Increasing applications of nano materials in medicine, construction, textiles, computers, and other consumer goods have lead to increasing concerns of their effect on human health and ecology during synthesis, manufacturing, use, and disposal of nano-materials. Though much scientific progress has been made in nano material synthesis, manufacturing, and application in consumer goods and other sectors such as medicine, textiles and more, not much progress has been made in understanding the adverse effects of nano materials on human health and the environment. Physical, chemical, toxicological characteristics of these nano materials and their fate in the environment are important in understanding their adverse effects on the environmental and human health. This study is aimed at developing a preliminary framework for risk assessment (RA) and risk management (RM) of nano materials based on fundamental principles of chemistry, physics, toxicology, and other related disciplines.

Thesis advisor: Chia-Kuang Tsung / Electrochemical energy storage and conversion applications benefit from the integration of nanostructures into the devices, as they have many more active sites per gram which enables excellent mass utilization of the active species. By controlling the surface of fuel cell catalysts, higher activity and efficiency can be achieved as compared to the bulk counterpart, with multiple catalyst facets of varying activity and efficiency. Nanostructured electrochemical capacitors have enhanced electrolyte diffusion over the surface of the electrode, facilitating high rate capability. Nanostructured materials for energy storage and conversion devices, such as electrochemical capacitors and proton exchange membrane fuel cells, can perform even better with the incorporation of carbon. High surface area carbon can enhance the activity of electrochemical capacitors by improving the conductivity of the electrode and/or enhancing the double layer capacitance. Carbon supports for fuel cell catalysts enable proper dispersion of active material without sacrificing conductivity. The work reported in this thesis is aimed toward improving the performance of electrochemical energy storage and conversion devices through novel incorporation of carbon. Carbon was first used to enhance the performance of electrocatalysts. By wrapping fuel cell catalysts in a porous carbon shell, the activity was increased over its bare and CNT-supported counterparts. The carbon shell synthetic method reported here is a good route to the production of a conductive host for Pd electrocatalysts with good contact and in one step with the formation of the Pd nanoparticles. Carbon was also used to enhance the performance of pseudocapacitors, first by incorporating it into the precursor spray solution in the generation of mesoporous metal oxides and then as a metal-organic framework-derived carbon host with dispersed electrochemically active metal oxides. A carbon network was generated from the pyrolysis of pore directing agents during the decomposition of precursor metal nitrates in the generation of mesoporous manganese oxides in a modified spray pyrolysis approach. The addition of Super P to the precursor spray solution further enhanced the conductivity of the material, enabling the formation of high-performing pseudocapacitors. Lastly, nitrogen-doped carbon cubes produced from thermally-treated parent ZIF-8 cubes were tested as electrochemical capacitors and found to have higher specific capacitance than the nitrogen-doped carbon generated from the parent ZIF-8 rhombic dodecahedra. ZIF-67 cubes were then thermally treated to yield cubic nitrogen-doped carbon hosts for the generated cobalt nanoparticles. Once the cobalt particles were oxidized, the cobalt oxide/carbon hybrid structure exhibited the best pseudocapacitive performance of the ZIF-derived carbon materials tested, exhibiting high specific capacitance and good capacitance retention with increased scan rates and prolonged cycling. Each of the materials tested for electrochemical energy storage and conversion saw an enhancement in performance with the addition of carbon. The results reported here illustrate the importance of carbon in electrochemical cells and the importance of continuing research to modify and improve the methods for carbon production and integration. / Thesis (PhD) — Boston College, 2016. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

