El business hacking como marco en la transformación empresarial tangible, medible y sontenible. La digitalización y las altas expectativas de los consumidores están cambiando radicalmente la forma en que interactuamos, y las organizaciones que saben cómo gestionarlo tendrán éxito. El marco de business hacking tiene como objetivo hacer que la transformación sea tangible y medible, haciendo que el cambio sea sostenible y encontrando nuevas formas de optimizar la cultura y el impacto empresarial. pasando por todo un modelo accionable de adquisiciòn y retenciòn basado en medios digitales

No description available.

Natural ageing is known to have a negative effect on the formability and bake-hardening response of Al-Mg-Si alloys. This is attributed to the formation of Mg and Si clusters during natural ageing. The clustering process was the subject of many studies in the literature, however, the formation mechanism and kinetics of it, continues to be poorly understood. The aim of this project is to shed some light on the cluster formation mechanism and measure clustering kinetics at low temperatures. A series of electrical resistivity measurements, positron annihilation lifetime spectroscopy and hardness tests were performed on samples aged over the temperature range of -20 to 50°C following solution treatment at temperatures of 525 and 560°C. A very good correlation between the results of various techniques was observed. In addition, three different stages in the clustering process were detected. Not surprisingly it was found that the excess quenched-in vacancies are the key players in the cluster formation process. In the first stage, annihilation of near-sink vacancies occurs while other vacancies start to bind with solute atoms and form clusters. In the second stage, clustering continues to take place but its rate slows down since the effective diffusion coefficient of vacancies decreases as they bind with more solute. Finally, the clustering process enters the third stage with much slower kinetics. Interestingly, positron annihilation lifetime also reaches a constant value at the beginning of stage III which suggests the stabilization of vacancies. Two hypothesis were then developed to explain the existence of stage III: one based on the immobilization of vacancies due to the increased binding with solute atoms and another one which considers the overlapping of solute diffusion profiles around the clusters. Finally it was shown that the resistivity change in stage II can be used to find the activation energy of clustering which is calculated to be approximately 46 kJ/mol. This is very close to the migration energy of vacancies and Mg atoms. Thus it was concluded that migration of these species is the major rate controlling parameter for the clustering process. / Thesis / Master of Applied Science (MASc)

This thesis presents the study of x-ray emission from femtosecond laser micromachining and laser ablation of semiconductors. Prior to femtosecond machining experiments we investigated the nature of radiation emitted during the irradiation of solid targets with 120 femtosecond pulses with energies between 500 nJ and 0.3 mJ at a 1 kHz repetition rate. We have shown that the majority of the radiation was emitted below 10 keV with the high energy edge extending up to 25 keV. Under our experimental conditions K line emission was observed from materials with Z<32. We have also measured the x-ray dose rates during laser machining of various targets on the order of 10 mSv/h at a distance of 13 cm from the target. The implications for work pace safety, micromachining control, and potential for pulsed x-ray line sources for spectroscopic and imaging applications are discussed. In our studies of single shot femtosecond ablation of selected semiconductors: Si, GaAs, and InP, we have concentrated on the studies of microstructure and composition of the material after irradiation with 120 femtosecond pulses with energies between 2 nJ and 2 µJ. The resulting surface morphology, structure and composition of the micron scale ablation features on the semiconductors were studied by electron microscopy and atomic force microscopy. We found that no sharp threshold in the surface morphology was observed with increasing pulse power; however three ablation stages were identified based on the characteristic features of the ablation craters. TEM analysis revealed essentially no crystal damage beneath and in the vicinity of the ablation craters. In case of the binary semiconductors 5-30 nm polycrystalline grains were found over the ablated surfaces. The results were discussed in terms of the existing state of knowledge of ablation dynamics. The implications for practical micromachining applications are also discussed. / Thesis / Master of Engineering (ME)

