A restauração de resina composta dental possui grande aplicação clínica. A polimerização da resina composta é feita através de um processo de fotoativação, que influenciará diretamente as propriedades finais do material restaurador. O estudo e o desenvolvimento das técnicas e dos dispositivos de fotopolimerização das resinas são fatores de grande relevância para melhorar a eficiência do uso da resina composta na Odontologia. Neste trabalho foram avaliadas três fontes de luz, laser de argônio e diodo emissor de luz azul (LED), em comparação com uma lâmpada de fotopolimerização convencional. Através do estabelecimento do diagrama PTT (Potência- Tempo-Temperatura), foram estabelecidos parâmetros seguros de utilização do laser de argônio, para evitar danos térmicos irreversíveis ao tecido pulpar. Na avaliação da dureza, em função da profundidade de penetração da luz no material, foram estabelecidos os parâmetros de operação do laser de argônio para a obtenção de valores de dureza semelhantes ou melhores aos obtidos com a lâmpada convencional. A microinfiltração, em restaurações classe V polimerizadas com o laser e a lâmpada convencional, não apresentou diferença estatisticamente significante quando comparadas às duas fontes de luz investigadas. A elaboração dos dispositivos à base de LEDs, assim como o estudo da dureza da resina composta curada, possibilitou uma análise do processo de cura e a determinação de parâmetros corretos de utilização dos arranjos de LEDs estudados. Nosso estudo termina com a proposta de um dispositivo alternativo para a fotoativação das resinas compostas. / The restorations based on composite resin have great application in modem dentistry. The composite polymerization is obtained by a photoactivation process. The final properties of materials are connected with the cure process. The development of photopolymerization procedures and devices is important to improve the cure efficiency and its quality. In this work, two light sources, argon laser and blue light-emitting diodes (LEDs), were studied and compared to a conventional cure lamp. In the PTT (Power-Time-Temperature) diagram it were established safe working parameters to argon laser application, in order to avoid pulpal damage. The microhardness was used to quantify mechanical properties. The observation of VHN as a function of the depth in the material, allowed us to determine the operational parameters where argon laser produces similar properties compared with the conventional lamp. The microleakage observed in class V restorations cured by laser or conventional lamp was investigated and the result did not show statistical difference when the two light sources were compared. Using the devices based on LEDs it was possible to study the cure process and establish the operational parameters when this alternative light source is considered for use in composite resin cure.

A restauração de resina composta dental possui grande aplicação clínica. A polimerização da resina composta é feita através de um processo de fotoativação, que influenciará diretamente as propriedades finais do material restaurador. O estudo e o desenvolvimento das técnicas e dos dispositivos de fotopolimerização das resinas são fatores de grande relevância para melhorar a eficiência do uso da resina composta na Odontologia. Neste trabalho foram avaliadas três fontes de luz, laser de argônio e diodo emissor de luz azul (LED), em comparação com uma lâmpada de fotopolimerização convencional. Através do estabelecimento do diagrama PTT (Potência- Tempo-Temperatura), foram estabelecidos parâmetros seguros de utilização do laser de argônio, para evitar danos térmicos irreversíveis ao tecido pulpar. Na avaliação da dureza, em função da profundidade de penetração da luz no material, foram estabelecidos os parâmetros de operação do laser de argônio para a obtenção de valores de dureza semelhantes ou melhores aos obtidos com a lâmpada convencional. A microinfiltração, em restaurações classe V polimerizadas com o laser e a lâmpada convencional, não apresentou diferença estatisticamente significante quando comparadas às duas fontes de luz investigadas. A elaboração dos dispositivos à base de LEDs, assim como o estudo da dureza da resina composta curada, possibilitou uma análise do processo de cura e a determinação de parâmetros corretos de utilização dos arranjos de LEDs estudados. Nosso estudo termina com a proposta de um dispositivo alternativo para a fotoativação das resinas compostas. / The restorations based on composite resin have great application in modem dentistry. The composite polymerization is obtained by a photoactivation process. The final properties of materials are connected with the cure process. The development of photopolymerization procedures and devices is important to improve the cure efficiency and its quality. In this work, two light sources, argon laser and blue light-emitting diodes (LEDs), were studied and compared to a conventional cure lamp. In the PTT (Power-Time-Temperature) diagram it were established safe working parameters to argon laser application, in order to avoid pulpal damage. The microhardness was used to quantify mechanical properties. The observation of VHN as a function of the depth in the material, allowed us to determine the operational parameters where argon laser produces similar properties compared with the conventional lamp. The microleakage observed in class V restorations cured by laser or conventional lamp was investigated and the result did not show statistical difference when the two light sources were compared. Using the devices based on LEDs it was possible to study the cure process and establish the operational parameters when this alternative light source is considered for use in composite resin cure.

