X-Ray Imaging of SAPO-34 Molecular Sieves at the Nanoscale: Influence of Steaming on the Methanol-to-Hydrocarbons Reaction

The effect of a severe steaming treatment on the physicochemical properties and catalytic performance of H-SAPO-34 molecular sieves during the methanol-to-hydrocarbons (MTH) reaction has been investigated with a combination of scanning transmission X-ray microscopy (STXM), catalytic testing, and bulk characterization techniques, including ammonia temperature programmed desorption and 27Al and 29Si magic angle spinning nuclear magnetic resonance. For this purpose, two samples, namely a calcined and a steamed H-SAPO-34 catalyst powder, have been compared. It has been found that calcined H-SAPO-34 displays a high selectivity towards light olefins, yet shows a poor stability as compared to a zeolite H-ZSM-5 catalyst. Moreover, in situ STXM at the carbon K-edge during the MTH reaction allows construction of nanoscale chemical maps of the hydrocarbon species formed within the H-SAPO-34 aggregates as a function of reaction time and steam post-treatment. It was found that there is an initial preferential formation of coke precursor species within the core of the H-SAPO-34 aggregates. For longer times on stream the formation of the coke precursor species is extended to the outer regions, progressively filling the entire H-SAPO-34 catalyst particle. In contrast, the hydrothermally treated H-SAPO-34 showed similar reaction selectivity, but decreased activity and catalyst stability with respect to its calcined counterpart. These variations in MTH performance are related to a faster and more homogeneous formation of coke precursor species filling up the entire steamed H-SAPO-34 catalyst particle. Finally, the chemical imaging capabilities of the STXM method at the Al and Si K-edge are illustrated by visualizing the silicon islands at the nanoscale before and after steaming H-SAPO-34.

Thermodynamic, surface and structural properties of liquid Co-Si alloys

The knowledge of thermophysical properties of liquid Co-Si alloys is a key requirement for manufacturing of composite materials by infiltration method. Despite this need, the experimental and predicted property data of the Co-Si system are scarce and often inconsistent between the various sources. In the present work the mixing behaviour of Co-Si melts has been analysed through the study of the concentration dependence of various thermodynamic, surface (surface tension and surface composition) and structural properties (concentration fluctuations in the long-wavelength limit and chemical short-range order parameter) in the framework of the Compound Formation Model (CFM) and Quasi Chemical Approximation for regular solutions (QCA). In addition, the surface tension of the Co22·5Si77.5 (in at%) eutectic alloy, that is proposed to be used as the infiltrant, has been measured by the pendant drop method at temperatures ranging from 1593 to 1773 K. The results obtained were discussed with respect to both, temperature and concentration, and subsequently compared with the model predictions and literature data.

B. Gregorii Turone[n]sis episcopi Historiarum pr[a]ecipue gallicaru[m] lib. X ; In vitas patrum fere sui temporis lib. I. ; De gloria confessorum praecipue gallorum lib. I. : Adonis Vie[n]ne[n]sis episcopi, sex aetatu[m] mu[n]di breues seu co[m]mentarii vsq[ue] ad Carolu[m] simplicem francorum regem.

Mode of access: Internet.

Muy Illustre Señor, En el pleyto que trata el Cardenal y Arçobispo de Toledo, don Gaspar de Quiroga por si, y por sus antecessores, y por su dignidad Arçobispal : contra don Francisco de los Cobos y de Luna, Co[n]de de Ricla, y Adelantado perpetuo de Caçorla : sobre que el dicho Cardenal y Arçobispo pide que se manden executar ciertos Motus propios dados por su Sanctidad del Papa Paulo Quarto en fauor de don Iuan Martinez Siliceo Arçobispo de Toledo : y por el Papa Pio Quinto en fauor de don fra y Bartholome de Carrança ... y que en execucion dellos se le de la possession del dicho Adelantamiento, y de las villas y rentas a el pertenecientes ...

