Multi-fluid Eulerian model of an electrospray in a host gas.

An Eulerian multifluid model is used to describe the evolution of an electrospray plume and the flow induced in the surrounding gas by the drag of the electrically charged spray droplets in the space between an injection electrode containing the electrospray source and a collector electrode. The spray is driven by the voltage applied between the two electrodes. Numerical computations and order-of-magnitude estimates for a quiescent gas show that the droplets begin to fly back toward the injection electrode at a certain critical value of the flux of droplets in the spray, which depends very much on the electrical conditions at the injection electrode. As the flux is increased toward its critical value, the electric field induced by the charge of the droplets partially balances the field due to the applied voltage in the vicinity of the injection electrode, leading to a spray that rapidly broadens at a distance from its origin of the order of the stopping distance at which the droplets lose their initial momentum and the effect of their inertia becomes negligible. The axial component of the electric field first changes sign in this region, causing the fly back. The flow induced in the gas significantly changes this picture in the conditions of typical experiments. A gas plume is induced by the drag of the droplets whose entrainment makes the radius of the spray away from the injection electrode smaller than in a quiescent gas, and convects the droplets across the region of negative axial electric field that appears around the origin of the spray when the flux of droplets is increased. This suppresses fly back and allows much higher fluxes to be reached than are possible in a quiescent gas. The limit of large droplet-to-gas mass ratio is discussed. Migration of satellite droplets to the shroud of the spray is reproduced by the Eulerian model, but this process is also affected by the motion of the gas. The gas flow preferentially pushes satellite droplets from the shroud to the core of the spray when the effect of the inertia of the droplets becomes negligible, and thus opposes the well-established electrostatic/inertial mechanism of segregation and may end up concentrating satellite droplets in an intermediate radial region of the spray.

Efficiency of electrodynamic tether thrusters

The performance efficiency of electrodynamic bare tethers acting as thrusters in low Earth orbit, as gauged by the ratio of the system mass dedicated to thrust over mission impulse, is analyzed and compared to the performance efficiency of electrical thrusters. Tether systems are much lighter for times beyond six months in space-tug operations, where there is a dedicated solar array, and beyond one month for reboost of the International Space Station, where the solar array is already in place. Bare-tether propulsive efficiency itself, with the tether considered as part of the power plant, is higher for space tugs. Tether optimization shows that thin tapes have greater propulsive efficiency and are less sensitive to plasma density variations in orbit than cylindrical tethers. The efficiency increases with tape length if some segment next to the power supply at the top is insulated to make the tether potential bias vanish at the lower end; multitape tethers must be used to keep the efficiency high at high thrust levels. The efficiency has a maximum for tether-hardware mass equal to the fraction of power-subsystem mass going into ohmic power, though the maximum is very flat. For space tugs, effects of induced-bias changes in orbit might need to be reduced by choosing a moderately large power-subsystem to tether-hardware mass ratio or by tracking the current-voltage characteristic of the solar array.

Conductive-tether design for de-orbiting from given altitude and inclination

A bare tether with thin-tape cross section is both i) the most effective electrodinamic tether for given length and mass, and ii) capable of effective design for an arbitrary mission through its three disparate dimensions. It handily beats the fully insulated tether that exchanges current at both ends, a result resting in advantages of 2D current collection as against 3D collection; it has much greater perimeter than the round bare tether and much lower fatal debris-impact rate, leading to greatly faster de-orbiting and greatly higher probability of survival; and it only allows multi-line tethers reaching a few hundred lines to stand competitive. In selecting the disparate values of length L, width w, and thickness h for a de-orbit mission, performance involves three criteria: a) tether-tospacecraft mass ratio must be small; b) probability of survival against the debris environment must be high; and c) de-orbiting must be fast to reduce manoeuvres for avoiding catastrophic collisions with big active/passive satellites around. Beyond determining tether mass through the product Lwh, main dimension parameters affecting performance are L/h2li characterizing ohmic effects, and w determining electron collection. An algorithm for optimal selection of tape dimensions is elaborated.

