Viscous-Flow Approach to In Situ Infiltration and In Vitro Saturated Hydraulic Conductivity Determination

Infiltration is dominantly gravity driven, and a viscous-flow approach was developed. Laminar film flow equilibrates gravity with the viscous force and a constant flow velocity evolves during a period lasting 3/2 times the duration of a constant input rate, qS. Film thickness F and the specific contact area L of the film per unit soil volume are the key parameters. Sprinkler irrigation produced in situ time series of volumetric water contents, θ(z,t), as determined with TDR probes. The wetting front velocity v and the time series of the mobile water content, w(z,t) were deduced from θ(z,t). In vitro steady flow in a core of saturated soil provided volume flux density, q(z,t), and flow velocity, v, as determined from a heat front velocity. The F and L parameters of the in situ and the in vitro experiments were compared. The macropore-flow restriction states that, for a particular permeable medium, the specific contact area L must be independent from qS i.e., dL/dqS = 0. If true, then the relationship of qS ∝ v3/2 could scale a wide range of input rates 0 ≤ qS ≤ saturated hydraulic conductivity, Ksat, into a permeable medium, and kinematic-wave theory would become a versatile tool to deal with non-equilibrium flow. The viscous-flow approach is based on hydromechanical principles similar to Darcy’s law, but currently it is not suited to deduce flow properties from specified individual spatial structures of permeable media.

Investigation of robotics-assisted tilt table technology for cardiopulmonary exercise testing in stroke patients

Due to the lack of exercise testing devices that can be employed in stroke patients with severe disability, the aim of this PhD research was to investigate the clinical feasibility of using a robotics-assisted tilt table (RATT) as a method for cardiopulmonary exercise testing (CPET) and exercise training in stroke patients. For this purpose, the RATT was augmented with force sensors, a visual feedback system and a work rate calculation algorithm. As the RATT had not been used previously for CPET, the first phase of this project focused on a feasibility study in 11 healthy able-bodied subjects. The results demonstrated substantial cardiopulmonary responses, no complications were found, and the method was deemed feasible. The second phase was to analyse validity and test-retest reliability of the primary CPET parameters obtained from the RATT in 18 healthy able-bodied subjects and to compare the outcomes to those obtained from standard exercise testing devices (a cycle ergometer and a treadmill). The results demonstrated that peak oxygen uptake (V'O2peak) and oxygen uptake at the submaximal exercise thresholds on the RATT were ̴20% lower than for the cycle ergometer and ̴30% lower than on the treadmill. A very high correlation was found between the RATT vs the cycle ergometer V'O2peak and the RATT vs the treadmill V'O2peak. Test-retest reliability of CPET parameters obtained from the RATT were similarly high to those for standard exercise testing devices. These findings suggested that the RATT is a valid and reliable device for CPET and that it has potential to be used in severely impaired patients. Thus, the third phase was to investigate using the RATT for CPET and exercise training in 8 severely disabled stroke patients. The method was technically implementable, well tolerated by the patients, and substantial cardiopulmonary responses were observed. Additionally, all patients could exercise at the recommended training intensity for 10 min bouts. Finally, an investigation of test-retest reliability and four-week changes in cardiopulmonary fitness was carried out in 17 stroke patients with various degrees of disability. Good to excellent test-retest reliability and repeatability were found for the main CPET variables. There was no significant difference in most CPET parameters over four weeks. In conclusion, based on the demonstrated validity, reliability and repeatability, the RATT was found to be a feasible and appropriate alternative exercise testing and training device for patients who have limitations for use of standard devices.

Growth rates and stable carbon and oxygen isotope record of corals from the Red Sea

Monthly delta18O records of 2 coral colonies (Porites cf. lutea and P. cf. nodifera) from different localities (Aqaba and Eilat) from the northern Gulf of Aqaba, Red Sea, were calibrated with recorded sea surface temperatures (SST) between 1988 and 2000. The results show high correlation coefficients between SST and delta18O. Seasonal variations of coral delta18O in both locations could explain 91% of the recorded SST. Different delta18O/SST relations from both colonies and from the same colonies were obtained, indicating that delta18O from coral skeletons were subject to an extension rate effect. Significant delta18O depletions are associated with high extension rates and higher values with low extension rates. The relation between coral skeletal delta18O and extension rate is not linear and can be described by a simple exponential model. An inverse relationship extends over extension rates from 1 to 5 mm/yr, while for more rapidly growing corals and portions of colonies the relation is constant and the extension rate does not appear to have a significant effect. We recommend that delta18O values be obtained from fast-growing corals or from portions in which the isotopic disequilibrium is fairly constant (extension rate >5 mm/yr). The results show that interspecific differences in corals may produce a significant delta18O profile offset between 2 colonies that is independent of environmental and extension-rate effects. We conclude that the rate of skeletal extension and the species of coral involved have an important influence on coral delta18O and must be considered when using delta18O records for paleoclimatic reconstructions.

