UNDERSTANDING PEOPLE'S ADOPTION OF INDIVIDUAL-USE RENEWABLE ENERGY TECHNOLOGY

This thesis attempts to understand why people adopt or reject individual-use renewable energy technologies (IURET). I used factors from Everett Rogers' Diffusion of Innovation Theory to understand how people's perceptions towards the characteristics of a given IURET (such as price, compatibility, complexity, etc.), the characteristics of the individual adopter (such as innovativeness and environmental awareness), and the communication network (inter-personal communications and mass media) can influence adoption. An online questionnaire was sent to 101randomly selected Michigan households (using random digit dialing) to ask people whether or not they had adopted at least one IURET and to assess the above-mentioned factors from Rogers' theory. Data analysis was then conducted in SPSS using Chi-squared and binary logistic regression to determine the relationship between adoption behaviors (the dependent variable) and the factors from Rogers' theory (the independent variables) while controlling for education. The results show that Rogers' factors of price and observability and the control variable of education were all significant in explaining adoption but the other factors of Rogers' theory were not. For example, if individuals perceive the price of IURET to be reasonable or if they observe their neighbors using these technologies, then they are more likely to adopt. These results indicate that, if we want to promote greater adoption of IURET, we should focus our efforts on making the price of IURET more affordable through incentives and other mechanisms. Adopters should also be given some form of reward if they provide free demonstrations of their IURET in use to their neighbors to take advantage of the observability effects.

ELECTROCATALYTIC PROCESSING OF RENEWABLE BIOMASS-DERIVED COMPOUNDS FOR PRODUCTION OF CHEMICALS, FUELS AND ELECTRICITY

The dual problems of sustaining the fast growth of human society and preserving the environment for future generations urge us to shift our focus from exploiting fossil oils to researching and developing more affordable, reliable and clean energy sources. Human beings had a long history that depended on meeting our energy demands with plant biomass, and the modern biorefinery technologies realize the effective conversion of biomass to production of transportation fuels, bulk and fine chemicals so to alleviate our reliance on fossil fuel resources of declining supply. With the aim of replacing as much non-renewable carbon from fossil oils with renewable carbon from biomass as possible, innovative R&D activities must strive to enhance the current biorefinery process and secure our energy future. Much of my Ph.D. research effort is centered on the study of electrocatalytic conversion of biomass-derived compounds to produce value-added chemicals, biofuels and electrical energy on model electrocatalysts in AEM/PEM-based continuous flow electrolysis cell and fuel cell reactors. High electricity generation performance was obtained when glycerol or crude glycerol was employed as fuels in AEMFCs. The study on selective electrocatalytic oxidation of glycerol shows an electrode potential-regulated product distribution where tartronate and mesoxalate can be selectively produced with electrode potential switch. This finding then led to the development of AEMFCs with selective production of valuable tartronate or mesoxalate with high selectivity and yield and cogeneration of electricity. Reaction mechanisms of electrocatalytic oxidation of ethylene glycol and 1,2-propanediol were further elucidated by means of an on-line sample collection technique and DFT modeling. Besides electro-oxidation of biorenewable alcohols to chemicals and electricity, electrocatalytic reduction of keto acids (e.g. levulinic acid) was also studied for upgrading biomass-based feedstock to biofuels while achieving renewable electricity storage. Meanwhile, ORR that is often coupled in AEMFCs on the cathode was investigated on non-PGM electrocatalyst with comparable activity to commercial Pt/C. The electro-biorefinery process could be coupled with traditional biorefinery operation and will play a significant role in our energy and chemical landscape.

Fabrication and characterization of room temperature operating single electron transistors using focused ion beam technologies

The single electron transistor (SET) is a Coulomb blockade device, whose operation is based on the controlled manipulation of individual electrons. Single electron transistors show immense potential to be used in future ultra lowpower devices, high density memory and also in high precision electrometry. Most SET devices operate at cryogenic temperatures, because the charging energy is much smaller than the thermal oscillations. The room temperature operation of these devices is possible with sub- 10nm nano-islands due to the inverse dependance of charging energy on the radius of the conducting nano-island. The fabrication of sub-10nm features with existing lithographic techniques is a technological challenge. Here we present the results for the first room temperature operating SET device fabricated using Focused Ion Beam deposition technology. The SET device, incorporates an array of tungsten nano-islands with an average diameter of 8nm. The SET devices shows clear Coulomb blockade for different gate voltages at room temperature. The charging energy of the device was calculated to be 160.0 meV; the capacitance per junction was found to be 0.94 atto F; and the tunnel resistance per junction was calculated to be 1.26 G Ω. The tunnel resistance is five orders of magnitude larger than the quantum of resistance (26 k Ω) and allows for the localization of electrons on the tungsten nano-island. The lower capacitance of the device combined with the high tunnel resistance, allows for the Coulomb blockade effects observed at room temperature. Different device configurations, minimizing the total capacitance of the device have been explored. The effect of the geometry of the nano electrodes on the device characteristics has been presented. Simulated device characteristics, based on the soliton model have been discussed. The first application of SET device as a gas sensor has been demonstrated.

