Electrostatic plasma instabilities excited by a high‐frequency electric field

The electrostatic plasma waves excited by a uniform, alternating electric field of arbitrary intensity are studied on the basis of the Vlasov equation; their dispersion relation, which involves the determinant of either of two infinite matrices, is derived. For ω0 ≫ ωpi (ω0 being the applied frequency and ωpi the ion plasma frequency) the waves may be classified in two groups, each satisfying a simple condition; this allows writing the dispersion relation in closed form. Both groups coalesce (resonance) if (a) ω0  ≈  ωpe/r (r any integer) and (b) the wavenumber k is small. A nonoscillatory instability is found; its distinction from the DuBois‐Goldman instability and its physical origin are discussed. Conditions for its excitation (in particular, upper limits to ω0,k, and k⋅vE,vE being the field‐induced electron velocity), and simple equations for the growth rate are given off‐resonance and at ω0  ≈  ωpi. The dependence of both threshold and maximum growth rate on various parameters is discussed, and the results are compared with those of Silin and Nishikawa. The threshold at ω0  ≈  ωpi/r,r  ≠  1, is studied.

Calculation of the spatial distribution of photovoltaic field by arbitrary 2D ilumination patterns en LiNbO3; application to photovoltaic particle trapping.

Patterns of evanescent photovoltaic field induced by illumination on a surface of lithium niobate (LN) have been calculated and compared with the experimental patterns of nano- and microparticles trapped by dielectrophoretic forces. A tool for this calculation has been developed. Calculo de distribución espacial de campo por efecto fotovoltaico con patrones arbitrarios de iluminación, en LiNbO3

Vortex pinning vs superconducting wire network: origin of periodic oscillations induced by applied magnetic fields in superconducting films with arrays of nanomagnets

Hybrid magnetic arrays embedded in superconducting films are ideal systems to study the competition between different physical (such as the coherence length) and structural length scales such as are available in artificially produced structures. This interplay leads to oscillation in many magnetically dependent superconducting properties such as the critical currents, resistivity and magnetization. These effects are generally analyzed using two distinct models based on vortex pinning or wire network. In this work, we show that for magnetic dot arrays, as opposed to antidot (i.e. holes) arrays, vortex pinning is the main mechanism for field induced oscillations in resistance R(H), critical current Ic(H), magnetization M(H) and ac-susceptibility χ ac(H) in a broad temperature range. Due to the coherence length divergence at Tc, a crossover to wire network behaviour is experimentally found. While pinning occurs in a wide temperature range up to Tc, wire network behaviour is only present in a very narrow temperature window close to Tc. In this temperature interval, contributions from both mechanisms are operational but can be experimentally distinguished.

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.

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.

Training-induced changes in drag-flick technique in female field hockey players

The penalty corner is one of the most important goal plays in field hockey. The drag-flick is used less by women than men in a penalty corner. The aim of this study was to describe training-induced changes in the drag-flick technique in female field hockey players. Four female players participated in the study. The VICON optoelectronic system (Oxford Metrics, Oxford, UK) measured the kinematic parameters of the drag-flick with six cameras sampling at 250 Hz, prior to and after training. Fifteen shots were captured for each subject. A Wilcoxon test assessed the differences between pre-training and post-training parameters. Two players received specific training twice a week for 8 weeks; the other two players did not train. The proposed drills improved the position of the stick at the beginning of the shot (p<0.05), the total distance of the shot (p<0.05)and the rotation radius at ball release (p<0.01). It was noted that all players had lost speed of the previous run. Further studies should include a larger sample, in order to provide more information on field hockey performance.

Rotation-Induced Breakdown of Torsional Quantum Control

Control of the torsional angles of nonrigid molecules is key for the development of emerging areas like molecular electronics and nanotechnology. Based on a rigorous calculation of the rotation-torsion-Stark energy levels of nonrigid biphenyl-like molecules, we show that, unlike previously believed, instantaneous rotation-torsion-Stark eigenstates of such molecules, interacting with a strong laser field, present a large degree of delocalization in the torsional coordinate even for the lowest energy states. This is due to a strong coupling between overall rotation and torsion leading to a breakdown of the torsional alignment. Thus, adiabatic control of changes on the planarity of this kind of molecule is essentially impossible unless the temperature is on the order of a few Kelvin.

