No description available.

abstract: The research of this dissertation involved quantitative characterization of electrostatic potential and charge distribution of semiconductor nanostructures using off-axis electron holography, as well as other electron microscopy techniques. The investigated nanostructures included Ge quantum dots, Ge/Si core/shell nanowires, and polytype heterostructures in ZnSe nanobelts. Hole densities were calculated for the first two systems, and the spontaneous polarization for wurtzite ZnSe was determined. Epitaxial Ge quantum dots (QDs) embedded in boron-doped silicon were studied. Reconstructed phase images showed extra phase shifts near the base of the QDs, which was attributed to hole accumulation in these regions. The resulting charge density was (0.03±0.003) holes/nm3, which corresponded to about 30 holes localized to a pyramidal, 25-nm-wide Ge QD. This value was in reasonable agreement with the average number of holes confined to each Ge dot determined using a capacitance-voltage measurement. Hole accumulation in Ge/Si core/shell nanowires was observed and quantified using off-axis electron holography and other electron microscopy techniques. High-angle annular-dark-field scanning transmission electron microscopy images and electron holograms were obtained from specific nanowires. The intensities of the former were utilized to calculate the projected thicknesses for both the Ge core and the Si shell. The excess phase shifts measured by electron holography across the nanowires indicated the presence of holes inside the Ge cores. The hole density in the core regions was calculated to be (0.4±0.2) /nm3 based on a simplified coaxial cylindrical model. Homogeneous zincblende/wurtzite heterostructure junctions in ZnSe nanobelts were studied. The observed electrostatic fields and charge accumulation were attributed to spontaneous polarization present in the wurtzite regions since the contributions from piezoelectric polarization were shown to be insignificant based on geometric phase analysis. The spontaneous polarization for the wurtzite ZnSe was calculated to be psp = -(0.0029±0.00013) C/m2, whereas a first principles' calculation gave psp = -0.0063 C/m2. The atomic arrangements and polarity continuity at the zincblende/wurtzite interface were determined through aberration-corrected high-angle annular-dark-field imaging, which revealed no polarity reversal across the interface. Overall, the successful outcomes of these studies confirmed the capability of off-axis electron holography to provide quantitative electrostatic information for nanostructured materials. / Dissertation/Thesis / Ph.D. Physics 2011

The quadrupolar interaction in sodium orthovanadate dodecahydrate, calcium orthovanadate, vanadinite, descloizite, zirconium divanadate, cadmium divanadate, potassium metavanadate and vanadium pentoxide, was studied by nuclear magnetic resonance. The v51 quadrupole coupling constants in these compounds show a strong correlation with the distortion of the tetrahedral symmetry around the vanadium ion. Vanadium pentoxide is an exception and shows a surprisingly small coupling constant. The point multipole model was found to be inadequate for the calculations of the electric field gradients in these compounds. A covalent model provides an explanation of the small magnitude of the coupling constant of vanadium pentoxide. However, because of the numbers of approximations in this model, only a qualitative correlation with the experimental results was achieved. In addition, the chemical shift tensor of the v51 resonance line in a single crystal of vanadium pentoxide was measured to be very large. This result was correlated with a large Van Vleck term in the magnetic susceptibility of vanadium pentoxide. / Thesis / Doctor of Philosophy (PhD)

