Biogeochemical reactions and vadose zone transport, in particular gas phase transport, are inherently coupled processes. To explore feedback mechanisms between these processes in a quantitative manner, multicomponent gas diffusion and advection are implemented into an existing reactive transport model that includes a full suite of geochemical reactions. Multicomponent gas diffusion is described based on the Dusty Gas Model, which provides the most generally applicable description for gas diffusion. Gas advection is described by Darcy's Law, which in the current formulation, is directly substituted into the transport equations. The model is used to investigate the interactions between geochemical reactions and transport processes with an emphasis to quantify reaction-induced gas migration in the vadose zone. Simulations of pyrite oxidation in mine tailings, gas attenuation in partially saturated landfill soil covers, and methane production and oxidation in aquifers contaminated by organic compounds demonstrate how biogeochemical reactions drive diffusive and advective transport of reactive and non-reactive gases. Pyrite oxidation in mine tailings causes a pressure reduction in the reaction zone and drives advective gas flow into the sediment column, enhancing the oxidation process. Release of carbon dioxide by carbonate mineral dissolution partly offsets pressure reduction, and illustrates the role of water-rock interaction on gas transport. Microbially mediated methane oxidation in landfill covers reduces the existing upward pressure gradient, thereby decreasing the contribution of advective methane emissions to the atmosphere and enhancing the net flux of atmospheric oxygen into the soil column. At an oil spill site, both generation of CH4 in the methanogenic zone and oxidation of CH4 in the methanotrophic zone contribute to drive advective and diffusive fluxes. The model confirmed that non-reactive gases tend to accumulate in zones of gas consumption and become depleted in zones of gas production. In most cases, the model was able to quantify existing conceptual models, but also proved useful to identify data gaps, sensitivity, and inconsistencies in conceptual models. The formulation of the model is general and can be applied to other vadose zone systems in which reaction-induced gas transport is of importance.

This thesis is an investigation of the anode of a direct methanol fuel cell (DMFC) through numerical modeling and simulation. This model attempts to help better understand the two phase flow phenomena in the anode as well as to explain some of the many problems on the anode side of a DMFC and show how changing some of the anode side properties could alleviate these problems. This type of modeling is important for designing and optimizing the DMFC for specific applications like portable electronics. Understanding the losses within the DMFC like removable of carbon dioxide, conversion losses, and methanol crossover from the anode to the cathode will help the DMFC become more commercially viable. The model is based on two phase flow in porous media combined with equilibrium between phases in a porous media with contributions from a capillary pressure difference. The effect of the physical parameters of the fuel cell like the thickness, permeability, and contact angle as well as the operating conditions like the temperature and methanol feed concentration, have on the performance of the DMFC during operation will be investigated. This will show how to remove the gas phase from the anode while enabling methanol to reach the catalyst layer and minimizing methanol crossover. / text

The quantum Spin Hall Insulator (QSHI) is a two-dimensional variant of a novel class of materials characterized by topological order, whose unique properties have recently triggered much interest and excitement in the condensed matter community. Most notably, the topological properties of these systems hold great promise in mitigating the difficult problem of decoherence in implementations of quantum computers. Although QSHI has been theoretically predicted in a few different materials, prior to the work presented in this thesis, only the HgTe/CdTe semiconductor system has shown direct evidence for the existence of this phase. Ideally insulating in the bulk, QSHI is characterized by one-dimensional channels at the sample perimeter, which have a helical property, with carrier spin tied to the carrier direction of motion, and protected from elastic back-scattering by time-reversal symmetry. In this thesis we present low temperature transport measurements, showing strong evidence for the existence of proposed helical edge channels in InAs/CaSb quantum wells, which thus emerge as an important alternate to HgTe/CdTe quantum wells in studies of two-dimensional topological insulators and superconductors. Surprisingly, edge modes persist in spite of comparable bulk conduction of non-trivial origin and show only weak dependence on magnetic field in mesoscopic devices. We elucidate that the seeming independence of edge on bulk transport comes due to the disparity in Fermi wave-vectors between the bulk and the edge, leading to a total internal reflection of the edge modes. Furthermore, low Schottky barrier of this material system and good interface to superconductors allows us to probe topological properties of helical channels in Andreev reflection measurements, opening a promising route towards the realization of topologically superconducting phases hosting exotic Majorana modes.