The present thesis deals with Nb-Si alloy composites in both bulk and multilayer forms. The work has been divided into two parts. First part (chapter 4-6) deals with Nb based silicides binary and ternary alloys with alloying additions like Ga and Al. These alloys are synthesized by vacuum arc melting and suction casting (non-equilibrium processing techniques). The studies on intermetallic coatings of Nb-Si alloys and Nb/Si multilayer synthesized by pulsed laser deposition technique have been presented in the second part (chapter7-8). Nb-Si alloys are one of the candidate materials for the advanced structural and microelectronic applications. There are few issues with these materials like poor oxidation resistance, low fracture toughness and brittleness which need to be solved. Microstructure plays a crucial role to control these properties. The main focus of this work is to understand the process of phase transformation and thereby control the microstructure in both bulk alloys and thin films. We have also investigated in a limited manner mechanical and environmental properties of bulk alloys. This thesis is subdivided into nine chapters. After a brief introduction in the first chapter, a brief overview on Nb-Si phase diagram and literature reviews on Nb-Si based alloys are presented with emphasis on the current work in the second chapter. Literature reviews on the phase formations sequence and stability in Nb-Si alloys thin films and Nb/Si multilayers are also discussed in the same chapter. In the third chapter different experimental techniques, processing parameters and characterization tools like XRD, SEM, TEM etc. are briefly discussed. Special emphasis is given on two non-equilibrium techniques: laser deposition technique to deposit the thin film/multilayer and vacuum suction casting to produce the 3 mm diameter rods of different Nb-Si alloys. The fourth chapter discusses the microstructural aspects of Nb-Si alloys prepared by suction casting and its mechanical behavior. The samples have the compositions hypoeutectic (Nb-10at.%Si and Nb-14at.%Si), eutectic (Nb-18.7at.%Si) and hypereutectic (Nb-22at.% Si and Nb-25at.% Si). SEM microstructural analyses of all the samples clearly show the enhancement in the volume fraction of eutectic and decease in the eutectic spacings in microstructure due to large undercooling. Rod eutectic is observed in most of places with irregular eutectic a few places in all samples. First check of phases has been done by XRD in all samples. Phase confirmation using TEM showed the eutectic between Nbss and Nb3Si phases in all samples. The primary phase for hypoeutectic alloys is Nbss (dendritic structure), Nb3Si phase for eutectic composition and β-Nb5Si3 phase for hypereutectic alloys. Compositional analysis using EDS and EPMA also supported the above results. No signature of eutectoid reaction (Nb3Si→Nb+α-Nb5Si3) is observed. Mechanical properties like hardness, strength, ductility and indentation fracture toughness have been determined for above mention alloy compositions. SEM micrographs showed that silicides fractured by cleavage and Nb phase in a ductile manner during the compression tests carried out at room temperature. We attempt to explain how the above mention mechanical properties change with alloy compositions and processing. Chapter five deals with the effect of Ga addition on the microstructure and mechanical properties of the Nb-Si alloy. The composition selected for this study is Nb-20.2at.%Si-2.7at.%Ga. The results of ternary alloy have been compared with the binary alloy composition Nb-18.7at.%Si. Phase analysis has been carried out using TEM and XRD. Ga addition has suppressed the formation of Nb3Si phase and promoted the formation of β-Nb5Si3 phase. Ga addition also established the eutectic between Nbss and β-Nb5Si3, which is a metastable eutectic. Ga added ternary alloy, on suction casting, yields ultrafine eutectic with nanometer length scale (50-100nm). From the compression tests, it is concluded that the combination of ultrafine eutectic (Nbss-β-Nb5Si3) and primary β-Nb5Si3 in ternary alloy results in a high compressive strength ~2.8±0.1 GPa with 4.3% plasticity. In contrast binary alloy under identical conditions shows the compressive strength ~1.35±0.1 GPa and 0.2% plasticity. Ga addition also enhances the indentation fracture toughness from 9.2±0.05 MPa√m (binary) to 24.11±0.5 MPa√m (ternary). Composite hardness values of the ternary and binary alloys are 1064±20 Hv and 1031±20 Hv respectively. Chapter six deals with Al added Nb-Si ternary alloy. Here we have discussed microstructural and mechanical properties like in chapter 5 along with oxidation behavior for the alloy composition Nb-12.7at.%Si-9at.%Al. SEM micrograph shows the presence of primary dendrites structure with ultra fine lamellar eutectic (50-100nm). Detailed TEM studies confirm the Nbss as primary phase present in form of dendrites. These dendrites contain the plate shape precipitates of δ-Nb11Si4 (body centered orthorhombic structure) phase in Nb matrix (primary dendrites). Eutectic phases are Nbss and β-Nb5Si3. The analysis of the results indicates that Al addition promote the formation of β-Nb5Si3 phase in the eutectic. The results of this ternary composition were also compared with the binary alloy composition Nb-18.7at.%Si. Compression tests have been carried out at room and elevated temperatures to measure the strength of the material. Al added ternary alloy yields the compressive strength value 1.6±0.01 GPa whereas binary alloy yields the compressive strength value 1.1±0.01 GPa. Enhancement in indentation fractured toughness is observed in Al added ternary alloy (20.4±0.5MPa√m) compare to binary alloy (9.2±0.05 MPa√m). Thermal analysis by TGA and DTA were used to see the oxidation behavior of Al added ternary alloy. Chapter seven deals with the deposition characteristics and the TEM studies on the laser deposited Nb-Si thin films. Films were deposited on the NaCl crystals and Si single crystal substrates. The compositions chosen in this case are Nb-25at.%Si, Nb-37.5at.%Si and Nb-66.7at.%Si. These compositions correspond to the equilibrium intermetallic compounds Nb3Si, Nb5Si3 and NbSi2 respectively. In this chapter we have briefly discussed the microstructural and phase evolutions in the intermetallic coatings. The smooth films quenched from the vapor and/or plasma state show amorphous structure. The sequence of crystallization was studied by hot stage TEM experiments as well as by cross sectional TEM in the films deposited at the elevated temperatures (600oC and 700oC) on Si substrates. During the hot stage experiment, crystallization is observed in Nb-25at.%Si film around 850oC with nucleation of metastable cubic Nb3Si phase. Occasionally metastable hexagonal Nb3Si3 phase has also been observed (close to Si substrate) along with cubic Nb3Si phase in the films at elevated temperatures. For Nb-37.5at.%Si film, crystallization is observed at 800oC with the nucleation of grains of metastable hexagonal Nb5Si3 phase. Cross-sectional TEM shows the presence of hexagonal Nb5Si3 phase along with few grains of NbSi3 (equilibrium) phase in the films deposited at elevated temperatures. Hot stage experiment of Nb-66.3at.%Si film showed the onset of crystallization much earlier at 400oC and complete crystallization at 600oC. This crystallization leads to the nucleation of grains of NbSi2 phase. Films of this composition deposited at elevated temperatures showed the presence of NbSi2 and metastable hexagonal Nb5Si3 phases (occasionally). The laser ablated films, besides the film matrix also contain the micron and submicron sized spherical droplets of different sizes. These droplets travel at very high velocities and impinge on the substrate resulting in a very high rate of heat transfer during solidification from liquid state. Therefore in this work we have also studied the microstructural evolution in the droplets for each composition. The phases observed in the droplets embedded in the matrix of Nb-25 at% Si alloy film are the bcc Nb and the cubic Nb3Si (metastable phase). The droplets in the matrix of Nb-37.5 at% Si alloy showed the bcc Nb and tetragonal β-Nb5Si3 phases. The phases observed in the droplets of in the Nb-66.3at.%Si alloy are the bcc Nb, tetragonal β-Nb5Si3 and the hexagonal NbSi2 (metastable phase). Chapter eight describes the synthesis and microstructural characterization using TEM of Nb/Si multilayers. The aim of this work is to check the stability and phase formation sequence in Nb/Si multilayer. Nb/Si multilayers were first annealed at different time intervals at 600oC and at different temperatures (for 2 hours) and then characterized by the cross-sectional transmission electron microscopy. As-deposited Nb layer is crystalline while Si layer is amorphous. Microstructural and compositional evidences suggest the intermixing between the Nb and Si layers at the interfaces. Nb/Si multilayer annealed at 600oC for 1 hour, NbSi2 was identified as the first crystalline nucleating phase. However amorphous silicide layers were also observed between Nb and NbSi2 layers. Metastable hexagonal Nb5Si3 was identified as the next crystalline phase that nucleated from the amorphous silicide layers at the interfaces of Nb and NbSi2 layers. Occasionally few grains of cubic Nb3Si phase were also observed after 8 hours of annealing at 600oC. In the chapter we have compared the results to the other reported works in Nb-Si bulk diffusion couples and also thin film couples. The final chapter summarizes the major conclusions of the present work and scope of future work.

