Ternary indium aluminum nitride (InXAl1-XN) semiconductor is an attractive material with a wide-range bandgap energy varied from ultraviolet (Eg(AlN): 6.2 eV) to near infrared (Eg(InN): 0.7 eV). With tuning composition, it can be widely used to many optoelectronic device applications. In this thesis, I have studied InXAl1-XN film deposited on Si (111) substrate using natural and isotopically enriched nitrogen as reactive gas by reactive magnetron sputter epitaxy (MSE). Four series of experiments were performed, which are I. InAlN presputtering, II. InAlN sputter deposition, III. InAlN direct deposition, and IV. InAlN direct deposition using isotopically enriched nitrogen. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDX). The θ-2θ XRD scan confirms that the designed composition x = 0.17 of InXAl1-XN film was obtained. TEM images shows that an amorphous interlayer with a thickness ranging from 1.2 nm to 1.5 nm was formed between Si substrate and InXAl1-XN film. However, high-resolution TEM shows that the interlayer actually contains partial crystalline structures. EDX line profile indicates that the chemical composition of the amorphous interlayer is silicon nitride (SiNX). By comparing d-spacing measurement of partial crystalline structures with EDX line profile, it reveals that partial SiNX crystal is formed in the interlayer. Nonetheless, the samples (IAD01, IAD02, IAD03, IAD04), grown without presputtering procedure, contain both crystalline SiNX and InXAl1-XN embedded in the amorphous interlayer. It means that SiNX and InXAl1-XN film can be directly grown on the substrate in the beginning of deposition. Moreover, the samples (IAD01, IAD03), quenched directly after deposition, have less crystalline structures in the interlayer then the samples (IAD02, IAD04), maintained at 800℃ for 20 min.

The aim of this thesis is to investigate the methodology of three dimensional chemical imaging of nanoparticles through the use of scanning transmission electron microscope (STEM) – energy dispersive X-ray (EDX) spectroscopy. In this thesis, an absorption correction factor is derived for spherical nanoparticles that can correct X-ray absorption effects. Quantification of EDX spectra of nanoparticles usually neglects X-ray absorption within the nanoparticle but may lead to erroneous results, thus an absorption correction is important for accurate compositional quantification. The absorption correction presented is verified through comparison with experimental data of Au X-ray peaks in spherical Au nanoparticles and is found to agree excellently. This absorption correction allows accurate compositional quantification of large ( > 100 nm) particles with STEM-EDX.Three dimensional chemical mapping is achievable through the use of EDX spectroscopy with electron tomography. Here, the methodology of STEM-EDX tomography is fully explored, with a focus on how to avoid artefacts introduced through detector shadowing and low counts per pixel. A varied-time acquisition scheme is proposed to correct for detector shadowing that is shown to provide a more constant intensity over a series of projections, allowing a higher fidelity reconstruction. The STEM-EDX tomography methodology presented is applied to the study of AgAu nanoparticles synthesized by the galvanic replacement reaction. The elemental distribution as a function of the composition of the as-synthesized nanoparticles is characterised and a reversal in the element segregated to the surface of the nanoparticles is found. The composition at which the reversal takes place is shown to correlate with a peak in the catalytic yield of a three component coupling reaction. It is hypothesized that a continuous Au surface results in the optimum catalytic conditions for the reaction studied, which guides the use of galvanically prepared AgAu nanoparticles as catalysts.

