Self-assembled MgxZn1−xO quantum dots (0 ≤ x ≤ 1) on different substrates using spray pyrolysis methodology

By using the spray pyrolysis methodology in its classical configuration we have grown self-assembled MgxZn1−xO quantum dots (size [similar]4–6 nm) in the overall range of compositions 0 ≤ x ≤ 1 on c-sapphire, Si (100) and quartz substrates. Composition of the quantum dots was determined by means of transmission electron microscopy-energy dispersive X-ray analysis (TEM-EDAX) and X-ray photoelectron spectroscopy. Selected area electron diffraction reveals the growth of single phase hexagonal MgxZn1−xO quantum dots with composition 0 ≤ x ≤ 0.32 by using a nominal concentration of Mg in the range 0 to 45%. Onset of Mg concentration about 50% (nominal) forces the hexagonal lattice to undergo a phase transition from hexagonal to a cubic structure which resulted in the growth of hexagonal and cubic phases of MgxZn1−xO in the intermediate range of Mg concentrations 50 to 85% (0.39 ≤ x ≤ 0.77), whereas higher nominal concentration of Mg ≥ 90% (0.81 ≤ x ≤ 1) leads to the growth of single phase cubic MgxZn1−xO quantum dots. High resolution transmission electron microscopy and fast Fourier transform confirm the results and show clearly distinguishable hexagonal and cubic crystal structures of the respective quantum dots. A difference of 0.24 eV was detected between the core levels (Zn 2p and Mg 1s) measured in quantum dots with hexagonal and cubic structures by X-ray photoemission. The shift of these core levels can be explained in the frame of the different coordination of cations in the hexagonal and cubic configurations. Finally, the optical absorption measurements performed on single phase hexagonal MgxZn1−xO QDs exhibited a clear shift in optical energy gap on increasing the Mg concentration from 0 to 40%, which is explained as an effect of substitution of Zn2+ by Mg2+ in the ZnO lattice.

Optical properties of ZnMgO films grown by spray pyrolysis and their application to UV photodetection

This work presents a comprehensive optical characterization of Zn1−xMgxO thin films grown by spray pyrolysis (SP). Absorption measurements show the high potential of this technique to tune the bandgap from 3.30 to 4.11 eV by changing the Mg acetate content in the precursor solution, leading to a change of the Mg-content ranging from 0 up to 35%, as measured by transmission electron microscopy-energy dispersive x-ray spectroscopy. The optical emission of the films obtained by cathodoluminescence and photoluminescence spectroscopy shows a blue shift of the peak position from 3.26 to 3.89 eV with increasing Mg incorporation, with a clear excitonic contribution even at high Mg contents. The linewidth broadening of the absorption and emission spectra as well as the magnitude of the observed Stokes shift are found to significantly increase with the Mg content. This is shown to be related to both potential fluctuations induced by pure statistical alloy disorder and the presence of a tail of band states, the latter dominating for medium Mg contents. Finally, metal–semiconductor–metal photodiodes were fabricated showing a high sensitivity and a blue shift in the cut-off energy from 3.32 to 4.02 eV, i.e., down to 308 nm. The photodiodes present large UV/dark contrast ratios (102 − 107), indicating the viability of SP as a growth technique to fabricate low cost (Zn, Mg)O-based UV photodetectors reaching short wavelengths.

