This thesis is centred around the study materials with novel electronic properties, including transition metals interacting with semiconductors and unique molecular systems. The idea of advancing modern computing is the basis for motivating the work in that the projects all have potential to be used in novel applications that would impact the efficiency and/or execution of current technology. We have studied two variations of transition metals as they appear in materials and two molecular systems. As for the transition metals interacting with semiconductors, we first discuss transition metal atoms introduced as impurities to a semiconductor lattice, and second, we discuss transition metal oxides that are naturally semiconducting. We have used a number of experimental and theoretical techniques to better understand these groups of materials. Materials prepared through high quality synthesis techniques were studied using x-ray spectroscopy made possible by synchrotron light sources. Computational software then allowed for the experiments to be interpreted by comparing them to the simulations. In the study of transition metals as impurities, we chose the Co:MoS2 system because MoS2 has had promising results with other transition metal dopants. We examined the electronic structure for two purposes: (1) to determine the local bonding environment and locations of the cobalt atoms in order to better understand the behaviour of Co as an impurity; and (2) the overall band gap of the system so that we could evaluate the system’s potential for use in applications. Experimental results combined with our theoretical simulations led us to conclude that the samples available were all metallic, and at low concentrations cobalt atoms were able to substitute directly into the MoS2 lattice. An examination of copper (II) oxide allowed us to investigate the ability to tune the band gap of a known semiconductor through a synthesis process that applied axial pressure to the sample. For a collection of samples prepared at different pressures, x-ray spectroscopy methods showed an increasing band gap with increasing synthesis pressure, a result that is most encouraging for the field of band gap engineering. Using soft x-ray spectroscopy to examine the conduction and valence bands of the two molecular systems, the potassium-doped hydrocarbons and Li2RuO3, was important for drawing conclusions about the materials’ composition and behaviour. Results showed the introduction of new states at the lower edge of the conduction band of K:phenanthrene, a possible reason for its low-temperature superconductivity. Li2RuO3’s electronic structure was examined and compared to calculations performed by collaborators.

This thesis is devoted to first-principles simulations of bio- and nano-materials,focusing on various soft x-ray spectra, ground-state energies and structures of isolated largemolecules, bulk materials, and small molecules in ambient solutions. K-edge near-edge x-ray absorption fine structure (NEXAFS) spectra, x-ray emission spectra, andresonant inelastic x-ray scattering spectra of DNA duplexes have been studied by means oftheoretical calculations at the density functional theory level. By comparing a sequence of DNAduplexes with increasing length, we have found that the stacking effect of base pairs has verysmall influence on all kinds of spectra, and suggested that the spectra of a general DNA can bewell reproduced by linear combinations of composed base pairs weighted by their ratio. The NEXAFS spectra study has been extended to other realistic systems. We have used cluster modelswith increasing sizes to represent the infinite crystals of nucleobases and nucleosides, infinitegraphene sheet, as well as a short peptide in water solution. And the equivalent core holeapproximation has been extensively adopted, which provides an efficient access to these largesystems. We have investigated the influence of external perturbations on the nitrogen NEXAFSspectra of guanine, cytosine, and guanosine crystals, and clarified early discrepancies betweenexperimental and calculated spectra. The effects of size, stacking, edge, and defects to theabsorption spectra of graphene have been systematically analyzed, and the debate on theinterpretation of the new feature has been resolved. We have illustrated the influence of watersolvent to a blocked alanine molecule by using the snapshots generated from molecular dynamics. Multi-scale computational study on four short peptides in a self-assembled cage is presented. It isshown that the conformation of a peptide within the cage does not corresponds to its lowest-energyconformation in vacuum, due to the Zn-O bond formed between the peptide and the cage, and theconfinement effect of the cage. Special emphasis has been paid on a linear-scaling method, the generalized energy basedfragmentation energy (GEBF) approach. We have derived the GEBF energy equation at the Hartree-Focklevel with the Born approximation of the electrostatic potential. Numerical calculations for amodel system have explained the accuracy of the GEBF equation and provides a starting point forfurther refinements. We have also presented an automatic and efficient implementation of the GEBFapproach which is applicable for general large molecules. / QC 20110404

This study is aimed at investigating the feasibility of using the radiometric technique as an alternative to traditional methods for determining soil physico-chemical parameters which are important for terroir characterization. In-situ and ex-situ radiometric analyses of soil from three vineyard blocks of Simonsig Wine Estate in the Stellenbosch district (Western Cape, South Africa) were studied. A mobile MEDUSA gamma-ray detection system comprising a CsI(Na) crystal (length 15 cm, diameter 7 cm) and associated electronics mounted on a portable trolley were used for partial terroir characterisation. Thereafter activity concentrations of 40K, 232Th series and 238U series in soil (top ~30 cm) from the measured MEDUSA spectra (0 – 3 MeV) were extracted by means of the full-spectrum analysis (FSA) method. A lead-shielded HPGe detector was used for analyzing collected soil samples while soil physico-chemical parameters were analysed using standard methods at research and commercial laboratories.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv. / Härtill 4 uppsatser.

