Conventional energetic materials which are based on monomolecular compounds such as trinitrotoluene (TNT) have relatively low volumetric energy density. The energy density can be significantly enhanced by the addition of metal particulates. Among all metals, aluminum is popular because of its high oxidation enthalpy, low cost, and relative safety. Micron-sized aluminum particles, which have relatively high ignition temperatures and burning times, have been most commonly employed. Ignition of micron-sized aluminum particles is typically achieved only upon melting of the oxide shell at 2350 K, thereby resulting in fairly high ignition delay. Novel approaches to reduce the ignition temperatures and burning times and enhance the energy content of the particle are necessary. Recently, there has been an enormous interest in nano-materials due to their unique physicochemical properties such as lower melting and ignition temperatures and shorter burning times. Favorably, tremendous developments in the synthesis technology of nano-materials have also been made in the recent past. Several metal-based energetic materials with nano-sized particles such as nano-thermites, nano-fluids, and metalized solid propellants are being actively studied. The “green” reactive mixture of nano-aluminum particles and water/ice mixture (ALICE) is being explored for various applications such as space and underwater propulsion, hydrogen generation, and fuel-cell technology. Strand burning experiments indicate that the burning rates of nano-aluminum and water mixtures surpass those of common energetic materials such as ammonium dinitramide (ADN), hydrazinium nitroformate (HNF), and cyclotetramethylene tetranitramine (HMX). Sufficient understanding of key physicochemical phenomena is, however, not present. Furthermore, the most critical parameters that dictate the burning rate have not been identified. A multi-zone theoretical framework is established to predict the burning properties and flame structure by solving conservation equations in each zone and enforcing the mass and energy continuities at the interfacial boundaries. An analytical expression for the burning rate is derived and physicochemical parameters that dictate the flame behavior are identified. An attempt is made to elucidate the rate-controlling combustion mechanism. The effect of bi-modal particle size distribution on the burning rate and flame structure are investigated. The results are compared with the experimental data and favorable agreement is achieved. The ignition and combustion characteristics of micron-sized aluminum particles can also be enhanced by replacing the inert alumina layer with favorable metallic coatings such as nickel. Experiments indicate that nickel-coated aluminum particles ignite at temperatures significantly lower than the melting point of the oxide film, 2350 K due to the presence of inter-metallic reactions. Nickel coating is also attractive for nano-sized aluminum particles due to its ability to maximize the active aluminum content. Understanding the thermo-chemical behavior of nickel-aluminum core-shell structured particles is of key importance to both propulsion and material synthesis applications. The current understanding is, however, far from complete. In the present study, molecular dynamics simulations are performed to investigate the melting behavior, diffusion characteristics, and inter-metallic reactions in nickel-coated nano-aluminum particles. Particular emphasis is on the effects of core size and shell thickness on all important phenomena. The properties of nickel-coated aluminum particles and aluminum-coated nickel particles are also compared. Considerable uncertainties pertaining to the ignition characteristics of nano-aluminum particles exist. Aluminum particles can spontaneously burn at room temperature, a phenomenon known as pyrophoricity. This is a major safety issue during particle synthesis, handling, and storage. The critical particle size below which nascent particles are pyrophoric is not well known. Energy balance analysis with accurate evaluation of material properties (including size dependent properties) is performed to estimate the critical particle size for nascent particles. The effect of oxide layer thickness on pyrophoricity of aluminum particles is studied. The ignition delay and ignition temperature of passivated aluminum particles are also calculated. Specific focus is placed on the effect of particle size. An attempt is made to explain the weak dependence of the ignition delay on particle size at nano-scales.

The research presented in this thesis firstly concerns the use of electrochemical techniques to develop approaches to wool processing which have a lower impact on the environment than conventional chemical methods. Wool is a sulfur rich substrate and current methods used in wool processing often rely on sulfur-based reducing agents such as metabisulfite. However, due to increasing concern over the environmental impacts of metabisulfite, alternative methods are of interest. Electrochemical techniques have been applied to the process of wool setting in the presence of thiol setting agents. Wool disulfide bonds are reduced during this process and the thiol setting agent is converted to the disulfide. Efficient conversion of the disulfide back to the thiol setting agent would allow catalytic amounts of thiols to be used in wool setting. The electroreduction of cystine and 2-hydroxyethyl disulfide has been examined at a range of metal and carbon electrodes to find efficient methods of generating the corresponding thiols, cysteine and 2-mercaptoethanol respectively. Gold and silver were identified as the most efficient electrode materials. In industrial wool processing, the use of large-scale metal electrodes is expensive and therefore, high surface area gold and silver nanoparticle electrodes were fabricated by electrochemically depositing the metals onto low-cost carbon substrates. The most efficient electrochemical system for generating the thiol setting agent involved the electroreduction of cystine at the gold nanoparticle electrode and this system was used to successfully demonstrate that wool setting can be achieved using relatively low concentrations of cysteine. Further research was carried out to investigate methods for the controlled preparation of metal nanoparticle electrodes and their utility for detecting hydrogen peroxide was examined. A simple and versatile approach for the preparation of tethered gold nanoparticle assemblies was developed by exploiting electrostatic interactions between citrate-capped gold nanoparticles and amine tether layers attached to carbon surfaces. The nanoparticle assemblies were optimised for the detection of hydrogen peroxide by selecting the size and density of electrostatically assembled nanoparticles. The number of amine functionalities on the surface and the assembly conditions controlled the nanoparticle density. Nanostructured palladium electrodes fabricated using vapour deposition methods to immobilise palladium nanoparticles directly onto carbon substrates were also examined for the electroanalysis of hydrogen peroxide.

