The systematic investigation of the x-ray diffraction symmetry of scapolites covering the whole range of solid solution show that all scapolites possess space group P4(2)/n, except the pure end-members, marialite and meionite, which will possess space group I4/m, if they exist. The intensity of the weak superlattice reflections violating the body-centred symmetry, continuously increases from zero at the marialite end-member as Me% increases, reaches a maximum around 37%+/-2% Me then approximately symmetrically decreases to 75% Me followed by a slower decrease to zero at the meionite end-member. Hence, all the intermediate scapolites of the marialite-meionite series actually have a pseudosymmetric structure, i. e., a pseudobody-centred structure, and as the chemical composition approaches both end-members, the scapolite structure approaches the structure with a body-centred lattice. The weak super-lattice reflections are directly related to the following two correlated factors: (1) the relative order-disorder of A1 and Si distribution in the tetrahedral framework, and (2) the structural distortion from the body-centred symmetry. Accompanied with the above facts is the systematic deviation of cell dimensions from the linear regression in such a way that the further the structure deviates from the body-centred symmetry, the smaller the cell volume and the a(o) become relative to the evaluated one from the linear regression. Scapolites are regarded as a continuous, perfect solid solution with a long-range disordering, and unlikely to be composed of submicroscopic twins or different domains. The structural analyses and refinements of three scapolites (ON8, 20% Me; XL, 52% Me; ON45, 93% Me) have been carried out by using 3-dimensional intensity data collected by integrated precession film techniques (ON8, ON45) and an automated single-crystal diffractometer (XL), and using the full-matrix least0squares method. The result has clarified the ambiguities arising from the previous studies and showed that the crystal structure is essentially continuous along the marialite-meionite series, with a slight structural variation as a function of chemical composition and ordering of Al, Si. Several important quantitative relationships regarding the crystal structure and crystal chemistry of the scapolite solid solution series have been established, namely, (1) the relationship between the superlattice intensity r(ΣI(h+k+l=2n+1)/ΣI(h+k+l=2n)) and the chemical index % Me. (2) the exponential relationship between the superlattice intensity ration r and the atomic displacement from the mirror plane consistent with the space group I4/m. (3) The linear relationship between the superlattice intensity ratio r and the difference of Al occupancy between T2 and T3 sites. (4) The Al occupancy (%) of tetrahedral sites as a function of the chemical composition of scapolites. The ordering of Al-Si, the c-axis displacement of (Ca, Na), the tilting of CO3 and the relative amount of CO3 and Cl in the same scapolite are all inter-related. The mechanism to cause all such related structural phenomena and even the abnormal stoichiometry of scapolite can all be interpreted in terms of the internal strain created by the two greatly different anions, Cl- and CO3-,sharing the same set of equivalent sites. / Thesis / Doctor of Philosophy (PhD)

O presente trabalho visou a caracterização dos cascalhos de perfuração de um poço de petróleo pertencente à Bacia de Santos, utilizando diferentes técnicas analíticas instrumentais. O enfoque foi dado a aplicação da difração de raios X como alternativa às práticas de estudo rotineiramente aplicadas na cabine de mud-logging, onde essencialmente são efetuadas classificações visuais das unidades litológicas do poço e geralmente em amostras de granulação fina, conferindo incertezas às descrições. Um total de 164 amostras de cascalhos foram analisadas quimicamente por espectroscopia por fluorescência de raios X e classificadas de acordo com suas similaridades mineralógicas utilizando o recurso de análise estatística multivariada de dados de difração de raios X. Esse recurso permitiu minimizar o conjunto de amostras para os estudos seguintes de caracterização. A definição e a quantificação dos minerais constituintes das amostras, assim como a determinação dos tamanhos e das formas das partículas por análise dinâmica de imagens foram efetuadas apenas em amostras representativas de cada um dos grupos de similaridades definidos. Os resultados foram comparados com os dados do perfil de acompanhamento geológico (dados de perfuração) e com as interpretações realizadas na cabine de mud-logging pelo geólogo, sendo identificada uma elevada correlação entre