ABSTRACT Inhibitors are one of the oldest methods of mitigating corrosion, which is still a current challenging and costly problem. However, traditional inhibitors are toxic and non-biodegradable, which goes against the principles of Green Chemistry, so named for valuing the use of biodegradable and environmentally friendly products. They can be obtained from plants and their residues that, when subjected to some type of processing, generate extracts or oils with important inhibitory potential. In most cases, green inhibitors are organic compounds classified relating to the mechanism as mixed, having polar functional groups that act as adsorption centers on the metallic surface. This study aimed to carry out a systematic review of the literature on inhibitors from species of Brazilian flora and used in an acid environment to prevent corrosion in carbon steel in a specific medium. Brazil presents a rich biodiversity of flora, with more than 46,200 species cataloged in 2020, which provides a wide field of research in this area. The review included 28 different plant species. The results found were promising, with emphasis on the use of parts of vegetables that are normally discarded and show the potential for development and improvement of green inhibitors for future application on an industrial scale.

RESUMO Os inibidores são um dos métodos mais antigos de combate à corrosão, que ainda hoje é um problema desafiador e caro. Porém, os inibidores tradicionais são tóxicos e não biodegradáveis, o que vai contra os princípios da Química Verde, assim denominada por valorizar o uso de produtos biodegradáveis e ambientalmente amigáveis. Os inibidores podem ser obtidos de plantas e seus resíduos que, quando submetidos a algum tipo de processamento, geram extratos ou óleos com importante potencial inibitório. Na maioria dos casos, os inibidores verdes são compostos orgânicos classificados, quanto ao mecanismo, como mistos, possuindo grupos funcionais polares que atuam como centros de adsorção na superfície metálica. Este estudo teve como objetivo realizar uma revisão sistemática da literatura sobre inibidores de espécies da flora brasileira e utilizados em ambiente ácido para prevenir a corrosão em aço carbono. O Brasil apresenta uma rica biodiversidade de flora, com mais de 46.200 espécies catalogadas em 2020, o que proporciona um amplo campo de pesquisa nesta área. A revisão incluiu 28 espécies de plantas diferentes. Os resultados encontrados foram promissores, com destaque para o uso de partes de vegetais que normalmente são descartadas e mostram o potencial de desenvolvimento e aprimoramento de inibidores verdes para futura aplicação em escala industrial.

The inhibition effect of the cocoa bean shell powder (CBSP) on SAE 1008 carbon steel was studied in acidic medium (HCl 0.5 mol L-1) by electrochemical techniques and gravimetric measurements. Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM) were used to the chemical and morphological characterization. The gravimetric and EIS results showed that the corrosion rate decreases with increasing inhibitor concentration, reaching the maximum value of 97.92% in 1.77 g L-1 inhibitor (highest concentration studied). Even at the lowest concentration (0.44 g L-1) good corrosion inhibition efficiency (96.03%) was observed. The polarization curves indicated that the CBSP acts as a mixed type inhibitor. The inhibitory molecules adsorption followed the Langmuir isotherm model. The inhibitor economic evaluation showed that the use of CBSP is 48-616 times cheaper than traditional inhibitors. The results showed that CBSP is an efficient corrosion inhibitor for carbon steel and its production is financially attractive.

ABSTRACT The malt bagasse is a solid residue, highly produced in the brewing industry. The presence of high levels of antioxidants in its composition makes this residue an attractive possibility as a corrosion inhibitor, besides being a sustainable and low cost alternative to the inorganic procedures currently used to prevent corrosion. In this sense, this work evaluated the efficiency of the malt bagasse powder as a corrosion inhibitor on the surface of AISI 1020 carbon steel, in different concentrations, in acidic medium 0.5 mol.L-1 HCl. The resistance to corrosion was tested by electrochemical techniques, such as electrochemical impedance spectroscopy (EIS) and anodic and cathodic polarization curves. The efficiency of the corrosion inhibitor was evaluated by weight loss tests. Fourier transform infrared spectroscopy (FTIR) and optical microscope surface image analysis were respectively used as chemical and morphological characterization techniques, respectively. From the EIS results, it can be said that the powder has its efficiency increased once the concentration is higher. On the other hand, the polarization curves shows the malt bagasse powder as an inhibitor presents both anodic and cathodic behavior. The weight loss results confirmed the electrochemical results, showing 92.5% efficiency for the 1.77 g.L-1 concentration. The adsorption isotherm on the steel surface follows Languimir’s Isotherm. The FTIR analysis indicates the presence of heteroatoms such as C, N, O, incorporated in functional groups that could be responsible for the inhibitory properties found in the powder. The images obtained from the optical microscope, showed that the corrosion process, in the presence of the inhibitor in the electrolyte, is retarded. Therefore, the results indicate that the malt bagasse powder has the potential to be a corrosion inhibitor for steel in acidic medium, adding value in the beer production chain.

