94,053 research outputs found

    Studies on Bis(imido) molybdenum complexes containing unsaturated hydrocarbon ligands

    No full text
    This thesis describes the synthesis and characterisation of molybdenum bis(imido) complexes containing unsaturated hydrocarbon ligands. A principal objective of the work was to examine the effect of various imido substituents on the coordination number of the complex and the orientations adopted by olefin and acetylene ligands. Chapter One highlights areas of transition metal chemistry relevant to the thesis, with particular emphasis on the psuedo-isolobal analogy between cyclopentadienyl and imido ligands, A convenient one-pot synthesis of molybdenum bis(imido) complexes of the type Mo(NR)(NR')Cl(_2).DME (R=R'=l-adamantyl, 2-t- BUC(_6)H(_4); R=2,6-i-Pr(_2)C(_6)H(_3), R'=t-Bu) is described in Chapter Two. Mo(N-l- adamantyl)(O)Cl(_2).DME has been synthesised, and its structure determined by single crystal X-ray diffraction.- The preparation of olefin complexes Mo(NR)(NR')(C(_2)H(_4))(PMe(_3))n (R=R'=l-adamantyl, n=l; R=R'=2-t-BuC(_6)H(_4), n=2; R=2,6-i-Pr(_2)C(_6)H(_3), R'=t- Bu, n=l) is outlined in Chapter Three. Structural information derived from NMR data has allowed comparison with metallocene-like olefin adducts. Chapter Four describes the synthesis of complexes containing σ-bound phenyl ligands (Mo(NR)(NR')(σ-C(_6)H(_5))(PMe(_3)) (R=R'=l-adamantyl, 2-t-BuC(_6)H(_4); R=2,6-i-Pr(_2)C(_6)H(_3), R'=t-Bu)) as potential precursors to benzyne complexes. Chapter Five describes the preparation of diphenylacetylene complexes Mo(NR)(NR')(PhC=CPh)(PMe(_3)), structural information derived from NMR data allows comparison with previously known metallocene-like acetylene complexes. Full experimental details for Chapters Two to Five are given in Chapter Six

    Synthesis, structural and magnetic properties of TM22+[MOIV(CN)(8)]center dot nH(2)O

    No full text
    Octacyanomolybdates (OCMs) TM2 divided by[Mo(CN)(8)]center dot nHO, where TM is Mn, Fe, Co, Ni, Cu were synthesised and characterised by IR spectroscopy and UV-VIS spectroscopy. The UV-VIS spectrum showed the intervalence charge transfer (IVCT) band between Mo-IV-CN-Cu-II and Mo-V-CN-Cu-I around 510 nm. Studied OCMs adopt tetragonal crystal structure. The H-1 NMR signals reflect the magnetic moment of the TM2- ions (mu(P)). The decay rates of free induction decay (FID) signals increase as pp and the applied static rf-field increases. The spin-lattice relaxation times at 27.7 MHz vary from 0.0187 ins (Mn) up to 0.45 ms (Cu). Magnetization measurements indicate long-range magnetic ordering of Mn- and Co- OCMs with the Curie temperature T-c = 4 K. The remaining OCMs (TM is Fe, Ni, Cu) are paramagnetic down to T = 1.9 K

    The first layered analogue of Sr<sub>2</sub>FeMoO<sub>6</sub>; the structure and electronic properties of Sr<sub>4</sub>FeMoO<sub>8</sub>

    No full text
    The n = 1 Ruddlesden–Popper phase Sr4FeMoO8 has been synthesised by high temperature ceramic methods under reducing conditions. Rietveld refinements of the structure against X-ray and neutron powder diffraction data shows that this phase adopts the space group I4/mmm (a = 3.92962(5), c = 12.6707(2) Å) and contains a crystallographically disordered arrangement of Fe and Mo on the single octahedral site in the structure. Mössbauer spectroscopy data show that iron is in the trivalent state and that the transition metals are fully disordered at a local scale. SQUID magnetometry measurements and low temperature neutron diffraction experiments have been used to examine the magnetic properties of this material. The magnetic susceptibility shows Curie–Weiss paramagnetism above a magnetic transition at 16(1) K. Below this temperature the sample shows magnetic hysteresis, but the neutron diffraction data show no evidence of the additional Bragg intensity associated with the formation of a magnetically ordered phase. The magnetic transition at 16 K is therefore assigned to the formation of a spin-glass phase. The absence of magnetic order in this material is due to the chemical disorder in the Fe/Mo occupancy of the octahedral site and thus the randomisation of the magnetic exchange interactions

    High-temperature oxidation resistance of ternary and quaternary Cr-(Mo)-Si-B2-z coatings — Influence of Mo addition

