Im binären Mn-Ga-System wurde für Legierungen mit 55 at.% bis 65 at.% Mangan die Phasenbildung der L10-Phase mit Röntgenbeugung und Differenzialkalorimetrie untersucht. Nach der Herstellung der L10-Phase in allen Legierungen erfolgte eine Untersuchung der intrinsischen magnetischen Eigenschaften. Die Mn55Ga45-Legierung zeigte dabei die höchste Sättigungsmagnetisierung mit µ0Ms = 0,81 T. Für diese Legierung erfolgten deshalb Versuche zur Verbesserung der extrinsischen Eigenschaften. Dazu wurden Pulver gemahlen und die Möglichkeit der Ausrichtung im Magnetfeld untersucht. Dabei konnte ein Texturgrad von 0,45 für Pulver mit einer Partikelgröße kleiner 10 µm erreicht und die Koerzitivfeldstärke um das 7-fache gegenüber der Volumenprobe erhöht werden. Weiterhin konnten die Pulverproben durch Heißkompaktieren bei 400 °C erneut zu einer Volumenprobe gepresst werden. Die dabei erhaltene Probe besitzt eine Koerzitivfeldstärke von 0,16 T und eine leicht reduzierte Sättigungsmagnetisierung auf Grund einer Packungsdichte von 83 %. Im ternären Mn-Al-Ga-System wurden Proben der Sollzusammensetzung Mn55Al45-xGax mit 5,625 < x < 22,5 hergestellt. Für Legierungen mit x >= 11,86 erwies sich eine Wärmebehandlung bei 600°C für 24 Stunden als ausreichend die reine L10-Phase zu erzeugen. Bei den Legierungen mit einem geringeren Ga-Anteil war eine zweistufige Wärmebehandlung notwendig, um ausschließlich L10 zu erhalten. Nach der ersten Wärmebehandlung bei 1100 °C entstand ein Phasengemisch aus gamma2 und L10(epsilon). Letzteres wurde aus der epsilon-Hochtemperaturphase gebildet. Durch die anschließende Wärmebehandlung bei 500 °C für 24 Stunden konnte die verbleibende gamma2-Phase in L10(gamma2) umgewandelt werden. Untersuchungen der lokalen Legierungszusammensetzung ergaben einen geringeren Mn-Anteil der L10(gamma2)-Phase im Vergleich zu L10(epsilon). Die Unterschiede in den zwei L10-Phasen konnten weiterhin durch eine Reflexaufspaltung in den Röntgenbeugungsaufnahmen sowie der Existenz zweier Curie-Temperaturen bestätigt werden. Die gemessenen Sättigungsmagnetisierungen ergaben eine Superposition beider Phasen und einen maximalen Wert von µ0Ms = 0,85 T. Untersuchungen der thermischen Stabilität der L10-Phasen bei 700 °C zeigten, dass die L10(gamma2)-Phase thermisch stabil ist und sich die L10(epsilon)-Phase langsam in beta-Mn und gamma2 zersetzt. Bei der Zersetzung war im Vergleich zum binären Mn-Al-System eine starke Steigerung der thermischen Stabilität durch die Substitution geringer Mengen Galliums zu erkennen. Über die zersetzungsbedingte Reduktion der Magnetisierung konnten Abschätzungen der Zersetzungskinetik getroffen werden.