Propiedades ópticas y estructurales de nanoestructuras de Zn(Cd)(Mg)O

En la presente tesis doctoral se ha realizado un estudio utilizando diferentes técnicas de crecimiento (RPE-MOCVD y spray pyrolysis) y estructuras (nanohilos, pozos y puntos cuánticos y capas) con el objetivo de desarrollar dispositivos que cubran desde el rango visible hasta el ultravioleta. Es por esta razón por la que se han elegido materiales basados en ZnO, debido a la posibilidades que estos ofrecen para variar su bandgap en un amplio rango de energías. Prueba de ello es que en este estudio se ha conseguido cubrir un rango espectral desde 1.86 hasta 4.11 eV, estudiandose además fenómenos físicos como son la difusión e incorporaci ón de la aleación o la adsorción de gases en la super_cie, lo que ha permitido la fabricación de diferentes fotodetectores de gran sensibilidad. Por todo ello, los resultados obtenidos en esta tesis suponen una gran contribución al conocimiento de las propiedades físicas de las aleaciones de Zn(Cd)O y Zn(Mg)O para potenciales aplicaciónes en dispositivos que operen en el rango visible y ultravioleta del espectro, respectivamente. En esta memoria se da en primer lugar una visión de las propiedades de materiales basados en ZnO, entrando en detalle en una de las ventajas que este presenta, la facilidad que tiene este material para formar nanoestructuras. En el capítulo 3 se dan los conceptos teóricos necesarios para comprender las propiedades ópticas de este tipo de materiales, mostrando también los resultados más reseñables obtenidos en ZnO. En los capítulos referentes a los resultados se pueden diferenciar dos grandes bloques. En el primer bloque de resultados se han analizado nanohilos y pozos cuánticos de Zn(Cd)O crecidos por la técnica de RPE-MOCVD (Capítulos 4 y 5). En el segundo se expondrá el estudio realizado sobre capas y puntos cuánticos de Zn(Mg)O crecidos por la técnica spray pyrolysis como se describe en mayor detalle a continuación. Nanohilos y pozos cuánticos de Zn(Cd)O crecidos por RPE-MOCVD Teóricamente aleando el ZnO con CdO es posible disminuir el valor del band- gap desde 3.37 eV hasta 0.95 eV, cubriendo por completo el espectro visible. El desarrollo del ternario Zn(Cd)O permitiría la fabricación de heteroestructuras y pozos cuánticos, muy importantes en el desarrollo de dispositivos optoelectrónicos que cubran la parte visible del espectro. Sin embargo, la diferencia de estructura cristalina entre estos dos materiales junto a la baja solubilidad del Cd y su alta presión de vapor, di_culta la obtención de material de alta calidad cristalina con alto contenido en Cd. En esta tesis doctoral se ha realizado una completa caracterización óptica y estructural de nanohilos de Zn(Cd)O credidos por la técnica de RPE-MOCVD. Estos nanohilos tinene unas longitudes comprendidas entre 1 y 3 _m y diámetros entre 100 y 200 nm. La concentración máxima introducida de Cd en estas estructuras ha sido de hasta un 54% manteniendo la estructura wurtzita del ZnO, siendo este el mayor contenido de Cd introducido hasta la fecha en nanostructuras basada en ZnO. Este hecho se traduce en una variación de la energía de emisión entre 3.31 y 1.86 eV con el aumento en Cd. El uso de diferentes técnicas de alta resoluci ón de caracterización estructural ha permitido demostrar la presencia de una sola fase estructural wurtzita sin observarse ningún indicio de separación de fases ni acumulación de Cd a lo largo del nanohilo para todos los contenidos de Cd. Con el propósito de fabricar dispositivos en nanohilos individuales, parte de esta tesis doctoral ha estado dedicada a estudiar el impacto que el recocido térmico tiene en las propiedades ópticas y eléctricas de nanohilos de Zn(Cd)O. El recocido térmico es un proceso clave en la optimización de dispositivos, ya sea para la obtenci ón de contactos óhmicos, reducción de defectos o difusión de dopantes por ejemplo. En este estudio se ha observado una mejora muy signi_cativa de las propiedades de emisión de los nanohilos cuando estos eran recocidos a temperaturas mayores que la de crecimiento (300 oC). En las muestras con Cd se ha observado además que el recocido también produce un desplazamiento de la emisión hacia mayores energías debido a una reducción homogénea del contenido de Cd. Medidas de fotoluminiscencia con resolución temporal muestran el impacto que tiene la localización del excitón en las _uctuaciones de potencial, debidas a una distribución estadística del Cd, en la dinámica de los portadores. Comparando el tiempo de vida de los portadores entre los nanohilos recocidos y sin recocer se ha observado un aumento de este parámetro en las estructuras recocidas. Este aumento es fundamentalmente debido a una reducción de centros de recombinación no radiativa asociados a defectos presentes a lo largo del nanohilo. Además, se ha estudiado la evolución de los tiempos de vida de los portadores en función de la temperatura, registrándose una menor estabilidad con la temperatura de los tiempos de vida en las muestras recocidas. Este resultado sugiere que el recocido térmico consigue reducir parte del desorden de la aleación en la estructura. Tras haber caracterizados los nanohilos se desarrollaron una serie de procesa dos para la fabricación de dispositivos basados en nanohilos individuales. Se fabricaron en concreto fotodetectores sensibles al UV, en los que se observó también la alta sensibilidad que muestran a la adsorción de gases en la super_cie, incrementada por la gran relación super_cie/volúmen característica de las nanoestructuras. Estos procesos de adsorción observados tienen un impacto directo sobre las propiedades ópticas y electricas de los dispositivos como se ha demostrado. Por ello que en esta tesis se hayan estudiado en detalle este tipo