The Suwannee River natural organic matter (SRNOM) was fractionated by preparative size-exclusion chromatography (SEC) into seven molecular weight (MW) fractions. The SRNOM and its MW fractions were subsequently analyzed for their concentrations of acidic functional groups by direct titrations, average MWs and MW distributions by semi-analytical SEC, and charge-to-MW distributions by capillary electrophoresis. Carboxyl concentrations in the MW fractions were inversely proportional to their average MWs. Conversely, the phenolic concentrations, though smaller than the carboxyl concentrations, were proportional to average MWs. Hysteresisthe non-overlap between sequential forward and reverse titrationswas observed for the SRNOM and its MW fractions, where the reverse titrations predicted a greater concentration of carboxylic acid groups than the forward titration. Because hysteresis is thought to be caused by the base-catalyzed hydrolysis of esters, this suggests that ester groups in the SRNOM are distributed over all MWs. Data for direct titrations, MW distributions, and capillary electrophoresis were evaluated by a computational scheme that solves for the most probable distribution of acidic functional groups and charges on solutes in the SRNOM and the MW fractions as a function of pH. Depending on the MW ranges of the samples, solutes in the SRNOM and the MW fractions are predicted to have from one to a maximum of 25 carboxyl groups per solute. Most phenolic groups are predicted to be on solutes that have a minimum of two carboxyl groups. At low pH, all samples have high relative abundances of solutes with the lowest charges. The charges of solutes are predicted to increase with increasing pH due to the sequential ionization of acidic functional groups. Depending on the MW ranges of the samples, the maximum probable charges of solutes in the SRNOM and the fractions at high pH are -12 to -30. By knowing the most probable distribution of charge and abundances of acidic functional groups, researchers will make better estimates of thermodynamic parameters and models that describe equilibria between metals and natural organic matter in the environment.

No description available.

In gas-solid fluidized beds, the generation of electrostatic charges due to continuous contacts between fluidizing particles, and the particles and the fluidization vessel wall, is unavoidable. Industrial operations, such as the production of polyethylene, are susceptible to significant operational challenges caused by electrostatics including reactor wall fouling, a problem known as “sheeting”. The formation of particle sheets can require shutdown periods for clean-up which results in significant economic losses. To gain a better understanding of the underlying mechanisms of electrostatic charging in gas-solid fluidized beds, in an attempt to eliminate or minimize this problem, a pilot-scale pressurized gas-solid fluidization system was designed and built, housing an online electrostatic charge measurement technique consisting of two Faraday cups. The system permits the study of the degree of particle wall fouling at pressures and temperatures up to 2600 kPa and 100°C, respectively, and gas velocities up to 1 m/s (covering a range including turbulent flow regime). The system also allowed, for the first time, the measurement of the fluidizing particles’ mass, net charge and size distribution in various regions of the bed, especially those related to the wall coating under the industrially relevant operating conditions of high pressures and gas velocities. Experimental trials were carried out using polyethylene resin received from commercial reactors to investigate the influence of pressure and gas velocity on the bed hydrodynamics and in turn, the degree of bed electrification. Mechanisms for particle charging, migration and adherence to the column wall were proposed. The size distribution of the gas bubbles shifted towards smaller bubbles as the operating pressure was raised. Thus, higher pressures lead to greater mixing within the bulk of the bed and resulted in a higher degree of particle wall fouling. Moreover, the extent of wall fouling increased linearly with the increase in gas velocity and as the bed transitioned to turbulent regime, due to the increase in particle-wall contacts. Bipolar charging was observed especially within the wall coating with smaller particles being negatively charged. Overall, particle-wall contacts generated negatively charged particles resulting in a net negative charge in the bed, whereas particle-particle contacts generated positively and negatively charged particles resulting in no net charge when entrainment was negligible. The formation of the wall layer and its extent was influenced by the gravitational and drag forces balancing the image force and Coulomb forces (created by the net charge of the bed and the metallic column wall as the attraction between oppositely charged particles).

<p> In Part I the one-electron charge distribution in the water molecule is obtained by demanding that this distribution balance the nuclear forces of repulsion and reproduce the observed dipole moment. Parameters contained in the molecular orbital description are then related to such concepts as hybridisation and bond polarities. </p> <p> In Part II the electronic forces of attraction and the one-electron charge distribution, calculated from near Hartree-Fock wave functions, are used to interpret the binding in the first-row diatomic hydrides. </p> / Thesis / Doctor of Philosophy (PhD)