Paleoceanography of sediment cores SO202-27-6 and MD01-2416

The glacial-to-Holocene evolution of subarctic Pacific surface water stratification and silicic acid (Si) dynamics is investigated based on new combined diatom oxygen (d18Odiat) and silicon (d30Sidiat) isotope records, along with new biogenic opal, subsurface foraminiferal d18O, alkenone-based sea surface temperature, sea ice, diatom, and core logging data from the NE Pacific. Our results suggest that d18Odiat values are primarily influenced by changes in freshwater discharge from the Cordilleran Ice Sheet (CIS), while corresponding d30Sidiat are primarily influenced by changes in Si supply to surface waters. Our data indicate enhanced glacial to mid Heinrich Stadial 1 (HS1) NE Pacific surface water stratification, generally limiting the Si supply to surface waters. However, we suggest that an increase in Si supply during early HS1, when surface waters were still stratified, is linked to increased North Pacific Intermediate Water formation. The coincidence between fresh surface waters during HS1 and enhanced ice-rafted debris sedimentation in the North Atlantic indicates a close link between CIS and Laurentide Ice Sheet dynamics and a dominant atmospheric control on CIS deglaciation. The Bølling/Allerød (B/A) is characterized by destratification in the subarctic Pacific and an increased supply of saline, Si-rich waters to surface waters. This change toward increased convection occurred prior to the Bølling warming and is likely triggered by a switch to sea ice-free conditions during late HS1. Our results furthermore indicate a decreased efficiency of the biological pump during late HS1 and the B/A (possibly also the Younger Dryas), suggesting that the subarctic Pacific has then been a source region of atmospheric CO2.

U-Th dating of marine sediments from the Bahamas slope

In order to understand the driving forces for Pleistocene climate change more fully we need to compare the timing of climate events with their possible forcing. In contrast to the last interglacial (marine isotope stage (MIS) 5) the timing of the penultimate interglacial (MIS 7) is poorly constrained. This study constrains its timing and structure by precise U-Th dating of high-resolution delta18O records from aragonite-rich Bahamian slope sediments of ODP Leg 166 (Sites 1008 and 1009). The major glacial-interglacial cycles in delta18O are distinct within these cores and some MIS 7 substages can be identified. These sediments are well suited for U-Th dating because they have uranium concentrations of up to 12 ppm and very low initial 230Th contributions with most samples showing 230Th/232Th activity ratio of >75. U and Th concentrations and isotope ratios were measured by thermal ionisation mass spectrometry and multiple collector inductively coupled plasma mass spectrometry, with the latter providing dramatically better precision. Twenty-nine of the 41 samples measured have a delta234U value close to modern seawater suggesting that they have experienced little diagenesis. Ages from 27 of the 41 samples were deemed reliable on the basis of both their U and their Th isotope ratios. Ages generally increase with depth, although we see a repeated section of stratigraphy in one core. Extrapolation of constant sedimentation rate through each substage suggests that the peak of MIS 7e lasted from ~237 to 228 ka and that 7c began at 215 ka. This timing is consistent with existing low precision radiometric dates from speleothem deposits. The beginning of both these substages appears to be slightly later than in orbitally tuned timescales. The end of MIS 7 is complex, but also appears to be somewhat later than is suggested by orbitally tuned timescales, although this event is not particularly well defined in these cores.

Recrystallization of amorphous nano-tracks and uniform layers generated by swift-ion-beam irradiation in lithium niobate.

The thermal annealing of amorphous tracks of nanometer-size diameter generated in lithium niobate (LiNbO3) by Bromine ions at 45 MeV, i.e., in the electronic stopping regime, has been investigated by RBS/C spectrometry in the temperature range from 250°C to 350°C. Relatively low fluences have been used (<1012 cm−2) to produce isolated tracks. However, the possible effect of track overlapping has been investigated by varying the fluence between 3×1011 cm−2 and 1012 cm−2. The annealing process follows a two-step kinetics. In a first stage (I) the track radius decreases linearly with the annealing time. It obeys an Arrhenius-type dependence on annealing temperature with activation energy around 1.5 eV. The second stage (II) operates after the track radius has decreased down to around 2.5 nm and shows a much lower radial velocity. The data for stage I appear consistent with a solid-phase epitaxial process that yields a constant recrystallization rate at the amorphous-crystalline boundary. HRTEM has been used to monitor the existence and the size of the annealed isolated tracks in the second stage. On the other hand, the thermal annealing of homogeneous (buried) amorphous layers has been investigated within the same temperature range, on samples irradiated with Fluorine at 20 MeV and fluences of ∼1014 cm−2. Optical techniques are very suitable for this case and have been used to monitor the recrystallization of the layers. The annealing process induces a displacement of the crystalline-amorphous boundary that is also linear with annealing time, and the recrystallization rates are consistent with those measured for tracks. The comparison of these data with those previously obtained for the heavily damaged (amorphous) layers produced by elastic nuclear collisions is summarily discussed.

