Numerical simulation of vacuum dezincing of lead alloy

Removing zinc by distillation can leave the lead bullion virtually free of zinc and also produces pure zinc crystals. Batch distillation is considered in a hemispherical kettle with water-cooled lid, under high vacuum (50 Pa or less). Sufficient zinc concentration at the evaporating surface is achieved by means of a mechanical stirrer. The numerical model is based on the multiphysics simulation package PHYSICA. The fluid flow module of the code is used to simulate the action of the stirring impeller and to determine the temperature and concentration fields throughout the liquid volume including the evaporating surface. The rate of zinc evaporation and condensation is then modelled using Langmuir’s equations. Diffusion of the zinc vapour through the residual air in the vacuum gap is also taken into account. Computed results show that the mixing is sufficient and the rate-limiting step of the process is the surface evaporation driven by the difference of the equilibrium vapour pressure and the actual partial pressure of zinc vapour. However, at higher zinc concentrations, the heat transfer through the growing zinc crystal crust towards the cold steel lid may become the limiting factor because the crystallization front may reach the melting point. The computational model can be very useful in optimising the process within its safe limits.

Adsorption of heavy metal ions and epoxidation catalysis using a new polyhedral oligomeric silsesquioxane

The objective of this research was the preparation of a silsesquioxane functionalized with eight chloropropyl chains (T8-PrCl) and of a new derivative functionalized with a pendant linear chain (2-amino-1,3,4-thiadiazole - ATD; T8-Pr-ATD). The two nanostructured materials were characterized by 13C and 29Si NMR, FTIR and elemental analysis. The new nanostructured material, octakis[3-(2-amino-1,3,4-thiadiazole)propyl] octasilsesquioxane (T8-Pr-ATD), was tested as a ligand for transition-metal ions with a special attention to adsorption isotherms. The adsorption was performed using a batchwise process and the organofunctionalized surface showed the ability to adsorb the metal ions Cu (II), Co (II), and Ni (II) from water and ethanol. The adsorption isotherms were fitted by Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R) model. The kinetics of adsorption of metals were performed using three models such as pseudo-first order, pseudo-second order and Elovich. The Langmuir and Elovich models were the most appropriate to describe the adsorption and kinetic data, respectively. Furthermore, the T8-Pr-ATD was successfully applied to the analysis of environmental samples (river and sea water). Subsequently, a new nanomaterial was prepared by functionalization of the T8-Pr-ATD with a Mo (II) organometallic complex (T8-Pr-ATD-Mo). Only a few works in the literature have reported this type of substitution, and none dealt with ATD and Mo (II) complexes. The new Mo-silsesquioxane organometallic nanomaterial was tested as precursor in the epoxidation of cyclooctene and styrene. © 2012 Elsevier B.V.

Obtenção e caracterização de carvão ativado de caroço de buriti (Mauritia flexuosa L. f.) para avaliar o processo de adsorção de uma solução de Cu (II)