Achieving high efficiency solar cells and concurrently driving down the cell cost has been among the key objectives for photovoltaic researchers to attain a lower levelized cost of energy (LCOE). While the performance of silicon (Si) based solar cells have almost saturated at an efficiency of ~25%, III-V compound semiconductor based solar cells have steadily shown performance improvement at approximately 1% (absolute) increase per year, with a recent record efficiency of 46%. However, the expensive cost has made it challenging for the high efficiency III-V solar cells to compete with the mainstream Si technology. Novel approaches to lower down the cost per watt for III-V solar cells will position them to be among the key contenders in the renewable energy sector. Integration of such high-efficiency III-V multijunction solar cells on significantly cheaper and large area Si substrate has the potential to address the future LCOE roadmaps by unifying the high-efficiency merits of III-V materials with low-cost and abundance of Si. However, the 4% lattice mismatch, thermal mismatch polar-on-nonpolar epitaxy makes the direct growth of GaAs on Si challenging, rendering the metamorphic cell sensitive to dislocations. The focus of this dissertation is to systematically investigate heterogeneously integrated III-V multijunction solar cells on Si substrate. Utilizing a combination of comprehensive solar cell modeling and experimental techniques, we seek to better understand the material properties and correlate them to improve the device performance, with simulation providing a very valuable feedback loop. Key technical design considerations and optimal performance projections are discussed for integrating metamorphic III-V multijunction solar cells on Si substrates for 1-sun and concentrated photovoltaics. Key factors limiting the “GaAs-on-Si” cell performance are identified, and novel approaches focused on minimizing threading dislocation density are discussed. Finally, we discuss a novel epitaxial growth path utilizing high-quality and thin epitaxial Ge layers directly grown on Si substrate to create virtual “Ge-on-Si” substrate for III-V-on-Si multijunction photovoltaics. With the plummeting price of Si solar cells accompanied with the tremendous headroom available for improving the III-V solar cell efficiencies, the future prospects for successful integration of III-V solar cell technology with Si substrate looks very promising to unlock an era of next generation of high-efficiency and low-cost photovoltaics. / Ph. D.

