Yes / Archaeological burial contexts may include a variety of white substances, but few analyses have been published. This study reports on the physico‐chemical characterization of such residues from seven archaeological sites. It is often assumed that white materials from burial contexts are lime. Our findings demonstrate that they can be gypsum, calcite (chalk), aragonite, brushite, degraded metal, natural (gum) resins or synthetic polymer–based products. These may be present as the result of diagenetic processes, funerary practices or modern contamination. This paper provides an analytical approach for the holistic investigation of white materials encountered in burial contexts. / Investments for the future’ (IdEx Bordeaux ANR‐10‐IDEX‐03‐02). Grant Number: ANR‐10‐IDEX‐03‐02; Collaborative Projects of the France‐Stanford Center for Interdisciplinary Studies; Collaborative Projects of the France–Stanford Center; French State. Grant Number: IdEx Bordeaux ANR‐10‐IDEX‐03‐02; Northern Archaeological Associates Ltd; PACEA; Wessex Archaeology; INRAP; Mersea Island Museum Trust; Vatican's Pontifical Commission for Sacred Archaeology; University of Reading; IRAMAT-CRP2A; University of Bradford; CEREGE

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This master thesis was a part of an ongoing project at Research institutes of Sweden (RISE) and Chalmers University of technology, studying the formation of white layers (WLs) upon hard machining AISI 52100 steel. With a focus on the nanocrystalline microstructure of the machined steel, X-ray diffraction (XRD), white light interferometry (WLI), optical microscopy (LOM) and scanning electron microscopy (SEM) was utilized in the analysis of gathering an in-depth understanding of the WL formation mechanism. By introducing varying cutting parameters as part of the machining process, the effect of cutting speed and tool wear could be observed to directly impact the WL formation and could be linked to the thermomechanical contribution to the formation mechanism. Both thermal and mechanical WLs were observed and could be distinguished by the occurrence of dark layers in thermal WLs. The purpose of this thesis was to observe the influence of retained austenite (RA) on WL formation and from the XRD analysis the residual stress for different RA content could not be concluded. Furthermore, SEM concluded differences in the microstructure where a higher abundance of carbides was observed in the case of lower RA, a phenomenon most likely originating in the heat treatment process. Indications of facilitated mechanical WL formation for lower RA was observed but could not be deemed conclusive. The RA content could not be concluded to have an impact on the surface roughness nor the residual stress where variations were rather linked to the cutting parameters.

Neste trabalho foram determinadas as concentrações elementares de Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sc, Sm, Ta, Tb, Th, U, Yb e Zn por meio da análise por ativação com nêutrons instrumental (INAA) em 204 fragmentos cerâmicos arqueológicos Marajoara, dos quais, 156 foram cedidos pelo Museu de Arqueologia e Etnologia da USP (MAE) e 48 cedidos pela Profª Denise Pahl Schaan, curadora do Museu do Marajó, além de 9 cerâmicas contemporâneas produzidas e comercializadas na Ilha do Marajó. Realizaram-se análises por espectroscopia de ressonância paramagnétca eletrônica (EPR) em 8 amostras arqueológicas e 1 amostra contemporânea para identificar a temperatura de queima e análises de difratometria de raio-X (XRD) em 13 amostras arqueológicas e 2 amostras contemporâneas para o estudo da composição mineralógica. O estudo das amostras discrepantes foi realizado por meio da distância Mahalanobis e o efeito do tempero adicionado à pasta cerâmica por meio do filtro modificado Mahalanobis. Os resultados foram interpretados utilizando-se a análise de conglomerados, análise de componentes principais e análise discriminante. A análise Procrustes, utilizada para o estudo de seleção de variáveis, mostrou que as variáveis Ce, Fe, Eu, Hf, K e Th são suficientes para caracterizar as amostras analisadas. O estudo comparativo entre as amostras arqueológicas e contemporâneas apresentou a formação de dois grupos bem definidos e próximos para as cerâmicas arqueológicas, e a formação de um terceiro grupo distante para as amostras contemporâneas, indicando que as amostras arqueológicas são bem diferentes das amostras contemporâneas. Tanto as análises de EPR, quanto de XRD, não apresentaram fatores relevantes para a diferenciação entre as amostras arqueológicas e contemporâneas. / In this study the elemental concentration of Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sc, Sm, Ta, Tb, Th, U, Yb and Zn were determined by instrumental neutron activation analysis (INAA) in 204 fragments of Marajoara archeological ceramics, of which 156 were provided by the Archeology and Etnology Museum of São Paulo University (MAE) and 48 were provided by Dr. Denise Pahl Schaan, Marajó Museum curator. Also, 9 contemporary ceramics produced and marketed at Marajó Island were analyzed. Electron paramagnetic resonance (EPR) analyses were performed in 8 archeological samples and 1 contemporary sample in order to identify the burning temperature of the samples. X-ray diffraction (XRD) analyses were performed in 13 archeological samples and 2 contemporary samples for the investigation of their mineralogical composition. Mahalanobis distance was used for the study of outlier while modified filter was used for the study of the temper added to the ceramic paste. Result interpretation was performed using cluster analysis, principal components analysis and discriminant analysis. Procrustes analysis was used for variable selection and it showed that the Ce, Fe, Eu, Hf, K and Th variables are adequate for the characterization of the analyzed samples. The comparative study among the archeological and contemporary ceramics showed the arrangement of two well-defined and close groups for the archeological samples and a third, distant group for the contemporary ones. This result indicates that the archeological and contemporary ceramics differ in their composition. EPR and XRD analysis were inconclusive for the differentiation of archeological and contemporaty ceramics.