Produziu-se carvão de caroço de buriti (CCB) a partir do rejeito da produção artesanal do fruto, destinado à extração de óleo, à temperatura de 400ºC. O CCB então foi ativado a temperaturas de 800ºC e 900ºC. Ensaios de adsorção foram executados para se avaliar o desempenho dessas temperaturas de ativação na adsorção de uma solução de cobre (II) de concentração inicial conhecida de 50 mg/L. Após a análise dos resultados, decidiu-se pela ativação do carvão a 900ºC. Caracterizou-se o carvão ativado do caroço de buriti (CACB) a 900ºC de acordo com as propriedades comerciais, tais como: área específica, porosimetria, densidades aparente e real, porosidade de um leito fixo, microscopia eletrônica de varredura, conteúdo de cinzas, pH, umidade, carbono fixo e grupos funcionais de superfície ácida presentes no CACB. Realizaram-se ensaios de equilíbrio de adsorção para se determinar a influência do diâmetro das partículas de CACB (D < 0,595 mm; 0,595 < D < 1,19 mm e D > 1,19 mm); a influência do tempo de contato adsorvente/adsorvato (15, 30, 60, 120, 180, 240 e 300 minutos); a influência do pH (3,00; 4,01; 5,18 e 6,00) e a influência da concentração inicial da solução de cobre (II) (5, 10, 30, 50, 80, 100 e 200 mg/L) para se avaliar a eficiência de remoção. Os resultados mostraram uma maior eficiência de remoção de cobre (II) para o diâmetro D < 0,595 mm; para o tempo de contato de 300 minutos; para o pH de 4,01 e para as concentrações iniciais de cobre (II) de 50 e 80 mg/L. Os modelos matemáticos de Langmuir e Freundlich foram aplicados para os dados de equilíbrio de adsorção. O modelo matemático de Langmuir foi o que melhor se ajustou aos dados de equilíbrio. De acordo com os dados da cinética de equilíbrio, observa-se que a partir do tempo de contato de 15 minutos todas as concentrações de equilíbrio ficaram abaixo do máximo permitido de 1,0 mg/L previsto pela legislação CONAMA nº 357/2005 para lançamento de efluentes em corpos receptores. Os resultados experimentais encontrados são indicativos de que é possível a remoção de cobre (II) de efluentes industriais utilizando CACB ativado fisicamente a 900ºC por um período de 60 minutos.

Bare-tether cathodic contact through thermoionic emission by low work-function materials

A new material, C12A7 : electride, which might present a work function as low as 0.6 eV and moderately high temperature stability, was recently proposed as coating for floating bare tethers. Arising from heating under space operation, current is emitted by thermionic emission along a thus coated cathodic segment. A preliminary study on the space-charge-limited (SCL) double layer in front of the cathodic segment is presented using Langmuir’s SCL electron current between cylindrical electrodes and orbital-motion-limited ion-collection sheath. A detailed calculation of current and bias profiles along the entire tether length is carried out with ohmic effects and the transition from SCL to full Richardson-Dushman emission included. Analysis shows that in the simplest drag mode, under typical orbital and tether conditions, thermionic emission leads to a short cathodic section and may eliminate the need for an active cathodic device and its corresponding gas feed requirements and power subsystem, which results in a truly “propellant-less” tether system for such basic applications as de-orbiting low earth orbit satellites.

Low Work-Function Thermionic Emission and Orbital-Motion-Limited Ion Collection at Bare-Tether Cathodic Contact