Melt convection and solid phase movement play an important role in solidification processes, which significantly influence the formation of grain structures and solute segregations. In general, the melt convection and grain movement are a result of buoyancy forces. The densities within melt are different due to the variation of temperature and concentration, leading to thermally and solutally driven melt convection. Similarly, the density differences between the grains and the bulk melt cause the grain movement, leading to solid sedimentation or grain floating, as the case may be. Free, unattached solid grains are produced by partial remelting and fragmentation of dendrites, by mechanical disturbances such as stirring or vibration and by heterogeneous nucleation of grains in solidification of grain-refined alloys. In this way, movement of solid crystals during solidification can be ascertained in the following two cases. In the first case, during columnar solidification of non-grain-refined alloys, solid movement is possible in the form of dendrite fragments detached from the columnar stalks by the process of remelting and fragmentation. Movement of grains during columnar solidification gives rise to altogether different microstructure from columnar to equiaxed. In the second case, during equiaxed solidification of grain-refined alloys, the movement of solid crystals is possible in the form of equiaxed dendrite crystals nucleated due to presence of grain refiners. The rate and manner by which the free solids settle (or float) will influence macrosegregation in metal castings. Control of the solidification process is possible through an understanding of the solid movement and its effect on macrosegregation and microstructure. With this viewpoint, the overall objective of the present thesis is to study, experimentally and numerically, the phenomenon of solid phase movement during solidification. Through this study, deeper insights of the role of solid phase movement in solidification are developed which can be used for possible control of quality in castings. Both columnar and equiaxed solidification are considered. Models for transport phenomena associated with columnar solidification with solid phase movement are rarely found in the literature, because of inherent difficulty associated with consideration of microscopic features such as remelting and fragmentation. To tackle this problem, solidification modules for remelting and fragmentation are developed first, followed by integration of these molecules in a macroscopic solidification model. A Rayleigh number based fragmentation criterion is developed for detachment of dendrite fragments from the developing mushy zone, which determines the conditions favorable for fragmentation of dendrites. The criterion developed is a function of net concentration difference, liquid fraction, permeability, growth rate of mushy layer, and thermophysical properties of the material. The effect of various solidification parameters on fragmentation is highlighted. The integrated continuum model developed is applied to stimulate the solidification of aqua-ammonia system in a side-cooled rectangular cavity. The numerical results are in good qualitative agreement with those of experiments reported in literature. A gentle ramp of the mushy zone due to settling of solid crystals, as also noticed in experimental literature, is observed towards the bottom of the cavity. The influence of various modeling parameters on solid phase movement and resulting macrosegregation is investigated through a parametric study. Movement of grains during columnar solidification gives rise to altogether different microstructure and sometimes may initiate a morphological transition of the microstructure from columnar to equiaxed if the number and size of equiaxed grains ahead of the columnar front become sufficient to arrest the columnar growth. The generalised model developed, considering solid phase movement during columnar solidification is used to predict columnar-to-equiaxed transition (CET) based on a prescribed cooling rate criterion. It is found that presence of convection significantly affects the solidification behaviour. Moreover, the movement of dendrite fragments and their accumulation at the columnar front further trigger the occurrence of CET. Cooling configuration, too significantly affects the nature of CET. In unidirectional solidification cases, the locations of CET are found to be in a plane parallel to the chill face. However, for the case of the non-unidirectional solidification (as in side-cooled cavity), the locations of CET need not be in a plane parallel to the chill face. In contrast to fixed columnar solidification, equiaxed solidification is poorly understood; in particular, the phenomena associated with solid crystal movement. Movement of unattached solid crystals, formed due to heterogeneous nucleation on grain-refiners, is induced by the convective currents as well as by buoyancy effects, causing the solid to sediment or to float, depending