esses dados. A avaliação da viabilidade de utilização de difratômetros de bancada durante a etapa de perfuração de um poço de petróleo foi também verificada considerando o levantamento de procedimentos de preparação amostras viáveis de serem aplicados no local (tempo adequado de pulverização e eventuais erros de amostragem) e a qualidade das respostas obtidas por diferentes equipamentos de difração de raios X (condições de análise e resolução de picos). O uso de difratômetros de bancada no estudo de cascalhos de perfuração se mostrou viável do ponto de vista operacional, trazendo diversas vantagens para a correta caracterização dos fragmentos, com melhor acurácia nos resultados, diminuição das incertezas e se mostrando uma ferramenta muito ágil. / The present research aimed at characterization of the drill cuttings of an oil well belonging to the Santos Basin, using different instrumental analytical techniques. The main focus was given to the application of X-ray diffraction as an alternative to the routinely applied mud-logging study practices, where essentially visual classifications of the lithological units of the well are carried out and generally in fine granulation samples, giving uncertainties to the descriptions. A total of 164 samples of drill cuttings were chemically analyzed by X-ray fluorescence spectroscopy and classified according to their mineralogical similarities using the multivariate statistical analysis of X-ray diffraction data. This feature allowed minimizing the sample set for subsequent characterization studies. The identification and quantification mineral phases present in all samples, as well as the determination of the sizes and forms of the particles by dynamic images analysis, were carried out only in representative samples of each one of the defined groups of similarities. Results were compared with the data of the geological monitoring profile (drilling data) and the interpretations carried out in the mud-logging unit by geologist, and a high correlation between these data was identified. The viability of using a bench scale diffractometers during the drilling stage of an oil well was also studied considering the feasibility study on representative samples to be applied on site (adequate pulverization time and possible sampling errors) and quality of the results obtained by different X-ray diffraction equipment (collecting conditions and resolution of spikes). The use of bench diffractometers in the study of drill cutting proved to be feasible from the operational point of view, bringing several advantages for the correct characterization of the fragments, with better accuracy in the results, decrease of the uncertainties and a very agile tool.

O presente trabalho visou a caracterização dos cascalhos de perfuração de um poço de petróleo pertencente à Bacia de Santos, utilizando diferentes técnicas analíticas instrumentais. O enfoque foi dado a aplicação da difração de raios X como alternativa às práticas de estudo rotineiramente aplicadas na cabine de mud-logging, onde essencialmente são efetuadas classificações visuais das unidades litológicas do poço e geralmente em amostras de granulação fina, conferindo incertezas às descrições. Um total de 164 amostras de cascalhos foram analisadas quimicamente por espectroscopia por fluorescência de raios X e classificadas de acordo com suas similaridades mineralógicas utilizando o recurso de análise estatística multivariada de dados de difração de raios X. Esse recurso permitiu minimizar o conjunto de amostras para os estudos seguintes de caracterização. A definição e a quantificação dos minerais constituintes das amostras, assim como a determinação dos tamanhos e das formas das partículas por análise dinâmica de imagens foram efetuadas apenas em amostras representativas de cada um dos grupos de similaridades definidos. Os resultados foram comparados com os dados do perfil de acompanhamento geológico (dados de perfuração) e com as interpretações realizadas na cabine de mud-logging pelo geólogo, sendo identificada uma elevada correlação entre esses dados. A avaliação da viabilidade de utilização de difratômetros de bancada durante a etapa de perfuração de um poço de petróleo foi também verificada considerando o levantamento de procedimentos de preparação amostras viáveis de serem aplicados no local (tempo adequado de pulverização e eventuais erros de amostragem) e a qualidade das respostas obtidas por diferentes equipamentos de difração de raios X (condições de análise e resolução de picos). O uso de difratômetros de bancada no estudo de cascalhos de perfuração se mostrou viável do ponto de vista operacional, trazendo diversas vantagens para a correta caracterização