<p> The purpose of this work was to develop a growth pathway for synthesis of high-quality ferromagnetic Ni-Mn-Ga shape memory thin films and to understand their functional properties. </p> <p>Two groups of Ni-Mn-Ga films were prepared using the pulsed laser deposition technique. One group was grown on (100) YSZ ((Zr,Y)O2 with ZrO2:Y2O2=92:8) and was used to study the thermal, magnetic, and magnetocaloric properties. The other group was deposited on (100) MgO. These films were fabricated into free-standing micro-bridges.</p> <p>These Ni-Mn-Ga films were synthesized in a previously unexplored high temperature deposition regime. The temperatures employed encouraged the development of the desired micrometer-size highly twinned martensite grain structure while the general problem of preferential evaporation of the volatile elements at elevated temperatures was solved by using a manganese and gallium enriched target.</p> <p> The films grown on (100) YSZ exhibit a self-reversible, magnetically induced reorientation of the martensite variants (MIR), which is temperature dependent. The mechanism associated with the self-activated reversibility in the MIR effect was established through a detailed characterization of the texture, microstructure, and magnetic domain structure of the films. </p> <p> The synthesized films also show a large magnetocaloric effect (MCE), which is particularly strong at low magnetic fields. The effect is associated with an overlapped ferromagnetic and martensitic phase transition. Detailed characterization of these transitions allow for an understanding of the role each phase transition plays in determining the level of enhancement to a standard MCE governed only by the ferromagnetic phase transition.</p> <p> Ni-Mn-Ga free-standing micro-bridges were fabricated using photolithography followed by wet chemical etching. Microstructural evolution of the martensitic variants resulting from changes to the stress field in the detached areas was studied in the context of potential film applications for micro-actuators.</p> / Thesis / Doctor of Philosophy (PhD)

Magnetic Structure of antiferromagnetic Mn₂P₂O₇ at 4.2º K has been established by neutron diffraction from a powder specimen. The magnetic unit cell is found to be the same size as the chemical unit cell. The spins are arranged in ferromagnetic sheets with the moments in each sheet aligned antiferromagnetically relative to its adjacent sheets. Neutron diffraction results in regard to the critical temperature (13±3)º K, and the spine being at an angle of 23º from the a-axis in the a-c plane have been found consistent with the ones obtained by Fowlis, Atkinson, Choh and Stager by susceptibility and NMR studies on the material. However, to confirm the angle with some precision, more work, probably with a single crystal, will be required. / Thesis / Master of Science (MSc)

Experiments were carried out on the solidification of iron-manganese alloys containing sulphur and carbon. The alloys were solidified under controlled conditions in a travelling furnace constructed especially for the investigation. Qualitative and quantitative metallography and electron-probe microanalysis were used to determine the solidification structure, dendrite arm spacings, solute concentration profiles and inclusion compositions. The results were interpreted in the light of existing knowledge and concepts especially developed for the purpose of this investigation. / Thesis / Doctor of Philosophy (PhD)

Single crystals of (Mg₉₉.₇₅Mn₀.₂₅)₂P₂O₇ have been investigated by esr through the temperature range from room temperature to 200ºC. One phase transition was observed extended through the temperature range between 59.5ºC to 63ºC where the α-and β phase coexist. Accurate spectra were recorded at 74ºC, 84ºC and 94ºC at the three magnetic axis, and the spin-Hamiltonian parameters were obtained from these data. The phase transition mechanism and the significance of the spin-Hamiltonian parameters in the theory of S-state splitting are discussed in the light of current literature. / Thesis / Master of Science (MSc)

No description available.

No description available.

Yes / The deactivation of the oxidative desulfurization (ODS) catalysts is a challenge and is a major concern in industrial catalytic processes. In this work, an activated carbon (AC) was prepared from agricultural waste and modified to withstand the ODS activity loss over time. The AC was impregnated with manganese and coated with aluminum oxide to prolong the activity lifetime. The catalysts were characterized by nitrogen adsorption-desorption, scanning electron microscope, energy dispersive X-ray, X-ray diffraction (XRD), thermogravimetric analysis (TGA), and transition electron microscope (TEM). The BET surface areas of the examined AC materials were 814.48 m2/g, 784.76 m2/g, and 755.03 m2/g for the AC, Mn/AC, and coated Mn/AC catalysts, respectively with a dominance of microporous pore size. The TGA showed that the coating layer retards the degradation of the active metal and suppresses phase transitions. XRD showed no change in the structure of the catalyst with a coating layer, and from the TEM analysis, the coating layer thickness was 3.6 nm. The kinetics of the ODS catalysts were investigated. It was shown that the ODS reaction follows the first-order kinetics and is not influenced by the coating layer. The activity decay was also investigated. It is found that the activation energy of the deactivation reaction over the coated catalyst was higher than the uncoated catalyst.