Extracting energy from Vortex-Induced Vibrations: A parametric study

Here, Vortex-Induced Vibrations (VIVs) of a circular cylinder are analyzed as a potential source for energy harvesting. To this end, VIV is described by a one-degree-of-freedom model where fluid forces are introduced from experimental data from forced vibration tests. The influence of some influencing parameters, like the mass ratio m∗ or the mechanical damping ζ in the energy conversion factor is investigated. The analysis reveals that: (i) the maximum efficiency ηM is principally influenced by the mass-damping parameter m∗ζ and there is an optimum value of m∗ζ where ηM presents a maximum; (ii) the range of reduced velocities with significant efficiency is mainly governed by m∗, and (iii) it seems that encouraging high efficiency values can be achieved for high Reynolds numbers.

Bare-tape scaling laws for de-orbit missions in a space debris environment

El entorno espacial actual hay un gran numero de micro-meteoritos y basura espacial generada por el hombre, lo cual plantea un riesgo para la seguridad de las operaciones en el espacio. La situación se agrava continuamente a causa de las colisiones de basura espacial en órbita, y los nuevos lanzamientos de satélites. Una parte significativa de esta basura son satélites muertos, y fragmentos de satélites resultantes de explosiones y colisiones de objetos en órbita. La mitigación de este problema se ha convertido en un tema de preocupación prioritario para todas las instituciones que participan en operaciones espaciales. Entre las soluciones existentes, las amarras electrodinámicas (EDT) proporcionan un eficiente dispositivo para el rápido de-orbitado de los satélites en órbita terrestre baja (LEO), al final de su vida útil. El campo de investigación de las amarras electrodinámicas (EDT) ha sido muy fructífero desde los años 70. Gracias a estudios teóricos, y a misiones para la demostración del funcionamiento de las amarras en órbita, esta tecnología se ha desarrollado muy rápidamente en las últimas décadas. Durante este período de investigación, se han identificado y superado múltiples problemas técnicos de diversa índole. Gran parte del funcionamiento básico del sistema EDT depende de su capacidad de supervivencia ante los micro-meteoritos y la basura espacial. Una amarra puede ser cortada completamente por una partícula cuando ésta tiene un diámetro mínimo. En caso de corte debido al impacto de partículas, una amarra en sí misma, podría ser un riesgo para otros satélites en funcionamiento. Por desgracia, tras varias demostraciones en órbita, no se ha podido concluir que este problema sea importante para el funcionamiento del sistema. En esta tesis, se presenta un análisis teórico de la capacidad de supervivencia de las amarras en el espacio. Este estudio demuestra las ventajas de las amarras de sección rectangular (cinta), en cuanto a la probabilidad de supervivencia durante la misión, frente a las amarras convencionales (cables de sección circular). Debido a su particular geometría (longitud mucho mayor que la sección transversal), una amarra puede tener un riesgo relativamente alto de ser cortado por un único impacto con una partícula de pequeñas dimensiones. Un cálculo analítico de la tasa de impactos fatales para una amarra cilindrica y de tipo cinta de igual longitud y masa, considerando el flujo de partículas de basura espacial del modelo ORDEM2000 de la NASA, muestra mayor probabilidad de supervivencia para las cintas. Dicho análisis ha sido comparado con un cálculo numérico empleando los modelos de flujo el ORDEM2000 y el MASTER2005 de ESA. Además se muestra que, para igual tiempo en órbita, una cinta tiene una probabilidad de supervivencia un orden y medio de magnitud mayor que una amarra cilindrica con igual masa y longitud. Por otra parte, de-orbitar una cinta desde una cierta altitud, es mucho más rápido, debido a su mayor perímetro que le permite capturar más corriente. Este es un factor adicional que incrementa la probabilidad de supervivencia de la cinta, al estar menos tiempo expuesta a los posibles impactos de basura espacial. Por este motivo, se puede afirmar finalmente y en sentido práctico, que la capacidad de supervivencia de la cinta es bastante alta, en comparación con la de la amarra cilindrica. El segundo objetivo de este trabajo, consiste en la elaboración de un modelo analítico, mejorando la aproximación del flujo de ORDEM2000 y MASTER2009, que permite calcular con precisión, la tasa de impacto fatal al año para una cinta en un rango de altitudes e inclinaciones, en lugar de unas condiciones particulares. Se obtiene el numero de corte por un cierto tiempo en función de la geometría de la cinta y propiedades de la órbita. Para las mismas condiciones, el modelo analítico, se compara con los resultados obtenidos del análisis numérico. Este modelo escalable ha sido esencial para la optimización del diseño de la amarra para las misiones de de-orbitado de los satélites, variando la masa del satélite y la altitud inicial de la órbita. El modelo de supervivencia se ha utilizado para construir una función objetivo con el fin de optimizar el diseño de amarras. La función objectivo es el producto del cociente entre la masa de la amarra y la del satélite y el numero de corte por un cierto tiempo. Combinando el modelo de supervivencia con una ecuación dinámica de la amarra donde aparece la fuerza de Lorentz, se elimina el tiempo y se escribe la función objetivo como función