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Membrane processes have received growing attention due to their low energy consumption and ease of operation. Thin-film composite reverse osmosis membranes based on polyamides are the most widely applied commercial membranes, because of their high flux and selectivity. However, their application for gas separation processes is still limited. This is the due to the presence of defects in the membrane when in the dry state. Traditionally, thin-film composite membranes are made by interfacial polymerization between a polar (aqueous) phase and a non-polar (organic) phase. The most commonly applied thin-film composite membranes are made by dissolving m-phenylene diamine in the aqueous phase and trimesoyl chloride in the organic phase. This work investigated the possibility of fabricating thin-film composite membranes when an aliphatic alcohol (methanol, ethanol or isopropanol) is used as the polar phase. This is further extended to examining the ability of a PDMS coating to plug the defects in such layers. The effects of temperature and support type on the membrane performance were also studied. Solubility tests were conducted to determine the solubility limit of commercial and in-house fabricated amine monomers in water, methanol, ethanol and isopropanol. Water-insoluble monomers were found to be soluble in ethanol and methanol. Gas permeation tests were conducted on membranes made using water, methanol, ethanol and isopropanol as the polar phase. The results showed that the membranes produced by aliphatic alcohols had higher selectivities. The highest H2/CO2 selectivity of ~ 26 was observed in the ethanol-based membranes when they were coated with PDMS and tested at 80 C. It was confirmed that PDMS is able to plug the defects in the membrane. Membranes made on the polysulfone support were found to have higher permeance and comparable selectivity relative to the membranes made on the polyacrylonitrile supports. It was also found that a change in the polar phase solvent is able to alter the morphology of the membranes. SEM micrographs showed clear differences in the surface structure of each membrane. The average thickness values obtained from ellipsometry measurements showed a correlation with the interface miscibility. The thickest membrane corresponded to the most miscible interface (IPA/Isopar).

A hetero-bimetallic alkoxide CrAl3(OiPr)12 was synthesised through metathesis of achromium(III)chloride THF complex (CrCl3 . 3 THF) and 3 KAl(OiPr)4.It was used as a single sourceprecursor to make oxide powders and films with 1:3 chromium/aluminium compositionthrough sol-gel synthesis. The final materials obtained and heat-treated samples of these wasstudied with thermogravimetric analysis (TG), X-ray diffraction (XRD) and IR spectroscopy. Itwas found that the as synthesised material was amorphous and elementally homogeneousand could be described as hydrated (oxo)-hydroxide with some loosely bonded carbonate,but no organics remaining. Above 600 oC crystallisation starts and eventually splits into twocorundum structured phases starting around 800 oC. At 1400  oC, the phases had joined backtogether in accordance with the Cr-Al-O phase diagram. Scanning Transmission ElectronMicroscopy with Electron Dispersive X-ray (STEM-EDX) tomography showed that the powderswere homogenous up to 800 oC, while after heating to 1000 oC showed chromiumenrichment in some crystals. Gracing Incidence X-ray diffraction (GI-XRD) on spin-coated filmsshowed that epitaxial growth might be achieved based on -Al2O3 (0001) substrate. The results show that the synthesis of the precursor and subsequent oxides was successful andyielded highly homogeneous gels that could be converted into oxide at ca. 600 oC andsubsequently be phase separated through spinodal decomposition at 1000 oC. The next stepwould be to try the precursor in the industrially used chemical vapour deposition (CVD)method.

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Over the past 15 years, research in the field of microfluidics has rapidly gained popularity. By seeking to miniaturize and automate separation-based analysis, microfluidic research seeks to improve current methods through decreased cost, analysis time, and sources of contamination. My work has focused on developing a novel fabrication method, based on standard microfabrication techniques, to create thin-film microfluidic devices. This microfabrication format makes it possible to generate devices that provide high efficiencies, enable mass fabrication, and provide a platform capable of integrating the microfluidic and electronic components necessary for a micro-total analysis system (μ-TAS). Device fabrication combines the processes of photolithography, thermal evaporation, plasma enhanced chemical vapor deposition (PECVD), and wet chemical etching to ultimately provide hollow-core channels. When these microcapillaries are filled with buffer and potentials are applied across them, control of the flow in the channels can be established. By designing intersecting microchannels having an offset “T†geometry, I have been able to inject and electrophoretically separate three fluorescently labeled amino acids and obtain efficiencies of over 2500 theoretical plates. Through the addition of commercially available electroosmotic flow reducing coatings, I have been able to improve the separation of these amino acids, decreasing the run time by approximately 6 fold and increasing the efficiency by as much as 10 fold. Through the use of these coatings I have also been able to carry out electrophoretic separations of three peptides. My most recent work has focused on the polymerization of acrylamide gels in these channels. A method for the selective placement of a gel has been developed using a prepolymer solution with a light-sensitive initiator. Further work to adjust the polymer pore size and interface with ampholyte-containing gels should allow methods such as capillary gel electrophoresis (CGE), preconcentration, and two dimensional (isolectric focusing and CGE) separations to be performed. The development of gel-based analysis methods, along with other fluidic and electrical capacities, should move thin-film microdevices toward the realization of the lab-on-a-chip concept.

