PREPARATION OF POLYELECTROLYTE MEMBRANES EMBEDDED WITH ZEOLITE NANOPARTICLES FOR ENHANCED PERFORMANCE IN FORWARD OSMOSIS

Water scarcity is a global issue that has already affected every continent. Membrane technology is considered as one of the most promising candidates for resolving this worsening issue. Among all the membrane processes, the emerging forward osmosis (FO) membrane process is osmotically-driven and has unique advantages compared with other traditional pressure-driven membrane processes. One of the major challenges to advancing the FO membrane process is the lack of a suitable membrane. Polyelectrolyte thin film prepared via layer-by-layer (LbL) technique has demonstrated its excellent performance in many applications including electronics, optics, sensors, etc. Recent studies have revealed the potential of polyelectrolyte thin films in acting as the active separation layer of FO membranes, but significant efforts are still needed to improve the membrane performance and understand the transport mechanisms. This dissertation introduces a novel approach to prepare a zeolite-embedded polyelectrolyte composite membrane for enhanced FO performance. This membrane takes advantages of the versatile LbL process to unprecedentedly incorporate high loading of zeolite nanoparticles, which are anticipated to facilitate water transport due to the uniquely interconnected structure of zeolites. Major topics discussed in this dissertation include: (1) the synthesis and evaluation of the polyelectrolyte-zeolite composite FO membrane, (2) the examination of the fouling resistance to identify its technical limitations, (3) the demonstration of the membrane regenerability as an effective strategy for membrane fouling control, and (4) the investigation of crosslinking effects on the membrane performance to elucidate the transport mechanisms involved in the zeolite-embedded polyelectrolyte membranes. Comparative studies have been made between polyelectrolyte membranes with and without zeolite incorporation. The findings suggest that the zeolite-embedded membrane, although slightly more susceptible to silica scaling, has demonstrated enhanced water flux and separation capability, good resistance to organic fouling, and complete regenerability for fouling control. Additionally, the embedded zeolite nanoparticles are proved to be able to create fast pathways for water transport. Overall, this work provides a novel strategy to create zeolite-polymer composite membranes with enhanced separation performance and unique fouling mitigation properties.

Advanced Adhesion Strength Testing Methods of Thin Film Multilayers in Electronic Packaging Systems

With the continued miniaturization and increasing performance of electronic devices, new technical challenges have arisen. One such issue is delamination occurring at critical interfaces inside the device. This major reliability issue can occur during the manufacturing process or during normal use of the device. Proper evaluation of the adhesion strength of critical interfaces early in the product development cycle can help reduce reliability issues and time-to-market of the product. However, conventional adhesion strength testing is inherently limited in the face of package miniaturization, which brings about further technical challenges to quantify design integrity and reliability. Although there are many different interfaces in today's advanced electronic packages, they can be generalized into two main categories: 1) rigid to rigid connections with a thin flexible polymeric layer in between, or 2) a thin film membrane on a rigid structure. Knowing that every technique has its own advantages and disadvantages, multiple testing methods must be enhanced and developed to be able to accommodate all the interfaces encountered for emerging electronic packaging technologies. For evaluating the adhesion strength of high adhesion strength interfaces in thin multilayer structures a novel adhesion test configuration called “single cantilever adhesion test (SCAT)” is proposed and implemented for an epoxy molding compound (EMC) and photo solder resist (PSR) interface. The test method is then shown to be capable of comparing and selecting the stronger of two potential EMC/PSR material sets. Additionally, a theoretical approach for establishing the applicable testing domain for a four-point bending test method was presented. For evaluating polymeric films on rigid substrates, major testing challenges are encountered for reducing testing scatter and for factoring in the potentially degrading effect of environmental conditioning on the material properties of the film. An advanced blister test with predefined area test method was developed that considers an elasto-plastic analytical solution and implemented for a conformal coating used to prevent tin whisker growth. The advanced blister testing with predefined area test method was then extended by employing a numerical method for evaluating the adhesion strength when the polymer’s film properties are unknown.