Made available in DSpace on 2014-10-09T12:43:32Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:58:20Z (GMT). No. of bitstreams: 1 06631.pdf: 7171449 bytes, checksum: 14579bbc0c3bfbe0058e6387b09d94f4 (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

In this work, alkaline earth aluminate phosphors doped with rare-earth ions and manganese were synthesized using combustion method. Several characterization techniques were used to study the structural and luminescent properties of the as-synthesized phosphors, namely X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), X-ray energy Dispersive Spectroscopy (EDS), Ultraviolet-Visible (UV-Vis) Spectroscopy, Photoluminescence (PL), and Thermoluminescence (TL). The structural properties were studied by collecting the XRD patterns of the samples using an X'Pert PRO PANalytical diffractometer with CuKα at λ = 0.15405 nm. The particle morphologies of the as-synthesized powder phosphors were investigated using a JEOL JSM-7500F field-emission scanning electron microscope (FE-SEM). The optical properties of the phosphors were studied using Perkin-Elmer Lambda 750s UV-Vis spectrometer, Jobin Yvon/SPEX FluoroLog spectrofluorometer (Model FL-1040) and Riso TL/OSL reader (Model DA-20). The as-prepared SrAl2O4:Eu 2+ ; SrAl2O4:Dy 3+; SrAl2O4:Mn 2+; phosphors were synthesized at an initiating temperature of 600 oC. The XRD patterns were consistent with the low temperature monoclinic structure of SrAl2O4 for all the as-synthesized phosphor powders. SEM measurements showed nano-rod like particles. The SrAl2O4:Eu 2+ ; SrAl2O4:Dy 3+; SrAl2O4:Mn 2+ samples were excited using a 450 W Xenon light source at 364 nm, 390 nm, and 426 nm respectively. A broad blue emission peak at 500 nm shown by the SrAl2O4:Eu 2+ sample is attributed to the 6 1 7 4f 5d 4f transition of the Eu 2+ ion. Also, the red sharp emission lines due to the 4f-4f transition of the Eu 3+ were observed. SrAl2O4:Dy3+ samples exhibited blue, green, and red emissions which can be atributed to the 4 6 9/2 15/2 F  H ,4 6 9/2 13/2 F  H , and 4 6 9 11 2 2 F  H transitions of Dy 3+ ions respectively. The two broad emissions (green at 513 nm and red at 650 nm) shown by 2+ 0.98 2 4 0.02 Sr Al O :Mn sample can be atributed to the 4 4 6 6 1 1 T ( G)  A ( S) transition of the Mn 2+ ion in the sample. The SrAl2O4:Eu 2+ , Dy 3+ ; SrAl2O4:Eu 2+, Mn 2+ ; SrAl2O4:Dy 3+, Mn 2+; and SrAl2O4:Eu 2+ ,Mn 2+, Dy 3+ phosphors were synthesized by combustion method at an initiating temperature of 600 oC. The blue emissions were observed in all the samples except SrAl2O4:Eu 2+ ,Mn 2+, Dy 3+ sample. The SrAl2O4:Eu 2+ ,Mn 2+, Dy 3+ phosphor showed the longest afterglow intensity. The BaAl2O4 doped with Eu 2+ , Mn 2+ and Dy 3+ phosphors synthesized at an initiating temperature of 600 oC using combustion method. The XRD patterns confirmed the hexagonal structure of BaAl2O4 in all the as-synthesized samples. A broad blue emission of the BaAl2O4:Eu 2+ sample at 490 nm is attributed to the 6 1 7 4f 5d 4f transition of the Eu 2+ ion in the sample. A red emission peak observed at 611 nm is due to the 4f - 4f transition of un-reduced Eu 3+ ions during the combustion reaction. A blue emission at 482 nm, a green emission at 575 nm, and a red emission at 663 nm of the BaAl2O4:Dy 3+ sample can be associated with 4 6 9/2 15/2 F  H ,4 6 9/2 13/2 F  H , and 4 6 9 11 2 2 F  H transitions of the Dy 3+ ions respectively. The green emission peaks exhibited by BaAl2O4:Mn 2+ sample at 512 nm is due to the 4 4 6 6 1 1 T ( G)  A ( S) transitions of the Mn 2+ ions. Barium aluminate phosphors doped with different concentrations of Dy 3+ ion were synthesized by combustion method at an initiating temperature of 600 oC. The XRD patterns confirmed the hexagonal structure of BaAl2O4. The emission peaks observed at 482 nm, 575 nm, and 663 nm are due to4 6 9/2 15/2 F  H ,4 6 9/2 13/2 F  H and 4 6 9 11 2 2 F  H transitions of Dy 3+ ion respectively. The PL measurements also confirmed the quenching of luminescence at higher concentrations of the Dy 3+ ion. The UV-Vis measurements has confirmed the increase in the band-gap of the BaAl2O4 sample followed by a decrease and an increase again as doping concentration of the Dy 3+ increased. The X-ray diffraction patterns of the Ca0.97M0.3Al2O4:Eu 2+ , Dy 3+ (M = Ba, Mg, and Sr) powder samples prepared by combustion method confirms the monoclinic structure of CaAl2O4 in all samples. A broad emission peak at 490 nm for both Ba 2+ and Mg 2+ substituted samples and the one for Sr 2+ substituted sample at 485nm are attributed to the 6 1 7 4f 5d 4f transition of the Eu 2+ . The decay curves confirmed that the Mg 2+ substituted sample has a longer persistence (phosphorescence) than all the other samples. / Physics / M. Sc. (Physics)

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.

Made available in DSpace on 2014-10-09T12:50:53Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:02Z (GMT). No. of bitstreams: 1 11109.pdf: 12432310 bytes, checksum: c0a31703a7116daea7b5d40b3ca371f2 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:33:59Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:55Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:41:41Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:07:06Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP