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Description
Atmospheric particulate matter has a substantial impact on global climate due to its ability to absorb/scatter solar radiation and act as cloud condensation nuclei (CCN). Yet, little is known about marine aerosol, in particular, the carbonaceous fraction. In the present work, particulate matter was collected, using High Volume (HiVol) samplers,

Atmospheric particulate matter has a substantial impact on global climate due to its ability to absorb/scatter solar radiation and act as cloud condensation nuclei (CCN). Yet, little is known about marine aerosol, in particular, the carbonaceous fraction. In the present work, particulate matter was collected, using High Volume (HiVol) samplers, onto quartz fiber substrates during a series of research cruises on the Atlantic Ocean. Samples were collected on board the R/V Endeavor on West–East (March–April, 2006) and East–West (June–July, 2006) transects in the North Atlantic, as well as on the R/V Polarstern during a North–South (October–November, 2005) transect along the western coast of Europe and Africa. The aerosol total carbon (TC) concentrations for the West–East (Narragansett, RI, USA to Nice, France) and East–West (Heraklion, Crete, Greece to Narragansett, RI, USA) transects were generally low over the open ocean (0.36±0.14 μg C/m3) and increased as the ship approached coastal areas (2.18±1.37 μg C/m3), due to increased terrestrial/anthropogenic aerosol inputs. The TC for the North–South transect samples decreased in the southern hemisphere with the exception of samples collected near the 15th parallel where calculations indicate the air mass back trajectories originated from the continent. Seasonal variation in organic carbon (OC) was seen in the northern hemisphere open ocean samples with average values of 0.45 μg/m3 and 0.26 μg/m3 for spring and summer, respectively. These low summer time values are consistent with SeaWiFS satellite images that show decreasing chlorophyll a concentration (a proxy for phytoplankton biomass) in the summer. There is also a statistically significant (p<0.05) decline in surface water fluorescence in the summer. Moreover, examination of water–soluble organic carbon (WSOC) shows that the summer aerosol samples appear to have a higher fraction of the lower molecular weight material, indicating that the samples may be more oxidized (aged). The seasonal variation in aerosol content seen during the two 2006 cruises is evidence that a primary biological marine source is a significant contributor to the carbonaceous particulate in the marine atmosphere and is consistent with previous studies of clean marine air masses.
ContributorsHill, Hansina Rae (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Committee member) / Hartnett, Hilairy (Committee member) / Arizona State University (Publisher)
Created2011
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Description
The photovoltaic (PV) modules are primarily characterized for their performance with respect to incident irradiance and operating temperature. This work deals with data collection and automation of data processing for the performance and thermal characterizations of PV modules. This is a two-part thesis: The primary part (part-1) deals with the

The photovoltaic (PV) modules are primarily characterized for their performance with respect to incident irradiance and operating temperature. This work deals with data collection and automation of data processing for the performance and thermal characterizations of PV modules. This is a two-part thesis: The primary part (part-1) deals with the software automation to generate performance matrix as per IEC 61853-1 standard using MPPT (maximum power point tracking) data at the module or system level; the secondary part (part-2) deals with the software automation to predict temperature of rooftop PV modules using the thermal model coefficients generated in the previous studies of the Photovoltaic Reliability Laboratory (PRL). Part 1: The IEC 61853-1 standard published in January 2011 specifies the generation of a target performance matrix of photovoltaic (PV) modules at various temperatures and irradiance levels. In a conventional method, this target matrix is generated using all the data points of several measured I-V curves and the translation procedures defined in IEC 60891 standard. In the proposed method, the target matrix is generated using only three commonly field measured parameters: Module temperature, Incident irradiance and MPPT (Maximum Peak Power Tracking) value. These parameters are loaded into the programmed Excel file and with a click of a button, IEC 61853-1 specified Pmppt matrix is displayed on the screen in about thirty seconds. Part 2: In a previous study at PRL, an extensive thermal model to predict operating temperature of rooftop PV modules was developed with a large number of empirical monthly coefficients for ambient temperature, irradiance and wind speed. Considering that there is large number of coefficients for each air gap of rooftop modules, it became necessary to automate the entire data processing to predict the temperature of rooftop PV modules at different air gaps. This part of the work was dedicated to automatically predict the temperature of rooftop modules at different air gaps for any month in a year just using only four input parameters: Month, Irradiance, Ambient temperature and Wind speed.
ContributorsKoka, Kartheek (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Rogers, Bradley (Committee member) / Macia, Narciso F. (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Human breath is a concoction of thousands of compounds having in it a breath-print of physiological processes in the body. Though breath provides a non-invasive and easy to handle biological fluid, its analysis for clinical diagnosis is not very common. Partly the reason for this absence is unavailability of cost