on density of solid compared to that of the bulk melt. While moving in the bulk melt these crystals can also remelt or grow. A series of casting experiments with AI-based alloys are performed to investigate the role and influence of movement of solid crystals on macrosegregation and microstructure evolution during equiaxed solidification. Controlled experiments are designed for studying, separately, settling and floatation of equiaxed crystals for different cooling conditions and configurations. Further, these experiments are carried out in convective and non-convective cases to understand the effect of convection on solid phase movement. Temperature measurements are performed at various locations in the mould during the experiments. After the cavity is solidified, microstructural and chemical analyses of the experimental samples are carried out, several notable features are observed in temperature histories, macrosegregation pattern, and microstructures due to settling/flotation phenomenon of solid crystals. It is found that the flow behavior of solid grains has a profound influence on the progress of solidification (in terms of grain size distribution and fraction eutectic) and macrosegregation distribution. In some cases, the induced flow due to solid phase movement can cause a flow reversal. The observations and quantitative data obtained from experiments, with the help of detailed solidification conditions provided, can be used for future validations of models for equiaxed solidification. Subsequently, numerical studies are carried out, using a modified version of the macroscopic model developed for columnar solidification with motion of solid crystals, to predict the transport phenomena during equiaxed solidification. The model is applied to simulate the solidification processes corresponding to each of the experimental cases performed in this study. For a better understanding of the phenomenon of movement of solid crystals, the following two special cases of solidification are also presented: 1) without movement of solid crystals and 2) movement of solid crystals without any relative velocity between solid and liquid phases. The numerical predictions showing nature of flow field and progress of solidification are substantiated by the experimental data for the thermal analysis, qualitative microstructural Images and quantitative microstructural analysis. It is concluded, with the help of various experiments and simulations, that movement of solid crystals influences the casting quality appreciably, in terms of macrosegregation and microstructures. It is expected that the improved understanding of the role and influence of solid phase movement during solidification processes (both columnar and equiaxed) obtained through this thesis will be useful for possible control of quality of as-cast products.

ZnO nanowires were grown using carbothermal reduction and convective vapor phase transport in a tube furnace. Si <100> substrates that were 20 mm x 76.2 mm were sputter coated with 2 nm to 50 nm gold which formed nanoparticles on the order of 50 nm in diameter through a process of Ostwald ripening upon being heated. Growth temperatures were varied from 800ºC to 1000ºC, flow rates were varied from 24 sccm to 3300 sccm, and growth durations were varied from 8 minutes to 5 hours. Vapor phase Zn, CO, and CO2, produced by carbothermal reduction and suspended in an Ar atmosphere, were flowed over the Si substrates. The Au nanoparticles formed an eutectic alloy with Zn, causing them to become liquid nanodroplets which catalyzed vapor-liquid-solid nanowire growth. The nanowires were also synthesized by self-catalyzing vapor-solid growth in some cases. Using the tube furnace never resulted in more than 50% of the substrate being covered by nanowires. It was found that a bench-top furnace could achieve nearly 100% nanowire coverage by placing the 20 mm x 76.2 mm sample face down in a quartz boat less than 2 mm above the source powder. This was because minimizing the distance between the sample and the source powder was critical to achieve macroscopically uniform growth consistently. / text

Afin de pouvoir utiliser les piles à combustible du type PEMFC dans une application automobile, leur coût doit être diminué et leur durée de vie doit être augmentée. De nombreux résultats montrent que la gestion de l'eau dans les piles PEMFC est essentielle sur ces aspects et qu’une meilleure maitrise contribuera a développer des piles plus performantes. La couche active cathodique (CCL, Cathode Catalyst Layer) est le lieu de production de l'eau ce qui en rend l'optimisation importante pour assurer une bonne gestion de l'eau. Dans ce travail, la méthode réseau de pores a été adaptée pour modéliser le transport diphasique dans la structure poreuse de la CCL. Dans l'état de l'art actuel, le modèle développé est le seul permettant d’analyser l'effet des proprietes locales de la CCL (structure, mouillabilite…) sur les mecanismes de transport diphasique. Cet outil de compréhension constitue également une base