This thesis presents a study of hybrid solar cells, specifically looking at various methods which can be employed in order to increase the power conversion efficiency of these devices. The experiments and results contained herein also present a very accurate picture of how rapidly the field of hybrid solar cells has progressed within the past three years. Chapters 1 and 2 present the background and motivation for the investigations undertaken, as well as the relevant theory underpinning solar cell operation. Chapter 2 also gives a brief review of the literature pertinent to the main types of devices investigated in this thesis; dye-sensitised solar cells, semiconductor sensitized solar cells and perovskite solar cells. Descriptions of the synthetic procedures, as well as the details of device fabrication and any measurement techniques used are outlined in Chapter 3. The first set of experimental results is presented in Chapter 4. This chapter outlines the synthesis of mesoporous single crystals (MSCs) of anatase TiO₂ as well as an investigation of its electronic properties. Having shown that this material has superior electronic properties to the conventionally used nanoparticle films, they were then integrated into low temperature processed dye-sensitised solar cells and achieved power conversion efficiencies of > 3%, exhibiting electron transport rates which were orders of magnitude higher than those obtained for the high temperature processed control films. Chapter 5 further investigates the use of MSCs in photovoltaic devices, this time utilising a more strongly absorbing inorganic sensitiser, Sb₂S₃. Utilising the readily tunable pore size of MSCs, these Sb₂S₃ devices showed an increase in voltage and fill factor which can be attributed to a decrease in recombination within these devices. This chapter also presents the use of Sb₂S₃ in the meso-superstructured configuration. This device architecture showed consistently higher voltages suggesting that in this architecture, charge transport occurs through the absorber and not the mesoporous scaffold. Chapters 6 and 7 focus on the use of hybrid organic-inorganic perovskites in photovoltaic devices. In Chapter 6 the mixed halide, lead-based perovskite, CH₃NH₃PbI_3-xCl_x is employed in a planar heterojunction device architecture. The effects of Lewis base passivation on this material are investigated by determining the photoluminescence (PL) lifetimes and quantum efficiencies of treated and untreated films. It is found that passivating films of this material using Lewis bases causes an increase in the PLQE at low fluences as well as increasing the PL lifetime. By globally fitting these results to a model the trap densities are extracted and it is found that using these surface treatments decreases the trap density of the perovskite films. Finally, these treatments are used in complete solar cells resulting in increased power conversion efficiencies and an improvement in the stabilised power output of the devices. Chapter 7 describes the materials synthesis and characterisation of the tin-based perovskite CH₃NH₃SnI₃ and presents the first operational, lead-free perovskite solar cell. The work presented in this thesis describes significant advances in the field of hybrid solar cells, specifically with regards to improvements made to the nanostructured electrode, and the development and implementation of more highly absorbing sensitizers. The improvements discussed here will prove to be quite important in the drive towards exploiting solar power as a clean, affordable source of energy.

L’incorporation croissante des (nanomatériaux) NMx dans les aliments et les emballages a contribué à une demande sociétale majeure au regard de l’évaluation des risques des NMx sur la santé. Toutefois, en raison des nombreux paramètres des NMx (taille, forme, structure cristalline, solubilité…), ainsi que des processus physiologiques (comme la digestion) pouvant impacter sur l’absorption et la réponse toxique des NMx, l’évaluation des risques des NMx est compliquée. De plus, leur évaluation in vitro est délicate en raison d’interférences (optiques, catalytiques…) lors de la réalisation des tests. Notre projet de recherche visait à déterminer, l’impact des paramètres d’hydrophobicité des NMx de TiO2 de structure cristalline rutile et l’impact de la solubilité des NMx d’Al0 et Al2O3 sur leur toxicité/génotoxicité au niveau intestinal (organe primo-exposé) et hépatique (organe d’accumulation). Les effets de ces NMx ont été étudiés par une combinaison de méthodes complémentaires in vivo par gavage sur rat, et in vitro sur les lignées humaines Caco-2 et HepaRG différenciées, tout en tenant compte des interférences in vitro. Aucune réponse toxique et génotoxique n’a été observée in vitro malgré la différence de revêtement hydrophobe/hydrophile des NMx de TiO2. Seuls les NMx d’Al2O3 ont induit des lésions oxydatives de l’ADN mais uniquement dans les cellules Caco-2, tandis que de fortes interférences ont empêché de conclure avec les NMx d’Al0. Aucun dommage chromosomique n’a été observé pour ces NMx. In vivo aucun effet génotoxique n’a été observé dans l’intestin, le colon et le foie mais des dommages à l’ADN ont été décelés avec les NMx d’Al2O3 dans la moelle osseuse. La comparaison des résultats avec ceux de la forme ionique AlCl3 suppose un mécanisme de génotoxcité indépendant de la solubilité des NMx d’Al0 et d’Al2O3 dans les milieux biologiques. Malgré les nombreux progrès en nanotoxicologie, l’ensemble de nos résultats