AbstractThe number and distances of metal-oxygen and metal-metal interactions were determined for various concentrations of aqueous metal nitrate solutions by modified x-ray diffraction techniques. The number of M-O interactions ranges from four to five in the 0.8 M and 1.2 M AgNO3 solutions and from six to nine in the 0.8 M, 1.2 M, and 1.6 M Pb(N03)2 solutions. The 1.6 M Ce(N03)3 solution has eight to nine Ce-O interactions, while one Hg-Hg interaction is found for the H92 (N03)2 solutions. For the silver and lead nitrate solutions, the number of M-0 interactions decreases with an increase in concentration. The cations also effect the number of interactions. Based on the nature of their RDF's, the lead and cerium ions are classified as positively hydrated and the silver ion is negatively hydrated.Ball State UniversityMuncie, IN 47306

Cold worked magnesium powder was investigated to determine the effect of annealing on the residual strains and heat of combustion. The residual rms strains, domain size, and fault probabilities were determined by Fourier analysis of X-ray diffraction data. The heat of combustion was determined by using an adiabatic calorimeter. The results of this study revealed a definite reduction in residual rms strain (0. 0008 to 0. 0003), fault probability (0.0014 to 0. 0001%), and heat of combustion (5662 to 5445 cal/gm) with annealing. The domain size showed an increase from 1400 to 7000 A.Ball State UniversityMuncie, IN 47306

Nitrochemicals are widely used as explosives, biocides and drugs. In addition, 3-nitro-tyrosine and other nitrated protein residues are important markers for many cardiovascular, neurodegenerative, and malignant conditions. Because of the wide presence of the nitrocompounds as toxins, potential nitrogen/carbon sources, and metabolic intermediates, different organisms have evolved to produce enzymes that can biodegrade nitrocompounds. The structural studies of the enzymes, which catalyze the removal of nitro group from nitrochemicals, are of considerable interest for both applied and fundamental reasons. The insights into the reaction mechanism of these enzymes can be used for designing efficient biocatalysts for bioremediation and for developing antibiotics for disease resistant microbes. Nitroalkane oxidase (NAO) produced by

A high-temperature x-ray diffraction furnace for use with the General Electric Model XRD-3 x-ray diffraction unit has been developed. The furnace, which was designed and constructed by the author, has an angular range of 0-165° 20. A constant temperature or continuously increasing temperature may be programmed through the temperature range of 20°C to 1000°C. Data on the high-temperature modifications of illite obtained with the high-temperature x-ray diffraction furnace indicate a contraction of the (110) spacing at 300°C and expansions at 725°C and 880°C which were not identifiable using the quench method. The existence of interlayer water in the illite structure to temperatures over 800°C is indicated, based upon the continuous decrease of the (002) basal periodicity with increasing temperature. A skeleton illite structure or a high-temperature illite phase with a d-spacing of 9.87A survives the third endothermic reaction observed by differential thermal analysis and forms a phase which is stable at 900°C. / text

The study of magnetic properties and structures of Zn and Cd substituted mixed ferrites has been carried out using Mossbauer spectroscopy and X-ray diffraction on powdered samples at about 300 K. Two series of mixed ferrites, (Cd, Zn)xCol-xFe2-xAlxO4 and (Cd, Zn)xCo0.9Fe1.7-xTi0.4O 4 (where 0≤ x≤1.0) were synthesized. In the former series the effect of simultaneous site dilution by Zn or Cd and Ai atoms on tetrahedral (A) and octahedral (B) sites is investigated and in the latter the effect of single site dilution by Zn or Cd is also studied. The Mossbauer spectra show that the compounds transform with increase in x from ordered to disordered magnetic states. Systematic decrease in the hyperfine fields indicating weakening of the magnetic coupling with an increase in x is observed. We report the presence of a cross over effect with respect to the hyperfine fields on A and B sites at low concentration of diamagnetic ions in the simultaneously diluted series. Both series of compounds show no significant changes in isomer shifts with x. Differences in the evolution of Fe atoms on A and B sites between Zn and Cd based compounds are observed. The results of our analysis show that Zn and Cd ions occupy both tetrahedral and octahedral sites. The spinel structure of the compounds studied in this work is confirmed by X-ray diffraction (XRD). The lattice parameters derived from XRD show systematic change with x consistent with Vergard's law. In Cd based samples an increase of the lattice parameter with x is explained on the basis of the size difference of the cations involved. However, an anomalous behavior of the lattice parameter is observed in Zn based samples. The average grain sizes of the samples were determined from the line width of the (311) XRD intensity lines using the Scherrer formula. These vary between 50 nm and 70 nm for all the samples except for Zn and Al substituted samples which show a systematic anomalous reduction for x ≥ 0.4 in grain size. The porosity, x-ray and bulk densities of the samples are also presented. / Thesis (M.Sc.)-University of Natal, Durban, 2002.