pour proposer des améliorations de la CCL afin d'améliorer les performances des piles. Les algorithmes d'invasion développés ont été analysés d'une façon détaillée. Le transport fluidique (gaz et liquide) est couplé avec le transport des charges (électrons et protons) par un modèle de réaction électrochimique. Les mécanismes de capillarité, de diffusion gazeuse et d’evaporation sont integres au modele afin d'avoir une représentation la plus complète possible du fonctionnement de la CCL. La description de la structure poreuse par un réseau de pore régulier, l'algorithme d'invasion de l'eau liquide et le modèle de la diffusion des gaz ont été validés par des comparaisons avec des résultats expérimentaux de la littérature ou spécifiques de ce travail. Le modèle est ensuite exploité pour analyser l'effet des paramètres de la CCL tels que la mouillabilité et la taille des pores sur les performances de la couche active. Les résultats permettent d’analyser de premieres idees de modifications de la CCL pour ameliorer la gestion de l’eau et les performances des PEMFC. / In order to use PEM fuel cells in an automotive application, their cost must be reduced and their lifetime must be increased. Many results show that water management is a critical issue in PEMFC optimization. The water is produced in the cathode active layer (CCL) which makes the optimization of this component very important to ensure a better water management in the PEMFC. In this work, the pore network method has been adapted to model the two-phase transport in the porous structure of the CCL. Considering the state of the art, this is the only model developed to analyze the effect of local properties of the CCL (structure, wetting ...) on the two-phase transport mechanisms. This model is proposed as a scientific tool to help understanding the fundamentals behind the transport phenomena inside the CCL and also to help in the conception of the future CCL. The liquid invasion algorithms developed in this work were analyzed in details. The fluids transport (gas and liquid) is coupled with the charges transport (electrons and protons) using an electrochemical reaction model. The capillary driven liquid transport, the gas phase diffusion and the evaporation process are all integrated into the model in order to have the most possible complete description of the CCL. The description of the porous structure by a regular network, the liquid invasion algorithm and the gas diffusion model all have been validated by comparisons with experimental results from literature or specific work . The model is then exploited to analyze the effect of parameters such as the CCL wettability and pore size distribution on the performance. The results allow analysis of initial ideas that can help in the conception of the CCL in order to improve the water management and the performances of the PEMFC.

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-08-16T11:47:56Z No. of bitstreams: 1 FABIANA MEDEIROS DO NASCIMENTO SILVA - TESE (PPGEQ) 2017.pdf: 6622967 bytes, checksum: bfed827814b744a5e9e9e565d28f0682 (MD5) / Made available in DSpace on 2018-08-16T11:47:56Z (GMT). No. of bitstreams: 1 FABIANA MEDEIROS DO NASCIMENTO SILVA - TESE (PPGEQ) 2017.pdf: 6622967 bytes, checksum: bfed827814b744a5e9e9e565d28f0682 (MD5) Previous issue date: 2017 / Capes / O presente trabalho tem como objetivo geral sintetizar as membranas zeolíticas (Mordenita/α-alumina), utilizando os métodos de síntese hidrotérmica, crescimento secundário: dip-coating e transporte em fase vapor, para serem avaliadas no processo de separação emulsão óleo/água. Dentro deste contexto foram avaliados alguns parâmetros, destacando-se, a influência do tempo de cristalização na síntese da zeólita mordenita, a influência do precursor (sulfato de alumínio e gibsita) na síntese da membrana zeolítica, influência dos métodos de síntese das membranas zeolíticas e os testes de permeação de água e o processo de separação emulsão óleo/água. A síntese da zeólita mordenita foi realizada utilizando o método hidrotérmico a 170°C, com tempos de cristalização de 24, 36, 48, 72, 96 e 120 horas, a fim de avaliar a cristalinidade da zeólita, e selecionar o melhor tempo para a síntese das membranas zeolíticas. Os suportes cerâmicos α-alumina foram preparados a partir da decomposição dos precursores sulfato de alumínio a 1000°C e gibsita a 1200ºC por 2 horas, e conformados, compactados e sinterizados a 1300ºC por 2h, e então submetidos às técnicas de caracterização: Difratometria de raios X (DRX), Adsorção Física de Nitrogênio, Microscopia Eletrônica de Varredura (MEV), Espectroscopia de Fluorescência de raios X por Energia Dispersiva (FRX-ED) e Termogravimétrica/Térmica Diferencial (TG/DTA). As membranas zeolíticas foram sintetizadas pelos métodos de síntese hidrotérmica, crescimento secundário: dip-coating e transporte em fase vapor a 170°C por 72h e caracterizadas por DRX e MEV. Os suportes cerâmicos e as membranas zeolíticas foram avaliadas em testes de permeação de água e no sistema de separação emulsão