Characterization of thermal and mechanical properties of polypropylene-based composites for fuel cell bipolar plates and development of educational tools in hydrogen and fuel cell technologies

In this project we developed conductive thermoplastic resins by adding varying amounts of three different carbon fillers: carbon black (CB), synthetic graphite (SG) and multi-walled carbon nanotubes (CNT) to a polypropylene matrix for application as fuel cell bipolar plates. This component of fuel cells provides mechanical support to the stack, circulates the gases that participate in the electrochemical reaction within the fuel cell and allows for removal of the excess heat from the system. The materials fabricated in this work were tested to determine their mechanical and thermal properties. These materials were produced by adding varying amounts of single carbon fillers to a polypropylene matrix (2.5 to 15 wt.% Ketjenblack EC-600 JD carbon black, 10 to 80 wt.% Asbury Carbon's Thermocarb TC-300 synthetic graphite, and 2.5 to 15 wt.% of Hyperion Catalysis International's FIBRILTM multi-walled carbon nanotubes) In addition, composite materials containing combinations of these three fillers were produced. The thermal conductivity results showed an increase in both through-plane and in-plane thermal conductivities, with the largest increase observed for synthetic graphite. The Department of Energy (DOE) had previously set a thermal conductivity goal of 20 W/m·K, which was surpassed by formulations containing 75 wt.% and 80 wt.% SG, yielding in-plane thermal conductivity values of 24.4 W/m·K and 33.6 W/m·K, respectively. In addition, composites containing 2.5 wt.% CB, 65 wt.% SG, and 6 wt.% CNT in PP had an in–plane thermal conductivity of 37 W/m·K. Flexural and tensile tests were conducted. All composite formulations exceeded the flexural strength target of 25 MPa set by DOE. The tensile and flexural modulus of the composites increased with higher concentration of carbon fillers. Carbon black and synthetic graphite caused a decrease in the tensile and flexural strengths of the composites. However, carbon nanotubes increased the composite tensile and flexural strengths. Mathematical models were applied to estimate through-plane and in-plane thermal conductivities of single and multiple filler formulations, and tensile modulus of single-filler formulations. For thermal conductivity, Nielsen's model yielded accurate thermal conductivity values when compared to experimental results obtained through the Flash method. For prediction of tensile modulus Nielsen's model yielded the smallest error between the predicted and experimental values. The second part of this project consisted of the development of a curriculum in Fuel Cell and Hydrogen Technologies to address different educational barriers identified by the Department of Energy. By the creation of new courses and enterprise programs in the areas of fuel cells and the use of hydrogen as an energy carrier, we introduced engineering students to the new technologies, policies and challenges present with this alternative energy. Feedback provided by students participating in these courses and enterprise programs indicate positive acceptance of the different educational tools. Results obtained from a survey applied to students after participating in these courses showed an increase in the knowledge and awareness of energy fundamentals, which indicates the modules developed in this project are effective in introducing students to alternative energy sources.

Sustainable Energy Production in the United States: Life Cycle Assessment of Biofuels and Bioenergy

