RESUMO As interações entre os minerais sulfetados e a química do meio de exposição, desde o processo de moagem dos minérios até a polpa de flotação, podem ser de caráter eletroquímico e/ou de natureza galvânica e influenciam a hidrofobicidade de suas superfícies, resultando em diferentes níveis de recuperação. Na literatura, a maioria dos trabalhos está relacionada à eletroquímica da galena (sulfeto de chumbo), esfarelita (sulfeto de zinco), pirita (sulfeto de ferro), calcopirita (sulfeto de cobre e ferro) e pentlandita (sulfeto de ferro e níquel). Medidas de potencial na polpa são bastante utilizadas para o controle e otimização da recuperação, entretanto, o procedimento apresenta limitações por não permitir compreender os mecanismos eletroquímicos envolvidos. Este trabalho de revisão apresenta e discute: os conceitos eletroquímicos envolvidos nestes processos, uma pesquisa bibliométrica sobre o tema, além de enfatizar as potencialidades da aplicação dos estudos com macro e microeletrodos para o entendimento da eletroquímica de minerais sulfetados. Da busca bibliométrica, obteve-se 85 artigos, sendo a primeira publicação em 1969, assim sendo uma área pouco explorada com pico máximo de 5 artigos em 1984, 1989, e em 2014. Austrália, África do Sul, Turquia, e Canadá, os quatro países que mais publicam, somam 50% dos documentos identificados. As reações que ocorrem, a ativação ou a presença de camadas de óxidos/hidróxidos e a adsorção de coletores na superfície dos minerais sulfetados têm sido investigadas por técnicas eletroquímicas para elucidar as eficiências dos processos de flotação. O uso do microeletrodo com cavidade, além da facilidade do preparo, pode permitir as análises em amostras de partículas minerais.

ABSTRACT The interactions between sulfide minerals and the chemistry of the exposure medium, from the grinding process to the flotation pulp, can be electrochemical and/or galvanic and influence the hydrophobicity of their surfaces, resulting in different levels of recovery. In the literature, most works are related to the electrochemistry of galena (lead sulfide), sphalerite (zinc sulfide), pyrite (iron sulfide), chalcopyrite (copper and iron sulfide), and pentlandite (iron and nickel sulfide). Potential measurements in the pulp are widely used to control and optimize recovery. However, some limitations exist as they do not allow understanding the electrochemical mechanisms involved. This review presents and discusses the electrochemical concepts involved in these processes, bibliometric research on the topic, and emphasizes the potential of applying studies using macro and microelectrodes to understand the electrochemistry of sulfide minerals. From the bibliometric search, 85 articles were obtained; the first was published in 1969, thus being an underexplored area with a maximum peak of 5 articles in 1984, 1989, and 2014. Australia, South Africa, Turkey, and Canada, the four countries that publish most, total 50% of the identified documents. The nature of the reactions, the activation or the presence of layers of oxides/hydroxides, and the adsorption of collectors on the surface of sulfide minerals have been investigated by electrochemical techniques to elucidate the efficiencies of flotation processes. The use of the cavity microelectrode (CME), in addition to the ease of preparation, may allow the analyses of mineral particulate samples.

Resumo Existe interesse na indústria cimenteira no uso de escórias de aciaria em cimento, porém são necessárias modificações químicas e/ou pirometalúrgicas para redução dos seus teores de CaO e MgO livre e de ferro. Entretanto, ainda não se abordaram os potenciais efeitos de sua aplicação na corrosão de armaduras, seja em meios sólidos (concreto endurecido) ou líquidos (águas de poro). Nesse contexto, o presente estudo apresenta a análise da corrosão do aço CA-50 em meios de águas de poro extraídas de pastas de cimento com 25% em massa de escória de aciaria (in natura ou modificada pirometalurgicamente) através de curvas de polarização, espectroscopia de impedância eletroquímica (EIE) e análises microestruturais. Para comparação, foram realizados ensaios em águas de poro de composições especificadas na literatura para cimento Portland comum e de escória de alto forno ativada com cimento, e posteriormente adicionou-se 1,0% de NaCl às soluções para simular agressividade. O aço se manteve passivo em todos os meios sem 1,0% de NaCl, porém os resultados de EIE indicaram características mais protetoras no meio representativo de escória de aciaria modificada. O principal produto de corrosão identificado pelas micrografias do aço após os ensaios nos meios agressivos foi a lepidocrocita (γ-FeOOH), e não houve corrosão do aço nos meios com escórias de aciaria e 1,0% de NaCl. Isso foi atribuído principalmente à maior alcalinidade destes meios em comparação com outras águas de poro convencionais, o que promoveu proteção mais prolongada do aço.

