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In this work an attempt is made to correlate polymer miscibility with diffusion and with molecular interactions. A system with lower critical solubility temperature has been selected, namely polystyrene (PS) and polyvinyl methyl ether (PVME). Most of the published work has been done on polymers in solutions or on solvent cast specimens and therefore on ternary systems. The role of solvent has not yet been fully evaluated and it was of interest to compare the results on solvent cast samples with those prepared by mechanical blending and by diffusion. Molecular interaction is dependent on functional groups present and for this reason experiments have been performed on PVME blends with PS of different levels of sulfonation (SPS). Selective deuteration (d-PS) was used to identify and assign some absorption peaks in the infrared spectra. DSC measurements have shown that only one Tg is present for all blends prepared by solvent casting. It was necessary to use an extreme quenching rate down to liquid nitrogen in order to preserve the high temperature (above 150°C) phase separated structure, represented by two Tg of homopolymers. The mechanically blended system, on the other hand, did not show a single T g of the blend, unless annealed for one day at 110°C. This confirms the results obtained by diffusion studies using light microscopy and neutron reflectivity, that the diffusion rates are extremely slow and therefore do not control the phase formation and separation processes. These experiments also indicate that the microstructures of solvent cast samples and samples prepared by mechanical blending are different. The Tg of mechanical blended polymers indicate, that the composition of diffusion swollen PS does not correspond to the phase diagram measured in solutions, confirming thus the above result. The FTIR studies at different temperatures have shown that changes in spectra of polymer blends, as reported in the literature can be explained by temperature changes in pure homopolymers. This indicates that molecular interactions, which are responsible for miscibility, are not detectable by infrared absorptions and are therefore of unspecified strength and location. The FTIR of SPSIPVME blends show that sulfonate groups on PS affect polymer miscibility through changes in configuration of molecules, rather than through direct interaction with the PVME, as suggested in the literature. An attempt has been made to study diffusion of SPS and polycarbonate (PC) system by neutron reflectivity. Preliminary results indicate that surface relaxation effects make the data interpretation difficult.

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The effect of stoichiometry on the pyrolytic decomposition, oxidation and ignition behaviour of synthetic violarite and pentlandite has been established. These minerals, of general formula (Fe,Ni)(subscript)3S(subscript)4 and (Fe,Ni)(subscript)9S(subscript)8 respectively, may vary considerably in Fe:Ni ratio. Pentlandite can also show some variation in metal:sulfur ratio. A series of samples, ranging in stoichiometry from Fe(subscript)0.96Ni(subscript)1.97S(subscript)4 to Fe(subscript)0.20Ni(subscript)2.72S(subscript)4 and Fe(subscript)5.80Ni(subscript)3.15S(subscript)8 to Fe(subscript)3.40Ni(subscript)5.55S(subscript)8, were synthesised and characterised using wet chemical analysis, electron probe micro-analysis (EPMA), scanning electron microscopy (SEM), X-ray diffraction (XRD), and Brunauer, Emmett and Teller (BET) surface area analysis.The thermal behaviour of these sulfides was examined using simultaneous Thermogravimetry-Differential Thermal Analysis (TG-DTA) at different heating rates and in different atmospheres. Partially reacted samples were collected at various temperatures and analysed using XRD, EPMA, SEM, optical microscopy (OM), and Fourier transform infrared (FTIR) spectroscopy. The endmembers of the violarite and pentlandite series were examined in detail to determine the effect of stoichiometry on the reaction mechanism. In this study the reaction mechanism refers to the sequence of reactions occurring during pyrolytic decomposition or oxidation of the sulfide minerals. Samples were sieved into four particle size fractions, 125-90, 90-63, 63-45 and 45-20 gm, to determine the effect of particle size on the reaction mechanism.When violarite was heated in an inert atmosphere at 10 degrees celsius min(subscript)-1, it initially decomposed to a monosulfide solid solution (mss), (Fe,Ni)(subscript)1-xS, and vaesite, (Ni,Fe)S(subscript)2, indicated by a ++ / sharp endothermic peak in the DTA trace. The decomposition temperature was found to be linearly dependent on the iron:nickel ratio, decreasing from 495 degrees celsius to 450 degrees celsius as the iron:nickel ratio decreased from 0.49 to 0.07. This was followed by a broader endothermic peak coinciding with a rapid mass loss, which was associated with the decomposition of vaesite to mss with the loss of sulfur. Between 615-805 degrees celsius the mss was converted to a high temperature form of heazlewoodite, (Fe,Ni)(subscript)3+/-S(subscript)2 melted incongruently at 835 degrees celsius and 805 degrees celsius for Fe(subscript)0.96Ni(subscript)1.97S(subscript)4 and Fe(subscript)0.20Ni(subscript)2.72S(subscript)4 respectively, with further loss of sulfur vapour forming a central sulfide liquid of general formula (Fe,Ni)(subscript)1+xS.Under similar experimental conditions, pentlandite pyrolytically decomposed forming mss and heazlewoodite with no associated loss of sulfur. The decomposition temperature decreased as the iron:nickel ratio deviated from the ideal value of 1:1. A maximum decomposition temperature of 610 degrees celsius was found at an iron:nickel ratio of 1.00, decreasing to 580 degrees celsius at a ratio of 1.84 and 0.61. Sulfur was evolved slowly at temperatures in excess of 760 degrees celsius as mss was converted to heazlewoodite, indicated by a gradual mass loss. The heazlewoodite then melted incongruently in excess of 840 degrees celsius indicated by a sharp endothermic peak, resulting in a further loss of sulfur.The oxidation of violarite and pentlandite was investigated at a heating rate of 10 degrees celsius min(subscript)-1 in an air atmosphere. The oxidation of violarite was initiated by decomposition to mss resulting in a rapid mass loss associated with the evolution of sulfur vapour, and an exothermic peak due to the gas phase oxidation of ++ / the sulfur. The iron sulfide component of the mss was then preferentially oxidised to iron(II) sulfate between 485-575 degrees celsius, upon which the sulfate decomposed and the remaining iron sulfide was preferentially oxidised to hematite. The mss core was then converted to (Fe,Ni)(subscript)3+/-xS(subscript)2 between 635-715 degrees celsius, resulting in the loss of further sulfur which was oxidised. The sulfide core, which consisted of predominantly Ni(subscript)3+/-xS(subscript)2 with a minor amount of iron still remaining in solid solution, incongruently melted at a constant temperature of 795 degrees celsius regardless of the initial stoichiometry of the violarite sample. This was followed by the rapid oxidation of the liquid sulfide resulting in a sharp exothermic peak in the DTA trace.For pentlandite, the TG-DTA curve exhibited an initial mass gain commencing at approximately 400 degrees celsius, which was attributed to the preferential oxidation of iron. Evidence from SEM indicated that iron migrated towards the oxygen interface, where it was oxidised to hematite. During this process the metal: sulfur ratio decreased and pentlandite was converted to mss. The iron sulfide component of the mss phase was then preferentially oxidised to hematite as indicated by a major exotherm, which occurred in the temperature range 575-665 degrees celsius, forming an oxide product layer around a nickel sulfide core. The oxidation of the remaining nickel sulfide followed the same reaction sequence to that of violarite.By increasing the heating rate to 40 degrees celsius min(subscript)-1, and carrying out the oxidation in pure oxygen, the tendency of the sulfides to ignite was established. Ignition was characterised by a highly exothermic reaction which coincided with a rapid mass loss over a short time period. Overheating of the samples above the programmed furnace ++ / temperature was also observed. Violarite exhibited ignition behaviour while pentlandite did not.Both sulfides were subjected to shock heating conditions (heating rate = 1500 - 5000 degrees celsius min(subscript)-1, oxygen atmosphere) using isothermal thermogravimetry (TG). This method produces heating rates analogous to those which are experienced in the reaction shaft of an industrial flash smelter. The effect of stoichiometry on ignition temperature and extent of oxidation for the entire series of synthetic violarites and pentlandites was determined. Partially ignited and ignited products were collected from isothermal TG experiments and were examined by OM, SEM and EPMA to establish the ignition mechanism.Both violarite and pentlandite ignited using the isothermal TG technique. A clear relationship was found between the stoichiometry of violarite and pentlandite and the ignition temperature, with an increase in the iron:nickel ratio causing a decrease in the ignition temperature. The ignition temperature also decreased as the size of the particles decreased.The extent of oxidation increased as the iron:nickel ratio increased, and also increased as the particle size decreased.