Elastic (stress-strain) halo associated to ion-induced nano-tracks in lithium niobate: role of crystal anisotropy

The elastic strain/stress fields (halo) around a compressed amorphous nano-track (core) caused by a single high-energy ion impact on LiNbO3 are calculated. A method is developed to approximately account for the effects of crystal anisotropy of LiNbO3 (symmetry 3m) on the stress fields for tracks oriented along the crystal axes (X, Y or Z). It only considers the zero-order (axial) harmonic contribution to the displacement field in the perpendicular plane and uses effective Poisson moduli for each particular orientation. The anisotropy is relatively small; however, it accounts for some differential features obtained for irradiations along the crystallographic axes X, Y and Z. In particular, the irradiation-induced disorder (including halo) and the associated surface swelling appear to be higher for irradiations along the X- or Y-axis in comparison with those along the Z-axis. Other irradiation effects can be explained by the model, e.g. fracture patterns or the morphology of pores after chemical etching of tracks. Moreover, it offers interesting predictions on the effect of irradiation on lattice parameters

Study of helical induced anisotropy in amorphous ribbons for sensor applications

Amorphous samples with helical induced anisotropy show magnetization processes that can be controlled by applying a longitudinal magnetic field simultaneously with an alternating current flowing through the sample. By varying the current amplitude and the phase difference between current and applied field, a wide range of coercivity and susceptibility values can be achieved. This work shows that the apparent coercive field and the susceptibility can be controlled in amorphous ribbons with helical anisotropy. These characteristics make these samples very suitable for their application as sensor cores, magnetic amplifiers, variable reluctance transformer cores, etc

New Intermediate band sulphide nanoparticles acting in the full visible light range spectra as an active photocatalyst

Nowadays one of the challenges of materials science is to find new technologies that will be able to make the most of renewable energies. An example of new proposals in this field are the intermediate-band (IB) materials, which promise higher efficiencies in photovoltaic applications (through the intermediate band solar cells), or in heterogeneous photocatalysis (using nanoparticles of them, for the light-induced degradation of pollutants or for the efficient photoevolution of hydrogen from water). An IB material consists in a semiconductor in which gap a new level is introduced [1], the intermediate band (IB), which should be partially filled by electrons and completely separated of the valence band (VB) and of the conduction band (CB). This scheme (figure 1) allows an electron from the VB to be promoted to the IB, and from the latter to the CB, upon absorption of photons with energy below the band gap Eg, so that energy can be absorbed in a wider range of the solar spectrum and a higher current can be obtained without sacrificing the photovoltage (or the chemical driving force) corresponding to the full bandgap Eg, thus increasing the overall efficiency. This concept, applied to photocatalysis, would allow using photons of a wider visible range while keeping the same redox capacity. It is important to note that this concept differs from the classic photocatalyst doping principle, which essentially tries just to decrease the bandgap. This new type of materials would keep the full bandgap potential but would use also lower energy photons. In our group several IB materials have been proposed, mainly for the photovoltaic application, based on extensively doping known semiconductors with transition metals [2], examining with DFT calculations their electronic structures. Here we refer to In2S3 and SnS2, which contain octahedral cations; when doped with Ti or V an IB is formed according to quantum calculations (see e.g. figure 2). We have used a solvotermal synthesis method to prepare in nanocrystalline form the In2S3 thiospinel and the layered compound SnS2 (which when undoped have bandgaps of 2.0 and 2.2 eV respectively) where the cation is substituted by vanadium at a ?10% level. This substitution has been studied, characterizing the materials by different physical and chemical techniques (TXRF, XRD, HR-TEM/EDS) (see e.g. figure 3) and verifying with UV spectrometry that this substitution introduces in the spectrum the sub-bandgap features predicted by the calculations (figure 4). For both sulphide type nanoparticles (doped and undoped) the photocatalytic activity was studied by following at room temperature the oxidation of formic acid in aqueous suspension, a simple reaction which is easily monitored by UV-Vis spectroscopy. The spectral response of the process is measured using a collection of band pass filters that allow only some wavelengths into the reaction system. Thanks to this method the spectral range in which the materials are active in the photodecomposition (which coincides with the band gap for the undoped samples) can be checked, proving that for the vanadium substituted samples this range is increased, making possible to cover all the visible light range. Furthermore it is checked that these new materials are more photocorrosion resistant than the toxic CdS witch is a well know compound frequently used in tests of visible light photocatalysis. These materials are thus promising not only for degradation of pollutants (or for photovoltaic cells) but also for efficient photoevolution of hydrogen from water; work in this direction is now being pursued.