Le contrôle d'accès permet de spécifier une partie de la politique de sécurité d'un système d'informations (SI). Une politique de contrôle d'accès (CA) permet de définir qui a accès à quoi et sous quelles conditions. Les concepts fondamentaux utilisés en CA sont : les permissions, les interdictions (ou prohibitions), les obligations et la séparation des devoirs (SoD). Les permissions permettent d'autoriser une personne à accéder à des ressources. Au contraire les prohibitions interdisent à une personne d'accéder à certaines ressources. Les obligations lient plusieurs actions. Elles permettent d'exprimer le fait qu'une action doit être réalisée en réponse à une première action. La SoD permet de sécuriser une procédure en confiant la réalisation des actions composant cette procédure à des agents différents. Différentes méthodes de modélisation de politiques de contrôle d'accès existent. L'originalité de la méthode EB3SEC issue de nos travaux repose sur deux points : • permettre d'exprimer tous les types de contraintes utilisées en CA dans un même modèle, • proposer une approche de modélisation basée sur les événements. En effet, aucune des méthodes actuelles ne présente ces deux caractéristiques, au contraire de la méthode EB3SEC. Nous avons défini un ensemble de patrons, chacun des patrons correspond à un type de contraintes de CA. Un modèle réalisé à l'aide de la méthode EB3SEC peut avoir différentes utilisations : • vérification et simulation, • implémentation. La vérification consiste à s'assurer que le modèle satisfait bien certaines propriétés, dont nous avons défini différents types. Principalement, les blocages doivent être détectés. Ils correspondent à des situations où une action n'est plus exécutable ou à des situations où plus aucune action n'est exécutable. Les méthodes actuelles des techniques de preuves par vérification de modèles ne permettent pas de vérifier les règles dynamiques de CA. Elles sont alors combinées à des méthodes de simulation. Une fois qu'un modèle a été vérifié, il peut être utilisé pour implémenter un filtre ou noyau de sécurité. Deux manières différentes ont été proposées pour réaliser cette implémentation : transformer le modèle EB3SEC vers un autre langage, tel XACML, possédant une implémentation ayant déjà atteint la maturité ou réaliser un noyau de sécurité utilisant le langage EB3SEC comme langage d'entrée. [symboles non conformes]