Yes / A comprehensive study of the thermal behavior of the 1:1 and 2:1 benzoic acid/isonicotinamide cocrystals is reported. The 1:1 material shows a simple unit cell expansion followed by melting upon heating. The 2:1 crystal exhibits more complex behavior. Its unit cell first expands upon heating, as a result of C–H···π interactions being lengthened. It then is converted into the 1:1 crystal, as demonstrated by significant changes in its X-ray diffraction pattern. The loss of 1 equiv of benzoic acid is confirmed by thermogravimetric analysis–mass spectrometry. Hot stage microscopy confirms that, as intuitively expected, the transformation begins at the crystal surface. The temperature at which conversion occurs is highly dependent on the sample mass and geometry, being reduced when the sample is under a gas flow or has a greater exposed surface area but increased when the heating rate is elevated.

Made available in DSpace on 2014-06-11T19:35:07Z (GMT). No. of bitstreams: 0 Previous issue date: 2006-07-31Bitstream added on 2014-06-13T20:06:30Z : No. of bitstreams: 1 rodrigues_ec_dr_araiq.pdf: 1115806 bytes, checksum: 386a1fe79443dfc59b7936e69cc0b5e7 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Foram sintetizados os 4-metoxibenzoatos de lantanídeos e ítrio trivalentes e no estado sólido. Esses compostos foram caracterizados e estudados utilizando-se as técnicas de análise elementar, complexometria, difratometria de raios x pelo método do pó, espectroscopia de absorção na região do infravermelho, termogravimetria-análise térmica diferencial simultânea (TG-DTA) e calorimetria exploratória diferencial (DSC). Os resultados permitiram obter informações sobre a estequiometria, desidratação, transformação polimórfica (transição de fase), modo de coordenação, comportamento térmico e decomposição térmica. / Solid 4-methoxybenzoates of trivalent lanthanides and yttrium have been synthesized. Elemental analysis, complexometry, X-ray powder diffractometry, infrared spectroscopy, simultaneous thermogravimetry and differential thermal analysis (TG-DTA), and differential scanning calorimetry (DSC) were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, polymorphic transformation (phase transition), coordination mode, thermal behaviour and thermal decomposition of the isolated compounds.