O presente estudo teve como objetivo avaliar, in vitro, os efeitos da radiação com cobalto-60 nas propriedades mecânicas, morfológicas e químicas do esmalte e da dentina de dentes permanentes através da: 1- microdureza longitudinal; 2- microscopia eletrônica de varredura (MEV); e 3- espectroscopia de energia dispersiva de raios X (EDX). A microdureza do esmalte e da dentina (n=12 hemissecções vestibulares) foi avaliada em três profundidades (superficial, média e profunda), antes e a cada 10 Gy de irradiação, até uma dose cumulativa de 60 Gy. A morfologia do esmalte e da dentina foi avaliada por meio de MEV (n=8 hemissecções), em 2 hemissecções vestibulares irradiadas com dose cumulativa de 30 Gy, 2 hemissecções vestibulares irradiadas com dose cumulativa de 60 Gy e 4 hemissecções palatinas não irradiadas. A composição química do esmalte e da dentina foi avaliada por meio de EDX (n=4 hemissecções), utilizando-se as mesmas hemissecções previamente submetidas à MEV (com dose cumulativa de 60 Gy de irradiação, e nas hemissecções não irradiadas). Os dados foram analisados quanto à sua distribuição e submetidos à Análise de Variância a dois critérios. Para a diferenciação das médias, empregou-se o teste de Fisher. O nível de significância adotado foi de 5%. Com relação à microdureza no esmalte, pôde-se observar que houve diferença estatisticamente significante entre os grupos (p < 0,05). A microdureza no esmalte não irradiado não apresentou diferença estatisticamente significante em comparação com a do esmalte após irradiação com doses de 40, 50 e 60 Gy (p > 0,05), e apresentou-se maior que os valores de microdureza nas doses de 10, 20 e 30 Gy (p < 0,05). Com relação à microdureza nas diferentes profundidades pôde-se observar diferença significante (p < 0,05) entre elas, observando-se no esmalte superficial seus maiores valores. Na análise morfológica do esmalte observou-se que os espécimes irradiados apresentaram alterações crescentes, em função do aumento da dose de radiação, em comparação ao esmalte não irradiado. A porção interprismática tornou-se mais evidente após as doses de 30 e 60 Gy. Em relação à microdureza da dentina, pôde-se observar que houve diferença significante entre os grupos (p < 0,05). A microdureza na dentina não irradiada não apresentou diferença estatisticamente significante em comparação com a microdureza na dose de 40 Gy (p > 0,05) e apresentou valores superiores aos observados nas doses de 10, 20, 30, 50 e 60 Gy (p < 0,05). Em relação à microdureza nas diferentes profundidades avaliadas pôde-se observar diferença significante (p < 0,05) entre elas, sendo que a dentina média apresentou seus maiores valores. Na análise morfológica da dentina observou-se a presença de fendas na estrutura dentinária, túbulos dentinários colabados/destruídos e fragmentação das fibras colágenas nas doses de 30 e 60 Gy, sendo as alterações mais intensas com aumento da dose de irradiação, para todas as regiões analisadas, em comparação à dentina não irradiada. Na análise química do esmalte e da dentina irradiados observou-se discreto aumento de oxigênio (O) e diminuição de fósforo (P) e cálcio (Ca), em comparação aos espécimes não irradiados. Os resultados permitiram concluir que a radioterapia não influenciou a microdureza do esmalte, como um todo, entretanto, quando analisou-se nas diferentes profundidades do esmalte, verificou-se um aumento da microdureza na região superficial. Na dentina, a radioterapia ocasionou diminuição da microdureza após praticamente todas as doses de radiação, em comparação à dentina não irradiada, sendo que na região da dentina média observaram-se seus menores dos valores. As alterações morfológicas das estruturas do esmalte e da dentina foram crescentes com o aumento das doses de irradiação observando-se a porção interprismática mais evidente, presença de fendas e túbulos dentinários colabados/destruídos e fragmentação progressiva das fibras colágenas. Quimicamente, após a irradiação, tanto no esmalte como na dentina, observouse um discreto aumento na porcentagem de oxigênio e redução nas porcentagens de fósforo e cálcio. / The present study had as objective to evaluate, in vitro, the effect of the radiation of 60 Cobalt (Co 60) in the mechanical, morphological and chemical properties of the enamel and of the dentine of permanent teeth by means of: 1- longitudinal microhardness; 2- scanning electron microscopy (SEM); and 3; energy dispersive X-ray spectroscopy (EDX). The microhardness of the enamel and of the dentine (n = 12 vestibular hemisections) was evaluated in three depths (superficial, medium and deep), before and at each 10 Gy of irradiation, until a total cumulative dose of 60 Gy. The morphology of the enamel and of the dentine was evaluated by means of a SEM (n = 8 hemisections), in 2 irradiated vestibular hemisections with total cumulative dose of 30 Gy, 2 irradiated vestibular hemisections with total cumulative dose of 60 Gy and 4 not irradiated palatine hemisections (control). The chemical composition of the enamel and of the dentine was evaluated by means of EDX (n = 4 hemisections), using the same hemisections previously submitted to SEM (with cumulative dose of 60 Gy of irradiation, and in the not irradiated hemisections). The data were analyzed about their distribution and submitted to the Analysis of Variance at two criteria. For the differentiation of the averages, the test of Fisher was used. The level of significance adopted was of 5%. About the longitudinal microhardness in the enamel, it was possible to be observed that there was no statistically significant difference between the groups (p < 0,05). The microhardness in the not irradiated enamel was similar to the enamel after the irradiation with doses of 40, 50 and 60 Gy (p > 0,05) and higher than the microhardness values in the