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The electrochemical behavior of polypyrrole (PPy)-coated carbon steel (CS) was investigated in aqueous NaCl solution by scanning electrochemical microscopy. Oxygen concentration and pH were monitored by placing Pt and Sb microelectrodes, respectively, over the CS sample surfaces while soaking them in corrosion media. The PPy layer provided anodic protection, as well as a physical barrier, against the corrosive effect. The ratio of these properties was dependent on the thickness of the coating. Electrosynthesis of PPy/CS was achieved in an aqueous solution of sodium tartrate and pyrrole using cyclic voltammetric and galvanostatic techniques. The coatings were characterized by X-ray photoelectron spectroscopy and scanning electron microscopy. The doping rate calculated from XPS spectra was estimated at 15 %. The corrosion protective extent of the coating was tested in 3 % NaCl solution using three different techniques: linear polarization, open circuit potential, and electrochemical impedance spectroscopy. PPy offered significant protection against corrosion, with the coating resistance decreasing as immersion time increased.

A corrosion spreading throughout the 304 stainless steel tubing of a water system to supply various buildings was observed, and also leaks were detected in welding zones. The same place is also crossed by a gas distribution network, with a helium pipe 316 of stainless steel that required periodic repairs more or less every two years, due to the presence of leaks. The tests showed that both types of stainless steel have suffered localized corrosion induced by hypochlorite ion, in a mechanism of dry/wet, and that the welding procedure performed on the 304 stainless steel is unacceptable. Some immediate procedures were undertaken to keep systems running, but recommendations were given for a final resolution of the problems.

Activated carbon xerogels with a cellular morphology were obtained from hydrothermally carbonized glucose-graphene oxide (GO) hybrids and tested as supercapacitor electrodes. The effect of the chemical activation (using KOH) on the nanometer-scale morphology, local structure, porous texture and surface chemistry of the resulting carbon materials was investigated and correlated with their electrochemical behaviour. The electrochemical performance of the activated xerogels was studied in a three-electrode cell using 1 M H2SO4 as the electrolyte. The results underlined the relevant role played by the xerogel nanomorphology; more specifically, xerogels with cellular structures exhibiting well-connected, continuous and very thin (∼5–15 nm) carbon walls (prepared with lower amounts of activating agent) favored ionic diffusion and electronic conduction compared to materials with broken, thicker walls (obtained from higher amounts of activating agent). The effect of nanomorphology and local structure was also made apparent when the xerogels were used as actual supercapacitor electrodes. Particularly, a symmetric capacitor assembled from a carbon xerogel with very thin walls and relatively high graphitic character delivered a much higher specific capacitance than that of a commercial activated carbon (223 vs 153 F g−1 at 100 mA g−1) as well as a significantly improved retention of capacitance at high current densities., This work was financed by QREN, ON2, FCT and FEDER (Project NORTE-07-0124- FEDER-000015 and NORTE-07-0162-FEDER-000050), and co-financed by FCT and FEDER through COMPETE 2020 (Project UID/EQU/50020/2013 - POCI-01-0145- FEDER-006984). Partial funding of this work by the Spanish MINECO and the European Regional Development Fund (projects MAT2015-69844-R and MAT2012- 34011) is also gratefully acknowledged.

Tinplate steel cans were used to store contact glue for shoes. A few months after its storage, the glue displayed a change in colour to a darker brown. The visual inspection of the interior of the cans showed the presence of corrosion of steel, which was evidenced by the typical colour of the iron oxides on the sheet. SEM/EDS and FTIR tests confirmed that the anomaly was due to the following factors: (a) a bad tin coating, small thickness and lack of homogeneity; (b) a degradation of glue, hydrolysis of chloroprene, which led to its acidification. Some recommendations are made to overcome similar situations within the same use of these packages looking at the specifications of tinplate.

Cathodic protection, often taught in curricular units, such as corrosion and materials science, is an important subject in the study of chemical engineering. The implementation of lab setups and experimental activities in this field, are core to promoting understanding of the underlying concepts and to developing &ldquo, hands-on&rdquo, skills fundamental to the success of future process engineers. This paper reports the influence of different variables on the electrical potential and current behaviors of an educational cathodic protection system operated with a single drainage point. The system comprised a steel bar cathode connected to a zinc sacrificial anode, both placed in aqueous medium. The study variables were the anode area, the cathode diameter, the NaCl electrolyte concentration and the anode placement. Each variable showed a specific influence on the attenuation curves, allowing us to conclude that: (1) increasing the sacrificial anode area, or decreasing the resistivity of the medium, promotes more electronegative potentials on the structure and higher currents, (2) increasing the cathode diameter decreases the protection capacity, (3) positioning the anode in the middle of the cathode lengthwise gives rise to a more balanced potential distribution, and (4), the attenuation curves, both for potential and current, can be successfully predicted using equations based on Morgan and Uhlig&rsquo, s work. High correlations were obtained between the experimental and modeling data for all the studied variables.

