SOUSA, J.B. Estudo da influência dos parâmetros operacionais na eletrodeposição de camadas eletrocatalíticas de ligas de Ni-Fe. 2007. 67 f. Dissertação (Mestrado em Ciências Química Inorgânica) – Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2007. / Submitted by irlana araujo (irlanaaraujo@gmail.com) on 2011-12-29T12:48:00Z No. of bitstreams: 1 2007_dis_Jos_Sousa.pdf: 1996703 bytes, checksum: cd18632d3c46b27ffca6accdda448896 (MD5) / Approved for entry into archive by Aline Nascimento(vieiraaline@yahoo.com.br) on 2012-02-14T14:33:02Z (GMT) No. of bitstreams: 1 2007_dis_Jos_Sousa.pdf: 1996703 bytes, checksum: cd18632d3c46b27ffca6accdda448896 (MD5) / Made available in DSpace on 2012-02-14T14:33:02Z (GMT). No. of bitstreams: 1 2007_dis_Jos_Sousa.pdf: 1996703 bytes, checksum: cd18632d3c46b27ffca6accdda448896 (MD5) Previous issue date: 2007-07-13 / The present work shows the study of the ultrasound irradiation influence in the electrodeposition of Ni-Fe coatings. The electrocatalytic performance of these coatings for the hydrogen evolution reaction (her) in alkaline medium was also evaluated. The Ni-Fe coatings were obtained from plating solutions containing 0.06 mol.dm-3 Ni2SO4.6H2O, 0.48 mol.dm-3 Na3C3H5O7.2H2O, 0.71 mol.dm-3 Na2CO3 and 0.16 mol.dm-3 (bath 1) and 0.04 mol.dm-3 FeSO4.7H2O (bath 2). It was also added 8.4 mL L-1 H2SO4 to maintain the pH below 1. The electrodepositions were carried out under galvanostatic control in the range of 10 mA cm-2 to 50 mA cm-2, at room temperature (≈ 28ºC) and at 55ºC in the presence and in the absence of ultrasound irradiation. All coatings were deposited on disk mild steel substrate with an exposed geometric area of 0.7 cm2. The hydrogen evolution reaction was studied in 0.5 mol.dm-3 NaOH. In all electrochemical experiments Pt was the auxiliary electrode and Hg/HgO, OH- (0,5 mol.dm-3) was the reference one. The coatings ware characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV) and the electrocatalytic properties of the Ni-Fe coating were evaluated by Tafel polarization and long-term performance tests. The results showed that the use of the ultrasound irradiation leads to an increase of the Fe content in the electrodeposits. Additionally, the coatings obtained in presence of ultrasound also present the best performance for her. / O presente trabalho mostra o estudo da influência da radiação de ultra-som sobre a eletrodeposição de ligas de Ni-Fe. Foram avaliados a estabilidade e o desempenho eletrocatalítico das ligas para a Reação de Desprendimento de Hidrogênio (RDH) em meio alcalino. As ligas eletrodepositadas de Ni-Fe foram obtidas em solução 0,06 mol.dm-3 de Ni2SO4.6H2O, 0,48 mol.dm-3 de Na3C3H5O7.2H2O, 0,71 mol.dm-3 de Na2CO3 e 0,16 mol.dm-3 (banho 1) e 0,04 mol.dm-3 de FeSO4.7H2O (banho 2). Foi adicionado 8,4 mL.L-1 de H2SO4 para manter o pH abaixo de 1. A eletrodeposição foi realizada sob controle galvanostático variando-se a densidade de corrente de 10 mA.cm-2 a 50 mA.cm-2, na temperatura ambiente (≡ 28ºC) e de 55ºC na presença e na ausência da radiação de ultra-som. Todos os revestimentos foram depositados em um disco de aço-carbono com área geométrica exposta de 0,7 cm2. A RDH foi estudada em solução de NaOH 0,5 mol.dm-3. Foi utilizada para todos os experimentos o eletrodo auxiliar de Pt e o eletrodo de referência de Hg/HgO, OH- (0,5 mol.dm-3). Os revestimentos foram caracterizados por Microscopia Eletrônica de Varredura (MEV), Voltametria Cíclica (VC) e as propriedades eletrocatalíticas das ligas de Ni-Fe foram avaliadas por Curva de Polarização de Tafel e por Operação Contínua. Os resultados mostraram que o ultra-som aumentou a quantidade de Fe eletrodepositada e as ligas obtidas sob a ação da radiação de ultra-som apresentaram o melhor desempenho para a RDH.