doses of 10, 20, e 30 Gy (p < 0,05). About the microhardness in the different depths it was observed significant difference (p < 0,05) between them, being observed in the superficial enamel the greatest values of microhardness. In the morphological analysis of the enamel it was observed that the irradiated specimens presented growing alterations, due to the increase of the radiation dose, comparing to the not irradiated enamel. There was no difficulty in observing the prisms and the crystals after the irradiation, however the interprismatic portion became more evident after the radiation doses of 30 and 60 Gy. About the longitudinal microhardness of the dentine, it could be observed that there was significant difference between the groups (p < 0,05). The microhardness of the not irradiated dentine was not statistically significant compared to the microhardness in the dose of 40 Gy (p > 0,05) and it presented higher values to the observed ones in the doses of 10, 20, 30, 50 and 60 Gy (p < 0,05). About the relation to the microhardness in the different evaluated depths it was possible to observe significant difference (p < 0,05) among them, being that the medium dentine presented the highest values of microhardness. In the morphological analysis of the dentine it was observed the presence of cracks in the dentine structure, collapsed/destroyed dentine tubules and fragmentation of the collagen fibers in the doses of 30 and 60 Gy, being the alterations more intense with the increase of the dose of irradiation, for all the analyzed regions, comparing to the not irradiated dentine. In the chemical analysis of the irradiated enamel and the dentine it was observed the slight increase of oxygen (O) and decrease of phosphorus (P) and Calcium (Ca), comparing to the not irradiated specimens. The result allowed to be concluded that the radiotherapy occasioned the decrease of the microhardness of the enamel after the doses from 10 to 30 Gy, but in the following doses there was an increase of the microhardness, which became similar to the not irradiated enamel, being that in the superficial region it was observed the biggest increase of the microhardness. In the dentin, the radiotherapy caused decrease of the microhardness after practically all doses of radiation, comparing to the not irradiated dentine, being that in the region of the medium dentine the lowest values of microhardness were observed. The morphological alterations of the enamel and of the dentine structure were growing with the increase of the radiation doses observing the more evident interprismatic portion, presence of cracks and collapsed/destroyed dentine tubules and progressive fragmentation of collagen fibers. Chemically, after the irradiation, not only in the enamel but also in the dentin, it was observed a slight increase of percentage of the oxygen and decrease in the percentages of phosphorus and calcium.

O presente estudo teve como objetivo avaliar, in vitro, os efeitos da radiação com cobalto-60 nas propriedades mecânicas, morfológicas e químicas do esmalte e da dentina de dentes permanentes através da: 1- microdureza longitudinal; 2- microscopia eletrônica de varredura (MEV); e 3- espectroscopia de energia dispersiva de raios X (EDX). A microdureza do esmalte e da dentina (n=12 hemissecções vestibulares) foi avaliada em três profundidades (superficial, média e profunda), antes e a cada 10 Gy de irradiação, até uma dose cumulativa de 60 Gy. A morfologia do esmalte e da dentina foi avaliada por meio de MEV (n=8 hemissecções), em 2 hemissecções vestibulares irradiadas com dose cumulativa de 30 Gy, 2 hemissecções vestibulares irradiadas com dose cumulativa de 60 Gy e 4 hemissecções palatinas não irradiadas. A composição química do esmalte e da dentina foi avaliada por meio de EDX (n=4 hemissecções), utilizando-se as mesmas hemissecções previamente submetidas à MEV (com dose cumulativa de 60 Gy de irradiação, e nas hemissecções não irradiadas). Os dados foram analisados quanto à sua distribuição e submetidos à Análise de Variância a dois critérios. Para a diferenciação das médias, empregou-se o teste de Fisher. O nível de significância adotado foi de 5%. Com relação à microdureza no esmalte, pôde-se observar que houve diferença estatisticamente significante entre os grupos (p < 0,05). A microdureza no esmalte não irradiado não apresentou diferença estatisticamente significante em comparação com a do esmalte após irradiação com doses de 40, 50 e 60 Gy (p > 0,05), e apresentou-se maior que os valores de microdureza nas doses de 10, 20 e 30 Gy (p < 0,05). Com relação à microdureza nas diferentes profundidades pôde-se observar diferença significante (p < 0,05) entre elas, observando-se no esmalte superficial seus maiores valores. Na análise morfológica do esmalte observou-se que os espécimes irradiados apresentaram alterações crescentes, em função do aumento da dose de radiação, em comparação ao esmalte não irradiado. A porção interprismática tornou-se mais evidente após as doses de 30 e 60 Gy. Em relação à microdureza da dentina, pôde-se observar que houve diferença significante entre os grupos (p < 0,05). A microdureza na dentina não irradiada não apresentou diferença estatisticamente significante em comparação com a microdureza na dose de 40 Gy (p > 0,05) e apresentou valores superiores aos observados nas doses de 10, 20, 30, 50 e 60 Gy (p < 0,05). Em relação à microdureza nas diferentes profundidades avaliadas pôde-se observar diferença significante (p < 0,05) entre elas, sendo que a dentina média apresentou seus maiores valores. Na análise morfológica da dentina observou-se a presença de fendas na estrutura dentinária, túbulos dentinários colabados/destruídos e fragmentação das fibras colágenas nas doses de 30 e 60 Gy, sendo as alterações mais intensas com aumento da