    No full text
    The Si-based alloying of transition metal diborides is a promising strategy to improve their limited oxidation resistance in high-temperature environments. In this study, we investigate the oxidation resistance of ternary and quaternary Cr-(Mo)-Si-B2-z coatings sputter-deposited from alloyed CrB2/TMSi2 targets (TM = Cr, Mo). The as-deposited Cr-(Mo)-Si-B2-z coatings are stabilized in the single-phased hexagonal AlB2-structure, except the high-Si containing Cr0.26Mo0.11Si0.24B0.39 presenting amorphous character. The Mo-containing Cr-Mo-Si-B2-z films exhibit relatively high hardness compared to their ternary Cr-Si-B2-z counterparts, obtaining up to 26 GPa due to the formation of (Cr,Mo)B2 solid solutions. The Si-alloying in ternary and quaternary coatings provides oxidation resistance up to 1200 °C, owing to the formation of highly protective double-layered scales consisting of SiO2 with a Cr2O3 layer on top, inhibiting oxygen inward diffusion. The quaternary Cr0.31Mo0.07Si0.15B0.47 coating is distinguished by superior oxidation resistance with lower porosity and void formation compared to the ternary Cr0.37Si0.16B0.47. Mo proved to be the key element for the higher stability and enhanced oxidation resistance due to the evolution of the MoSi2 phase at ~600 °C. This phase formation controls the Si diffusion and mobility within the microstructure, thus reducing the porosity and governing the Si supply to form SiO2 scale. The quaternary Cr0.31Mo0.07Si0.15B0.47 coating maintained an oxidation resistance up to 30 h at 1200 °C by forming a 2.5 μm dense amorphous Si-based oxide scale with a thin Cr2O3 on top

    Half-lives of the T-z=1/2 series nuclei, Zr-81 and Mo-86

    No full text
    The nuclei Zr-81 and Mo-85 with T-z = 1/2 have been reinvestigated via The nuclei Zr-81 and Mo-85 with T-z = 1/2 have been reinvestigated vi

    The Benefits of Being Economics Professor A (and not Z)

    No full text
    Alphabetic name ordering on multi-authored academic papers, which is the convention in the economics discipline and various other disciplines, is to the advantage of people whose last name initials are placed early in the alphabet. As it turns out, Professor A, who has been a first author more often than Professor Z, will have published more articles and experienced afaster growth rate over the course of her career as a result of reputation and visibility. Moreover, authors know that name ordering matters and indeed take ordering seriously: Several characteristics of an author group composition determine the decision to deviate from the default alphabetic name order to a significant extent.performance measurement, incentives, economists, name ordering

    High-temperature oxidation resistance of ternary and quaternary Cr-(Mo)-Si-B2-z coatings — Influence of Mo addition

    No full text
    The Si-based alloying of transition metal diborides is a promising strategy to improve their limited oxidation resistance in high-temperature environments. In this study, we investigate the oxidation resistance of ternary and quaternary Cr-(Mo)-Si-B2-z coatings sputter-deposited from alloyed CrB2/TMSi2 targets (TM = Cr, Mo). The asdeposited Cr-(Mo)-Si-B2-z coatings are stabilized in the single-phased hexagonal AlB2-structure, except the high-Si containing Cr0.26Mo0.11Si0.24B0.39 presenting amorphous character. The Mo-containing Cr-Mo-Si-B2-z films exhibit relatively high hardness compared to their ternary Cr-Si-B2-z counterparts, obtaining up to 26 GPa due to the formation of (Cr,Mo)B-2 solid solutions. The Si-alloying in ternary and quaternary coatings provides oxidation resistance up to 1200 degrees C, owing to the formation of highly protective double-layered scales consisting of SiO2 with a Cr2O3 layer on top, inhibiting oxygen inward diffusion. The quaternary Cr0.31Mo0.07Si0.15B0.47 coating is distinguished by superior oxidation resistance with lower porosity and void formation compared to the ternary Cr0.37Si0.16B0.47. Mo proved to be the key element for the higher stability and enhanced oxidation resistance due to the evolution of the MoSi2 phase at similar to 600 degrees C. This phase formation controls the Si diffusion and mobility within the microstructure, thus reducing the porosity and governing the Si supply to form SiO2 scale. The quaternary Cr0.31Mo0.07Si0.15B0.47 coating maintained an oxidation resistance up to 30 h at 1200 degrees C by forming a 2.5 mu m dense amorphous Si-based oxide scale with a thin Cr2O3 on top

    A Review of Creep Deformation and Rupture Mechanisms of Cr-Mo Alloy for the Development of Creep Damage Constitutive Equations under Lower Stress