Human breath is a concoction of thousands of compounds having in it a breath-print of physiological processes in the body. Though breath provides a non-invasive and easy to handle biological fluid, its analysis for clinical diagnosis is not very common. Partly the reason for this absence is unavailability of cost effective and convenient tools for such analysis. Scientific literature is full of novel sensor ideas but it is challenging to develop a working device, which are few. These challenges include trace level detection, presence of hundreds of interfering compounds, excessive humidity, different sampling regulations and personal variability. To meet these challenges as well as deliver a low cost solution, optical sensors based on specific colorimetric chemical reactions on mesoporous membranes have been developed. Sensor hardware utilizing cost effective and ubiquitously available light source (LED) and detector (webcam/photo diodes) has been developed and optimized for sensitive detection. Sample conditioning mouthpiece suitable for portable sensors is developed and integrated. The sensors are capable of communication with mobile phones realizing the idea of m-health for easy personal health monitoring in free living conditions. Nitric oxide and Acetone are chosen as analytes of interest. Nitric oxide levels in the breath correlate with lung inflammation which makes it useful for asthma management. Acetone levels increase during ketosis resulting from fat metabolism in the body. Monitoring breath acetone thus provides useful information to people with type1 diabetes, epileptic children on ketogenic diets and people following fitness plans for weight loss.
ContributorsPrabhakar, Amlendu (Author) / Tao, Nongjian (Thesis advisor) / Forzani, Erica (Committee member) / Lindsay, Stuart (Committee member) / Arizona State University (Publisher)
Created2013
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Description
In today's world there is a great need for sensing methods as tools to provide critical information to solve today's problems in security applications. Real time detection of trace chemicals, such as explosives, in a complex environment containing various interferents using a portable device that can be reliably deployed in

In today's world there is a great need for sensing methods as tools to provide critical information to solve today's problems in security applications. Real time detection of trace chemicals, such as explosives, in a complex environment containing various interferents using a portable device that can be reliably deployed in a field has been a difficult challenge. A hybrid nanosensor based on the electrochemical reduction of trinitrotoluene (TNT) and the interaction of the reduction products with conducting polymer nanojunctions in an ionic liquid was fabricated. The sensor simultaneously measures the electrochemical current from the reduction of TNT and the conductance change of the polymer nanojunction caused from the reduction product. The hybrid detection mechanism, together with the unique selective preconcentration capability of the ionic liquid, provides a selective, fast, and sensitive detection of TNT. The sensor, in its current form, is capable of detecting parts per trillion level TNT in the presence of various interferents within a few minutes. A novel hybrid electrochemical-colorimetric (EC-C) sensing platform was also designed and fabricated to meet these challenges. The hybrid sensor is based on electrochemical reactions of trace explosives, colorimetric detection of the reaction products, and unique properties of the explosives in an ionic liquid (IL). This approach affords not only increased sensitivity but also selectivity as evident from the demonstrated null rate of false positives and low detection limits. Using an inexpensive webcam a detection limit of part per billion in volume (ppbV) has been achieved and demonstrated selective detection of explosives in the presence of common interferences (perfumes, mouth wash, cleaners, petroleum products, etc.). The works presented in this dissertation, were published in the Journal of the American Chemical Society (JACS, 2009) and Nano Letters (2010), won first place in the National Defense Research contest in (2009) and has been granted a patent (WO 2010/030874 A1). In addition, other work related to conductive polymer junctions and their sensing capabilities has been published in Applied Physics Letters (2005) and IEEE sensors journal (2008).
ContributorsDiaz Aguilar, Alvaro (Author) / Tao, Nongjian (Thesis advisor) / Tsui, Raymond (Committee member) / Barnaby, Hugh (Committee member) / Yu, Hongbin (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Studying charge transport through single molecules tethered between two metal electrodes is of fundamental importance in molecular electronics. Over the years, a variety of methods have been developed in attempts of performing such measurements. However, the limitation of these techniques is still one of the factors that prohibit one from

