Alkyl-arenes are important industry feedstock chemicals that are used as solvents, pharmaceutical precursors, and polymer monomer units. One alkyl-arene, ethylbenzene, is the main focus of this dissertation, and is produced in the million ton a year scale. As alkyl-arenes are important commodity chemicals, catalytic olefin hydroarylation is a lucrative alternative for their production rather than Friedel-Crafts alkylation or various coupling reactions that have lower atom economy, require strong acids, or are energetically demanding. Currently catalytic olefin hydroarylation still suffers from decomposition pathways of the active catalytic complexes, side reactions that lead to waste products, and unfavorable activation barriers, which represent high temperature and pressure. Modifications to the catalytically active system bipyridine platinum(II) (bpyPtII), through computational methods, are explored herein. The work presented here investigates catalytic olefin hydroarylation in order to mitigate the aforementioned difficulties. Included in this study are changes to the electronic profile of the supporting ligand, bpy, through the addition of electron withdrawing or electron donating R groups (methoxy, nitro), definite ligand replacements such as bpy to hydridotris(pyrazolyl)borate (Tp), changes in metal oxidation (II to IV), and replacing the metal center from Pt to Ni. Nickel was selected as a possible alternative to platinum as it is more Earth abundant reducing the monetary requirement for the catalyst. In addition to having a different catalytic energetic profile from platinum. Ni as expected could only facilitate single step hydrogen atom transfers due to its inability to access higher oxidations states.

This thesis describes the processing and characterization of uniform, interpenetrating, nickel-cubic stabilized zirconia composites. This work was performed in support of future development in the study and modelling of Metal-Ceramic (M/C) Functionally Graded Materials. Since it is of fundamental interest to understand the relationship between microstructure and behaviour in these materials, the characterization has focused on uniform composites. To minimize experimentation while maximizing productivity, the material grades selected for this study include M:C ratios by volume of 25:75, 50:50, and 75:25, along with the elemental materials (i.e. 100% nickel and 100% cubic zirconia). Solid state powder processing was developed including the steps: colloidal processing (by tape casting), lamination, organic burnout, hydrogen reduction of metal oxides, and hot press consolidation. These techniques support the even distribution of phases and yield high density composites (>98% of theoretical). Unfortunately the nickel powder used in this study produced atypical properties which complicated the analysis of mechanical behaviour. Composite thermal dilation, elastic, and mechanical properties were determined. Through analysis of residual stresses and fracture behaviour ideas regarding the modelling of M/C composites and FGMs are addressed. Continuum modelling approaches seem appropriate. / Thesis / Master of Engineering (ME)

O presente trabalho está relacionado a estudos de superligas à base de Ni, cujas microestruturas multifásicas apresentam propriedades satisfatórias para aplicações em altas temperaturas. O Nb e o Ta são componentes importantes nesta classe de materiais, estando normalmente associados às fases endurecedoras ?\' e \'\'. Desta forma, a determinação das relações de fases no sistema Ni-Nb-Ta na região rica em Ni corresponde a uma importante contribuição para a literatura referente, especialmente para os trabalhos ligados à construção de base de dados termodinâmicos. Assim, foi definido como objetivo principal a proposição das relações de fases na região rica em Ni do sistema Ni-Nb-Ta para a temperatura de 1050oC. As ligas foram obtidas por fusão a arco e tradas termicamente a 1050ºC por no mínimo 120 h. Amostras no estado bruto de fusão e tratadas termicamente foram caracterizadas microestruturalmente (MEV e DRX) e por microanálise química (EDS). Na região de estudo, observou-se as fases Niss, Ni8Ta, Ni3(Nb,Ta), Ni2(Nb,Ta), e ? (NiTa; Ni6Nb7), sem a presença de qualquer fase ternária. Observou-se uma solubilidade completa de Nb e Ta nas fases Ni3(Nb,Ta) e ?. A fase Ni2Ta apresentou uma solubilidade de Nb próxima de 13% at. Não foi possível determinar a região de solubilidade de Nb na fase Ni8Ta. / This work is related to studies of Ni-based superalloys, which multiphase microstructures have satisfactory properties for high temperature applications. The Nb and Ta are important components in this class of materials and is typically associated with the hardening phases ? \' and .\'\' Thus, the determination of phase relationships in the system Ni-Nb-Ta in the Ni-rich region represents an important contribution to the literature, especially for determination of related thermodynamic data. Thus, the main objective of this work was to propose the phase relationships in the Ni-rich region of the system Ni-Nb-Ta at 1050oC. The alloys were obtained by arc melting and heat-treated at 1050 º C for at least 120 h. Samples in the a-scast and heat treated states were characterized via (SEM and XRD) and chemical microanalysis (EDS). In the region of study, the observed phases were Niss, Ni8Ta, Ni3(Nb, Ta), Ni2(Nb,Ta), and ? (NiTa; Ni6Nb7) without the presence of any ternary phase. There was a complete solubility of Nb and Ta in the Ni3(Nb,Ta) and ? phases. The Ni2Ta showed a solubility of Nb close to 13% at. It was not possible to determine the region of solubility of Nb in the Ni8Ta phase.