Foi desenvolvida e construída uma cavidade bombeadora para um meio de ganho de Cr:LiSAF na forma de bastão, bombeado por duas lâmpadas, visando sua operação como amplificador de pulsos ultracurtos a taxas de repetição elevadas, e com redução da carga térmica sobre o meio de ganho. A cavidade e o meio de ganho foram caracterizados sob operação como laser e como amplificador de pulsos ultracurtos. Atuando como laser, obtivemos 30 Hz de taxa de repetição e 20 W de potência média, resultado inédito, e ganho máximo de 1,5 por passagem. Alterando as características do bombeamento, foi possível operar o laser a 8 Hz e 16 W de potência média, com ganho máximo de 3,6 por passagem. A cavidade bombeadora, na configuração de maior ganho, foi integrada e sincronizada a um sistema Chirped Pulse Amplification baseado em cristais de Ti:Safira, concebido e construído visando a sua conjugação com o amplificador de Cr:LiSAF. O amplficiador introduziu um fator de amplificação de 150 em pulsos de 20 ps, produzindo pulsos com potência de pico de 0,5 TW. Também foi apresentada uma nova técnica para medida do limiar de ablação por pulsos ultracurtos, e sua teoria analítica foi desenvolvida. Esta técnica foi utilizada na determinação do limiar de ablação de cristais de Cr:LiSAF no regime de 20 ps. / We have developed and built a pumping cavity for a Cr:LiSAF rod, pumped by two flashlamps, in order to operate it as an ultrashort laser pulse amplifier at the highest possible repetition rate, under reduced thermal load. The pumping cavity and the gain medium were characterized under laser and ultrashort pulse amplifier operation. Operating as a laser, 30 Hz repetition rate and 20 W average power were obtained for the first time at a maximum gain per pass of 1.5. Changing the pumping characteristics, the laser provided 16 W at 8 Hz repetition rate, at a maximum gain of 3.6. The cavity, in the highest gain configuration, was integrated and synchronized to a Ti:Sapphire Chirped Pulse Amplification system, conceived and built to comprise the Cr:LiSAF amplifier. The amplifier provided amplification by a factor 150 to the 20 ps stretched pulses, resulting in pulses with 0.5 TW of peak power. Also, a new technique to measure ultrashort pulses ablation threshold was presented, and its analytical theory was developed. This technique was used to determine the ablation threshold for Cr:LiSAF crystals in the 20 ps regime.