de la geometría de la cinta y las propietades de la órbita. Este modelo de optimización, condujo al desarrollo de un software, que esta en proceso de registro por parte de la UPM. La etapa final de este estudio, consiste en la estimación del número de impactos fatales, en una cinta, utilizando por primera vez una ecuación de límite balístico experimental. Esta ecuación ha sido desarollada para cintas, y permite representar los efectos tanto de la velocidad de impacto como el ángulo de impacto. Los resultados obtenidos demuestran que la cinta es altamente resistente a los impactos de basura espacial, y para una cinta con una sección transversal definida, el número de impactos críticos debidos a partículas no rastreables es significativamente menor. ABSTRACT The current space environment, consisting of man-made debris and tiny meteoroids, poses a risk to safe operations in space, and the situation is continuously deteriorating due to in-orbit debris collisions and to new satellite launches. Among these debris a significant portion is due to dead satellites and fragments of satellites resulted from explosions and in-orbit collisions. Mitigation of space debris has become an issue of first concern for all the institutions involved in space operations. Bare electrodynamic tethers (EDT) can provide an efficient mechanism for rapid de-orbiting of defunct satellites from low Earth orbit (LEO) at end of life. The research on EDT has been a fruitful field since the 70’s. Thanks to both theoretical studies and in orbit demonstration missions, this technology has been developed very fast in the following decades. During this period, several technical issues were identified and overcome. The core functionality of EDT system greatly depends on their survivability to the micrometeoroids and orbital debris, and a tether can become itself a kind of debris for other operating satellites in case of cutoff due to particle impact; however, this very issue is still inconclusive and conflicting after having a number of space demonstrations. A tether can be completely cut by debris having some minimal diameter. This thesis presents a theoretical analysis of the survivability of tethers in space. The study demonstrates the advantages of tape tethers over conventional round wires particularly on the survivability during the mission. Because of its particular geometry (length very much larger than cross-sectional dimensions), a tether may have a relatively high risk of being severed by the single impact of small debris. As a first approach to the problem, survival probability has been compared for a round and a tape tether of equal mass and length. The rates of fatal impact of orbital debris on round and tape tether, evaluated with an analytical approximation to debris flux modeled by NASA’s ORDEM2000, shows much higher survival probability for tapes. A comparative numerical analysis using debris flux model ORDEM2000 and ESA’s MASTER2005 shows good agreement with the analytical result. It also shows that, for a given time in orbit, a tape has a probability of survival of about one and a half orders of magnitude higher than a round tether of equal mass and length. Because de-orbiting from a given altitude is much faster for the tape due to its larger perimeter, its probability of survival in a practical sense is quite high. As the next step, an analytical model derived in this work allows to calculate accurately the fatal impact rate per year for a tape tether. The model uses power laws for debris-size ranges, in both ORDEM2000 and MASTER2009 debris flux models, to calculate tape tether survivability at different LEO altitudes. The analytical model, which depends on tape dimensions (width, thickness) and orbital parameters (inclinations, altitudes) is then compared with fully numerical results for different orbit inclinations, altitudes and tape width for both ORDEM2000 and MASTER2009 flux data. This scalable model not only estimates the fatal impact count but has proved essential in optimizing tether design for satellite de-orbit missions varying satellite mass and initial orbital altitude and inclination. Within the frame of this dissertation, a simple analysis has been finally presented, showing the scalable property of tape tether, thanks to the survivability model developed, that allows analyze and compare de-orbit performance for a large range of satellite mass and orbit properties. The work explicitly shows the product of tether-to-satellite mass-ratio and fatal impact count as a function of tether geometry and orbital parameters. Combining the tether dynamic equation involving Lorentz drag with space debris impact survivability model, eliminates time from the expression. Hence the product, is independent of tether de-orbit history and just depends on mission constraints and tether length, width and thickness. This optimization model finally led to the development of a friendly software tool named BETsMA, currently in process of registration by UPM. For the final step, an estimation of fatal impact rate on a tape tether has been done, using for the first time an experimental ballistic limit equation that was derived for tapes and accounts for the effects of both the impact velocity and impact angle. It is shown that tape tethers are highly resistant to space debris impacts and considering a tape tether with a defined cross section, the number of critical events due to impact with non-trackable debris is always significantly low.