Neste trabalho foram determinadas as concentrações elementares de Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sc, Sm, Ta, Tb, Th, U, Yb e Zn por meio da análise por ativação com nêutrons instrumental (INAA) em 204 fragmentos cerâmicos arqueológicos Marajoara, dos quais, 156 foram cedidos pelo Museu de Arqueologia e Etnologia da USP (MAE) e 48 cedidos pela Profª Denise Pahl Schaan, curadora do Museu do Marajó, além de 9 cerâmicas contemporâneas produzidas e comercializadas na Ilha do Marajó. Realizaram-se análises por espectroscopia de ressonância paramagnétca eletrônica (EPR) em 8 amostras arqueológicas e 1 amostra contemporânea para identificar a temperatura de queima e análises de difratometria de raio-X (XRD) em 13 amostras arqueológicas e 2 amostras contemporâneas para o estudo da composição mineralógica. O estudo das amostras discrepantes foi realizado por meio da distância Mahalanobis e o efeito do tempero adicionado à pasta cerâmica por meio do filtro modificado Mahalanobis. Os resultados foram interpretados utilizando-se a análise de conglomerados, análise de componentes principais e análise discriminante. A análise Procrustes, utilizada para o estudo de seleção de variáveis, mostrou que as variáveis Ce, Fe, Eu, Hf, K e Th são suficientes para caracterizar as amostras analisadas. O estudo comparativo entre as amostras arqueológicas e contemporâneas apresentou a formação de dois grupos bem definidos e próximos para as cerâmicas arqueológicas, e a formação de um terceiro grupo distante para as amostras contemporâneas, indicando que as amostras arqueológicas são bem diferentes das amostras contemporâneas. Tanto as análises de EPR, quanto de XRD, não apresentaram fatores relevantes para a diferenciação entre as amostras arqueológicas e contemporâneas. / In this study the elemental concentration of Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sc, Sm, Ta, Tb, Th, U, Yb and Zn were determined by instrumental neutron activation analysis (INAA) in 204 fragments of Marajoara archeological ceramics, of which 156 were provided by the Archeology and Etnology Museum of São Paulo University (MAE) and 48 were provided by Dr. Denise Pahl Schaan, Marajó Museum curator. Also, 9 contemporary ceramics produced and marketed at Marajó Island were analyzed. Electron paramagnetic resonance (EPR) analyses were performed in 8 archeological samples and 1 contemporary sample in order to identify the burning temperature of the samples. X-ray diffraction (XRD) analyses were performed in 13 archeological samples and 2 contemporary samples for the investigation of their mineralogical composition. Mahalanobis distance was used for the study of outlier while modified filter was used for the study of the temper added to the ceramic paste. Result interpretation was performed using cluster analysis, principal components analysis and discriminant analysis. Procrustes analysis was used for variable selection and it showed that the Ce, Fe, Eu, Hf, K and Th variables are adequate for the characterization of the analyzed samples. The comparative study among the archeological and contemporary ceramics showed the arrangement of two well-defined and close groups for the archeological samples and a third, distant group for the contemporary ones. This result indicates that the archeological and contemporary ceramics differ in their composition. EPR and XRD analysis were inconclusive for the differentiation of archeological and contemporaty ceramics.

