This study was to investigate the reaction behavior of nanoscale [Fe3O4]MgO and trichlorothylene (TCE) in aqueous solutions. In addition, effects of environmental variables on TCE removal from a simulated groundwater system were investigated. At first, two types of metal oxide composites containing both nanoscale Fe3O4 and MgO (designated H-[Fe3O4]MgO and S-[Fe3O4]MgO, respectively) were prepared. Then they were characterized and verified by various apparatuses and methods including X-ray diffractometry, scanning electron microscopy, transmission electron microscopy, specific surface area measurements. Since the substrate of S-[Fe3O4]MgO with a molar ratio of Fe3O4/MgO = 1/5 (designated S1/5-[Fe3O4]MgO) had a much greater specific surface area than that of the substrate of S-[Fe3O4]MgO with a molar ratio of Fe3O4/MgO = 5/5 (designated S5/5-[Fe3O4]MgO), S1/5-[Fe3O4]MgO was selected as the model composite for the treatment of TCE in this study. Results of batch tests showed that S1/5-[Fe3O4]MgO had the best treatment performance among various metal oxides and their composites. For an initial TCE concentration of 10 mg/L, however, only 45% removal could be achieved by 5.0 g/L of dispersed S1/5-[Fe3O4]MgO. Nevertheless, a greater removal efficiency could be obtained for a higher initial TCE concentration in a simulated groundwater system. Test results also showed that a lower temperature and higher pH would retard the relevant reaction rates in TCE removal. In the simulated groundwater system employed in this work, the existence of humic acid (< 10 mg/L) played an insignificant role in affecting the TCE removal. Analysis of TCE adsorption on S1/5-[Fe3O4]MgO in aqueous solution indicated that a Langmuir-type of chemical adsorption would have a better fit. Results of gas chromatography further showed the existence of small to trace amounts of TCE degradation products including cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, vinyl chloride, ethene and methane, etc. Thus, the relevant reaction mechanisms and pathways for the destructive adsorption were proposed.

This study was to investigate the reaction behavior of laboratory-prepared nanoscale adsorbents (Fe3O4 and H-[Fe3O4]MgO) and inorganic pollutants (NO3-, Cd2+and Cr6+) in simulated groundwater. First, Fe3O4 and the composites of nanoscale Fe3O4 and MgO were prepared using chemical co-precipitation method. Then they were characterized and verified by various apparatuses and methods including X-ray diffractometry, scanning electron microscopy, Zetasizer, and specific surface area measurements. Second, the nanoscale adsorbents were used to adsorb inorganic pollutants in simulated groundwater of different conditions. The relevant reaction behavior and mechanisms were also investigated. Results of this research showed that Fe3O4 and H-[Fe3O4]MgO had the greater adsorption amount when the initial concentration of inorganic pollutants was higher than lower. The adsorption rate of inorganic pollutants at 28¢J was greater than that of at 18¢J. The experimental results also showed that at a higher pH environment or the existence of humic acid in simulated groundwater would increase the removal efficiency of Cd2+, but decrease the removal efficiency of NO3- and Cr6+. Analysis of inorganic pollutants adsorption on nanoscale adsorbents in simulated groundwater indicated that a Langmuir-type of chemical adsorption and pseudo-second-order reaction kinetic equation would have better fit. In this study, it was also found that nanoscale adsorbents not only adsorbed inorganic pollutants but also reduced NO3- and Cr6+ to NO2-, NH4+, and Cr3+ at pH=3, respectively. Thus, the nanoscale adsorbents (Fe3O4 and H-[Fe3O4]MgO) prepared and were capable of reductively adsorbing inorganic pollutants (e.g., NO3- and Cr6+) for environmental remediation.