dose de irradiação, para todas as regiões analisadas, em comparação à dentina não irradiada. Na análise química do esmalte e da dentina irradiados observou-se discreto aumento de oxigênio (O) e diminuição de fósforo (P) e cálcio (Ca), em comparação aos espécimes não irradiados. Os resultados permitiram concluir que a radioterapia não influenciou a microdureza do esmalte, como um todo, entretanto, quando analisou-se nas diferentes profundidades do esmalte, verificou-se um aumento da microdureza na região superficial. Na dentina, a radioterapia ocasionou diminuição da microdureza após praticamente todas as doses de radiação, em comparação à dentina não irradiada, sendo que na região da dentina média observaram-se seus menores dos valores. As alterações morfológicas das estruturas do esmalte e da dentina foram crescentes com o aumento das doses de irradiação observando-se a porção interprismática mais evidente, presença de fendas e túbulos dentinários colabados/destruídos e fragmentação progressiva das fibras colágenas. Quimicamente, após a irradiação, tanto no esmalte como na dentina, observouse um discreto aumento na porcentagem de oxigênio e redução nas porcentagens de fósforo e cálcio. / The present study had as objective to evaluate, in vitro, the effect of the radiation of 60 Cobalt (Co 60) in the mechanical, morphological and chemical properties of the enamel and of the dentine of permanent teeth by means of: 1- longitudinal microhardness; 2- scanning electron microscopy (SEM); and 3; energy dispersive X-ray spectroscopy (EDX). The microhardness of the enamel and of the dentine (n = 12 vestibular hemisections) was evaluated in three depths (superficial, medium and deep), before and at each 10 Gy of irradiation, until a total cumulative dose of 60 Gy. The morphology of the enamel and of the dentine was evaluated by means of a SEM (n = 8 hemisections), in 2 irradiated vestibular hemisections with total cumulative dose of 30 Gy, 2 irradiated vestibular hemisections with total cumulative dose of 60 Gy and 4 not irradiated palatine hemisections (control). The chemical composition of the enamel and of the dentine was evaluated by means of EDX (n = 4 hemisections), using the same hemisections previously submitted to SEM (with cumulative dose of 60 Gy of irradiation, and in the not irradiated hemisections). The data were analyzed about their distribution and submitted to the Analysis of Variance at two criteria. For the differentiation of the averages, the test of Fisher was used. The level of significance adopted was of 5%. About the longitudinal microhardness in the enamel, it was possible to be observed that there was no statistically significant difference between the groups (p < 0,05). The microhardness in the not irradiated enamel was similar to the enamel after the irradiation with doses of 40, 50 and 60 Gy (p > 0,05) and higher than the microhardness values in the doses of 10, 20, e 30 Gy (p < 0,05). About the microhardness in the different depths it was observed significant difference (p < 0,05) between them, being observed in the superficial enamel the greatest values of microhardness. In the morphological analysis of the enamel it was observed that the irradiated specimens presented growing alterations, due to the increase of the radiation dose, comparing to the not irradiated enamel. There was no difficulty in observing the prisms and the crystals after the irradiation, however the interprismatic portion became more evident after the radiation doses of 30 and 60 Gy. About the longitudinal microhardness of the dentine, it could be observed that there was significant difference between the groups (p < 0,05). The microhardness of the not irradiated dentine was not statistically significant compared to the microhardness in the dose of 40 Gy (p > 0,05) and it presented higher values to the observed ones in the doses of 10, 20, 30, 50 and 60 Gy (p < 0,05). About the relation to the microhardness in the different evaluated depths it was possible to observe significant difference (p < 0,05) among them, being that the medium dentine presented the highest values of microhardness. In the morphological analysis of the dentine it was observed the presence of cracks in the dentine structure, collapsed/destroyed dentine tubules and fragmentation of the collagen fibers in the doses of 30 and 60 Gy, being the alterations more intense with the increase of the dose of irradiation, for all the analyzed regions, comparing to the not irradiated dentine. In the chemical analysis of the irradiated enamel and the dentine it was observed the slight increase of oxygen (O) and decrease of phosphorus (P) and Calcium (Ca), comparing to the not irradiated specimens. The result allowed to be concluded that the radiotherapy occasioned the decrease of the microhardness of the enamel after the doses from 10 to 30 Gy, but in the following doses there was an increase of the microhardness, which became similar to the not irradiated enamel, being that in the superficial region it was observed the biggest increase of the microhardness. In the dentin, the radiotherapy caused decrease of the microhardness after practically all doses of radiation, comparing to the not irradiated dentine, being that in the region of the medium dentine the lowest values of microhardness were observed. The morphological alterations of the enamel and of the dentine structure were growing with the increase of the radiation doses observing the more evident interprismatic portion, presence of cracks and collapsed/destroyed dentine tubules and progressive fragmentation of collagen fibers. Chemically, after the irradiation, not only in the enamel but also in the dentin, it was observed a slight increase of percentage of the oxygen and decrease in the percentages of phosphorus and calcium.

