Structure and thermal properties of yttrium alumino-phosphate glasses

The structure and thermal properties of yttrium alumino-phosphate glasses, of nominal composition (Y2O3)(0.31-z)(Al2O3)(z)(P2O5)(0.69) with 0 less than or similar to z less than or similar to 0.31, were studied by using a combination of neutron diffraction, Al-27 and P-31 magic angle spinning nuclear magnetic resonance, differential scanning calorimetry and thermal gravimetric analysis methods. The Vickers hardness of the glasses was also measured. The data are compared to those obtained for pseudo-binary Al2O3-P2O5 glasses and the structure of all these materials is rationalized in terms of a generic model for vitreous phosphate materials in which Y3+ and Al3+ act as modifying cations that bind only to the terminal (non-bridging) oxygen atoms of PO4 tetrahedra. The results are used to help elucidate the phenomenon of rare-earth clustering in phosphate glasses which can be reduced by substituting Al3+ ions for rare-earth R3+ ions at fixed modifier content.

A structural investigation of the alkali metal site distribution within bioactive glass using neutron diffraction and multinuclear solid state NMR

The atomic-scale structure of Bioglass and the effect of substituting lithium for sodium within these glasses have been investigated using neutron diffraction and solid state magic angle spinning (MAS) NMR. Applying an effective isomorphic substitution difference function to the neutron diffraction data has enabled the Na-O and Li-O nearest-neighbour correlations to be isolated from the overlapping Ca-O, O-(P)-O and O-(Si)-O correlations. These results reveal that Na and Li behave in a similar manner within the glassy matrix and do not disrupt the short range order of the network former. Residual differences are attributed solely to the variation in ionic radius between the two species. Successful simplification of the 2

An examination of the calcium and strontium site distribution in bioactive glasses through isomorphic neutron diffraction, X-ray diffraction, EXAFS and multinuclear solid state NMR.

Strontium has been substituted for calcium in the glass series (SiO2)49.46(Na2O)26.38(P2O5)1.07(CaO)23.08x(SrO)x (where x = 0, 11.54, 23.08) to elucidate their underlying atomic-scale structural characteristics as a basis for understanding features related to the bioactivity. These bioactive glasses have been investigated using isomorphic neutron and X-ray diffraction, Sr K-edge EXAFS and solid state 17O, 23Na, 29Si, 31P and 43Ca magic-angle-spinning (MAS) NMR. An effective isomorphic substitution first-order difference function has been applied to the neutron diffraction data, confirming that Ca and Sr behave in a similar manner within the glass network, with residual differences attributed to solely the variation in ionic radius between the two species. The diffraction data provides the first direct experimental evidence of split Ca–O nearest-neighbour correlations in these melt quench bioactive glasses, together with an analogous splitting of the Sr–O correlations; the correlations are attributed to the metal ions correlated either to bridging or to non-bridging oxygen atoms. Triple quantum (3Q) 43Ca MAS NMR corroborates the split Ca–O correlations. Successful simplification of the 2 < r (A) < 3 region via the difference method has also revealed two distinct Na environments. These environments are attributed to sodium correlated either to bridging or to nonbridging oxygen atoms. Complementary multinuclear MAS NMR, Sr K-edge EXAFS and X-ray diffraction data supports the structural model presented. The structural sites present will be intimately related to their release properties in physiological fluids such as plasma and saliva, and hence the bioactivity of the material. Detailed structural knowledge is therefore a prerequisite for optimising material design.

Effect of calcium source on structure and properties of sol-gel derived bioactive glasses