"This dissertation is devoted to the computational investigation of supersonic gas flows in rectangular nanochannels with scales between 100 nm and 1000 nm, using an unstructured three-dimensional Direct Simulation Monte Carlo (U3DSMC) methodology. This dissertation also contributes to the computational mathematics background of the U3DSMC method with validations and verifications at the micronscale and nanoscale, as well as with the investigation of the statistical fluctuations and errors associated with U3DSMC simulations at the nanoscale. The U3DSMC code is validated by comparisons with previous two dimensional DSMC simulations of flows in micron-scale rectangular channels. The simulation involves the supersonic flow of nitrogen into a microchannel with height of 1.2 m and width of 6 m. The free stream conditions correspond to a pressure of 72,450 Pa, Mach number , Knudsen number and mean free path nm. The U3DSMC centerline temperature, heat flux to the wall, and mean velocity as a function of the transverse direction are in very good agreement with previous 2D results. Statistical fluctuations and errors in U3DSMC have added significance in nanoscale domains because the number of real particles can be very small inside a computational cell. The effect of the number of samples, the number of computational particles in a Delaunay cell, and the Mach number on the fractional errors of density, velocity and temperature are investigated for uniform and pressure-driven nanoscale flows. The uniform nanoflow is implemented by applying a and free stream boundary condition with m-3, K, nm in a domain that requires resolution of a characteristic length scale nm. The pressure-driven flows consider a nanochannel of 500 nm height, 100 nm width and 4 m length. Subsonic boundary conditions are applied with inlet pressure 101,325 Pa and outlet pressure of 10132.5 Pa. The analysis shows that U3DSMC simulations at nanoscales featuring 10-30 particles per Delaunay cell result in statistical errors that are consistent with theoretical estimates. The rarefied flow of nitrogen with speed ratio of 2, 5, and 10, pressure of 10.132 kPa into rectangular nanochannels with height of 100, 500 and 1000 nm is investigated using U3DSMC. The investigation considers rarefaction effects with =0.481, 0.962, 4.81, geometric effects with nanochannel aspect ratios of (L/H) from AR=1, 10, 100 and back-pressure effects with imposed pressures from 0 to 200 kPa. The computational domain features a buffer region upstream of the inlet and the nanochannel walls are assumed to be diffusively reflecting at the free stream temperature of 273 K. The analysis is based on the phase space distributions as well as macroscopic flow variables sampled in cells along the centerline. The phase space distributions show the formation of a disturbance region ahead of the inlet due to slow particles backstreaming through the inlet and the formation of a density enhancement with its maximum inside the nanochannel. The velocity phase-space distributions show a low-speed particle population generated inside the nanochannel due to wall collisions which is superimposed with the free stream high-speed population. The mean velocity decreases, while the number density increases in the buffer region. The translational temperature increases in the buffer region and reaches its maximum near the inlet. For AR=10 and 100 nanochannels the gas reaches near equilibrium with the wall temperature. The heat transfer rate is largest near the inlet region where non-equilibrium effects are dominant. For =0.481, 0.962, 4.81, vacuum back pressure, and AR=1, the nanoflow is supersonic throughout the nanochannel, while for AR=10 and 100, the nanoflow is subsonic at the inlet and becomes sonic at the outlet. For =0.962, AR=1, and imposed back pressure of 120 kPa and 200 kPa, the nanoflow becomes subsonic at the outlet. For =0.962 and AR=10, the outlet pressure nearly matches the imposed back pressure with the nanoflow becoming sonic at 40 kPa and subsonic at 100 kPa. Heat transfer rates at the inlet and mass flow rates at the outlet are in good agreement with those obtained from theoretical free-molecular models. The flows in these nanochannels share qualitative characteristics found in microchannels ad well as continuum compressible flows in channels with friction and heat loss. The rarefied flow of nitrogen with speed ratio of 2, 5, 10, at an atmospheric pressure of 101.32 kPa into rectangular nanochannels with height of 100 and 500 nm is investigated using U3DSMC. The investigation considers rarefaction effects with =0.0962 and 4.81, geometric effects with nanochannel aspect ratios of (L/H) of AR=1 and 10 and vacuum back-pressure. Phase plots and sample-averaged macroscopic parameters are used in the analysis. Under vacuum back pressure the centerline velocity decreases in the buffer region from its free stream value. For 0.481, 0.0962 and AR=1 the Mach number is supersonic at the inlet and remains supersonic throughout the nanochannel. For 0.481, 0.0962 and AR=10, the flow becomes subsonic at the inlet and shows a sharp increase in pressure. The Mach number, subsequently, increases and reaches the sonic point at the outlet. For 0.481, 0.0962 and AR=1 the translational temperature reaches a maximum near the inlet and decreases monotonically up to the outlet. For 0.481, 0.0962 and AR=10, the translational temperature reaches a maximum near the inlet and then decreases to come in near equilibration with the wall temperature of 273 K. "

