Cellulosic fibers sized from the macro-scale to the nano-scale were prepared hierarchically from kenaf bast fibers using chemicals. The process began with a hermetical alkaline retting followed by a bleaching treatment. The bleached fibers were hydrolyzed using inorganic acid, from which microfibers and cellulose nanowhiskers (CNWs) were fabricated. Inorganic nanoparticle impregnation (INI) was used to treat the retted fibers for the improvement of the interfacial compatibility between the fiber and polypropylene (PP) matrix. The retted fibers and INI-treated fibers were used as reinforcement for the PP polymer composites. Film casting process was used to make CNW/PVA composites. The hermetical retting process used in this study produced fibers with high cellulose contents (81-92%) by removing the lignin and hemicelluloses. Higher retting temperature resulted in higher fiber surface hardness and elastic moduli. The tensile strengths and tensile moduli of the fibers decreased as the temperature increased. The SEM images showed the micropores in the cell wall structure for the fibers retted at over 130°C, providing the possibility to anchor nanoparticles into the cell wall. Surface morphology of the INI-treated fibers was examined with SEM, and showed that the CaCO3 nanoparticle crystals grew onto the fiber surface. Energy-dispersive X-ray spectroscopy (EDS) was used to verify the CaCO3 particle deposits on the fiber surface. As the size scale of the fibers decreased, the fiber crystallinity increased from 49.9% (retted fibers) to 83.9% (CNWs). About 23% á-cellulose in the raw kenaf bast fibers had been converted into CNWs. The retted fibers without INI treatment had poor compatibility with the polypropylene matrix. The INI treatment improved the compatibility between the fibers and the PP matrix, resulting in an improvement in kenaf fiber/PP composite tensile moduli and tensile strengths. The CNWs prepared from kenaf bast fiber gave excellent reinforcement for PVA composites. A nine percent increase of CNWs in the CNW/PVA composites yielded significant improvements in tensile strength and modulus of about 46% and 152%, respectively, compared with pure PVA.

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The goal of this work is to further understand the relationships between porous electrode microstructure and mass transport properties. This understanding allows us to predict and improve cell performance from fundamental principles. The investigated battery systems are the widely used rechargeable Li-ion battery and the non-rechargeable alkaline battery. This work includes three main contributions in the battery field listed below. Direct Measurement of Effective Electronic Transport in Porous Li-ion Electrodes. An accurate assessment of the electronic conductivity of electrodes is necessary for understanding and optimizing battery performance. The bulk electronic conductivity of porous LiCoO2-based cathodes was measured as a function of porosity, pressure, carbon fraction, and the presence of an electrolyte. The measurements were performed by delamination of thin-film electrodes from their aluminum current collectors and by use of a four-line probe. Imaging and Correlating Microstructure To Conductivity. Transport properties of porous electrodes are strongly related to microstructure. An experimental 3D microstructure is needed not only for computation of direct transport properties, but also for a detailed electrode microstructure characterization. This work utilized X-ray tomography and focused ion beam (FIB)/scanning electron microscopy (SEM) to obtain the 3D structures of alkaline battery cathodes. FIB/SEM has the advantage of detecting carbon additives; thus, it was the main tomography tool employed. Additionally, protocols and techniques for acquiring, processing and segmenting series of FIB/SEM images were developed as part of this work. FIB/SEM images were also used to correlate electrodes' microstructure to their respective conductivities for both Li-ion and alkaline batteries. Electrode Microstructure Metrics and the 3D Stochastic Grid Model. A detailed characterization of microstructure was conducted in this work, including characterization of the volume fraction, nearest neighbor probability, domain size distribution, shape factor, and Fourier transform coefficient. These metrics are compared between 2D FIB/SEM, 3D FIB/SEM and X-ray structures. Among those metrics, the first three metrics are used as a basis for SG model parameterization. The 3D stochastic grid (SG) model is based on Monte Carlo techniques, in which a small set of fundamental inter-domain parameters are used to generate structures. This allows us to predict electrode microstructure and its effects on both electronic and ionic properties.