Optimum sizing of bare-tape tethers for de-orbiting satellites at end of mission

De-orbiting satellites at end of mission would prevent generation of new space debris. A proposed de-orbit technology involves a bare conductive tape-tether, which uses neither propellant nor power supply while generating power for on-board use during de-orbiting. The present work shows how to select tape dimensions for a generic mission so as to satisfy requirements of very small tether-to-satellite mass ratio mt/MS and probability Nf of tether cut by small debris, while keeping de-orbit time tf short and product tf ×× tether length low to reduce maneuvers in avoiding collisions with large debris. Design is here discussed for particular missions (initial orbit of 720 km altitude and 63° and 92° inclinations, and 3 disparate MS values, 37.5, 375, and 3750 kg), proving it scalable. At mid-inclination and a mass-ratio of a few percent, de-orbit time takes about 2 weeks and Nf is a small fraction of 1%, with tape dimensions ranging from 1 to 6 cm, 10 to 54 μμm, and 2.8 to 8.6 km. Performance drop from middle to high inclination proved moderate: if allowing for twice as large mt/MS, increases are reduced to a factor of 4 in tf and a slight one in Nf, except for multi-ton satellites, somewhat more requiring because efficient orbital-motion-limited electron collection restricts tape-width values, resulting in tape length (slightly) increasing too.

Propellantless deorbiting of space debris by bare electrodynamic tethers : final report

A Space tether is a thin, multi-kilometers long conductive wire, joining a satellite and some opposite end mass, and keeping vertical in orbit by the gravity-gradient. The ambient plasma, being highly conductive, is equipotential in its own co-moving frame. In the tether frame, in relative motion however, there is in the plasma a motional electric field of order of 100 V/km, product of (near) orbital velocity and geomagnetic field. The electromotive force established over the tether length allows plasma contactor devices to collect electrons at one polarized-positive (anodic) end and eject electrons at the opposite end, setting up a current along a standard, fully insulated tether. The Lorentz force exerted on the current by the geomagnetic field itself is always drag; this relies on just thermodynamics, like air drag. The bare tether concept, introduced in 1992 at the Universidad Politécnica de Madrid (UPM), takes away the insulation and has electrons collected over the tether segment coming out polarized positive; the concept rests on 2D (Langmuir probe) current-collection in plasmas being greatly more efficient than 3D collection. A Plasma Contactor ejects electrons at the cathodic end. A bare tether with a thin-tape cross section has much greater perimeter and de-orbits much faster than a (corresponding) round bare tether of equal length and mass. Further, tethers being long and thin, they are prone to cuts by abundant small space debris, but BETs has shown that the tape has a probability of being cut per unit time smaller by more than one order of magnitude than the corresponding round tether (debris comparable to its width are much less abundant than debris comparable to the radius of the corresponding round tether). Also, the tape collects much more current, and de-orbits much faster, than a corresponding multi-line “tape” made of thin round wires cross-connected to survive debris cuts. Tethers use a dissipative mechanism quite different from air drag and can de-orbit in just a few months; also, tape tethers are much lighter than round tethers of equal length and perimeter, which can capture equal current. The 3 disparate tape dimensions allow easily scalable design. Switching the cathodic Contactor off-on allows maneuvering to avoid catastrophic collisions with big tracked debris. Lorentz braking is as reliable as air drag. Tethers are still reasonably effective at high inclinations, where the motional field is small, because the geomagnetic field is not just a dipole along the Earth polar axis. BETs is the EC FP7/Space Project 262972, financed in about 1.8 million euros, from 1 November 2010 to 31 January 2014, and carrying out RTD work on de-orbiting space debris. Coordinated by UPM, it has partners Università di Padova, ONERA-Toulouse, Colorado State University, SME Emxys, DLR–Bremen, and Fundación Tecnalia. BETs work involves 1) Designing, building, and ground-testing basic hardware subsystems Cathodic Plasma Contactor, Tether Deployment Mechanism, Power Control Module, and Tape with crosswise and lengthwise structure. 2) Testing current collection and verifying tether dynamical stability. 3) Preliminary design of tape dimensions for a generic mission, conducive to low system-to-satellite mass ratio and probability of cut by small debris, and ohmic-effects regime of tether current for fast de-orbiting. Reaching TRL 4-5, BETs appears ready for in-orbit demostration.

