Doctor of Philosophy / Department of Chemistry / Eric A. Maatta / Polyoxometalates have attracted much attention over the last few decades and have been studied in a wide variety of fields such as catalysis, medicine, imaging, photochromism, and magnetic materials. While many of these systems are easy to prepare, the ability to functionalize polyoxometalates is an ongoing challenge. Two approaches used to functionalize polyoxometalates involve insertion of metal fragments into a lacunary polyoxometalate or the direct replacement of terminal oxo ligands with the isoelectronic organoimido ligand. This process has been proven successful in many cases and with a wide variety of organoimido compounds. One of our group’s goals has been to synthesize a functionalized hexamolybdate species that is capable of metal coordination. However, previous results have been hindered because the electron withdrawing effect of the cluster is transmitted to the metal binding sites. In order to combat the electron withdrawing effect of the cluster, 4-amino piperidine dithiocarbamate ligands, which have no conjugation in the ring and are capable of metal binding, have been synthesized and characterized. A series of transition metal complexes have been made and a single crystal has been grown of a nickel(II) complex. Attempts to attach these species to clusters are described. Imido hexamolybdate clusters have been functionalized with styryl and iodophenyl groups. The styrene functionalized hexamolybdate was copolymerized with 4- chloromethylstyrene in moderate yields. This copolymer has the capabilities for further substitution at the chloromethyl group. The iodophenyl functionalized hexamolybdate was fully characterized including a single-crystal X-ray structural determination. This functionalized hexamolybdate can be used in carbon-carbon bond formation through coupling reactions. A chromium(V) nitrido polyoxometalate has been synthesized from a lacunary Keggin precursor and characterized. This nitrido species shows promise as a nitrogen transfer agent. Likewise, this nitrido species could be an entry point to other derivatives through reactions with various nucleophiles and electrophiles.

No description available.

No description available.

Os aços inoxidáveis duplex são materiais com um excelente desempenho, devido às suas sobressalentes propriedades mecânicas e excelente resistência à corrosão. Uma composição química adequada e microestrutura balanceada são as responsáveis por esta combinação de propriedades. No entanto, são estes mesmos fatores que os fazem especialmente susceptíveis à precipitação de fases intermetálicas, com efeitos maléficos no seu desempenho. Durante os ciclos térmicos de uma soldagem multipasse, a precipitação de intermetálicos é crítica. Foi desenvolvido um método para simular os ciclos térmicos de uma solda multipasse. Usando este método, foi estudada a precipitação de nitreto de cromo e fase sigma na zona afetada pelo calor submetida a temperaturas abaixo de 950°C dos aços inoxidáveis duplex UNS S31803 e S32550. Foram estudadas energias de soldagem na faixa de 0,4 a 1,0 kJ/mm. Foi determinada mediante extração de precipitados, seguida de difração de raios X na câmara de Debye-Scherrer e microscopia eletrônica de transmissão, a precipitação de nitreto de cromo para energias de soldagem de 0,4 a 1,0 kJ/mm e de fase sigma para energias de soldagem de 0,6-1,0 KJ/mm, no UNS S32550. Já o UNS S31803 não apresentou precipitação alguma para as energias de soldagem estudadas. Baseando-se nos resultados verifica-se que durante uma soldagem multipasse o UNS S31803 é menos propenso que o UNS S32550 à precipitação de intermetálicos na zona afetada pelo calor submetida a temperaturas abaixo de 950°C. / Duplex stainless steels belong to a group of high performance stainless steels regarding to corrosion and mechanical properties. These achievements are related to a suitable chemical composition and a balanced microstructure. During welding thermal cycles the microstructure changes and, consequently, corrosion and mechanical properties might be impaired due to a precipitation of intermetallic phases. This precipitation is an issue to be addressed for multipass welding. It was developed a method for simulate the multipass welding thermal cycles. Using this method chromium nitride and sigma phase precipitation was studied in a simulated heat affected zone of multipass welding (three passes) of UNS S31803 and UNS S32550 duplex stainless steels with different heat inputs (0,4 to 1,0 kJ/mm). The HAZ simulated region was below 950°C maximum temperature. Microstructural characterization of simulated samples showed discontinuous films of a precipitated phase at ferrite/ferrite grain boundaries and ferrite/austenite interfaces were observed only in a UNS S32550 duplex grade for all heat inputs simulated. This suggests that sigma phase and chromium nitride precipitation took place during sample thermocycling. X-ray diffraction in a Debye-Scherrer chamber of extracted precipitates and electron diffraction by TEM confirmed the presence of chromium nitrides for all range of heat input studied and sigma phase for heat input above 0,6 kJ/mm. On the other hand, microstructural analysis of UNS S31803 simulated samples did not present precipitation of intermetallic phases in the tested temperature range of HAZ. Based on these results, UNS S31803 is more resistant than UNS S32550 to intermetallic phases precipitation in multipass welding.

