Abstract The aim of this study was to obtain ionic quantification in periradicular medium after diffusion tests of the solution used inside root canals during the electrochemical dissolution of endodontic file fragments and the NiTi-containing dissolution product via an apical foramen. Thirty single-rooted extracted human teeth had root canals prepared and were attached to Eppendorf tubes filled with sterile saline. The samples were divided into 3 groups (n = 10) according to the solution used inside the root canal during the diffusion tests: Group 1: [NaF 12 g/L + NaCl 1 g/L]; Group 2: [NaF 12 g/L + NaCl 1 g/L + NiTi 0.50 g/L]; Group 3: [NaF 6 g/L + NaCl 0.5 g/L + NiTi 0.25 g/L]. The sample in each Eppendorf tube was then analyzed to assay the ionic quantification in periradicular medium. The groups were compared in relation to ionic quantifications (Kruskal-Wallis and Dunn’s tests, p ≤ 0.05). Group 2 showed significantly higher F-, Ni and Ti quantities than groups 1 and 3 (p < 0.05). Group 3 showed significantly higher Ti and Ni quantities than group 1, where no measurable quantities of Ti and Ni were observed (p < 0.05). The conclusions were that a 50% dilution of the NiTi-containing dissolution product resulted in significantly lower F-, Ni and Ti quantities compared to the undiluted product. The quantifications observed here suggest that irrigation is recommendable during the electrochemical dissolution process to reduce the resultant ion concentrations in both the root canal and the periradicular medium.

Commercial archwires NiTiCu (Ormco) and NiTi (Morelli) and samples of the corresponding raw materials were tested to assess the influence of Cu addition and sterilization on the corrosion resistance and biocompatibility. Raw materials samples and commercial archwires exhibited similar corrosion resistance when compared. The addition of Cu decreased the corrosion resistance of NiTi alloy, whiling the sterilization process had no influence. The biocompatibility tests were carried out in different extracts of the alloys and no cytotoxicity effects were observed for the ionic concentrations used. SEM and Confocal laser analysis permitted to observe the localized corrosion morphology obtained after anodic polarization tests. Although Cu addition on NiTi can be introduced to better adjust the mechanical resistance, this third element induced detrimental effect on the corrosion resistance of raw materials and commercial archwires.

RESUMO A utilização de tratamentos eletroquímicos como recurso tecnológico alternativo para o tratamento de efluentes industriais tem atraído considerável atenção, apresentando características vantajosas como facilidade de automação, alta eficiência e versatilidade em menor tempo de tratamento, além de requerer menor espaço físico para suas instalações. A diminuição do uso de produtos químicos para o tratamento, uma vez que o elétron é o principal reagente no processo, e a possibilidade de reaproveitamento de coprodutos gerados também se configuram em importantes oportunidades dentro do atual cenário global de sustentabilidade e energia. Essas tecnologias comportam ainda o uso de fontes renováveis de energia. Um coproduto catódico de grande interesse ambiental e econômico é o hidrogênio, potencialmente coletado e armazenado. Nesse contexto, os materiais são de importância fundamental, pois a eficiência e sustentabilidade dos processos eletroquímicos dependem da utilização de materiais com propriedades como baixa impedância eletroquímica e elevada resistência à corrosão, além de elevada atividade para a oxidação dos compostos de interesse, em especial os materiais selecionados para as etapas anódicas. O objetivo deste artigo é apresentar, em linhas gerais, um dos trabalhos desenvolvidos no Labcorr voltados para o tratamento eletroquímico de efluentes industriais visando a remoção de N-NH3 e DQO. Técnicas eletroquímicas foram utilizadas para a seleção dos materiais usados como anodos e catodos. Configurações para utilização de NaOCl como oxidante indireto no processo foram avaliadas. Os resultados mostraram que um reator de placas paralelas com anodos DSA e catodos de aço carbono e injeções de NaOCl ao início do tratamento e em ponto intermediário do processo foram efetivos na remoção dos compostos desejados, indicando ainda boa oportunidade para o reaproveitamento de produtos como nitrito e hidrogênio, o primeiro como inibidor de corrosão e o segundo podendo ser utilizado como fonte de energia para alimentar o próprio sistema de tratamento de forma semiautônoma.

ABSTRACT The electrochemical treatment as an alternative technological resource for the treatment of industrial effluents has attracted considerable attention through the last years because of important characteristics such as easy automation, high efficiency and versatility in a short period of time besides requiring less physical space for its units. As the electron is the main “reagent” in an electrochemical process, the use of chemicals is reduced. This and the possibility of using coproducts generated during the electrochemical treatment processes configure relevant opportunities in the actual global energy and sustainability scenario. These technologies may include the use of renewable energy sources such as Hydrogen, a cathodic coproduct of great ambiental and economical interest that could be obtained and stored. In this context, the selection of electrodes materials, especially those for anodic steps, are fundamental. The efficiency and sustainability of the electrochemical processes relies on materials with properties such as low electrochemical impedance and high corrosion resistance besides high electro activity for the oxidation of the compounds of interest. The purpose of this article is to present some of the results of the electrochemical treatment developed by Labcorr aiming the removal of NH3-N and COD from industrial effluents. Electrochemical techniques were used for anodic and cathodic materials selection. The use of NaOCl as indirect oxidant was evaluated. Results indicated that a parallel plate reactor with DSA anodes and carbon steel cathodes and NaOCl injections at the beginning of the treatment process and in an intermediary point was an effective configuration for the removal of the compounds of interest. There is also a good indication of the possibility of nitrite and Hydrogen obtainment. The former could be used as corrosion inhibitor and the later as an energy source for the electrochemical treatment system in a semi-autonomous way.

