Thesis (Ph.D.)--Drexel University, 2008. / Includes abstract and vita. Includes bibliographical references (leaves 119-139).

[Truncated abstract] In this dissertation an investigation into the utility of mechanochemically synthesized nanopowders for intermediate temperature solid oxide fuel cell components is reported. The results are presented in the following parts: the synthesis and characterisation of precursors for ceramic and cermet components for the fuel cell; the physical and electrical characterisation of the electrolyte and electrodes; and the fabrication, operation and analysis of the resulting fuel cells. Samarium-doped (20 mol%) ceria (SDC) nanopowder was fabricated by the solid-state mechanochemical reaction between SmCl3 with NaOH and Ce(OH)4 in 85 vol% dilution with NaCl. A milling time of 4 hours and heat treatment for 2 hours at 700°C yielded a material with equivalent particle and crystallite sizes of 17 nm. The existence of a complete solid solution was affirmed by electron energy loss spectroscopy and x-ray diffraction analysis. Doped-ceria compacts were sintered for 4 hours at 1350°C forming ceramics of 88% theoretical density. The ionic conductivity in flowing air was 0.009 S/cm, superior to commercially supplied nanoscale SDC. Anode precursor composite NiO-SDC nanopowder was synthesized by milling Ni(OH)2 with the previously defined SDC formulation ... Anode-supported fuel cells were fabricated on a substrate of at least 500 'm 55wt%NiO-SDC with 17vol% graphite pore formers. Suspensions of SDC were deposited by aerosol on the sintered bilayer at a thickness around 5 'm. A cathode of 10% SDC (SmSr)0.5CoO3 was deposited onto the sintered electrolyte and after firing had a thickness of around 25 'm. Operation of fuel cells in single-chamber mixtures of CH4 and air diluted in argon were successful and gave power outputs of 483 'W/cm2. Operation in undiluted 25 vol% CH4:air gave a power output of 5.5 mW/cm2. It was shown that a large polarisation resistance of 4.1 Ω.cm2 existed and this was assigned to losses in the anode, namely mass transport limitation associated with the catalytic combustion of methane and insufficient porosity. The large surface area of Ni appeared to allow more methane to combust and hence prevented its electrochemical reaction from occurring, thus limiting the performance of the cell. The synthesis procedures, ceramic processing and fabrication techniques and testing methods are discussed and contribute significant understanding to the fields of ceramic science and fuel cell technology.