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / O presente trabalho mostra o estudo da influÃncia da radiaÃÃo de ultra-som sobre a eletrodeposiÃÃo de ligas de Ni-Fe. Foram avaliados a estabilidade e o desempenho eletrocatalÃtico das ligas para a ReaÃÃo de Desprendimento de HidrogÃnio (RDH) em meio alcalino. As ligas eletrodepositadas de Ni-Fe foram obtidas em soluÃÃo 0,06 mol.dm-3 de Ni2SO4.6H2O, 0,48 mol.dm-3 de Na3C3H5O7.2H2O, 0,71 mol.dm-3 de Na2CO3 e 0,16 mol.dm-3 (banho 1) e 0,04 mol.dm-3 de FeSO4.7H2O (banho 2). Foi adicionado 8,4 mL.L-1 de H2SO4 para manter o pH abaixo de 1. A eletrodeposiÃÃo foi realizada sob controle galvanostÃtico variando-se a densidade de corrente de 10 mA.cm-2 a 50 mA.cm-2, na temperatura ambiente (≡ 28ÂC) e de 55ÂC na presenÃa e na ausÃncia da radiaÃÃo de ultra-som. Todos os revestimentos foram depositados em um disco de aÃo-carbono com Ãrea geomÃtrica exposta de 0,7 cm2. A RDH foi estudada em soluÃÃo de NaOH 0,5 mol.dm-3. Foi utilizada para todos os experimentos o eletrodo auxiliar de Pt e o eletrodo de referÃncia de Hg/HgO, OH- (0,5 mol.dm-3). Os revestimentos foram caracterizados por Microscopia EletrÃnica de Varredura (MEV), Voltametria CÃclica (VC) e as propriedades eletrocatalÃticas das ligas de Ni-Fe foram avaliadas por Curva de PolarizaÃÃo de Tafel e por OperaÃÃo ContÃnua. Os resultados mostraram que o ultra-som aumentou a quantidade de Fe eletrodepositada e as ligas obtidas sob a aÃÃo da radiaÃÃo de ultra-som apresentaram o melhor desempenho para a RDH. / The present work shows the study of the ultrasound irradiation influence in the electrodeposition of Ni-Fe coatings. The electrocatalytic performance of these coatings for the hydrogen evolution reaction (her) in alkaline medium was also evaluated. The Ni-Fe coatings were obtained from plating solutions containing 0.06 mol.dm-3 Ni2SO4.6H2O, 0.48 mol.dm-3 Na3C3H5O7.2H2O, 0.71 mol.dm-3 Na2CO3 and 0.16 mol.dm-3 (bath 1) and 0.04 mol.dm-3 FeSO4.7H2O (bath 2). It was also added 8.4 mL L-1 H2SO4 to maintain the pH below 1. The electrodepositions were carried out under galvanostatic control in the range of 10 mA cm-2 to 50 mA cm-2, at room temperature (≈ 28ÂC) and at 55ÂC in the presence and in the absence of ultrasound irradiation. All coatings were deposited on disk mild steel substrate with an exposed geometric area of 0.7 cm2. The hydrogen evolution reaction was studied in 0.5 mol.dm-3 NaOH. In all electrochemical experiments Pt was the auxiliary electrode and Hg/HgO, OH- (0,5 mol.dm-3) was the reference one. The coatings ware characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV) and the electrocatalytic properties of the Ni-Fe coating were evaluated by Tafel polarization and long-term performance tests. The results showed that the use of the ultrasound irradiation leads to an increase of the Fe content in the electrodeposits. Additionally, the coatings obtained in presence of ultrasound also present the best performance for her.

The purpose of this thesis is to effectively model the time history of the temperature distribution during the selective laser sintering process and use this information to investigate the resulting relative density. The temperature is a critical parameter of the process because it directly effects the overall quality of the part. First, an efficient, affordable, and reliable simulation was developed within the finite element software, Abaqus. Next, the results from the simulations were compared to the experimental results performed by Wang et al. (2016). The FEA model consisted of a 3 layer simulation. Multiple simulations at various laser recipes were conducted using W-Ni-Fe as the powder material. The P/v (laser power/scanning speed) was plotted against the resulting total time above the melting temperature for various simulation. It was concluded that a linear relationship exists between the P/v parameters used in the laser recipe and the resulting time above the melting temperature. The average R2 values for the W-Ni-Fe simulations for layer 1, 2, 3 were 0.962, 0.950, and 0.939, respectively. Additionally, the experimental results from the Wang et al. (2016) study confirmed that a linear relationship is present. Thus, it can be concluded that the P/v parameters used within the laser recipe has a direct relation to the resulting relative density of the SLS part.