The electrochemical behaviour of dimethylamine borane and borohydride on platinum electrodes was investigated by cyclic voltammetry and polarization curves in discharges processes. Several overlapping peaks appear in the domain of hydrogen oxidation, i.e., in the potential range of −1.25 V to −0.50 V versus Ag/AgCl, mainly with the borohydride. This behaviour is associated with the hydrolysis of BH 4 − or (CH 3 ) 2 NHBH 3 . As a consequence of secondary reactions the borohydride and dimethylamine borane oxidation in 3 M NaOH solution shows, respectively, a four- to six-electron process and a four- to five-electron process in direct fuel cells. The direct oxidation of the borohydride exhibits a peak at about −0.07 V versus Ag/AgCl, while the dimethylamine borane peak is at about −0.03 V versus Ag/AgCl. For the 0.04 M concentration the borohydride displays a power density of 31 W m −2 which is 16% higher than that of the dimethylamine borane.

Cerium oxide/multiwalled carbon nanotube composites with different oxide loadings (5–60 wt. %) were prepared by sol-gel deposition of the oxide onto the carbon support. The morphology, texture and surface properties of the prepared materials were studied and correlated with their electrochemical behavior. The different charge storage mechanisms occurring on the surface of the composites were successfully identified by a newly developed electrochemical method, namely the combination of sweep wave voltammetry with deconvolution analysis in 1 M H 2 SO 4 . The deposition of moderate oxide loadings (up to 10 wt. %) leads to small and well distributed oxide particles on the nanotubes surface. Therefore, the appearance of defects on the oxide structure is favored, promoting both electronic conduction and faradaic activity. Curiously, cerium oxide loadings above 10 wt. % induce a higher dispersion of the carbon support. This convenient synergism enhances the electroactive area of the composites by increasing molecular diffusion.

The electrochemical behaviour of stainless steel electrode in 0.1 M sodium saccharinate solution in the absence and the presence of the monomer were investigated using several electrochemical techniques such as cyclic voltammetry, galvanostatic and potentiostatic. The XPS analysis was used to study the elementary composition of the obtained polymer and to estimate the doping level of the PPy obtained under this electrolytic conditions. Moreover, the characterization of the coating was achieved by SEM, IR and Raman. In this context, samples of PPy in oxidized and reduced state synthesized galvanostatically on stainless steel grid were used to investigate the behaviour of the polymer toward acetone vapor.

The recovery of tungsten from alkaline leach solutions has been studied examining the effect of temperature, pH, Ca/WO3 molar ratio and nature of the precipitated calcium tungstate. The precipitation kinetics of calcium tungstate, upon the addition of aqueous sodium tungstate to calcium solutions, was followed by potentiometric measurements using a calcium ion-selective electrode. Two models, a crystal growth model and a second-order reaction opposed by zero-order reaction, have been used to test the experimental data. Both models show that the apparent activation energy of CaWO4 precipitation falls in the range 58 to 67 kJ mol− 1. The kinetic data shows that the maximum recovery of precipitated calcium tungstate occurs at pH ≥ 8.5 with a 10% excess of CaCl2 at 50 °C over a period of 20 min using sodium tungstate solutions of 100 g L− 1 and 150 g L− 1 WO3.

The electrosynthesis of polypyrrole (PPy) has been achieved on aluminium in aqueous medium of malic acid by means of cyclic voltammetry, potentiostatic and galvanostatic techniques. Scanning electron microscopy (SEM) and X-ray microanalysis by dispersion energy spectroscopy (EDS) applying on surfaces show that the PPy coating is developed from the metal surface through the cracks of the initial Al 2 O 3 layer. Moreover, the results reveal that the homogeneity of the film achieved increases with the time of electropolymerization. A mechanism involving the participation of the supporting electrolyte and the pyrrole (Py) in distinct active sites was proposed based on the linear sweep voltammetry. It is observed for all the applied electrochemical techniques that the pyrrole concentration has to be higher than 0.1 M to allow the polypyrrole electrodeposition in acid medium. Scanning electron microscopy, secondary electrons (SE) and backscattering electrons (BE), shows that the PPy coating obtained in galvanostatic and potentiostatic modes starts with small islands at weak applied potentials or current densities. The corrosion results in 3% NaCl medium show that the PPy coating decreases the corrosion behaviour of the aluminium. The bilayer Al 2 O 3 /PPy shows a capacitor with future applications.