RESUMO Os inibidores naturais são obtidos a partir de extratos de plantas ou de material biodegradável e acarretam a redução da intensidade de dissolução dos metais, diminuindo a sua taxa de corrosão. Pesquisas realizadas nos últimos anos relatam que muitos vegetais apresentam, em sua constituição, compostos com ação antioxidante, principalmente polifenóis. Nesse trabalho, será apresentado o histórico do desenvolvimento de inibidores naturais a partir de extratos de frutas para aplicação em meios neutros e ácidos realizado no Laboratório de Corrosão da COPPE, Labcorr/COPPE/UFRJ. Os extratos analisados foram casca de laranja, casca de manga, casca de maracujá, casca de caju, semente de mamão e bagaço de uva. Os extratos foram obtidos por três metodologias diferentes de extração: extração por infusão, extração por gradiente de polaridade e extração hidroalcoólica. As eficiências de inibição dos extratos testados foram obtidas através de ensaios de perda de massa. O meio neutro estudado simula a composição da água dos sistemas de resfriamento industrial com elevado ciclo de concentração, com 1050 ppm de cloreto, 450 ppm de íon cálcio e 160 ppm de íon bicarbonato e com pH 7,5. Os extratos tiveram um bom desempenho nos dois meios estudados. O extrato concentrado de bagaço de uva teve a melhor eficiência de inibição nos ensaios de perda de massa em 72 horas de imersão no meio neutro, cujo valor foi 74%. A eficiência dos inibidores estudados foi mais significativa em meio de ácido clorídrico 1 mol·L-1, com eficiências superiores a 93% em 24 horas de imersão.

ABSTRACT The corrosion inhibitors are obtained from natural plant extracts or biodegradable material, and cause a reduction in the intensity of dissolution of metals by lowering their corrosion. Research conducted in recent years report that many plants have, in their constitution, compounds with antioxidant activity, mainly polyphenols. This paper will present the history of the development of natural inhibitors from fruit extracts for application in neutral and acid media carried out in Labcorr / COPPE / UFRJ. The orange peel, mango peel, passion fruit peel, cashew peel, papaya seed and grape pomace extracts were analyzed. The extracts were obtained by three different extraction methodologies: infusion extraction, polarity gradient extraction and hydroalcohol extraction. The inhibition efficiencies of the extracts tested were obtained by weight- loss tests. The neutral medium studied simulates the composition of water of industrial cooling systems with high concentration cycle, with 1050 ppm of chloride, 450 ppm of calcium and 160 ppm of bicarbonate and pH 7.5. The performance of extracts was good in both media studied. The concentrated grape pomace extracts had the best inhibition efficiency in the weight-loss tests with a period of 72 hours of immersion in neutral medium, whose value was of 74%. The efficiency of these inhibitors was more significant in 1 mol·L-1 hydrochloric acid media, with efficiencies above 93% in a period of 24 hours of immersion.

In this paper, aqueous extracts of mango and orange peels were shown to be good corrosion inhibitors for carbon steel in a 1 mol L- 1 HCl solution. The inhibition efficiency increased as the extract concentration increased over a concentration range of 200-600 mg L- 1, varying from 79 to 96% (mango) and 84 to 91% (orange) using Tafel plots and from 69 to 94% (mango) and 76 to 90% (orange) using electrochemical impedance. In the presence of 400 mg L- 1 of mango and orange peel extracts, the weight loss measurements showed an increase in the inhibition efficiency with immersion time, where the best results after 24 h of immersion were 97% and 95%, respectively. The adsorption of the extract components on the surface of the carbon steel follows the Langmuir adsorption isotherm. With the extraction procedure used in this work, it can be surmised that it is likely that the more polar heterosides in the extracts are responsible for the corrosion inhibition of carbon steel in an acid solution.

Very often hydrochloric acid is employed in acidification operations aiming to dissolve the mineral matrix in petroleum wheel operations, which always require intense use of corrosion inhibitors. This work presents an evaluation of common indicators, phenolfthaleine, fluorescein, methylene blue, alizarine S and methyl orange, as corrosion inhibitors for carbon steel in HCl 15% w/v at temperatures of 26, 40 and 60 ºC. Fluorescein and methyl orange show excelent corrosion inhibition efficiencies at 26 ºC; however at 60 ºC only fluorescein shows good corrosion inhibition when employed with alcohol and/or formaldehyde. For the fluorescein 1% w/v + formaldehyde 0.6% w/v mixture we present polarization and impedance curves and adsorption isotherms.