L'introduction d'atomes d'azote sur des squelettes organiques reste une étape clé pour la synthèse de molécules bioactives alcaloïdes. Depuis quelques années, l'insertion catalytique de nitrène sur les alcènes ou pour la fonctionnalisation des liaisons C-H est devenue un outil indéniable pour une telle introduction. Cependant, les systèmes catalytiques homogènes habituellement utilisés pour cette transformation présentent des inconvénients tels que la stabilité ou la séparation après réaction. Des catalyseurs supportés recyclables sont alors apparus comme une alternative intéressante pour surmonter ces problèmes. Dans le cadre de notre intérêt continu pour le développement de méthodologies durables, nous avons conçu de nouveaux catalyseurs valorisables efficaces, conformes aux principes de la chimie verte. Ici, la première insertion de nitrène pour l'aziridination en utilisant une nanoferrite chargée de cuivre réutilisable comme catalyseur sera présentée. Les propriétés magnétiques des nanoparticules permettent une récupération facile de ces catalyseurs avec un simple aimant externe. Nous montrerons que les catalyseurs peuvent être réutilisés 5 fois avec une conversion totale du styrène et de bons rendements, même après 5 essais. Les investigations après caractérisation complète ont montré une réduction de la charge de cuivre au fur et à mesure des cycles, ce qui peut être dû à un ancrage faible. Ce résultat nous incite à explorer différents linkers entre les nanoparticules magnétiques et le cuivre afin de diminuer cette lixiviation. Plusieurs lieurs présentant des fonctions différentes d'ancrage MNP et de chélation de Cu seront présentés. En outre, l'extrapolation réussie de cette méthodologie à des dérivés de styrène substitués pauvres en électrons ou riches en électrons sera démontrée, ainsi que l'aziridination d'oléfines à longue chaîne qui seront exposées / Introduction of nitrogen atoms onto organic skeletons remains a key step for the synthesis of alkaloid bioactive molecules. Since a few years, catalytic nitrene insertion on alkenes or for C-H bond functionalization has emerged as an undeniable tool for such introduction. However, homogeneous catalytic systems usually used for this transformation present some drawbacks such as stability, or separation after reaction. Recyclable supported catalysts have then arisen as a valuable alternative to overcome these issues.As part of our continued interest for the development of sustainable methodologies, we designed new and efficient recoverable catalysts fitting by the way the green chemistry principles. Here, the first nitrene insertion for aziridination using a reusable copper-loaded nanoferrite as catalyst will be presented. Magnetic properties of the nanoparticles allow an easy retrieval of those catalysts with a simple external magnet. We will show that the catalysts could be reused for 5 times with total conversion of styrene and good yields, even after 5 runs.Investigations after full characterization showed a reduction of copper loading as the runs, which can be due to a weak anchoring. This result prompts us to explore different linkers between magnetic nanoparticles and copper in order to decrease this leaching. Several linkers exhibiting different MNP-anchoring and Cu-chelating functions will be presented. Also, the successful extrapolation of this methodology to electron-poor or electron-rich substituted styrene derivatives will be demonstrated as well as the aziridination of long chain olefins which will be exhibited.