Es konnte eine Grundsatzbestätigung des Reaktionsprinzips zur Bildung eines Ni–CO22–-Adduktes durch Deprotonierung eines Ni-Formiat-Komplexes erreicht und die Stöchiometrie dieser Reaktion aufgeklärt werden. Das gebildete Ni–CO22–-Addukt ist ein strukturelles und funktionelles Modell des Ni–CO22–-Adduktes der Ni,Fe-CODH. Durch Isotopenmarkierung und die Untersuchung der Umsetzung mit CO2 konnte außerdem die Beteiligung eines analogen Ni–CO22–-Intermediates in der Reduktion von CO2 an Ni0-Komplexen gezeigt und der Reaktionsmechanismus aufgeklärt werden. Im zweiten Teil wird die quantitative Bildung von CO aus dem Ni–CO22–-Addukt beschrieben. Außerdem konnten die verwandten Na+- und K+-Komplexe dargestellt und Struktur-Reaktivitäts-Beziehungen abgeleitet werden. Durch Einsatz substöchiometrischer Mengen des Gegenions K+ konnte kontrolliert Ni(I)- und CO2•–-Chemie ausgelöst werden. Es kam zur Bildung eines Ni(I)-Formiat- und eines Ni-Oxalat-Komplexes; bei hohen Konzentrationen entstand sogar ein gemischter Ni-Oxalat-Mesoxalat-Komplex. Die Bildung von Mesoxalat (C3O64-) aus einzelnen CO2-Bausteinen war bisher nur postuliert worden. Im dritten Teil wurde ein Ni(II)-Vorläuferkomplex jeweils mit Cobaltocen oder Decamethylcobaltocen reduziert. Es konnten die entsprechenden NiI-Verbindungen mit Cobaltocenium-Gegenionen als Feststoffe charakterisiert werden. Wurden jedoch Lösungen der entsprechenden Verbindungen untersucht, zeigte sich im Falle des Komplexes mit Cobaltoceneinheit, dass ein Redox-Gleichgewicht vorliegt, welches bei Raumtemperatur weit auf der Seite der Ausgangsverbindungen liegt und nicht den Nachweis der charakteristischen spektroskopischen Eigenschaften von Ni(I)-Verbindungen zulässt. Dennoch reagiert die Verbindung aus dem Gleichgewicht heraus mit CO2 und als Produkt wurde ein mononuklearer Ni-Carbonat-Komplex identifiziert. / A confirmation of the reaction principle for the formation of a Ni-CO22- adduct by deprotonation of a Ni formate complex was achieved and the stoichiometry of this reaction was elucidated. The Ni-CO22- adduct formed is a structural and functional model of the Ni-CO22- adduct of Ni,Fe-CODH. Isotopic labelling and investigation of the reaction with CO2 also revealed the involvement of an analogous Ni-CO22- intermediate in the reduction of CO2 on Ni0 complexes and elucidated the reaction mechanism. In the second part, the quantitative formation of CO from the Ni-CO22- adduct is described. Furthermore, the related Na+- and K+-complexes could be obtained and structure-reactivity relationships could be derived. By using sub-stoichiometric amounts of the counterion K+, Ni(I) and CO2-- chemistry could be triggered in a controlled manner. A Ni(I)-formate and a Ni--oxalate complex were formed; at high concentrations even a mixed Ni--oxalate-mesoxalate complex was formed. The formation of mesoxalate (C3O64-) from individual CO2 building blocks had previously only been postulated. In the third part, a Ni(II) precursor complex was reduced with cobaltocene or decamethylcobaltocene, respectively. It was possible to characterise the corresponding NiI compounds with cobaltocenium counterions as solids. When solutions of the corresponding compounds were examined, it was shown in the case of the complex with cobaltocenium unit that a redox equilibrium exists which is far on the side of the parent compounds at room temperature and does not allow the detection of the characteristic spectroscopic properties of Ni(I) compounds. Nevertheless, the compound reacts out of equilibrium with CO2 and a mononuclear Ni-carbonate complex was identified as the product.