Studying charge transport through single molecules tethered between two metal electrodes is of fundamental importance in molecular electronics. Over the years, a variety of methods have been developed in attempts of performing such measurements. However, the limitation of these techniques is still one of the factors that prohibit one from gaining a thorough understanding of single molecule junctions. Firstly, the time resolution of experiments is typically limited to milli to microseconds, while molecular dynamics simulations are carried out on the time scale of pico to nanoseconds. A huge gap therefore persists between the theory and the experiments. This thesis demonstrates a nanosecond scale measurement of the gold atomic contact breakdown process. A combined setup of DC and AC circuits is employed, where the AC circuit reveals interesting observations in nanosecond scale not previously seen using conventional DC circuits. The breakdown time of gold atomic contacts is determined to be faster than 0.1 ns and subtle atomic events are observed within nanoseconds. Furthermore, a new method based on the scanning tunneling microscope break junction (STM-BJ) technique is developed to rapidly record thousands of I-V curves from repeatedly formed single molecule junctions. 2-dimensional I-V and conductance-voltage (G-V) histograms constructed using the acquired data allow for more meaningful statistical analysis to single molecule I-V characteristics. The bias voltage adds an additional dimension to the conventional single molecule conductance measurement. This method also allows one to perform transition voltage spectra (TVS) for individual junctions and to study the correlation between the conductance and the tunneling barrier height. The variation of measured conductance values is found to be primarily determined by the poorly defined contact geometry between the molecule and metal electrodes, rather than the tunnel barrier height. In addition, the rapid I-V technique is also found useful in studying thermoelectric effect in single molecule junctions. When applying a temperature gradient between the STM tip and substrate in air, the offset current at zero bias in the I-V characteristics is a measure of thermoelectric current. The rapid I-V technique allows for statistical analysis of such offset current at different temperature gradients and thus the Seebeck coefficient of single molecule junctions is measured. Combining with single molecule TVS, the Seebeck coefficient is also found to be a measure of tunnel barrier height.
ContributorsGuo, Shaoyin (Author) / Tao, Nongjian (Thesis advisor) / Bennett, Peter (Committee member) / Ning, Cun-Zheng (Committee member) / Yu, Hongbin (Committee member) / Arizona State University (Publisher)
Created2012
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Description
With a recent shift to a more environmentally conscious society, low-carbon and non-carbon producing energy production methods are being investigated and applied all over the world. Of these methods, fuel cells show great potential for clean energy production. A fuel cell is an electrochemical energy conversion device which directly converts

With a recent shift to a more environmentally conscious society, low-carbon and non-carbon producing energy production methods are being investigated and applied all over the world. Of these methods, fuel cells show great potential for clean energy production. A fuel cell is an electrochemical energy conversion device which directly converts chemical energy into electrical energy. Proton exchange membrane fuel cells (PEMFCs) are a highly researched energy source for automotive and stationary power applications. In order to produce the power required to meet Department of Energy requirements, platinum (Pt) must be used as a catalyst material in PEMFCs. Platinum, however, is very expensive and extensive research is being conducted to develop ways to reduce the amount of platinum used in PEMFCs. In the current study, three catalyst synthesis techniques were investigated and evaluated on their effectiveness to produce platinum-on copper (Pt@Cu) core-shell nanocatalyst on multi-walled carbon nanotube (MWCNT) support material. These three methods were direct deposition method, two-phase surfactant method, and single-phase surfactant method, in which direct deposition did not use a surfactant for particle size control and the surfactant methods did. The catalyst materials synthesized were evaluated by visual inspection and fuel cell performance. Samples which produced high fuel cell power output were evaluated using transmission electron microscopy (TEM) imaging. After evaluation, it was concluded that the direct deposition technique was effective in synthesizing Pt@Cu core-shell nanocatalyst on MWCNTs support when a rinsing process was used before adding platinum. The peak power density achieved by the rinsed core-shell catalyst was 618 mW.cm-2 , 13 percent greater than that of commercial platinum-carbon (Pt/C) catalyst. Transmission electron microscopy imaging revealed the core-shell catalyst contained Pt shells and platinum-copper alloy cores. Rinsing with deionized (DI) water was shown to be a crucial step in core-shell catalyst deposition as it reduced the number of platinum colloids on the carbon nanotube surface. After evaluation, it was concluded that the two-phase surfactant and single-phase surfactant synthesis methods were not effective at producing core-shell nanocatalyst with the parameters investigated.
ContributorsAdame, Anthony (Author) / Madakannan, Arunachalanadar (Thesis advisor) / Peng, Xihong (Committee member) / Tamizhmani, Govindasamy (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Low temperature fuel cells are very attractive energy conversion technology for automotive applications due to their qualities of being clean, quiet, efficient and good peak power densities. However, due to high cost and limited durability and reliability, commercialization of this technology has not been possible as yet. The high fuel