Cette thèse vise à maitriser la synthèse MPCVD de films hétéroépitaxiés de diamant de haute qualité cristalline sur substrat d’iridium pour la réalisation de dosimètres en radiothérapie. Cet objectif nous a conduits à élaborer la couche d’iridium épitaxiée sur des substrats SrtiO3 (001). Un bâti sous vide équipé d’un canon à électrons a donc été développé et calibré. Les couches obtenues ont été caractérisées par DRX et présentent une qualité structurale équivalente à l’état de l’art. Le procédé de nucléation (BEN) - MPCVD induit sur la surface de l’iridium des « domaines » spécifiques à la nucléation du diamant sur iridium. Un travail important a été mené sur l’optimisation du (BEN) - MPCVD de façon à obtenir un procédé fiable et reproductible pour obtenir des « domaines » homogènes sur une surface de 5x5mm2 d’Ir/SrtiO3. Des études de caractérisation de surface (MEB, XPS, AES) des « domaines » nous ont permis de dresser leur carte d’identité chimique et morphologique. Nous démontrons ainsi qu’ils contiennent des nuclei de diamant. De plus, la propagation de ces « domaines » semble suivre des directions préférentielles [110] induites par l’épitaxie de l’iridium au cours du temps durant l’étape de (BEN)-MPCVD. A partir de ces résultats, des films de diamant hétéroépitaxiés autosupportés de 100&#956-m ont été élaborés. La corrélation entre la qualité cristalline du diamant hétéroépitaxié et sa réponse en détection a été menée avec l’équipe dosimétrie du LCD. Des inhomogénéités de la structure cristalline due à la présence de défauts structuraux ont été mises en évidence. Afin d’étudier localement ces échantillons, une campagne de mesure par microfaisceau X a été réalisée sur la ligne Diffabs du Synchrotron Soleil. L’assemblage des différentes connaissances acquises lors de cette thèse a permis de fabriquer et de caractériser un premier détecteur à base de diamant hétéroépitaxié au LCD / This thesis aims to master the MPCVD synthesis of heteroepitaxial diamond films of high crystalline quality on iridium substrate for radiotherapy dosimeters. This objective has led us to develop the epitaxial iridium layer grown on SrtiO3 substrates (001). A vacuum frame equipped with an electron gun has been developed and calibrated. The obtained layers characterized by XRD, possess a structural quality equivalent to the state of the art/in literature. Bias Enhanced Nucleation (BEN)- MPCVD induces nucleation of « domains » on the iridium surface, according a unique nucleation pathway. Significant work has been conducted on (BEN)-MPCVD optimization to obtain a reliable and reproducible method for generating homogeneous « domains » on a surface of 5x5mm2. Combined characterizations (SEM, XPS, AES) of « domains » surface enabled us to establish the identity card of their chemical and morphological properties. We demonstrate that they contain diamond nuclei. In addition, the temporal expansion of these « domains » seems to follow preferential directions <110> of iridium lattice during the (BEN)-MPCVD stage. From these results, self-supported heteroepitaxial diamond films 100&#956-m thick have been grown. The correlation between their crystalline quality and their detection response was conducted with the LCD dosimeter team. The inhomogeneities in the crystal structure due to structural defects have been identified. To study more locally these samples, a measurement campaign was carried out by microbeam X on the DIFFABS line at Soleil Synchrotron. The combination of the different knowledges acquired during this thesis has allowed the fabrication and characterization of the first detector based on heteropitaxial diamond at the LCD laboratory.