de procesos, ideando maneras para tener un mayor control sobre ellos. Finalmente se crecieron estructuras de pozos cuántico de ZnCdO/ZnO en nanohilos con contenidos de Cd nominales de 54 %. Las medidas ópticas realizadas mostraron como al aumentar la anchura del pozo de 0.7 a 10 nm, la emisión relacionada con el pozo se desplazaba entre 3.30 y 1.97 eV. Este gran desplazamiento representa el mayor obtenido hasta la fecha en pozos cuánticos de ZnCdO/ZnO. Sin embargo, al caracterizar estructuralmente estas muestras se observó la presencia de procesos de difusión de Cd entre el pozo y la barrera. Como se ha podido medir, este tipo de procesos reducen sustancialmente la concentración de Cd en el pozo al difundirse parte a la barrera. cambiando completamente la estructura de bandas nominal de estas estructuras. Este estudio demuestra la importancia del impacto de los procesos de difusión en la interpretación de los efectos de con_namiento cuántico para este tipo de estructuras. Capas y puntos cuánticos de Zn(Mg)O crecidos por spray pyrolysis La técnica de spray pyrolysis, debido a su simplicidad, bajo coste y capacidad de crecer sobre grandes áreas conservando una alta calidad cristalina presenta un gran interés en la comunidad cientí_ca para el potencial desarrollo de dispositivos comerciales. En esta tesis se ha estudiado las propiedades ópticas y eléctricas de capas y puntos cuánticos de Zn(Mg)O crecidos por esta técnica. Al contrario que pasa con el Cd, al introducir Mg en la estructura wurtzita de ZnO se consigue aumentar el bandgap del semiconductor. Sin embargo, al igual que pasa con el CdO, la diferencia de estructura cristalina entre el ZnO y el MgO limita la cantidad de Mg que se puede incorporar, haciendo que para una cierta concentración de Mg aparezcan el fenómeno de separación de fases. En esta tesis se ha conseguido incorporar hasta un contenido de Mg del 35% en la estructura wurtzita del ZnO utilizando la técnica de spray pyrolysis, resultado que representa la mayor concentración de Mg publicada hasta la fecha. Este hecho ha posibilitado variar la energía del borde de absorción desde 3.30 a 4.11 eV. En estas capas se ha realizado una completa caracterización óptica observándose una diferencia entre las energías del borde de absorción y del máximo de emisión creciente con el contenido en Mg. Esta diferencia, conocida como desplazamiento de Stokes, es debida en parte a la presencia de _uctuaciones de potencial producidas por un desorden estadístico de la aleación. Se han fabricado fotodetectores MSM de alta calidad utilizando las capas de Zn(Mg)O previamente caracterizadas, observándose un desplazamiento del borde de absorción con el aumento en Mg desde 3.32 a 4.02 eV. Estos dispositivos muestran altos valores de responsividad (10-103 A/W) y altos contrastes entre la responsividad bajo iluminación y oscuridad (10-107). Estos resultados son en parte debidos a la presencia de mecanismos de ganancia y una reducción de la corriente de oscuridad en las muestras con alto contenido de Mg. Utilizando esta misma técnica de crecimiento se han crecido puntos de Zn(Mg)O con concentraciones nominales de Mg entre 0 y 100 %, con dimensiones medias entre 4 y 6 nm. Las medidas estructurales realizadas muestran que hasta un valor de Mg de 45 %, los puntos están compuestos por una única fase estructural, wurtzita. A partir de esa concentración de Mg aparece una fase cúbica en los puntos, coexistiendo con la fase hexagonal hasta una concentración nominales del 85 %. Para concentraciones mayores de Mg, los puntos muestran una única fase estructural cúbica. Medidas de absorción realizadas en estos puntos de Zn(Mg)O muestran un desplazamiento del borde de absorción entre 3.33 y 3.55 eV cuando la concentraci ón de Mg en los puntos aumenta hasta el 40 %. Este desplazamiento observado es debido solamente a la fase wurtzita del Zn(Mg)O donde se incorpora el Mg. ABSTRACT This PhD theis presents a study using di_erent growth techniques (RPEMOCVD and spray pyrolysis) and structures (nanowires, quantum dots and wells and layers) in order to develop devices that extend from the visible to the ultraviolet range. For this reason ZnO based materials have been choosen, because they o_er the possibility to tunne the bandgap in this energy range. Proof of this is that this study has managed to cover a spectral range from 1.86 to 4.11 eV, also being studied physical phenomena such as di_usion and incorporation of alloy or adsorption of gases on the surface, allowing the develop di_erent highly sensitive photodetectors. Therefore, the results obtained in this thesis are a great contribution two large blockso the knowledge of the physical properties of alloys Zn(Cd)O and Zn(Mg)O for potential applications in devices that operate in the visible and ultraviolet range, respectively. In the _rst chapter, the general properties of ZnO-based materials are presented, showing the facilities that these kind of materials o_er to obtain di_erent nanoestructures. In Chapter 3, optical theoretical concepts are given to understand the optical properties of these materials, also showing the most signi_cant results of ZnO. In the chapters related with the results, two blocks could be distinguish. In the _rst one, Zn(Cd)O nanowires and quantum wells grown by RPE-MOCVD have been analyzed (Chapters 4 and 5). The second block of results shows the study performed in Zn(Mg)O _lms and quantum dots grown by spray pyrolysis. Zn(Cd)O nanowires and quantum wells grown by RPE-MOCVD In summary, the results of the PhD thesis are a great contribution to the knowledge of the physical properties of Zn(Cd)O and Zn(Mg)O alloys and their application for high performance devices operating in the visible and UV ranges, respectively. The performance of