Graphene has great potential for energy storage and conversion applications due to its outstanding electrical conductivity, large surface area and chemical stability. However, the pristine graphene offers unsatisfactory performance as a result of several intrinsic limitations such as aggregation and inertness. The functionalization of graphene is considered as a powerful way to modify the physical and chemical properties of graphene, and improve the material performance, which unfortunately still being preliminary and need further knowledge on controllable functionalization methods and the structure-property relationships. This thesis aims to provide in-depth understanding on these aspects. We firstly explored oxygen-functionalized graphene for supercapacitor electrodes. A mild solvothermal method was developed for graphene preparation from the reduction of graphene oxide; the solvent-dependent reduction kinetics is an interesting finding in this method that could be attributed to the solvent-graphene oxide interactions. Using the solvothermal method, oxygen-functionalized graphene with controlled density of oxygen functional groups was prepared by tuning the reduction time. The oxygen-containing groups, primarily phenols and quinones, reduce the graphene aggregation, improve the wetting properties and introduce the pseudocapacitance. Consequently, excellent supercapacitive performance was achieved. Nitrogen-doped graphene was synthesized by the pyrolysis of graphene oxide with nitrogen-containing molecules and used as an electrocatalyst for oxygen reduction reactions. We achieved the structural control of the nitrogen-doped graphene, mainly the content of graphitic nitrogen, by manipulating the pyrolysis temperature and the structure of nitrogen-containing molecules; these experiments help understand the evolution of the bonding configurations of nitrogen dopants during pyrolysis. Superior catalytic activity of the prepared nitrogen-doped graphene was found, due to the enriched content of graphitic nitrogen that is most active for the oxygen reduction reaction. Moreover, we demonstrated a facile strategy of producing superhydrophobic octadecylamine-functionalized graphite oxide films. The long hydrocarbon chain in octadecylamine reduces the surface energy of the graphene oxide film, resulting in a high water contact angle and low hysteresis. The reaction mechanism and the effect of hydrocarbon chain length were systematically investigated. In addition to the researches on graphene-based materials, some results on advanced carbon nanomaterials and polymer composites for electronic packaging will also be discussed as appendix to the thesis. These include carbon nanotube-based capacitive deionizer and gas sensor, and hexagonal boron nitride-epoxy composites for high thermal conductivity underfill.

Microstructure changes that occur during the deformation and heat treatments involved in wrought processing of metals are of central importance in achieving the desired properties or performance characteristics in the finished products. However, thorough understanding of the evolution of microstructure during thermo-mechanical processing of metallic materials is largely hampered by lack of methods for characterizing reliably their local (anisotropic) properties at the sub-micron length scales. Recently, remarkable advances in nanoindentation data analysis techniques have been made which now make it possible to obtain quantitative information about the local mechanical properties of constituent individual grains in polycrystalline metallic samples. In this work, a novel approach that combines mechanical property information obtained from spherical nanoindentation with the complementary structure information measured locally at the indentation site, using Electron Backscattered Diffraction (EBSD), is used to systematically investigate the local structure-property relationships in fcc metals. This work is focused on obtaining insights into the changes in local stored energies of polycrystalline metallic samples as a function of their crystal orientation at increasing deformation levels. Furthermore, using the same approach, the evolution of mechanical properties in the grain boundary regions in these samples is studied in order to better understand the role of such interfaces during deformation and recrystallization processes. The findings provide valuable information regarding development of stored energy gradients in polycrystalline materials during macroscopic deformation.