Die vorliegende Promotion beinhaltet die Untersuchung von irregulären Kohlenstoff-Nanostrukturen, die mittels Hochenergie-Kugelmahlen hergestellt wurden. Die wissenschaftliche Herausforderung besteht darin, die strukturelle Vielfalt dieser Nanostrukturen experimentell zu erfassen, zu klassifizieren und bezüglich ausgewählter Eigenschaften zu bewerten, sowie mit den Herstellungsparametern in Zusammenhang zu bringen. Die Pulver konnten nach den Mahlungen hinsichtlich ihrer Struktur in zwei grundsätzliche Typen eingeteilt werden: (I) ein Nanopulver, das aus graphitischen Stapelpaketen besteht, welche in eine amorphe Matrix eingebettet sind, (II) ein vollständig amorphisiertes Pulver. Die Strukturanalyse in Bezug auf die Mahlbedingungen (Mahlatmosphäre, Mahltemperatur) zeigt, dass die Dauer der Nanostrukturierung sowie die Anzahl und Größe von graphitischen Stapelpaketen gezielt beeinflusst werden kann. Außerdem konnten Hinweise gefunden werden, die darauf hindeuten, dass Mahlen bei tiefen Temperaturen oder unter Wasserstoffatmosphäre die Agglomeration der Nanopartikel verringern kann. Das Kugelmahlen ermöglicht es ebenfalls, die spezifische Oberfläche des Graphitpulvers von 5,5 m2/g auf 725 m2/g innerhalb von fünf Mahlstunden zu erhöhen. Der Anteil der Verunreinigungen (Fe) liegt dabei nicht höher als 0,05 wt%. Es ist jedoch zu beachten, dass sämtliche Eigenschaften stark von den verschiedenen Mahlparametern (Mahltemperatur, Mahlmaterial) abhängen. Die für Adsorptionsuntersuchungen optimalen Eigenschaften (große spezifische Oberfläche, erhöhte Reaktivität, geringe Verunreinigungen) werden schon nach kurzer Mahldauer erreicht. Wiederholungsmahlungen und Wiederholungsmessungen verschiedener Eigenschaften (spezifische Oberfläche, Verbrennungstemperatur) machen deutlich, dass die Ergebnisse reproduzierbar sind, und dass keine Alterungserscheinungen während der Lagerung unter Argonatmosphäre im Zeitraum von einem Jahr auftreten. Die Wasserstoffspeicherung an nanostrukturierten Kohlenstoffpulvern konnte nachgewiesen werden. Die maximalen Speicherkapazitäten für Temperaturen nahe 77 K lagen bei 1,5 wt%. Für niedrigere Temperaturen Tist = 35 K zeigten sich höhere Speicherkapazitäten von bis zu 5 wt%. Die Korrelation der ermittelten Speicherkapazitäten mit den theoretisch erreichbaren Werten in Bezug auf die Oberfläche der Proben zeigt, dass im Experiment deutlich höhere Werte erhalten werden. Dies lässt den Schluss zu, dass neben der Speicherung an der Oberfläche der Pulver ein weiterer Speichermechanismus innerhalb der Mikroporen der Proben stattfindet.

The thesis deals with the study of magnesium oxide burned by various burning regimes and his possibilities of its usage as potential expansion additive. The theoretical part of the thesis concerns mainly the volume changes and how they can be influenced. The practical part focuses on monitoring morphology, phase composition and the hydration process of magnesium oxide.

The main purpose for this paper is to study iron artefacts excavated in the Black Earth harbour district of Birka. This locale, positioned on the island Björkö in Adelsö par. Sweden, is one of the mayor sites in regard to the Scandinavian Viking age. The how and why of the corrosive process will be touched upon. Specifically how archaeological iron interacts with the soil in which it is found, and what can be done to prevent unnecessary decay after excavation. This, in turn, leads to an observation of how methods have changed in regard to the conservation of archaeological iron, from the processes used in the early days of the field, to the more present day with the method utilized in this study. The conservation of said artefacts is for this study accomplished through the use of a conventional chemical method called EDTA. The usability of this method with waterlogged metallic artefacts is tested. The product of the conservation work revealed the objects to be mostly, iron rivets, bolts or nails. Not too surprising when the articles came from an area widely believed to be a harbour. This specific chemical solution proved not to be a sufficient conservation method for the waterlogged metal objects examined in this paper. This was due to the notably hard crust that covered the objects and the structural fragility of the artefacts. Specific analyses of some of the artefacts were undertaken due to the emergence of substantial amounts of depositions in the final steps of the process. Using XRD, XRF and IR-spectroscopy, the depositions were analysed and the result showed that the depositions most likely consists of a blend of non-water-soluble iron phosphates.