óleo/água de um efluente sintético, utilizando um processo de separação por membrana (PSM). Os ensaios foram realizados nas condições de concentração inicial da emulsão 100 mg.L-1, temperatura de 25 °C e pressão de 2,5 bar, permitindo avaliar a permeabilidade e a seletividade a partir da variação da concentração do permeado em (mg.L-1) e da percentagem de rejeição ao óleo (%R). A partir dos resultados obtidos para a síntese dos materiais, pode-se observar a efetiva formação da zeólita mordenita em fase pura e cristalina. Os precursores foram decompostos de maneira satisfatória obtendo a fase α-alumina. A manutenção da fase α-alumina pós-produção dos suportes cerâmicos foi confirmada após caracterização. De acordo com os resultados exibidos pelas análises de DRX e MEV as membranas zeolíticas MZMOR/α-alumina apresentaram uma distribuição homogênea e uniforme dos cristais zeolíticos correspondentes à fase mordenita, sem a presença de impurezas, livres de defeitos e sem fissuras, confirmando a formação da estrutura da membrana zeolítica pelos três métodos de síntese, utilizados neste trabalho. A zeólita mordenita se mostrou excelente em relação à adesão e formação da camada zeolítica sobre o suporte cerâmico α-alumina. A partir da avaliação da permeabilidade e seletividade nos testes de separação da emulsão óleo/água, pode-se concluir que a inserção da zeólita mordenita aos suportes cerâmicos melhorou o processo de separação da emulsão óleo/água. Em termos de eficiência no processo de separação, considera-se que a membrana zeolítica MZMOR/α – Al2O3 (SHGB) foi a que apresentou melhor relação entre fluxo e capacidade seletiva, mostrando a eficácia da utilização das membranas zeolíticas. Todas as membranas zeolíticas sintetizadas e avaliadas mostraram-se promissoras. / The objective of the present work is to synthesize zeolite membranes (Mordenite/α-alumina) using hydrothermal synthesis, secondary growth: dip-coating and vapor-phase transport, to be evaluated in the oil/water emulsion separation process. The influence of the crystallization time on the synthesis of the mordenite zeolite, the influence of the precursor (aluminum sulphate and gibsite) on the synthesis of the zeolite membrane, influence of the synthesis methods of the zeolite membranes and the water permeation tests and the oil/water emulsion separation process. The synthesis of the mordenite zeolite was performed using the hydrothermal method at 170°C, with crystallization times of 24, 36, 48, 72, 96 and 120 hours, in order to evaluate the crystallinity of the zeolite, and to select the best time for the synthesis of zeolite membranes. The α-alumina ceramic supports were prepared from the decomposition of the aluminum sulfate precursors at 1000°C and gibsite at 1200°C for 2 hours, and conformed, compacted and sintered at 1300°C for 2h, and then submitted to the characterization techniques: (XRD), Nitrogen Physical Adsorption, Scanning Electron Microscopy (SEM), X-ray Fluorescence Spectroscopy (FRX-ED) and Thermogravimetric/Differential Thermal (TG/DTA). The zeolite membranes were synthesized by hydrothermal synthesis, secondary growth: dip-coating and vapor-phase transport at 170°C for 72 hours and characterized by XRD and SEM. Ceramic supports and zeolite membranes were evaluated in water permeation tests and in the oil/water emulsion separation system of a synthetic effluent using a membrane separation process. The tests were carried out under the conditions of initial concentration of the emulsion 100 mg.L-1, temperature of 25°C and pressure of 2,5 bar, allowing to evaluate the permeability and the selectivity from the variation of the permeate concentration in (mg. L-1) and the percentage of oil rejection (% R). From the results obtained for the synthesis of the materials, it is possible to observe the effective formation of zeolite mordenite in pure and crystalline phase. The precursors were satisfactorily decomposed to give the α-alumina phase. The maintenance of the post-production α-alumina phase of the ceramic supports was confirmed after characterization. The MZMOR/α-alumina zeolite membranes presented a homogeneous and uniform distribution of the zeolite crystals corresponding to the mordenite phase, without the presence of impurities, free of defects and without cracks, confirming the formation of the structure of the zeolite membrane by the three methods of synthesis, used in this work. The mordenite zeolite showed excellent adhesion and formation of the zeolitic layer on the ceramic support α-alumina. From the evaluation of the permeability and selectivity in the oil/water emulsion separation tests, it can be concluded that the insertion of the mordenite zeolite to the ceramic supports improved the separation process of the oil/water emulsion. In terms of efficiency in the separation process, the zeolite membrane MZMOR/α-Al2O3(SHGB) was considered to have the best relationship between flow and selectivity, showing the efficacy of zeolite membranes. All zeolite membranes synthesized and evaluated were promising.