Photovoltaic LiNbO3particles: Applications to Biomedicine/Biophotonics

Recently, a novel method to trap and pattern ensembles of nanoparticles has been proposed and tested. It relies on the photovoltaic (PV) properties of certain ferroelectric crystals such as LiNbO3 [1,2]. These crystals, when suitably doped, develop very high electric fields in response to illumination with light of suitable wavelength. The PV effect lies in the asymmetrical excitation of electrons giving rise to PV currents and associated space-charge fields (photorefractive effect). The field generated in the bulk of the sample propagates to the surrounding medium as evanescent fields. When dielectric or metal nanoparticles are deposited on the surface of the sample the evanescent fields give rise to either electrophoretic or dielectrophoretic forces, depending on the charge state of the particles, that induce the trapping and patterning effects [3,4]. The purpose of this work has been to explore the effects of such PV fields in the biology and biomedical areas. A first work was able to show the necrotic effects induced by such fields on He-La tumour cells grown on the surface of an illuminated iron-doped LiNbO3 crystal [5]. In principle, it is conceived that LiNbO3 nanoparticles may be advantageously used for such biomedical purposes considering the possibility of such nanoparticles being incorporated into the cells. Previous experiments using microparticles have been performed [5] with similar results to those achieved with the substrate. Therefore, the purpose of this work has been to fabricate and characterize the LiNbO3 nanoparticles and assess their necrotic effects when they are incorporated on a culture of tumour cells. Two different preparation methods have been used: 1) mechanical grinding from crystals, and 2) bottom-up sol-gel chemical synthesis from metal-ethoxide precursors. This later method leads to a more uniform size distribution of smaller particles (down to around 50 nm). Fig. 1(a) and 1(b) shows SEM images of the nanoparticles obtained with both method. An ad hoc software taking into account the physical properties of the crystal, particullarly donor and aceptor concentrations has been developped in order to estimate the electric field generated in noparticles. In a first stage simulations of the electric current of nanoparticles, in a conductive media, due to the PV effect have been carried out by MonteCarlo simulations using the Kutharev 1-centre transport model equations [6] . Special attention has been paid to the dependence on particle size and [Fe2+]/[Fe3+]. First results on cubic particles shows large dispersion for small sizes due to the random number of donors and its effective concentration (Fig 2). The necrotic (toxicity) effect of nanoparticles incorporated into a tumour cell culture subjected to 30 min. illumination with a blue LED is shown in Fig.3. For each type of nanoparticle the percent of cell survival in dark and illumination conditions has been plot as a function of the particle dilution factor. Fig. 1a corresponds to mechanical grinding particles whereas 1b and 1c refer to chemically synthesized particles with two oxidation states. The light effect is larger with mechanical grinding nanoparticles, but dark toxicity is also higher. For chemically synthesized nanoparticles dark toxicity is low but only in oxidized samples, where the PV effect is known to be larger, the light effect is appreciable. These preliminary results demonstrate that Fe:LiNbO· nanoparticles have a biological damaging effect on cells, although there are many points that should be clarified and much space for PV nanoparticles optimization. In particular, it appears necessary to determine the fraction of nanoparticles that become incorporated into the cells and the possible existence of threshold size effects. This work has been supported by MINECO under grant MAT2011-28379-C03.