Catalisadores à base de óxidos metálicos têm sido muito utilizados nas indústrias do petróleo, de química fina e no controle de poluição. A seleção adequada do óxido metálico como suporte, do catalisador e o uso de coberturas superficiais menores que uma monocamada dos componentes ativos, onde somente espécies MOx estão presentes sobre a superfície dos óxidos suportes, pode ser uma exigência para modificar as propriedades catalíticas de modo a obter uma boa eficiência do catalisador durante a reação. Óxidos metálicos do grupo V suportados têm uma grande variedade de aplicações catalíticas, e têm sido extensivamente investigados nos últimos anos. Catalisadores à base de óxido de vanádio suportado possuem excelentes propriedades redox e são principalmente empregados como catalisadores em processos de oxidação seletiva. Óxido de tântalo mássico é um sólido ácido com propriedades catalíticas e diversas aplicações têm sido reportadas. O suporte foi preparado pelo método de coprecipitação, utilizando proporções de 15 e 30% p/p de Ta2O5 em Al2O3. A adição de V2O5 sobre o suporte Ta2O5-Al2O3 foi realizada através de impregnação úmida com excesso de solvente, água, formando catalisadores com 2, 4 e 8 átomos de vanádio/nm². A fim de alcançar o objetivo deste trabalho, as seguintes técnicas de caracterização foram utilizadas: volumetria de N2 para determinação da área específica e volume de poros, redução à temperatura programada (RTP), difratometria de raios-X (XRD), espectroscopia na região do infravermelho com transformada de Fourier (FTIR), FTIR com adsorção de piridina e espectroscopia Laser Raman. As propriedades ácidas e/ou básicas dos suportes e catalisadores foram avaliadas através da reação de decomposição do isopropanol. As propriedades texturais do suporte foram modificadas pela adição crescente do vanádio ao suporte, efeito este atribuído ao bloqueio dos microporos pelas espécies de vanádio superficiais. A metodologia empregada na preparação do suporte revelou um material amorfo ao DRX. Nos catalisadores, a adição crescente de vanádio promove a formação de cristais de V2O5 superficiais nas amostras com 4 e 8 átomos de V/nm². Nos resultados de RTP, os catalisadores apresentaram um único pico de redução do vanádio que corresponde à redução de V2O5 a V6O13. Nas análises de FTIR com adsorção de piridina verificou-se a diminuição da força dos sítios ácidos de Lewis, presentes em todos os catalisadores, com a adição de vanádio. Somente nos catalisadores com 8 átomos de V/nm² foram detectadas bandas referentes a sítios ácidos de Br?nsted. Nas análises de espectroscopia Raman não foi observada nenhuma banda característica de espécies VOx isoladas nas amostras, porém para coberturas abaixo de uma monocamada de V foram observadas bandas de espécies poliméricas. Bandas Raman de cristais de V2O5 foram características somente na amostra com 8 átomos de V/nm². A presença de sítios ácidos foi confirmada pela presença de propeno e éter diisopropílico como produtos da desidratação do isopropanol em todos os catalisadores. Com a adição de vanádio, sítios básicos ou redox também foram verificados pela presença de acetona produzida pela desidrogenação do isopropanol. / Metal oxides based catalysts have been very used in petroleum industry, fine chemical and pollution control. The adequate selection of the metal oxide as a support and catalyst, and the use of superficial covering with active compounds lower than a monolayer, where only MOx species are present on the support oxide surface, can be a requirement to modify the catalytic properties in order to have a good catalyst efficiency during the reaction. Supported metal oxides of group V have a large variety of catalytic applications, and have been widely investigated in the last years. Supported vanadium oxide based catalysts have excellent redox properties and they are mainly used as selective oxidation catalyst. Tantalum oxide is an acid solid with catalytic properties and many applications of supported tantalum oxide based catalysts have been reported. The supports were prepared by coprecipitation method, using the proportions of 15 and 30% of Ta2O5 in Al2O3. The addition of V2O5 on the support Ta2O5-Al2O3 was performed using the wet impregnation method with excess of solvent, water, forming catalysts with 2, 4 and 8 atoms of V/nm². In order to achieve the purpose of this work, the following characterization techniques were used: N2 volumetry to determine specific area and pore volume, temperature programmed reduction (TPR), X-ray difratometry, Fourier transform infrared spectroscopy (FTIR) and Laser Raman spectroscopy. The acid/ basic properties of the support and catalysts were evaluated through isopropanol decomposition reaction. The textural properties of the supported were modified by the increasing addition of vanadium, effect attributed to micropores blocked by superficial vanadium species. The used methodology in the support preparation showed an amorphous material to XRD. In the catalysts, the increasing addition of vanadium promotes the formation of V2O5 superficial crystals in the samples with 4 and 8 atoms of V/nm². In the TPR results, the catalysts presented only one reduction peak corresponding to the V2O5 a V6O13 reduction. In the FTIR analysis with adsorbed pyridine, it was observed a decrease of acidity at Lewis acid sites, which were present in all catalysts samples. In the Raman spectroscopy analysis, it was not observed any characteristic band of isolated VOx species in the sample, although covering lower than a monolayer of vanadium, it was observed V=O bands due to surface polymeric vanadium oxide species. V2O5 crystal Raman bands were characteristics only in samples with 8 atoms of V/nm². The presence of acid sites was confirmed by the production of propane and diisopropyl ether as product of isopropanol dehydratation, observed for all catalysts. With V charge, basic and redox sites were verified as well by the production of acetone at isopropanol dehydrogenation.