a souligné la difficulté d’obtenir des conclusions fiables avec des tests classiques utilisés pour les produits chimiques in vitro, la difficulté d’extrapolation in vitro/in vivo des effets des NMx et le besoin de poursuivre les recherches pour disposer de méthodes et d’outils permettant d’évaluer les effets des NMx de manière fiable. / The growing incorporation of nanomaterials (NMs) into food and packaging has contributed to the increasing demand for the assessment of the health hazards of these particles. However, this task is rendered difficult since the numerous intrinsic parameters (size, shape, crystalline structure, solubility ...), as well as physiological processes (such as digestion) can have an impact on the absorption and toxicological responses of NMs. Moreover, their evaluation in vitro is complicated by various sources of interference (optical, catalytic …) with toxicity tests. Our research project aimed to evaluate, the impact of hydrophobicity of rutile TiO2 NMs and solubility of AlO and Al2O3 NMs on their intestinal (first-exposed organ) and hepatic (accumulation organ) toxicity/genotoxicity. The effects of these NMs were investigated by a combination of complementary methods, in the rat in vivo by gavage, and in vitro using differentiated human Caco-2 and HepaRG cell lines, while taking into account potential interference with in vitro tests. No toxic/genotoxic response was observed in vitro despite the difference of hydrophobic/hydrophilic surface coating for TiO2 NMs. Only Al2O3 induced oxidative DNA damage solely in Caco-2 cells, while significant interference led to inconclusive results for AlO NMx. No chromosomal damage was observed for Al0 or Al2O3 NMx. In vivo no genotoxic effect was observed in the intestine, colon and liver but DNA damage was detected with Al2O3NMx in the bone marrow. Comparison of results with those for the ionic form AlCl3 demonstrated that effects observed were not related to the solubility of Al0 and d’ Al2O3 NMs in the biological environment. Despite considerable progress in nanotoxicology, our results have highlighted the difficulty to obtain reliable re sults with the traditional toxicity tests used for chemical compounds in vitro, the difficulty associated with the in vitro/in vivo extrapolation of the effects of NMs, as well as the need to continue research aimed at developing robust and reliable methods and tools for the evaluation of the effects of NMs.

Orientador: Prof. Dr. Flavio Leandro de Souza / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, 2016. / Com a crescente demanda energética mundial e a necessidade de desenvolvimento nos métodos renováveis para obtenção de energia surge o interesse nas Células Fotoeletroquímicas, dispositivos que possibilitam a conversão da energia da radiação solar em energia química na forma de hidrogênio molecular. Grande parte da pesquisa na área das células fotoeletroquímicas é voltada para a eficiência de conversão energética e barateamento de custos de produção. Com base nisso o presente trabalho tem foco no desenvolvimento de eletrodos usados nesse dispositivo, sintetizados usando hematita em condição hidrotermal, buscando a melhoria dos métodos de síntese para redução de custos, impacto ambiental e eficiência energética. A síntese utilizada teve o intuito de reduzir ao máximo a quantidade de reagentes à base de cloro, que podem interferir negativamente no crescimento das estruturas e analisar a influência de alguns parâmetros alterados durante o processo: tempo de síntese, atmosfera de tratamento térmico e concentração de reagentes. Foi concluído, com base nas caracterizações morfológicas e eletroquímicas aplicadas nas amostras, que a síntese hidrotermal utilizada gerou eletrodos fotossensíveis sendo mais efetiva nos tempos de 1 hora, com tratamento térmico em atmosfera de nitrogênio e com uso de 0,076 mol.L-1 de sulfato de sódio e 0,15 mol.L-1 de cloreto de ferro, contribuindo com a redução da quantidade de cloro utilizado. A melhor fotocorrente obtida para os eletrodos foi por meio da amostra F1Ny chegando a 0,936 mA.cm-2. / The increase of global energy demand and the need for renewable sources results on the interest in devices know as photoelectrochemical cells. This device enables the conversion of solar radiation energy into chemical energy in the form of molecular hydrogen. Most of the research in the area of the photoelectrochemical cells is focused on the energy conversion efficiency and reduction of production costs. This work aimed the development of electrodes used in photoelectrochemical cells, synthesized using hematite in hydrothermal condition, seeking the improvement of synthesis methods to reduce costs, environmental impact and energy efficiency. The synthesis used was intended to reduce the amount of chlorine based reagents that can negatively impact the growth of structures and analyze the influence of some parameters changes during the process: synthesis time, atmosphere used in the heat treatment and reagents concentration. It was concluded through morphological and electrochemical characterization that the hydrothermal synthesis has generated photosensitive electrodes. The most promising electrode produced was synthesized for 1 hour, them treated in nitrogen atmosphere and using 0.076 mol.L-1 of sulfate sodium and 0.15 mol.L-1 of iron chloride, contributing to reduce the amount of chlorine used in relation to other methods generally discussed in the literature. The best photocurrent obtained was 0.936 mA.cm-2.