Foi desenvolvida e construída uma cavidade bombeadora para um meio de ganho de Cr:LiSAF na forma de bastão, bombeado por duas lâmpadas, visando sua operação como amplificador de pulsos ultracurtos a taxas de repetição elevadas, e com redução da carga térmica sobre o meio de ganho. A cavidade e o meio de ganho foram caracterizados sob operação como laser e como amplificador de pulsos ultracurtos. Atuando como laser, obtivemos 30 Hz de taxa de repetição e 20 W de potência média, resultado inédito, e ganho máximo de 1,5 por passagem. Alterando as características do bombeamento, foi possível operar o laser a 8 Hz e 16 W de potência média, com ganho máximo de 3,6 por passagem. A cavidade bombeadora, na configuração de maior ganho, foi integrada e sincronizada a um sistema Chirped Pulse Amplification baseado em cristais de Ti:Safira, concebido e construído visando a sua conjugação com o amplificador de Cr:LiSAF. O amplficiador introduziu um fator de amplificação de 150 em pulsos de 20 ps, produzindo pulsos com potência de pico de 0,5 TW. Também foi apresentada uma nova técnica para medida do limiar de ablação por pulsos ultracurtos, e sua teoria analítica foi desenvolvida. Esta técnica foi utilizada na determinação do limiar de ablação de cristais de Cr:LiSAF no regime de 20 ps. / We have developed and built a pumping cavity for a Cr:LiSAF rod, pumped by two flashlamps, in order to operate it as an ultrashort laser pulse amplifier at the highest possible repetition rate, under reduced thermal load. The pumping cavity and the gain medium were characterized under laser and ultrashort pulse amplifier operation. Operating as a laser, 30 Hz repetition rate and 20 W average power were obtained for the first time at a maximum gain per pass of 1.5. Changing the pumping characteristics, the laser provided 16 W at 8 Hz repetition rate, at a maximum gain of 3.6. The cavity, in the highest gain configuration, was integrated and synchronized to a Ti:Sapphire Chirped Pulse Amplification system, conceived and built to comprise the Cr:LiSAF amplifier. The amplifier provided amplification by a factor 150 to the 20 ps stretched pulses, resulting in pulses with 0.5 TW of peak power. Also, a new technique to measure ultrashort pulses ablation threshold was presented, and its analytical theory was developed. This technique was used to determine the ablation threshold for Cr:LiSAF crystals in the 20 ps regime.

Submitted to the Faculty of Arts in partial fulfilment or fulfilment of the requirements for the Doctor of Philosophy in the History Department at the University of Zululand, 1999. / J.L. Dube is one of the Zulu Natalians who, being an African nationalist, involved himself in the affairs of his kith and kin. He is the founder of the first African established school in Natal, viz. Ohlange. He also succeeded to establish and publish ILANGA LASE NATAL as a medium of contact among the Africans who were economically, politically and socially acute. Dube set himself the task of revealing the failures of Shepstonism. He pointed out how it could have been utilised to promote acceptable administration of Africans. He even pinpointed the type of reforms that the Africans yearned for. When this was not heeded, he involved himself unflinchingly in politics. He organised fellow-Christian Africans with success. Dube was, however, an exponent of non-violent political change. He wished that in its dealings with the Africans, the government would be fair, objective and humane. Dube remonstrated against the subjugation of the Africans by the colonial government. He preferred that the Africans should be consulted, and elevated in the scale of civilization. For this to happen, he pressed that the attitudes of the whites towards blacks would have to change. The unwieldy officialdom, obscenely abusive party politics, and unequal treatment of whites and blacks at law would also have to be remedied or replaced. He advocated that land should be equitably distributed and Africans introduced to a new mode of land ownership. The whites would have to reduce then-excessive demands for land and African labour. He also demanded a worth¬while education system for the blacks that would promote all their human aspects. The government was urged to adequately financially provide for and control African education. It should not leave this to the lot of missionary societies. Dube also pressed for the enfranchisement and representation of Africans in the Natal legislature. It was only then that the government would quickly apprehend, comprehend, and redress problems that related to Africans. Subsequent to the 1906 rebellion, Dube was hopeful that there would be an end to maladministration of African affairs. He was highly expectant that the recommendations of NNAC, the drive of the new governor, the new direction of policy, though late, would put the colony on a new course. However, then the movement towards Union was afoot. It remained to be seen what would transpire. / Human Sciences University of Zululand Research Fund Commeetee, Research Council (HSRC), Anglo American and De Beers Cahairman's Fund

The concurrent spreading of a boundary layer type diffusion flame is studied. The impossibility of obtaining a low velocity laminar flow without any perturbation induced by buoyancy has lead to the development of an experimental apparatus for use in micro-gravity facilities. Based on previous experimental observations, an original numerical approach has been developed showing, first the dominating role of the radiative heat transfer on the structure of the flame and second the major role of the soot on the extinction phenomenon at the flame trailing edge. The influence of the forced flow velocity, the fuel injection velocity and oxygen concentration on the geometry of the flame has been examined by imaging of CH* and OH* radicals spontaneous emission. Laser-Induced Incandescence (LII) is used to determine the soot field concentration in the flame. The soot formation has been studied by Laser Induced Fluorescence (LIF) of Polycyclic Aromatic Hydrocarbons (PAHs). The interaction between the reaction zone and the field of soot formation/oxidation is taken into account to analyze the flame length. These results can be used as the experimental input data for a future complete validation of numerical model simulating the soot formation and oxidation in this kind of flame.

Pós nanocristalinos de Ba1-xCaxTiO3(0≤ x ≤ 0.30) foram sintetizados pela primeira vez por meio do método dos precursores poliméricos modificados, em temperaturas relativamente baixas (500°C). Para a densificação dos corpos cerâmicos duas técnicas distintas foram utilizadas: a sinterização convencional, utilizando um forno elétrico; e a sinterização a laser, na qual um laser de CO2 foi utilizado como principal fonte de calor. Os corpos cerâmicos sinterizados pelas duas técnicas apresentaram um tamanho médio de grãos em torno de 500 nm, porém uma maior densidade relativa foi obtida nas cerâmicas sinterizadas a laser, chegando a 99%, além de boa transparência, ∼42% a 940 nm para a amostra com 30 mol% de Ca com espessura de 0.5 mm. Também verificamos por meio de simulação numérica, que a equação de condução de calor na aproximação linear, considerando uma fonte de calor com perfil gaussiano, descreve qualitativamente o comportamento observado durante a sinterização a laser no seu estágio final. Por meio da técnica de espectroscopia de impedância foi feita a caracterização dielétrica dos corpos cerâmicos, nos quais três pontos principais foram estudados: i) o efeito do tamanho de grãos; ii) a influência da concentração de Ca; e iii) a influência do método de sinterização. Com a variação do tamanho do grão foram observadas mudanças na intensidade do pico de transição ferro-paraelétrica, na temperatura de Curie e na permissividade relativa à temperatura ambiente. Para concentrações de Ca até 15 mol%, as cerâmicas apresentaram uma transição de Curie estreita semelhante ao BaTiO3,enquanto que para concentrações maiores, uma transição de fase difusa foi observada. A sinterização a laser resultou em corpos cerâmicos com constante dielétrica 30% maior, e menor perda dielétrica do que as cerâmicas sinterizadas convencionalmente. Finalmente, foi proposto um modelo baseando-se na formação de vacâncias de oxigênio para o aumento da condutividade elétrica com a substituição de Ca. / Ba1-xCaxTiO3 (0 ≤ x ≤ 0.30) nanocrystalline powders were successfully synthesized for the first time at relative low temperature (500 °C) by a modified polymeric precursor method. The densification of the ceramics was made by two distinct techniques: conventional sintering using an electric furnace; and by a laser sintering process in which a CO2 laser is used as the main heating source. It was achieved dense ceramics with an average grain size about 500 nm from both techniques. However, the laser sintered ceramics presented a higher relative density (99 %) and a transparency of 42% at 940 nm in the sample with 30 mol% of Ca. By numerical simulation of the thermal conduction equation on the linear approximation case and taking account a thermal source with a gaussian profile, it was possible to describe qualitatively the final stage of the laser sintering process. The dielectric characterization of the ceramic bodies were carried out by the impedance spectroscopy technique and three main effects were studied: i) the grain size effect; ii) the Ca concentration influence; and, iii) the sintering technique influence. Modifying the grain size led to changes in the ferro-paraelectric transition magnitude, on the Curie temperature value and in the relative permittivity at room temperature. For Ca2+ concentrations up to 15 mol% the sintered ceramics presented a sharp Curie transition like BaTiO3,while for higher Ca concentrations a diffuse phase transition was observed. The laser sintered ceramics presented a dielectric constant 30% higher than the conventional sintering and a lower dielectric loss. Finally, we have proposed a model based on the oxygen vacancies formation to explain the conductivity increase with the Ca2+ substitution.