The aim was to determine the most effective calcium precursor for synthesis of sol-gel hybrids and for improving homogeneity of sol-gel bioactive glasses. Sol-gel derived bioactive calcium silicate glasses are one of the most promising materials for bone regeneration. Inorganic/organic hybrid materials, which are synthesized by incorporating a polymer into the sol-gel process, have also recently been produced to improve toughness. Calcium nitrate is conventionally used as the calcium source, but it has several disadvantages. Calcium nitrate causes inhomogeneity by forming calcium-rich regions, and it requires high temperature treatment (>400 C) for calcium to be incorporated into the silicate network. Nitrates are also toxic and need to be burnt off. Calcium nitrate therefore cannot be used in the synthesis of hybrids as the highest temperature used in the process is typically 40-60 C. Therefore, a different precursor is needed that can incorporate calcium into the silica network and enhance the homogeneity of the glasses at low (room) temperature. In this work, calcium methoxyethoxide (CME) was used to synthesize sol-gel bioactive glasses with a range of final processing temperatures from 60 to 800 C. Comparison is made between the use of CME and calcium chloride and calcium nitrate. Using advanced probe techniques, the temperature at which Ca is incorporated into the network was identified for 70S30C (70 mol % SiO, 30 mol % CaO) for each of the calcium precursors. When CaCl was used, the Ca did not seem to enter the network at any of the temperatures used. In contrast, Ca from CME entered the silica network at room temperature, as confirmed by X-ray diffraction, Si magic angle spinning nuclear magnetic resonance spectroscopy, and dissolution studies. CME should be used in preference to calcium salts for hybrid synthesis and may improve homogeneity of sol-gel glasses.

Structural characterization of titanium-doped Bioglass using isotopic substitution neutron diffraction

Melt quenched silicate glasses containing calcium, phosphorus and alkali metals have the ability to promote bone regeneration and to fuse to living bone. Of these glasses 45S5 Bioglass® is the most widely used being sold in over 35 countries as a bone graft product for medical and dental applications; particulate 45S5 is also incorporated into toothpastes to help remineralize the surface of teeth. Recently it has been suggested that adding titanium dioxide can increase the bioactivity of these materials. This work investigates the structural consequences of incorporating 4 mol% TiO2 into Bioglass® using isotopic substitution (of the Ti) applied to neutron diffraction and X-ray Absorption Near Edge Structure (XANES). We present the first isotopic substitution data applied to melt quench derived Bioglass or its derivatives. Results show that titanium is on average surrounded by 5.2(1) nearest neighbor oxygen atoms. This implies an upper limit of 40% four-fold coordinated titanium and shows that the network connectivity is reduced from 2.11 to 1.97 for small quantities of titanium. Titanium XANES micro-fluorescence confirms the titanium environment is homogenous on the micron length scale within these glasses. Solid state magic angle spinning (MAS) NMR confirms the network connectivity model proposed. Furthermore, the results show the intermediate range order containing Na-O, Ca-O, O-P-O and O-Si-O correlations are unaffected by the addition of small quantities of TiO2 into these systems.

Bioactive sol-gel glasses at the atomic scale:the complementary use of advanced probe and computer modeling methods

Sol-gel-synthesized bioactive glasses may be formed via a hydrolysis condensation reaction, silica being introduced in the form of tetraethyl orthosilicate (TEOS), and calcium is typically added in the form of calcium nitrate. The synthesis reaction proceeds in an aqueous environment; the resultant gel is dried, before stabilization by heat treatment. These materials, being amorphous, are complex at the level of their atomic-scale structure, but their bulk properties may only be properly understood on the basis of that structural insight. Thus, a full understanding of their structure-property relationship may only be achieved through the application of a coherent suite of leading-edge experimental probes, coupled with the cogent use of advanced computer simulation methods. Using as an exemplar a calcia-silica sol-gel glass of the kind developed by Larry Hench, in the memory of whom this paper is dedicated, we illustrate the successful use of high-energy X-ray and neutron scattering (diffraction) methods, magic-angle spinning solid-state NMR, and molecular dynamics simulation as components to a powerful methodology for the study of amorphous materials.

Crueldad, simulacion, absurdo y amenaza: Barbarie del drama moderno y tradicion hermetica en los esperpentos de Ramon del Valle-Inclan

