective microelectrode (ISME), with internal solid contact, based on the use of a neutral carrier morin as ionophore is reported. The ability of the ISME to image local ion concentration distributions was tested on aluminum alloy surfaces freely corroding in an aqueous solution containing chloride ions. The microelectrode was then used as the sensing tip for scanning electrochemical microscopy (SECM) in potentiometric operation to monitor the reactive sites associated with the dissolution of aluminum that developed in the 2098−T351 Al−Cu−Li alloy as a result of welding by the Friction Stir Welding (FSW) process. The ISME detected differences in the local concentrations of Al3+ species arising from the 2098−T351 Al−Cu−Li alloy (base material) and from the coupled weld joint/heat affected zones (WJ/HAZ) of the alloy produced by the FSW process. More active domains for Al3+ dissolution were found in the HAZ regions coupled to WJ, more specially in the HAZ of the advancing side (AS). These results demonstrate that the Al3+−ISME presented in this work can be used to monitor corrosion sites on aluminum alloys surfaces with combined chemical and spatial resolution.
Naphthenic acid corrosion of API 5L X70 steel in aqueous/oil environment using electrochemical surface-resolved and analytical techniques
2022 - SILVA, REJANE M.P.; SUFFREDINI, HUGO B.; BASTOS, IVAN N.; SANTOS, LUIS F.; SIMOES, ALDA M.P.
Naphthenic acid corrosion of steel is studied in crude oil/aqueous phase system at ambient temperature, using a biphasic stagnant liquid without emulsification, by means of electrochemical measurements and surface analysis. The in-situ electrochemical impedance is assigned to the processes occurring at the aqueous phase. Corrosion occurred only in the region of the aqueous phase, as crater-shaped pits that eventually coalesced, generating a nearly uniform attack in the vicinity of the oil phase. The impedance values, normalized to the aqueous region only, reveal corrosion rate increasing with the ratio of crude oil/water. Despite the localized character of the anodic oxidation, the iron naphthenate corrosion products became partitioned between the two phases. Surface-resolved electrochemical techniques in aqueous solution revealed enhanced activity of the regions pre-exposed to oil.
Influence of chloride ions concentration on the development of severe localised corrosion and its effects on the electrochemical response of the 2198-T8 alloy
2021 - MACHADO, CARULINE de S.C.; SILVA, REJANE M.P. da; ARAUJO, JOAO V. de S.; MILAGRE, MARIANA X.; DONATUS, UYIME; VIVEIROS, BARBARA V.G. de; KLUMPP, RAFAEL E.; COSTA, ISOLDA
The development of severe localised corrosion (SLC) on the 2198-T8 alloy was investigated in solutions of various NaCl concentrations (0.001, 0.005 and 0.01 mol L−1). Immersion tests, optical profilometry, conventional and local electrochemical analyses were performed to evaluate the corrosion behaviour of the alloy. Immersion tests showed that the alloy is susceptible to SLC in all conditions, although the pits sizes were dependent on the solution concentration. The largest anodic areas, corresponding to SLC sites, were observed for the sample immersed in 0.001 mol L−1 NaCl, whereas pits with similar sizes were observed for the samples immersed in solutions with 0.005 and 0.01 mol L−1 of NaCl. Moreover, the maximum depth of attack was observed for the sample immersed in 0.001 mol L−1 NaCl. These results were in agreement with the scanning ionselective electrode technique (SIET) maps which showed stronger acidification on the sample exposed to 0.001 mol L−1 NaCl solution.
O processo de anodização do alumínio e suas ligas
2021 - ARAUJO, JOAO V. de S.; SILVA, REJANE M.P. da; KLUMPP, RAFAEL E.; COSTA, ISOLDA
Al and its alloys are found in several industrial applications. However, like most metals, this material is not immune to corrosion, being necessary to be protected against corrosion. One of the methods most commonly employed to improve the corrosion resistance of Al alloys is the anodizing process, which consists of thickening of the natural oxide (Al2O3) presents in Al through anodic oxidation. The anodizing process is accomplished by immersion of the Al alloy into an acid bath and passing an electric current through it. This process produces two layers: a barrier layer thicker than the natural oxide and a layer with regular arrangement of nanopores (porous layer). This duplex structure forms the anodized layer with a large specific surface area. With the advent of nanotechnology, this layer has been applied in other areas due to its low cost, stability, absence of toxicity, and biocompatibility. In this context, this paper addresses a historical and electrochemical review of the anodizing process of Al and its alloys, presenting the main events that culminated in the development of the current processes and the understanding of the relationship between the chemical reactions and the mechanisms that occur during nucleation and development of the oxide layer.