Pós nanocristalinos de Ba1-xCaxTiO3(0≤ x ≤ 0.30) foram sintetizados pela primeira vez por meio do método dos precursores poliméricos modificados, em temperaturas relativamente baixas (500°C). Para a densificação dos corpos cerâmicos duas técnicas distintas foram utilizadas: a sinterização convencional, utilizando um forno elétrico; e a sinterização a laser, na qual um laser de CO2 foi utilizado como principal fonte de calor. Os corpos cerâmicos sinterizados pelas duas técnicas apresentaram um tamanho médio de grãos em torno de 500 nm, porém uma maior densidade relativa foi obtida nas cerâmicas sinterizadas a laser, chegando a 99%, além de boa transparência, ∼42% a 940 nm para a amostra com 30 mol% de Ca com espessura de 0.5 mm. Também verificamos por meio de simulação numérica, que a equação de condução de calor na aproximação linear, considerando uma fonte de calor com perfil gaussiano, descreve qualitativamente o comportamento observado durante a sinterização a laser no seu estágio final. Por meio da técnica de espectroscopia de impedância foi feita a caracterização dielétrica dos corpos cerâmicos, nos quais três pontos principais foram estudados: i) o efeito do tamanho de grãos; ii) a influência da concentração de Ca; e iii) a influência do método de sinterização. Com a variação do tamanho do grão foram observadas mudanças na intensidade do pico de transição ferro-paraelétrica, na temperatura de Curie e na permissividade relativa à temperatura ambiente. Para concentrações de Ca até 15 mol%, as cerâmicas apresentaram uma transição de Curie estreita semelhante ao BaTiO3,enquanto que para concentrações maiores, uma transição de fase difusa foi observada. A sinterização a laser resultou em corpos cerâmicos com constante dielétrica 30% maior, e menor perda dielétrica do que as cerâmicas sinterizadas convencionalmente. Finalmente, foi proposto um modelo baseando-se na formação de vacâncias de oxigênio para o aumento da condutividade elétrica com a substituição de Ca. / Ba1-xCaxTiO3 (0 ≤ x ≤ 0.30) nanocrystalline powders were successfully synthesized for the first time at relative low temperature (500 °C) by a modified polymeric precursor method. The densification of the ceramics was made by two distinct techniques: conventional sintering using an electric furnace; and by a laser sintering process in which a CO2 laser is used as the main heating source. It was achieved dense ceramics with an average grain size about 500 nm from both techniques. However, the laser sintered ceramics presented a higher relative density (99 %) and a transparency of 42% at 940 nm in the sample with 30 mol% of Ca. By numerical simulation of the thermal conduction equation on the linear approximation case and taking account a thermal source with a gaussian profile, it was possible to describe qualitatively the final stage of the laser sintering process. The dielectric characterization of the ceramic bodies were carried out by the impedance spectroscopy technique and three main effects were studied: i) the grain size effect; ii) the Ca concentration influence; and, iii) the sintering technique influence. Modifying the grain size led to changes in the ferro-paraelectric transition magnitude, on the Curie temperature value and in the relative permittivity at room temperature. For Ca2+ concentrations up to 15 mol% the sintered ceramics presented a sharp Curie transition like BaTiO3,while for higher Ca concentrations a diffuse phase transition was observed. The laser sintered ceramics presented a dielectric constant 30% higher than the conventional sintering and a lower dielectric loss. Finally, we have proposed a model based on the oxygen vacancies formation to explain the conductivity increase with the Ca2+ substitution.