Os aços inoxidáveis duplex (AIDs) são materiais com um excelente desempenho tanto mecânico como à corrosão. Inúmeras pesquisas tem sido desenvolvidas para aprimorar a soldabilidade destas ligas. Algumas transformações de fase, que são passíveis de ocorrer durante o processo de soldagem, podem prejudicar seriamente o desempenho das juntas. Foram simuladas microestruturas da região da zona afetada pelo calor submetida a temperaturas elevadas (ZACTE), utilizando um modelo proposto de fluxo de calor. Abordaram-se aspectos fundamentais da precipitação de austenita secundária, de nitreto de cromo e as suas interações na ZACTE de soldas multipasse. Finalmente, foram realizados testes de tenacidade e de resistência à corrosão para avaliar o efeito das transformações de fase estudadas no desempenho das juntas soldadas. Os tratamento térmicos e simulações da ZACTE foram realizadas num equipamento GleebleÒ. As microestruturas foram analisadas mediante microscopia ótica e eletrônica de varredura e de transmissão. Junto com a microscopia eletrônica foram realizadas microanálises químicas das fases estudadas. Baseando-se nos resultados obtidos, verificou-se que nem todos os AIDs são susceptíveis de ferritizar. Este fato tem uma grande influência no comportamento metalúrgico e na soldabilidade destes aços. Quanto aos aspectos fundamentais da metalurgia destes aços, observou-se uma estreita interação entre a precipitação da austenita secundária e os nitretos de cromo, chegando-se a propor um mecanismo de nucleação da austenita secundária intragranular a partir dos nitretos. Por último, foi constatado que o efeito deletério da austenita secundária intragranular na resistência à corrosão pode ser evitado mediante a adequada elaboração do procedimento de soldagem. / Duplex stainless steels (DSS) have excellent mechanical and corrosion properties. Many researches have been developed regarding the weldability of these alloys. There are some phase transformations that take place during the welding process, which may impair the welded joint behavior. High temperature heat-affected zone (HTHAZ) microstructures were simulated using a proposed heat flow model. Fundamental aspects of the secondary austenite and chromium nitride precipitation, and its interactions in the HTHAZ of multipass welds, were studied. In addition, toughness and corrosion tests were done to evaluate the influence of the studied phase transformations on the weld behavior. A GleebleÒ system was used to do the heat treatments and HTHAZ simulations. The microstructures were analyzed by means of optic and electron microscopy. Along with the electron microscopy it was done chemical microanalysis of the studied phases. Based on results, it was verified that not all DSSs can be ferritized. This fact has a strong influence on metallurgical behavior and weldability of these alloys. Regarding to the metallurgical fundamental aspects of these steels, it was observed a remarkable interaction between secondary austenite and chromium nitride precipitation. Thus, it was proposed a mechanism of intragranular secondary austenite precipitation from chromium nitrides. It was also verified, how the deleterious effect of intragranular secondary austenite in the corrosion resistance can be avoided by means of appropriate welding procedures.