Low temperature fuel cells are very attractive energy conversion technology for automotive applications due to their qualities of being clean, quiet, efficient and good peak power densities. However, due to high cost and limited durability and reliability, commercialization of this technology has not been possible as yet. The high fuel cell cost is mostly due to the expensive noble catalyst Pt. Alkaline fuel cell (AFC) systems, have potential to make use of non-noble catalysts and thus, provides with a solution of overall lower cost. Therefore, this issue has been addressed in this thesis work. Hydrogen-oxygen fuel cells using an alkaline anion exchange membrane were prepared and evaluated. Various non-platinum catalyst materials were investigated by fabricating membrane-electrode assemblies (MEAs) using Tokuyama membrane (# A201) and compared with commercial noble metal catalysts. Co and Fe phthalocyanine catalyst materials were synthesized using multi-walled carbon nanotubes (MWCNTs) as support materials. X-ray photoelectron spectroscopic study was conducted in order to examine the surface composition. The electroreduction of oxygen has been investigated on Fe phthalocyanine/MWCNT, Co phthalocyanine/MWCNT and commercial Pt/C catalysts. The oxygen reduction reaction kinetics on these catalyst materials were evaluated using rotating disk electrodes in 0.1 M KOH solution and the current density values were consistently higher for Co phthalocyanine based electrodes compared to Fe phthalocyanine. The fuel cell performance of the MEAs with Co and Fe phthalocyanines and Tanaka Kikinzoku Kogyo Pt/C cathode catalysts were 100, 60 and 120 mW cm-2 using H22 and O2 gases. This thesis also includes work on synthesizing nitrogen doped MWCNTs using post-doping and In-Situ methods. Post-doped N-MWNCTs were prepared through heat treatment with NH4OH as nitrogen source. Characterization was done through fuel cell testing, which gave peak power density ~40mW.cm-2. For In-Situ N-MWCT, pyridine was used as nitrogen source. The sample characterization was done using Raman spectroscopy and RBS, which showed the presence ~3 at.% of nitrogen on the carbon surface.
ContributorsShah, QuratulAin Jawed (Author) / Madakannan, Arunachalanadar (Thesis advisor) / Tamizhmani, Govindasamy (Committee member) / Macia, Narciso (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Hydrogenases catalyze the interconversion of protons, electrons, and hydrogen according to the reaction: 2H+ + 2e- <-> H2 while using only earth abundant metals, namely nickel and iron for catalysis. The enzymatic turnover of Clostridium acetobutylicum [FeFe]-hydrogenase has been investigated through the use of electrochemical and scanning probe techniques. Scanning

Hydrogenases catalyze the interconversion of protons, electrons, and hydrogen according to the reaction: 2H+ + 2e- <-> H2 while using only earth abundant metals, namely nickel and iron for catalysis. The enzymatic turnover of Clostridium acetobutylicum [FeFe]-hydrogenase has been investigated through the use of electrochemical and scanning probe techniques. Scanning tunneling microscopy (STM) imaging revealed sub-monolayer surface coverage. Cyclic voltammetry yielded a catalytic, cathodic hydrogen production signal similar to that observed for a platinum electrode. From the direct observation of single enzymes and the macroscopic electrochemical measurements obtained from the same electrode, the apparent turnover frequency (TOF) per single enzyme molecule as a function of potential was determined. The TOF at 0.7 V vs. Ag/AgCl for the four SAMs yielded a decay constant for electronic coupling (β) through the SAM of ~ 0.82 Å -1, in excellent agreement with published values for similar SAMs. One mechanism used by plants to protect against damage is called nonphotochemical quenching (NPQ). Triggered by low pH in the thylakoid lumen, NPQ leads to conversion of excess excitation energy in the antenna system to heat before it can initiate production of harmful chemical species by photosynthetic reaction centers. Here a synthetic hexad molecule that functionally mimics the role of the antenna in NPQ is described. When the hexad is dissolved in an organic solvent, five zinc porphyrin antenna moieties absorb light, exchange excitation energy, and ultimately decay by normal photophysical processes. However, when acid is added, a pH-sensitive dye moiety is converted to a form that rapidly quenches the first excited singlet states of all five porphyrins, converting the excitation energy to heat and rendering the porphyrins kinetically incompetent to perform useful photochemistry. Charge transport was also studied in single-molecule junctions formed with a 1,7-pyrrolidine-substituted 3,4,9,10-Perylenetetracarboxylic diimide (PTCDI) molecule. A reduction in the highest occupied (HOMO) and lowest unoccupied (LUMO) molecular orbitals energy gap due to the electronic properties of the substituents is seen when compared to an unsubstituted-PTCDI. The small HOMO-LUMO energy gap allows for switching between electron- and hole-dominated charge transport with a gate voltage, thus demonstrating a single-molecule ambipolar field effect transistor.
ContributorsMadden, Christopher (Author) / Moore, Thomas A. (Thesis advisor) / Jones, Anne (Committee member) / Tao, Nongjian (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Power rating photovoltaic modules at six irradiance and four temperature matrix levels of IEC 61853-1 draft standard is one of the most important requirements to accurately predict energy production of photovoltaic modules at different climatic conditions. Two studies were carried out in this investigation: a measurement repeatability study and a