Le silicium (Si) sous forme dissoute (DSi) est indispensable à la croissance des diatomées, (microalgues) qui sont un élément clé des réseaux trophiques aquatiques terrestres et océaniques et qui jouent un rôle majeur dans le cycle global du carbone. La construction d’un modèle global du cycle de Si le long du continuum aquatique continent-océan a permis de mettre en évidence l’importance de la zone de transition fleuve-mer pour le transfert du silicium continental vers les océans. Ce transfert est influencé par les diatomées planctoniques qui fixent le DSi et, en sédimentant, retiennent une partie du silicium continental dans les sédiments des estuaires. Les modifications des flux de Si continentaux par les diatomées planctoniques dans les estuaires ont été clarifiées par : 1) des expériences sur l’écophysiologie d’une diatomée d’eau douce euryhaline (Cyclotella meneghiniana) particulièrement peu affectée par l’augmentation de salinité subi par le plancton lors de son transport des fleuves à la mer, 2) l’étude de la dissolution de la silice biogénique (bSiO2) qui constitue la coque externe des diatomées, et notamment l’effet de la salinité et des bactéries sur ce processus de recyclage du DSi, 3) la reconstitution du mélange des eaux et des diatomées dans un estuaire par l’expérimentation (3 espèces de diatomées dans un gradient salin artificiel) et par la construction et l’utilisation d’un modèle de Si dans la zone de mélange estuarienne. Les résultats soulignent notamment l’importance des variations de salinité, de la turbidité de l’eau, de la nature des diatomées de rivière (sténohalines versus euryhalines) et de la viabilité des cellules sur les transformations et la rétention du silicium dans la zone de transition fleuve-mer.

Weathering releases lithogenic elements to soil and stream waters that support life in catchment ecosystems. Seasonal and inter-annual variations in hydrologic conditions change subsurface flowpaths, modifying the influence of weathering on stream waters. This study, over two climatically variable years, determined seasonal and inter-annual changes in solute sources to streams using a multi-tracer approach including major cations, strontium isotopes, germanium (Ge)/silica ratios, carbon species, and trace metals. Stream water cations display constant concentrations although discharge response was highly variable, suggesting that there is a consistent subsurface water supply. However, Sr isotope ratios, and concentrations of Ge, Fe, Al, and dissolved organic carbon, which originate from shallow soil waters, increase with the hydrograph during a wet winter snowmelt. This indicates that during a year with a thick snowpack, stream waters contain components of both shallow soilwater and groundwater during snowmelt, whereas during all other times groundwater contributes predominantly to the stream.

MSc (Occupational Therapy), Faculty of Health Sciences, University of the Witwatersrand / As there are no occupation based outcome measures evaluating the effect of occupational therapy in the pre-school child with an Autism Spectrum Disorder (ASD) an Occupational Performance Questionnaire (OPQ) was developed to address this. The OPQ was tested for content validity and reliability before a 12 month intervention study to establish construct validity and response to change in children with ASD receiving Occupational Therapy using a Sensory Integration frame of reference (OT-SI) was done. The results of 19 subjects on the OPQ were compared with the results on two other standardised measures -the Short Sensory Profile (SSP), and Parenting Stress Index (PSI-SF) at six monthly intervals. Convergent validity between family impact on the OPQ and the PSI-SF was moderate but for occupation performance on the OPQ and the SSP it changed from negligible to moderate over 12 months. The OPQ is responsive to change as correlations between improvements in the three outcome measures were moderate. The OPQ was found to still need attention in terms of item reliability and validity.