ABSTRACT Carbon steel is used in various applications because of its excellent weldability, good mechanical resistance and low cost. However, its application becomes restricted due to its low corrosion resistance in neutral and acidic media, and it is necessary to use processes to retard the corrosive mechanism, such as the use of inhibitors. Many of the effective synthetic inhibitors used are associated with high cost and some have a high toxicity. In recent years, studies of corrosion inhibitors obtained from natural products have been increasing because they are environmentally sustainable and presents low-cost. Therefore, in the present study, different concentrations of the cocoa shell powder (Theobroma cacao) and hydroalcoholic extract were evaluated as a corrosion inhibitors of SAE 1008 carbon steel in 0.5 mol.L-1 sodium chloride solution. The inhibitory action of the cocoa residue was studied through gravimetric technique and electrochemical impedance spectroscopy (EIS). For the chemical characterization of the inhibitor, the Fourier Transform Infrared Spectroscopy (FTIR) was used. The EIS results showed that the corrosion inhibition efficiency of the steel decreased with the inhibitor concentration, reaching maximum values of 55.97% and 72.93%, for cocoa shell powder and hydroalcoholic extract, respectively. The gravimetric data confirmed the electrochemical results and through the study of the adsorption mechanism it was verified that the adsorbed inhibitor molecules follow the Flory-Huggins isotherm model, for both forms of the inhibitor. For all the concentrations evaluated, the cocoa shell powder did not represent an efficient corrosion inhibitor. In contrast, for the hydroalcoholic extract, at the concentration of 0.44 g.L-1, a good performance was verified as a corrosion inhibitor of SAE 1008 carbon steel in 0.5 mol.L-1 sodium chloride solution.

RESUMO O aço galvanizado é obtido pela imersão do aço carbono em um banho de zinco fundido, sendo esse material muito utilizado na indústria automotiva e de eletrodomésticos. Como todo material metálico, é suscetível à corrosão quando exposto a ambientes corrosivos, necessitando assim de tratamento de superfície para proteção. Atualmente, são utilizados como pré-tratamentos a fosfatização e a cromatização, ambos com restrições ambientais e à saúde humana. O aço galvanizado é obtido pela imersão do aço carbono em um banho de zinco fundido, sendo esse material muito utilizado na indústria automotiva, petroquímica, química, naval, aeronáutica e de linha branca. Apresenta maior resistência à corrosão do que o aço carbono quando exposto a ambientes corrosivos. Para aumentar sua durabilidade e sua resistência à corrosão, passa por um tratamento superficial que seja aderente à sua superfície. Por esta razão, atualmente, são utilizados a fosfatização e a cromatização como pós-tratamento à galvanização, ambos com restrições ambientais e à saúde humana. Por essa razão, estuda-se a viabilidade do uso de silanos como possíveis substitutos a essas substâncias por serem menos tóxicos. O silano é um composto organofuncional que atua como agente de acoplamento entre superfícies orgânicas e inorgânicas, bem como pode fornecer proteção contra a corrosão. O objetivo deste trabalho é avaliar a resistência à corrosão do aço galvanizado tratado com filme de silano viniltrietoxisilano (VS) nas condições de hidrólise: concentração de silano (2%, 3% e 4% de silano) e tempo de hidrólise da solução (30 min, 45 min e 60 min), mantendo fixos o pH 4,0 da solução solvente água/etanol (50% v/v), a temperatura de cura (150ºC) e o tempo de cura (120 min). A resistência à corrosão do aço galvanizado tratado com filme de silano VS foi avaliada através de técnicas eletroquímicas como potencial de circuito aberto, espectroscopia de impedância eletroquímica (EIE), resistência à polarização linear (Rp) e curvas de polarização potenciodinâmicas em solução de NaCl 0,1 mol.L-1.A resistência à corrosão do aço galvanizado tratado com filme de silano VS foi avaliada através das seguintes técnicas eletroquímicas: potencial de circuito aberto (OCP), espectroscopia de impedância eletroquímica (EIE), resistência à polarização linear (Rp) e curvas de polarização potenciodinâmicas em solução de NaCl 0,1 mol.L-1. A caracterização química dos filmes foi feita através da técnica de espectroscopia na região do infravermelho (IR). A caracterização morfológica do aço galvanizado tratado foi analisada por microscopia eletrônica de varredura (MEV) e espectroscopia de dispersão de energia de raios X (EDS). Os resultados obtidos para as condições estudadas mostraram a formação de um filme eficiente na proteção contra a corrosão quando o aço galvanizado é pré-tratado com filme obtido na concentração de 4% de silano e 60 min de tempo de hidrólise. Os resultados eletroquímicos indicaram a formação de um filme eficiente na proteção contra a corrosão quando o aço galvanizado é tratado com filme obtido na concentração de 4% de silano e 60 min de tempo de hidrólise. As imagens de MEV revelaram uma menor formação de produto de corrosão quando o aço galvanizado é tratado com o filme de silano e os espectros de EDS apresentaram picos de Si indicando a aderência do filme no superfície do aço galvanizado. Já os espectros na região do IR apresentaram bandas de compostos contendo Si o que revelam a presença do filme de silano na superfície do substrato.