Una amarra electrodinámica (electrodynamic tether) opera sobre principios electromagnéticos intercambiando momento con la magnetosfera planetaria e interactuando con su ionosfera. Es un subsistema pasivo fiable para desorbitar etapas de cohetes agotadas y satélites al final de su misión, mitigando el crecimiento de la basura espacial. Una amarra sin aislamiento captura electrones del plasma ambiente a lo largo de su segmento polarizado positivamente, el cual puede alcanzar varios kilómetros de longitud, mientras que emite electrones de vuelta al plasma mediante un contactor de plasma activo de baja impedancia en su extremo catódico, tal como un cátodo hueco (hollow cathode). En ausencia de un contactor catódico activo, la corriente que circula por una amarra desnuda en órbita es nula en ambos extremos de la amarra y se dice que ésta está flotando eléctricamente. Para emisión termoiónica despreciable y captura de corriente en condiciones limitadas por movimiento orbital (orbital-motion-limited, OML), el cociente entre las longitudes de los segmentos anódico y catódico es muy pequeño debido a la disparidad de masas entre iones y electrones. Tal modo de operación resulta en una corriente media y fuerza de Lorentz bajas en la amarra, la cual es poco eficiente como dispositivo para desorbitar. El electride C12A7 : e−, que podría presentar una función de trabajo (work function) tan baja como W = 0.6 eV y un comportamiento estable a temperaturas relativamente altas, ha sido propuesto como recubrimiento para amarras desnudas. La emisión termoiónica a lo largo de un segmento así recubierto y bajo el calentamiento de la operación espacial, puede ser más eficiente que la captura iónica. En el modo más simple de fuerza de frenado, podría eliminar la necesidad de un contactor catódico activo y su correspondientes requisitos de alimentación de gas y subsistema de potencia, lo que resultaría en un sistema real de amarra “sin combustible”. Con este recubrimiento de bajo W, cada segmento elemental del segmento catódico de una amarra desnuda de kilómetros de longitud emitiría corriente como si fuese parte de una sonda cilíndrica, caliente y uniformemente polarizada al potencial local de la amarra. La operación es similar a la de una sonda de Langmuir 2D tanto en los segmentos catódico como anódico. Sin embargo, en presencia de emisión, los electrones emitidos resultan en carga espacial (space charge) negativa, la cual reduce el campo eléctrico que los acelera hacia fuera, o incluso puede desacelerarlos y hacerlos volver a la sonda. Se forma una doble vainas (double sheath) estable con electrones emitidos desde la sonda e iones provenientes del plasma ambiente. La densidad de corriente termoiónica, variando a lo largo del segmento catódico, podría seguir dos leyes distintas bajo diferentes condiciones: (i) la ley de corriente limitada por la carga espacial (space-charge-limited, SCL) o (ii) la ley de Richardson-Dushman (RDS). Se presenta un estudio preliminar sobre la corriente SCL frente a una sonda emisora usando la teoría de vainas (sheath) formada por la captura iónica en condiciones OML, y la corriente electrónica SCL entre los electrodos cilíndricos según Langmuir. El modelo, que incluye efectos óhmicos y el efecto de transición de emisión SCL a emisión RDS, proporciona los perfiles de corriente y potencial a lo largo de la longitud completa de la amarra. El análisis muestra que en el modo más simple de fuerza de frenado, bajo condiciones orbitales y de amarras típicas, la emisión termoiónica proporciona un contacto catódico eficiente y resulta en una sección catódica pequeña. En el análisis anterior, tanto la transición de emisión SCL a RD como la propia ley de emisión SCL consiste en un modelo muy simplificado. Por ello, a continuación se ha estudiado con detalle la solución de vaina estacionaria de una sonda con emisión termoiónica polarizada negativamente respecto a un plasma isotrópico, no colisional y sin campo magnético. La existencia de posibles partículas atrapadas ha sido ignorada y el estudio incluye tanto un estudio semi-analítico mediante técnica asintóticas como soluciones numéricas completas del problema. Bajo las tres condiciones (i) alto potencial, (ii) R = Rmax para la validez de la captura iónica OML, y (iii) potencial monotónico, se desarrolla un análisis asintótico auto-consistente para la estructura de plasma compleja que contiene las tres especies de cargas (electrones e iones del plasma, electrones emitidos), y cuatro regiones espaciales distintas, utilizando teorías de movimiento orbital y modelos cinéticos de las especies. Aunque los electrones emitidos presentan carga espacial despreciable muy lejos de la sonda, su efecto no se puede despreciar en el análisis global de la estructura de la vaina y de dos capas finas entre la vaina y la región cuasi-neutra. El análisis proporciona las condiciones paramétricas para que la corriente sea SCL. También muestra que la emisión termoiónica aumenta el radio máximo de la sonda para operar dentro del régimen OML y que la emisión de electrones es mucho más eficiente que la captura iónica para el segmento catódico de la amarra. En el código numérico, los movimientos orbitales de las tres especies son modelados para potenciales tanto monotónico como no-monotónico, y sonda de radio R arbitrario (dentro o más allá del régimen de OML para la captura iónica). Aprovechando la existencia de dos invariante, el sistema de ecuaciones Poisson-Vlasov se escribe como