Francisco de los Cobos fue nombrado adelantado de Cazorla en 1545

Dell' historia ecclesiastica di Piacenza di Pietro Maria Campi canonico Piacentino parte prima [-terza] : nella quale si spiegano le attioni de' santi, de' beati, e de' vescoui della città di Piacenza, e l'antichissima immunità , e giurisditione di quella chiesa, con le fondationi di molti luoghi sacri, et insieme le varie donationi, e gratie riportate da' sommi pontefici, imperadori, rè, e principi, e si fà anche mentione di molte famiglie, huomini illustri, e maggiori successi d'Italia : con l'origine de' nomi de' villaggi, terre, e castella del Piacentino ... e nel fine vn' Apologia del medesimo autore per l'innocente, e santa vita del B. Gregorio papa X. Piacentino, e la vita Latina antichissima dello stesso pontefice non mai più vscita in luce ... ; Parte seconda.

Mode of access: Internet.

De la pirotechnia. Libri X. : doue ampiamente si tratta non solo di ogni sorte & diuersita di miniere, ma anchora quanto si ricerca intorno a la prattica di quelle cose di quel che si appartiene a l'arte de la fusione ouer gitto de metalli come d'ogni altra cosa simile a questa /

CCBE S. XVI,

Determination of strontium segregation in modified hypoeutectic Al-Si alloy by micro X-ray fluorescence analysis

Analysis of intra- and inter-phase distribution of modifying elements in aluminium-silicon alloys is difficult due to the low concentrations used. This research utilises a mu-XRF (X-ray fluorescence) technique at the SPring-8 synchrotron radiation facility X-ray source and reveals that the modifying element strontium segregates exclusively to the eutectic silicon phase and the distribution of strontium within this phase is relatively homogeneous. This has important implications for the fundamental mechanisms of eutectic modification in hypoeutectic aluminium-silicon alloys. (c) 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A DIALÉTICA ENTRE O CONHECIMENTO DE SI E O CONHECIMENTO DE DEUS NO LIVRO X DAS CONFISSÕES DE SANTO AGOSTINHO

O conhecimento de si e o conhecimento de Deus estabelecem uma relação fundamental na obra mais conhecida de Agostinho, Confissões. O livro X das Confissões contém as narrativas centrais para a análise da dialética entre o conhecimento de si e o conhecimento de Deus, que tem como chave de leitura a memória para a constituição do cogito existencial. É examinada a relação que existe, no texto narrativo de Agostinho, entre a interpretação da Escritura e a constituição do si, em que há aspectos do discurso interior e abordagem no quadro da teoria narrativa que é dada a partir do conceito de identidade narrativa. A constituição do si é desenvolvida na dialética interna do personagem entre a afirmação de si e a negação de si, que apresenta a imanência do homem como característica pessoal e, ao mesmo tempo, o desejo de transcendência daquilo que o ser humano tem de mais íntimo em relação a Deus. Esta é uma análise da tensão existente entre a visão que o ser humano tem da consciência de si e a que ele tem de Deus, na busca pela felicidade.(AU)

Structural properties of a family of hydrogen-bonded co-crystals formed between gemfibrozil and hydroxy derivatives of t-butylamine, determined directly from powder X-ray diffraction data

We report the formation and structural properties of co-crystals containing gemfibrozil and hydroxy derivatives of t-butylamine H2NC(CH3)3-n(CH2OH)n, with n=0, 1, 2 and 3. In each case, a 1:1 co-crystal is formed, with transfer of a proton from the carboxylic acid group of gemfibrozil to the amino group of the t-butylamine derivative. All of the co-crystal materials prepared are polycrystalline powders, and do not contain single crystals of suitable size and/or quality for single crystal X-ray diffraction studies. Structure determination of these materials has been carried out directly from powder X-ray diffraction data, using the direct-space Genetic Algorithm technique for structure solution followed by Rietveld refinement. The structural chemistry of this series of co-crystal materials reveals well-defined structural trends within the first three members of the family (n=0, 1, 2), but significantly contrasting structural properties for the member with n=3. © 2007 Elsevier Inc. All rights reserved.