    No full text
    This paper presents a review of creep deformation and rupture mechanisms of low Cr-Mo alloy for the development of its creep damage constitutive equations under lower stress. The most popular KRH (Kachanov-Robatnov-Hayhurst) formulation was not necessarily developed and calibrated for low stress and can not depict the creep strain accurately under multi-axial state of stress due to the three-dimensional generalization method used. This paper summarizes a critical analysis on the cavity nucleation and growth, and the deformation mechanisms and creep damage evolution characteristics at the temperature ranging for 723 K to 923 K (450 °C to 650 °C), particularly under low stress level (0.2-0.4ογ) in order to form the physical base for the development of creep damage constitutive equation. Moreover, it covers the influence of the stress level, states of stress, and the failure criterion

    Nitretação por plasma de ferro puro enriquecido superficialmente com molibdênio

    No full text
    Dissertação (mestrado) - Universidade Federal de Santa Catarina, Centro Tecnológico. Programa de Pós-Graduação em Ciência e Engenharia de Materiais.Neste trabalho, amostras de ferro puro, sinterizadas e enriquecidas superficialmente com molibdênio via plasma, foram submetidas ao tratamento termoquímico de nitretação por plasma, visando melhorar as propriedades mecânicas na região superficial das amostras. Foram realizados estudos em diferentes condições para tratamento superficial de nitretação por plasma variando-se a mistura gasosa N2-H2 e a temperatura de nitretação. Duas temperaturas de nitretação (450o C e 540o C) e duas concentrações de nitrogênio na mistura nitretante N2-H2 (baixa concentração 5% de N2 e alta concentração 75% de N2) foram empregadas para realização do trabalho. Com a escolha dessas variáveis no processo de nitretação foi possível definir a melhor condição de nitretação para endurecimento da camada enriquecida com Mo. A caracterização microestrutural das camadas enriquecidas e nitretadas foram realizadas por microscopia ótica (MO) e microscopia eletrônica de varredura (MEV) e as fases presentes por difração de raios X (DRX). Testes de microdureza avaliaram o endurecimento das camadas obtidas. Os resultados mostram que ocorre um aumento significativo na dureza da camada enriquecida com molibdênio e nitretada. A presença de Mo na região superficial da amostra leva a formação de microestruturas com diferentes morfologias dependentes da temperatura e do teor de nitrogênio no processo de nitretação. Não foi possível identificar fases relativas à formação de nitretos de molibdênio ou nitretos mistos de Fe-Mo-N nas análises de DRX para as amostras enriquecidas e nitretadas por plasma, mas acredita-se que eles estão presentes devido ao aumento no perfil de microdureza das amostras enriquecidas. Amostras de Mo puro também foram nitretadas nas mesmas condições com a finalidade de comparar as amostras, verificar a formação de MoN e avaliar o comportamento do perfil de microdureza. Este trabalho mostrou que a nitretação de compactados metálicos enriquecidos superficialmente com Mo, melhora a dureza da camada nitretada.In this work, aiming to improve the surface properties, unalloyed iron samples, sintered and enriched superficially with molybdenum by Plasma, were subjected to the thermochemical treatment of nitriding by Plasma. Studies of the nitriding treatments by plasma were carried out in different conditions: varying to gas mixture (H2-N2) and temperature of nitriding. Two different temperatures (450o C and 540o C) and two concentrations of nitrogen in the gas mixture N2-H2 (low concentration 5% of N2 and high concentration 75% N2) were investigated. With the choice of the variables to the realized nitriding process, it was possible to define the best condition of nitriding process to hardening of the molybdenum enriched layer. The surfaces of the samples were characterized by Electronic Scanning Microscopy (SEM). The microstructural characterizations of the enriched and nitrided layers were done by optical microscopy (OM) and SEM and the phases present by X-ray (XRD) diffraction. Tests of hardness were done to assess the properties of layers obtained. The results show that there is a significant increase in the hardness of the nitrided molybdenum enriched surface layer. The presence of Mo in the surface of the samples leads to the formation of microstructures with different morphologies dependents on temperature and nitrogen content used in the nitriding process. It was not possible to identify the formation of molybdenum nitrides phases (MoN) or mixed nitrides (Fe-Mo-N) in the analysis of XRD for the nitrided enriched samples by plasma. In spit of this, it is believed that they are present, due to the increase in the hardness nitrided enriched layer. Samples of unalloyed Mo were also nitrided under the same conditions in order to compare and to verify the formation of MoN and to evaluate the behavior of the microhardness profile. This study showed that nitriding of sintered metals and superficially molybdenum enriched, improves the hardness of the nitrided layer
    corecore