Philosophiae Doctor - PhD (Chemistry) / Nanomaterials have been found to undeniably possess superior properties than bulk structures across many fields of study including natural science, medicine, materials science, electronics etc. The study of nano-sized structures has the ability to address the current world crisis in energy demand and climate change. The development of materials that have various applications will allow for quick and cost effective solutions. Nanomaterials of Sn and Bi are the core of the electronic industry for their use in micro packaging components. These nanomaterials are also used as electrocatalysts in fuel cells and carbon dioxide conversion, and as electrodes for rechargeable sodium ion batteries. There are various methods used to make these nanostructures including solid state methods, hydrothermal methods, sputtering, and vacuum deposition techniques. These methods lack the ability to control the structure of material at an atomic level to fine tune the properties of the final product. This study aims to use E-ALD technique to synthesis thin films of Sn and Bi for various energy applications, and reports the use of E-ALD in battery applications for the first time. Thin films were synthesised by developing a deposition sequence and optimising this deposition sequence by varying deposition parameters. These parameters include deposition potential, and concentration of precursor solution. The thin films were characterised using cyclic voltammetry, linear sweep voltammetry, chronoamperometry for electrochemical activity. These were also characterised using scanning electron microscope for morphology, x-ray diffraction for crystal phases, energy dispersive spectroscopy for elemental mapping, and focused ion beam scanning electron microscope for thickness. The elemental content was analysed using electron probe micro analysis and inductively coupled plasma mass spectrometry. The electrochemical impedance charge and discharge profile were used for electrochemical battery tests.

One-dimensional (1D) nanomaterials are of great importance for a number of potential applications. However, in order to realize this potential a thorough understanding of the charge-carrier dynamics in these materials is required, since these largely determine the optoelectronic properties of the materials in question. This thesis investigates the charge-carrier dynamics of two 1D nanomaterials, single-walled carbon nanotubes (CNTs) and tungsten-oxide nanowires (WOxNWs), with the goal of better understanding the nature of their optoelectronic responses, and how nanomaterial geometry and morphology influence these responses. We do this using terahertz time-domain spectroscopy (THz-TDS) and optical pump - terahertz probe time-domain spectroscopy (OPTP). Firstly, we discuss how to properly analyse and interpret the data obtained from these experiments when measuring 1D nanomaterials. While the data obtained from THz-TDS is fairly straight-forward to analyse, OPTP experimental data can be far from trivial. Depending on the relative size of the sample geometry compared to the probe wavelength, various approximations can be used to simplify the extraction of their ultrafast response. We present a general method, based on the transfer matrix method, for evaluating the applicability of these approximations for a given multilayer structure, and show the limitations of the most commonly used approximations. We find that these approximations are only valid in extreme cases where the thickness of the sample is several orders of magnitude smaller or larger than the wavelength, which highlight the danger originating from improper use of these approximations. We then move on to investigate how the charge-carrier dynamics of our CNTs is influenced by nanotube length and density. This is done through studying the nature of the broad THz resonance observed in finite-length CNTs, and how the nanotube length and density affects this resonance. We do this by measuring the conductivity spectra of thin films comprising bundled CNTs of different average lengths in the frequency range 0.3-1000 THz and temperature interval 10-530 K. From this we show that the observed temperature-induced changes in the terahertz conductivity spectra depend strongly on the average CNT length, with a conductivity around 1 THz that increases/decreases as the temperature increases for short/long tubes. This behaviour originates from the temperature dependence of the electron scattering rate, which results in a subsequent broadening of the observed THz conductivity peak at higher temperatures and a shift to lower frequencies for increasing CNT length. Finally, we show that the change in conductivity with temperature depends not only on