The purpose of this dissertation is to demonstrate that the esperpentos by the Spanish playwright Ramón del Valle-Inclán (1866–1936), represent a culminating moment of theatrical precepts of modern European drama, while perpetuating the ancient esoteric traditions of the Iberian Peninsula. Focusing on four plays—Los cuernos de Don Friolera (1920), Luces de Bohemia (1921), Las galas del difunto (1926) y La hija del Capitán (1927)—the research elucidates how this interpretation furthers understanding of the process that embraces the anti-realistic clamours during the initial decades of the XX century, up to the subsequent climax of the aesthetics of Cruelty, Absurdity, Simulation, and Menace. ^ In search for an ideal scenic language capable of reflecting the grotesque character and mystical essence of the esperpentos, this project examines the most significant works of philosophers from the hermetic tradition such as Plato, Pithagoras, Aquinas, and Flamel. Other important authors are Éliphas Lévy and H. P. Blavatsky, two personalities of great preponderance in the spiritual effervescence and occultist apotheosis at the turn of the 20th century. Finally, the mystical ideas of Spanish philosopher Roso de Luna and the psychological works on alchemy and magic by Jung find their conceptual correspondence in Valle-Inclán's aesthetic manifesto, La lámpara maravillosa. ^ The ultimate objective of this dissertation is to provide a proposal for a mise en scène of the esperpentos, aesthetically based on the simultaneous scenarios of the New Stagecraft and conceptually inspired by the mystical principles of the hermetic tradition. The comparative approach of this study establishes a dialogue between modernity and the esoteric tradition that results in a new Koncept for their representation, providing a simultaneous scenario, far from realistic theatre, and more coherent to house the magical substance of the esperpentos. ^

Chemical characterization of dissolved organic nitrogen in an oligotrophic subtropical coastal ecosystem

Water samples were collected from rivers and estuarine environments within the Florida Coastal Everglades (FCE) ecosystem, USA, and ultrafiltered dissolved organic matter (UDOM; 1 kDa) was isolated for characterization of its source, bioavailability and diagenetic state. A combination of techniques, including 15N cross-polarization magic angle spinning nuclear magnetic resonance (15N CPMAS NMR) and X-ray photoelectron spectroscopy (XPS), were used to analyze the N components of UDOM. The concentrations and compositions of total hydrolysable amino acids (HAAs) were analyzed to estimate UDOM bioavailability and diagenetic state. Optical properties (UV–visible and fluorescence) and the stable isotope ratios of C and N were measured to assess the source and dynamics of UDOM. Spectroscopic analyses consistently showed that the major N species of UDOM are in amide form, but significant contributions of aromatic-N were also observed. XPS showed a very high pyridinic-N concentration in the FCE–UDOM (21.7 ± 2.7%) compared with those in other environments. The sources of this aromatic-N are unclear, but could include soot and charred materials from wild fires. Relatively high total HAA concentrations (4 ± 2% UDOC or 27 ± 4% UDON) are indicative of bioavailable components, and HAA compositions suggest FCE–UDOM has not undergone extensive diagenetic processing. These observations can be attributed to the low microbial activity and a continuous supply of fresh UDOM in this oligotrophic ecosystem. Marsh plants appear to be the dominant source of UDOM in freshwater regions of the FCE, whereas seagrasses and algae are the dominant sources of UDOM in Florida Bay. This study demonstrates the utility of a multi-technique and multi-proxy approach to advance our understanding of DON biogeochemistry.

Quantitative and Qualitative Aspects of Dissolved Organic Carbon Leached from Senescent Plants in an Oligotrophic Wetland