This thesis addresses the evolution of nanoscale ripple patterns on solid surfaces during low-energy ion sputtering. Particular attention is paid to the long-time regime in which the surface evolution is dominated by nonlinear processes. This is explored in simulation and experiment. In numerical simulations, the influence of anisotropy on the evolution of the surface patterns in the anisotropic stochastic Kuramoto-Sivashinsky (KS) equation with and without damping is studied. For a strong nonlinear anisotropy, a 90 rotation of the initial ripple pattern is observed and explained by anisotropic renormalization properties of the anisotropic KS equation. This explanation is supported by comparison with analytical predictions. In contrast to the isotropic stochastic KS equation, interrupted ripple coarsening is found in the presence of low damping. This coarsening seems to be a nonlinear anisotropy effect that occurs only in a narrow range of the nonlinear anisotropy parameter. Ex-situ atomic force microscopy (AFM) investigations of Si(100) surfaces sputtered with sub-keV Ar ions under oblique ion incidence show the formation of a periodic ripple pattern. This pattern is oriented normal to the direction of the ion beam and has a periodicity well below 100 nm. With increasing ion fluence, the ripple pattern is superposed by larger corrugations that form another quasi-periodic pattern at high fluences. This ripple-like pattern is oriented parallel to the direction of the ion beam and has a periodicity of around one micrometer. Interrupted wavelength coarsening is observed for both patterns. A dynamic scaling analysis of the AFM images shows the appearance of anisotropic scaling at large lateral scales and high fluences. Based on comparison with the predictions of different nonlinear continuum models, the recent hydrodynamic model of ion erosion, a generalization of the anisotropic KS equation, is considered as a potentially powerful continuum description of this experiment. In further in-situ experiments, the dependence of the dynamic scaling behavior of the sputtered Si surface on small variations of the angle of incidence is investigated by grazing incidence small angle X-ray scattering (GISAXS). A transition from strongly anisotropic to isotropic scaling is observed. This indicates the presence of at least two fixed points in the system, an anisotropic and an isotropic one. The dynamic scaling exponents of the isotropic fixed point are in reasonable agreement with those of the Kardar-Parisi-Zhang (KPZ) equation. It remains to be seen whether the hydrodynamic model is able to show such a transition from anisotropic to isotropic KPZ-like scaling.

We use normal mode decomposition to obtain phonon properties from quasi-harmonic lattice dynamics calculations and classical molecular dynamics simulations in unstrained Lennard-Jones argon superlattices with perfect and mixed interfaces. Debye scaling of phonon lifetimes at low frequencies in both perfect and mixed superlattices and Rayleigh scaling for intermediate frequencies in mixed superlattices is observed. For short period mixed superlattices, lifetimes below the Ioffe-Regel limit are observed. The relaxation-time approximation of the Boltzmann transport equation is used to predict cross-plane and in-plane thermal conductivity. We find that using a dispersion relation which includes the secondary periodicity is required to predict thermal conductivity. The assumption of perturbative disorder, where Tamura elastic mass defect scattering theory can be applied, was found to be valid for predicting cross-plane thermal conductivities but not in-plane thermal conductivities in mixed superlattices.

Steps on surfaces have long been explored for their own sake, and exploited as growth mediators. However, another type of linear surface defect - the domain boundary - has been largely neglected. Here we introduce domain boundaries of the 5x5 dimer-adatom-stacking fault reconstruction, explore their properties and demonstrate that they too can be used to mediate growth in a useful manner. When a thin layer of Ge is grown on Si(111) lattice strain induces the overlayer to reconstruct as Ge5x5. Using solid phase epitaxy, many domains of 5x5 can be grown. The domain interiors have excellent order, and with careful annealing, the boundaries that separate them are straight and uniform. Well-ordered boundaries propagate along the two high symmetry directions <1 -1> or <1 1> and are called A-type or B-type respectively. Boundaries of the second type are unique to Ge5x5. Registration with the substrate restricts the misfit between domains to discrete possibilities which are labeled according to a modified version of the system used for domain boundaries of Si(111)7x7. The distribution of observed boundary types is strongly peaked and reflects the relative energies of boundaries of different character. The expanded labeling scheme can be used to sketch the kinetic processes which lead to the distribution peaks. The dominant boundary by far is the one known as B[-2 2], which accounts for almost half of all observed boundaries. The atomic structure for this type of boundary has been established as a truncated 7x7 unit cell. Thus, these boundaries are linear arrays of quasi-7x7 embedded in a sea of 5x5. On the Si(111)7x7 surface the Group 13 elements, when deposited at sub-ML coverages and low temperatures, form magic clusters. The perfect uniformity and precise registration that earns them the moniker ‘magic’ make these clusters unusual among self-organized atomic scale objects. The clusters that form on 5x5 lack the uniformity of their counterparts on 7x7. However, with many domains, deposited In or Ga segregate to the quasi-7x7 B[-2 2] boundaries and there form magic clusters. The boundary thus acts as a template for growing straight lines of precisely spaced, atomically identical, nanoscale clusters. / Thesis (Ph.D, Physics, Engineering Physics and Astronomy) -- Queen's University, 2009-07-29 08:50:16.874