The United States of America is making great efforts to transform the renewable and abundant biomass resources into cost-competitive, high-performance biofuels, bioproducts, and biopower. This is the key to increase domestic production of transportation fuels and renewable energy, and reduce greenhouse gas and other pollutant emissions. This dissertation focuses specifically on assessing the life cycle environmental impacts of biofuels and bioenergy produced from renewable feedstocks, such as lignocellulosic biomass, renewable oils and fats. The first part of the dissertation presents the life cycle greenhouse gas (GHG) emissions and energy demands of renewable diesel (RD) and hydroprocessed jet fuels (HRJ). The feedstocks include soybean, camelina, field pennycress, jatropha, algae, tallow and etc. Results show that RD and HRJ produced from these feedstocks reduce GHG emissions by over 50% compared to comparably performing petroleum fuels. Fossil energy requirements are also significantly reduced. The second part of this dissertation discusses the life cycle GHG emissions, energy demands and other environmental aspects of pyrolysis oil as well as pyrolysis oil derived biofuels and bioenergy. The feedstocks include waste materials such as sawmill residues, logging residues, sugarcane bagasse and corn stover, and short rotation forestry feedstocks such as hybrid poplar and willow. These LCA results show that as much as 98% GHG emission savings is possible relative to a petroleum heavy fuel oil. Life cycle GHG savings of 77 to 99% were estimated for power generation from pyrolysis oil combustion relative to fossil fuels combustion for electricity, depending on the biomass feedstock and combustion technologies used. Transportation fuels hydroprocessed from pyrolysis oil show over 60% of GHG reductions compared to petroleum gasoline and diesel. The energy required to produce pyrolysis oil and pyrolysis oil derived biofuels and bioelectricity are mainly from renewable biomass, as opposed to fossil energy. Other environmental benefits include human health, ecosystem quality and fossil resources. The third part of the dissertation addresses the direct land use change (dLUC) impact of forest based biofuels and bioenergy. An intensive harvest of aspen in Michigan is investigated to understand the GHG mitigation with biofuels and bioenergy production. The study shows that the intensive harvest of aspen in MI compared to business as usual (BAU) harvesting can produce 18.5 billion gallons of ethanol to blend with gasoline for the transport sector over the next 250 years, or 32.2 billion gallons of bio-oil by the fast pyrolysis process, which can be combusted to generate electricity or upgraded to gasoline and diesel. Intensive harvesting of these forests can result in carbon loss initially in the aspen forest, but eventually accumulates more carbon in the ecosystem, which translates to a CO2 credit from the dLUC impact. Time required for the forest-based biofuels to reach carbon neutrality is approximately 60 years. The last part of the dissertation describes the use of depolymerization model as a tool to understand the kinetic behavior of hemicellulose hydrolysis under dilute acid conditions. Experiments are carried out to measure the concentrations of xylose and xylooligomers during dilute acid hydrolysis of aspen. The experiment data are used to fine tune the parameters of the depolymerization model. The results show that the depolymerization model successfully predicts the xylose monomer profile in the reaction, however, it overestimates the concentrations of xylooligomers.

CHARACTERIZATION OF THERMAL AND MECHANICAL PROPERTIES OF POLYPROPYLENE–BASED COMPOSITES FOR FUEL CELL BIPOLAR PLATES AND DEVELOPMENT OF EDUCATIONAL TOOLS IN HYDROGEN AND FUEL CELL TECHNOLOGIES

In this project we developed conductive thermoplastic resins by adding varying amounts of three different carbon fillers: carbon black (CB), synthetic graphite (SG) and multi–walled carbon nanotubes (CNT) to a polypropylene matrix for application as fuel cell bipolar plates. This component of fuel cells provides mechanical support to the stack, circulates the gases that participate in the electrochemical reaction within the fuel cell and allows for removal of the excess heat from the system. The materials fabricated in this work were tested to determine their mechanical and thermal properties. These materials were produced by adding varying amounts of single carbon fillers to a polypropylene matrix (2.5 to 15 wt.% Ketjenblack EC-600 JD carbon black, 10 to 80 wt.% Asbury Carbons’ Thermocarb TC-300 synthetic graphite, and 2.5 to 15 wt.% of Hyperion Catalysis International’s FIBRILTM multi-walled carbon nanotubes) In addition, composite materials containing combinations of these three fillers were produced. The thermal conductivity results showed an increase in both through–plane and in–plane thermal conductivities, with the largest increase observed for synthetic graphite. The Department of Energy (DOE) had previously set a thermal conductivity goal of 20 W/m·K, which was surpassed by formulations containing 75 wt.% and 80 wt.% SG, yielding in–plane thermal conductivity values of 24.4 W/m·K and 33.6 W/m·K, respectively. In addition, composites containing 2.5 wt.% CB, 65 wt.% SG, and 6 wt.% CNT in PP had an in–plane thermal conductivity of 37 W/m·K. Flexural and tensile tests were conducted. All composite formulations exceeded the flexural strength target of 25 MPa set by DOE. The tensile and flexural modulus of the composites increased with higher concentration of carbon fillers. Carbon black and synthetic graphite caused a decrease in the tensile and flexural strengths of the composites. However, carbon nanotubes increased the composite tensile and flexural strengths. Mathematical models were applied to estimate through–plane and in–plane thermal conductivities of single and multiple filler formulations, and tensile modulus of single–filler formulations. For thermal conductivity, Nielsen’s model yielded accurate thermal conductivity values when compared to experimental results obtained through the Flash method. For prediction of tensile modulus Nielsen’s model yielded the smallest error between the predicted and experimental values. The second part of this project consisted of the development of a curriculum in Fuel Cell and Hydrogen Technologies to address different educational barriers identified by the Department of Energy. By the creation of new courses and enterprise programs in the areas of fuel cells and the use of hydrogen as an energy carrier, we introduced engineering students to the new technologies, policies and challenges present with this alternative energy. Feedback provided by students participating in these courses and enterprise programs indicate positive acceptance of the different educational tools. Results obtained from a survey applied to students after participating in these courses showed an increase in the knowledge and awareness of energy fundamentals, which indicates the modules developed in this project are effective in introducing students to alternative energy sources.