Pulsating emission of droplets from an electrified meniscus.

A numerical description is given for the pulsating emission of droplets from an electrified meniscus of an inviscid liquid of infinite electrical conductivity which is injected at a constant flow rate into a region of uniform, continuous or time periodic, electric field. Under a continuous field, the meniscus attains a periodic regime in which bursts of tiny droplets are emitted from its tip. At low electric fields this regime consists of sequences of emission bursts interspersed with sequences of meniscus oscillations without droplet emission, while at higher fields the bursts occur periodically. These results are in qualitative agreement with experimental results in the literature. Under a time periodic electric field with square waveform, the electric stress that acts on the surface of the liquid while the field is on may generate a tip that emits tiny droplets or may accelerate part of the meniscus and lead to a second emission mode in which a few large droplets are emitted after the electric field is turned off. Conditions under which each emission mode or a combination of the two are realized are discussed for low frequency oscillatory fields. A simplified model is proposed for high electric field frequencies, of the order of the capillary frequency of the meniscus. This model allows computing the average emission rate as a function of the amplitude, duration and bias of the electric field square wave, and shows that droplet emission fails to follow the applied field above a certain frequency

Effect of Stress Level on the High Temperature Deformation and Fracture Mechanisms of Ti-45Al-2Nb-2Mn-0.8 vol. pct TiB2: An In Situ Experimental Study

The effect of the applied stress on the deformation and crack nucleation and propagation mechanisms of a c-TiAl intermetallic alloy (Ti-45Al-2Nb-2Mn (at. pct)-0.8 vol. pct TiB2) was examined by means of in situ tensile (constant strain rate) and tensile-creep (constant load) experiments performed at 973 K (700 �C) using a scanning electron microscope. Colony boundary cracking developed during the secondary stage in creep tests at 300 and 400 MPa and during the tertiary stage of the creep tests performed at higher stresses. Colony boundary cracking was also observed in the constant strain rate tensile test. Interlamellar ledges were only found during the tensile-creep tests at high stresses (r>400 MPa) and during the constant strain rate tensile test. Quantitative measurements of the nature of the crack propagation path along secondary cracks and along the primary crack indicated that colony boundaries were preferential sites for crack propagation under all the conditions investigated. The frequency of interlamellar cracking increased with stress, but this fracture mechanism was always of secondary importance. Translamellar cracking was only observed along the primary crack.

Análisis y simulación numérica de problemas electrohidrodinámicos relacionados con el electrospray