The dissertation presented here describes two research projects that may, at first glance, seem unrelated. Their unifying principle is the measurement of electrical impedance for the detection and analysis of biological materials. Impedance measurements have long been employed and studied in scientific fields, and the dissertation begins with a summary of historical methodology, applications, and terminology. Utilizing impedance measurements for microscopic imaging is the driving motivation for Scanning Impedance Imaging (SII). This technique manifests the distribution of electrical impedance inside biological tissues and is described after the dissertation's introduction. SII can provide micron-scale imaging resolution by scanning a shielded microprobe over a sample placed on a conducting plane. A known voltage is applied to the microprobe and the sample immersed in a conductive aqueous medium. Both the probe height and the shield spacing were evaluated and optimized and two hardware configurations were developed to implement image scanning. A combined value ρh (resistivity × height) was used to represent impedance for heterogeneous samples. Experiments on photosensitive polymers, a butterfly wing, an oxide coated silicon wafer and cancer cells were performed and impedance images obtained. Impedance measurements for sensitive detection are demonstrated using a microchip capable of capillary electrophoresis separations. The chip was built using exclusively thin film deposition techniques, fully compatible with microelectronics batch processing. Standard photolithography provided control of the spacing between impedance measurement electrodes used in and overall channel geometry. The chip's performance was tested using concentrations of sodium chloride and calcium chloride ranging from 1 µM to 1 mM in a 5 mM MES/His buffer. Separations were performed by applying different voltages to reservoirs positioned at the four fluid channel openings. Impedance detection was performed by applying a small AC voltage (1 Vrms, 250 kHz) to the insulated electrodes positioned inside the fluid channels. Electropherograms were obtained and signal-to-noise ratio (S/N) was calculated. Measurements indicated that the trend of S/N as a function of molar concentrations was consistent with bulk conductivity tests and the chip's detection limit was below 1 µM for both sodium and calcium cations.

The material properties of low stress silicon nitride make it a possible replacement material for beryllium in X-ray windows. In this study, X-ray windows made of LPCVD deposited low stress silicon nitride are fabricated and characterized. The Young's modulus of the LPCVD low stress silicon nitride are characterized and found to be 226±23 GPa. The residual stress is characterized using two different methods and is found to be 127±25 MPa and 141±0.28 MPa. Two support structure geometries for the low stress silicon nitride X-ray windows are used. X-ray windows with thicknesses of 100 nm and 200 nm are suspended on a silicon rib support structure. A freestanding circular geometry is used for a 600 nm thick X-ray window. The 100 nm and 200 nm thick low stress silicon nitride X-ray windows with a silicon support structure are burst tested, cycling tested and leak rate tested. The average burst pressure for the 100 and 200 nm films on a silicon support structure are 1.4 atm and 2.2 atm respectively. Both 100 nm and 200 nm windows are able to withstand a difference in pressure of 1 atm for over 100 cycles with a leak rate of less than 10-10 mbar-L/s.The low stress silicon nitride with 100 nm and 200 nm thicknesses, the 600 nm freestanding low stress silicon nitride windows and freestanding 8 micron thick beryllium windows are mechanical shock resistance tested. The support structure low stress silicon nitride and beryllium windows are tested with an applied vacuum. The freestanding 600 nm thick low stress silicon nitride windows burst at 0.4 atm and are therefore mechanical shock wave tested without an applied vacuum. The support structure low stress silicon nitride windows fractured when subjected to an acceleration of roughly 5,000 g. The 8 micron thick beryllium windows are subjected to accelerations of over 30,000 g without fracturing. A quasistatic model is used to show that for low stress silicon nitride with a freestanding circular geometry, an acceleration of 106 g is required to have the same order of magnitude of stress caused by a pressure differential of 1 atm. Low stress silicon nitride can act as a replacement for beryllium in X-ray windows, but the support geometry, residual stress, and strength of the material need to be optimized.

Metal-Organic Frameworks (MOFs) are an important class of materials that are gaining increasing relevance for many fields including energy storage, CO2 capture, photovoltaics, and catalysis. MOF mediated synthesis (MOFMS) is the decomposition of a MOF to form an amorphous carbon material decorated with metal nanoparticles. MOF thin films are an area where MOFMS has not been thoroughly explored, yet they are likely to be industrially relevant due to their potential application as highly dispersed, sinter resistant supported catalysts. In this work, we have developed a method for the growth of copper- and zinc-based MOF thin films on silicon- and aluminum- based wafers. A series of decomposition processes have allowed us to determine which variables can be used to design the final nanoparticle decorated product. These variables include oxygen/nitrogen ratios, the impact of water in atmospheric decomposition, substrate composition, and reduction under hydrogen. A high degree of control over the final thin film product is achieved, with the ability to make a carbon supported CuO structure with features between 1-5 nm, or CuO nanoparticles ranging from 10-500 nm, as well as finely tuned carbon/Cu ratios. Partially reduced Cu nanoparticles were obtained and used in the dehydrogenation of ethanol and methanol. Finally, alloyed nanoparticles were obtained through the growth and decomposition of Cu/Zn mixed-metal MOFs. Understanding the growth and decomposition variables as applied to supported MOF-thin films will enable development of next generation nanomaterials for use in catalysis.