The use of industrial painting is one of the methods for corrosion protection of metals and requires a suitable surface treatment on the metallic substrate for better adhesion between metal and paint film. In cases where the substrate presents low thickness (less than 2 mm), the phosphating pretreatment is widely used, despite of such process generates harmful residues to environment and human health. In this context, the sol-gel method has been highlighted as an easy and a cheap process, and less harmful to the environment. This work shows the development of carbon steel AISI 1005 pre-treatment by sol-gel method using niobium and/or aluminium-containing-resins, synthetized by Pechini method. Electrochemical and performance analysis were carried out in samples coated by the resins, which showed analogous behavior to phosphated systems. The proposed pre-treatment has potential for phosphating process replacement, because the morphology of the deposited layers enhanced the metallic contact surface with the organic coating, increasing its mechanical and polar adhesion. Such observation can justify its better anticorrosive performance, comparing to the untreated substrate.

The behavior of roasted coffee extract and its isolated high molecular weight fraction have been investigated as carbon steel corrosion inhibitors in HCl solution by weight loss measurements, potentiodynamic polarization curves, electrochemical impedance and scanning electron microscopy analysis. All results showed that the high molecular weight fraction, rich in melanoidins, present an important role in the inhibitory action of the roasted coffee extract in the acid corrosion of carbon steel.

The effect of two papaya seed extracts (infusion and acid extracts) on the corrosion of carbon steel in 1 mol L-1 HCl was examined. The efficiency for inhibiting the corrosion of C-steel in 1 mol L-1 HCl increased with the extract concentration and decreased slightly with the temperature. The inhibitory property of the extract is discussed in terms of the mechanism by which its components adsorb onto the C-steel surface decreasing the active surface area. This adsorption process obeyed a Langmuir adsorption isotherm. The infusion extract which presented more phenolic compounds than the acid extract showed higher inhibition efficiency. The apparent activation energy (Ea) for the dissolution of C-steel slightly increased when the infusion extract was used.

The inhibitory effect of Bauhinia purpurea (Fabaceae) extract was studied in the corrosion of carbon steel in 1.0 mol∙L-1 sulfuric acid solution. This plant was collected from the Brazilian rainforest. The carbon steel protection was observed by varying the extract concentration from 50 to 500 mg∙L-1. Polarization curves revealed that this extract acted as an adsorption inhibitor decreasing both anodic and cathodic density currents. Weight loss measurements showed that the extract remains stable for at least 72 hours. The adsorption process of this extract obeyed the Langmuir adsorption isotherm. Lastly, Arrhenius plot suggested the physical adsorption of the extract.

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.

Neste estudo, um método eletroquímico é proposto utilizando análise por injeção em fluxo e detecção amperométrica com eletrodos impressos de carbono para determinação de morfolina com intuito de monitorar a qualidade de inibidores de corrosão à base de morfolina e a concentração residual de inibidores que controlam a corrosão interna em dutos da indústria de petróleo. O método amperométrico apresentou um alto coeficiente de correlação linear (r = 0,9941) com uma resposta linear na faixa de concentração de 20-120 mg L-1, um limite de detecção de 10 mg L-1 e um limite de quantificação de 30 mg L-1. Além disso, o método mostrou ser preciso, linear e homocedástico. A recuperação do método amperométrico foi de 100 ± 6%, e a recuperação para amostra real de condensado foi de 99 ± 2%. Portanto, o método proposto é promissor para análise de inibidores comerciais à base de morfolina em dutos da indústria de petróleo com metodologias simples e de baixo custo comparadas com as técnicas de cromatografia iônica.

In this study, an electrochemical method is proposed using flow injection analysis and amperometric detection with screen-printed carbon electrodes for morpholine determination to monitor the quality of morpholine-based commercial inhibitors and the residual concentration of inhibitors that control internal corrosion in oil industry pipelines. The amperometric method resulted in a strong linear correlation coefficient (r = 0.9941) with a linear response over a concentration range of 20-120 mg L-1, a limit of detection of 10 mg L-1 and a limit of quantification of 30 mg L-1. In addition, the method has been shown to be precise, linear and homoscedastic. The recovery for the amperometric method was 100 ± 6%, and the recovery for the real condensate sample was 99 ± 2%. Thus, the proposed method is promising for analysing morpholine-based commercial inhibitors in oil industry pipelines with simple and low-cost methodologies compared with ion chromatography techniques.

Métodos amperométrico e espectrofotométrico foram desenvolvidos para determinar a concentração do traçador iodeto em água produzida de reservatórios de petróleo marítimos. O método amperométrico exibiu uma resposta linear na faixa de 1 a 10 mg L-1 com limites de detecção e de quantificação de 0,2 e 0,6 mg L-1, respectivamente. O método espectrofotométrico também apresentou uma resposta linear na faixa de 1 a 10 mg L-1 com limites de detecção e de quantificação de 1 e 3 mg L-1, respectivamente. Ambos os métodos mostraram-se precisos, lineares, homocedásticos e suas recuperações foram de 101 ± 2 e 100 ± 3%, respectivamente, enquanto que as recuperações para amostras de água produzida de reservatórios (acrescidas de iodeto) foram de 97 ± 7 e 100 ± 3%, respectivamente. Altos teores de sulfato interferem no método espectrofotométrico. Ambos os métodos são alternativas promissoras, simples e baratas à cromatografia iônica para detecção do traçador iodeto em amostras de água produzida de reservatórios de petróleo.