una ecuación integro-diferencial, la cual se discretiza mediante un método de diferencias finitas. El sistema de ecuaciones algebraicas no lineal resultante se ha resuelto de con un método Newton-Raphson paralelizado. Los resultados, comparados satisfactoriamente con el análisis analítico, proporcionan la emisión de corriente y la estructura del plasma y del potencial electrostático. ABSTRACT An electrodynamic tether operates on electromagnetic principles and exchanges momentum through the planetary magnetosphere, by continuously interacting with the ionosphere. It is a reliable passive subsystem to deorbit spent rocket stages and satellites at its end of mission, mitigating the growth of orbital debris. A tether left bare of insulation collects electrons by its own uninsulated and positively biased segment with kilometer range, while electrons are emitted by a low-impedance active device at the cathodic end, such as a hollow cathode, to emit the full electron current. In the absence of an active cathodic device, the current flowing along an orbiting bare tether vanishes at both ends and the tether is said to be electrically floating. For negligible thermionic emission and orbital-motion-limited (OML) collection throughout the entire tether (electron/ion collection at anodic/cathodic segment, respectively), the anodic-to-cathodic length ratio is very small due to ions being much heavier, which results in low average current and Lorentz drag. The electride C12A7 : e−, which might present a possible work function as low as W = 0.6 eV and moderately high temperature stability, has been proposed as coating for floating bare tethers. Thermionic emission along a thus coated cathodic segment, under heating in space operation, can be more efficient than ion collection and, in the simplest drag mode, may eliminate the need for an active cathodic device and its corresponding gas-feed requirements and power subsystem, which would result in a truly “propellant-less” tether system. With this low-W coating, each elemental segment on the cathodic segment of a kilometers-long floating bare-tether would emit current as if it were part of a hot cylindrical probe uniformly polarized at the local tether bias, under 2D probe conditions that are also applied to the anodic-segment analysis. In the presence of emission, emitted electrons result in negative space charge, which decreases the electric field that accelerates them outwards, or even reverses it, decelerating electrons near the emitting probe. A double sheath would be established with electrons being emitted from the probe and ions coming from the ambient plasma. The thermionic current density, varying along the cathodic segment, might follow two distinct laws under different con ditions: i) space-charge-limited (SCL) emission or ii) full Richardson-Dushman (RDS) emission. A preliminary study on the SCL current in front of an emissive probe is presented using the orbital-motion-limited (OML) ion-collection sheath and Langmuir’s SCL electron current between cylindrical electrodes. A detailed calculation of current and bias profiles along the entire tether length is carried out with ohmic effects considered and the transition from SCL to full RDS emission is included. Analysis shows that in the simplest drag mode, under typical orbital and tether conditions, thermionic emission provides efficient cathodic contact and leads to a short cathodic section. In the previous analysis, both the transition between SCL and RDS emission and the current law for SCL condition have used a very simple model. To continue, considering an isotropic, unmagnetized, colissionless plasma and a stationary sheath, the probe-plasma contact is studied in detail for a negatively biased probe with thermionic emission. The possible trapped particles are ignored and this study includes both semianalytical solutions using asymptotic analysis and complete numerical solutions. Under conditions of i) high bias, ii) R = Rmax for ion OML collection validity, and iii) monotonic potential, a self-consistent asymptotic analysis is carried out for the complex plasma structure involving all three charge species (plasma electrons and ions, and emitted electrons) and four distinct spatial regions using orbital motion theories and kinetic modeling of the species. Although emitted electrons present negligible space charge far away from the probe, their effect cannot be neglected in the global analysis for the sheath structure and two thin layers in between the sheath and the quasineutral region. The parametric conditions for the current to be space-chargelimited are obtained. It is found that thermionic emission increases the range of probe radius for OML validity and is greatly more effective than ion collection for cathodic contact of tethers. In the numerical code, the orbital motions of all three species are modeled for both monotonic and non-monotonic potential, and for any probe radius R (within or beyond OML regime for ion collection). Taking advantage of two constants of motion (energy and angular momentum), the Poisson-Vlasov equation is described by an integro differential equation, which is discretized using finite difference method. The non-linear algebraic equations are solved using a parallel implementation of the Newton-Raphson method. The results, which show good agreement with the analytical results, provide the results for thermionic current, the sheath structure, and the electrostatic potential.