Use of amperometric and potentiometric probes in scanning electrochemical microscopy for the spatially-resolved monitoring of severe localized corrosion sites on aluminum alloy 2098-T351
2021 - SILVA, REJANE M.P. da; IZQUIERDO, JAVIER; MILAGRE, MARIANA X.; BETANCOR-ABREU, ABENCHARA M.; COSTA, ISOLDA; SOUTO, RICARDO M.
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.
On the local corrosion behavior of coupled welded zones of the 2098-T351 Al-Cu-Li alloy produced by Friction Stir Welding (FSW)
2021 - SILVA, REJANE M.P. da; IZQUIERDO, JAVIER; MILAGRE, MARIANA X.; BETANCOR-ABREU, ABENCHARA M.; OLIVEIRA, LEANDRO A. de; ANTUNES, RENATO A.; SOUTO, RICARDO M.; COSTA, ISOLDA
Localized electrochemical methods supported by surface analytical characterizations were employed to investigate galvanic coupling effects and local electrochemical activity developed along the welded zones in Friction Stir Welded 2098-T351 Al-Cu-Li alloy. The investigation was carried out in the coupled weld joint/heat affected zones (WJ/HAZ) for both, the retreating (RS) and the advancing (AS) sides. The correlation between the surface chemistry, the microstructural characteristics and the electrochemical activity of these welded areas was studied. The results showed the development of galvanic interactions within and between the WJ and HAZ regions, which were imaged using the scanning vibrating electrode technique (SVET), and scanning electrochemical microscopy (SECM). SVET analyses showed that HAZ was more susceptible to the development of anodic sites than WJ. SECM in amperometric operation mode showed that WJ coupled to HAZ exhibited higher oxygen consumption and higher cathodic activity compared to HAZ. Furthermore, SECM in potentiometric operation showed alkalinization around WJ and increased acidity in HAZ, mainly at sites of severe localized corrosion (SLC). Based on the SVET and SECM results in combination with the surface analyses, it is proposed that the microgalvanic cells formed within these welded zones are due to the presence of secondary phases in the 2098-T351 alloy and their interactions with the adjacent matrix.
Corrosion protection of the AA2198-T8 alloy by environmentally friendly organic-inorganic sol-gel coating based on bis-1,2-(triethoxysilyl) ethane
2021 - KLUMPP, RAFAEL E.; DONATUS, UYIME; SILVA, REJANE M.P. da; ANTUNES, RENATO A.; MACHADO, CARULINE de S.C.; MILAGRE, MARIANA X.; ARAUJO, JOAO V. de S.; VIVEIROS, BARBARA V.G. de; COSTA, ISOLDA
In this work, a surface coating composed of organic‐inorganic hybrid sol‐gel based on bis‐1,2‐(triethoxysilyl) (BTSE) ethane was applied on AA2198‐T8 samples, and its effect on corrosion resistance was investigated and compared with that of a chromate layer formed in a solution with hexavalent chromium ions. The corrosion resistance of BTSE coated samples was evaluated by immersion tests in sodium chloride solution (0.005 mol/L NaCl) and monitored by global electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and local electrochemical techniques such as scanning vibrating electrode technique (SVET) and scanning electrochemical microscopy (SECM). The formed coating layers were characterized by X‐ray photoelectron spectroscopy (XPS). The results pointed out that the BTSE is an effective alternative coating for corrosion protection of new generation Al‐Cu‐Li alloys and could replace chromates obtained in toxic and carcinogenic CrVI containing solutions leading to improved corrosion protection.