From tropics to tundra: Global convergence in plant functioning

Despite striking differences in climate, soils, and evolutionary history among diverse biomes ranging from tropical and temperate forests to alpine tundra and desert, we found similar interspecific relationships among leaf structure and function and plant growth in all biomes. Our results thus demonstrate convergent evolution and global generality in plant functioning, despite the enormous diversity of plant species and biomes. For 280 plant species from two global data sets, we found that potential carbon gain (photosynthesis) and carbon loss (respiration) increase in similar proportion with decreasing leaf life-span, increasing leaf nitrogen concentration, and increasing leaf surface area-to-mass ratio. Productivity of individual plants and of leaves in vegetation canopies also changes in constant proportion to leaf life-span and surface area-to-mass ratio. These global plant functional relationships have significant implications for global scale modeling of vegetation–atmosphere CO2 exchange.

Avaliação de elementos potencialmente tóxicos em tintas

Neste trabalho são apresentados os resultados da determinação, por ICP OES, de elementos tóxicos e/ou potencialmente tóxicos (AI, Cr, Ni, Cu, Cd, As, Co e Pb) em tintas de acabamento imobiliário à base de água ou de solvente orgânico. Foram desenvolvidas e comparadas método de digestão de amostras utilizando diferentes misturas ácidas em bombas de decomposição, em fomo de microondas (sistema com radiação focalizada e com cavidade) e método de cinzas. O Método de digestão utilizando fomo de microondas com cavidade permitiu solubilização rápida e eficiente de todos os tipos de tintas testados, em tempo inferior a 35 minutos. As método apresentaram valores aceitáveis para a maioria dos elementos nos testes de adição e recuperação dos analitos. Os resíduos resultantes da digestão foram avaliados por MEV-EDS e não apresentaram os elementos estudados, comprovando a eficiência da metodologia. Mercúrio foi determinado usando um Analisador Direto de Mercúrio (DMA) e apresentou valores entre 43,0 ± 4,5 e 188 ± 9 µg Kg-1, valor considerado baixo quando comparado ao limite de 100 mg Kg-1, estabelecido na norma NRR 10004 para disposição de resíduos sólidos sem instalações especiais. O estudo da migração dos elementos para o ambiente após a exposição da tinta a agentes \"agressores\" , como raios ultravioletas e umidade, foi realizado usando câmara do tipo \"Weather-Ometer\" (envelhecimento acelerado). A avaliação dos resultados foi feita por MEV EDS e ICP OES. As micrografias de MEV mostraram que houve mudança na morfologia do polímero que foi submetido ao intemperismo acelerado. Os resultados obtidos não foram conclusivos quanto à migração dos analitos em função da baixa razão entre as massas degradada e não degradada das amostras. Uma proposta de metodologia para a avaliação por ICP OES das tintas e da disponibilidade de elementos tóxicos e potencialmente tóxicos, baseada na lixiviação de amostras secas em ambiente controlado é apresentada. São mostrados resultados de lixiviação de AI, Cr, Ni, Cu, Cd, As, Co e Pb com vários extratores e tempos diferentes de extração. Os resultados mostram que ocorre a migração de alguns elementos para as soluções estudadas e que, dos extratores avaliados, a chuva ácida apresentou maior potencial de lixiviação.

Desenvolvimento da modelagem de turbulência e interação fluido-estrutura para as vibrações induzidas por vórtices de cilindro rígido.