tube length, but also varies with tube density. We record the effective conductivities of composite films comprising mixtures of WS2 nanotubes and CNTs vs CNT density for frequencies in the range 0.3-1 THz, finding that the conductivity increases/decreases for low/high density films as the temperature increases. This effect arises due to the density dependence of the effective length of conducting pathways in the composite films, which again leads to a shift and temperature dependent broadening of the THz conductivity peak. Next, we investigate the conflicting reports regarding the ultrafast photoconductive response of films of CNTs, which apparently exhibit photoconductivities that can vastly differ, even in sign. Here we observe explicitly that the THz photoconductivity of CNT films is a highly variable quantity which correlates with the length of the CNTs, while the specific type of CNT has little influence. Moreover, by comparing the photo-induced change in THz conductivity with heat-induced changes, we show that both occur primarily due to heat-generated modification of the Drude electron relaxation rate, resulting in a broadening of the plasmonic resonance present in finite-length metallic and doped semiconducting CNTs. This clarifies the nature of the photo-response of CNT films and demonstrates the need to carefully consider the geometry of the CNTs, specifically the length, when considering them for application in optoelectronic devices. We then move on to consider our WOxNWs. We measure the terahertz conductivity and photoconductivity spectra of thin films compromising tungsten-oxide (WOx) nanowires of average diameters 4 nm and 100 nm, and oxygen deficiencies WO2.72 and WO3 using THz-TDS and OPTP. From this we present the first experimental evidence of a metal-to-insulator transition in WOx nanowires, which occurs when the oxygen content is increased from x=2.72 -> 3 and manifests itself as a massive drop in the THz conductivity due to a shift in the Fermi level from the conduction band down into the bandgap. Furthermore we present the first experimental measurements of the photoexcited charge-carrier dynamics of WOx nanowires on a picosecond timescale and map the influence of oxygen-content and nanowire diameter. From this we show that the decay-dynamics of the nanowires is characterized by a fast decay of < 1 ps, followed by slow decay of 3-10 ps, which we attribute to saturable carrier trapping at the surface of the nanowires.

abstract: Nanomaterials have attracted considerable attention in recent research due to their wide applications in various fields such as material science, physical science, electrical engineering, and biomedical engineering. Researchers have developed many methods for synthesizing different types of nanostructures and have further applied them in various applications. However, in many cases, a molecular level understanding of nanoparticles and their associated surface chemistry is lacking investigation. Understanding the surface chemistry of nanomaterials is of great significance for obtaining a better understanding of the properties and functions of the nanomaterials. Nuclear magnetic resonance (NMR) spectroscopy can provide a familiar means of looking at the molecular structure of molecules bound to surfaces of nanomaterials as well as a method to determine the size of nanoparticles in solution. Here, a combination of NMR spectroscopic techniques including one- and two-dimensional NMR spectroscopies was used to investigate the surface chemistry and physical properties of some common nanomaterials, including for example, thiol-protected gold nanostructures and biomolecule-capped silica nanoparticles. Silk is a natural protein fiber that features unique properties such as excellent mechanical properties, biocompatibility, and non-linear optical properties. These appealing physical properties originate from the silk structure, and therefore, the structural analysis of silk is of great importance for revealing the mystery of these impressive properties and developing novel silk-based biomaterials as well. Here, solid-state NMR spectroscopy was used to elucidate the secondary structure of silk proteins in N. clavipes spider dragline silk and B. mori silkworm silk. It is found that the Gly-Gly-X (X=Leu, Tyr, Gln) motif in spider dragline silk is not in a β-sheet or α-helix structure and is very likely to be present in a disordered structure with evidence for 31-helix confirmation. In addition, the conformations of the Ala, Ser, and Tyr residues in silk fibroin of B. mori were investigated and it indicates that the Ala, Ser, and Tyr residues are all present in disordered structures in silk I (before spinning), while show different conformations in silk II (after spinning). Specifically, in silk II, the Ala and Tyr residues are present in both disordered structures and β-sheet structures, and the Ser residues are present primarily in β-sheet structures. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2017

