Critical magnetic elds in superconducting systems with semi-metallic bands

In this work, we study the Zeeman splitting effects in the parallel magnetic field versus temperature phase diagram of two-dimensional superconductors with one graphene-like band and the orbital effects of perpendicular magnetic fields in isotropic two-dimensional semi-metallic superconductors. We show that when parallel magnetic fields are applied to graphene and as the intraband interaction decreases to a critical value, the width of the metastability region present in the phase diagram decreases, vanishing completely at that critical value. In the case of two-band superconductors with one graphene-like band, a new critical interaction, associated primarily with the graphene-like band, is required in order for a second metastability region to be present in the phase diagram. For intermediate values of this interaction, a low-temperature first-order transition line bifurcates at an intermediate temperature into a first-order transition between superconducting phases and a second-order transition line between the normal and the superconducting states. In our study on the upper critical fields in generic semi-metallic superconductors, we find that the pair propagator decays faster than that of a superconductor with a metallic band. As result, the zero field band gap equation does not have solution for weak intraband interactions, meaning that there is a critical intraband interaction value in order for a superconducting phase to be present in semi-metallic superconductors. Finally, we show that the out-of-plane critical magnetic field versus temperature phase diagram displays a positive curvature, contrasting with the parabolic-like behaviour typical of metallic superconductors.

Lógica borrosa para la estimación de estados críticos de una pila de combustible PEM

La determinación en tiempo real de los estados críticos de operación de la pila de combustible de membrana intercambio protónico (siglas en ingles, PEM) es uno de los principales retos para los sistemas de control de pilas de combustible PEM. En este trabajo, se presenta el desarrollo e implementación de un método no invasivo de bajo coste basado en técnicas de decisión borrosa que permite estimar los estados críticos de operación de la pila de combustible PEM. La estimación se realiza mediante perturbaciones al estado de operación de la pila y el análisis posterior de la evolución temporal del voltaje generado por la pila. La implementación de esta técnica de estimulación-percepción de estado de la pila de combustible para la detección de estados críticos constituye una novedad y un paso hacia el control autónomo en óptimas condiciones de la operación de las pilas de combustible PEM.

Flowers of Gomphrena globosa L. as an alternatve source of betacyanins: optimization of the extraction using response surface methodology

Betacyanins are betalain pigments that display a red-violet colour which have been reported to be three times stronger than the red-violet dye produced by anthocyanins [1]. The applications of betacyanins cover a wide range of matrices, mainly as additives or ingredients in the food industry, cosmetics, pharmaceuticals and livestock feed. Although, being less commonly used than anthocyanins and carotenoids, betacyanins are stable between pH 3 to 7 and suitable for colouring in low acid matrices. In addition, betacyanins have been reported to display interesting medicinal character as powerful antioxidant and chemopreventive compounds either in vitro or in vivo models [2]. Betacyanins are obtained mainly from the red beet of Beta vulgaris plant (between I 0 to 20 mg per I 00 g pulp) but alternative primary sources are needed [3]. In addition, independently of the source used, the effect of the variables that affect the extraction of betacyanins have not been properly described and quantified. Therefore, the aim of this study was to identifY and optimize the conditions that maximize betacyanins extraction using the tepals of Gomphrena globosa L. flowers as an alternative source. Assisted by the statistical technique of response surface methodology, an experimental design was developed for testing the significant explanatory variables of the extraction (time, temperature, solid-liquid ratio and ethanolwater ratio). The identification was performed using high-performance liquid chromatography coupled with a photodiode array detector and mass spectrometry with electron spray ionization (HPLC-PDAMS/ ESI) and the response was measured by the quantification of these compounds using HPLC-PDA. Afterwards, a response surface analysis was performed to evaluate the results. The major betacyanin compounds identified were gomphrenin 11 and Ill and isogomphrenin IJ and Ill. The highest total betacyanins content was obtained by using the following conditions: 45 min of extraction. time, 35•c, 35 g/L of solid-liquid ratio and 25% of ethanol. These values would not be found without optimizing the conditions of the betacyanins extraction, which moreover showed contrary trends to what it has been described in the scientific bibliography. More specifically, concerning the time and temperature variables, an increase of both values (from the common ones used in the bibliography) showed a considerable improvement on the betacyanins extraction yield without displaying any type of degradation patterns.