Power rating photovoltaic modules at six irradiance and four temperature matrix levels of IEC 61853-1 draft standard is one of the most important requirements to accurately predict energy production of photovoltaic modules at different climatic conditions. Two studies were carried out in this investigation: a measurement repeatability study and a translation procedure validation study. The repeatability study was carried out to define a testing methodology that allows generating repeatable power rating results under outdoor conditions. The validation study was carried out to validate the accuracy of the four translation procedures: the first three procedures are from the IEC 60891 standard and the fourth procedure is reported by NREL. These translation procedures are needed to translate the measured data from the actual test conditions to the reporting rating conditions required by the IEC 61853-1 draft standard. All the measurements were carried out outdoors on clear days using a manual, 2-axis tracker, located in Mesa/Tempe, Arizona. Four module technologies were investigated: crystalline silicon, amorphous silicon, cadmium telluride, and copper indium gallium selenide. The modules were cooled and then allowed to naturally warm up to obtain current-voltage data at different temperatures. Several black mesh screens with a wide range of transmittance were used for varying irradiance levels. From the measurements repeatability study, it was determined that: (i) a certain minimum distance (2 inches) should be maintained between module surface and the screen surface; (ii) the reference cell should be kept outside the screen (calibrated screen) as opposed to inside the screen (uncalibrated screen); and (iii) the air mass should not exceed 2.5. From the translation procedure validation study, it was determined that the accuracy of the translation procedure depends on the irradiance and temperature range of translation. The difference between measured and translatet power at maximum power point (Pmax) is determined to be less than 3% for all the technologies, all the irradiance/ temperature ranges investigated and all the procedures except Procedure 2 of IEC 60891 standard. For the Procedure 2, the difference was found to fall between 3% and 17% depending on the irradiance range used for the translation. The difference of 17% is very large and unacceptable. This work recommends reinvestigating the cause for this large difference for Procedure 2. Finally, a complete power rating matrix for each of the four module technologies has been successfully generated as per IEC 61853-1 draft standard.
ContributorsPaghasian, Karen (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Madakannan, Arunachalandar (Committee member) / Macia, Narciso F. (Committee member) / Arizona State University (Publisher)
Created2010
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Description
Photovoltaic (PV) modules appear to have three classifications of failure: Infant mortality, normal-life failure, and end-of-life failure. Little is known of the end-of-life failures experienced by PV modules due to their inherent longevity. Accelerated Life Testing (ALT) has been at the crux of this lifespan prediction; however, without naturally failing

Photovoltaic (PV) modules appear to have three classifications of failure: Infant mortality, normal-life failure, and end-of-life failure. Little is known of the end-of-life failures experienced by PV modules due to their inherent longevity. Accelerated Life Testing (ALT) has been at the crux of this lifespan prediction; however, without naturally failing modules an accurate acceleration factor cannot be determined for use in ALT. By observing modules that have been aged in the field, a comparison can be made with modules undergoing accelerated testing. In this study an investigation on about 1900 aged (10-17 years) grid-tied PV modules installed in the desert climatic condition of Arizona was undertaken. The investigation was comprised of a check sheet that documented any visual defects and their severity, infrared (IR) scanning, and current-voltage (I-V) curve measurements. After data was collected on modules, an analysis was performed to classify the failure modes and to determine the annual performance degradation rates.
ContributorsSuleske, Adam Alfred (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Rogers, Bradley (Committee member) / Macia, Narciso (Committee member) / Arizona State University (Publisher)
Created2010