Esta tese apresenta o desenvolvimento e aplicação de modelos de turbulência, transição laminar-turbulenta e de interações fluido-estrutura ao escoamento externo em cilindro rígido estacionário e em vibrações induzidas por vórtices. Tais desenvolvimentos foram realizados no código ReFRESCO, baseado em técnicas de dinâmica de fluidos computacional (CFD). Realizou-se um estudo quanto ao desempenho do modelo k- SST em extensa faixa de números de Reynolds, segundo o qual se identificaram as deficiências de modelagem para este escoamento. A modelagem adaptativa das escalas (SAS) e o modelo de transição por correlações locais (LCTM), ambos combinados ao SST, melhoraram a aderência aos resultados experimentais para este escoamento, em uma contribuição original deste trabalho. A aplicação de técnicas de verificação e validação possibilitou a estimação de incertezas e erros para os modelos e números de Reynolds e também de identificada como outra contribuição deste trabalho. A combinação da modelagem em SST, SAS e LCTM com movimentos impostos de realizada para números de Reynolds moderados, diferentes frequências e amplitudes de vibração, algo que poucas publicações abordam em detalhes. Com relação aos movimentos livres, este trabalho traz contribuições com a aplicação dos modelos SST e SAS ao estudo de vibrações induzidas por vórtices em dois graus de liberdade, baixa razão de massa e números de Reynolds moderados, mais altos do que normalmente observados na literatura. Por fim, a investigação da importância relativa de efeitos da turbulência aos casos de movimentos livres e impostos, com relação ao caso de cilindro estacionário, comprovou a conjetura formulada na parte inicial deste trabalho, no que tange à escolha do modelo de turbulência em determinadas aplicações. Tal escolha mostrou-se menos decisiva no caso do cilindro em movimento imposto e ainda menos nos movimentos livres, em comparação ao caso estacionário, uma vez que a resposta em movimentos do corpo filtra grande parte dos efeitos turbulentos de ordem superior. Esta observação mostra-se relevante, uma vez que pode permitir simplificações na modelagem e aplicação de ferramentas de CFD em uma classe importante de projetos de engenharia.

A VLT/FLAMES survey for massive binaries in Westerlund 1. III. The WC9d binary W239 and implications for massive stellar evolution

Context. There is growing evidence that a treatment of binarity amongst OB stars is essential for a full theory of stellar evolution. However the binary properties of massive stars – frequency, mass ratio & orbital separation – are still poorly constrained. Aims. In order to address this shortcoming we have undertaken a multiepoch spectroscopic study of the stellar population of the young massive cluster Westerlund 1. In this paper we present an investigation into the nature of the dusty Wolf-Rayet star and candidate binary W239. Methods. To accomplish this we have utilised our spectroscopic data in conjunction with multi-year optical and near-IR photometric observations in order to search for binary signatures. Comparison of these data to synthetic non-LTE model atmosphere spectra were used to derive the fundamental properties of the WC9 primary. Results. We found W239 to have an orbital period of only ~5.05 days, making it one of the most compact WC binaries yet identified. Analysis of the long term near-IR lightcurve reveals a significant flare between 2004-6. We interpret this as evidence for a third massive stellar component in the system in a long period (>6 yr), eccentric orbit, with dust production occuring at periastron leading to the flare. The presence of a near-IR excess characteristic of hot (~1300 K) dust at every epoch is consistent with the expectation that the subset of persistent dust forming WC stars are short (<1 yr) period binaries, although confirmation will require further observations. Non-LTE model atmosphere analysis of the spectrum reveals the physical properties of the WC9 component to be fully consistent with other Galactic examples. Conclusions. The simultaneous presence of both short period Wolf-Rayet binaries and cool hypergiants within Wd 1 provides compelling evidence for a bifurcation in the post-Main Sequence evolution of massive stars due to binarity. Short period O+OB binaries will evolve directly to the Wolf-Rayet phase, either due to an episode of binary mediated mass loss – likely via case A mass transfer or a contact configuration – or via chemically homogenous evolution. Conversely, long period binaries and single stars will instead undergo a red loop across the HR diagram via a cool hypergiant phase. Future analysis of the full spectroscopic dataset for Wd 1 will constrain the proportion of massive stars experiencing each pathway; hence quantifying the importance of binarity in massive stellar evolution up to and beyond supernova and the resultant production of relativistic remnants.