Os aços inoxidáveis duplex (AIDs) são materiais com um excelente desempenho tanto mecânico como à corrosão. Inúmeras pesquisas tem sido desenvolvidas para aprimorar a soldabilidade destas ligas. Algumas transformações de fase, que são passíveis de ocorrer durante o processo de soldagem, podem prejudicar seriamente o desempenho das juntas. Foram simuladas microestruturas da região da zona afetada pelo calor submetida a temperaturas elevadas (ZACTE), utilizando um modelo proposto de fluxo de calor. Abordaram-se aspectos fundamentais da precipitação de austenita secundária, de nitreto de cromo e as suas interações na ZACTE de soldas multipasse. Finalmente, foram realizados testes de tenacidade e de resistência à corrosão para avaliar o efeito das transformações de fase estudadas no desempenho das juntas soldadas. Os tratamento térmicos e simulações da ZACTE foram realizadas num equipamento GleebleÒ. As microestruturas foram analisadas mediante microscopia ótica e eletrônica de varredura e de transmissão. Junto com a microscopia eletrônica foram realizadas microanálises químicas das fases estudadas. Baseando-se nos resultados obtidos, verificou-se que nem todos os AIDs são susceptíveis de ferritizar. Este fato tem uma grande influência no comportamento metalúrgico e na soldabilidade destes aços. Quanto aos aspectos fundamentais da metalurgia destes aços, observou-se uma estreita interação entre a precipitação da austenita secundária e os nitretos de cromo, chegando-se a propor um mecanismo de nucleação da austenita secundária intragranular a partir dos nitretos. Por último, foi constatado que o efeito deletério da austenita secundária intragranular na resistência à corrosão pode ser evitado mediante a adequada elaboração do procedimento de soldagem. / Duplex stainless steels (DSS) have excellent mechanical and corrosion properties. Many researches have been developed regarding the weldability of these alloys. There are some phase transformations that take place during the welding process, which may impair the welded joint behavior. High temperature heat-affected zone (HTHAZ) microstructures were simulated using a proposed heat flow model. Fundamental aspects of the secondary austenite and chromium nitride precipitation, and its interactions in the HTHAZ of multipass welds, were studied. In addition, toughness and corrosion tests were done to evaluate the influence of the studied phase transformations on the weld behavior. A GleebleÒ system was used to do the heat treatments and HTHAZ simulations. The microstructures were analyzed by means of optic and electron microscopy. Along with the electron microscopy it was done chemical microanalysis of the studied phases. Based on results, it was verified that not all DSSs can be ferritized. This fact has a strong influence on metallurgical behavior and weldability of these alloys. Regarding to the metallurgical fundamental aspects of these steels, it was observed a remarkable interaction between secondary austenite and chromium nitride precipitation. Thus, it was proposed a mechanism of intragranular secondary austenite precipitation from chromium nitrides. It was also verified, how the deleterious effect of intragranular secondary austenite in the corrosion resistance can be avoided by means of appropriate welding procedures.

Os aços inoxidáveis duplex são materiais com um excelente desempenho, devido às suas sobressalentes propriedades mecânicas e excelente resistência à corrosão. Uma composição química adequada e microestrutura balanceada são as responsáveis por esta combinação de propriedades. No entanto, são estes mesmos fatores que os fazem especialmente susceptíveis à precipitação de fases intermetálicas, com efeitos maléficos no seu desempenho. Durante os ciclos térmicos de uma soldagem multipasse, a precipitação de intermetálicos é crítica. Foi desenvolvido um método para simular os ciclos térmicos de uma solda multipasse. Usando este método, foi estudada a precipitação de nitreto de cromo e fase sigma na zona afetada pelo calor submetida a temperaturas abaixo de 950°C dos aços inoxidáveis duplex UNS S31803 e S32550. Foram estudadas energias de soldagem na faixa de 0,4 a 1,0 kJ/mm. Foi determinada mediante extração de precipitados, seguida de difração de raios X na câmara de Debye-Scherrer e microscopia eletrônica de transmissão, a precipitação de nitreto de cromo para energias de soldagem de 0,4 a 1,0 kJ/mm e de fase sigma para energias de soldagem de 0,6-1,0 KJ/mm, no UNS S32550. Já o UNS S31803 não apresentou precipitação alguma para as energias de soldagem estudadas. Baseando-se nos resultados verifica-se que durante uma soldagem multipasse o UNS S31803 é menos propenso que o UNS S32550 à precipitação de intermetálicos na zona afetada pelo calor submetida a temperaturas abaixo de 950°C. / Duplex stainless steels belong to a group of high performance stainless steels regarding to corrosion and mechanical properties. These achievements are related to a suitable chemical composition and a balanced microstructure. During welding thermal cycles the microstructure changes and, consequently, corrosion and mechanical properties might be impaired due to a precipitation of intermetallic phases. This precipitation is an issue to be addressed for multipass welding. It was developed a method for simulate the multipass welding thermal cycles. Using this method chromium nitride and sigma phase precipitation was studied in a simulated heat affected zone of multipass welding (three passes) of UNS S31803 and UNS S32550 duplex stainless steels with different heat inputs (0,4 to 1,0 kJ/mm). The HAZ simulated region was below 950°C maximum temperature. Microstructural characterization of simulated samples showed discontinuous films of a precipitated phase at ferrite/ferrite grain boundaries and ferrite/austenite interfaces were observed only in a UNS S32550 duplex grade for all heat inputs simulated. This suggests that sigma phase and chromium nitride precipitation took place during sample thermocycling. X-ray diffraction in a Debye-Scherrer chamber of extracted precipitates and electron diffraction by TEM confirmed the presence of chromium nitrides for all range of heat input studied and sigma phase for heat input above 0,6 kJ/mm. On the other hand, microstructural analysis of UNS S31803 simulated samples did not present precipitation of intermetallic phases in the tested temperature range of HAZ. Based on these results, UNS S31803 is more resistant than UNS S32550 to intermetallic phases precipitation in multipass welding.