Made available in DSpace on 2014-06-11T19:23:29Z (GMT). No. of bitstreams: 0 Previous issue date: 2006-03-08Bitstream added on 2014-06-13T19:50:17Z : No. of bitstreams: 1 antonio_sg_me_bauru.pdf: 3160547 bytes, checksum: 9d2a5b8b4f185ebe13b3880b18a9443c (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Os espinélios têm como sua fórmula unitária geral (A1-iBi)[AiB2-i]O4 (0 =i =1), em que os parênteses são os sítios tetraédricos, os colchetes representam os sítios octaédricos e i é o grau de inversão que representa a distribuição dos cátions na rede cristalográfica. Para i igual a 1 o espinélio é chamado de inverso e tem os cátions distribuídos nos sítios tetraédrico e octaédrico de acordo com a fórmula (B)[AB]O4 e igual a 0 o espinélio é chamado de normal com a fórmula (A)[B2]O4, e para 0 < i < 1 os cátions A e B estão distribuídos entre os dois sítios randomicamente e são chamados de parcialmente invertidos ou mistos. As propriedades desses materiais dependem dos tipos de cátions e do grau de inversão. Neste trabalho utilizamos o processo de combustão, o qual tem sido apresentado como um método eficiente para a produção de partículas nanométricas, para a obtenção do sistema Ni1-d Co d Fe2O4 (d = 0; o; u; ; 1). Os materiais resultantes foram caracterizados usando o método de Rietveld para determinar a distribuição dos cátions nos sítios tetraédrico e octaédrico. Análises de espectroscopia Mössbauer foram utilizadas para corroborar os resultados obtidos pelo Método de Rietveld. A principal variável para promover a síntese de óxidos por reação de combustão e otimizá-la é a razão combustível/oxidante, que foram variadas de 1X (estequiométrica), 1,5X e 2X (dobro) e estabelecida o dobro para o desenvolvimento do trabalho. Observamos também, indicações que a razão combustível/oxidante deve variar para cada estequiometria (d ), e que o Co e Ni ocupam apenas os sítios octaédricos. O método de Rietveld e a luz síncrotron permitiram a determinação da estequiometria em cada composição, e os cálculos de microdeformação mostram a existência de flutuação composicional. / The spinels have the general unity formulae (A1-iBi)[AiB2-i]O4 (0 =i =1), where () represents the tetrahedral sites, [ ] represents the octahedral sites and i is the degree of inversion that represents the distribution of cations in the crystal lattice. For i equal to 1 it is the inverted spinel (B)[AB]O4 and i = 0 it is the normal spinel (A)[B2]O4, and for 0 < i < 1 the cations A and B are randomly distributed between the two sites. The properties of these materials depend on the types of cations and the degree of inversion. In this work we use the combustion process, which has been presented as an efficient method for the production of nanometrics particles, for the attainment of the system Ni1-d Co d Fe2O4 (d = 0; o; u; ; 1). The resulting materials were characterized using the Rietveld Method (RM) to determine the cations distribution in the tetrahedral and octahedral sites. Analyses of Mössbauer spectroscopy carried through by E. Miola and H. Rechenberg had been also used to corroborate the results obtained using Rietveld Method. The main variable to promote the oxide synthesis through combustion reaction is the fuel/oxidant ratio that, in this work, varied from stoichiometric (ratio = 1) up to two times (ratio = 2). We observe that the ratio varies from one stoichiometry to another(d ), and that Co and Ni occupy only the octahedral sites. We observe, also, that the procedure is not yet adjusted to get itself homogeneous material, since the materials present particles with very varied sizes and degree of agglomeration. The Rietveld method and the synchrotron light allowed the determination of the stoichiometry for each composition.