Multiphase transport phenomena primarily encompass the fundamental principles and applications concerning the systems where overall dynamics are precept by phase change evolution. On the other hand, multiscale transport phenomena essentially corroborate to a domain where the transport characteristics often contain components at disparate scales. Relevant examples as appropriate to multiphase and multiscale thermofluidic transport phenomena comprise solid-liquid phase change during conventional solidification process and hydrodynamics through narrow confinements. The additional effect of superimposed magnetic field over such multiphase and multiscale systems may give rise to intriguing transport characteristics, significantly unique in nature as compared to flows without it. The present investigation focuses on multiphase, multi-scale transport phenomena in physical systems subjected to the superimposed magnetic field, considering four important and inter-linked aspects. To begin with, for a multiphase system concerning binary alloy solidification, a normal mode linear stability analysis has been carried out to investigate stationary and oscillatory convective stability in the mushy layer in the presence of external magnetic field. The stability results indicate that the critical Rayleigh number for stationary convection shows a linear relationship with increasing Ham (mush Hartmann number). Magnetohydrodynamic effect imparts a stabilizing influence during stationary convection. In comparison to that of stationary convective mode, the oscillatory mode appears to be critically susceptible at higher values of  (a function of the Stefan number and concentration ratio), and vice versa for lower  values. Analogous to the behaviour for stationary convection, the magnetic field also offers a stabilizing effect in oscillatory convection and thus influences global stability of the mushy layer. Increasing magnetic strength shows reduction in the wavenumber and in the number of rolls formed in the mushy layer. In multiscale paradigm, the combined electroosmotic and pressure-driven transport through narrow confinements have been firstly analyzed with an effect of spatially varying non–uniform magnetic field. It has been found that a confluence of the steric interactions with the degree of wall charging (zeta potential) may result in heat transfer enhancement, and overall reduction in entropy generation of the system under appropriate conditions. In particular, it is revealed that a judicious selection of spatially varying magnetic field strength may lead to an augmentation in the heat transfer rate. It is also inferred that incorporating non–uniformity in distribution of the applied magnetic field translates the system to be dominated by the heat transfer irreversibility. Proceeding further, a semi-analytical investigation has been carried out considering implications of magnetohydrodynamic forces and interfacial slip on the heat transfer characteristics of streaming potential mediated flow in narrow fluidic confinements. An augmentation in the streaming potential field as attributable to the wall slip activated enhanced electromagnetohydrodynamic transport of the ionic species within the EDL has been found. Furthermore, the implications of Stern layer conductivity and magnetohydrodynamic influence on system irreversibility have been shown through analysis of entropy generation due to fluid friction and heat transfer. The results being obtained in this analysis have significant scientific and technological consequences in the context of novel design of future generation energy efficient devices, and can be useful in the further advancement of theory, simulation, and experimental work. Finally, the combined consequences of interfacial electrokinetics, rheology, and superimposed magnetic field subjected to a non-Newtonian (power-law obeying) fluid in a narrow confinement are studied in this work. The theoretical results demonstrate that the applied magnetic field imparts a retarding influence in the induced streaming potential development, whereas, triggers the heat transfer magnitude. Moreover, additional influences of power law index show reduction in heat transfer as well as the streaming potential magnitude. It is unveiled that the optimal combinations of power law index and the magnetic field lead to the minimization of the global total entropy generation in the system.