Variable-density jet flows induced by concentrated sources of momentum and energy

The planar and axisymmetric variable-density flows induced in a quiescent gas by a concentrated source of momentum that is simultaneously either a source or a sink of energy are investigated for application to the description of the velocity and temperature far fields in laminar gaseous jets with either large or small values of the initial jet-to-ambient temperature ratio. The source fluxes of momentum and heat are used to construct the characteristic scales of velocity and length in the region where the density differences are of the order of the ambient density, which is slender for the large values of the Reynolds number considered herein. The problem reduces to the integration of the dimensionless boundary-layer conservation equations, giving a solution that depends on the gas transport properties but is otherwise free of parameters. The boundary conditions at the jet exit for integration are obtained by analysing the self-similar flow that appears near the heat source in planar and axisymmetric configurations and also near the heat sink in the planar case. Numerical integrations of the boundary-layer equations with these conditions give solutions that describe accurately the velocity and temperature fields of very hot planar and round jets and also of very cold plane jets in the far field region where the density and temperature differences are comparable to the ambient values. Simple scaling arguments indicate that the point source description does not apply, however, to cold round jets, whose far field region is not large compared with the jet development region, as verified by numerical integrations

CCD image sensor induced error in PIV applications

The readout procedure of charge-coupled device (CCD) cameras is known to generate some image degradation in different scientific imaging fields, especially in astrophysics. In the particular field of particle image velocimetry (PIV), widely extended in the scientific community, the readout procedure of the interline CCD sensor induces a bias in the registered position of particle images. This work proposes simple procedures to predict the magnitude of the associated measurement error. Generally, there are differences in the position bias for the different images of a certain particle at each PIV frame. This leads to a substantial bias error in the PIV velocity measurement (~0.1 pixels). This is the order of magnitude that other typical PIV errors such as peak-locking may reach. Based on modern CCD technology and architecture, this work offers a description of the readout phenomenon and proposes a modeling for the CCD readout bias error magnitude. This bias, in turn, generates a velocity measurement bias error when there is an illumination difference between two successive PIV exposures. The model predictions match the experiments performed with two 12-bit-depth interline CCD cameras (MegaPlus ES 4.0/E incorporating the Kodak KAI-4000M CCD sensor with 4 megapixels). For different cameras, only two constant values are needed to fit the proposed calibration model and predict the error from the readout procedure. Tests by different researchers using different cameras would allow verification of the model, that can be used to optimize acquisition setups. Simple procedures to obtain these two calibration values are also described.

Thermoelectric assessment of laser peening induced effects on a metallic biomedical Ti6Al4V

Laser peening has recently emerged as a useful technique to overcome detrimental effects associated to another well-known surface modification processes such as shot peening or grit blasting used in the biomedical field. It is worth to notice that besides the primary residual stress effect, thermally induced effects might also cause subtle surface and subsurface microstructural changes that might influence corrosion resistance. Moreover, since maximum loads use to occur at the surface, they could also play a critical role in the fatigue strength. In this work, plates of Ti-6Al-4V alloy of 7 mm in thickness were modified by laser peening without using a sacrificial outer layer. Irradiation by a Q-switched Nd-YAG laser (9.4 ns pulse length) working in fundamental harmonic at 2.8 J/pulse and with water as confining medium was used. Laser pulses with a 1.5 mm diameter at an equivalent overlapping density (EOD) of 5000 cm-2 were applied. Attempts to analyze the global induced effects after laser peening were addressed by using the contacting and non-contacting thermoelectric power (TEP) techniques. It was demonstrated that the thermoelectric method is entirely insensitive to surface topography while it is uniquely sensitive to subtle variations in thermoelectric properties, which are associated with the different material effects induced by different surface modification treatments. These results indicate that the stress-dependence of the thermoelectric power in metals produces sufficient contrast to detect and quantitatively characterize regions under compressive residual stress based on their thermoelectric power contrast with respect to the surrounding intact material. However, further research is needed to better separate residual stress effects from secondary material effects, especially in the case of low-conductivity engineering materials like titanium alloys.

