Thesis (Ph. D.)--University of Queensland, 2001. / Includes bibliographical references.

Three solution models: ideal, regular, and quasi- regular, were used to predict the melting point of eutectic mixtures containing Polyethylene Glycol (PEG) 400 and PEG 4000 with nine poorly water- soluble drugs: 1-naphthoic acid, estrone, griseofulvin, indomethacin, phenobarbital, paracetamol, salicylic acid, salicylamide and naproxen. PEG 400 was physically mixed with drug at different weight percentages to determine the melting points of the pure drugs and the melting point depression using Differential Scanning Calorimetry (DSC). The PEG 4000 eutectic mixtures were processed by the solvent evaporation method. In both the PEG 400 and PEG 4000 study, the quasi-regular solution model accounted for the most realistic conditions of entropy and enthalpy of the mixtures compared to ideal and regular solution models.

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As três famílias de ligas de maior importância comercial para a indústria de fundição apresentam a formação de eutéticos do tipo facetado/não-facetado durante a solidificação: os ferros fundidos com grafita (eutético austenita/grafita), os ferros fundidos brancos (eutético austenita/carboneto) e as ligas Al-Si (eutético alfa/silício). No caso dos ferros fundidos brancos, a morfologia dos carbonetos eutéticos exerce influência decisiva sobre o comportamento mecânico e a resistência à degradação (em função de solicitações como abrasão ou ciclos térmicos e/ou mecânicos) das ligas resistentes a desgaste pertencentes ao sistema Fe-C-X (em que X representa um ou mais dos elementos Cr, V, Mo, W e, mais raramente, Nb). Investigou-se o efeito do potencial nucleante do banho metálico sobre o eutético de ligas do sistema Fe-C-V, e conseqüentemente sobre a morfologia do carboneto. As alterações de morfologia do eutético austentita/carboneto VC em função da adição de alumínio ou titânio foram avaliadas por meio de microscopias óptica e eletrônica de varredura. Observou-se que a adição de alumínio ou titânio, em ligas com teores residuais de oxigênio ou nitrogênio, promoveu alteração do eutético VC de irregular para fibroso (no caso da adição de alumínio) e para divorciado (no caso da adição de titânio). Conclui-se que a presença de partículas nucleantes induziu a nucleação seletiva da fase facetada (carboneto VC) a temperaturas mais elevadas, diminuindo o grau de cooperação durante o crescimento do eutético. / The three most commercially important families of alloys for the foundry industry show the formation of faceted/non-faceted eutectics type during solidification: cast irons with graphite (austenite/graphite eutectic), white cast irons (austenite/carbide eutectic) and Al-Si alloys (alfa/silicon eutectic). In the case of white cast irons, the eutectic carbide morphology has decisive influence on mechanical behavior and on degradation resistance (due to solicitation such as abrasion or thermal and/or mechanical cycling) of wearing resistant alloys of the Fe-C-X system (where X stands for one or more of the following elements: Cr, V, Mo, W and, seldom, Nb). The metallic bath nucleant potential on the eutectic of the Fe-C-V system and, thus, on the carbide morphology, were investigated. It was evaluated the nucleant potential for aluminum and titanium addition to the bath. The morphologies changes for the austenite/carbide eutectic were evaluated by optical and scanning electronic microscopy. It was observed that aluminum or titanium addition in alloys with residual content of oxygen or nitrogen promoted VC eutectic morphology change from irregular to fibrous (when aluminum is added) and to divorced (when titanium is added). It is concluded that the presence of nucleant agents in the metallic bath induced the preferred nucleation of the faceted phase at higher temperatures, decreasing the cooperation during the eutectic growth.

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Eutectic Fe-C, Ni-C and Fe-C-Si alloys have been solidified directionally in an electron-beam floating zone apparatus under carefully controlled conditions and the resulting morphologies in these alloy systems have been studied as a function of rate. In addition, the transition from the stable iron-graphite (grey iron) to the metastable iron-iron carbide (white iron) mode has been observed and has been related to the iron-carbon/iron-iron carbide double phase diagram by means of undercooling measurements. Interlamellar spacing measurements carried out on both the graphitic and carbidic modes using material of the same composition and purity under identical experimental conditions showed a λaR-1/2 and a λaR-1/3 relationship in the iron-graphite and iron-iron carbide eutectic systems, respectively. / Thesis / Doctor of Philosophy (PhD)

This doctoral thesis is focused on applying visible light photocatalysis and deep eutectic solvents in organic transformations and combining the two to develop sustainable procedures. Chapter 1 deals with using visible-light photocatalysis to synthesize olefins via decarboxylative alkenylation from readily available carboxylic acids and vinyl sulfones. The developed protocol employs a metal-free, eco-friendly photocatalyst using a vitamin B2-derived species, achieving alkenes in a highly diastereoselective manner. Further transformations of the obtained compound were carried out while also analysing the reaction mechanism through an array of theoretical calculations and experimental procedures. Chapter 2 consists of the elaboration of a sustainable methodology for the aerobic photooxidation of xanthenes, thioxanthene and 9,10-dihydroacridines, employing a recyclable eutectic mixture as solvent and riboflavin tetraacetate as photocatalyst. This methodology's sustainability was further demonstrated by calculating a series of green metrics. Chapter 3 deals with synthesizing and characterizing novel chiral deep eutectic solvents and their application in asymmetric organocatalysis as combined solvent/organocatalyst. Thus, chiral ammonium salts were prepared and combined with other compounds, forming eutectic mixtures characterized by different procedures and later employed in the enantioselective addition of cyclohexanone to trans-β-nitrostyrene.

Glass forming ability (GFA) in the Pr-rich Pr-(Cu, Ni)-Al alloys at or near the eutectic points was systematically studied. It was found that the GFA in the pseudo-ternary alloys of Pr-(Cu, Ni)-Al is higher than that of the ternary alloys of Pr-Cu-Al. Two eutectic compositions in Pr-(Cu, Ni)-Al alloys were found by DSC, namely, Pr₆₈(Cu₀.₅Ni₀.₅)₂₅Al₇ and Pr₅₂(Cu₀.₅Ni₀.₅)₂₅Al₂₃ (at %). The later one shows better GFA than the first one. However, the best GFA was obtained at an off-eutectic composition of Pr₅₄(Cu₀.₅Ni₀.₅)₃₀Al₁₆, which can be formed in fully amorphous rod with diameter of 1.5 mm by copper mould casting. The deviation of the best GFA composition from the eutectic point [Pr₆₈(Cu₀.₅Ni₀.₅)₂₅Al₇] was explained in terms of the asymmetric coupled eutectic zone and the higher glass transition temperature Tg on the hypereutectic side. / Singapore-MIT Alliance (SMA)