An X-ray micro-fluorescence study to investigate the distribution of Al, Si, P and Ca ions in the surrounding soft tissue after implantation of a calcium phosphate-mullite ceramic composite in a rabbit animal model

Synthetic calcium phosphates, despite their bioactivity, are brittle. Calcium phosphate-mullite composites have been suggested as potential dental and bone replacement materials which exhibit increased toughness. Aluminium, present in mullite, has however been linked to bone demineralisation and neurotoxicity: it is therefore important to characterise the materials fully in order to understand their in vivo behaviour. The present work reports the compositional mapping of the interfacial region of a calcium phosphate-20 wt% mullite biocomposite/soft tissue interface, obtained from the samples implanted into the long bones of healthy rabbits according to standard protocols (ISO-10993) for up to 12 weeks. X-ray micro-fluorescence was used to map simultaneously the distribution of Al, P, Si and Ca across the ceramic-soft tissue interface. A well defined and sharp interface region was present between the ceramic and the surrounding soft tissue for each time period examined. The concentration of Al in the surrounding tissue was found to fall by two orders of magnitude, to the background level, within similar to 35 mu m of the implanted ceramic.

Effects of rare-earth co-doping on the local structure of rare-earth phosphate glasses using high and low energy X-ray diffraction

Rare-earth co-doping in inorganic materials has a long-held tradition of facilitating highly desirable optoelectronic properties for their application to the laser industry. This study concentrates specifically on rare-earth phosphate glasses, (R2O3)x(R'2O3)y(P2O5)1-(x+y), where (R, R') denotes (Ce, Er) or (La, Nd) co-doping and the total rare-earth composition corresponds to a range between metaphosphate, RP3O9, and ultraphosphate, RP5O14. Thereupon, the effects of rare-earth co-doping on the local structure are assessed at the atomic level. Pair-distribution function analysis of high-energy X-ray diffraction data (Qmax = 28 Å-1) is employed to make this assessment. Results reveal a stark structural invariance to rare-earth co-doping which bears testament to the open-framework and rigid nature of these glasses. A range of desirable attributes of these glasses unfold from this finding; in particular, a structural simplicity that will enable facile molecular engineering of rare-earth phosphate glasses with 'dial-up' lasing properties. When considered together with other factors, this finding also demonstrates additional prospects for these co-doped rare-earth phosphate glasses in nuclear waste storage applications. This study also reveals, for the first time, the ability to distinguish between P-O and PO bonding in these rare-earth phosphate glasses from X-ray diffraction data in a fully quantitative manner. Complementary analysis of high-energy X-ray diffraction data on single rare-earth phosphate glasses of similar rare-earth composition to the co-doped materials is also presented in this context. In a technical sense, all high-energy X-ray diffraction data on these glasses are compared with analogous low-energy diffraction data; their salient differences reveal distinct advantages of high-energy X-ray diffraction data for the study of amorphous materials. © 2013 The Owner Societies.

Desenvolvimento de material BaCexPr1-xO3 (0 ≤ X ≤ 1) com estrutura perovskita para oxidação catalítica do CO a CO2 em reator de leito fixo