<p>This research study has been devoted to the study of magnetic properties and magnetic transport of nanocrystalline Ni and Ni-15% Fe alloys consisting of randomly oriented grains with an average size of 23 and 12 (nm), respectively. The structures of the deposits were confirmed by the XRD analysis using Rietveld refinement technique. The as-deposited Ni and Ni-15%Fe sample was comprised exclusively of the γ phase with lattice parameter of 3.5270 (nm) and 3.5424 (nm), respectively. The small increase in lattice parameter was attributed to the replacement of iron solutes in the Ni sites in lattice. Texture analysis of nanocrystalline Ni and Ni-15%Fe revealed that textures components of both materials is qualitatively the same and vary in terms of volume fraction. Both material showed strong <100> fibre texture with some contribution of the <111> component. The calculated volume fraction of the <100> and <111> components were respectively 17.157% and 3.201% for Ni and, 22.032% and 6.160% for Ni-15%Fe and the rest being confined to the random texture.</p> <p>Magnetic measurements show that all samples exhibit low loss hysteresis loops with high permeabilities. The presence of 15%Fe in Ni leads to enhancement of the saturation magnetization (M_s) regardless of the direction of the applied field. M_s shows an increase from 60.169 (emu/gr) in nanocrystalline Ni to 93.67 (emu/gr) in Ni-15%Fe sample at T=2K. No strong temperature–dependence of the magnetization was observed for samples, but the magnetization of the Ni-15%Fe samples at T=2K were slightly higher than that of T=298K. The coercivity values of nanocrystalline Ni-15%Fe were in all cases smaller than that of nanocrystalline Ni samples. Good agreement between random anisotropy model (RAM) theory and experiment for nanocrystalline Ni and Ni-15%Fe samples was observed. The ferromagnetic exchange length (L_ex) was larger than the average grain size (D) for samples at all times. The effective magnetic anisotropy constants (K_eff) of the nanocrystalline Ni and Ni-15%Fe alloys were measured using the law of approach to saturation. At T=2K, the K_eff of Ni-15%Fe samples were measured to be 1.7037´10⁵ (erg/cm³) and 2.71996 ´10⁵ (erg/cm³) at field parallel and perpendicular, respectively. These values were almost half of the values obtained for nanocrystalline Ni samples 4.66091´10⁵ (erg/cm³) and 4.19703´10⁵ (erg/cm³). Temperature dependence measurements showed that K_eff constants decrease with increasing temperature. The angular dependence MR studies on nanocrystalline Ni and Ni-15%Fe resulted in a twofold, and a fourfold symmetric behaviour, respectively. The field dependence MR measured at various sample tilt with respect to the applied field, showed various trends from pure positive MR to pure negative MR, which partially could be explained by magnetocrystalline anisotropy of the samples.</p> / Master of Applied Science (MASc)

The martensite and magnetic transformations in Ni-Fe-Ga ferromagnetic shape memory alloys are very sensitive to both alloy chemistry and thermal history. A series of Ni-Fe-Ga alloys near the prototype Heusler composition (X2YZ) were fabricated and homogenized at 1423 °K, and a Ni₅₃Fe₁₉Ga₂₈ alloy was subsequently annealed at various temperatures below and above the B2/L21 ordering temperature. Calorimetry and magnetometry were employed to measure the martensite transformation temperatures and Curie temperatures. Compositional variations of only a few atomic percent result in martensite start temperatures and Curie temperatures that differ by about 230 °K degrees and 35 °K degrees, respectively. Various one-hour anneals of the Ni₅₃Fe₁₉Ga₂₈ alloy shift the martensite start temperature and the Curie temperature by almost 70 °K degrees. Transmission electron microscopy investigations were conducted on the annealed Ni₅₃Fe₁₉Ga₂₈ alloy. The considerable variations in the martensite and magnetic transformations in these alloys are discussed in terms of microstructural differences resulting from alloy chemistry and heat treatments. The phase-field method has been successfully employed during the past ten years to simulate a wide variety of microstructural evolution in materials. Phase-field computational models describe the microstructure of a material by using a set of field variables whose evolution is governed by thermodynamic functionals and kinetic continuum equations. A two dimensional phase-field model that demonstrates the ferromagnetic shape memory effect in Ni2MnGa is presented. Free energy functionals are based on the phase-field microelasticity and micromagnetic theories; they account for energy contributions from martensite variant boundaries, elastic strain, applied stress, magnetocrystalline anisotropy, magnetic domain walls, magnetostatic potential, and applied magnetic fields. The time-dependent Ginzburg-Landau and Landau-Lifshitz kinetic continuum equations are employed to track the microstructural and magnetic responses in ferromagnetic shape memory alloys to applied stress and magnetic fields. The model results show expected microstructural responses to these applied fields and could be potentially utilized to generate quantitative predictions of the ferromagnetic shape memory effect in these alloys. / Ph. D.

The aim of my diploma thesis was to explore the influence of manganese ions put into nickel nitrate structure. The attention was focused mainly on the stabilization of nickel nitrate a modification, which could not change into b modification. The theoretical part of my thesis focused on applied materials, kinds of acumulators, basic parameters of acumulators and the description of chosen methods of measurement employed. It contained the electrodeposition, the impedance spectroscopy and the cyclic voltammetry. The task of the experimental part was to measure the effect of manganese ions put into potassium hydroxide structure. Proportions of Ni (nickel nitrate) : Mn (manganese nitrate) 10:0, 7:3, 5:5, 6:1 and 6:4 were blended for the measurement. By means of the electrodeposition, there was a thin layer of nickel hydroxide with an admixture of manganese ions from nickel nitrate and manganese nitrate dilution put on the nickel plate. After the spread of the thin layer on the nickel plate, the measurement by the method of cyclic voltammetry followed. The next task consisted in trying to add KOH (potassium hydroxide) anionic and cationic surfactant into the dilution.