La presente tesis es un estudio analítico y numérico del electrospray. En la configuración más sencilla, un caudal constante del líquido a atomizar, que debe tener una cierta conductividad eléctrica, se inyecta en un medio dieléctrico (un gas u otro líquido inmiscible con el primero) a través de un tubo capilar metálico. Entre este tubo y un electrodo lejano se aplica un voltaje continuo que origina un campo eléctrico en el líquido conductor y en el espacio que lo rodea. El campo eléctrico induce una corriente eléctrica en el líquido, que acumula carga en su superficie, y da lugar a un esfuerzo eléctrico sobre la superficie, que tiende a alargarla en la dirección del campo eléctrico. El líquido forma un menisco en el extremo del tubo capilar cuando el campo eléctrico es suficientemente intenso y el caudal suficientemente pequeño. Las variaciones de presión y los esfuerzos viscosos asociados al movimiento del líquido son despreciables en la mayor parte de este menisco, siendo dominantes los esfuerzos eléctrico y de tensión superficial que actúan sobre la superficie del líquido. En el modo de funcionamiento llamado de conochorro, el balance de estos esfuerzos hace que el menisco adopte una forma cónica (el cono de Taylor) en una región intermedia entre el extremo del tubo y la punta del menisco. La velocidad del líquido aumenta al acercarse al vértice del cono, lo cual propicia que las variaciones de la presión en el líquido generadas por la inercia o por la viscosidad entren en juego, desequilibrando el balance de esfuerzos mencionado antes. Como consecuencia, del vértice del cono sale un delgado chorro de líquido, que transporta la carga eléctrica que se acumula en la superficie. La acción del campo eléctrico tangente a la superficie sobre esta carga origina una tracción eléctrica que tiende a alargar el chorro. Esta tracción no es relevante en el menisco, donde el campo eléctrico tangente a la superficie es muy pequeño, pero se hace importante en el chorro, donde es la causa del movimiento del líquido. Lejos del cono, el chorro puede o bien desarrollar una inestabilidad asimétrica que lo transforma en una espiral (whipping) o bien romperse en un spray de gotas prácticamente monodispersas cargadas eléctricamente. La corriente eléctrica transportada por el líquido es la suma de la corriente de conducción en el interior del líquido y la corriente debida a la convección de la carga acumulada en su superficie. La primera domina en el menisco y la segunda en el chorro lejano, mientras que las dos son comparables en una región intermedia de transferencia de corriente situada al comienzo del chorro aunque aguas abajo de la región de transición cono-chorro, en la que el menisco deja de ser un cono de Taylor. Para un campo exterior dado, la acumulación de carga eléctrica en la superficie del líquido reduce el campo eléctrico en el interior del mismo, que llega a anularse cuando la carga alcanza un estado final de equilibrio. El tiempo característico de este proceso es el tiempo de relajación dieléctrica, que es una propiedad del líquido. Cuando el tiempo de residencia del líquido en la región de transición cono-chorro (o en otra región del campo fluido) es grande frente al tiempo de relajación dieléctrica, la carga superficial sigue una sucesión de estados de equilibrio y apantalla al líquido del campo exterior. Cuando esta condición deja de cumplirse, aparecen efectos de relajación de carga, que se traducen en que el campo exterior penetra en el líquido, a no ser que su constante dieléctrica sea muy alta, en cuyo caso el campo inducido por la carga de polarización evita la entrada del campo exterior en el menisco y en una cierta región del chorro. La carga eléctrica en equilibrio en la superficie de un menisco cónico intensifica el campo eléctrico y determina su variación espacial hasta distancias aguas abajo del menisco del orden de su tamaño. Este campo, calculado por Taylor, es independiente del voltaje aplicado, por lo que las condiciones locales del flujo y el valor de la corriente eléctrica son también independientes del voltaje en tanto los tamaños de las regiones que determinan estas propiedades sean pequeños frente al tamaño del menisco. Los resultados experimentales publicados en la literatura muestran que existe un caudal mínimo para el que el modo cono-chorro que acabamos de describir deja de existir. El valor medio y la desviación típica de la distribución de tamaños de las gotas generadas por un electrospray son mínimos cuando se opera cerca del caudal mínimo. A pesar de que los mecanismos responsables del caudal mínimo han sido muy estudiados, no hay aún una teoría completa del mismo, si bien su existencia parece estar ligada a la aparición de efectos de relajación de carga en la región de transición cono-chorro. En esta tesis, se presentan estimaciones de orden de magnitud, algunas existentes y otras nuevas, que muestran los balances dominantes responsables de las distintas regiones de la estructura asintótica de la solución en varios casos de interés. Cuando la inercia del líquido juega un papel en la transición cono-chorro, los resultados muestran que la región de transferencia de corriente, donde la mayor parte de la corriente pasa a la superficie, está en el chorro aguas abajo de la región de transición cono-chorro. Los efectos de relajación de carga aparecen de forma simultánea en el chorro y la región de transición cuando el caudal se disminuye hasta valores de un cierto orden. Para caudales aún menores, los efectos de relajación de carga se notan en el menisco, en una región grande comparada con la de transición cono-chorro. Cuando el efecto de las fuerzas de viscosidad es dominante en la región de transición, la región de transferencia de corriente está en el chorro pero muy próxima a la región de transición cono-chorro. Al ir disminuyendo el caudal, los efectos de relajación de carga aparecen progresivamente en el chorro, en la región de transición y por último en el menisco. Cuando el caudal es mucho mayor que el mínimo del modo cono-chorro, el menisco deja de ser cónico. El campo eléctrico debido al voltaje aplicado domina en la región de transferencia de corriente, y tanto la corriente eléctrica como el tamaño de las diferentes regiones del problema pasan a depender del voltaje