Concrete substructures are often subjected to environmental deterioration, such as sulfate and acid attack, which leads to severe damage and causes structure degradation or even failure. In order to improve the durability of concrete, the High Performance Concrete (HPC) has become widely used by partially replacing cement with pozzolanic materials. However, HPC degradation mechanisms in sulfate and acidic environments are not completely understood. It is therefore important to evaluate the performance of the HPC in such conditions and predict concrete service life by establishing degradation models. This study began with a review of available environmental data in the State of Florida. A total of seven bridges have been inspected. Concrete cores were taken from these bridge piles and were subjected for microstructural analysis using Scanning Electron Microscope (SEM). Ettringite is found to be the products of sulfate attack in sulfate and acidic condition. In order to quantitatively analyze concrete deterioration level, an image processing program is designed using Matlab to obtain quantitative data. Crack percentage (Acrack/Asurface) is used to evaluate concrete deterioration. Thereafter, correlation analysis was performed to find the correlation between five related variables and concrete deterioration. Environmental sulfate concentration and bridge age were found to be positively correlated, while environmental pH level was found to be negatively correlated. Besides environmental conditions, concrete property factor was also included in the equation. It was derived from laboratory testing data. Experimental tests were carried out implementing accelerated expansion test under controlled environment. Specimens of eight different mix designs were prepared. The effect of pozzolanic replacement rate was taken into consideration in the empirical equation. And the empirical equation was validated with existing bridges. Results show that the proposed equations compared well with field test results with a maximum deviation of ± 20%. Two examples showing how to use the proposed equations are provided to guide the practical implementation. In conclusion, the proposed approach of relating microcracks to deterioration is a better method than existing diffusion and sorption models since sulfate attack cause cracking in concrete. Imaging technique provided in this study can also be used to quantitatively analyze concrete samples.

For the automotive sector, plastics play the most important role when designing interior and exterior parts for cars. Currently, most parts are made from petroleum-based plastics but alternatives are needed to replace environmentally harmful materials while providing the appropriate mechanical performance and preferably reduce the cost for the final product. The objective of this work was to explore the use of soy flakes as natural filler in a composite with polypropylene and to investigate the mechanical properties, water absorption and thermal behaviour. For a better understanding of the filler, the soy flakes were characterized extensively with analytical and microscopic methods. Two types of soy fillers were investigated, soy flakes, provided by Bunge Inc., with a 48 wt-% protein content and an industrial soy based filler with 44 wt-% protein content and provided by Ford. The size of the soy flakes after milling was mainly between 50 and 200 µm and below 50 µm for the industrial filler. The aspect ratio for all filler was below 5. The soy flakes were used after milling and subjected to two pre-treatment methods: (1) one hour in a 50 °C pH 9 water solution in a 1 : 9 solid-liquid ratio; (2) one hour in a 50 °C pH 9 1M NaCl solution in a 1 : 9 solid-liquid ratio. A control filler, without pre-treatment was considered. The soy flakes were also compared to an industrial soy based filler provided by Ford (soy flour (Ford)). The thermogravimetric analysis showed an onset of degradation at 170 °C for the treated filler (ISH2O and ISNaCl) and 160 °C for the untreated filler. The biocomposites formulation consisted of 30 wt-% filler, and polypropylene with/without 0.35 wt-% anti-oxidant Irganox 1010 and with/without the addition of MA-PP as coupling agent. All biocomposites were compounded in a mini-extruder, pressed into bars by injection moulding and tested subsequently. The mechanical properties of the biocomposites are promising. An increase of the E-modulus was observed when compared to pure polypropylene. The addition of MA-PP as coupling agent increased the yield strength of the biocomposites. When pure polypropylene and the biocomposites were compared no difference could be seen for their yield strength. The thermal behaviour deduced from differential scanning calorimetry, revealed a similar behaviour for the biocomposites and the pure polypropylene. Only the samples treated in the presence of NaCl and without a coupling agent, appear to have a slightly higher degree of crystallinity. The melt flow index was slightly increased for the biocomposites containing soy flakes pre-treated with NaCl and decreased for biocomposites containing the soy flour. The water absorption behaviour of the biocomposites was quite similar at the beginning with a slightly lower absorption for the materials with coupling agent. After three months, all samples except the ones treated with water showed a weight loss that can be due to the leaching of the water soluble components in the untreated filler and the NaCl treated filler. In conclusion, soy flakes represent an attractive filler when used in a polypropylene matrix if an aqueous alkaline pre-treatment is performed. The aqueous alkaline extraction also leads to the recovery of the proteins that can be used in food products while the remaining insoluble material is used for the biocomposites, avoiding the competition with the use of soy for food products...