Desenvolvimento de eletrocatalisadores de PdM (M= Ni, Cu, Ag) para reação de redução de oxigênio em meio básico na ausência e presença de álcool

Tese (Doutorado em Tecnologia Nuclear)

Sn@Pt and Rh@Pt core–shell nanoparticles synthesis for glycerol oxidation

The development and optimization of electrocatalysts for application in fuel cell systems have been the focus of a variety of studies where core–shell structures have been considered as a promising alternative among the materials studied. We synthesized core–shell nanoparticles of Sn x @Pt y and Rh x @Pt y (Sn@Pt, Sn@Pt2, Sn@Pt3, Rh@Pt, Rh@Pt2, and Rh@Pt3) through a reduction methodology using sodium borohydride. These nanoparticles were electrochemically characterized by cyclic voltammetry and further analyzed by cyclic voltammetry studying their catalytic activity toward glycerol electro-oxidation; chronoamperometry and potentiostatic polarization experiments were also carried out. The physical characterization was carried out by X-ray diffraction, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy. The onset potential for glycerol oxidation was shifted in 130 and 120 mV on the Sn@Pt3/C and Rh@Pt3/C catalysts, respectively, compared to commercial Pt/C, while the stationary pseudo-current density, taken at 600 mV, increased 2-fold and 5-fold for these catalysts related to Pt/C, respectively. Thus, the catalysts synthesized by the developed methodology have enhanced catalytic activity toward the electro-oxidation of glycerol, representing an interesting alternative for fuel cell systems.

Oxygen reduction reaction in ionic liquids: an overview

The oxygen reduction reaction has been the subject of intensive research during decades due to their importance in life processes such as biological respiration, and also as a cathodic process in energy storage devices (e.g. fuel cells and air batteries). Detailed reviews on the oxygen reduction reaction in aqueous and non-aqueous media are available in the literature but it is lacking in the case of ionic liquids. Therefore a comprehensive review on the oxygen reduction reaction (ORR) in ionic liquids is described in this chapter in order to compile the state of the art from a fundamental point of view and improve the current knowledge towards not only fundamental but also practical applications. The oxygen reduction reaction mechanism in neat imidazolium, pyrrolidinium, quaternary ammonium, and phosphonium-based ionic liquids, which mainly undergo one-electron pathway leading to the generation of superoxide anion (O2•-), is the main topic of this chapter. The reversibility of the O2/O2•- redox couple is highly dependent on the composition of the ionic liquid, as an example superoxide is more stable in the presence of aliphatic and alicyclic cations than in the presence of aromatic rings. Furthermore, the influence of protic and aprotic additives in the ORR mechanism is also explained in this chapter together with the influence in electrochemical parameters such as formal potential, E0'.

Effect of coiling treatment on microstructural development and precipitate strengthening of a strip cast steel

The effect of a simulated coiling treatment on a strip cast Nb-containing steel has been investigated. A lath ferritic supersaturated microstructure was observed in the as-cast condition with no coiling. The microstructure remained lath like during coiling at high temperature (850 °C) and the formation of chemically complex Nb-rich precipitates containing C, N, Si and S was observed. Coiling at an intermediate temperature (700 °C) caused the formation of polygonal ferrite with a dendritic morphology due to chemical micro-segregation. The polygonal ferrite contained Nb(C,N) precipitates. The microstructure remained lath like at the lowest coiling temperature (600 °C). In the latter case the precipitation of Nb-rich clusters was observed, and atom probe tomography revealed them to be ∼85% Fe. Small angle neutron scattering and transmission electron microscopy were used to quantify precipitation kinetics during coiling and the mechanical properties were evaluated with a shear punch apparatus. A yield strength model was developed to describe the observed mechanical behaviour, and this showed that the two largest contributors to strength were the bainitic microstructure and the Nb-rich precipitates. Strategies to further strengthen these materials are suggested.

AN EXPERIMENTAL INVESTIGATION INTO THE EFFECTS OF BIODIESEL BLENDS ON PARTICULATE MATTER OXIDATION IN A CATALYZED PARTICULATE FILTER DURING ACTIVE REGENERATION

Active regeneration experiments were carried out on a production 2007 Cummins 8.9L ISL engine and associated DOC and CPF aftertreatment system. The effects of SME biodiesel blends were investigated in this study in order to determine the PM oxidation kinetics associated with active regeneration, and to determine the effect of biodiesel on them. The experimental data from this study will also be used to calibrate the MTU-1D CPF model. Accurately predicting the PM mass retained in the CPF and the oxidation characteristics will provide the basis for computation in the ECU that will minimize the fuel penalty associated with active regeneration. An active regeneration test procedure was developed based on previous experimentation at MTU. During each experiment, the PM mass in the CPF is determined by weighing the filter at various phases. In addition, DOC and CPF pressure drop, particle size distribution, gaseous emissions, temperature, and PM concentration data are collected and recorded throughout each experiment. The experiments covered a range of CPF inlet temperatures using ULSD, B10, and B20 blends of biodiesel. The majority of the tests were performed at CPF PM loading of 2.2 g/L with in-cylinder dosing, although 4.1 g/L and a post-turbo dosing injector were also used. The PM oxidation characteristics at different test conditions were studied in order to determine the effects of biodiesel on PM oxidation during active regeneration. A PM reaction rate calculation method was developed to determine the global activation energy and the corresponding pre-exponential factor for all test fuels. The changing sum of the total flow resistance of the wall, cake, and channels was also determined as part of the data analysis process in order to check on the integrity of the data and to correct input data to be consistent with the expected trends of the resistance based on the engine conditions used in the test procedure. It was determined that increasing the percent biodiesel content in the test fuel tends to increase the PM reaction rate and the regeneration efficiency of fuel dosing, i.e., at a constant CPF inlet temperature, B20 test fuel resulted in the highest PM reaction rate and regeneration efficiency of fuel dosing. Increasing the CPF inlet temperature also increases PM reaction rate and regeneration efficiency of fuel dosing. Performing active regeneration with B20 as opposed to ULSD allows for a lower CPF temperature to be used to reach the same level of regeneration efficiency, or it allows for a shorter regeneration time at a constant CPF temperature, resulting in decreased fuel consumption for the engine during active regeneration in either scenario.