Reações de O-desmetilação oxidativa estão entre as várias oxidações realizadas pelas enzimas do citocromo P-450. Entretanto, poucos estudos de O-desmetilação catalisadas por enzimas do citocromo P-450 ou modelos químicos baseados em metaloporfirinas sintéticas têm resultado em dúvidas acerca do mecanismo da O-desmetilação destes compostos orgânicos. Neste trabalho, foi estudada a O-desmetilação oxidativa, com PhIO, do benzil metil éter e alguns de seus derivados para substituídos (com os grupos doadores de elétrons -OCH3 e -CH3 e os grupos retiradores -NO2 e -Cl) catalisada pelas Mn(III)P [Mn(TPP)]Cl, [Mn{T(4-N-MePy)P}](PF6)5, [Mn(TMP)]Cl, [Mn(TDCSPP)]Cl e [Mn(TFPP)]Cl para verificar o efeito destes diferentes catalisadores na conversão e seletividade de produtos da O-desmetilação oxidativa e avaliar o efeito dos diversos substituintes citados no mecanismo de O-desalquilação. Inicialmente, realizou-se o estudo das oxidações catalíticas do metil benzil éter. Todas as reações catalisadas pelas MnP se mostram seletivas, sendo que o benzaldeído foi o produto comum a todas as oxidações. A melhor condição encontrada foi 1:50:1224 (catalisador/oxidante/substrato). Em relação às reações com os substratos contendo os substituintes na posição -para, as reações de oxidações catalíticas do p-metóxibenzil metil éter por PhIO não se mostraram tão seletivas quanto as do metil benzil éter, mostrando claramente que o grupo metóxi alterou a reatividade do aril éter original. Mesmo assim, o p-metoxibenzaldeído ainda foi o produto principal, sendo a conversão ao álcool p-metoxibenzílico observada em escala menor. Já com o substrato p-nitrobenzil metil éter, novamente o efeito provocado pelo substituinte na posição para no anel benzênico pôde ser percebida na distribuição final dos produtos, sendo que houve seletividade total para a formação de p-nitrobenzaldeído em detrimento ao álcool p-nitrobenzóico. Em relação aos dois últimos substratos da série proposta, metil p-metilbenzil éter e metil p-clorobenzil éter, de um modo geral, as reações realizadas com o p-clorobenzil metil éter não se mostraram tão seletivas quanto as do metil p-nitrobenzil éter, mostrando que o grupo cloro aumentou a reatividade do cloroéter em relação ao éter com o substituinte nitro- original. Mesmo assim, o p-clorobenzaldeído foi o produto principal, sendo a conversão ao álcool p-clorobenzílico observada em menor escala. Em relação às reações de oxidação do p-metilbenzil metil éter, observou-se que os resultados experimentais são semelhantes aos encontrados para o metil benzil éter. Esses resultados corroboram o principal mecanismo proposto para os sistemas modelo do citocromo P-450 que envolve abstração inicial do átomo de hidrogênio, o mecanismo por recombinação de oxigênio. / O-dealkylation oxidative reactions are among the several oxidations accomplished by the cytochrome P-450 enzymes. However, few studies on O-dealkylation catalyzed by such enzymes or chemical models based on synthetic metalloporphyrins have resulted in doubts concerning the mechanism of these reactions involving organic compounds. In this work, we studied the oxidative O-dealkylation by PhIO of benzyl methyl ether and some of its para-substituted derivatives (with the electron donor groups -OCH3 and -CH3 and the electronwithdrawing groups -NO2 and -Cl) catalyzed by the following Mn(III)P: [Mn(TPP)]Cl, [Mn{T(4-N-MePy)P}] (PF6)5, [Mn(TMP)]Cl, [Mn(TDCSPP)] Cl, and [Mn(TFPP)]Cl. Our aim was to verify the effect of these different catalysts on the conversion yields and product selectivity, as well as evaluate the effect of the several substituents on the ether on the O-dealkylation mechanism. We initially studied the catalytic oxidation of methyl benzyl ether. All the reactions catalyzed by the various MnPs were selective, and benzaldehyde was the product common to all oxidations. The best reaction condition was catalyst/oxidant/substrate molar ration = 1:50:1224. As for the reactions with the substituted substrates, the catalytic oxidation of p-methoxybenzyl methyl ether by PhIO was not as selective as the ones of methyl benzyl ether, clearly showing that the methoxy group affects the reactivity of the original aryl ether. Nevertheless, p-methoxybenzaldehyde was still the main product, being the conversion to p-methoxybenzylic alcohol observed in minor amount. With the substrate p-nitrobenzyl methyl ether, the effect of the electronwithdrawing substituent in the para- position of the aromatic ring could be observed in the final product distribution once again, and total selectivity toward the formation of p-nitrobenzaldehyde to the detriment of p-nitrobenzoic alcohol was observed. In relation to the two last substrates of the proposed series, the methyl p-methylbenzyl and methyl p-chlorobenzyl ethers, the reactions accomplished with p-chlorobenzyl methyl ether were not as selective as the ones carried out with methyl p-nitrobenzyl ether, showing that the chloro group increased the reactivity of the chloro-ether in relation to the ether with the original nitro- substituent. Even so, p-chlorobenzaldehyde was the main product, being the conversion to the p-chlorobenzylic alcohol observed in smaller amount. Concerning the oxidation reactions of p-methylbenzyl methyl ether, the experimental results were similar to those obtained in the case of methyl benzyl ether. These results corroborate the main mechanism proposed for the cytochrome P-450 model systems, which involves initial hydrogen atom abstraction, followed by oxygen rebound.