One-dimensional (1D) nanostructures have gained tremendous attention over the last decade due to their wide range of potential applications. Particularly, ZnO 1D nanostructures have been investigated with great interest due to their versatility in synthesis with potential applications in electronics, optics, optoelectronics, sensors, photocatalysts and nanogenerators. The thesis deals with the challenges and the answer to grow ZnO 1D nanostructure by vapor phase transport (VPT) continuously without any length limitation. The conventional VPT technique has been modified for the non-catalytic growth of ultralong ZnO 1D nanostructures and branched structures in large area with controllable aspect ratio. It has been shown that the aspect ratio can be controlled both by thermodynamically (temperature) and kinetically (vapour flux). The thesis also deals with the fabrication of carbon nanotube (CNT) -ZnO based multifunctional devices and the field emission performance of ZnO nanowires by employing various strategies. The entire thesis has been organised as follows: Chapter 1 deals with Introduction. In this chapter, importance of ultralong nanowires and significance of ultralong ZnO nanowires has been discussed. Various efforts to grow ultralong ZnO nanowire with their advantages and disadvantages have been summarised. Lastly the significance of forming ZnO nanowires based nano hybrid structures and importance of doping in ZnO nanowires and has also been discussed. Chapter 2 deals with experimental procedure and characterization. In this chapter, a single step VPT method for the growth of ultralong ZnO nanowires that incorporates local oxidation barrier for the source has been described. The synthesized nanowires were characterised by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman & photoluminescence. Chapter 3 deals with growth of ZnO nanowires, controlling the aspect ratio of ZnO nanowires, and role of other experimental aspects. In this chapter, a way to grow nanowires continuously without any apparent length limitation, a way to control the diameter of the nanowires kinetically without catalyst particle or seed layer and obtaining smaller diameter of the nanowires by non-catalytic growth as compared to that set by the thermodynamic limit has been discussed. Furthermore, the significance and importance of local oxidation barrier on source for protecting them from degradation, ensuring the continuous supply of vapour and enabling the thermodynamically and kinetically controlled growth of nanowires has been discussed. Lastly, the scheme for large area deposition and a method to use same source material for several depositions has been presented. Chapter 4 deals with multifunctional device based on CNT -ZnO Nanowire Hybrid Architectures same device can be used as a rectifier, a transistor and a photodetector. In this chapter, the fabrication of CNT arrays-ZnO nanowires based hybrid architectures that exhibit excellent high current Schottky like behavior with p-type conductivity of ZnO has been discussed. CNT-ZnO hybrid structures that can be used as high current p-type field effect transistors (FETs) and deliver currents of the order of milliamperes has been presented. Furthermore, the p-type nature of ZnO and possible mechanism for the rectifying characteristics of CNT-ZnO has been discussed. Lastly, the use of hybrid structures as ultraviolet detectors where the current on-off ratio and the response time can be controlled by the gate voltage has been presented and also an explanation for photoresponse behaviour has been provided. Chapter 5 deals with the substrate-assisted doping of ZnO nanowires grown by this technique. In this chapter, the non-catalytic growth of ZnO nanowires on multiwalled carbon nanotubes (MWCNTs) and soda lime glass (SLG) with controlled aspect ratio has been presented. The elemental mapping to confirm the presence and distribution of carbon and sodium in ZnO nanowires and the transport studies on both carbon and sodium doped ZnO has also been presented. Furthermore the stability of carbon doped ZnO has also been presented. Lastly, the advantage of growing ZnO nanowires on MWCNTs and overall advantage associated with this technique has been discussed. Chapter 6 deals with formation of ZnO nanowire branched structures. In this chapter, a possibility to grow ZnO nanowires on already grown ZnO nanowires has been demonstrated. The formation of branched structure during multiple growth of ZnO nanowire on ZnO nanowire has been presented and evolution of aspect ratio in these branched structures has been discussed. Furthermore, the advantage of using ZnO branched structures and also the ZnO nanoneedles on MWCNT mat for field emission has been presented. Chapter 7 summarizes all the findings of the thesis.

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