aplicado. Como resultado de esta dependencia, el plano caudal-voltaje se divide en diferentes regiones que se analizan separadamente. Para caudales suficientemente grandes, la inercia del líquido termina dominando frente a las fuerzas de la viscosidad. Estos resultados teóricos se han validado con simulaciones numéricas. Para ello se ha formulado un modelo simplificado del flujo, el campo eléctrico y el transporte de carga en el menisco y el chorro del electrospray. El movimiento del líquido se supone casi unidireccional y se describe usando la aproximación de Cosserat para un chorro esbelto. Esta aproximación, ampliamente usada en la literatura, permite simular con relativa facilidad múltiples casos y cubrir amplios rangos de valores de los parámetros reteniendo los efectos de la viscosidad y la inercia del líquido. Los campos eléctricos dentro y fuera del liquido están acoplados y se calculan sin simplificación alguna usando un método de elementos de contorno. La solución estacionaria del problema se calcula mediante un método iterativo. Para explorar el espacio de los parámetros, se comienza calculando una solución para valores fijos de las propiedades del líquido, el voltaje aplicado y el caudal. A continuación, se usa un método de continuación que permite delinear la frontera del dominio de existencia del modo cono-chorro, donde el método iterativo deja de converger. Cuando el efecto de la inercia del líquido domina en la región de transición cono-chorro, el caudal mínimo para el cual el método iterativo deja de converger es del orden del valor estimado del caudal para el que comienza a haber efectos de relajación de carga en el chorro y el cono. Aunque las simulaciones no convergen por debajo de dicho caudal, el valor de la corriente eléctrica para valores del caudal ligeramente mayores parece ajustarse a las estimaciones para caudales menores, reflejando un posible cambio en los balances aplicables. Por el contrario, cuando las fuerzas viscosas dominan en la región de transición, se pueden obtener soluciones estacionarias para caudales bastante menores que aquel para el que aparecen efectos de relajación de carga en la región de transición cono-chorro. Los resultados numéricos obtenidos para estos pequeños caudales se ajustan perfectamente a las estimaciones de orden de magnitud que se describen en la memoria. Por último, se incluyen como anexos dos estudios teóricos que han surgido de forma natural durante el desarrollo de la tesis. El primero hace referencia a la singularidad en el campo eléctrico que aparece en la línea de contacto entre el líquido y el tubo capilar en la mayoría de las simulaciones. Primero se estudia en qué situaciones el campo eléctrico tiende a infinito en la línea de contacto. Después, se comprueba que dicha singularidad no supone un fallo en la descripción del problema y que además no afecta a la solución lejos de la línea de contacto. También se analiza si los esfuerzos eléctricos infinitamente grandes a los que da lugar dicha singularidad pueden ser compensados por el resto de esfuerzos que actúan en la superficie del líquido. El segundo estudio busca determinar el tamaño de la región de apantallamiento en un chorro de líquido dieléctrico sin carga superficial. En esta región, el campo exterior es compensado parcialmente por el campo que induce la carga de polarización en la superficie del líquido, de forma que en el interior del líquido el campo eléctrico es mucho menor que en el exterior. Una región como ésta aparece en las estimaciones cuando los efectos de relajación de carga son importantes en la región de transferencia de corriente en el chorro. ABSTRACT This aim of this dissertation is a theoretical and numerical analysis of an electrospray. In its most simple configuration, a constant flow rate of the liquid to be atomized, which has to be an electrical conductor, is injected into a dielectric medium (a gas or another inmiscible fluid) through a metallic capillary tube. A constant voltage is applied between this tube and a distant electrode that produces an electric field in the liquid and the surrounding medium. This electric field induces an electric current in the liquid that accumulates charge at its surface and leads to electric stresses that stretch the surface in the direction of the electric field. A meniscus appears on the end of the capillary tube when the electric field is sufficiently high and the flow rate is small. Pressure variations and viscous stresses due to the motion of the liquid are negligible in most of the meniscus, where normal electric and surface tension stresses acting on the surface are dominant. In the so-called cone-jet mode, the balance of these stresses forces the surface to adopt a conical shape -Taylor cone- in a intermediate region between the end of the tube and the tip of the meniscus. When approaching the cone apex, the velocity of the liquid increases and leads to pressure variations that eventually disturb the balance of surfaces tension and electric stresses. A thin jet emerges then from the tip of the meniscus that transports the charge accumulated at its surface. The electric field tangent to the surface of the jet acts on this charge and continuously stretches the jet. This electric force is negligible in the meniscus, where the component of the electric field tangent to the surface is small, but becomes very important in the jet. Far from the cone, the jet can either develop an asymmetrical instability named “whipping”, whereby the jet winds into a spiral, or break into a spray of small, nearly monodisperse, charged droplets. The electric current transported by the liquid has two components, the conduction current in the bulk of the liquid and the convection current due to the transport of the surface charge by the flow. The first component dominates in the meniscus, the second one in the far jet, and both are comparable in a current transfer region located in the jet downstream of the cone-jet transition region where the meniscus ceases to be a Taylor cone. Given an external electric field, the charge that accumulates at the surface of the liquid reduces the electric field inside the liquid, until an equilibrium is reached in which the electric field induced by the surface charge counters the external electric field