Freshwater ecosystems will likely become sinks for future silver loadings as a result of increased nanosilver (n-Ag) use in industrial and commercial applications. A series of bioassays was performed to assess how n-Ag toxicity may be influenced by abiotic factors associated with natural freshwater ecosystems. Additionally, these bioassays provide insight into how environmentally relevant concentrations of n-Ag may sublethaly affect the freshwater benthic gastropod, Physa acuta, that plays pivotal roles in maintaining the structure and function of freshwater ecosystems. In sediment with no benthic organic carbon (BOC), gastropod vital rates decreased in treatments containing any n-Ag, gastropods in sediment with relatively low BOC appeared to trade off growth for reproduction at high n-Ag treatments, while gastropod vital rates in high BOC sediment remained unaffected at all nanosilver treatments. Sediment type may abate nanosilver toxicity as a result of organic carbon content. Effects of n-Ag on gastropod vital rates were not dependant on pH, suggesting aqueous pH does not directly influence n-Ag toxicity. Nanosilver (0.2 μg/L) stressed gastropods, altering their growth and reproduction tradeoff dynamics. Nanosilver concentrations modeled to exist in natural freshwaters, disrupted gastropod ability to detect and respond to a natural predator, while greater n-Ag concentrations stimulated gastropods to exhibit contaminant avoidance behavior and thereby attempted to flee their habitat. This study provides direction in understanding how adverse n-Ag effects may be influenced by abiotic parameters, while assessing sublethal effects of n-Ag on freshwater gastropods that are likely to occur in natural freshwater ecosystems, given current estimates of environmental n-Ag concentrations. / Department of Biology

Within recent years, allotropic structures of carbon have been produced in the forms of tubes and ribbons which offer the promise of extraordinary electronic and thermal properties. Here we present analyses of oligophenyl and oligoacene systems–infinite, one-dimensional chains of benzene rings linked along the armchair and zigzag directions. These one-dimensional structures, which are amenable to calculation by analytical means, exhibit features very similar to carbon nanotubes and nanoribbons. Using a tight-binding Hamiltonian we analytically determine the density of states, local density of states, and energy-band structure for the phenyl and the acene. We also examine the effect of disorder on the energies and the corresponding states. / Department of Physics and Astronomy

Titania based electrode materials are promising candidates to replace widely used graphite as negative electrode material in lithium ion batteries (LIB), due to their increased safety, volumetric capacity, and high rate performance.In this thesis different low-cost synthesis approaches are evaluated to prepare nanostructured TiO2 with various phase composition and morphology. The influence of these parameters on its ability to reversibly insert lithium are studied in electrochemical measurements. In this regard we also investigated the effect of aliovalent doping and porous structures on the insertion properties of two main polymorphs of TiO2, Anatase and TiO2(b), revealing encouraging results in overcoming the low charge transfer, which is the main drawback of titanium oxide based materials.In order to understand the mechanism of lithium storage process of the two synthesized TiO2 phases, diffraction and spectroscopic characterization methods were carried out under operando conditions. We show that, regardless of their chemical similarity, both phases reveal very different lithium insertion processes, leading to distinct electrochemical cycling properties.Another field of interest is the adaptation of electrode components to the nanostructured TiO2 active insertion material. The choice of binder, carbon additive, and electrolyte components can have significant impacts on the performance. Especially the origin and prevention of parasitic side reactions were in the focus of our work, as these pose an under estimated hindrance in the application of titania based electrode materials in LIB.

In order to improve the optical losses of spherical silicon solar cells, new fabrication designs were presented. The new device structures are fabricated based on integration of nanostructures into spherical silicon solar cells. These new device structures include: spherical silicon solar cells integrated with nanostructured antireflection coating layers, spherical silicon solar cells with hemispherical nanopit texturing, and cells integrated with colloidal quantum dots. Silicon spheres were characterized by means of transmission electron microscopy (TEM), single-crystal x-ray diffraction and x-ray powder diffraction to establish the crystallinity nature of the silicon spheres. Furthermore, the material properties of silicon spheres including surface morphology, microwave photoconductivity decay lifetime, and impurity elemental distributions were studied. Silicon nitride antireflection coating layers were developed and deposited onto the spherical silicon solar cells, using a PECVD system. A low temperature hydrogenation plasma technique was developed to improve the passivation quality of the spherical silicon solar cells. The spectral response of silicon spheres with and without a silicon nitride antireflection coating was studied. We have successfully developed and integrated a nanostructured antireflection coating layer into spherical silicon solar cells. The nanostructured porous layer consists of graded-size silicon nanocrystals and quantum-size Si nanoparticles embedded in an oxide matrix. This layer has been characterized by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), Scanning tunneling TEM, energy filtered TEM, transmission electron diffraction (TED), electron energy loss spectroscopy (EELS), energy dispersive x-ray (EDX), Raman spectroscopy and photoluminescence spectroscopy (PL). We developed a novel technique of electrochemical etching for silicon surface texturing using a liquid-phase deposition of oxide mask. Using a focus ion-beam (FIB) technique, cross-sectional TEM samples were prepared to investigate the nature of texturing and the composition of the deposited mask. The hemispherical nanopit texturing was successfully integrated into spherical silicon solar cells and the etching mechanisms and the chemical reactions were discussed. CdSe colloidal quantum dots with diameter of about 2.8nm were integrated into a graded-density nanoporous layer. This structure was implemented on the emitter of the spherical silicon solar cells and the spectral response with and without incorporation of QDs was studied.