With a view to design processes based on gas-solid reactiontowards the production of fine-grained novel alloys andintermetallics, studies of the reduction of the mixed oxides ofFe and Mo by hydrogen towards the production of Fe-Mo alloyshave been carried out in the present work. The route offersexcellent potentials toward the bulk production of nano-grainedmaterial of tailored-composition in bulk in a green processpath. As a case study, the reduction of the mixed oxides ofiron and molybdenum were carried out from the viewpoint ofmaterials processing, chemical reaction kinetics, as well asmechanical and structural properties. The reduction kinetics ofthin layer of fine oxide particles of Fe2MoO4 was studied usingthermogravimetric technique. This technique allowed determiningreduction parameters such as temperature of reduction as wellas the activation energies for the chemical reaction as therate-controlling step. The end products were analyzed by X-raydiffraction. The reduction product was found to be reduced topure, homogeneous Fe2Mo. In order to examine the upscaling ofthe process, production of the alloy in larger amounts wascarried out in a laboratory-scale fluidized reactor and theprocess parameters were optimized. It was found that, under theconditions of the experiments, the chemical reaction was therate-controlling step. TEM, SEM and X-ray analyses of thereaction product showed the presence of a monolithicintermetallic with micro- and nanocrystalline structure. Themechanical properties of this alloy were determined.Compositions of microcrystalline Fe-Mo alloys were varied byreducing mixtures of Fe2MoO4 with MoO2 or FeO with differentFe/Mo ratios. The products after the reduction consisted of twophases, viz. intermetallic FexMoy compound and metallic Fe orMo. XRD analyses revealed that the former had microcrystallinestructure while the latter were in crystalline form. This workshows that gas-solid reaction method, together with powdermetallurgy technique is a promising process route towards theproduction of novel metallic alloys such as Fe2Mo intermetallicwith micro- and nanocrystalline grains. <b>Key words</b>: nanoalloys, intermetallics, iron-molybdenumalloy, hydrogen reduction, thermogravimetry, fluidized bed,mechanical properties, structure

Although extensive literature exists on NMR of water in MCM-41, the origin of a number of NMR spectral features in this material had not been understood. Specifically, the OH proton resonance observed in the dry material disappears completely as it is hydrated to 0.2 mono-layer hydration level. The purpose of this study was to gain insight into the physical basics for these spectral features and in the process broaden our understanding of behaviour/interactions of water molecules in porous material. First, measurements of MAS spectra as a function of temperature and hydration, at very low hydrations, made possible a definitive spectral peak assignment. Second, using 1D and 2D selective inversion recovery and magnetization exchange experiments, as well as MAS and non-MAS techniques, magnetization exchange between the water protons and surface OH group protons was quantified. The present results lead to the conclusion that chemical exchange is not responsible for producing the observed changes in proton spectra in MCM-41 as this material is hydrated up to the 0.2 mono-layer hydration level. This represents an important result as it is at odds with what is assumed in the literature in this connection and means that previous conclusions about hydration dynamics in this material need to be revisited. A dynamics model of water interaction with the surface OH hydration sites was introduced to explain the observed proton spectra. The model can successfully predict the observed chemical shifts and temperature dependent changes of proton spectra in the very low hydration MCM-41.