A single-step electropolymerization of pyrrole on zinc-coated steel electrodes in aqueous medium was investigated under several techniques (potentiodynamic, galvanostatic and potentiostatic modes) by using carboxylate salts, such as the citrate, the succinate, the oxalate, the malate and the tartrate. Adherent and homogeneous PPy coatings were obtained only with tartrate counter-ions. The corrosion behaviour of zinc-coated steel electrodes electrochemical modified by PPy films were estimated by open circuit potential and DC polarization in NaCl, HCl and H2SO4 aggressive solutions. The obtained results show that the PPy coatings increase the corrosion potential and reduce the corrosion current. The salt spray test results show that the PPy coating prepared under ultrasonic waves is more resistant than those obtained in normal conditions.

The electrosynthesis of polypyrrole (PPy) on copper and brass (Cu–Zn alloy) electrodes was performed by anodic oxidation of pyrrole in a sodium tartrate (C4H4Na2O6 0.2 M) aqueous solution. The tartrate counter-ions slow the dissolution of the working electrode by leading to formation of a passivation layer on its surface, and pyrrole electropolymerization takes place. Strongly adherent and homogeneous polypyrrole films were electrodeposited on Cu and Cu–Zn alloy electrodes using different electrochemical techniques, such as potentiodynamic, galvanostatic and potentiostatic modes. The current densities of electropolymerization on brass are generally greater than those observed on copper. The corrosion behaviour of copper-coated electrodes, electrochemically modified by PPy films, was estimated by DC polarization and weight loss at different current densities in 0.1 M HCl solution. The synthesized polypyrrole films were characterised by several microscopic and spectroscopic techniques such as scanning electron microscopy, X-ray photo electron spectroscopy, Fourier transform infrared and Raman analysis. Galvanostatically deposited PPy films are shown to be an alternative to common black-nickel or black-chromium as a decorative top-coating.

The kinetics of the leaching reaction of synthetic scheelite with hydrochloric acid was studied to determine the effect of pH and temperature in the formation of tungstic acid. Conversion data obtained from leaching in a temperature range of 28–100 °C and pH between 1.5 and 3.0 are interpreted in terms of the predominating tungsten species present in the leaching liquors. The results show that it is possible to digest the synthetic scheelite in the acidic hydrochloric medium without the formation of tungstic acid by monitoring and controlling the pH, and controlling the temperature in the domain of metatungstates. In this case, the experimental results match with the shrinking core model, and show that the solids leaching is kinetically under both chemical and mass transfer control.

Hierarchical carbons with different boron contents (from 0.42 to 2.37 wt.%) were prepared by combination of soft-templating and hydrothermal approaches. This newly developed strategy enables adequate control of the chemical state of the boron functionalities in carbon materials since the self-generated pressures favour B–C bond formation. The total content of oxygen increases simultaneously with the boron content, and its speciation is also influenced by the boron chemical state distribution: the presence of C–B–C (BC 3 and BC 2 O) species induces the oxidation of phenols to carbonyls. The electrochemical performance of the prepared carbons was tested in a three-electrode cell configuration (1 M H 2 SO 4 ) showing good specific capacitances per BET specific surface area (20–36 μF/cm 2 ). The presence of boron on the carbon backbone improves both the charge propagation and the pseudocapacitive properties. Nevertheless, the electrochemical properties are only enhanced up to some level of boron doping (around 1.8 wt.%). A two-electrode supercapacitor built with a carbon prepared by a mild hydrothermal synthesis (50 °C during 28 h) delivered energy densities similar to those of commercial activated carbons. This could lead to high volumetric capacitance, since the boron doped carbons present much higher density.

