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Made available in DSpace on 2014-10-09T12:50:39Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:58:59Z (GMT). No. of bitstreams: 1 00051.pdf: 1323615 bytes, checksum: 560d14914e0156e890a27864c7db81e2 (MD5) / Dissertacao (Mestrado) / IEA/D / Instituto de Fisica, Universidade de Sao Paulo - IF/USP

Made available in DSpace on 2014-10-09T12:38:46Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:03:02Z (GMT). No. of bitstreams: 1 12890.pdf: 2186659 bytes, checksum: 087fa0b384ece6d4147a0d60df0a8644 (MD5) / Tese (Doutoramento) / IPEN/T / Universitaet Karlsruhe - Fakultaet fuer Maschinenbau

Made available in DSpace on 2014-10-09T12:29:56Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:09:55Z (GMT). No. of bitstreams: 1 00357.pdf: 772989 bytes, checksum: ccc94f3c8138d33bfe2494d41721d680 (MD5) / Dissertacao (Mestrado) / IEA/D / Instituto de Quimica, Universidade de Sao Paulo - IQ/USP

Dans le domaine des cellules solaires de type couches minces, les composés dérivés de Cu2ZnSnS4 (CZTS) suscitent un intérêt croissant au fil des années. Grâce à un composé CZTS pauvre en Cu et pour lequel une partie du sélénium est substituée par du soufre, le rendement photovoltaïque maximal obtenu est de 12.6%. Plusieurs études suggèrent que des défauts de type Cu/Zn produisent un changement de la structure cristallographique la faisant passer de kësterite (groupe d’espace I4) à kësterite désordonnée (groupe d’espace I42m). Le désordre Cu/Zn ainsi que la distribution S/Se peuvent agir sur les performances des cellules solaires. L'objectif de cette thèse est l'étude approfondie de la structure des composés Cu2ZnSn(S,Se)4 (CZTSSe). Les échantillons étudiés ont été synthétisés par voie céramique et ont été caractérisés par les différentes techniques disponibles au laboratoire ainsi que par diffraction haute résolution et diffraction anomale sur monocristal au synchrotron SOLEIL. La combinaison de la diffraction des rayons-X, l’analyse élémentaire par dispersion d’énergie et la spectroscopie RMN ont permis d’en apprendre plus sur la structure et l’agencement des atomes en fonction du rapport S/(S+Se) ou de l’écart à la stoechiométrie CZTSSe. Les résultats principaux sont les suivants : les composés forment une solution solide de CZTSe à CZTS décrite dans la structure kësterite. De plus, bien qu’il soit possible d’observer des différences d’ordre à l’échelle locale, à longue distance, les anions et les atomes de cuivre et de zinc sont distribués aléatoirement, quelque soit le traitement thermique subi par l’échantillon ou l’écart à la stoechiométrie. / Cu2ZnSnS4-derived compounds (CZTS) show an increasing interest in the field of low-cost thin film solar cells. The best solar energy conversion efficiencies of CZTS-based devices, up to 12.6%, are obtained for both copper-poor and mixed S/Se compounds. Several studies suggest that Cu/Zn antisite defects can occur, leading to the modification of the kësterite structure (space group I4) to the so-called disordered kesterite which is of higher symmetry (space group I42m). In the mixed S/Se compounds, the question of the cationic and anionic disorder is of high importance for solar cells efficiency and as not been already addressed through a crystal structure point of view. This study is dealing with a thorough chemical crystallographic investigation of Cu2ZnSn(S,Se)4 compounds. The studied compounds have been synthesized via a ceramic route and have been characterized by the use of different techniques available in the laboratory and also with the use of the high resolution powder diffraction as well as the anomalous single crystal diffraction at the Synchrotron SOLEIL. Thanks to the combination of X-ray diffraction, energy dispersive X-ray spectroscopy and NMR spectroscopy, transmission electronic microscopy, precise information about the structure and the microstructure as a function of S/(S+Se) ratio or the actual deviation from the 2:1:1:4 stoichiometry is provided. The existence of a full solid solution between CZTSe and CZTS with the full disordered kesterite structure is definitely demonstrated. However, at the local scale, there is a difference of order between compounds according to the cooling or to the stoichiometric deviation.

