This thesis examines the mechanisms of magnetic particle deposition and retention in human airways for magnetically targeted drug delivery. As this is a novel application, fundamental studies were performed to establish the necessary background knowledge for further development. Magnetic particle deposition from an aerosol in simulated airway conditions was studied using numerical and experimental models. The model results showed qualitative agreement; discrepancies were due to particle aggregation, which enhances deposition. Aerosol flow rate had a limited effect; the main factor in effective deposition was the proximity of the particle trajectories to the magnets. This spatial bias shows the importance of particle distribution in the flow as well as magnetic field geometry. These studies demonstrated the feasibility of capturing magnet particles from aerosol in airway conditions. For retention, clearance of particles due to motion of the mucus lining of the airways must be overcome. Particle retention was studied in vitro using various liquids to simulate mucus and identify relevant parameters. An ex vivo animal tissue model was used to demonstrate feasibility. Retention of 3-5 m diameter iron particles was achieved at reduced liquid/mucus viscosities. Larger (~100 m) particles were retained at normal mucus viscosities. The size dependence shows that particle aggregation after deposition is crucial for effective retention. In vitro retention experiments showed aggregate size is correlated with liquid viscosity, i.e. formation of aggregates is limited by forces opposing particle motion along the mucus layer interface. To determine these forces, particle motion on various air-liquid interfaces, chosen to simulate different mucus properties in isolation, was studied. When surfactants are present, as in the mucus layer, particle motion is limited by a velocity-dependent surface tension gradient as well as viscous drag. Pulling particles through the mucus layer into the tissue beneath was also considered as a potential retention strategy. The force required to pull particles through the mucus layer was also studied using various liquids to simulate mucus properties. In addition to the surface tension force holding the particles at the interface, hydrodynamic forces must be overcome to pull particles into or out of a liquid film such as the mucus layer.

Herein are presented collective studies of amino acid-based surfactants, also known as lipoamino acids, at liquid interfaces. Chapter III describes an investigation of domain morphology of N-Stearoylglutamic acid (N-SGA) Langmuir monolayers at the air/water interface by epifluorescence microscopy. Anisotropic feather-like domains were observed in L-enantiomeric monolayers while symmetric circular domains were found in racemic N-SGA monolayers. At a surface pressure of 30 mN/m the enantiomeric domains melted at 31 ??C while the racemic domains melted at 27 ??C. This result is exactly opposite to the behavior found in bulk crystals where the racemate melts at a higher temperature. These results were explained in terms of different molecular packing and hydrogen bonding between bulk crystals and two-dimensional thin films for enantiomeric and racemic compounds. Chapter IV summarizes the investigations of hydrogen bonding in N-acyl amino acid monolayers by vibrational sum-frequency spectroscopy (VSFS). The intermolecular hydrogen bonding interaction between the adjacent molecules through amide-amide groups in N-stearoylalanine (N-SA) is characterized by an NH stretch peak at 3311 cm-1. This is the first time that the amide NH stretching signals have been detected with the VSFS technique. A similar peak was detected at 3341 cm-1on N-SGA monolayer. The higher frequency indicates that the H-bond strength is weaker due to the larger size of the glutamic acid residue. The NH stretch mode can thus be used as a fingerprint of hydrogen bonding among amide-amide groups. A peak at 3050 cm-1 due to hydrogen bonding among carboxyl groups was also resolved from the VSFS spectra. Molecular models of intermolecular hydrogen bonding were proposed.