We conducted a series of experiments whereby dissolved organic matter (DOM) was leached from various wetland and estuarine plants, namely sawgrass (Cladium jamaicense), spikerush (Eleocharis cellulosa), red mangrove (Rhizophora mangle), cattail (Typha domingensis), periphyton (dry and wet mat), and a seagrass (turtle grass; Thalassia testudinum). All are abundant in the Florida Coastal Everglades (FCE) except for cattail, but this species has a potential to proliferate in this environment. Senescent plant samples were immersed into ultrapure water with and without addition of 0.1% NaN3 (w/ and w/o NaN3, respectively) for 36 days. We replaced the water every 3 days. The amount of dissolved organic carbon (DOC), sugars, and phenols in the leachates were analyzed. The contribution of plant leachates to the ultrafiltered high molecular weight fraction of DOM (>1 kDa; UDOM) in natural waters in the FCE was also investigated. UDOM in plant leachates was obtained by tangential flow ultrafiltration and its carbon and phenolic compound compositions were analyzed using solid state 13C cross-polarization magic angle spinning nuclear magnetic resonance (13C CPMAS NMR) spectroscopy and thermochemolysis in the presence of tetramethylammonium hydroxide (TMAH thermochemolysis), respectively. The maximum yield of DOC leached from plants over the 36-day incubations ranged from 13.0 to 55.2 g C kg−1 dry weight. This amount was lower in w/o NaN3 treatments (more DOC was consumed by microbes than produced) except for periphyton. During the first 2 weeks of the 5 week incubation period, 60–85% of the total amount of DOC was leached, and exponential decay models fit the leaching rates except for periphyton w/o NaN3. Leached DOC (w/ NaN3) contained different concentrations of sugars and phenols depending on the plant types (1.09–7.22 and 0.38–12.4 g C kg−1 dry weight, respectively), and those biomolecules comprised 8–34% and 4–28% of the total DOC, respectively. This result shows that polyphenols that readily leach from senescent plants can be an important source of chromophoric DOM (CDOM) in wetland environments. The O-alkyl C was found to be the major C form (55±9%) of UDOM in plant leachates as determined by 13C CPMAS NMR. The relative abundance of alkyl C and carbonyl C was consistently lower in plant-leached UDOM than that in natural water UDOM in the FCE, which suggests that these constituents increase in relative abundance during diagenetic processing. TMAH thermochemolysis analysis revealed that the phenolic composition was different among the UDOM leached from different plants, and was expected to serve as a source indicator of UDOM in natural water. Polyphenols are, however, very reactive and photosensitive in aquatic environments, and thus may loose their plant-specific molecular characteristics shortly. Our study suggests that variations in vegetative cover across a wetland landscape will affect the quantity and quality of DOM leached into the water, and such differences in DOM characteristics may affect other biogeochemical processes.

The Enchanter's Spell: J.R.R. Tolkien's Mythopoetic Response to Modernism

J.R.R. Tolkien was not only an author of fantasy but also a philologist who theorized about myth. Theorists have employed various methods of analyzing myth, and this thesis integrates several analyses, including Tolkien’s. I address the roles of doctrine, ritual, cross-cultural patterns, mythic expressions in literature, the literary effect of myth, evolution of language and consciousness, and individual invention over inheritance and diffusion. Beyond Tolkien’s English and Catholic background, I argue for eclectic influence on Tolkien, including resonance with Buddhism. Tolkien views mythopoeia, literary mythmaking, in terms of sub-creation, human invention in the image of God as creator. Key mythopoetic tools include eucatastrophe, the happy ending’s sudden turn to poignant joy, and enchantment, the realization of imagined wonder, which is epitomized by the character of Tom Bombadil and contrasted with modernist techno-magic seeking to alter and dominate the world. I conclude by interpreting Tolkien’s mythmaking as a form of mysticism.

The Saints of Banias

THE SAINTS OF BANIAS is a novel set in a fictional slavetown during the Reconstruction Era. The work seeks to blend myth, magic, and history to create a world that is both believable and otherworldly. The novel follows Beah, an ex-slave girl travelling to the town of Banias in hopes of finding her mother; Prophet Moon, an itinerant vision-seer who offers to help Beah with her goal; and the founder of the town, Claude Banias, who struggles to protect Banias from bloodthirsty radicals. As the characters’ lives intertwine, they face more challenges and secrets. THE SAINTS OF BANIAS is loosely based on the biblical story of David and Bathsheba, with Claude acting as David, Beah as Bathsheba, and Prophet Moon as a hybrid of Nathan and Uriah. The novel primarily explores destructive love, the value of hope, and the price of preserving a culture.

Fatores capazes de influenciar o encantamento do cliente de turismo de lazer a partir da experiência em parques temáticos

