Browsing Theses and Dissertations by Subject "Nanoparticles"
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EFFECT OF MECHANICAL VIBRATION ON PLATINUM PARTICLE AGGLOMERATION AND GROWTH IN PROTON EXCHANGE MEMBRANE FUEL CELL CATALYST LAYERThe objective of the current research is to study the effect of mechanical vibration on catalyst layer degradation via Platinum (Pt) particle agglomeration and growth in the membrane electrode assembly (MEA) of a proton exchange membrane fuel cell (PEM Fuel Cell). This study is of great importance, since many PEM fuel cells operate under a vibrating environment, such as the case of vehicular applications, and this may influence the catalyst layer degradation and fuel cell performance. Through extensive literature review, there are only few researches that have been studied the effect of mechanical vibration on PEM fuel cells. These studies focused only on PEM fuel cell performance under vibration for less than 50 hours and none of them considered the degradation of the fuel cell components, such as MEA and its catalyst layer. To study the effect of the mechanical vibration on the catalyst layer an accelerated test with potential cycling was specially designed to simulate a typical vehicle driving condition. The length of the accelerated test was designed to be 300 hour with potential cycling comprised of idle running, constant load, triangle (variable) load and overload running at various mechanical vibration conditions. These mechanical vibration conditions were as follows: 1g 20 Hz, 1g 40 Hz, 4g 20 Hz and 4g 40 Hz. No vibration tests were also conducted to study the influence of operating time and were used as a baseline for comparison study. The series of accelerated tests were followed by microscopy and spectroscopy analyses using environmental scanning electron microscopy (ESEM), transmission electron microscopy (TEM) and X-Ray diffraction (XRD). An ESEM was used to qualitatively analyze pristine and degraded catalyst. TEM and XRD were used to quantitatively analyze catalyst layer degradation via Pt agglomeration and growth in pristine and degraded states. For each test condition, PEM fuel cell performance by means of Voltage - Current (VI) curves was monitored and recorded. It was observed that the mean diameter of Pt particles tested under mechanical vibration is 10% smaller than the ones that were tested under no vibration conditions. The Pt particles in the order of 2 to 2.5 nm in the pristine state have grown to 6.14 nm (after 300 hour accelerated test at no vibration condition), to 5.64 nm (after 300 hours accelerated test under 4g 20 Hz vibration condition) and to 5.55 nm (after 300 hours accelerated test under 1g 20 Hz vibration condition). The mean Pt particle diameters, after 300 hour accelerated test under 1g 40 Hz and 4g 40 Hz vibration conditions, were 5.89 nm. With an increase of the mean Pt particle diameter, the active surface area of the catalyst layer of the MEA decreases and as a result, performance of MEA and PEM fuel also decreases. It was observed that performance of the MEA tested under no vibration condition is about 10% lower than the one tested under 1g 20 Hz. The VI curve showed that the lowest performance of the MEA after 300 hour accelerated test corresponded to no vibration conditions and equaled to 7.85 Watts at 0.5 V (Pt particle size ~ 6.14 nm) and highest performance, corresponded to the MEA tested under 1g 20 Hz, and equaled to 8.66 Watts at 0.5 V (Pt particle size ~ 5.55 nm).
INTERACTIONS BETWEEN METAL OXIDES AND/OR NATURAL ORGANIC MATTER AND THEIR INFLUENCE ON THE OXIDATIVE REACTIVITY OF MANGANESE DIOXIDEMn oxides have high redox potentials and are known to be very reactive, rendering many contaminants susceptible to degradation via oxidation. Although Mn oxides typically occur as mixtures with other metal oxides (e.g., Fe, Al, and Si oxides) and natural organic matter (NOM) in soils and aquatic environments, most studies to date have studied the reactivity of Mn oxides as a single oxide system. This study, for the first time, examined the effect of representative metal oxides (Al2O3, SiO2, TiO2, and Fe oxides) and NOM or NOM-model compounds (Aldrich humic acid (AHA), Leonardite humic acid (LHA), pyromellitic acid (PA) and alginate) on the oxidative reactivity of MnO2, as quantified by the oxidation kinetics of triclosan (a widely used phenolic antibacterial agent) as a probe compound. The study also examined the effect of soluble metal ions released from the oxide surfaces on MnO2 reactivity. In binary oxide mixtures, Al2O3 decreased the reactivity of MnO2 as a result of both heteroaggregation and complexation of soluble Al ions with MnO2. At pH 5, the surface charge of MnO2 is negative while that of Al2O3 is positive resulting in intensive heteroaggregation between the two oxides. Up to 3.15 mM of soluble Al ions were detected in the supernatant of 10 g/L of Al2O3 at pH 5.0 whereas the soluble Al concentration was 0.76 mM in the mixed Al2O3 + MnO2 system at the same pH. The lower amount of soluble Al in the