This study aims to investigate the mechanical and fatigue behavior of additively manufactured metallic materials. Several challenges associated with different metal additive manufacturing (AM) techniques (i.e. laser-powder bed fusion and direct laser deposition) have been addressed experimentally and numerically. Experiments have been carried out to study the effects of process inter-layer time interval – i.e. either building the samples one-at-a-time or multi-at-a-time (in-parallel) – on the microstructural features and mechanical properties of 316L stainless steel samples, fabricated via a direct laser deposition (DLD). Next, the effect of building orientation – i.e. the orientation in which AM parts are built – on microstructure, tensile, and fatigue behaviors of 17-4 PH stainless steel, fabricated via a laser-powder bed fusion (L-PBF) method was investigated. Afterwards, the effect of surface finishing – here, as-built versus machined – on uniaxial fatigue behavior and failure mechanisms of Inconel 718 fabricated via a laser-powder bed fusion technique was sought. The numerical studies, as part of this dissertation, aimed to model the mechanical behavior of AM materials, under monotonic and cyclic loading, based on the observations and findings from the experiments. Despite significant research efforts for optimizing process parameters, achieving a homogenous, defectree AM product – immediately after fabrication – has not yet been fully demonstrated. Thus, one solution for ensuring the adoption of AM materials for application should center on predicting the variations in mechanical behavior of AM parts based on their resultant microstructure. In this regard, an internal state variable (ISV) plasticity-damage model was employed to quantify the damage evolution in DLD 316L SS, under tensile loading, using the microstructural features associated with the manufacturing process. Finally, fatigue behavior of AM parts has been modeled based on the crack-growth concept. Using the FASTRAN code, the fatigue-life of L-PBF Inconel 718 was accurately calculated using the size and shape of process-induced voids in the material. In addition, the maximum valley depth of the surface profile was found to be an appropriate representative of the initial surface flaw for fatigue-life prediction of AM materials in an as-built surface condition.

Les verres de phosphates de zinc et gallium contenant de l’argent ont permis des développements originauxau travers de la structuration d’architectures photoniques multi-échelles innovantes en volume, en surfaceou sur fibre, et également à travers l’ingénierie de composition chimique du matériau. Un taux accru d’oxyded’argent permet de maximiser la quantité de paires au sein de la matrice vitreuse lors de la synthèse dumatériau. Ce dimère favorise les processus d’agrégation conduisant à la formation d’espèces lors del’interaction locale entre le verre et le laser femtoseconde infrarouge. Une étude par spectroscopie RPEmenée sur des échantillons irradiés par des sources ionisantes a permis de montrer que le débit de dose estprépondérant quant au contrôle des processus chimiques. Des centres à électron et à trou sont les espècesmajoritairement stabilisées à faible débit de dose, alors que la formation d’agrégats d’argent luminescentsintervient pour des puissances crête élevées typiques des lasers ultra-courts. Le caractère local de lastructuration par Direct Laser Writing a permis de créer des objets 3D originaux. L’analyse fine de ladistribution chimique au sein d’objets fluorescents a permis de montrer clairement une zone de déplétion enions argent au centre. Les effets de migration d’ions depuis le centre du faisceau laser vers le bord externea ainsi été mis en évidence. Le dopage des verres photosensibles par des ions europium a permis de montrerdes effets de synergie entre agrégats d’argent photo-inscrits et lanthanides trivalent. En effet, une exaltationde l’émission de luminescence de ces derniers à l’endroit des structurations laser a été mesurée. / The silver-containing phosphate glasses allowed original developments throughout the microstructuring ofarchitectures for innovative photonic in the volume, at the surface or in the fibered material. The chemicalengineering of the material plays an important role from this point of view. An increasing silver oxide ratioleads to an important quantity of pairs in the pristine glass matrix. This dimer in favor of the aggregationprocess bringing to the production of species during the interaction between the glass and the infraredfemtosecond laser. A study conducted by EPR spectroscopy on irradiated samples (ionizing sources)demonstrated that the dose rate is predominant for the control of the involved chemical process. Mainly,electron and holes are stabilized at low dose rate whereas the formation of luminescent silver clusters occursfor high peak power typical of ultra-short lasers. The Direct Laser Writing process allows local structuring ofthe matter and resulted in original tridimensional patterns. The fine chemical distribution analysis insideannular fluorescent objects clearly showed a depletion zone of the silver concentration in the center. Ionicmigration effects from the center towards the edges of the laser beam are then highlighted. The Eu3+-dopedphotosensitive glasses emphasized a synergy between photo-induced silver clusters and trivalentlanthanides. Indeed, a luminescence exaltation associated to the europium emission is measured.