O presente trabalho está relacionado a estudos de superligas à base de Ni, cujas microestruturas multifásicas apresentam propriedades satisfatórias para aplicações em altas temperaturas. O Nb e o Ta são componentes importantes nesta classe de materiais, estando normalmente associados às fases endurecedoras ?\' e \'\'. Desta forma, a determinação das relações de fases no sistema Ni-Nb-Ta na região rica em Ni corresponde a uma importante contribuição para a literatura referente, especialmente para os trabalhos ligados à construção de base de dados termodinâmicos. Assim, foi definido como objetivo principal a proposição das relações de fases na região rica em Ni do sistema Ni-Nb-Ta para a temperatura de 1050oC. As ligas foram obtidas por fusão a arco e tradas termicamente a 1050ºC por no mínimo 120 h. Amostras no estado bruto de fusão e tratadas termicamente foram caracterizadas microestruturalmente (MEV e DRX) e por microanálise química (EDS). Na região de estudo, observou-se as fases Niss, Ni8Ta, Ni3(Nb,Ta), Ni2(Nb,Ta), e ? (NiTa; Ni6Nb7), sem a presença de qualquer fase ternária. Observou-se uma solubilidade completa de Nb e Ta nas fases Ni3(Nb,Ta) e ?. A fase Ni2Ta apresentou uma solubilidade de Nb próxima de 13% at. Não foi possível determinar a região de solubilidade de Nb na fase Ni8Ta. / This work is related to studies of Ni-based superalloys, which multiphase microstructures have satisfactory properties for high temperature applications. The Nb and Ta are important components in this class of materials and is typically associated with the hardening phases ? \' and .\'\' Thus, the determination of phase relationships in the system Ni-Nb-Ta in the Ni-rich region represents an important contribution to the literature, especially for determination of related thermodynamic data. Thus, the main objective of this work was to propose the phase relationships in the Ni-rich region of the system Ni-Nb-Ta at 1050oC. The alloys were obtained by arc melting and heat-treated at 1050 º C for at least 120 h. Samples in the a-scast and heat treated states were characterized via (SEM and XRD) and chemical microanalysis (EDS). In the region of study, the observed phases were Niss, Ni8Ta, Ni3(Nb, Ta), Ni2(Nb,Ta), and ? (NiTa; Ni6Nb7) without the presence of any ternary phase. There was a complete solubility of Nb and Ta in the Ni3(Nb,Ta) and ? phases. The Ni2Ta showed a solubility of Nb close to 13% at. It was not possible to determine the region of solubility of Nb in the Ni8Ta phase.

Arbetet handlar om styrning och reglering av stegmotorer och permanentmagnetmotorer, genom attanvända det grafiska programmeringsspråket Labview från National Instruments (NI) tillsammansmed hårdvara i form av NI CompactRIO och NI USB datainsamlingskort. Implementeringen har sketti form av en robot med ett för uppgiften specialbyggt styrsystem, PWM – styrning av enpermanentmagnetmotor och en egenkonstruerad manöverdosa. / This report deals about controlling and regulating stepping motors and PM-motors by using thegraphical programming language NI Labview, with hardware NI CompactRIO and NI DAQ-USB.The implementation has been done by controlling a robot with a for the task built system, controllinga PM-motor by PWM and a own created controller.