Com o aumento da demanda por empreendimentos no ramo do entretenimento, observa-se o aumento da competitividade no setor de turismo, gerando a necessidade de diferenciação em meio aos demais, visando à fidelização de clientes. Nesse sentido, os profissionais de Marketing passaram a acreditar que, para oferecer algo que fosse capaz de fidelizar os clientes, as empresas deveriam oferecer um produto ou serviço que fosse além das necessidades dos consumidores, surgindo então o termo “encantamento do cliente”. Nesse contexto, o presente estudo tem o objetivo de analisar fatores considerados como capazes de influenciar o encantamento do cliente (Customer Delight) de turismo de lazer, a partir de experiências em parques temáticos, por meio de uma abordagem baseada na Teoria da Avaliação Cognitiva. Para tanto, a investigação apresentou caráter exploratório-descritivo com enfoque analítico-quantitativo. A pesquisa foi do tipo Levantamento (Survey). Os dados foram coletados a partir de um público composto por 176 adolescentes que viajaram em excursão para o Walt Disney World, localizado em Orlando, Flórida, em junho de 2014, por uma agência de viagem localizada na cidade de Natal/ RN. O parque escolhido para objeto da pesquisa foi o Magic Kingdom. Para análise das respostas, foram utilizadas as análises descritiva, fatorial exploratória e confirmatória, assim como a modelagem de equações estruturais. Os resultados apontam para um grande nível de encantamento do entrevistado com o objeto, seja relacionado com a importância do objetivo da viagem, assim como à dimensão Inesperado da viagem. Pelas relações causais encontradas, observou-se que as dimensões “Coerência do Objetivo” e “Importância do Objetivo”, ambas consideradas como antecedentes do Encantamento, têm impactos significativos na formação do Encantamento do Cliente. As constatações permitiram ampliar a compreensão sobre o comportamento do consumidor no turismo de lazer.

ESPÍRITOS DO UNIVERSO RESPONSÁVEIS PELO DESTINO: ESTUDO EXEGÉTICO EM COLOSSENSES 2.8-3.4

Esta dissertação de mestrado analisará a expressão grega ta. stoicei/a tou/ ko,smou, “os elementos do mundo”, que ocorre na carta de Colossenses nos versículos 8 e 20 do segundo capítulo. Será feito um estudo exegético na perícope bíblica 2.8-3.4 da referida carta, bem como uma análise histórica especificamente do termo stoicei/a. O estudo desta expressão é importante para poder se compreender a filosofia colossense mencionada em Cl 2.8. A igreja cristã na cidade de Colossos estava inserida em um contexto social religioso sincrético. Esse sincretismo é percebido claramente em textos de magia como os Papiros Mágicos Gregos, muito comuns na região da Ásia Menor, a mesma onde a igreja colossense estava situada. O sincretismo religioso, envolvendo crenças judaicas e pagãs, reflete as bases dessa filosofia. O autor da carta aos Colossenses refuta a crença nos “elementos do mundo”, bem como a subserviência aos mesmos. Dentre outras crenças, acreditava-se que esses “elementos” poderiam influenciar os acontecimentos sobre a terra e o destino das pessoas. Questões que envolvem práticas acéticas, adoração a anjos e observância de calendário litúrgico, dão os contornos dessa filosofia. O autor da carta enfatiza o senhorio de Cristo, bem como as obras dele em favor dos cristãos colossenses, que proporcionavam a eles, segurança quanto a terem um bom destino. E, além disso, é assegurada uma liberdade aos cristãos colossenses que não podia lhes ser cerceada por quaisquer outras crenças religiosas. Então, as obras de Cristo, bem como o seu senhorio, são os principais argumentos utilizados pelo autor da carta, a fim de afirmar aos cristãos em Colossos que eles não precisam mais temer o destino e nem se submeter aos “elementos do mundo”.

Doug Henning on Barbara Walter's NBC TV-Show "Not for Women Only"

General note: Title and date provided by Bettye Lane.

Using knowledge management to give context to analytics and big data and reduce strategic risk

At the moment, the phrases “big data” and “analytics” are often being used as if they were magic incantations that will solve all an organization’s problems at a stroke. The reality is that data on its own, even with the application of analytics, will not solve any problems. The resources that analytics and big data can consume represent a significant strategic risk if applied ineffectively. Any analysis of data needs to be guided, and to lead to action. So while analytics may lead to knowledge and intelligence (in the military sense of that term), it also needs the input of knowledge and intelligence (in the human sense of that term). And somebody then has to do something new or different as a result of the new insights, or it won’t have been done to any purpose. Using an analytics example concerning accounts payable in the public sector in Canada, this paper reviews thinking from the domains of analytics, risk management and knowledge management, to show some of the pitfalls, and to present a holistic picture of how knowledge management might help tackle the challenges of big data and analytics.