Abstract There is an interest in the cement industry in the use of steel slags in cement, but chemical and/or pyrometallurgical modifications are necessary to reduce the free CaO, MgO, and iron contents. However, the potential effects of its application in the reinforcement corrosion, whether in solid (concrete) or liquid medium (pore water), have not yet been addressed. In this context, the present study shows a corrosion analysis of the CA-50 steel in pore water medium extracted from cement pastes with 25% by weight of steel slag, in natural state or pyrometallurgical modified, by means of polarization curves, electrochemical impedance spectroscopy (EIS), and microstructural analysis. For comparison, tests were performed in pore waters presented in literature and representative from Ordinary Portland Cement (OPC) or activated Blast Furnace Slag (BFS) and, to simulate aggressive conditions, 1.0% NaCl was also added to the solutions. The steel remained passive in all media without 1.0% NaCl, but the EIS results indicated more protective characteristics in the medium simulating the modified steel slag. The main corrosion product identified by SEM images after the tests on aggressive media was lepidocrocite (γ-FeOOH), and the steel did not corrode in media with steel slags and 1.0% NaCl. This was attributed mainly to the higher alkalinity of these media in comparison to other usual pore waters, promoting longer protection of the steel.

High strength low alloy (HSLA) steels are used for the construction of pipelines for oil and natural gas transportation. For such applications pipelines must exhibit mechanical resistance and resistance to corrosion and hydrogen induced cracking (HIC). API 5L X65 steels are the main materials used for this purpose. However, for economic reasons, the use of steels of superior grades would be of interest. This work presents a comparative study of the corrosion and HIC resistances of an API 5L X65 and an API 5L X80 steel in deaerated solution A of NACE TM0284 standard. Electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization experiments were performed in non-sour and sour (H2S-saturated) media, and HIC resistance tests were carried out in the sour medium. Scanning electron microscopy (SEM) and optical microscopy (OM) characterizations of polished and corroded samples were also done. Electrochemical tests showed that the API 5L X80 steel is slightly more susceptible to surface corrosion, which can be probably linked to its higher inclusion content and smaller grain sizes, it was also susceptible to HIC. Mn and S-rich inclusions found in the crack path indicate that this microstructural feature may play a key role in crack propagation and HIC susceptibility

Corrosion represents high losses to the economy, therefore, researches on the minimization of its damages in materials, mainly the metallic ones, are necessary. Among the various alternatives of protection against corrosion, there is the application of corrosion inhibitors that can minimize or even stop the corrosive process of metallic materials. However, at present, substances usually used as corrosion inhibitors present high toxicity, being considered harmful components to the environment and to human health. Therefore, there is an urgent need for studies on viable corrosion inhibitors, by considering not only economic but also environmental costs. The present work studied the use of cocoa bark extract (Theobrama cacao L), for possible replacement of benzotriazole (BTAH) in the corrosion inhibition of ASTM 1020 carbon steel (CS- ASTM 1020) in 18.23 g.L-1 hydrochloric acid media. Weight loss measurements, anodic and cathodic potentiodynamic polarization curves and electrochemical impedance experiments were carried out. The results showed that the addition of the extract to the electrolyte effectively hinder the corrosion process and indicated its adsorption on the electrode surface. In addition, the inhibiting efficiency of the cocoa bark extract was only slightly inferior to BTAH, showing that it can be an environmentally friendly option to toxic inhibitors.

ABSTRACT Metallic corrosion can be delayed using corrosion inhibitors. However, several industrial corrosion inhibitors are toxic and harmful to the environment and to the human health. In this context, in the last decades, research has been developed to investigate the performance of low toxicity corrosion inhibitors as green inhibitors obtained from vegetables, which are environmentally acceptable. The present work studied the corrosion inhibition efficiency of peel garlic extract (Allium sativum. L.) for possible replacement of benzotriazole (BTAH) on the corrosion inhibition of ASTM 1020 carbon steel (CS-1020) in 0.5 mol. L−1 hydrochloric acid media. Weight loss measurements, anodic and cathodic potentiodynamic curves and electrochemical impedance (EIS) experiments were carried out. The Fourier transformed infrared spectroscopy (FTIR) was carried out to evaluate the chemical compounds. The morphological characterization was obtained to observe the inhibitor effect in the corrosion products on substrate surface. The results showed that the addition of both inhibitors effectively hinder the corrosion process and indicated their adsorption on the electrode surface. The inhibiting efficiency of the peel garlic extract was only slightly inferior to BTAH showing that the former inhibitor can be an environmentally friendly option to toxic inhibitors. The FTIR analysis showed the presence of chemical compounds which presents antioxidant properties.

The inhibition effect of castor bark powder obtained from Ricinus communis on AISI 1020 carbon steel in acidic media (HCl 0.5 mol.L-1) has been studied by electrochemical impedance spectroscopy (EIS), polarization curves, scanning vibrating electrode technique (SVET) and weight loss measurements. Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) were employed as characterization techniques. The EIS and gravimetric results showed that the inhibitory efficiency increases with inhibitor concentration achieving 83%. Polarization curves indicated that the castor bark powder acts as mixed inhibitor. The adsorption of the powder components on the metal surface follows the Langmuir isotherm. The FTIR analyses indicate the presence of C, N and O heteroatoms, incorporated in functional groups mainly related to the presence of carboxylic acids as ricinoleic acid, which could be responsible for the inhibitory properties of the powder. SEM analyses showed that the corrosion process was retarded in the presence of inhibitor in the electrolyte, which was confirmed by SVET measurements. Therefore, the results indicate that castor bark powder has potential to be a corrosion inhibitor for carbon steel in acidic media.

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.

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.