This contribution explores the applicability of nickel-based metallic foams as active electrodes and as electrocatalyst support materials. A comprehensive characterization of Ni and multi-component Ni-based foams is presented and includes the analysis of their structural, chemical, and electrochemical properties. Several materials and surface science techniques as well as electrochemical methods are used to examine the structural characteristics, surface morphology, and surface-chemical composition of these materials. X-ray photoelectron spectroscopy is employed to analyze the surface and near-surface chemical composition. The specific and electrochemically active surface areas (As, Aecsa) are determined using cyclic voltammetry (CV). The foams exhibit structural robustness typical of bulk materials and they have large As, in the 200 – 600 cm2 g–1 range. In addition, they are dual-porosity materials and possess both macro and meso pores. Nickel foam electrodes are applied as electrocatalysts for the oxidation of isopropanol. The process is studied under well-defined experimental conditions using cyclic voltammetry. The outcome of these experiments demonstrates that isopropanol oxidation requires the presence of -NiOOH on the Ni foam electrode. This surface oxide is generated at potentials near the potential of the isopropanol oxidation; however, the two processes do not occur exactly at the same potentials. The Ni foam anodes sustain a current density of ca. 2.6 mA cm–2 throughout an electrolysis time of up to 600 minutes without significant loss of electrocatalytic activity. Isopropanol is converted to acetone at a rate of ca. 5.6 mM per hour. The applicability of Ni foams as support materials for Pt is investigated. Platinum particles are deposited on Ni foam in low loading amounts via the chemical reduction of Pt2+ and Pt4+ originating from aqueous Pt salt solutions. The resulting Pt / Ni foams are characterized using electrochemical, analytical, and materials analysis techniques, including SEM to examine the morphology of the deposited material, CV to evaluate the Aecsa of the deposited Pt, and inductively coupled plasma optical emission spectrometry (ICP-OES) to determine the mass of deposited Pt. The Pt / Ni foams are applied as electrocatalysts for hydrogen evolution, hydrogen reduction, oxygen evolution, and oxygen reduction reactions in alkaline electrolyte. / Thesis (Ph.D, Chemistry) -- Queen's University, 2013-12-06 13:28:17.471

Open celled micro and nano foams fabricated from polymers and metals have attracted tremendous attention in the recent past because of their applications in numerous areas such as catalyst carriers, filtration media, ion exchange membranes and tissue engineering scaffolds. In this study open celled polymer micro- and nano foams with controllable pore size and porosity were fabricated via solid state foaming of immiscible blends. The polymer foams were used as templates for fabricating nickel foams using an ethanol based electroless plating process. Thermal conductivity of micro- and nano foams was studied as a function of pore size and porosity using finite element and molecular dynamics based models. The effect of pore size and porosity on performance of phase change material infiltrated metal foams for thermal management was investigated via numerical models. Open celled micro foams were fabricated via solid state foaming of ethylene acrylic acid (EAA) and polystyrene (PS) co-continuous blends. Blending temperature was the main parameters affecting the formation of co-continuous structure. Gas saturation and foaming studies were performed to determine ideal processing conditions for the blend. The results indicated that saturation pressure and foaming temperature were major process parameters determining the porosity of the foamed samples. Open celled polymer templates were obtained by selective extraction of PS phase using dichloromethane (DCM). Foaming resulted in faster extraction of PS and also in a higher porosity. Open celled nano foams were fabricated via solid state foaming of polyetherimide (PEI) and polyethersulfone (PES). The effect of process parameters namely saturation pressure and temperature, desorption time, and foaming temperature and time on porosity and pore size was studied. A high gas concentration and foaming temperature were required to obtain nano pore-sized foams. Throughout the cross section there existed regions with varying pore size and porosity and solid skins at the surface regions of the foam. A solvent surface dissolution process using dimethylformamide (DMF) was employed to access the internal porous structure. Micro- and nano cellular nickel foams were fabricated from EAA and PES templates via electroless plating. The structure of the nickel foams was an inverse of the polymer templates. Ethanol based electroless plating solutions were used to ensure infiltration into the porous structure because of the small pore sizes. Finite element and molecular dynamics based models were developed to predict thermal conductivity of polymer foams as a function of pore size and porosity. Pore sizes ranging from 1 nm to 1 mm were studied. Models were partially validated using experimental data. The results showed that pore size has significant effect on thermal conductivity even for microcellular and conventional foams. When the pore size is reduced to the nanometer scale, the thermal conductivity of the nano foam dramatically reduces and the value could be lower than that of air for certain porosity levels. The extremely low thermal conductivity of polymer nanofoams is possibly due to increased phonon-phonon scattering in the solid phases of the polymer matrix in addition to low thermal conductivity of gas trapped in nano sized pores. Finite element based models were also developed to study the effect of pore size and porosity on performance of phase change material infiltrated metal foams for thermal management applications. The results showed that foams with smaller pore sizes can delay the temperature rise of the heat source for an extended period of time by rapidly dissipating heat in the phase change material. The lower temperatures resulting from the use of a smaller pore size metal foam could significantly increase the lifetime of IC chips. / text

Cette thèse présente la synthèse de graphène par CVD catalytique sur feuille de cuivre, wafers de silicium revêtus de nickel et sur mousse de nickel. Les dépôts ont été réalisé à partir de méthane et d'éthylène. Pour l'ensemble de ces substrats, les études faites ont permis de mieux appréhender les mécanismes de croissance et de déterminer les paramètres opératoires optimaux. Des tests applicatifs ont été effectué pour utiliser le graphène synthétisé comme électrode d'OLED et de batterie Li-ion. / This study concerns graphene synthesis by catalytic CVD (Chemical Vapor Deposition) on copper foils, silicon wafers coated with nickel and nickel foam. Deposits have been synthesized from methane and ethylene. For the whole substrates studied, the results obtained have allowed to better understand the mechanisms of nucleation/growth of graphene and to determine the optimal operating parameters. Some applicative tests have been performed in the fields of OLED and Li-ion battery.