Novel and known metal organic frameworks with copper(II), sodium and 1,2,4,5-benzenetetracarboxylate were prepared by ambient precipitation, solvothermal and gel-synthesis methods, and characterized by single-crystal X-ray diffraction, X-ray powder diffraction, infrared spectroscopy, differential scanning calorimetry, and thermogravimetry with FTIR evolved-gas analysis. Some of these complexes were investigated for guest inclusion properties with water (the original guest species), methanol, ethanol and pyridine. The gel-synthesis products were the most interesting. The novel threedimensional metal-organic framework complex Cu₂ Na(OH)L·7H₂O (where L=1,2,4,5-benzenetetracarboxylate) -formed by gel-synthesis- is a covalent three-dimensional metal organic framework polymer with open channels containing both guest water molecules and water molecules coordinated to sodium. The structure collapsed on dehydration, but was essentially restored to the original structure on rehydration in moist air. On exposure of the dehydrated material to methanol and ethanol vapour, significant uptake of these solvents was observed, and the resolvated structures closely resembled that of the parent material. On heating in dry nitrogen, small amounts of methanol and ethanol remained until about 280 °C, when loss of the remaining guest triggered decomposition of the framework. The related complex, Cu₂¼(OH)½ L·7½H₂O (or possibly Cu₂⅓ (OH)⅔L·8H₂O) -formed by gel-synthesis- had a different physical appearance to Cu₂Na(OH)L·7H₂O above, but had nearly identical X-ray diffraction pattern, mid-infrared spectrum and thermal behaviour. The novel complex Cu₄Na₄L₃·14H₂O -formed by gel-synthesis- is a covalent three-dimensional metal-organic framework with small channels containing both guest water molecules and water coordinated to sodium and copper. Upon dehydration the structure collapsed, but on rehydration in moist air the original structure was partly restored. The dehydrated material did not absorb methanol. Known two-dimensional polymeric complexes [Cu₂L·6H₂O]·4H₂O and [Cu₂L·4H₂O]·2H₂O were also obtained by gel-synthesis, and were characterized and investigated for guest inclusion properties. The structures of these complexes collapsed on dehydration, and were only partly restored on rehydration in saturated water vapour. The dehydrated materials did not absorb methanol. The two-dimensional polymeric mixed-ligand complex Cu₂(pyridine)₄·6H₂O -formed very slowly by gel-synthesis- was characterized by TG-FTIR, and was shown to undergo a complicated decomposition involving the loss of water and pyridine, carbon dioxide and carbon monoxide in various stages. Solvothermal synthesis did not yield materials suitable for single-crystal X-ray diffraction studies or inclusion studies, producing only an anhydrous or hemihydrate complex with the formula Cu₂L·0.65H2O. Ambient precipitation syntheses did not yield materials suitable for singlecrystal diffraction studies, forming products approximately equivalent to the complexes [Cu₂L·6H₂O]·4H₂O and Cu₂¼(OH)½L·7 ½H₂O above. During the course of the above study it was discovered that, on changing the DSC purge from nitrogen to argon, the normally exothermic carboxylate decompositions appeared to become endothermic. The effects of the supposedly inert atmospheres of argon and nitrogen on the decomposition-mechanism of copper(II) oxalate -a well-studied copper carboxylate- were therefore studied by DSC, TG, TG-FTIR and XRPD. DSC experiments were performed in nitrogen and argon at different flow-rates, in various mixtures of nitrogen and argon, and at various heating rates. Regardless of the proportions of nitrogen and argon, the DSC residues consisted mainly of copper metal, a small amount of copper(I) oxide (cuprite) and, in some circumstances, traces of copper(II) oxide (tenorite). Also, regardless of whether TG-FTIR experiments were performed under argon or nitrogen, the gaseous decomposition products consisted mainly of carbon dioxide, with traces of carbon monoxide being detected over part of the decomposition period. Various explanations for the thermal behaviour are discussed, and it is possible that small amounts of O2 or monatomic oxygen were given off during the decomposition under argon. The design and implementation of a low-cost prototype X-ray proportional counter detector system, consisting of a hybrid analog-digital computer built using commonly available electronic components, is presented. This system was designed to replace ageing discrete-transistor designs still in use in earlier X-ray diffractometers. The prototype performs the functions of pulse-shaping, pulseheight discrimination, counting and scaling, and provides both digital and scaled analog outputs.

Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, 2016. / For decades, clays have been applicable as commercial catalysts mostly for cracking in petroleum industries. Clays are also used for development of useful catalysts for various other industrial applications. Hence, this work was aimed to synthesize clay-based catalysts from clay minerals (Kaolin, bentonite and talc) that will be active for the conversion of bioethanol to fuel hydrocarbons. Catalyst characterisation techniques employed on the samples produced in this work include the Energy Dispersive Spectroscopy (EDS), Scanning Electron Microscopy (SEM) and the X-Ray Diffraction pattern (XRD). All catalytic reactions were carried out in a fixed bed reactor (at fixed reaction condition of 6 hour and 350 ⁰C) and corresponding reaction products (liquid and gaseous) were analysed through a Gas Chromatograph- Flame Ionisation Detector (GC-FID) and Gas Chromatograph Mass Spectrometer (GC/MS). The activity of clays in their non-modified state was studied and they were all found active for bioethanol conversion to hydrocarbons. Bentonite was the most active catalyst with bioethanol of 84.95 % and this through subsequent beneficiation and acid-modification approach, led to increased bioethanol conversion of 87.3 %. EDS/SEM characterisation of the catalyst in line to the above modification and increased catalyst activity, revealed that the structural morphology of bentonite and the concentration of basic structural elements (in terms of Si/Al ratio) was increased.

nÃo hà / As ligas de ZircÃnio tÃm maior aplicabilidade na indÃstria nuclear, sÃo utilizadas na fabricaÃÃo de tubos que compÃem uma estrutura metÃlica, denominada de elemento combustÃvel, que forma o nÃcleo dos reatores nucleares. Os referidos tubos sÃo utilizados no revestimento de pastilhas cerÃmicas de diÃxido de urÃnio enriquecido e podem sofrer precipitaÃÃo de hidretos em condiÃÃes operacionais. Esse efeito à deletÃrio Ãs citadas ligas, tendo em vista a reduÃÃo da ductibilidade a depender da morfologia dos hidretos formados. A morfologia dos hidretos e a sua respectiva susceptibilidade à formaÃÃo foram avaliados em amostras de ligas de comerciais de zircÃnio Zircaloyâ4Â, Zirlo e M5â. As amostras foram hidrogenadas em autoclave, nas condiÃÃes de pressÃo e temperatura de um reator nuclear. Posteriormente foram feitas anÃlises microestruturais das ligas e verificaÃÃo da morfologia hidretos metÃlicos formados, por microscopia Ãptica e de varredura eletrÃnica, bem como foi utilizada a tÃcnica de difraÃÃo de Raios X, a fim de identificar a presenÃa de hidretos. Hidretos circunferenciais, foram formados, pela referida condiÃÃo de hidrogenaÃÃo, somente na liga M5â e hidretos radiais, que sÃo indesejÃveis por serem pontos nucleadores de trincas, formaram-se nas liga Zirlo e M5â para condiÃÃes mais severas de hidrogenaÃÃo. Para ambos os tipos de hidrogenaÃÃo nÃo se verificou, nas micrografias, a presenÃa de hidretos no Zircaloyâ4Â, no entanto, picos de hidretos foram evidenciados por difraÃÃo de raios X, para a condiÃÃo de hidrogenaÃÃo mais severa. / Zirconium alloys have greater applicability in the nuclear industry are used in the manufacture of tubes that make up a metal structure , called the fuel element , and form the core of nuclear reactors . Such tubes are used in the coating of ceramic pellets of enriched uranium dioxide and precipitation of hydrides can undergo in operating conditions . This effect is detrimental to the aforementioned alloys , with a view to reducing the ductility depending on the morphology of hydrides . The morphology of hydrides and their respective susceptibility to formation were evaluated in samples of commercial zirconium alloys Zircaloy - 4 Â, ZIRLO  and M5 â . The samples were hydrogenated in an autoclave under the conditions of pressure and temperature of a nuclear reactor . Later microstructural analysis and verification of alloy metal hydrides formed morphology , were made by optical microscopy and scanning electron as well as the technique of X-ray diffraction was used to identify the presence of hydrides. Circumferential hydrides were formed, by hydrogenation condition that only the radial hydrides and M5 â alloy, which are undesirable to be more deleterious to mechanical properties, the alloy is formed Zirloâ M5Â, and for more severe hydrogenation conditions. For both types of hydrogenation was not observed in the presence of hydrides Zircaloy-4 Â.