Obtaining of tungstic oxide from wolframite concentrates involves the production of synthetic scheelite and/or tungstic acid as intermediate products. The present work studies the influence of different factors affecting the particle size of these compounds and also investigates the correlation between its granulometry and the final grain size of WO 3 . The research included as main goals (i) the study of the effect on the synthetic scheelite grain size of the following parameters—concentration and amount of calcium chloride; concentration of tungstate solution and type of mixing and stirring, (ii) the study of the correlation between granulometric sizes of synthetic scheelite and final tungstic oxide granulometric sizes, (iii) the study of the effect of temperature, type of agitation, concentration and amount of hydrochloric acid on the recovery and particle size of tungstic oxide. Conditions to produce WO 3 powders with tailor-made micrometric grain size from 10 to 0.5 μm are presented.

The electrodeposition of polypyrrole (PPy) on aluminium electrodes has been achieved in phosphoric acid medium by using potentiodynamic, potentiostatic and galvanostatic techniques. The corrosion behavior of polypyrrole on aluminium in sodium chloride medium has been investigated by open circuit potential and electrochemical impedance spectroscopy. A mechanism to explain the beneficial effect of PPy-doping dihydrogenophosphate ion in the passivation of aluminium is proposed. A electrodeposição do polipirrole (PPy) sobre alumínio em soluções de ácido fosfórico foi obtida através de técnicas potenciodinâmicas, potenciostáticas e galvanostáticas. O comportamento do alumínio revestido com polipirrole em meio de cloreto de sódio foi investigado através do potencial de circuito aberto e espectroscopia de impedância electroquímica. É proposto um mecanismo para explicar o efeito benéfico do íon dihidrogenofosfato na passivação do alumínio.

A criminalidade é algo que afeta as nossas vidas, bem como a forma de viver em sociedade. O conhecimento da realidade sócio-criminal é de extrema importância para o desenvolvimento das sociedades. As temáticas da criminalidade e segurança têm vindo, nos últimos tempos, a ser alvo de enorme pressão pela comunicação social, pelo governo e pela comunidade civil. Desta forma, urge a necessidade de encontrar novas leituras de informação, a nível regional e local, sobre áreas de ocorrências ou incidentes associados à criminalidade e incivilidade - as áreas de intervenção das forças de segurança - de forma a melhor se compreender as suas causas. Só assim se poderá agir, numa ótica da prevenção e combate ao fenómeno. A diversidade espacial do nosso território é conhecida e estudada desde há muito, contudo, raramente se pensa e articula este conhecimento com os fenómenos criminais. A criminalidade está diretamente articulada com a geografia e com os fenómenos que ocorrem num determinado território. Segundo as teorias da criminologia, tratar apenas dados reportados é insuficiente para efetuar uma análise correta da criminalidade e criar políticas de segurança e prevenção do fenómeno criminal. Com o desenvolvimento de aplicações de Sistemas de Informação Geográfica (SIG) desde 1990, os analistas criminais em todo o mundo têm usado e ponderado os princípios da Geografia de forma a perceber e criar mecanismos de prevenção e segurança da população. Vários especialistas afirmam que o mapeamento da criminalidade tem um impacto no entendimento do crime e dos problemas sociais. Desta forma, a geografia aplicada tem um papel preponderante neste tipo de fenómeno, no sentido em que se conhecermos uma determinada área e a forma como essa afeta as áreas de proximidade, podemos perceber como e onde se localiza determinado fenómeno ou acontecimento. Isto é a Geografia da criminalidade, uma importante ferramenta de apoio à decisão em questões de segurança pública e prevenção do crime. Esta apresentação tem assim como objetivos principais: (i) perceber a dimensão e espacialização das forças de segurança, (ii) reconhecer áreas problemáticas e vulneráveis da cidade de Lisboa, (iii) propor soluções de segurança e prevenção da criminalidade com o reforço de unidades e instalações policiais.

The present work proposes the development of a bio-battery composed by an ultrathin monolithic structure of an electrospun cellulose acetate membrane, over which was deposited metallic thin film electrodes by thermal evaporation on both surfaces. The electrochemical characterization of the bio-batteries was performed under simulated body fluids like sweat and blood plasma [salt solution – 0.9% (w/w) NaCl]. Reversible electrochemical reactions were detected through the cellulose acetate structure. Thus, a stable electrochemical behavior was achieved for a bio-battery with silver and aluminum thin films as electrodes. This device exhibits the ability to supply a power density higher than 3 μW cm −2 . Finally, a bio-battery prototype was tested on a sweated skin, demonstrating the potential of applicability of this bio-device as a micropower source.