latter system is the result of Al ion adsorption by MnO2. The experiments with the addition of 0.001 to 0.1 mM Al3+ to MnO2 suspension indicated the triclosan oxidation rate constant decreased from 0.24 to 0.03 h-1 due to surface complexation. Fe oxides which are also negatively charged at pH 5 inhibited the reactivity of MnO2 through heteroaggregation. The concentration of soluble Fe(III) ions ( 4 mg-TOC/L or [alginate/PA] > 10 mg/L, a lower extent of heteroaggregation was also observed due to the negatively charged surfaces for all oxides. Similar effects on aggregation and MnO2 reactivity as discussed above were observed for ternary MnO2‒Al2O3‒NOM systems. HAs, particularly at high concentrations (2.0 to 12.5 mg-C/L), alleviated the effect of soluble Al ions on MnO2 reactivity as a result of the formation of soluble Al-HA complexes. Alginate and PA, however, did not form soluble complexes with Al ions so they did not affect the effect of Al ions on MnO2 reactivity. Despite the above observations, the amount of Al ions dissolved in MnO2+Al2O3+NOM mixtures was too low, as a result of NOMs adsorption on the surface to passivate oxide dissolution, to have a major impact on MnO2 reactivity. In conclusion, this study provided, for the first time, a systematical understanding of the redox activity of MnO2 in complex model systems. With this new knowledge, the gap between single oxide systems and complex environmental systems is much narrower so that it is possible to have a more accurate prediction of the fate of contaminants in the environment.
Iron Oxide Nanoparticle Surface Modification: Synthesis and CharacterizationMultifunctional nanomaterials can be engineered to aid in the diagnosis of diseases, enable efficient drug delivery, monitor treatment progress over time, and evaluate treatment outcomes. This strategy, known as theranostics, focuses on the combination of diagnostic and therapeutic techniques to provide new clinically safe and efficient personalized treatments. The evaluation of different nanomaterials’ properties and their customization for specific medical applications has therefore been a significant area of interest within the scientific community. Iron oxide nanoparticles, specifically those based on iron (II, III) oxide (magnetite, Fe3O4), have been prominently investigated for biomedical, theranostic applications due to their documented superparamagnetism, high biocompatibility, and other unique physicochemical properties. The aim of this thesis is to establish a viable set of methods for preparing magnetite (iron oxide) nanoparticles through hydrothermal synthesis and modifying their surfaces with organic functional groups in order to both modulate surface chemistry and facilitate the attachment of molecules such as peptides via covalent bond formations. Modifying their surfaces with biomolecules such as peptides can further increase their uptake into cells, which is a necessary step in the mechanisms of their desired biomedical applications. The methods of nanoparticle synthesis, surface functionalization, and characterization involving electron microscopy (e.g., SEM, TEM), zeta potential measurements, size analysis (i.e., DLS), and FT-IR spectroscopy will be presented.
TAILORING DRUG-CARRIER INTERACTIONS IN POLY(SIALIC ACID) MICELLES FOR USE AS CANCER THERAPEUTIC CARRIERSAlthough great progress has been made, cancer still remains one of the most prevalent maladies plaguing mankind. New treatment methodologies using nanoparticles have come to the forefront by allowing for enhanced delivery of therapeutics to the tumor site. The design of the nanoparticle should allow for long circulation times, tumor-specific targeting and efficient release at the site of action. This requires that both the external shell and internal core of the nanoparticle be carefully selected to meet the maximal criteria of each of these steps. Poly(sialic acid) (PSA), a naturally occurring polysaccharide, meets all of the benchmarks of an effective exterior coating yet remains relatively unexplored in the field of drug delivery. Due to stealth properties, natural tumor targeting ability, and inherent pH-responsive elements, PSA has frequently been viewed as a “next-generation” surface coating. Just as important, the internal composition of the carrier should aid in effective drug loading but also rapid release. The selection of the core containing groups as well as therapeutic should be maximized in order to customize the carrier to drug. Here, we have developed PSA micelles composed of various internal groups selected to maximize drug loading and facilitate release. Loading of the chemotherapeutic doxorubicin was optimized through variations in non-covalent bonding forces between drug and carrier. Furthermore, PSA micelles composed of internal pH-responsive groups of varying hydrophobicity were also developed to tailor micelle swelling points at conditions analogous towards those found upon cellular uptake. Both of these were effective delivery platforms towards MCF-7 human breast adenocarcinoma cells.