the device is still limited due to alloy solubility and p-doping stability, which opens a door for future research in this _eld. Theoretically, annealing ZnO with CdO allows to reduce the bandgap from 3.37 to 0.95 eV, covering the whole visible spectrum. The development of ZnCdO alloys allows the fabrication of heterostructures and quantum wells, necessary for the development of high performance optoelectronic devices. However, the di_erent crystal structures between CdO and ZnO and the low solubility of Cd and its high vapor pressure, hinders the growth of ZnCdO alloys with high Cd contents. In this PhD thesis Zn(Cd)O nanowires have been optically and structurally characterized, obtaining a maximum Cd content of 54% while maintaining their wurtzite structure. This Cd content, which allows lowering the bandgap down to 1.86 eV, is the highest concentration ever reported in nanostructures based on ZnO. The combination of optical and structural characterization techniques used during this thesis has allowed the demonstration of the presence of a single wurtzite structure, without observing any indication of phase separation or Cd accumulation along the nanowire. Annealing processes are essential in the fabrication of optoelectronic devices. For this reason, a complete study of the annealing e_ects in the optical and electrical properties of Zn(Cd)O nanowires has been performed. In the _rst place, annealing nanowires at higher temperatures than their growth temperature (300 oC) allows a signi_cant improvement of their emission properties. However, in the samples that contain Cd a shift in the emission towards higher energies has been observed due to a homogeneous reduction of the Cd content in the nanowires. Time resolved photoluminescence measurements show the impact of the exciton localization in the potential _uctuations due to a statistical alloy disorder. An increase in the carrier lifetime has been obtained for the annealed nanowires. This increase is mainly due to the reduction of non-radiative recombination centers associated with the defects present in the material. Furthermore, temperature dependent time resolved photoluminescence measurements suggest a reduction of the alloy disorder in the annealed samples. In this thesis, single nanowire photodetectors with a high responsivity in the UV range have been demonstrated. Due to the high surface/volume ratio, these structures are very sensitive to gas adsorption at the surface, which largely de_nes the optical and electrical properties of the material and, therefore, of the device. With the aim of obtaining time stable devices, the dynamic adsorption-desorption processes have been studied, developing di_erent approaches that allow a higher control over them. Finally, ZnCdO/ZnO quantum wells have been grown with a nominal Cd concentration of 54% inside the well. The performed optical measurements show that increasing the well width from 0.7 to 10 nm, shifts the emission related with the well from 3.30 to 1.97 eV. This result represents the highest shift reported in the literature. However, a detailed structural characterization shows the presence of di_usion phenomena which substantially reduce the concentration of Cd in the well, while increasing it in the barrier. This type of phenomena should be considered when ac curately interpretating the quantum con_nement e_ects in Zn(Cd)O/ZnO quantum wells. Theoretically, annealing ZnO with CdO allows to decrease the bandgap from 3.37 to 0.95 eV, covering the whole visible spectrum. Zn(Mg)O _lms and quantum dots grown by spray pyrolysis Due to its simplicity, low-cost and capacity to grow over large areas conserving a high crystal quality, spray pyrolysis technique presents a great interest in the scienti_c community for developing comercial devices. In this thesis, a complete study of the optical and structural properties of Zn(Mg)O _lms and quantum dots grown by spray pyrolysis has been performed. Contrary to Zn(Cd)O alloys, when introducing Mg in the ZnO wurtzite structure an increase in the bandgap in obtained. Once again, the di_erence in the crystal structure of ZnO and MgO limits the amount of Mg that can be introduced before phase separation appears. In this PhD thesis, a maximum Mg content of 35% has been incorporated in the wurtzite structure using spray pyrolysis. This variation in the Mg content translates into an increase of the absorption edge from 3.30 to 4.11 eV. Up to this date, this result represents the highest Mg content introduced by spray pyrolysis in a ZnO wurzite structure reported in the literature. The comparison of the emission and absorption spectra shows the presence of an increasing Stokes shift with Mg content. This phenomenon is partialy related with the presence of potential _uctuations due to an statistic alloy disorder. MSM photodetectors have been processed on previously characterized Zn(Mg)O _lms. These devices have shown a shift in the absorption edge from 3.32 to 4.02 eV with the increase in Mg content, high responsivity values (10-103 A/W) and high contrast ratios between illuminated and dark responsivities (10-107). These values are explained by the presence of a gain mechanism and a reduction of dark current in the ZnMgO samples. Zn(Mg)O quantum dots have also been grown using spray pyrolysis with Mg concentrations between 0 and 100% and with average widths ranging 4 to 6 nm. Structural measurements show that at a Mg concentration of 45% the cubic phase appears, coexisting with the hexagonal phase up to an 85% concentration of Mg content. From 85% onwards the quantum dots show only the cubic phase. Absorption measurements performed in these structures reveal a shift in the absorption edge from 3.33 to 3.55 eV when the Mg content increases up to 40 %.