In this work we present a carbon free gas diffusion electrode (GDE) design. It is a first step towards improvement of technologies like alkaline fuel cells, some alkaline electrolyzes and metal-air-batteries by circumventing carbon degradation. A nickel-mesh was made hydrophobic and subsequently electrochemically coated with MnOx as electrocatalyst. By this, a carbon free GDE was prepared. The contact angle, specific surface area (BET), pore size distribution, crystal phase (XRD) and electrochemical properties were determined. The deposition scan rate (rscan) during dynamic MnOx deposition altered the macro surface structure, pore size distribution and deposited mass. High catalyst masses with high specific surface area were achieved by lower rscan, but hydrophobicity was decreased. Impedance spectroscopy showed that higher MnOx mass will increase the ohmic resistance, because of the low conductivity of oxides, such as MnOx. The diffusion of dissolved oxygen is the major contributor to the total resistance. However, the polarization resistance was reduced by increased specific surface area of MnOx. It was concluded that the ORR and OER are limited by diffusion in this design but nevertheless showed reasonable activity for ±10 mA cm−2 corresponding to ∼8 Ω cm−2 while references exhibited ∼3.5 Ω cm−2 .

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Alkaline fuel cells are a promising technology, with their sturdy design and many applications they are held back mostly by their cost. By introducing a catalyst, the activation energy of the cell can be reduced to an overcomable amount. Unfortunately, due to the high cost and sparse availability of the most used catalyst metal today, platinum, it has become apparent that a new suitable catalyst must be found in order to make the fuel cells economically feasible. Silver and palladium have been proposed as promising alternatives, sharing a majority of the traits but with a fraction of the cost. The original aim of this project was to study the performance of electrodes in an alkaline electrolyte loaded with different ratios of palladium and silver. However, due to the COVID-19 situation the project was not able to be completed and the aim of the project changed. The new aim was divided into two parts. The first one being to study how the initial concentration of silver ions affects the size of the obtained particles. This was achieved by a radiolysis-based method of synthesis in an aqueous solution. The second aim was to study the performance of the electrodes loaded with different amounts of silver and different average particle size. However, this part was not possible to conduct either. Therefore, results from a previous study performed by I. L. Soroka et al. was used for discussion. The results point towards a lower initial concentration achieving a smaller average particle size and a lower loading of catalyst on the electrode can be compensated by a smaller average particle size of the catalyst.

The use of the periplasmic alkaline phosphatase (PhoA) reporter protein from E. coli has been critical for definition of the topology of transmembrane proteins of multiple bacterial species. This report demonstrates development of a PhoA reporter system in B. burgdorferi. Codon usage of the E. coli phoA in B. burgdorferi was analyzed and an optimized version of the gene was obtained. In order to assess the differential activity of the reporter system, two optimized PhoA-fusion construct using B. burgdorferi proteins were engineered: one using the periplasmic protein OppAIV and one using the cytoplasmic protein PncA. The activity of PhoA requires periplasmic localization. The periplasmic OppAIV-PhoA fusion as well as the cytoplasmic PncA-PhoA fusion produced detectable PhoA protein in E. coli and in B. burgdorferi. The periplasmic fusion construct, but not the cytoplasmic fusion construct, resulted in functional alkaline phosphatase (AP) activity in E. coli, as observed by blue colonies on agar plates containing a chromogenic substrate for AP. In contrast, both of the fusion constructs produced limited detectable levels of functional alkaline phosphatase activity in B. burgdorferi, as observed by yellow color change in liquid protein lysate containing a chromogenic substrate for AP. Development of a PhoA fusion reporter system for use in B. burgdorferi will provide a new molecular genetics tool for analyzing the topology of B. burgdorferi transmembrane proteins. These types of studies are critical for understanding the function of B. burgdorferi transport systems and may identify novel molecular approaches for the treatment of Lyme disease.

The research presented in this thesis focuses on developing new functional polymeric materials that can conduct ions, H+, or OH- or Li+. The motivation behind this work was to understand the similarities and/or differences in the structure property relationships between polymer membranes and the conductivity of H+ and OH- ions, and between polymer membranes and the anhydrous conductivity of H+ and Li+ ions. This understanding is critical to developing durable polymer membranes with high H+, OH- and Li+ ion conductivity for proton exchange membrane fuel cells (PEMFCs), alkaline anion exchange membrane fuel cells (AAEMFCs) and lithium ion batteries respectively. Chapter 1 describes the basic functioning of PEMFCs, AAEMFCs and lithium ion batteries, the challenges associated with each research topic, and the fundamental mechanisms of ion transport. The proton conducting properties of poly(4-vinyl-1H-1,2,3-triazole) were investigated on a macroscopic scale by impedance spectroscopy and microscopic scale by solid state MAS NMR. It was found that proton conductivity is independent of molecular weight of the polymer, but influenced by orders of magnitude by the presence of residual dimethylformamide. To improve the mechanical properties of otherwise liquid-like 1H-1,2,3-triazole functionalized polysiloxane homopolymers, hybrid inorganic-organic proton exchange membranes (PEMs) containing 1H-viii 1,2,3-triazole grafted alkoxy silanes were synthesized, using sol-gel chemistry. This method enabled self-supporting membranes having proton conductivity comparable to uncrosslinked homopolymers. One of the biggest challenges with AEMs for use in AAEMFCs is finding a cationic polyelectrolyte that is chemically stable at elevated temperatures in high pH environment. Novel triazolium ionic salts were developed, having greater chemical stability under alkaline conditions compared to existing imidazolium ionic salts. However, the chemical stability of triazolium cations was not sufficient for AAEMFC applications. Excellent chemical stability of (C5H5)2Co+ in 2 M NaOH at 80°C over 30 days was demonstrated and polymerizable vinyl functionalized cobaltocenium monomers were synthesized. This work paves the way for future development of AEMs containing cobaltocenium moieties to facilitate hydroxide ion transport. Polymers containing covalently attached cyclic carbonates were synthesized and doped with lithium triflate and their lithium ion conductivities were investigated. The findings highlight the importance of high charge carrier density and flexibility of the polymer matrix to achieve high lithium ion conductivity. These results are similar to the key factors influencing anhydrous proton transport.