The optical properties of metallic nanostructures are a subject of considerable fundamental and technological importance due to their coupling to surface plasmons. Plasmonic nanostructures are receiving a great deal of attention for their possible applications. The development of novel methods for nanostructure fabrication and new theoretical approaches for the understanding of their optical properties is making the field of nanophotonics an area of intense current interest. In this work, surface plasmons properties are investigated for three major applications in the field of nanophotonic and plasmonics: photonic integrated circuits, nonlinear optics and chemical/biological sensors. A new method is developed for the analysis of photonic integrated circuits based on surface plasmon polaritons. An analytical expression is presented for the phase of reflection above the critical angle which includes the polarization and mode-shape properties of surface plasmon polaritons. This improves the accuracy of the geometric optics method, while retaining the analyticity of the method. The nonlinear optics involving surface plasmons in nanostructured metals is studied. A non-centrosymmetric nanostructure in gold film is studied comprehensively where aperture shape is chosen to have an apex to increase the local field. A systematic study of the influence of array periodicity and aperture shape is provided. The conditions for maximum second harmonic generation are discussed in terms of local field enhancement, excitation of the localized surface plasmon resonances and the influence of array periodicity. Different metallic nanostructures with biosensors applications are studied. We demonstrate surface plasmon resonance sensing based on the polarization dependence of extraordinary optical transmission through a biaxial nanohole array. The usual spectral diversity of spectrometer-based sensing was replaced with polarization diversity while using a single wavelength laser source and a single array. This is particular useful to the on-going microfluidic integration of nanohole surface plasmon resonance, where it is cost-effective to have an efficient semiconductor laser source and intensity detector. Furthermore, after a substantial fabrication effort to create nanohole array plat-form, we demonstrate flow-through nanohole arrays as combined nanoplasmonic and nanofluidic elements. In this work the fluid is flowed through the holes and shows a six-fold improvement in the binding rate for low concentration samples. This exhibits many features that are particularly promising for sensing technologies.

Mechanical milling (alloying) is one of the non-equilibrium techniques used to prepare alloys with exceptional properties. This technique was employed in this research to develop a new class of Al- and Mg-based nanocomposite alloys using SPEX high energy milling. These nanocomposites are characterized by the dispersion of nanocrystals in an amorphous matrix. Zirconium was added to the Al-Mg alloys for the purpose of promoting glass formability. As-milled samples were annealed at 400°C for 1 hour to investigate the thermal stability of the nanostructure. The phase evolution of the resulting alloys was studied using XRD and TEM/EDS, which showed a strong dependence of the resulting metastable phases on the starting alloys compositions. / The nanocomposite structure was developed at Zr concentrations of 20 and 35 at.% regardless of the Al/Mg ratio and with some traces of oxidation. However, the amount of amorphous phase was varied in each case depending on the Al concentration into the alloy, since in low Al-containing alloys the amount of amorphous phase was less pronounced. It was found that higher Zr concentrations will lead to greater refinement of the nanostructure. These nanocomposites showed improved mechanical properties, in terms of higher hardness values, in addition to improved thermal stability. The improvement in thermal stability was attributed to the presence of Al3Zr which proved to contribute significantly to retarding grain growth via grain boundary pinning. / Additionally, the employment of mechanical alloying was beneficial in producing Al3Zr in the cubic L12 ordered structure which improves the ductility of the alloy. Moreover, the homogeneity ranges of gamma-Al 12Mg17 and Al3Zr were extended significantly due to the nature of the non-equilibrium processing. In this research, the alloy with the maximum hardness was Al40Mg25Zr35, which has an average hardness value close to 780 HV and average crystallite size of about 10 nm. A common observation in the alloys that showed a higher hardness values combined with improved thermal stability, is that they contain higher Al and Zr concentrations. / Le broyage mécanique est une technique hors équilibre qui permet la fabricationde nouveaux alliages avec des propriétés exceptionnelles. Lors de cette recherche, unbroyeur SPEX 8000 a été utilisé pour développer une nouvelle classe denanocomposites à base d'aluminium et de magnésium. Ces nanocomposites tirent leurspécificité de leur dispersion de nanocrystaux dans une matrice amorphe. Duzirconium a été ajouté aux alliages d'aluminium et de magnésium pour promouvoirl'amorphisation. Les échantillons de poudres broyées ont été recuits à 400°C pour 1heure pour évaluer la stabilité thermique des différentes phases. Leur évolution a étécaractérisée par diffraction par rayon-X et par MEBIEDS. TI fut démontré que lesphases métastables obtenues dépendent fortement de la composition des alliages dedépart.