For the automotive sector, plastics play the most important role when designing interior and exterior parts for cars. Currently, most parts are made from petroleum-based plastics but alternatives are needed to replace environmentally harmful materials while providing the appropriate mechanical performance and preferably reduce the cost for the final product. The objective of this work was to explore the use of soy flakes as natural filler in a composite with polypropylene and to investigate the mechanical properties, water absorption and thermal behaviour. For a better understanding of the filler, the soy flakes were characterized extensively with analytical and microscopic methods. Two types of soy fillers were investigated, soy flakes, provided by Bunge Inc., with a 48 wt-% protein content and an industrial soy based filler with 44 wt-% protein content and provided by Ford. The size of the soy flakes after milling was mainly between 50 and 200 µm and below 50 µm for the industrial filler. The aspect ratio for all filler was below 5. The soy flakes were used after milling and subjected to two pre-treatment methods: (1) one hour in a 50 °C pH 9 water solution in a 1 : 9 solid-liquid ratio; (2) one hour in a 50 °C pH 9 1M NaCl solution in a 1 : 9 solid-liquid ratio. A control filler, without pre-treatment was considered. The soy flakes were also compared to an industrial soy based filler provided by Ford (soy flour (Ford)). The thermogravimetric analysis showed an onset of degradation at 170 °C for the treated filler (ISH2O and ISNaCl) and 160 °C for the untreated filler. The biocomposites formulation consisted of 30 wt-% filler, and polypropylene with/without 0.35 wt-% anti-oxidant Irganox 1010 and with/without the addition of MA-PP as coupling agent. All biocomposites were compounded in a mini-extruder, pressed into bars by injection moulding and tested subsequently. The mechanical properties of the biocomposites are promising. An increase of the E-modulus was observed when compared to pure polypropylene. The addition of MA-PP as coupling agent increased the yield strength of the biocomposites. When pure polypropylene and the biocomposites were compared no difference could be seen for their yield strength. The thermal behaviour deduced from differential scanning calorimetry, revealed a similar behaviour for the biocomposites and the pure polypropylene. Only the samples treated in the presence of NaCl and without a coupling agent, appear to have a slightly higher degree of crystallinity. The melt flow index was slightly increased for the biocomposites containing soy flakes pre-treated with NaCl and decreased for biocomposites containing the soy flour. The water absorption behaviour of the biocomposites was quite similar at the beginning with a slightly lower absorption for the materials with coupling agent. After three months, all samples except the ones treated with water showed a weight loss that can be due to the leaching of the water soluble components in the untreated filler and the NaCl treated filler. In conclusion, soy flakes represent an attractive filler when used in a polypropylene matrix if an aqueous alkaline pre-treatment is performed. The aqueous alkaline extraction also leads to the recovery of the proteins that can be used in food products while the remaining insoluble material is used for the biocomposites, avoiding the competition with the use of soy for food products...