Les nanoparticules d'argile sont des ressources naturelles largement disponibles et peu coûteuses présentant de nombreuses caractéristiques telles qu'une grande surface spécifique, une imperméabilité aux gaz, ainsi que des propriétés mécaniques et thermiques élevées. Elles ont donc attiré depuis plus de trois décennies une attention particulière, notamment pour le renforcement des matériaux à base de polymères. Cependant, les nanoparticules d'argile à l'état natif souffrent d'une incompatibilité, donc de faibles interactions interfaciales et de d'une mauvaise dispersion avec/dans la plupart des matériaux polymères organiques à cause de leur hydrophilie intrinsèque et des fortes interactions entre les feuillets constitutifs. Ainsi, l'un des principaux défis dans le développement de nanocomposites polymères à base d'argile (NAPs) avec des propriétés mécaniques avancées repose sur le contrôle au niveau à l'échelle moléculaire des propriétés interfaciales entre l'argile et la matrice polymère. En tenant compte des critères du développement durable, du génie civil et de l'économie verte, nous avons développé, dans la première partie de cette thèse, des nano-renforts réactifs et pré-exfoliés qui peuvent être incorporés dans une grande série de matrices (bio)polymères en donnant lieu à de fortes interactions avec les dites matrices et conduisant pour un à des comportements mécaniques améliorés. Afin de mieux répondre à ces spécificités, nous avons mis en oeuvre des approches vertes pour la préparation de ces nano-renforts génériques, à savoir la photopolymérisation a été utilisée comme faible consommateur d'énergie et une méthode rapide et peu énergivore pour la fonctionnalisation de surface des argiles, un protocole sans solvant a été utilisé pour préparer des nanocomposites ternaires, tandis que des biopolymères (amidon, cellulose) ou des précurseurs d'origine biologique (huiles végétales époxydées) ont servi de milieux de dispersion. Les résultats principaux issus de cette première partie peuvent être résumés comme suit : - La morphologie et la réactivité des nano-renforts d'argile sont aisément contrôlées en ajustant le temps de photo-polymérisation et en choisissant un monomère vinylique approprié. - Les méthodes de préparation permettent la préparation d'échantillons de à l'échelle des grammes. - La chimie surface des nano-renforts réactifs et pré-exfoliés peut être ajustée afin d'assurer la compatibilité avec les des biopolymères préformés thermoplastiques et des résines thermodurcissables, tels que l'amidon et les résines époxyde biosourcées, respectivement. - Les propriétés mécaniques des nanocomposites ternaires ainsi obtenus sont fortement améliorées comparés aux en comparaison des matrices polymères pures grâce à la dispersion homogène et fine des feuillets du nano-renfort dans la matrice polymère et aux fortes interactions interfaciales entre ces deux constituants / Clay nanoparticles (CNP) are abundantly available low-cost natural resources with numerous positive attributes such as large surface area, impermeability to gas, superior mechanical and thermal properties so that they have attracted over the last three decades significant attention, notably for the reinforcement of polymer-based materials. However, CNP suffer from incompatibility, hence weak interfacial interactions and poor dispersion with/in most of organic polymeric materials because of their intrinsic hydrophilicity and strong interlayer interactions. This limitation is one of the major reasons why polymer nanocomposites have to date remained mainly in laboratories. Thus, one of the key challenges in developing clay-based polymer nanocomposites (PCNs) with advanced thermo-mechanical, gas barrier...properties relies on the control at the molecular level of the interface properties of clay nanoplatelets-filled polymer resins. Taking into account the criteria for sustainable development, civil engineering and green economy, we have developed, in the first part of this thesis, reactive and pre-exfoliated clay nanofillers that may be further incorporated in a diverse set of biopolymer matrices and giving rise to strong energy interactions with the said matrices for improved mechanical behavior. To ensure a closer fit of these specifications we have implemented green approaches for the preparation of these generic nanofillers, namely photopolymerisation was used as a low energy consumption and fast method for the surface functionalization of native clays, solvent-free