Microbial nanowires : an electrifying tale

Electromicrobiology has gained momentum in the last ten years with advances in microbial fuel cells and the discovery of microbial nanowires (MNWs). The list of MNWs producing microorganisms is growing and providing intriguing insights into the presence of such microorganisms in diverse environments and the potential roles MNWs can perform. This review discusses the MNWs produced by different microorganisms, including their structure, composition and role in electron transfer through MNWs. Two hypotheses, metallic-like conductivity and an electron hopping model, have been proposed for electron transfer and we present a current understanding of both these hypotheses. MNWs are not only poised to change the way we see microorganisms but may also impact the fields of bioenergy, biogeochemistry and bioremediation, hence their potential applications in these fields are highlighted here.

Low temperature synthesis of carbon nanotubes on indium tin oxide electrodes for organic solar cells

The electrical performance of indium tin oxide (ITO) coated glass was improved by including a controlled layer of carbon nanotubes directly on top of the ITO film. Multi-wall carbon nanotubes (MWCNTs) were synthesized by chemical vapor deposition, using ultra-thin Fe layers as catalyst. The process parameters (temperature, gas flow and duration) were carefully refined to obtain the appropriate size and density of MWCNTs with a minimum decrease of the light harvesting in the cell. When used as anodes for organic solar cells based on poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM), the MWCNT-enhanced electrodes are found to improve the charge carrier extraction from the photoactive blend, thanks to the additional percolation paths provided by the CNTs. The work function of as-modified ITO surfaces was measured by the Kelvin probe method to be 4.95 eV, resulting in an improved matching to the highest occupied molecular orbital level of the P3HT. This is in turn expected to increase the hole transport and collection at the anode, contributing to the significant increase of current density and open circuit voltage observed in test cells created with such MWCNT-enhanced electrodes.

Solid-state chemistry of high-temperature oxide superconductors:The experimental situation

High-temperature superconductivity in oxides of the type(La, Ln)2?xBax(Sr)xCuO4, Y(Ln)Ba2Cu3O7??, La3?xBa3+xCu6O14, and related systems is discussed with emphasis on aspects related to experimental solid-state chemistry. All of these oxides possess perovskite-related structures. Oxygen-excess and La-deficient La2CuO4 also exhibit superconductivity in the 20�40 K just as La2?xBax(Srx)CuO4; these oxides are orthorhombic in the superconductivity phase. The crucial role of oxygen stoichiometry in the superconductivity ofYBa2Cu3O7?? (Tc = 95 ± 5K) is examined; this oxide remains orthorhombic up to ? ? 0.6 and becomes tetragonal and nonsuperconducting beyond this value of ?. Oxygen stoichiometry in this and related oxides has to be understood in terms of structure and disorder. The structure of La3?xBa3+xCu6O14 is related to that of YBa2Cu3O7, the orthorhombic structure manifesting itself when the population of O1 oxygens (along the Cusingle bondOsingle bondCu chains) is preponderant compared to that of O5 oxygens (along thea-axis); nearly equal populations of O1 and O5 sites give rise to the tetragonal structure. A transition from a high-Tc (95 K) superconductivity regime to a low-Tc (not, vert, similar60 K) regime occurs in YBa2Cu3O7?? accompanying a change in ?. There is no evidence for Cu3+ in these nominally mixed valent copper oxides. Instead, holes are present on oxygens giving rise to O? or O2?2 species, the concentration of these species increasing with the lowering of temperature. Certain interesting aspects of the superconducting oxides such as domain or twin boundaries, Raman spectra, microwave absorption, and anomalous high-temperature resistivity drops are presented along with the important material parameters. Preparative aspects of the superconducting oxides are briefly discussed. Phase transitions seem to occur atTc as well as at not, vert, similar240 K in YBa2Cu3O7.