dos fragmentos, com melhor acurácia nos resultados, diminuição das incertezas e se mostrando uma ferramenta muito ágil. / The present research aimed at characterization of the drill cuttings of an oil well belonging to the Santos Basin, using different instrumental analytical techniques. The main focus was given to the application of X-ray diffraction as an alternative to the routinely applied mud-logging study practices, where essentially visual classifications of the lithological units of the well are carried out and generally in fine granulation samples, giving uncertainties to the descriptions. A total of 164 samples of drill cuttings were chemically analyzed by X-ray fluorescence spectroscopy and classified according to their mineralogical similarities using the multivariate statistical analysis of X-ray diffraction data. This feature allowed minimizing the sample set for subsequent characterization studies. The identification and quantification mineral phases present in all samples, as well as the determination of the sizes and forms of the particles by dynamic images analysis, were carried out only in representative samples of each one of the defined groups of similarities. Results were compared with the data of the geological monitoring profile (drilling data) and the interpretations carried out in the mud-logging unit by geologist, and a high correlation between these data was identified. The viability of using a bench scale diffractometers during the drilling stage of an oil well was also studied considering the feasibility study on representative samples to be applied on site (adequate pulverization time and possible sampling errors) and quality of the results obtained by different X-ray diffraction equipment (collecting conditions and resolution of spikes). The use of bench diffractometers in the study of drill cutting proved to be feasible from the operational point of view, bringing several advantages for the correct characterization of the fragments, with better accuracy in the results, decrease of the uncertainties and a very agile tool.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18591号 / 工博第3952号 / 新制||工||1607(附属図書館) / 31491 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 河合 潤, 教授 酒井 明, 教授 伊藤 秋男 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Indiana University-Purdue University Indianapolis (IUPUI) / The innovation and investigation of catalysts in proton exchange membrane fuel cells are included in this thesis. In the first part of this work, stability of the catalyst support of PEMFC catalyst is investigated. Nanoscale platinum particles were loaded on two different kinds of carbon supports, nano graphene sheets and functionalized carbon black/graphene hybrid were developed by the liquid phase reaction. The crystal structure of two kinds of catalysts was characterized by X-ray diffractometer (XRD). The morphology and particle size were characterized by scanning electron microscope (SEM) and transmission electron microscope (TEM). Pt loading was measured by thermal gravimetric analysis (TGA). The Brunauer, Emmett and Teller (BET) method was applied to test the surface area of the catalysts. The electrochemical surface area (ECSA) and mass activity during oxygen reduction reaction (ORR) process for two kinds of catalyst were tested by cyclic voltammetry method under different conditions. The stability of the catalysts were tested by accelerated durability test (ADT). The results show that although the mass activity of Pt/graphene is much lower, the stability of it is much better than that of the commercial catalyst. After adding functionalized carbon black (FCB) as spacer, the stability of the catalyst is preserved and at the meantime, the mass activity becomes higher than 20% Pt/XC72 catalyst. The lower mass activity of both catalysts are due to the limitation of the electrolyte diffusion into the carbon support because of the aggregation nature of graphene nano-sheets. After introducing functional carbon black as spacer, the mass activity and ECSA increased dramatically which proved that FCB can be applied to prevent the restacking of graphene and hence solved the diffusion problem. In the meantime, the durability was still keeping the same as Pt/graphene catalyst. In the second part of the work, the restacking problem was solved by introducing FCB as spacers between functionalized graphene nanosheets. The same measurement was applied to test the electrochemical performance of Pt/FCB/FG catalyst. The new catalyst showed a higher mass activity compared to Pt/graphene catalyst which meant the restacking problem was partially solved. The durability of the Pt/FCB/FG catalyst was still excellent.