protocols were applied to prepare polymer nanocomposites, while biopolymers (starch, cellulose) or bio-based precursors (epoxidized vegetal oils) served as dispersion media. By controlling the preparation conditions, reactive clay nanofillers with adjustable interlayer spacing and chemical surface reactivity were prepared. Of particular interest is that the layered-like structure of the clay nano ller is preserved while the d-interlayer spacing can be increased though increasing the photopolymerization time, i.e. amount of polymer within the clay nanosheets. Our major results from the the first part can be summarized as follows: Morphology and reactivity of clay nanofillers are easily controlled though adjusting the photopolymerization time and selecting adequate vinyl monomer. - The newly preparation methods allow preparation of samples beyond the gram-scale. - Reactive and surface chemistry of pre-exfoliated clay nanofillers can be tuned to provide compatibility with both conventional preformed biopolymers and bio-based epoxy resins. - The mechanical properties of the resulting polymer nanocomposites are improved as compared to the neat polymeric matrices owing to the strong interface interaction between fillers and dispersion matrices

Les propriétés mécaniques des petits objets diffèrent fortement de celles du matériau massif à partir du moment où leurs dimensions deviennent comparables ou inférieures à celles du libre parcours moyen des dislocations (typiquement quelques microns). Par exemple, leur limite élastique augmente quand leur taille diminue. D'autre part les nanostructures sont exposées à de fortes contraintes, telles que celles imposées par les relations épitaxiales avec le substrat.Il existe donc un besoin clair (supporté par des intérêts industriels) d'une meilleure compréhension des phénomènes physiques qui gouvernent les propriétés des matériaux aux échelles nanométriques.Le laboratoire SIMAP est engagé dans ce domaine de recherche et s'y attelle en combinant croissance d'échantillons, méthodes de caractérisation en laboratoire, méthodes numériques et techniques synchrotron.Une des expériences clés développées par notre équipe est la caractérisation in situ des mécanismes de déformation induits par une pointe d'AFM sur une nanostructure par la diffraction des rayons X cohérents. La diffraction des rayons-X cohérents est une technique émergente de synchrotron; qui permet la mesure détaillée de la structure du cristal, y compris le champ de déformation 3D et les défauts potentiels dans des objets micro ou nano structurés. En principe, une image 3D de la structure de l'échantillon peut-être obtenue à partir des données de diffraction cohérente. En pratique, reconstruire une image de l'échantillon peut s'avérer délicat en présence d'un champ de déformation inhomogène et de nombreux défauts cristallins. Le profil du front d'onde qui est généralement assez éloigné d'une onde plane, peut encore ajouter une complication supplémentaire au problème. Dans ces travaux de thèse, il est démontré qu'une image 3D de l'objet peut être reconstruite dans le cas de systèmes modérément complexes. / The mechanical properties of small objects deviate strongly from the bulk behaviour, as soon as their size becomes comparable or smaller to the dislocation mean free path (typically a few microns). For instance, their elastic limit increase when their size is reduced. On a another hand, nanostructures are exposed to strong constraints, such as that imposed by epitaxial relations with a substrate. Altogether, there is a clear need (supported by industrial interests) for a better understanding of the fundamental phenomena that govern the mechanical properties of materials at the nanometre scale. The lab SIMaP is engaged in this research and tackles the topic by combining sample growth, laboratory characterisation methods, numerical models, and synchrotron techniques.One key experiment developed by our team is the in situ characterisation of the deformation mechanism induced by an AFM tip on a nanostructure using Coherent X-ray Diffraction (CXD). CXD is an emerging synchrotron technique that allows the detailed measurement of the crystal structure,including strain field and defects, of micro/nano-objects. In principle, a 3D image of the structure of the sample can be obtained from the CXD data. However, it remains difficult in realistic cases, when the strain is very inhomogeneous and crystal defects numerous. The problem is further complicated by the wavefront of the beam, which is usually far from a plane wave, particularly when the AFM tip shadows part of the incoming beam. In this PHD work, it is demonstrated that a 3D image of the object can be reconstructed in case of moderately complex systems.