<p>With a view to design processes based on gas-solid reactiontowards the production of fine-grained novel alloys andintermetallics, studies of the reduction of the mixed oxides ofFe and Mo by hydrogen towards the production of Fe-Mo alloyshave been carried out in the present work. The route offersexcellent potentials toward the bulk production of nano-grainedmaterial of tailored-composition in bulk in a green processpath. As a case study, the reduction of the mixed oxides ofiron and molybdenum were carried out from the viewpoint ofmaterials processing, chemical reaction kinetics, as well asmechanical and structural properties. The reduction kinetics ofthin layer of fine oxide particles of Fe2MoO4 was studied usingthermogravimetric technique. This technique allowed determiningreduction parameters such as temperature of reduction as wellas the activation energies for the chemical reaction as therate-controlling step. The end products were analyzed by X-raydiffraction. The reduction product was found to be reduced topure, homogeneous Fe2Mo. In order to examine the upscaling ofthe process, production of the alloy in larger amounts wascarried out in a laboratory-scale fluidized reactor and theprocess parameters were optimized. It was found that, under theconditions of the experiments, the chemical reaction was therate-controlling step. TEM, SEM and X-ray analyses of thereaction product showed the presence of a monolithicintermetallic with micro- and nanocrystalline structure. Themechanical properties of this alloy were determined.Compositions of microcrystalline Fe-Mo alloys were varied byreducing mixtures of Fe2MoO4 with MoO2 or FeO with differentFe/Mo ratios. The products after the reduction consisted of twophases, viz. intermetallic FexMoy compound and metallic Fe orMo. XRD analyses revealed that the former had microcrystallinestructure while the latter were in crystalline form. This workshows that gas-solid reaction method, together with powdermetallurgy technique is a promising process route towards theproduction of novel metallic alloys such as Fe2Mo intermetallicwith micro- and nanocrystalline grains.</p><p><b>Key words</b>: nanoalloys, intermetallics, iron-molybdenumalloy, hydrogen reduction, thermogravimetry, fluidized bed,mechanical properties, structure</p>

Currently, the imprint lithography steppers are designed to only pattern one field of 26 x 33 mm at a time. This choice is based on the desire to mix-and-match to the standard optical lithography tools whose field size is also 26 x 33 mm. Throughput can be increased if more than one field can be imprinted simultaneously. The problem with adding a field to the imprinting template is that each field has overlay errors associated with it that are created when the template is manufactured and when the corresponding prior field is manufactured on the wafer. The current process is able to correct these template and wafer overlay errors using a precision stage and actuators that elastically deform the template. The same method cannot be used when there are two fields because the fields are not independent and interact with each other. Correcting the errors in one of the fields tend to increase the error in the second field. vii In this thesis, a new control method has been created to account for the dependent motion. A new template concept was also created to try to limit the interaction between the two fields. The new control algorithm was tested in simulation to see if it could correct the current 1-field setup as well as the new concept of having more than one field on a template. The control algorithm was also used to test applications where the overlay errors in only one direction need to be corrected. The control algorithm was tested on a solid single field template, the baseline case, and was able to achieve 1.3 nm overlay, which is consistent with the current method. The algorithm was then tested on the dual field concepts. The range of alignment errors needed to get 5 nm overlay are too tight for current manufacturing but the compliant concept did have more relaxed ranges than the solid dual field template. With more research, the compliant template concept might be changed to allow for wider ranges. The tests with correction in only one direction had promising data that should be investigated further. / text

Although extensive literature exists on NMR of water in MCM-41, the origin of a number of NMR spectral features in this material had not been understood. Specifically, the OH proton resonance observed in the dry material disappears completely as it is hydrated to 0.2 mono-layer hydration level. The purpose of this study was to gain insight into the physical basics for these spectral features and in the process broaden our understanding of behaviour/interactions of water molecules in porous material. First, measurements of MAS spectra as a function of temperature and hydration, at very low hydrations, made possible a definitive spectral peak assignment. Second, using 1D and 2D selective inversion recovery and magnetization exchange experiments, as well as MAS and non-MAS techniques, magnetization exchange between the water protons and surface OH group protons was quantified. The present results lead to the conclusion that chemical exchange is not responsible for producing the observed changes in proton spectra in MCM-41 as this material is hydrated up to the 0.2 mono-layer hydration level. This represents an important result as it is at odds with what is assumed in the literature in this connection and means that previous conclusions about hydration dynamics in this material need to be revisited. A dynamics model of water interaction with the surface OH hydration sites was introduced to explain the observed proton spectra. The model can successfully predict the observed chemical shifts and temperature dependent changes of proton spectra in the very low hydration MCM-41.

This thesis describes the development and the verification of a novel micro probe system for high accurancy downscaled Coordinate Measuring Machines (CMMs).