Thesis (M.Sc (Chemistry)) --University of Limpopo, 2013 / Since their discovery in 1991, CNTs have shown extraordinary properties and as result, these materials are being investigated for several different applications. Synthesis and electrochemical application of CNTs for hydrogen storage provide new possibilities for replacement of gasoline use in vehicles due to its cost and negative environmental impact. The study investigated the metal nanoparticles modified multi-walled carbon nanotubes as possible storage material for hydrogen. Herein, carbon nanotubes were successfully synthesized by pyrolysis of iron (II) phthalocyanine under Ar/H2 reducing atmosphere at 900 oC for 30 min. The micro-structural information of the as-prepared carbon nanotubes was examined by Transmission electron microscopy (TEM). It was found that the prepared CNTs were multi-walled with iron particles impurities present on the surface. Synthesized MWCNTs were found to have open tips as shown by TEM images. These materials were purified and functionalized with acid groups as confirmed by Fourier transform infra-red spectroscopy (FTIR). A successful decoration of MWCNTs by Cu, CuO, Fe, Fe2O3, Ni and NiO nanoparticles was confirmed by Scanning electron miscroscopy (SEM) and Transmission electron microscopy (TEM). TEM images showed that metal nanoparticles and metal oxides were well dispersed on the surface of the MWCNTs. The chemical composition of the as-prepared MWCNTs was confirmed by XRD (showing the presence of metal impurities and amorphous carbon). Synthesized materials were applied in electrochemical techniques such as cyclic voltammetry, chronopotentiometry and controlled potential electrolysis. These techniques have shown that modification of glassy carbon bare electrode (GCE) with carbon nanotubes decorated with metal nanoparticles (Cu, Ni and Fe), improves the current density, charge-discharge voltages and discharge capacity for hydrogen storage (in a 6 M KOH aqueous electrolyte). It was shown that MWCNTs exhibit high conductivity, porosity and high surface area for hydrogen storage. The increase in discharge capacity was as follows: GCE < GCE-MWCNT < GCE-MWCNT-M (M = Cu, Ni, Fe and/or metal oxides). This confirmed a successful modification of GCE with MWCNTs and MWCNT-M (M = Cu, Ni, Fe and/or metal oxides). The maximum discharge capacity of 8 nAh/g was obtained by GCE-MWCNTs-Ni electrode, corresponding to an H/C value of 28.32 x 10 It was confirmed that both Ni loading and MWCNTs loading have an impact on the current response, charge-discharge voltages and discharge capacity. A maximum current density and discharge current was reached when a 4wt% nickel was loaded. A decrease in current density and discharge current was observed for nickel loading of higher than 4wt%. Thus suggests a possible decrease in surface area of the adsorbed material on the surface of the electrode for hydrogen storage. As more MWCNTs were added, a decrease in current density was observed. A 2wt% MWCNTs gave higher discharge current and this was possibly due to less hindrance on the surface of the electrode for hydrogen to diffuse. It was shown that calcining the metal nanoparticles result in particles agglomeration, as confirmed by Transmision electron microscopy (TEM). This resulted in a decrease in surface area of the working electrode. A low current response was observed compared to the uncalcined Ni nanoparticles. The highest exchange current density was obtained while using a GCE-MWCNT-Nical as compared to the GCE-MWCNT-Niuncal electrode. The applied discharge current in CPE was also shown to have influence on the discharge capacity. An increase in discharge capacity for the GCE-MWCNT-Ni (2wt% MWCNTs and 4wt% Ni) electrode was observed as more discharge current was applied. A decrease in discharge capacity for hydrogen was observed as more content of the MWCNT-Niuncal nanocomposite are added on the active surface area of the glassy carbon electrode.

This investigation is focused on the understanding of mechanical and chemical reaction behaviors of stoichiometric mixtures of nano- and micro-scale aluminum and hematite (Fe2O3) powders dispersed in epoxy. Epoxy-cast Al+Fe2O3 thermite composites are an example of a structural energetic material that can simultaneously release energy while providing structural strength. The structural and energetic response of this material system is investigated by characterizing the mechanical behavior under high-strain rate and shock loading conditions. The mechanical response and reaction behavior are closely interlinked through deformation characteristics. It is, therefore, desirable to understand the deformation behavior up to and beyond failure and establish the necessary stress and strain states required for initiating chemical reactions. The composite s behavior has been altered by changing two main processing parameters; the reactants particle size and the relative volume fraction of the epoxy matrix. This study also establishes processing techniques necessary for incorporating nanometric-scale reactants into energetic material systems. The mechanochemical behavior of epoxy-cast Al+Fe2O3 composites and the influence of epoxy volume fraction have been evaluated for a variety of loading conditions over a broad range of strain rates, which include low-strain rate or quasistatic loading experiments (10-4 to 10-2 1/s), medium-strain rate Charpy and Taylor impacts (103 to 104 1/s), and high-strain rate parallel-plate impacts (105 to 106 1/s). In general, structural strength and toughness have been observed to improve as the volume fraction of epoxy decreases, regardless of the loading strain rate regime explored. Hugoniot experiments show damage occurring at approximately the same critical impact stress for compositions prepared with significantly different volume fractions of the epoxy binder phase. Additionally, Taylor impact experiments have indicated evidence for strain-induced chemical reactions, which subject the composite to large shear accompanied by temperature increase and associated softening, preceding these reactions. Overall, the work aims to establish an understanding of the microstructural influence on mechanical behavior and chemical reactivity exhibited by epoxy-cast Al+Fe2O3 materials when exposed to high stress and high-strain loading conditions. The understanding of fundamental aspects and the results of impact experiment measurements provide information needed for the design of structural energetic materials.