Dans ce travail de thèse a été développé et étudié un nouveau type d'objet semiconducteur magnétique : des boîtes quantiques de CdMnTe insérées dans des nanofils de ZnTe/ZnMgTe constituant une structure de type cœur-coquille. L'objectif était d'étudier la croissance par épitaxie par jets moléculaires et les propriétés fondamentales de ces hétéro-structures complexes. Dans ce but deux aspects principaux ont été abordés : i) la qualité et le contrôle des propriétés structurales, électroniques et magnétiques de ces objets, grâce à une maîtrise de leur croissance et ii) l'obtention d'informations quantitatives locales sur la composition chimique de ces nanostructures inhomogènes. Pour atteindre ces objectifs, nous avons divisé notre étude en quatre étapes. La première étape de ce travail a été concentrée sur l'étude quantitative de la formation des particules d'or servant de catalyseurs à la croissance des nanofils. La seconde étape a porté sur l'analyse des mécanismes de croissance et des paramètres gouvernant la croissance des fils de ZnTe. En particulier deux types de fils ont été observés : des fils cylindriques de structure wurtzite et des fils coniques de structures zinc-blende. Un modèle de croissance guidée par la diffusion a été utilisé pour rendre compte de certains des résultats quantitatifs présentés dans cette partie. La troisième étape a concerné l'insertion de boîtes quantiques de CdMnTe dans des nanofils de structure cœur-coquille ZnTe/ZnMgTe. Une étude préalable des paramètres pertinents influençant les propriétés magnéto-optiques de ces objets, tels que le confinement de la boîte quantique, l'incorporation du Mn et l'anisotropie de contrainte créée par la structure, a été menée. La quatrième et dernière étape de ce travail a porté sur l'interprétation quantitative de mesures d'analyse dispersive en énergie effectuées sur des nanofils de structure cœur-multicoquille. Un modèle géométrique a été proposé, permettant de retrouver la forme, les dimensions et la composition chimique des boîtes quantiques et des coquilles. Cette étude a été couplée à des mesures de caractérisation telles que la cathodo-luminescence, la micro-photo-luminescence et la spectroscopie magnéto-optique effectuées sur le même nanofil. / In this PhD work a novel type of magnetic semiconductor object has been developed: Cd(Mn)Te quantum dots embedded in ZnTe/ZnMgTe core-shell nanowires. The goal was to investigate the growth, by molecular beam epitaxy, and the fundamental properties of these complex heterostructures. For that purpose, two main issues were addressed: i) gaining control of the structural, electronic and magnetic properties of these quantum objects by mastering their growth; and ii) obtaining quantitative local knowledge on the chemical composition of those non-homogeneous nanostructures. To tackle these topics, our research was divided into four stages. The first stage was devoted to perform a quantitative study of the formation process of the Au particles that catalyze the growth of nanowires. The second stage involved the analysis of the mechanisms and parameters governing the growth of ZnTe nanowires. In particular, two different types of nanowires were found: cone-shaped nanowires with the zinc-blende crystal structure and cylinder-shaped nanowires with the hexagonal wurtzite structure. A diffusion-driven growth model is employed to fit some of the quantitative results presented in this part. The third stage focused on the insertion of pure CdTe quantum dots containing Mn ions in the core-shell nanowires. An initial study of the relevant parameters influencing the magneto-optical properties of these objects, such as the quantum dot confinement, the Mn incorporation, and the strain anisotropy, was performed. The four and last stage of this work concerned the quantitative interpretation of Energy-Dispersive X-ray spectroscopy measurements performed on single core-multishell nanowires. A geometrical model was proposed to retrieve the shape, the size and the local composition of the quantum dot insertions and of the multiple layers of the heterostructures. This study was coupled to other complementary characterization measurements on the same nanowire, such as cathodo-luminescence, micro-photo-luminescence and magneto-optical spectroscopy.