Barium Cerate (BaCeO3) is perovskite type structure of ABO3, wherein A and B are metal cations. These materials, or doped, have been studied by having characteristics that make them promising for the application in fuel cells solid oxide, hydrogen and oxygen permeation, as catalysts, etc .. However, as the ceramic materials mixed conductivity have been produced by different synthesis methods, some conditions directly influence the final properties, one of the most important doping Site B, which may have direct influence on the crystallite size, which in turn directly influences their catalytic activity. In this study, perovskite-type (BaCexO3) had cerium gradually replaced by praseodymium to obtain ternary type materials BaCexPr1-xO3 and BaPrO3 binaries. These materials were synthesized by EDTA/Citrate complexing method and the material characterized via XRD, SEM and BET for the identification of their structure, morphology and surface area. Moreover were performed on all materials, catalytic test in a fixed bed reactor for the identification of that person responsible for complete conversion of CO to CO2 at low operating temperature, which step can be used as the subsequent production of synthesis gas (CO + H2) from methane oxidation. In the present work the crystalline phase having the orthorhombic structure was obtained for all compositions, with a morphology consisting of agglomerated particles being more pronounced with increasing praseodymium in the crystal structure. The average crystal size was between 100 nm and 142,2 nm. The surface areas were 2,62 m²g-1 for the BaCeO3 composition, 3,03 m²g-1 to BaCe0,5Pr0,5O3 composition and 2,37 m²g-1 to BaPrO3 composition. Regarding the catalytic tests, we can conclude that the optimal flow reactor operation was 50 ml / min and the composition regarding the maximum rate of conversion to the lowest temperature was BaCeO3 to 400° C. Meanwhile, there was found that the partially replaced by praseodymium, cerium, there was a decrease in the catalytic activity of the material.

Evaluation of the castability of a Co-Cr-Mo-W alloy varying the investing technique

O objetivo deste estudo foi comparar a fusibilidade de ligas de Co-Cr-Mo-W (Remanium 2000), Ni-Cr (Durabond) e Co-Cr-Mo (Vera-PDI), incluídas em revestimentos à base de fosfato, sílica ou utilizando uma técnica mista. Uma rede de nylon quadrada (10 X 10 mm) com 100 espaços abertos serviu de modelo para construção de padrões de cera, que foram incluídos com revestimento à base de sílica, revestimento fosfatado e técnica mista (camada de revestimento fosfatado com 2 mm de espessura + revestimento à base de sílica). Quarenta e cinco espécimes (5 para cada condição experimental) foram fundidos sob chama de gás-oxigênio e a seguir jateados com óxido de alumínio. O número de segmentos fundidos completos foi contado para obter uma percentagem designada como "valor de fusibilidade", representando a precisão da liga em reproduzir os detalhes do molde. A análise estatística por meio de ANOVA a dois critérios e teste Tukey mostrou que, comparando-se as ligas, a Remanium 2000 teve fusibilidade estaticamente semelhante (p>0,05) à da Vera PDI e inferior à da liga Durabond (p<0,05). Considerando os resultados da técnica mista, a liga Remanium 2000 teve menor valor de fusibilidade (p<0,05) que as ligas Durabond e Vera PDI, que apresentaram valores estatisticamente semelhantes entre si (p>0,05). Concluindo, a fusibilidade da liga de Co-Cr-Mo-W (Remanium 2000) foi comparável à da liga de Co-Cr (Vera PDI) e inferior à da liga de Ni-Cr alloy (Durabond). À exceção da liga Remanium 2000, a técnica de inclusão mista aumentou consideravelmente a capacidade das ligas testadas de reproduzir os detalhes do molde, quando comparada à técnica de inclusão em revestimento fosfatado. A técnica de inclusão mista representa uma alternativa para melhorar a fusibilidade de ligas de metais básicos sem afetar a qualidade superficial das peças metálicas.

Evaluation of the castability of a Co-Cr-Mo-W alloy varying the investing technique

