Local degradation of structural, mechanical, electrical and chemical properties of membrane electrode assembly in polymer electrolyte fuel cell

Polymer electrolyte fuel cell (PEMFC) is promising source of clean power in many applications ranging from portable electronics to automotive and land-based power generation. However, widespread commercialization of PEMFC is primarily challenged by degradation. The mechanisms of fuel cell degradation are not well understood. Even though the numbers of installed units around the world continue to increase and dominate the pre-markets, the present lifetime requirements for fuel cells cannot be guarantee, creating the need for a more comprehensive knowledge of material’s ageing mechanism. The objective of this project is to conduct experiments on membrane electrode assembly (MEA) components of PEMFC to study structural, mechanical, electrical and chemical changes during ageing and understanding failure/degradation mechanism. The first part of this project was devoted to surface roughness analysis on catalyst layer (CL) and gas diffusion layer (GDL) using surface mapping microscopy. This study was motivated by the need to have a quantitative understanding of the GDL and CL surface morphology at the submicron level to predict interfacial contact resistance. Nanoindentation studies using atomic force microscope (AFM) were introduced to investigate the effect of degradation on mechanical properties of CL. The elastic modulus was decreased by 45 % in end of life (EOL) CL as compare to beginning of life (BOL) CL. In another set of experiment, conductive AFM (cAFM) was used to probe the local electric current in CL. The conductivity drops by 62 % in EOL CL. The future task will include characterization of MEA degradation using Raman and Fourier transform infrared (FTIR) spectroscopy. Raman spectroscopy will help to detect degree of structural disorder in CL during degradation. FTIR will help to study the effect of CO in CL. XRD will be used to determine Pt particle size and its crystallinity. In-situ conductive AFM studies using electrochemical cell on CL to correlate its structure with oxygen reduction reaction (ORR) reactivity

Induction of Microalgal Lipids for Biodiesel Production in Tandem with Sequestration of High Carbon Dioxide Concentration

There is no doubt that sufficient energy supply is indispensable for the fulfillment of our fossil fuel crises in a stainable fashion. There have been many attempts in deriving biodiesel fuel from different bioenergy crops including corn, canola, soybean, palm, sugar cane and vegetable oil. However, there are some significant challenges, including depleting feedstock supplies, land use change impacts and food use competition, which lead to high prices and inability to completely displace fossil fuel [1-2]. In recent years, use of microalgae as an alternative biodiesel feedstock has gained renewed interest as these fuels are becoming increasingly economically viable, renewable, and carbon-neutral energy sources. One reason for this renewed interest derives from its promising growth giving it the ability to meet global transport fuel demand constraints with fewer energy supplies without compromising the global food supply. In this study, Chlorella protothecoides microalgae were cultivated under different conditions to produce high-yield biomass with high lipid content which would be converted into biodiesel fuel in tandem with the mitigation of high carbon dioxide concentration. The effects of CO2 using atmospheric and 15% CO2 concentration and light intensity of 35 and 140 µmol m-2s-1 on the microalgae growth and lipid induction were studied. The approach used was to culture microalgal Chlorella protothecoides with inoculation of 1×105 cells/ml in a 250-ml Erlenmeyer flask, irradiated with cool white fluorescent light at ambient temperature. Using these conditions we were able to determine the most suitable operating conditions for cultivating the green microalgae to produce high biomass and lipids. Nile red dye was used as a hydrophobic fluorescent probe to detect the induced intracellular lipids. Also, gas chromatograph mass spectroscopy was used to determine the CO2 concentrations in each culture flask using the closed continuous loop system. The goal was to study how the 15% CO2 concentration was being used up by the microalgae during cultivation. The results show that the condition of high light intensity of 140 µmol m-2s-1 with 15% CO2 concentration obtain high cell concentration of 7 x 105 cells mL-1 after culturing Chlorella protothecoides for 9 to 10 day in both open and closed systems respectively. Higher lipid content was estimated as indicated by fluorescence intensity with 1.3 to 2.5 times CO2 reduction emitted by power plants. The particle size of Chlorella protothecoides increased as well due to induction of lipid accumulation by the cells when culture under these condition (140 µmol m-2s-1 with 15% CO2 concentration).

STUDIES OF FUNCTIONALIZED NANOPARTICLES FOR SMART SELF-ASSEMBLY AND AS CONTROLLED DRUG DELIVERY

This dissertation is related to the studies of functionalized nanoparticles for self-assembly and as controlled drug delivery system. The whole topic is composed of two parts. In the first part, the research was conducted to design and synthesize a new type of ionic peptide-functionalized copolymer conjugates for self-assembly into nanoparticle fibers and 3D scaffolds with the ability of multi-drug loading and governing the release rate of each drug for tissue engineering. The self-assembly study confirmed that such peptide-functionalized amphiphilic copolymers underwent different self-assembly behavior. The bigger nanoparticles were more easily assembled into nanoparticle fibers and 3D scaffolds with larger pore size, while the smaller nanoparticle underwent faster self-assembly to form more compact 3D scaffolds with smaller porosity but more stable structure. Controlled release studies confirmed the ability of governing simultaneous release of different model drugs with independent release rate from a same scaffold. Cytotoxicity tests showed that all synthesized peptides, copolymers and peptide-copolymer conjugates were biocompatible with SW-620 cell lines and NIH3T3 cell lines. This new type of self-assembled scaffolds combined the advantages of peptide nanofibers and versatile controlled release of polymeric nanoparticles to achieve simultaneous multi-drug loading and controlled release of each drug, uniform distribution and flexibility of hydrogel scaffolds. The investigations in second part were first to design and synthesize organic biocide-loaded nanoparticles for low-leaching wood preservation using a cost-effective one-pot method to synthesize amphiphilic chitosan-g-PMMA nanoparticles loading with ~25-28 wt.% of the fungicide tebuconazole with particle size of ~100 nm diameter by FESEM. FESEM analysis confirmed efficient penetration of nanoparticles throughout the treated wooden stake with dimension of 19 × 19 × 455 mm^3. Leaching studies showed that biocide introduced into sapwood via nanoparticles leached only ~9% compared with the amount leached from tebuconazole solution-treated control, while soil jar tests showed that the nanoparticle-treated wood blocks were effectively protected from biological decay tested against G. trabeum, a brown rot fungus. Copper oxide nanoparticles with and without polymer stabilizers were also investigated to use as inorganic wood preservatives to clarify the factor affecting copper leaching from treated wood. Copper oxide nanoparticles with uniform diameters of ~10 nm and ~50 nm were prepared, and the leachates from southern pine sapwood treated with these nanoparticles were analyzed. It was found by TEM and EDS analysis that significant numbers of nanoparticles leached from the treated wood. The 50 nm nanoparticles leached slightly less than a soluble copper salt control, but 10 nm nanoparticles leached substantially more than the control. The effect of polymer stabilizers on nanoparticle leaching was also investigated. Results showed that polymer stabilizers increased leaching. The trends showed that nanoparticle size was a major factor in copper leaching.