<p>Arbetet handlar om styrning och reglering av stegmotorer och permanentmagnetmotorer, genom attanvända det grafiska programmeringsspråket Labview från National Instruments (NI) tillsammansmed hårdvara i form av NI CompactRIO och NI USB datainsamlingskort. Implementeringen har sketti form av en robot med ett för uppgiften specialbyggt styrsystem, PWM – styrning av enpermanentmagnetmotor och en egenkonstruerad manöverdosa.</p> / <p>This report deals about controlling and regulating stepping motors and PM-motors by using thegraphical programming language NI Labview, with hardware NI CompactRIO and NI DAQ-USB.The implementation has been done by controlling a robot with a for the task built system, controllinga PM-motor by PWM and a own created controller.</p>

A força de adesão entre resinas e ligas de metais básicos resulta do embricamento mecânico entre a superfície do metal e a resina e da interação química entre óxidos presentes na superfície dos metais e monômeros adesivos das resinas compostas. A literatura, entretanto, mostra que ainda persistem algumas dúvidas sobre a interação entre os diversos tipos de sistemas adesivos e metais básicos, por isso, essa pesquisa visa: verificar se a presença do Be na composição de ligas a base de Ni-Cr influencia a união metal básico/resina; comparar dois cimentos resinosos adesivos nessa função e verificar a influência da utilização de condicionadores (primers) adesivos metálicos para ligas nobres sobre essa união. Após 2500 termociclos, foram realizados testes de resistência à tração em 160 corpos-de-prova, que consistiam de dois discos de Ni-Cr-Be (Verabond – Aalba Dental Inc., Cordelia, CA-USA) com 6 mm de diâmetro e 2 mm de espessura cimentados entre si, e dois discos de Ni-Cr (Durabond - Odonto Comercial Importadora Ltda, São Paulo, SP), com as mesmas dimensões, cimentados entre si. Foram utilizadas diferentes marcas comerciais de sistemas adesivos: os cimentos resinosos adesivos, Panavia F (Kuraray Co. Ltd.), Bistite II DC (Tokuyama Corp.) e os agente de união (primers adesivos metálicos), Alloy Primer (Kuraray Co. Ltd. ), Metaltite (Tokuyama Corp.) e Cesead Opaque Primer (Kuraray Co. Ltd.). Discos cimentados sem primers serviram como grupo controle. Os resultados mostraram que houve diferença estatisticamente significante entre as duas ligas (Ni-Cr-Be –24,82 ± 7,6 MPa e Ni-Cr - 22,32 ± 7,9 MPa). Já para os cimentos houve superioridade adesiva do cimento Panavia F, que obteve média de resitência adesiva de 27,49 ± 4,8 MPa, sobre o cimento Bistite II, que obteve média de resistência adesiva de 19,63 ± 8,4 MPa. Os primers utilizados não apresentaram influência positiva sobre o Panavia F já que os grupos sem primer para esse cimento obtiveram média de 28,18 ± 5,6 MPa que é equivalente a média dos outros grupos com Panavia. Entretanto, para o cimento Bistite II DC os primers Alloy Primer e Metaltite obtiveram as menores médias, 12,7 ± 7,6 MPa e 15,71 ± 4,8 MPa respectivamente, enquanto sem primer, ou com o Cesead Opaque Primer, as médias foram significantemente superiores, 24.47 ± 6 MPa e 25.70 ± 6,8 Mpa respectivamente. Diante dos resultados conclui-se que os primers adesivos metálicos não potencializaram a adesão de cimentos resinosos adesivos sobre ligas de Ni-Cr. / The bond strength for resin and basic metals comes from the interaction between oxides in the metal surface and adhesive monomers in the composite resins composition. The literature shows that still are some questions about this interaction so this research intends to: verify if the presence of Be at Ni-Cr alloy plays some influence for this union, compare two resin luting cements at this function and study the influence the use of metal primers for noble metals in this mecanism of adhesion. After 2500 thermocycles, tensile bond strength tests were loaded at 160 specimens, which consisted of two metals discs with 6 mm in diameter and 2 mm thick from a Ni-Cr-Be alloy (Verabond – Aalba Dental Inc., Cordelia, CA-USA) bonded togheter and two metal discs from a Ni-Cr alloy (Durabond - Odonto Comercial Importadora Ltda, São Paulo, SP) bonded togheter. Diferent brand adhesive systems were used: the resin cements, Panavia F (Kuraray Co. Ltd.) and Bistite II DC (Tokuyama Corp.) and the metal primers, Alloy Primer (Kuraray Co. Ltd.), Metaltite (Tokuyama Corp.) and Cesead Opaque Primer (Kuraray Co. Ltd.). Nonprimed specimens served as control group. The results indicated that there is statiscal diferences beetwen the two alloys (Ni-Cr-Be –24,82 ± 7,6 MPa e Ni-Cr - 22,32 ± 7,9 MPa). Panavia F had founded greater bond strength (27,49 ± 4,8 MPa) than Bistite DC (19,63 ± 8,4 MPa). The metal primers did not show any positive influence for the Panavia bond strength when we considere that the no primer group had 28,18 ± 5,6 MPa bond strength media which were equivalente to the others Panavia´s groups. However for the Bistite cement, the bond strength for Alloy primer and Metaltite were the lower medias, 12,7 ± 7,6 MPa and 15,71 ± 4,8 MPa respectivally, while the no primer or the Cesead Opaque Primer groups showed superior medias 24,47 ± 6 MPa and 25,70 ± 6,8 MPa respectivally. The outcome of this research shows that the metal primers used did not incresead the bond strength between resin cements and Ni-Cr alloys.