Herein are presented collective studies of amino acid-based surfactants, also known as lipoamino acids, at liquid interfaces. Chapter III describes an investigation of domain morphology of N-Stearoylglutamic acid (N-SGA) Langmuir monolayers at the air/water interface by epifluorescence microscopy. Anisotropic feather-like domains were observed in L-enantiomeric monolayers while symmetric circular domains were found in racemic N-SGA monolayers. At a surface pressure of 30 mN/m the enantiomeric domains melted at 31 ??C while the racemic domains melted at 27 ??C. This result is exactly opposite to the behavior found in bulk crystals where the racemate melts at a higher temperature. These results were explained in terms of different molecular packing and hydrogen bonding between bulk crystals and two-dimensional thin films for enantiomeric and racemic compounds. Chapter IV summarizes the investigations of hydrogen bonding in N-acyl amino acid monolayers by vibrational sum-frequency spectroscopy (VSFS). The intermolecular hydrogen bonding interaction between the adjacent molecules through amide-amide groups in N-stearoylalanine (N-SA) is characterized by an NH stretch peak at 3311 cm-1. This is the first time that the amide NH stretching signals have been detected with the VSFS technique. A similar peak was detected at 3341 cm-1on N-SGA monolayer. The higher frequency indicates that the H-bond strength is weaker due to the larger size of the glutamic acid residue. The NH stretch mode can thus be used as a fingerprint of hydrogen bonding among amide-amide groups. A peak at 3050 cm-1 due to hydrogen bonding among carboxyl groups was also resolved from the VSFS spectra. Molecular models of intermolecular hydrogen bonding were proposed.

Liquid dispersions of colloidal particles play a big role in nature and as industrial products or intermediates. Their material properties are largely determined by the liquid-mediated particle-particle interaction. In water-based systems, electric charge is ubiquitous and electrostatic particle interaction often is the primary factor in stabilizing dispersions against decomposition by aggregation and sedimentation. Very nonpolar liquids, by contrast, are usually considered free of charge, because their low dielectric constant raises the electrostatic cost of separating opposite charges above the available thermal energy. Defying this conventional wisdom, nonpolar solutions of certain ionic surfactants do support mobile ions and surface charges. Even some nonionic surfactants have recently been found to raise the conductivity of nonpolar oils and promote surface charging of suspended particles, but this counter-intuitive behavior is not yet widely acknowledged, nor is the mechanism of charging understood. The present study provides the first characterization of the electrostatic particle interaction caused by nonionizable surfactants in nonpolar oils. The methods used in this study are video microscopy experiments where particle positions of equilibrium ensembles are obtained and translated into particle interactions. Experimentally, equilibrium particle positions are monitored by digital video microscopy, and subjected to liquid structure analysis in order to find the energy of interaction between two particles. The observed interaction energy profiles agree well with a screened-Coulomb potential, thus confirming the presence of both surface charge and mobile ions in solution. In contrast to recently reported electrostatic particle interactions induced by ionic surfactants in nonpolar solution, the present study finds evidence of charge screening both above and below the surfactant's critical micelle concentration, CMC. Fitted Debye screening lengths are much larger than in aqueous systems, but similar to the Debye length in nonpolar oils reported for micellar solutions of ionic surfactants cite{hsu_charge_2005}. Radial distribution functions obtained from experiments are compared to Monte-Carlo simulations with input potentials obtained from a fit to the interaction measurement. The measured electrostatic forces and fitted surface potentials are fairly substantial and easily capable of stabilizing colloidal dispersions. Although few in number, surface charges formed on polymer particle surfaces submerged in nonpolar solutions of nonionizable surfactants create surface potentials comparable to those in aqueous systems.