No description available.

Among emerging materials systems for thermoelectric applications, the early transition-metal nitrides based on ScN and CrN show unexpectedly promising properties. These properties are determined by high Seebeck coefficient, low thermal conductivity, and high electrical conductivity. There is, however, still a need to improve the thermoelectric properties. One idea is to introduce dopants or alloying elements to alter the concentration, mobility, and/or type of charge carriers, such as in (Cr1-xVx)N. Another is to focus on the different scattering mechanisms, such as to reduce the scattering of electrons and increase the scattering of phonons, thus increasing the electrical conductivity while lowering the thermal conductivity. Electrical conductivity can be altered by grain boundary modifications, such as larger grains as well as metallic inclusions, for a smoother interface for the electrons. Such nanoinclusions could potentially also act as phonon scattering centra. Phonon scattering can also occur by site substitution of isoelectronic but heavier atoms, which could reduce the phonon mean free path while retaining the electrical conductivity. For CrN, the obvious substitutions are Mo or W.This thesis investigates these effects for CrN-based materials, and how to control the growth of them in a DC-magnetron sputtering system.First, an optimization study for CrN was made, here the power was fixed while the temperature and nitrogen content were varied. Second, the effect of in-situ annealing at the deposition temperature was investigated. Here, both films with pure CrN and films with a mix of CrN and Cr2N were annealed. It was found that temperature, pressure, and ambient gas have a large effect on the decomposition of CrN to Cr2N. Third, alloying with V and Mo was implemented. It was found that Mo quickly breaks the rock-salt structure, and for further investigation of CrMoN and Cr(Mo,V)N systems, other deposition methods which allows for lower deposition rates need to be investigated.The sample deemed best was the CrVN-sample, showing a Seebeck coefficient of -141 μV/K, resistivity of 1520 μΩ∙cm and a power factor of 1.3 mW/mK2.

In fuel cells, stacks of several hundred bipolar plates are combined in membrane electrode assemblies, in which the electrochemical reactions take place. As a result, it must be possible to produce the bipolar plates cost-efficiently. In addition, the corrosion resistance in the surrounding medium and the electrical conductivity have to be sufficiently high. As stainless steels show passivation over time, more expensive materials, like graphite or noble-metal coatings, are used. This paper describes an alternative coating, which can fulfil the above-mentioned requirements. Using electroplating, Cr coatings with thicknesses > 20 µm can be deposited at low costs and REACH compliant. Subsequently, the Cr layers are gas nitrided resulting in a dense Cr-N coating with electrical and corrosion properties exceeding the ones of common stainless steels. Using this new approach, well-performing fuel cells could be produced cost-efficiently.