As ligas do sistema Fe-Mn-Al-C constituem-se numa das famílias mais promissoras para o atendimento dos requisitos crescentes de disponibilidade de aços com altas relações resistência/peso, principalmente nas indústrias de transporte aeronáutica e automotiva, visando a redução no consumo de combustível e a consequente emissão de CO2. Suas densidades, cerca de 10% a 13% inferiores aos dos aços convencionais e a possibilidade de aumento de resistência mecânica por tratamentos de endurecimento pela precipitação de carboneto k (Fe,Mn)Al3C possibilitam a obtenção de elevadas resistências específicas. O uso de técnicas da Engenharia de Superfícies, associadas aos tratamentos térmicos adequados, podem ampliar a faixa de desempenho dessas ligas. Neste trabalho foram realizados tratamentos termoquímicos de boretação em sais fundidos, nitrocementação a plasma e cromização por pó em amostras de um aço com a composição Fe-31,2Mn-7,5Al-1,3Si-0,9C (% em peso), visando à obtenção de camadas de elevados desempenhos mecânicos e físicos. As camadas produzidas foram caracterizadas por meio de ensaios micrográficos, de dureza, desgaste e corrosão. Todos os tipos de tratamentos produziram camadas com resistências ao desgaste muito superiores às do substrato, com destaque para os tratamentos de boretação e de cromização, que produziram camadas com resistências ao desgaste cerca de nove e seis vezes superiores às do substrato, respectivamente. O tratamento de cromização produziu camada com resistência à corrosão por pites muito superior à do substrato. / The alloys of the Fe-Mn-Al-C system belong to one of the most promising families to meet the increasing requirements of availability of steels with high resistance/weight ratio, particularly in the aeronautics and automotive industries, aimed at reducing the consumption of fuel and consequent CO2 emissions. Their densities, between 10% to 13% lower than those of conventional steels, and the possibility of increased strength by hardening treatment by the precipitation of k carbides (Fe, Mn)Al3C, allow to obtain high specific resistance. The use of techniques of surface engineering, attached to suitable heat treatment, can extend the performance range of these alloys. In this work were carried out thermochemical boriding treatment in molten salts, plasma nitrocarburizing and pack chromizing in a Fe-31,2Mn 7,5Al-1,3Si-0,9C(wt%) steel, in order to obtain coatings with high mechanical and physical performances. The layers produced were characterized using micrographic, hardness, wear and corrosion tests. All treatments produced layers with wear resistance superior to that the substrate, especially the boriding and chromizing treatments, which produced layers with wear resistance around nine and six times higher than that of substrate, respectively. The chromizing treatment produced layer with pitting corrosion resistance superior to that of the substrate.