In-season calcium-spray formulations improve calcium balance and fruit quality traits of peach.

Experiments to evaluate the effect of in-season calcium (Ca) sprays on late-season peach (Prunus persica L. Batsch cv. Calrico) were carried out for a 2-year period. Calcium formulations (0.5% and 1.0% in 2008 and only 0.5% tested in 2009) supplied either as CaCl2 or Ca propionate in combination with two or three adjuvants (0.05% of the nonionic surfactants Tween 20 and Break Thru, and 0.5% carboxymethylcellulose, CMC) were sprayed four to five times over the growing season. Peach mesocarp and endocarp Ca concentrations were determined on a 15-day basis from the beginning of May until the end of June. Further tissue analyses were performed at harvest. A decreasing trend in fruit Ca concentrations over the growing season was always observed regardless of the Ca treatments. Both in 2008 and 2009, significant tissue Ca increments associated with the application of Ca-containing sprays in combination with adjuvants were only observed in June, which may be coincident with the period of pit hardening. In 2008, both at harvest and after cold storage, the total soluble-solids concentration (° Brix) of fruits supplied with Ca propionate (0.5% and 1.0% Ca) was always lower as compared to the rest of treatments. The application of multiple Ca-containing sprays increased firmness at harvest and after cold storage, especially when CaCl2 was the active ingredient used. Supplying the adjuvants Tween 20 and CMC increased fruit acidity both at harvest and after cold storage. Evaluation of the development of physiological disorders after cold storage (2 weeks at 0°C) indicated a lower susceptibility of Ca-treated fruits to internal browning. Fruits treated with multiple CaCl2-, CMC-, and Break Thru®-containing sprays during the growing season were significantly less prone to the development of chilling injuries as compared to untreated peaches.