The scope of this project is to collect and interpret geochemical and textural data of iron-nickel (Fe-Ni) spherules in impact melt from the Monturaqui Impact Crater, Chile to investigate the processes accounting for the compositional variations. Major element data are collected on in situ spherules in one thin section and three epoxy rounds by electron microprobe and major element, trace element, and platinum group element data are collected by inductively coupled plasma mass spectrometry on spherules separated from impact glass by electric pulse disintegration (Figure 1C-1D). Major element, trace element, and platinum group element data are collected on a piece of iron shale from Monturaqui by using both instruments. Though the variation of the major elements within Fe-Ni spherules has been well documented, the variations of trace elements have not been rigorously investigated. This study aims to document the variations seen in major elements, trace elements, and platinum group elements in the Fe-Ni spherules relative to the iron impactor. The impactor was originally classified as a group I coarse octahedrite based on the Ni content of Fe-Ni spherules in the impact melt as well as the morphology of the iron shale (Bunch and Cassidy, 1972; Buchwald, 1975). For this study, major element, trace element, and platinum group element data were collected on a piece of iron shale from Monturaqui to provide a more robust classification.

The work outlined herein presents an investigation of synthetic model complexes of relevance to the active sites of Ni(II)-containing enzymes, particularly urease, glyoxalase I, and acireductone dioxygenase. The research focuses on studying the structural and reactivity features of nickel complexes with biologically relevant substrates. The anion of acetohydroxamic acid is a well-known inhibitor of urease enzymes, including those isolated from Klebsiella aerogenes and Bacillus pasteurii. A precursor to the acetohydroxamate coordination in ureases is proposed to be an interaction between Ni(II) and acetohydroxamic acid. By using a novel supporting chelate ligand capable of secondary hydrogen bonding interactions a novel pseudo-octahedral, Ni(II) acetohydroxamic acid complex has been isolated and characterized. Detailed analysis of the structural features and acetohydroxamic displacement reactivity of this complex has provided fundamental chemical insight toward understanding of the inhibition mechanism in urease enzymes. Glyoxalase I (Glx I) catalyzes one step of the cellular detoxification pathway for α-ketoaldehydes (e.g. methylglyoxal) in humans and bacteria. The GlxI enzyme from E. coli is a Ni(II)-containing enzyme that catalyzes the isomerization of a hemithioacetal to produce a thioester. Of relevance to this enzyme, the first example of a Ni(II) complex that promotes a hemithioacetal isomerization is reported herein. In order to monitor this type of reaction a new approach involving a a deuterium-labeled hemithioacetal (PhC(O)CH(OH)SCD3) and 2H NMR was employed. Acireductone dioxygenases (ARDs) catalyze aliphatic oxidative C-C bond cleavage of an acireductone (1,2-dihydroxy-3-oxo-5-(methylthio)pent-1-ene) intermediate in the methionine salvage pathway. A unique aspect of these enzymes is that the regioselectivity of the dioxygenase reaction depends on the metal ion bound in the active site. Outlined herein are descriptions of the synthesis, characterization, and O2 reactivity of a novel trinuclear Ni(II) enediolate complex of relevance to the proposed enzyme/substrate adduct in Ni(II)-ARD. Efforts have also been made toward the preparation of C(1)-H acireductone compounds using a combined synthetic/enzymatic approach. A phenyl appended-C(1)-H acireductone was isolated and introduced to a Ni(II) precursor complex. This reaction produced spectroscopic changes consistent with the formation of a new Ni(II) acireductone complex. Preliminary studies of the O2 reactivity of this complex are reported.