Made available in DSpace on 2014-10-09T12:50:39Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:58:59Z (GMT). No. of bitstreams: 1 00051.pdf: 1323615 bytes, checksum: 560d14914e0156e890a27864c7db81e2 (MD5) / Dissertacao (Mestrado) / IEA/D / Instituto de Fisica, Universidade de Sao Paulo - IF/USP

Made available in DSpace on 2014-10-09T12:38:46Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:03:02Z (GMT). No. of bitstreams: 1 12890.pdf: 2186659 bytes, checksum: 087fa0b384ece6d4147a0d60df0a8644 (MD5) / Tese (Doutoramento) / IPEN/T / Universitaet Karlsruhe - Fakultaet fuer Maschinenbau

M.Ing. (Mechanical Engineering) / The dissertation explores the applications and limitations of optic Fibre Bragg Grating (FBG) sensors for the purpose of structural health monitoring of high performance composite aerospace structures. The absence of a set of stringent performance criteria governing the form and function of a sensory system for embedded high performance applications highlights the major hurdle to be overcome before widespread acceptance of these technologies becomes apparent. The dissertation therefore develops through an extensive literature study a basic framework of performance criteria to be met by the sensory system upon which a prototype Structural Health Monitoring (SHM) system can be further developed. The resolution of the performance criteria into categories of mechanical and non-mechanical performance allows independent evaluation of factors that directly affect the performance of the sensor (in terms of strength, embeddability and load carrying ability) as well as its functional performance (in terms of orientation, spatial resolution and measurement philosophy). The literature study uses the non-mechanical performance limitations as a guideline for the selection of Fibre Bragg Grating (FBG) sensors as the sensory mechanism. The mechanical performance limitations of these specific sensors are then called into question and evaluated. Independent experiment campaigns are therefore developed to evaluate the mechanical and non-mechanical performance limitations such that a set of performance criteria can be developed governing the use of embedded sensory systems. Non mechanical performance with particular emphasis on sensor placement and orientation is investigated by simulating a fixed-free Euler Bernoulli cantilever using the Finite Element Method (FEM). The ability of the sensor to identify structural changes by measuring changes in modal response shows good results. Furthermore the inability of modal based monitoring to identify structural changes in the vicinity of modal inflection points is identified as an opportunity to locate structural deficiencies by monitoring multiple modes with known inflection point positions. The method also provides recommendations of sensor placement and orientation (close to the beam fixture and parallel with the neutral axis) such that the effectiveness of strain component measurements from all measurable modes is maximised. Mechanical performance of embedded FBG sensors is evaluated through an extensive fracture testing program which measures the fracture strains of fibre samples subjected to two-point bending. The fracture test program allows the quantification of the effects of the presence of the fibre’s protective polymer coating on fibre embeddability in composites, the consequent effects that the removal of this coating has on the mechanical performance and fracture behaviour of FBG sensors. These effects are qualified and mitigatory measures developed to improve the mechanical performance. A system of crack masking, hydrofluoric acid etching and fibre treatment is developed and statistical data analysis methods are employed and refined such that improvements in the mechanical properties of the FBG sensors can be quantified. An evaluation of the effectiveness of the proposed mechanical performance improvements yields good results culminating in the development of a comprehensive set of mechanical performance criteria to facilitate further development of a reliable SHM system.

Magister Scientiae - MSc / In this study we report on the effect of the deposition parameters on the morphology and structural properties of CNTs, synthesized by means of the hot-wire chemical vapour deposition technique. SEM, Raman and XRD results show that the optimum deposition conditions for the HWCVD synthesis of aligned MWCNTs, with diameters between 50 and 150 nm and lengths in the micrometer range are: Furnace temperature of 500 ºC, deposition pressure between 150 and 200 Torr, methane/hydrogen dilution of 0.67 and a substrateto- filament distance of 10 cm. / South Africa