Dans ce travail de thèse a été développé et étudié un nouveau type d'objet semiconducteur magnétique : des boîtes quantiques de CdMnTe insérées dans des nanofils de ZnTe/ZnMgTe constituant une structure de type cœur-coquille. L'objectif était d'étudier la croissance par épitaxie par jets moléculaires et les propriétés fondamentales de ces hétéro-structures complexes. Dans ce but deux aspects principaux ont été abordés : i) la qualité et le contrôle des propriétés structurales, électroniques et magnétiques de ces objets, grâce à une maîtrise de leur croissance et ii) l'obtention d'informations quantitatives locales sur la composition chimique de ces nanostructures inhomogènes. Pour atteindre ces objectifs, nous avons divisé notre étude en quatre étapes. La première étape de ce travail a été concentrée sur l'étude quantitative de la formation des particules d'or servant de catalyseurs à la croissance des nanofils. La seconde étape a porté sur l'analyse des mécanismes de croissance et des paramètres gouvernant la croissance des fils de ZnTe. En particulier deux types de fils ont été observés : des fils cylindriques de structure wurtzite et des fils coniques de structures zinc-blende. Un modèle de croissance guidée par la diffusion a été utilisé pour rendre compte de certains des résultats quantitatifs présentés dans cette partie. La troisième étape a concerné l'insertion de boîtes quantiques de CdMnTe dans des nanofils de structure cœur-coquille ZnTe/ZnMgTe. Une étude préalable des paramètres pertinents influençant les propriétés magnéto-optiques de ces objets, tels que le confinement de la boîte quantique, l'incorporation du Mn et l'anisotropie de contrainte créée par la structure, a été menée. La quatrième et dernière étape de ce travail a porté sur l'interprétation quantitative de mesures d'analyse dispersive en énergie effectuées sur des nanofils de structure cœur-multicoquille. Un modèle géométrique a été proposé, permettant de retrouver la forme, les dimensions et la composition chimique des boîtes quantiques et des coquilles. Cette étude a été couplée à des mesures de caractérisation telles que la cathodo-luminescence, la micro-photo-luminescence et la spectroscopie magnéto-optique effectuées sur le même nanofil. / In this PhD work a novel type of magnetic semiconductor object has been developed: Cd(Mn)Te quantum dots embedded in ZnTe/ZnMgTe core-shell nanowires. The goal was to investigate the growth, by molecular beam epitaxy, and the fundamental properties of these complex heterostructures. For that purpose, two main issues were addressed: i) gaining control of the structural, electronic and magnetic properties of these quantum objects by mastering their growth; and ii) obtaining quantitative local knowledge on the chemical composition of those non-homogeneous nanostructures. To tackle these topics, our research was divided into four stages. The first stage was devoted to perform a quantitative study of the formation process of the Au particles that catalyze the growth of nanowires. The second stage involved the analysis of the mechanisms and parameters governing the growth of ZnTe nanowires. In particular, two different types of nanowires were found: cone-shaped nanowires with the zinc-blende crystal structure and cylinder-shaped nanowires with the hexagonal wurtzite structure. A diffusion-driven growth model is employed to fit some of the quantitative results presented in this part. The third stage focused on the insertion of pure CdTe quantum dots containing Mn ions in the core-shell nanowires. An initial study of the relevant parameters influencing the magneto-optical properties of these objects, such as the quantum dot confinement, the Mn incorporation, and the strain anisotropy, was performed. The four and last stage of this work concerned the quantitative interpretation of Energy-Dispersive X-ray spectroscopy measurements performed on single core-multishell nanowires. A geometrical model was proposed to retrieve the shape, the size and the local composition of the quantum dot insertions and of the multiple layers of the heterostructures. This study was coupled to other complementary characterization measurements on the same nanowire, such as cathodo-luminescence, micro-photo-luminescence and magneto-optical spectroscopy.

>Magister Scientiae - MSc / In this study PbSe quantum dots (QDs) were successfully synthesized via the organometallic and aqueous routes. Optical characterization was carried out using photoluminescence (PL) spectroscopy, structural and morphological characterization were carried out using X-ray diffraction (XRD) and transmission electron microscopy (TEM). Energy-dispersive X-ray spectroscopy (EDS) was used to determine the composition of the QDs. All the synthesized QDs were found to have emissions within the near-infrared region of the spectrum (≥1000 nm) with most of them being less than 5 nm in size. The aqueous synthesized QDs had a perfect Gaussian emission spectrum with a FWHM of ~23 nm indicating pure band gap emission and narrow size distribution respectively. The QDs were determined to have a cubic rock-salt crystal structure consistent with bulk PbSe. The aqueous synthesized QDs were however not stable in solution with the QDs precipitating after approximately 48 h. The organometallic synthesized QDs were transferred into the aqueous phase by exchanging the surface oleic acid ligands with 11-mercaptoundecanoic acid ligands. The ligand exchanged QDs were however stable in solution for over two weeks. The effects of reaction parameters on the optical and structural properties of the organometallic synthesized QDs were investigated by varying the reaction time, temperature, ligand purity, lead and selenium sources. It was observed that larger QDs were formed with longer reaction times, with reactions proceeding faster at higher reaction temperatures than at lower temperatures. Varying the ligand purity was found to have minimal effects on the properties of the synthesized QDs. The lead and selenium sources contributed largely to the properties of the QDs with lead oxide producing spherical QDs which were smaller compared to the cubic QDs produced from lead acetate. TBPSe was seen to produce smaller QDs as compared to TOPSe. The cytotoxity of the synthesized QDs was determined following the WST-1 cell viability assay with the QDs being found to be non-toxic at all the tested concentrations