ABSTRACT Galvanized steel is obtained by immersing the carbon steel in a molten zinc bath widely employed in the automotive, petrochemical, chemical, marine, aeronautical and white-good appliances. It has higher corrosion resistance than carbon steel when exposed to corrosive environments. To increase its durability and corrosion resistance, it undergoes a surface treatment that is adherent to its surface. For this reason, phosphatization and chromatization are currently used as an after treatment to galvanization, both with environmental restrictions and human health. Due to the presence of toxic and carcinogenic products – in the chromatization or phosphatization - and to minimize the impact on the environment, the development of silane films as alternative pretreatments have been studied due to their good physical barrier properties against diffusion of oxygen to the metal interface and improve corrosion resistance. The aim of this work is to evaluate a corrosion resistance performance of galvanized steel coated with vinyltriethoxysilane (VS) film under hydrolysis conditions: silane concentration (2%, 3% and 4% %v) and hydrolysis time (30 min, 45 min and 60 min). The fixed variables were: the solvent solution used was water/ethanol (50% v/v) at pH 4.0, the curing time of 120 min and the curing temperature of 150°C in an oven. The corrosion resistance of pre-treated galvanized steel with VS silane film was evaluated by the following electrochemical techniques: open circuit potential (OCP), electrochemical impedance spectroscopy (EIS), linear polarization resistance (Rp) and potentiodynamic polarization curves in 0.1 mol.L-1 NaCl solution. The chemical properties of films were analyzed by infrared spectroscopy technique (IR). The galvanized steel and the film surface morphology were observed by scanning electron microscopy (SEM) and X-ray energy dispersion spectroscopy (EDX). The electrochemical results indicated the formation of an efficient corrosion protection film when galvanized steel is treated with film obtained at 4% silane concentration and 60 min hydrolysis time. SEM images revealed less corrosion product formation when galvanized steel is treated with silane film and EDS spectra showed Si peaks indicating the adhesion of the film to the galvanized steel surface. The spectra in the IR region showed bands of Si-containing compounds that reveal the presence of silane film on the substrate surface.

ABSTRACT In this work, the wettability of the galvannealed surface pretreated with the hybrid silane APTES/GPTMS film was measured by sessile drop method. The coatings were applied on the substrate from dip-coating method and dried in an oven. The study followed an experimental factorial design, 3³, with contact angle as response. The corrosion resistance was evaluated by electrochemical techniques and the surface morphology was characterized by scanning electron microscopy. The wettability results showed the best condition for galvannealed steel pretreated with the hybrid silane film for 2:1 APTES:GPTMS ratio, 2% silane concentration and 150 min of hydrolysis time, because the result may be related to a higher rate of hydrolysis of the silanes that is influenced by both the functional group present and by the type and number of hydrolyzed groups, resulting consequently in a higher availability of silanol groups in solution, promoting a greater crosslinking of the film on the metallic substrate.

RESUMO Silanos são compostos organo funcionais utilizados como agentes de acoplamentos entre interfaces orgânicoinorgânicas, com boas propriedades de adesão. Por esta razão, o uso de silanos como pré-tratamento para aços, vem ganhando espaço já que também são geradores de resíduos de menor toxidade ao meio ambiente e à saúde humana. Para melhorar a barreira de proteção do filme de silano e conferir propriedades de autorreparação, esses filmes podem ser modificados com íons cério. Assim, esse trabalho tem como objetivo avaliar a resistência à corrosão do filme de silanoviniltrimetoxisilano (VTMOS) modificado com íons Ce(III) ou íons Ce(IV) aplicado em aço carbono, utilizando a espectroscopia de impedância eletroquímica (EIE), técnica de varredura por eletrodo vibratório (Scanning Vibrating Electrode Technique -SVET), microscopia eletrônica de varredura (MEV) e transformada de Fourier de espectroscopia na região do infravermelho (Fourier Transform Infrared Spectroscopy -FTIR). Os resultados mostraram que os filmes com adição de íons Ce(IV) apresentaram uma melhor resistência à corrosão se comparados aos filmes com íons Ce(III), isto porque o filme formado com a adição de íons Ce(IV) mostrou um melhor efeito barreira devido à uma maior reticulação do filme.

ABSTRACT Silanes are organo functional compounds used as coupling agents between organic-inorganic interfaces, with good adhesion properties. For this reason, the use of silanes as pre-treatment for carbon steel is becoming more and more applicable , since they are also generators of less toxicity residues to the environmental and human health. In order to improve the barrier protection of the silane film and confer self-healing properties, these films can be modified by addition of cerium ions. Thus, these work aims to evaluate the corrosion resistance of vinythrimethoxysilane (VTMOS) film modified with Ce(III) ions or Ce(IV) ions for carbon steel, using the electrochemical impedance spectroscopy (EIS), scanning vibrating electrode technique (SVET), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The results show that Ce(IV) ions addition improved better corrosion resistance than the films with Ce(III) ions. The higher barrier effect is since the film formed in the presence of Ce(IV) ions is better reticulated.

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.