THERMODYNMICS AND STRUCTURE OF POLY(ETHYLENE OXIDE) IN MIXTURES OF WATER AND ETHANOL

Poly(ethylene oxide) (PEO) is one of the most researched synthetic polymers due to the complex behavior which arises from the interplay of the hydrophilic and hydrophobic sites on the polymer chain. PEO in ethanol forms an opaque gel-like mixture with a partially crystalline structure. Addition of a small amount of water disrupts the gel: 5 wt % PEO in ethanol becomes a transparent solution with the addition of 4 vol % water. The phase behavior of PEO in mixed solvents have been studied using small-angle neutron scattering (SANS). PEO solutions (5 wt % PEO) which contain 4 vol % - 10 vol % (and higher) water behave as an athermal polymer solution and the phase behavior changes from UCST to LCST rapidly as the fraction of water is increased. 2 wt % PEO in water and 10 wt % PEO in ethanol/ water mixtures are examined to assess the role of hydration. The observed phase behavior is consistent with a hydration layer forming upon the addition of water as the system shifts from UCST to LCST behavior. At the molecular level, two or three water molecules can hydrate one PEO monomer (water molecules form a sheath around the PEO macromolecule) which is consistent with the suppression of crystallization and change in the mentioned phase behavior as observed by SANS. The clustering effect of aqueous PEO solution (M.W of PEO = 90,000 g/mol) is monitored as an excess scattering intensity at low-Q. Clustering intensity at Q = 0.004 Å^-1 is used for evaluating the clustering effect. The clustering intensity is proportional to the inverse temperature and levels off when the temperature is less than 50 ˚C. When the temperature is increased over 50 ˚C, the clustering intensity starts decreasing. The clustering of PEO is monitored in ethanol/ water mixtures. The clustering intensity increases as the fraction of water is increased. Based on the solvation intensity behavior, we confirmed that the ethanol/ water mixtures obey a random solvent mixing rule, whereby solvent mixtures are better at solvating the polymer that any of the two solvents. The solution behavior of PEO in ethanol was investigated in the presence of salt (CaCl2) using SANS. Binding of Ca2+ ions to the PEO oxygens transforms the neutral polymer to a weakly charged polyelectrolyte. We observed that the PEO/ethanol solution is better solvated at higher salt concentration due to the electrostatic repulsion of weakly charged monomers. The association of the Ca2+ ions with the PEO oxygen atoms transforms the neutral polymer to a weakly charged polyelectrolyte and gives rise to repulsive interactions between the PEO/Ca2+ complexes. Addition of salt disrupts the gel, which is consistent with better solvation as the salt concentration is increased. Moreover, SANS shows that the phase behavior of PEO/ethanol changes from UCST to LCST as the salt concentration is increased.

Understanding the Reaction Mechanism of Nanocomposite Thermites

Nanocomposite energetics are a relatively new class of materials that combine nanoscale fuels and oxidizers to allow for the rapid release of large amounts of energy. In thermite systems (metal fuel with metal oxide oxidizer), the use of nanomaterials has been illustrated to increase reactivity by multiple orders of magnitude as a result of the higher specific surface area and smaller diffusion length scales. However, the highly dynamic and nanoscale processes intrinsic to these materials, as well as heating rate dependencies, have limited our understanding of the underlying processes that control reaction and propagation. For my dissertation, I have employed a variety of experimental approaches that have allowed me to probe these processes at heating rates representative of free combustion with the goal of understanding the fundamental mechanisms. Dynamic transmission electron microscopy (DTEM) was used to study the in situ morphological change that occurs in nanocomposite thermite materials subjected to rapid (10^11 K/s) heating. Aluminum nanoparticle (Al-NP) aggregates were found to lose their nanostructure through coalescence in as little as 10 ns, which is much faster than any other timescale of combustion. Further study of nanoscale reaction with CuO determined that a condensed phase interfacial reaction could occur within 0.5-5 µs in a manner consistent with bulk reaction, which supports that this mechanism plays a dominant role in the overall reaction process. Ta nanocomposites were also studied to determine if a high melting point (3280 K) affects the loss of nanostructure and rate of reaction. The condensed phase reaction pathway was further explored using reactive multilayers sputter deposited onto thin Pt wires to allow for temperature jump (T-Jump) heating at rates of ~5x10^5 K/s. High speed video and a time of flight mass spectrometry (TOFMS) were used to observe ignition temperature and speciation as a function of bilayer thickness. The ignition process was modeled and a low activation energy for effective diffusivity was determined. T-Jump TOFMS along with constant volume combustion cell studies were also used to determine the effect of gas release in nanoparticle systems by comparing the reaction properties of CuO and Cu2O.