CoordenaÃÃo de AperfeÃoamento de Pessoal de NÃvel Superior / The present work describes the use of a grinding dust almost granite raw feedstock to the process of ceramic injection molding at low pressures. The main objective was to demonstrate the technical feasibility of using a low-cost raw material for parts for applications where these were not subjected to large mechanical stresses. Initially it selected a powder from the extraction of a granite commercial value called White Savannah. The material was characterized by chemical and petrographic analysis (for microprobe), and microscopy Scanning electron diffraction and X-ray. After several unsuccessful attempts to use the powder in the raw state, it was subjected to a simple procedure for comminution by grinding and subsequent selection by sieving. The obtained fines were mixed with binder to carnauba wax base, developed in previous research. Rheological studies helped determine the optimum amount of binder and powder in the mixture to be injected. Thermogravimetric analysis was used to establish a ramp for removal of the binder by thermal degradation after injection. The binder removal step was performed without introducing macrodefeitos. The parts were sintered in air in a muffle furnace at temperatures between 1200 0 C to 1280 0 C. Next, the pieces were evaluated in terms of density, porosity, shrinkage and hardness. The best results in terms of appearance, shape maintenance and combination of physical and mechanical properties were obtained with the parts sintered at 1250 0 C. The values &#8203;&#8203;obtained for these properties were deemed reasonable when compared to results obtained with previously manufactured parts using other granite waste. / O presente trabalho descreve a utilizac&#807;a&#771;o de um po&#769; residual de granito em estado quase bruto como mate&#769;ria-prima para o processo de moldagem cera&#770;mica por injec&#807;a&#771;o a baixas presso&#771;es. O objetivo principal era demonstrar a viabilidade te&#769;cnica de se utilizar uma mate&#769;ria-prima de baixo custo para obter pec&#807;as para aplicac&#807;o&#771;es em que essas na&#771;o fossem submetidas a grandes esforc&#807;os meca&#770;nicos. Inicialmente foi selecionado um po&#769; proveniente da extrac&#807;a&#771;o de um granito de valor comercial denominado Branco Savana. O material foi caracterizado por ana&#769;lises petrogra&#769;fica e qu&#305;&#769;mica (por microssonda), ale&#769;m de microscopia eletro&#770;nica de varredura e difrac&#807;a&#771;o de raios-X. Apo&#769;s algumas tentativas infrut&#305;&#769;feras de se utilizar o po&#769; no estado bruto, o mesmo foi submetido a um procedimento simples de cominuic&#807;a&#771;o por moagem e posterior selec&#807;a&#771;o por peneiramento. Os finos obtidos foram misturados ao ligante a&#768; base de cera de carnau&#769;ba, desenvolvido em pesquisas anteriores. Estudos reolo&#769;gicos ajudaram a determinar a quantidade o&#769;tima de ligante e po&#769; na mistura a ser injetada. A ana&#769;lise termogravime&#769;trica foi utilizada para se estabelecer uma rampa para a retirada do ligante por degradac&#807;a&#771;o te&#769;rmica, apo&#769;s a injec&#807;a&#771;o. A etapa de retirada do ligante foi realizada sem introduc&#807;a&#771;o de macrodefeitos. As pec&#807;as foram sinterizadas ao ar, em forno mufla, a temperaturas entre 1200 0 C e 1280 0 C. Em seguida as pec&#807;as foram caracterizadas quanto a&#768; densidade, porosidade, contrac&#807;a&#771;o, e microdureza. Os melhores resultados em termos de apare&#770;ncia, manutenc&#807;a&#771;o do formato e combinac&#807;a&#771;o de propriedades f&#305;&#769;sicas e meca&#770;nicas foram obtidos com as pec&#807;as sinterizadas a 1250 0 C. Os valores obtidos para essas propriedades foram considerados razoa&#769;veis, quando comparados aos resultados atingidos com pec&#807;as fabricadas anteriormente, utilizando outros res&#305;&#769;duos gran&#305;&#769;ticos.