Microstructure and mechanical properties at high temperature of SiC-matrix by electrophoretic deposition and polymer infiltration and pyrolysis process

The EFDA-ITER programme for materials wants to develop new structural materials for future nuclear magnetic fusion reactors. In this context, special attention must be paid in the development of new composite materials that could support the hard working conditions of the nuclear fusion reactors: high temperature, high stresses, and high radiation.

Sheath vaporization of a monodisperse fuel-spray jet

The group vaporization of a monodisperse fuel-spray jet discharging into a hot coflowing gaseous stream is investigated for steady flow by numerical and asymptotic methods with a two-continua formulation used for the description of the gas and liquid phases. The jet is assumed to be slender and laminar, as occurs when the Reynolds number is moderately large, so that the boundary-layer form of the conservation equations can be employed in the analysis. Two dimensionless parameters are found to control the flow structure, namely the spray dilution parameter 1, defined as the mass of liquid fuel per unit mass of gas in the spray stream, and the group vaporization parameter e, defined as the ratio of the characteristic time of spray evolution due to droplet vaporization to the characteristic diffusion time across the jet. It is observed that, for the small values of e often encountered in applications, vaporization occurs only in a thin layer separating the spray from the outer droplet-free stream. This regime of sheath vaporization, which is controlled by heat conduction, is amenable to a simplified asymptotic description, independent of ε,in which the location of the vaporization layer is determined numerically as a free boundary in a parabolic problem involving matching of the separate solutions in the external streams, with appropriate jump conditions obtained from analysis of the quasi-steady vaporization front. Separate consideration of dilute and dense sprays, corresponding, respectively, to the asymptotic limits λ<<1 and λ>>1, enables simplified descriptions to be obtained for the different flow variables, including explicit analytic expressions for the spray penetration distance.

Dynamics of thermal ignition of spray flames in mixing layers

Conditions are identified under which analyses of laminar mixing layers can shed light on aspects of turbulent spray combustion. With this in mind, laminar spray-combustion models are formulated for both non-premixed and partially premixed systems. The laminar mixing layer separating a hot-air stream from a monodisperse spray carried by either an inert gas or air is investigated numerically and analytically in an effort to increase understanding of the ignition process leading to stabilization of high-speed spray combustion. The problem is formulated in an Eulerian framework, with the conservation equations written in the boundary-layer approximation and with a one-step Arrhenius model adopted for the chemistry description. The numerical integrations unveil two different types of ignition behaviour depending on the fuel availability in the reaction kernel, which in turn depends on the rates of droplet vaporization and fuel-vapour diffusion. When sufficient fuel is available near the hot boundary, as occurs when the thermochemical properties of heptane are employed for the fuel in the integrations, combustion is established through a precipitous temperature increase at a well-defined thermal-runaway location, a phenomenon that is amenable to a theoretical analysis based on activation-energy asymptotics, presented here, following earlier ideas developed in describing unsteady gaseous ignition in mixing layers. By way of contrast, when the amount of fuel vapour reaching the hot boundary is small, as is observed in the computations employing the thermochemical properties of methanol, the incipient chemical reaction gives rise to a slowly developing lean deflagration that consumes the available fuel as it propagates across the mixing layer towards the spray. The flame structure that develops downstream from the ignition point depends on the fuel considered and also on the spray carrier gas, with fuel sprays carried by air displaying either a lean deflagration bounding a region of distributed reaction or a distinct double-flame structure with a rich premixed flame on the spray side and a diffusion flame on the air side. Results are calculated for the distributions of mixture fraction and scalar dissipation rate across the mixing layer that reveal complexities that serve to identify differences between spray-flamelet and gaseous-flamelet problems.