In 1960's Gordon Moore predicted that the increase in the number of components in integrated circuits would exponentially decrease the relative manufacturing cost per component with time. The semiconductor industry has managed to keep that pace for nearly 45 years and one of the main contributors to this phenomenal improvement in technology is advancement in the field of lithography. However, the technical challenges ahead are severe and the future roadmap laid by the International Technology Roadmap for Semiconductors looks mostly red (i.e. no solution has been found to specific problem). There are efforts in the industry and academia directed toward development of newer, alternative lithographic techniques. Step and Flash Imprint Lithography (SFIL) has recently emerged as one of the most promising alternatives, capable of producing high resolution patterns. While it has numerous advantages over conventional photolithography, several engineering challenges must be overcome to eliminate defects due to the nature of contact imprinting if SFIL is to be a viable alternative technique for manufacturing tomorrow's integrated circuits. The complete filling of template features is vital in order for the SFIL imprint process to truly replicate the template features. The feature filling phenomena for SFIL was analyzed by studying diffusion of a gas, entrapped in the features, through liquid imprint resist. A simulation of the dynamics of feature filling for different pattern configurations and process conditions during the SFIL imprint step is presented. Simulations show that initial filling is pressure-controlled and very rapid; while the rest of the feature filling is diffusion-controlled, but fast enough that diffusion of entrapped gas is not a cause for non-filling of features. A theory describing pinning of an air-liquid interface at the feature edge of a template during the SFIL imprint step was developed, which shows that pinning is the main cause of non-filling of features. Pinning occurs when the pressure at the air-liquid interface reaches the pressure of the bulk liquid. At this condition, there is no pressure gradient or driving force to move the liquid and fill the feature. The effect of several parameters on pinning was examined. A SFIL process window was established and template modifications are proposed that minimize the pinning at the feature edge while still preventing any extrusion along the mesa (pattern containing area on the template) edge. Part of semiconductor manufacturing community believes that optical lithography has the capability to drive this industry further and is committed to the continuous improvement of current optical patterning approaches. Some of the major challenges with shrinking critical dimensions (CDs) in coming years are the control of line-edge roughness (LER) and other related defects. The current CDs are such that the presence or absence of even a single polymer molecule can have a considerable impact on LER. Therefore molecular level understanding of each step in the patterning process is required. Computer simulations are a cost-effective approach to explore the huge process space. Mesoscale modeling is one promising approach to simulations because it captures the stochastic phenomena at a molecular level within reasonable computational time. The modeling and simulation of the post-exposure bake (PEB) and the photoresist dissolution steps are presented. The new simulator enables efficient exploration of the statistical excursions that lead to LER and the formation of insoluble residues during the dissolution process. The relative contributions of the PEB and the dissolution step to the LER have also been examined in the low/high frequency domain. The simulations were also used to assess the commonly proposed measures to reduce LER. The goal of the work was to achieve quantification of the effect of changes in resist composition, developer concentration, and process variables on LER and the associated defectivity. / text

No description available.

Interactions of colloidal particles with surfaces occur in natural and engineered systems, and they influence the transport of contaminants through diffusion, aggregation, filtration, and sedimentation. To quantify the transport and fate of colloidal particles and their influence on environmental systems, it is important to understand their interactions with surfaces. These interactions are influenced by physical and chemical surface properties such as hydrophobicity, charge density, and roughness, as well as environmental conditions such as relative humidity (RH). In atmospheric systems, RH induces the capillary force and also influences the contributions of van der Waals and electrostatic forces. To investigate the role of surface properties and RH in the interaction of colloidal particles with surfaces, atomic force microscopy was employed to measure the adhesion and friction forces of colloidal particles including Bacillus thuringiensis spores, silica, and gold at various experimental conditions with several types of surfaces including mica, silica, and radioactive gold. Contributions to the adhesion force by van der Waals, capillary, and electrostatic forces were theoretically calculated and compared to measured forces. Through experimental results and theoretical studies, it was identified how surface properties of interacting surfaces and experimental conditions influence the interfacial interactions of colloidal particles in atmospheric systems. The role of RH in adhesion and friction depends on the hydrophobicity or contact angles of interacting surfaces and surface roughness. Relative humidity also influences the contribution of electrostatic force to the total adhesion force by screening the strength of surface potential or providing a passage for charge leakage. The results of this thesis provide a better understanding of particulate processes that are influenced by the interactions of colloidal particles with surfaces and can be useful in monitoring and control of contamination in atmospheric systems.

Thesis (Ph. D.)--University of Missouri-Columbia, 2007. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on February 29, 2008) Vita. Includes bibliographical references.

Thesis (Ph.D.)--University of Melbourne, Dept. of Mathematics and Statistics, 2007. / Typescript. Includes bibliographical references (leaves 143-151).

Thèse (M.Eng.) -- Université du Québec à Chicoutimi, 2007. / La p. de t. porte en outre: Mémoire présenté à l'Université du Québec à Chicoutimi comme exigence partielle de la maîtrise en ingénierie. CaQCU Bibliogr.: f. 184-186. Document électronique également accessible en format PDF. CaQCU