and shields the liquid from this field. The characteristic time of this process is the electric relaxation time, which is a property of the liquid. When the residence time of the liquid in the cone-jet transition region (or in other region of the flow) is greater than the electric relaxation time, the surface charge follows a succession of equilibrium states and continuously shield the liquid from the external field. When this condition is not satisfied, charge relaxation effects appear and the external field penetrates into the liquid unless the liquid permittivity is large. For very polar liquids, the field due to the polarization charge at the surface prevents the external field from entering the liquid in the cone and in certain region of the jet. The charge at the surface of a conical meniscus intensifies the electric field around the cone, determining its spatial variation up to distances downstream of the apex of the order of the size of the meniscus. This electric field, first computed by Taylor, is independent of the applied voltage. Therefore local flow characteristics and the electric current carried by the jet are also independent of the applied voltage provided the size of the regions that determine these magnitudes are small compared with the size of the meniscus. Many experiments in the literature show the existence of a minimum flow rate below which the cone-jet mode cannot be established. The mean value and the standard deviation of the electrospray droplet size distribution are minimum when the device is operated near the minimum flow rate. There is no complete explanation of the minimum flow rate, even though possible mechanisms have been extensively studied. The existence of a minimum flow rate seems to be connected with the appearance of charge relaxation effects in the transition region. In this dissertation, order of magnitude estimations are worked out that show the dominant balances in the different regions of the asymptotic structure of the solution for different conditions of interest. When the inertia of the liquid plays a role in the cone-jet transition region, the region where most of the electric current is transfered to the surface lies in the jet downstream the cone-jet transition region. When the flow rate decreases to a certain value, charge relaxation effects appear simultaneously in the jet and in the transition region. For smaller values of the flow rate, charge relaxation effects are important in a region of the meniscus larger than the transition region. When viscous forces dominate in the flow in the cone-jet transition region, the current transfer region is located in the jet immediately after the transition region. When flow rate is decreased, charge relaxation effects appears gradually, first in the jet, then in the transition region, and finally in the meniscus. When flow rate is much larger than the cone-jet mode minimum, the meniscus ceases to be a cone. The electric current and the structure of the solution begin to depend on the applied voltage. The flow rate-voltage plane splits into different regions that are analyzed separately. For sufficiently large flow rates, the effect of the inertia of the liquid always becomes greater than the effect of the viscous forces. A set of numerical simulations have been carried out in order to validate the theoretical results. A simplified model of the problem has been devised to compute the flow, the electric field and the surface charge in the meniscus and the jet of an electrospray. The motion of the liquid is assumed to be quasi-unidirectional and described by Cosserat’s approximation for a slender jet. This widely used approximation allows to easily compute multiple configurations and to explore wide ranges of values of the governing parameters, retaining the effects of the viscosity and the inertia of the liquid. Electric fields inside and outside the liquid are coupled and are computed without any simplification using a boundary elements method. The stationary solution of the problem is obtained by means of an iterative method. To explore the parameter space, a solution is first computed for a set of values of the liquid properties, the flow rate and the applied voltage, an then a continuation method is used to find the boundaries of the cone-jet mode domain of existence, where the iterative method ceases to converge. When the inertia of the liquid dominates in the cone-jet transition region, the iterative method ceases to converge for values of the flow rate for which order-of-magnitude estimates first predict charge relaxation effects to be important in the cone and the jet. The electric current computed for values of the flow rate slightly above the minimum for which convergence is obtained seems to agree with estimates worked out for lower flow rates. When viscous forces dominate in the transition region, stationary solutions can be obtained for flow rates significantly smaller than the one for which charge relaxation effects first appear in the transition region. Numerical results obtained for those small values of the flow rate agree with our order of magnitude estimates. Theoretical analyses of two issues that have arisen naturally during the thesis are summarized in two appendices. The first appendix contains a study of the singularity of the electric field that most of the simulations show at the contact line between the liquid and the capillary tube. The electric field near the contact line is analyzed to determine the ranges of geometrical configurations and liquid permittivity where a singularity appears. Further estimates show that this singularity does not entail a failure in the description of the problem and does not affect the solution far from the contact line. The infinite electric stresses that appear at the contact line can be effectively balanced by surface tension. The second appendix contains an analysis of the size and slenderness of the shielded region of a dielectric liquid in the absence of free surface charge. In this region, the external electric field is partially offset by the polarization charge so that the inner electric field is much lower than the outer one. A similar region appears in the estimates when charge relaxation effects are important in the current transfer region.