Made available in DSpace on 2016-12-08T17:19:30Z (GMT). No. of bitstreams: 1 00Dissertacao_Ricardo.pdf: 90863 bytes, checksum: 1aca1721eadf252d5e0ad6faddc68cd5 (MD5) Previous issue date: 2007-07-11 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The nanotechnology can be understood as the term used to describe the creation, manipulation and exploration of materials in nanometric scale. This Science is used for study nanostructured materials, constituted of atoms, molecules and/or particles. Brazil comes detaching some areas development some nanotechnology products, for applications in chemical analyses, medical and odontologic treatments and in the development of nanoparticles, nanotube, nanowires and cristalografic analysis. The nanoestructured powder-ceramic synthesis calcium phosphate and materials nanocomposites are promising in surgical applications medical-odontologics in the setting of prothesis, wedding bone, in coverings for the implantations, the stabilization of implantations and as matrical element in the reconstitution of the bone structure. This work had as objective the characterization of powder nanoestructured calcium phosphate and nanocomposite calcium phosphate/SiO2n, in the percentile nanometric silicom compositions (SiO2n) of 5%, 10% and 15% in volume; through the techniques of scanning electron microscopy, X-ray diffractometry and the method of numerical simulation were used for determination of surface area nanopowder. The studies using the method of numerical simulation had been carried through on the ones powder nanoestructured gotten of the calcination 9000C/2h. This method can be an innovative methodology, in the determination of surface area nanoparticles, since, the results obted in this work if approach to the values found for BET. The gotten results of these studies, had evidenced the presence for powder nanoestructured phase b-calcium phosphate calcinations 9000C/2h, b and a - calcium phosphate ones powder thermal treatment 1300ºC/2h. The morphology of the bone matrix calcium phosphate, gotten of the drying in rotoevaporador, is formed by nanoparticles agglomerated with average size 20nm. For the ones powder gotten nanocomposites the drying it observed type of morphology the same, more the presence of nanopartículas of SiO2n. For the powder gotten of the calcination and the thermal treatment, it was evidenced to have modification of the morphology of particles, being observed the germination and growth of the average diameter of nanopartículas in function of the temperature. The method of numerical simulation, allowed to identify the surface of average area of nanopartilces for the powder nanoestrutured gotten the calcination. A preliminary study of citotoxidade and the cellular viability was also become fullfilled, on the powder nanoestrutured gotten of the calcination and the thermal treatment. The gotten results of this study are entertainers and the values of the index of cellular viability had on average presented up 80% for all the nanoestrutured compositions of powder from in the tests of 24h, 48h and 72h. / A nanotecnologia pode ser entendida como sendo o termo utilizado para descrever a criação, manipulação e exploração de materiais em escala nanométrica. Esta Ciência é utilizada para investigação de materiais nanoestruturados, constituídos por átomos, moléculas e/ou partículas. O Brasil vem se destacando em algumas áreas de desenvolvimento de alguns produtos nanotecnológicos, destes se destacam os produtos utilizados em aplicações de análises químicas, tratamentos médicos e odontológicos, o desenvolvimento de nanopartículas, nanotubos, nanofios e análises cristalográficas. A síntese e caracterização de pós biocerâmicos nanoestruturados de fosfato de cálcio e nanocompósitos é um método promissor de produção de pós biocerâmicos com características morfológicas, de superfície de área e da microporosidadeade favoráveis para uso em aplicações cirúrgicas médico-odontológicas, na fixação de próteses, enchimento ósseo, em revestimentos de implantes, na estabilização de implantes e como elemento matricial na reconstituição da estrutura óssea. Este trabalho teve como objetivo a caracterização de pós nanoestruturados de fosfato de cálcio e nanocompósito fosfato de cálcio/SiO2n, nas composições percentuais de sílica nanométrica (SiO2n) de 5%, 10% e 15% em volume; através das técnicas de microsopcopia eletrônica de varredura, difratometria de raios-X e o método de simulação numérica foi utilizado para determinação da superfície de área das nanopartículas. Os estudos utilizando o método de simulação numérica foram realizados sobre os pós nanoestruturados obtidos da calcinação a 9000C/2h. Este método pode ser uma metodologia inovadora, na determinação de superfície de área de nanopartículas, visto que, os resultados obidos neste trabalho se aproximam dos valores encontrados por BET. Os resultados obtidos destes estudos, evidenciaram a presença da fase fosfato de cálcio-b para os pós nanoestruturados obtidos da calcinação a 900ºC/2h e as fases fosfato de cálcio a e b, para os pós obtidos do tratamento térmico a 1300ºC/2h. A morfologia da matriz óssea de fosfato de cálcio, obtida da secagem em rotoevaporador, é formada por nanopartículas aglomeradas com tamanho médio inferior a 20nm. Para os pós nanocompósitos obtidos da secagem observou o mesmo tipo de morfologia, mais a presença das nanopartículas de SiO2n. Para os pós obtidos da calcinação e do tratamento térmico, constatou-se haver modificação da morfologia das partículas, observando a germinação e crescimento do diâmetro médio das nanopartículas em função da temperatura. O método de simulação numérica, permitiu identificar a superfície de área média das nanopartículas para os pós nanoestruturados obtidos da calcinação. Realizou-se também um estudo preliminar de citotoxidade e da viabilidade celular, sobre os pós nanoestruturados obtidos da calcinação e do tratamento térmico. Os resultados obtidos deste estudo são animadores e os valores do índice de viabilidade celular apresentaram-se em média superior a 80% para todas as composições de pós nanoestruturados a partir de nos testes de 24h, 48h e 72h.