Biodiesel production by transesterification of sludge in supercritical conditions

In this study wastewater treatment plant (WWTP) sludge was subjected to a reactive pyrolysis treatment to produce a high quality pyro-oil. Sludge was treated in supercritical conditions in the presence of methanol using hexane as cosolvent in a high pressure lab-autoclave. The variables affecting the pyro-oil yield and the product quality, such as mass ratio of alcohol to sludge, presence of cosolvent and temperature, were investigated. It was found that the use of a non-polar cosolvent (hexane) presents advantages in the production of high quality pyro-oil from sludge: increase of the non-polar pyro-oil yield and a considerable reduction of the amount of methanol needed to carry out the transesterification of fatty acids present in the sludge.

Hybrid magnetic graphitic nanocomposites for catalytic wet peroxide oxidation applications

Hybrid magnetic graphitic nanocomposites (MGNC) prepared by inclusion of magnetite nanoparticles (obtained by coprecipitation) into an organic-organic self-assembly system, followed by calcination, revealed high activity for the catalytic wet peroxide oxidation (CWPO) of 4-nitrophenol solutions (5 g L-l), with pollutant removais up to 1245 mg g-' h-l being obtained when considering the mass ratio [pollutant]/[catalyst] =10. The stability of the MGNC catalyst against metal leaching was ascribed to the confinement effect of the carbon based material. These observations, together with the magnetically recoverable characteristics of MGNC, open new prospects for the wide use of this catalyst in highly efficient CWPO applications.

Pseudo-ternary phase diagrams of aqueous mixtures of Quil A, cholesterol and phospholipid prepared by the lipid-film hydration method

Pseudo-ternary phase diagrams of the polar lipids Quil A, cholesterol (Chol) and phosphatidylcholine (PC) in aqueous mixtures prepared by the lipid film hydration method (where dried lipid film of phospholipids and cholesterol are hydrated by an aqueous solution of Quil A) were investigated in terms of the types of particulate structures formed therein. Negative staining transmission electron microscopy and polarized light microscopy were used to characterize the colloidal and coarse dispersed particles present in the systems. Pseudo-ternary phase diagrams were established for lipid mixtures hydrated in water and in Tris buffer (pH 7.4). The effect of equilibration time was also studied with respect to systems hydrated in water where the samples were stored for 2 months at 4degreesC. Depending on the mass ratio of Quil A, Chol and PC in the systems, various colloidal particles including ISCOM matrices, liposomes, ring-like micelles and worm-like micelles were observed. Other colloidal particles were also observed as minor structures in the presence of these predominant colloids including helices, layered structures and lamellae (hexagonal pattern of ring-like micelles). In terms of the conditions which appeared to promote the formation of ISCOM matrices, the area of the phase diagrams associated with systems containing these structures increased in the order: hydrated in water/short equilibration period < hydrated in buffer/short equilibration period < hydrated in water/prolonged equilibration period. ISCOM matrices appeared to form over time from samples, which initially contained a high concentration of ring-like micelles suggesting that these colloidal structures may be precursors to ISCOM matrix formation. Helices were also frequently found in samples containing ISCOM matrices as a minor colloidal structure. Equilibration time and presence of buffer salts also promoted the formation of liposomes in systems not containing Quil A. These parameters however, did not appear to significantly affect the occurrence and predominance of other structures present in the pseudo-binary systems containing Quil A. Pseudo-ternary phase diagrams of PC, Chol and Quil A are important to identify combinations which will produce different colloidal structures, particularly ISCOM matrices, by the method of lipid film hydration. Colloidal structures comprising these three components are readily prepared by hydration of dried lipid films and may have application in vaccine delivery where the functionality of ISCOMs has clearly been demonstrated. (C) 2003 Elsevier B.V. All rights reserved.

The interlayer swelling and molecular packing in organoclays

Understanding the interlayer swelling and molecular packing in organoclays is important to the formation and design of polymer nanocomposites. This paper presents recent experimental and molecular simulation studies on a variety of organoclays that show a linear relationship between the increase of d-spacing and the mass ratio between organic and clay. A denser molecular packing is observed in organoclays containing surfactants with hydroxyl-ethyl units. Moreover, our simulation results show that the head (nitrogen) groups are essentially tethered to the clay surface while the long hydrocarbon chains tend to adopt a layering structure with disordered conformation, which contrasts with the previous assumptions of either the chains lying parallel to the clay surface or being tilted at rather precise angles. (c) 2005 Elsevier Inc. All rights reserved.