Time-motion analysis on Chinese male field hockey players

The aim of the study was to evaluate the match work-rate of Chinese field hockey players by analyzing the distance covered at different intensities pooled by specific positions during different periods of matches. Thirty-eight players from twenty-four male field hockey matches at the 11th Chinese National Games were filmed and analyzed.

Time-motion analysis on Chinese male field hockey players

The aim of the study was to evaluate the match work-rate of Chinese field hockey players by analyzing the distance covered at different intensities pooled by specific positions during different periods of matches. Thirty-eight players from twenty-four male field hockey matches at the 11th Chinese National Games were filmed and analyzed.mas

Operational water balance in irrigation districts

In pressure irrigation-water distribution networks, applied water volume is usually controlled opening a valve during a calculated time interval, and assuming constant flow rate. In general, pressure regulating devices for controlling the discharged flow rate by irrigation units are needed due to the variability of pressure conditions.

Force-mediated kinetics of single P-selectin/ligand complexes observed by atomic force microscopy

Leukocytes roll along the endothelium of postcapillary venules in response to inflammatory signals. Rolling under the hydrodynamic drag forces of blood flow is mediated by the interaction between selectins and their ligands across the leukocyte and endothelial cell surfaces. Here we present force-spectroscopy experiments on single complexes of P-selectin and P-selectin glycoprotein ligand-1 by atomic force microscopy to determine the intrinsic molecular properties of this dynamic adhesion process. By modeling intermolecular and intramolecular forces as well as the adhesion probability in atomic force microscopy experiments we gain information on rupture forces, elasticity, and kinetics of the P-selectin/P-selectin glycoprotein ligand-1 interaction. The complexes are able to withstand forces up to 165 pN and show a chain-like elasticity with a molecular spring constant of 5.3 pN nm−1 and a persistence length of 0.35 nm. The dissociation constant (off-rate) varies over three orders of magnitude from 0.02 s−1 under zero force up to 15 s−1 under external applied forces. Rupture force and lifetime of the complexes are not constant, but directly depend on the applied force per unit time, which is a product of the intrinsic molecular elasticity and the external pulling velocity. The high strength of binding combined with force-dependent rate constants and high molecular elasticity are tailored to support physiological leukocyte rolling.

Investigação do mecanismo cinético da reação de redução de oxigênio em solventes não aquosos

O aumento no consumo energético e a crescente preocupação ambiental frente à emissão de gases poluentes criam um apelo mundial favorável para pesquisas de novas tecnologias não poluentes de fontes de energia. Baterias recarregáveis de lítio-ar em solventes não aquosos possuem uma alta densidade de energia teórica (5200 Wh kg-1), o que as tornam promissoras para aplicação em dispositivos estacionários e em veículos elétricos. Entretanto, muitos problemas relacionados ao cátodo necessitam ser contornados para permitir a aplicação desta tecnologia, por exemplo, a baixa reversibilidade das reações, baixa potência e instabilidades dos materiais empregados nos eletrodos e dos solventes eletrolíticos. Assim, neste trabalho um modelo cinético foi empregado para os dados experimentais de espectroscopia de impedância eletroquímica, para a obtenção das constantes cinéticas das etapas elementares do mecanismo da reação de redução de oxigênio (RRO), o que permitiu investigar a influência de parâmetros como o tipo e tamanho de partícula do eletrocatalisador, o papel do solvente utilizado na RRO e compreender melhor as reações ocorridas no cátodo dessa bateria. A investigação inicial se deu com a utilização de sistemas menos complexos como uma folha de platina ou eletrodo de carbono vítreo como eletrodos de trabalho em 1,2-dimetoxietano (DME)/perclorato de lítio (LiClO4). A seguir, sistemas complexos com a presença de nanopartículas de carbono favoreceu o processo de adsorção das moléculas de oxigênio e aumentou ligeiramente (uma ordem de magnitude) a etapa de formação de superóxido de lítio (etapa determinante de reação) quando comparada com os eletrodos de platina e carbono vítreo, atribuída à presença dos grupos laterais mediando à transferência eletrônica para as moléculas de oxigênio. No entanto, foi observada uma rápida passivação da superfície eletrocatalítica através da formação de filmes finos de Li2O2 e Li2CO3 aumentando o sobrepotencial da bateria durante a carga (diferença de potencial entre a carga e descarga > 1 V). Adicionalmente, a incorporação das nanopartículas de platina (Ptnp), ao invés da folha de platina, resultou no aumento da constante cinética da etapa determinante da reação em duas ordens de magnitude, o qual pode ser atribuído a uma mudança das propriedades eletrônicas na banda d metálica em função do tamanho nanométrico das partículas, e estas modificações contribuíram para uma melhor eficiência energética quando comparado ao sistema sem a presença de eletrocatalisador. Entretanto, as Ptnp se mostraram não específicas para a RRO, catalisando as reações de degradação do solvente eletrolítico e diminuindo rapidamente a eficiência energética do dispositivo prático, devido ao acúmulo de material no eletrodo. O emprego de líquido iônico como solvente eletrolítico, ao invés de DME, promoveu uma maior estabilização do intermediário superóxido formado na primeira etapa de transferência eletrônica, devido à interação com os cátions do líquido iônico em solução, o qual resultou em um valor de constante cinética da formação do superóxido de três ordens de magnitude maior que o obtido com o mesmo eletrodo de carbono vítreo em DME, além de diminuir as reações de degradação do solvente. Estes fatores podem contribuir para uma maior potência e ciclabilidade da bateria de lítio-ar operando com líquidos iônicos.