Made available in DSpace on 2016-12-08T17:19:30Z (GMT). No. of bitstreams: 1 pre_textuais.pdf: 199931 bytes, checksum: eb713778427903d3a744b4a961bc8e13 (MD5) Previous issue date: 2007-07-04 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The synthesis of nanostructured calcium phosphate powders, and nanocomposite has called attention in different areas of biomedical, and odontological applications mainly in the replacement, and regeneration of bone tissues. This is due, mainly, because these nanomaterials present good biocompatibility and mineralogical characteristics similar of human skeleton apatite. These nanomaterials also offer good bone tissue reabsorption, osteointegration, and osteoinduction towards the inner part of nanomaterial structure, which accelerate new bone tissue regenaration, reconstitution, and formation. This work goal has been focused on optimization of aqueous suspension synthesis method, from a calcium phosphate SiO2n nanostructured and nanocomposites calcium phosphate matrix bone in the concentration of 5, 10 and 15% in silicon nanometric volume spread in the bone matrix inter-intragranular position. This method has allowed obtaining nanostructured powders through small agglomerated particles with size below 100 nm. Nanostructured powders originated from this synthesis have undergone calcinations through a temperature of 900o.C/2h aimed to eliminate organic material stemmed from the synthesis process, and for calcium phosphate phase. Presented results are related to synthesis method, morphological characterization, microstructural, nanostructural, and mineralogical of the thermal behavior for nanostructured obtained from 900oC/2h calcinations, from thermal treatment through a temperature of 1300oC/2h for syntherized and annealing biomaterials. The mechanical properties were determined by different compositions of nanostructured biomaterial obtained from 1300oC/2h syntherization annealing at a temperature of 1100oC/30min. A preliminary citotoxity and cellular viability study has also been made on the nanostructured powders obtained from calcinations and thermal treatment. Results obtained from this study are encouraging, and cellular viability index have presented an average higher than 80% for all compositions of nanostructured powders after 24 hours. / A síntese de pós nanoestruturados de fosfatos de cálcio e nanocompósitos tem despertado interesses em diferentes áreas de aplicações biomédicas e odontológicas, principalmente na substituição e na regeneração de tecido ósseo. Isto se deve principalmente por estes nanomateriais apresentarem boa biocompatibilidade e características mineralógicas semelhantes a da apatita do esqueleto humano. Estes nanomateriais oferecem também uma boa reabsorção, osteointegração e osteoindução do tecido ósseo para o interior da estrutura do nanomaterial, o que acelera a regeneração, a reconstituição e a formação do novo tecido ósseo. O objetivo deste trabalho se concentrou na otimização do método de síntese via úmida, de uma matriz óssea de fosfato de cálcio nanoestruturado e nanocompósitos fosfato de cálcio/SiO2n, nas concentrações de 5, 10 e 15% em volume de sílica nanométrica dispersa em posição inter-intragranular na matriz óssea. Este método permitiu a obtenção de pós nanoestruturados formados por finas partículas aglomeradas com tamanho menor que 100 nm. Os pós nanoestruturados obtidos da síntese, foram calcinados a temperatura de 900oC/2h, com objetivo de eliminação de material orgânico, resultante do processo de síntese e para formação da fase fosfato de cálcio- Ò. Os resultados apresentados estão relacionados ao método de síntese, à caracterização morfológica, microestrutural, nanoestrutural, mineralógica do comportamento térmico para os pós nanoestruturados obtidos da calcinação a 900oC/2h e do tratamento térmico a temperatura de 1300oC/2h, e para os biomateriais sinterizados e recozidos. As propriedades mecânicas foram determinadas para as diferentes composições de biomateriais nanoestruturados obtidos da sinterização a 1300oC/2h e recozidos a temperatura de 1100oC/30min. Realizouse também um estudo preliminar de citotoxidade e da viabilidade celular, sobre os pós nanoestruturados obtidos da calcinação e do tratamento termico. Os resultados obtidos deste estudo são animadores e os valores do índice de viabilidade celular apresentaram-se em média superiores a 80% para todas as composições de pós nanoestruturados a partir de 24h.