A força de adesão entre resinas e ligas de metais básicos resulta do embricamento mecânico entre a superfície do metal e a resina e da interação química entre óxidos presentes na superfície dos metais e monômeros adesivos das resinas compostas. A literatura, entretanto, mostra que ainda persistem algumas dúvidas sobre a interação entre os diversos tipos de sistemas adesivos e metais básicos, por isso, essa pesquisa visa: verificar se a presença do Be na composição de ligas a base de Ni-Cr influencia a união metal básico/resina; comparar dois cimentos resinosos adesivos nessa função e verificar a influência da utilização de condicionadores (primers) adesivos metálicos para ligas nobres sobre essa união. Após 2500 termociclos, foram realizados testes de resistência à tração em 160 corpos-de-prova, que consistiam de dois discos de Ni-Cr-Be (Verabond – Aalba Dental Inc., Cordelia, CA-USA) com 6 mm de diâmetro e 2 mm de espessura cimentados entre si, e dois discos de Ni-Cr (Durabond - Odonto Comercial Importadora Ltda, São Paulo, SP), com as mesmas dimensões, cimentados entre si. Foram utilizadas diferentes marcas comerciais de sistemas adesivos: os cimentos resinosos adesivos, Panavia F (Kuraray Co. Ltd.), Bistite II DC (Tokuyama Corp.) e os agente de união (primers adesivos metálicos), Alloy Primer (Kuraray Co. Ltd. ), Metaltite (Tokuyama Corp.) e Cesead Opaque Primer (Kuraray Co. Ltd.). Discos cimentados sem primers serviram como grupo controle. Os resultados mostraram que houve diferença estatisticamente significante entre as duas ligas (Ni-Cr-Be –24,82 ± 7,6 MPa e Ni-Cr - 22,32 ± 7,9 MPa). Já para os cimentos houve superioridade adesiva do cimento Panavia F, que obteve média de resitência adesiva de 27,49 ± 4,8 MPa, sobre o cimento Bistite II, que obteve média de resistência adesiva de 19,63 ± 8,4 MPa. Os primers utilizados não apresentaram influência positiva sobre o Panavia F já que os grupos sem primer para esse cimento obtiveram média de 28,18 ± 5,6 MPa que é equivalente a média dos outros grupos com Panavia. Entretanto, para o cimento Bistite II DC os primers Alloy Primer e Metaltite obtiveram as menores médias, 12,7 ± 7,6 MPa e 15,71 ± 4,8 MPa respectivamente, enquanto sem primer, ou com o Cesead Opaque Primer, as médias foram significantemente superiores, 24.47 ± 6 MPa e 25.70 ± 6,8 Mpa respectivamente. Diante dos resultados conclui-se que os primers adesivos metálicos não potencializaram a adesão de cimentos resinosos adesivos sobre ligas de Ni-Cr. / The bond strength for resin and basic metals comes from the interaction between oxides in the metal surface and adhesive monomers in the composite resins composition. The literature shows that still are some questions about this interaction so this research intends to: verify if the presence of Be at Ni-Cr alloy plays some influence for this union, compare two resin luting cements at this function and study the influence the use of metal primers for noble metals in this mecanism of adhesion. After 2500 thermocycles, tensile bond strength tests were loaded at 160 specimens, which consisted of two metals discs with 6 mm in diameter and 2 mm thick from a Ni-Cr-Be alloy (Verabond – Aalba Dental Inc., Cordelia, CA-USA) bonded togheter and two metal discs from a Ni-Cr alloy (Durabond - Odonto Comercial Importadora Ltda, São Paulo, SP) bonded togheter. Diferent brand adhesive systems were used: the resin cements, Panavia F (Kuraray Co. Ltd.) and Bistite II DC (Tokuyama Corp.) and the metal primers, Alloy Primer (Kuraray Co. Ltd.), Metaltite (Tokuyama Corp.) and Cesead Opaque Primer (Kuraray Co. Ltd.). Nonprimed specimens served as control group. The results indicated that there is statiscal diferences beetwen the two alloys (Ni-Cr-Be –24,82 ± 7,6 MPa e Ni-Cr - 22,32 ± 7,9 MPa). Panavia F had founded greater bond strength (27,49 ± 4,8 MPa) than Bistite DC (19,63 ± 8,4 MPa). The metal primers did not show any positive influence for the Panavia bond strength when we considere that the no primer group had 28,18 ± 5,6 MPa bond strength media which were equivalente to the others Panavia´s groups. However for the Bistite cement, the bond strength for Alloy primer and Metaltite were the lower medias, 12,7 ± 7,6 MPa and 15,71 ± 4,8 MPa respectivally, while the no primer or the Cesead Opaque Primer groups showed superior medias 24,47 ± 6 MPa and 25,70 ± 6,8 MPa respectivally. The outcome of this research shows that the metal primers used did not incresead the bond strength between resin cements and Ni-Cr alloys.