Flamelet structures in spray ignition

In typical liquid-fueled burners the fuel is injected as a high-velocity liquid jet that breaks up to form the spray. The initial heating and vaporization of the liquid fuel rely on the relatively large temperatures of the sourrounding gas, which may include hot combustion products and preheated air. The heat exchange between the liquid and the gas phases is enhanced by droplet dispersion arising from the turbulent motion. Chemical reaction takes place once molecular mixing between the fuel vapor and the oxidizer has occurred in mixing layers separating the spray flow from the hot air stream. Since in most applications the injection velocities are much larger than the premixed-flame propagation velocity, combustion stabilization relies on autoignition of the fuel-oxygen mixture, with the combustion stand-off distance being controlled by the interaction of turbulent transport, droplet heating and vaporization, and gas-phase chemical reactions. In this study, conditions are identified under which analyses of laminar flamelets canshed light on aspects of turbulent spray ignition. This study extends earlier fundamental work by Liñan & Crespo (1976) on ignition in gaseous mixing layers to ignition of sprays. Studies of laminar mixing layers have been found to be instrumental in developing un-derstanding of turbulent combustion (Peters 2000), including the ignition of turbulent gaseous diffusion flames (Mastorakos 2009). For the spray problem at hand, the configuration selected, shown in Figure 1, involves a coflow mixing layer formed between a stream of hot air moving at velocity UA and a monodisperse spray moving at velocity USUA. The boundary-layer approximation will be used below to describe the resulting sl ender flow, which exhibits different igniting behaviors depending on the characteristics of t he fuel. In this approximation, consideration of the case U A = U S enables laminar ignition distances to be related to ignition times of unstrained spray flamelets, thereby pro viding quantitative information of direct applicability in regions of low scala r dissipation-rate in turbulent reactive flows (see the discussion in pp. 181–186 of Peters (2000)) . This report is organized as follows. Effects of droplet dispersion dynamics on ignition of sprays in turbulent mixing layers are discussed in Section 2. The formulation f or ignition in laminar mixing layers is outlined in Sections 3 and 4. The results are presented in Section 5. In Section 6, the mixture-fraction field and associated scalar dissipat ion rates for spray ignition are discussed. Finally, some brief conclusions are drawn in Section 7.

Desulfurization of pyrolysis fuel produced from waste lube oils, tyres and plastics

Sulphur compounds remaining in petroleum fractions from topping, hydroskimming or deep conversion processes are a growing concern for oil refiners since in the lapse of a few years the sulphur specification for motor fuels has dropped from 500 mg/kg to 10 mg/kg in most European countries. This increasingly stringent regulation has forced refineries to greatly improve their hydrodesulfurization units, increasing the desulfurization rates and thus consuming huge amounts of hydrogen.

Regimes of spray vaporization and combustion in counterflow configurations

This article addresses the problem of spray vaporization and combustion in axisymmetric opposed-jet configurations involving a stream of hot air counterflowing against a stream of nitrogen carrying a spray of fuel droplets. The Reynolds numbers of the jets are assumed to be large, so that mixing of the two streams is restricted to a thin mixing layer that separates the counterflowing streams. The evolution of the droplets in their feed stream from the injection location is seen to depend fundamentally on the value of the droplet Stokes number, St, defined as the ratio of the droplet acceleration time to the mixing layer strain time close to the stagnation point. Two different regimes of spray vaporization and combustion can be identified depending on the value of St. For values of St below a critical value, equal to 1/4 for dilute sprays with small values of the spray liquid mass loading ratio, the droplets decelerate to approach the gas stagnation plane with a vanishing axial velocity. In this case, the droplets located initially near the axis reach the mixing layer, where they can vaporize due to the heat received from the hot air, producing fuel vapor that can burn with the oxygen in a diffusion flame located on the air side of the mixing layer. The character of the spray combustion is different for values of St of order unity, because the droplets cross the stagnation plane and move into the opposing air stream, reaching distances that are much larger than the mixing layer thickness before they turn around. The vaporization of these crossing droplets, and also the combustion of the fuel vapor generated by them, occur in the hot air stream, without significant effects of molecular diffusion, generating a vaporization-assisted nonpremixed flame that stands on the air side outside the mixing layer. Separate formulations will be given below for these two regimes of combustion, with attention restricted to the near-stagnation-point region, where the solution is self-similar and all variables are only dependent on the distance to the stagnation plane. The resulting formulations display a reduced number of controlling parameters that effectively embody dependences of the structure of the spray flame on spray dilution, droplet inertia, and fuel preferential diffusion. Sample solutions are given for the limiting cases of pure vaporization and of infinitely fast chemistry, with the latter limit formulated in terms of chemistry-free coupling functions that allow for general nonunity Lewis numbers of the fuel vapor.