Efeito das farinhas de jatobá-do-cerrado (Hymenaea stigonocarpa Mart.) in natura e extrusada no metabolismo lipídico e parâmetros fermentativos em hamsters e resposta glicêmica em humanos após a extrusão

Introdução: A polpa farinácea do jatobá-do-cerrado (Hymenaea stigonocarpa Mart.) apresenta alto teor de fibra alimentar, em média 60 g/100 g, que são importantes para a redução do risco e controle de doenças crônicas não transmissíveis (DCNT). A extrusão termoplástica neutraliza aromas intensos, proporciona a formação de amido resistente, aumenta a fibra alimentar solúvel e melhora a textura do produto final. Objetivo: Estudar o efeito das farinhas de jatobá-do-cerrado in natura (FIN) e extrusada (FE) no metabolismo lipídico e parâmetros fermentativos em hamsters, bem como verificar a resposta glicêmica em humanos após a extrusão. Métodos: Processo de extrusão: velocidade de 200 rpm; matriz com 4 mm de diâmetro; taxa de compressão 3:1; alimentação constante de 70 gramas/minuto; temperatura de 150 °C; proporção farinha de jatobá-do-cerrado e amido de milho: 70:30 por cento e umidade a 25 por cento . Foi realizado um experimento animal com hamsters durante 21 dias, em que se analisou alguns parâmetros do metabolismo lipídico e colônico (fermentativos) dos animais, divididos em quatro grupos experimentais, se diferenciando pela dieta. As dietas controle (GC), in natura (GFI) e extrusada (GFE) eram hipercolesterolemizantes (13,5 por cento de gordura de coco e 0,1 por cento de colesterol) e a dieta referência (GR) com óleo de soja como fonte lipídica, não. Todas as dietas apresentavam 15 por cento de fibra alimentar, sendo que as dietas GR e GC tinham como fonte de fibra a celulose, e as dietas GFI e GFE tiveram as próprias fibras como fonte. A resposta glicêmica em humanos foi verificada por meio do ensaio do índice glicêmico e carga glicêmica da FE, com dez voluntários saudáveis que consumiram 25 gramas de carboidratos disponíveis do alimento teste (farinha extrusada) ou do pão branco como alimento controle. Resultados: Não foi observada diferença significativa entre o peso final, ingestão diária média e total, ganho de peso e CEA entre os animais dos quatro grupos. A concentração de triglicerídeos foi menor em 41 por cento e 38 por cento nos animais que receberam as dietas GFI e GFE, em relação aqueles que receberam a dieta GC, assim como também para o colesterol total (55 por cento e 47 por cento ), LDL-c (70 por cento e 53 por cento ) e não-HDL-c (63 por cento e 49 por cento ) séricos, lipídeos totais hepáticos (39 por cento e 45 por cento ) e o peso dos fígados dos animais também foi menor (21 por cento em ambos os grupos). Não houve diferença no colesterol hepático e excretado nas fezes dos animais dos quatro grupos. Os animais do GFE excretaram 57 por cento mais ácidos biliares nas fezes que os animais do GC. Com relação aos parâmetros fermentativos, observou-se maior excreção de fibras (1,24 ± 0,08 e 1,52 ± 0,09 gramas) nos animais dos grupos GR e GC respectivamente, em relação aos do GFI e GFE (0,50 e 0,48 gramas), porém o escore fecal (3,50 ± 0,19 e 3,38 ± 0,18) e o grau de fermentação (54 e 52 por cento ) foi maior nos animais dos grupos GFI e GFE. Houve uma maior produção de AGCC no ceco dos animais dos grupos GFI e GFE (80 e 57,5 µmol/g de ceco respectivamente) e maior diminuição do pH no conteúdo cecal nos animais do grupo GFI (7,49 ± 0,10), em relação ao GC (8,06 ± 0,13). Os ácidos acético e propiônico, estiveram presentes em maior quantidade no ceco dos animais dos grupos GFI (58,5 e 6,1 µmol/g de ceco) e GFE (42,5 e 6,6 µmol/g de ceco) e os animais do GFI produziram mais ácido butírico (15 µmol/g de ceco), em relação aos demais grupos. Quanto à resposta glicêmica da farinha pós extrusão, não houve diferença entre a área de resposta glicêmica da farinha extrusada e do pão branco, o índice glicêmico da farinha extrusada (glicose como controle) foi classificado como moderado, e a carga glicêmica (na porção de 30 gramas), baixa. Conclusão: As FIN e FE favoreceram a redução do colesterol total, LDL-c, não-HDL-c e dos triglicerídeos séricos, além da diminuição do acúmulo de lipídeos hepáticos. Foi observado também aumento expressivo na formação de AGCC e no grau de fermentação. A FE proporcionou um aumento na excreção de ácidos biliares nas fezes e apresentou índice glicêmico moderado e baixa carga glicêmica.