High sensitivity biosensors based on shear mode AIN resonators for in liquid operation

El diagnóstico y detección temprana de enfermedades son clave para reducir la tasa de mortalidad, las hospitalizaciones de larga duración y el desaprovechamiento de recursos. En los últimos años se ha impulsado, mediante un aumento de la financiación, el desarrollo de nuevos biosensores de bajo coste capaces de detectar y cuantificar cantidades muy pequeñas de especies biológicas de una forma barata y sencilla. El trabajo presentado en esta Tesis Doctoral describe la investigación llevada a cabo en el desarrollo de sensores gravimétricos basados en resonadores de ondas acústicas de volumen (BAW) de estructura maciza (SMR). Los dispositivos emplean películas delgadas de A1N como material piezoeléctrico y operan en modo de cizalladura, para así poder detectar especies biológicas en medio líquido. El principio de funcionamiento de estos sensores se basa en la variación que experimenta la frecuencia de resonancia al quedar una pequeña masa adherida a su superficie. Necesitan operar en modo de cizalladura para que su resonancia no se atenúe al trabajar en medio líquido, así como ofrecer una superficie capaz de ser funcionalizada específicamente para la especie biológica a detectar. El reto planteado en esta tesis requiere un acercamiento pluridisciplinar al problema que incluye el estudio de los diferentes materiales que constituyen la estructura multicapa que forma un SMR, el diseño y fabricación del dispositivo y del sistema de fluídica, la funcionalización bioquímica de la superficie del sensor, la demostración de la capacidad de detección de especies biológicas y finalmente el diseño y fabricación de la electrónica asociada para la detección de la señal eléctrica. Todas esas tareas han sido abordadas en las distintas etapas del desarrollo de esta tesis y las contribuciones más relevantes se describen en el documento. En el campo de desarrollo de los materiales, se propone un proceso en dos etapas para la pulverización reactiva de capas de A1N que contengan microcristales inclinados capaces de excitar el modo de cizalladura. Se caracteriza la velocidad acústica del modo de cizalladura en todos los materiales que componen la estructura, con el fin de poder obtener un diseño más adecuado del reflector acústico. Se propone un nuevo tipo de material aislante de alta impedancia acústica consistente en capas de W03 pulverizadas que presenta ciertas ventajas tecnológicas frente a las capas convencionales de Ta205. Respecto del diseño del transductor, se estudia la influencia que tienen los con tactos eléctricos extendidos del resonador necesarios para poder adaptar el sistema de fluídica a la estructura. Los resultados indican que es necesario trabajar sobre sustratos aislantes (tanto el soporte como el espejo acústico) para evitar efectos parásitos asociados al uso de capas metálicas bajo los electrodos del resonador que dañan su resonancia. Se analiza la influencia de las diferentes capas del dispositivo en el coeficiente de temperatura de la frecuencia (TCF) del resonador llegando a la conclusión de que las dos últimas capas del reflector acústico afectan significativamente al TCF del SMR, pudiendo reducirse ajusfando adecuadamente sus espesores. De acuerdo con los resultados de estos estudios, se han diseñado finalmente resonadores SMR operando a f .3 GHz en modo de cizalladura, con un área activa de 65000 /xm2, contactos eléctricos que se extienden f .7 mm y factores de calidad en líquido de f 50. Las extensiones eléctricas permiten adaptar el resonador a un sistema de fluídica de metacrilato. Para la detección de especies biológicas se realiza un montaje experimental que permite circular 800 ¡A por la superficie del sensor a través de un circuito cerrado que trabaja a volumen constante. La circulación de soluciones iónicas sobre el sensor descubierto pone de manifiesto que las altas frecuencias de operación previenen los cortocircuitos y por tanto el aislamiento de los electrodos es prescindible. Se desarrolla un protocolo ad-hoc de funcionalización basado en el proceso estándar APTESGlutaraldehído. Se proponen dos alternativas novedosas para la funcionalización de las áreas activas del sensor basadas en el uso de capas de oxidación de Ir02 y su activación a través de un plasma de oxígeno que no daña al dispositivo. Ambos procesos contribuyen a simplificar notablemente la funcionalización de los sensores gravimétricos. Se utilizan anticuerpos y aptámeros como receptores para detectar trombina, anticuerpo monoclonal IgG de ratón y bacteria sonicadas. Una calibración preliminar del sensor con depósitos de capas finas de Si02 