The Bingham porphyry Cu-Au-Mo deposit, Utah, may only be world-class because of substantial contributions of sulfur and metals from mafic alkaline magma to an otherwise unremarkable calc-alkaline system. Volcanic mafic alkaline rocks in the district are enriched in Cr, Ni, and Ba as well as ore-related constituents of Cu, Au, platinum group elements (PGE) and S. The bulk of the volcanic section that is comagmatic with ore-related porphyries is dacitic to trachytic in composition, but has inherited the geochemical signature of high Cr, Ni, and Ba from magma mixing with the mafic alkaline rocks. The volcanic section that most closely correlates in time with ore-related porphyries is very heterogeneous containing clasts of scoriaceous latite, latitic minette and flows of melanephelinite, shoshonite and olivine latite in addition to the volumetrically dominant dacite/trachyte. Bingham ore-related porphyries show ample evidence of prior mixing with mafic alkaline magmas. Intrusive porphyries that have not been previously studied well have several chemical and mineralogical indications of magma mixing. These "mixed" lithologies include the hybrid quartz monzonite porphyry, biotite porphyry, and minette dikes. Even some of the more silicic latite and monzonite porphyries retain high Cr and Ba contents indicative of mixing and contain trace amounts of sapphire ( Magma mixing calculations suggest about 10% of the monzonitic/latitic ore-related magma may have been derived from mafic alkaline magma similar to the melanephelinite. If the original S content of the mafic magma was about 2000-4000 ppm, comparable to similar magmas, then the mafic magma may have been responsible for contributing more than half of the S and a significant portion of the Cu, Au, and PGE in the Bingham deposit.

The Iron and Manitou Islands complexes are 560 m.y. old. They were associated with a magma chamber lying at moderate depth below these complexes, On a regional scale the emplacement is controlled by the Nipissing graben system, an extension of the St. Lawrence rift system, along which an alkaline igneous province, 560 m.y. old, is well developed. A variety of rock types is developed in these complexes in spite of their small size. This is a result of extensive differentiation, interaction of late fractions with already crystallized early fractions, interaction of a "fluid phase" with country rocks, partial melting of country rocks, and finally various late hydrothermal alterations. The high degree of differentiation is probably a consequence of the high amount of volatile components in the magma which lowers its viscosity, extends its crystallization range, and consequently enhances fractional crystallization. In addition, liquid immiscibility played an important role in the differentiation. During differentiation the pyroxenes changed in composition from Ca-rich varieties through aegirine-augite to acmite, There is no evidence of an immiscibility gap between Ca-rich and Na-rich pyroxenes as has been proposed by Aoki (1964) but criticized by later investigators, Members of the phlogopite-biotite solid solution series exhibit a compositional range from annite-12 to annite-63. The characteristic assemblage melilite; Ca-rich pyroxene, and olivine (partially or completely replaced olivine phenocrysts) occurring in some lamprophyres indicates low silica activity, 10^(-1.6) to 10^(-1.2). However, the silica activity of the Lamprophyres is not restricted to the above range since the presence of sphene in some Lamprophyre dykes indicates silica activity above this range. The required condition of excess sodium silicate for the crystallization of acmite in synthetic melts seems to be required in nature too. Lamprophyres have a crystallization temperature of about 950°C. Fenitization of the country rocks takes place from relatively low temperature, probably 480°F, to about 740°C where partial melting of the rocks occur. The development of the graben system and the alkaline igneous activity are both believed to be related to devolatilization processes in the mantle. / Thesis / Master of Science (MSc)