O objetivo deste estudo foi comparar a fusibilidade de ligas de Co-Cr-Mo-W (Remanium 2000), Ni-Cr (Durabond) e Co-Cr-Mo (Vera-PDI), incluídas em revestimentos à base de fosfato, sílica ou utilizando uma técnica mista. Uma rede de nylon quadrada (10 X 10 mm) com 100 espaços abertos serviu de modelo para construção de padrões de cera, que foram incluídos com revestimento à base de sílica, revestimento fosfatado e técnica mista (camada de revestimento fosfatado com 2 mm de espessura + revestimento à base de sílica). Quarenta e cinco espécimes (5 para cada condição experimental) foram fundidos sob chama de gás-oxigênio e a seguir jateados com óxido de alumínio. O número de segmentos fundidos completos foi contado para obter uma percentagem designada como "valor de fusibilidade", representando a precisão da liga em reproduzir os detalhes do molde. A análise estatística por meio de ANOVA a dois critérios e teste Tukey mostrou que, comparando-se as ligas, a Remanium 2000 teve fusibilidade estaticamente semelhante (p>0,05) à da Vera PDI e inferior à da liga Durabond (p<0,05). Considerando os resultados da técnica mista, a liga Remanium 2000 teve menor valor de fusibilidade (p<0,05) que as ligas Durabond e Vera PDI, que apresentaram valores estatisticamente semelhantes entre si (p>0,05). Concluindo, a fusibilidade da liga de Co-Cr-Mo-W (Remanium 2000) foi comparável à da liga de Co-Cr (Vera PDI) e inferior à da liga de Ni-Cr alloy (Durabond). À exceção da liga Remanium 2000, a técnica de inclusão mista aumentou consideravelmente a capacidade das ligas testadas de reproduzir os detalhes do molde, quando comparada à técnica de inclusão em revestimento fosfatado. A técnica de inclusão mista representa uma alternativa para melhorar a fusibilidade de ligas de metais básicos sem afetar a qualidade superficial das peças metálicas.

IRAS 00183-7111: ALMA and X-ray view of an ultra luminous infrared galaxy

The aim of this Thesis work is to study the multi-frequency properties of the Ultra Luminous Infrared Galaxy (ULIRG) IRAS 00183-7111 (I00183) at z = 0.327, connecting ALMA sub-mm/mm observations with those at high energies in order to place constraints on the properties of its central power source and verify whether the gas traced by the CO may be responsible for the obscuration observed in X-rays. I00183 was selected from the so-called Spoon diagnostic diagram (Spoon et al. 2007) for mid-infrared spectra of infrared galaxies based on the equivalent width of the 6.2 μm Polycyclic Aromatic Hydrocarbon (PAH) emission feature versus the 9.7 μm silicate strength. Such features are a powerful tool to investigate the contribution of star formation and AGN activity in this class of objects. I00183 was selected from the top-left region of the plot where the most obscured sources, characterized by a strong Si absorption feature, are located. To link the sub-mm/mm to the X-ray properties of I00183, ALMA archival Cycle 0 data in Band 3 (87 GHz) and Band 6 (270 GHz) have been calibrated and analyzed, using CASA software. ALMA Cycle 0 was the Early Science program for which data reprocessing is strongly suggested. The main work of this Thesis consisted in reprocessing raw data to provide an improvement with respect to the available archival products and results, which were obtained using standard procedures. The high-energy data consists of Chandra, XMM-Newton and NuSTAR observations which provide a broad coverage of the spectrum in the energy range 0.5 − 30 keV. Chandra and XMM archival data were used, with an exposure time of 22 and 22.2 ks, respectively; their reduction was carried out using CIAO and SAS software. The 100 ks NuSTAR are still private and the spectra were obtained by courtesy of the PI (K. Iwasawa). A detailed spectral analysis was done using XSPEC software; the spectral shape was reproduced starting from simple phenomenological models, and then more physical models were introduced to account for the complex mechanisms that involve this source. In Chapter 1, an overview of the scientific background is discussed, with a focus on the target, I00183, and the Spoon diagnostic diagram, from which it was originally selected. In Chapter 2, the basic principles of interferometry are briefly introduced, with a description of the calibration theory applied to interferometric observations. In Chapter 3, ALMA and its capabilities, both current and future, are shown, explaining also the complex structure of the ALMA archive. In Chapter 4, the calibration of ALMA data is presented and discussed, showing also the obtained imaging products. In Chapter 5, the analysis and discussion of the main results obtained from ALMA data is presented. In Chapter 6, the X-ray observations, data reduction and spectral analysis are reported, with a brief introduction to the basic principle of X-ray astronomy and the instruments from which the observations were carried out. Finally, the overall work is summarized, with particular emphasis on the main obtained results and the possible future perspectives.