Amperometric and spectrophotometric methods were developed for measuring iodide tracer concentration in water produced from offshore oil reservoirs. The amperometric method exhibited a linear response from 1 to 10 mg L-1 with limits of detection and of quantification of 0.2 and 0.6 mg L-1, respectively. The spectrophotometric method also exhibited a linear response from 1 to 10 mg L-1 with limits of detection and of quantification of 1 and 3 mg L-1, respectively. Both methods showed to be accurate, linear, homoscedastic and their recoveries were 101 ± 2 and 100 ± 3%, respectively, while the recoveries for produced reservoir water samples (fortified with iodide) were 97 ± 7 and 100 ± 3%, respectively. High amounts of sulfate interfere in the spectrophotometric method. Both methods are promising, simple and inexpensive alternatives to ion chromatography for the detection of iodide tracer in produced water reservoir samples.

In the present work, cysteine and allyl alcohol were added to citrate baths as additives to Cu-Zn coatings on steel substrates. In order to verify the effects of the deposition parameters (current density, mechanical stirring speed, and additives) on the coating composition, electrochemical behavior, morphology, and microstructure properties of Cu-Zn coatings, the electrodeposition of the alloy was carried out using an experimental composite design 2³, in which these parameters were considered the entry variables and the measured properties were the response variables. The confidence level was 95% and the results were shown as response surface diagrams. It was possible to verify that the current density affected the zinc content in the coating, while the coating produced from cysteine-contained bath presented the worse anticorrosive performance. In a general way, it was possible to observe that the studied parameters affected the morphology, grain size, and the electrochemical behavior of these coatings, although only a few response variables were statistically influenced by them.

A method based on enzymatic activities was developed using three enzymes (glycerokinase, glycerol-3-phosphate oxidase and peroxidase) and colorimetric detection for the determination of glycerol in biodiesel. The enzymatic conversion of glycerol produces H2O2 that is eliminated by the action of peroxidase, an oxygen acceptor and 4- aminoantipirine, producing water and a colored compound, which was analyzed. This method showed good linear correlation coefficient (r = 0.9937) in the concentration range of 4.95 x 10-5 to 3.96 x 10-4% (w/w) and had experimental limits of detection and quantitation of 7.10 x 10-6 and 2.10 x 10-5% (w/w), respectively.

Horse radish peroxidase (HRP) from Armoracia rusticana catalyses the oxidation of (R)-limonene into the oxidized derivatives carveol and carvone. This study compares the direct addition (DA) of hydrogen peroxide with its continuous electrogeneration (EG) during the enzymatic oxidation of (R)-limonene. Reaction mixtures containing HRP, (R)-limonene as substrate, and hydrogen peroxide, added directly or electrogenerated, in 100 mM sodium-potassium phosphate buffer pH 7.0, at 25ºC were studied. Two electrochemical systems for the hydrogen peroxide electrogeneration were evaluated, both containing as auxiliary electrode (AE) a platinum wire and saturated calomel electrode (SCE) as reference. Reticulated vitreous carbon foam (RVCF) and an electrolytic copper web (CW) were evaluated as working electrodes (WE). Results were compared in terms of hydrogen peroxide electrogeneration, (R)-limonene residual concentration or conversion and product selectivity. Best results in terms of maximum H2O2 concentration (1.2 mM) were obtained using the CW electrode at -620 mV SCE, and continuous aeration. Use of the EG system under optimized conditions, which included the use of acetone (30% v/v) as a cosolvent in a 3 hrs enzymatic reaction, lead to a 45% conversion of (R)-limonene into carveol and carvone (2:1). In comparison to the results obtained with DA, the use of EG also improved the half-life of the enzyme.

Chloroperoxidase (CPO) from Caldariomyces fumago catalyses the oxidation of several chlorinated phenols (CP) commonly found in industrial waste waters in the presence of hydrogen peroxide. This study compares the direct addition of hydrogen peroxide (DA) with its continuous electrogeneration (EG) during the enzymatic oxidation of CP. Reaction mixtures were studied containing chemically modified CPO, hydrogen peroxide and the phenolic substrates: phenol (P), 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and pentachlorophenol (PCP), in 100 mM sodium-potassium phosphate buffer pH 6.0, at 25ºC. Results were compared in terms of residual phenol concentration (oxidation efficiency), precipitate formation (removal) and residual enzyme activity (stability). With the electrochemical system evaluated at -620 mV SCE, and continuous aeration the maximum H2O2 concentration of 1.2 mM was obtained. Under this conditions and after 4 hrs using EG, no phenol or 4-CP were detected, and 97%, 93% and 88% of 2,4-DCP, 2,4,6-TCP and PCP were degraded, respectively. The use of EG improves enzyme half-life time in comparison to the results obtained by DA

Nas gestantes com insuficiência istmocervical (IIC) nas quais já houve cervicodilatação e prolabamento das membranas existe dificuldade técnica para realizar-se a circlagem para conseguir o prolongamento da gravidez até que haja maturidade fetal suficiente para garantir a sobrevida do concepto. Descrevemos um caso de IIC com prolabamento de membranas na 21ª semana, em que se realizou a diminuição da pressão intra-uterina por amniocentese com drenagem de líquido amniótico até a reintrodução das membranas para o interior da cavidade uterina, o que permitiu a tração dos lábios do colo e a realização da circlagem com menor trauma mecânico. Esta medida proporcionou a evolução da gravidez por 12 semanas e a sobrevida do concepto.

In pregnant women with cervical incompetence in whom there is also dilatation of the cervix and prolapsed membranes there are technical difficulties in performing cerclage in order to prolongate pregnancy until sufficient fetal maturity assures survival of the newborn. We describe a case of cervical incompetence with prolapsed membranes at 21 weeks of gestation, in which we caused the decrease of intrauterine pressure with drainage of amniotic fluid by amniocentesis, until reintroduction of membranes into the uterine cavity was possible. This procedure allowed traction of cervical lips and cerclage with less mechanical trauma, warranting the evolution of pregnancy for 12 weeks and fetal survival