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This thesis describes a novel concept for a field-effect transistor based on metallic channels. Latest research demonstrates that the bulk (3D) properties of many materials begin to change when confined to 2D sheets, or 1D nanowires. Particularly, the bandgap increases and the density of states decreases. In this work, this effect is explored further to demonstrate its application to field-effect transistors. Certain metals such as Gold and Silver in these dimensions have extremely low density of states in particular energy regions and through gate modulation can be partially depleted from electrons thus creating conditions for field-effect. A simulation study of Gold channel FET demonstrates ION/IOFF of 30 and superior current driving capability compared to the state-of-the art 22nm SiGe ETSOI as well as 30nm nanotube transistors.

This thesis describes a novel concept for a field-effect transistor based on metallic channels. Latest research demonstrates that the bulk (3D) properties of many materials begin to change when confined to 2D sheets, or 1D nanowires. Particularly, the bandgap increases and the density of states decreases. In this work, this effect is explored further to demonstrate its application to field-effect transistors. Certain metals such as Gold and Silver in these dimensions have extremely low density of states in particular energy regions and through gate modulation can be partially depleted from electrons thus creating conditions for field-effect. A simulation study of Gold channel FET demonstrates ION/IOFF of 30 and superior current driving capability compared to the state-of-the art 22nm SiGe ETSOI as well as 30nm nanotube transistors.

We use normal mode decomposition to obtain phonon properties from quasi-harmonic lattice dynamics calculations and classical molecular dynamics simulations in unstrained Lennard-Jones argon superlattices with perfect and mixed interfaces. Debye scaling of phonon lifetimes at low frequencies in both perfect and mixed superlattices and Rayleigh scaling for intermediate frequencies in mixed superlattices is observed. For short period mixed superlattices, lifetimes below the Ioffe-Regel limit are observed. The relaxation-time approximation of the Boltzmann transport equation is used to predict cross-plane and in-plane thermal conductivity. We find that using a dispersion relation which includes the secondary periodicity is required to predict thermal conductivity. The assumption of perturbative disorder, where Tamura elastic mass defect scattering theory can be applied, was found to be valid for predicting cross-plane thermal conductivities but not in-plane thermal conductivities in mixed superlattices.

Thermochemical Nanolithography (TCNL) is a scanning probe microscope (SPM) based lithographic technique modified with a semi-conducting cantilever. This cantilever is capable of locally heating a surface and with a well-engineered substrate, this spatially confined heating induces chemical or physical transformation. While previous works focused primarily on proof of principle and binary studies, there is limited research on controlling and understanding the underlying mechanisms governing the technique. In this thesis, a chemical kinetics model is employed to explain the driving mechanisms and to control the technique. The first part focuses on studying surface reactions. By coupling a thermally activated organic polymer with fluorescence microscopy, the chemical kinetics model is not only verified but also applied to control the surface reactions. The work is then expanded to include 3D effects, and some preliminary results are introduced. Finally, applications are discussed.