de densidad y espesor conocidos permite obtener una sensibilidad de 1800 kHz/pg-cm2 y un límite de detección of 4.2 pg. Finalmente se propone el prototipo de un circuito electrónico de excitación y lectura de bajo coste diseñado empleando teoría de circuitos de microondas. Aunque su diseño y funcionamiento admite mejoras, constituye la última etapa de un sistema completo de bajo coste para el diagnóstico de especies biológicas basado en resonadores SMR de A1N. ABSTRACT Early diagnosis and detection of diseases are essential for reducing mortality rate and preventing long-term hospitalization and waste of resources. These requirements have boosted the efforts and funding on the research of accurate and reliable means for detection and quantification of biological species, also known as biosensors. The work presented in this thesis describes the development and fabrication of gravimetric biosensors based on piezoelectric AlN bulk acoustic wave (BAW) solidly mounted resonators (SMRs) for detection of biological species in liquid media. These type of devices base their sensing principles in the variation that their resonant frequency suffers when a mass is attached to their surface. They need to operate in the shear mode to maintain a strong resonance in liquid and an adequate functionalisation of their sensing area to guarantee that only the targeted molecules cause the shift. The challenges that need to be overcome to achieve piezoelectric BAW resonators for high sensitivity detection in fluids require a multidisciplinary approach, that include the study of the materials involved, the design of the device and the fluidic system, the biochemical functionalisation of the active area, the experimental proof-of-concept with different target species and the design of an electronic readout circuit. All this tasks have been tackled at different stages of the thesis and the relevant contributions are described in the document. In the field of materials, a two-stage sputtering deposition process has been developed to obtain good-quality AlN films with uniformly tilted grains required to excite the shear mode. The shear acoustic velocities of the materials composing the acoustic reflector have been accurately studied to ensure an optimum design of the reflector stack. WO3 sputtered films have been proposed as high acoustic impedance material for insulating acoustic reflectors. They display several technological advantages for the processing of the resonators. Regarding the design, a study of the influence of the electrical extensions necessary to fit a fluidic system on the performance of the devices has been performed. The results indicate that high resistivity substrates and insulating reflectors are necessary to avoid the hindering of the resonance due to the parasitic effects induced by the extensions. The influence of the different layers of the stack on the resultant TCF of the SMRs has also been investigated. The two layers of the reflector closer to the piezoelectric layer have a significant influence on the TCF, which can be reduced by modifying their thicknesses accordingly. The data provided by these studies has led to the final design of the devices, which operate at 1.3 GHz in the shear mode and display an active area of 65000 /xm2 and electrical extensions of 1.7 mm while keeping a Qahear=150 in liquid. The extensions enable to fit a custom-made fluidic system made of methacrylate. To perform the biosensing experiments, an experimental setup with a liquid closed circuit operating at constant flow has been developed. Buffers of ionic characteristics have been tested on non-isolated devices, revealing that high operation frequencies prevent the risk of short circuit. An ad-hoc functionalisation protocol based on the standard APTES - Glutaraldehyde process has been developed. It includes two new processes that simplify the fabrication of the transducers: the use of IrO2 as oxidation layer and its functionalisation through an O2 plasma treatment that does not damage the resonators. Both antibodies and aptamers are used as receptors. In liquid sensing proof-of-concept experiments with thrombin, IgG mouse monoclonal antibody and sonicated bacteria have been displayed. A preliminary calibration of the devices using SiO2 layers reveals a sensitivity of 1800 kHz/pg-cm2 and a limit of detection of 4.2 pg. Finally, a first prototype of a low-cost electronic readout circuit designed using a standard microwave approach has been developed. Although its performance can be significantly improved, it is an effective first approach to the final stage of a portable low-cost diagnostic system based on shear mode AlN SMRs.