[ES] Debido a la crisis climática, es necesario encontrar fuentes alternativas para la climatización de locales y la producción de agua caliente sanitaria (ACS). Las bombas de calor se presentan como una alternativa excelente para sustituir a las calderas y así poder reducir las emisiones de gases contaminantes. En obra nueva, si se dispone de acceso al terreno o a una masa de agua, las bombas de calor agua-agua o salmuera-agua son altamente recomendadas debido a sus numerosas ventajas. El principal problema que presentan las bombas de calor es el refrigerante que contienen, ya que en la actualidad no existe refrigerante que sea a la vez barato, seguro y con propiedades termodinámicas óptimas. La tendencia en el futuro cercano en bombas de calor utilizadas para la calefacción de locales es volver al uso de refrigerantes naturales como los hidrocarburos y las hidrofluorolefinas. Estos refrigerantes presentan problemas de seguridad debido a su inflamabilidad o toxicidad y es por eso que, en caso de carecer de medidas de seguridad adicionales, la cantidad de refrigerante está limitada. En esta tesis se presenta un trabajo experimental sobre una bomba de calor salmuera-agua trabajando con poca cantidad de R290. La campaña experimental fue pensada para obtener resultados beneficiosos sobre cuál es el actual potencial de este tipo de tecnología tras la limitación de la carga de refrigerante, para desarrollar formas de reducción de carga de refrigerante en los sistemas y para mejorar las simulaciones de predicción de la cantidad necesaria de refrigerante. La campaña experimental está dividida en dos partes, cada una enfocada en uno de los siguientes objetivos: la primera en conocer el actual comportamiento anual de esa bomba de calor y la segunda para desarrollar estrategias de reducción de carga de refrigerante. En cada campaña experimental se almaceno tanto los datos de funcionamiento como la cantidad de refrigerante que había en cada uno de los componentes. La instalación estaba equipada con las herramientas necesarias para la toma de datos durante el funcionamiento de la bomba de calor y también era capaz de sectorizarla asilando cada uno de los componentes para poder extraer y pesar el refrigerante y así conocer que cantidad había en cada zona. Con los datos recogidos, se ha podido observar diferencias entre la predicción de carga de refrigerante en los diferentes componentes y la medida experimentalmente, y también se ha encontrado alguna de las causas de esa discrepancia, pudiendo así corregir el modelo. Para ello, se ha desarrollado un modelo de compresor y al modelo existente de intercambiadores de calor se le ha añadido un volumen muerto de refrigerante. Con estos cambios la predicción ha mejorado notablemente en el modelo utilizado y en la actualidad se puede utilizar para conocer una aproximación del refrigerante necesario. / [CA] A causa de la crisi climàtica, és necessari enden fonts alternatives per a la climatització dels locals i la endencia d'aigua calenta sanitaria (ACS). Les bombes de calor es presenten com una alternativa excel·lent per a substituir a les calderes i així poder reduir les emissions de gasos contaminants. En obra nova, si es disposa d'accés al terreny o a una massa d'aigua, les bombes de calor aigua-aigua o salmorra-aigua són endencia recomanades a causa dels seus nombrosos avantatges. El principal problema que presenten les bombes de calor és el refrigerant que contenen, ja que en l'actualitat no existeix refrigerant que siga alhora barat, segur i amb propietats termodinàmiques òptimes. La tendencia actual en bombes de calor utilitzades per a la calefacció d'espais, és tornar a l'ús de refrigerants naturals com els hidrocarburs i les hidrofluorolefines. Aquests refrigerants presenten problemes de seguretat a causa de la seua inflamabilitat o toxicitat i és per això que, en cas de mancar de mesures de seguretat addicionals, la quantitat de refrigerant està limitada. En aquesta tesi es presenta un treball experimental sobre una bomba de calor salmorra-aigua treballant amb poca quantitat de R290. La campanya experimental va ser pensada per a obtindre resultats beneficiosos sobre quin és l'actual potencial d'aquesta mena de tecnologia després de la limitació de la càrrega de refrigerant, per a desenvolupar formes de reducció de càrrega de refrigerant en els sistemes i per a millorar les simulacions de predicció de la quantitat necessària de refrigerant. La campanya experimental està dividida en dues parts, cadascuna enfocada en un dels següents objectius: la primera a conéixer l'actual comportament anual d'aqueixa bomba de calor i la segona per a desenvolupar estratègies de reducció de càrrega de refrigerant. En cada campanya experimental s'emmagatzeme tant les dades de funcionament com la quantitat de refrigerant que hi havia en cadascun dels components. La instal·lació estava equipada amb les eines necessàries per a la presa de dades durant el funcionament de la bomba de calor i també era capaç de sectoritzar-la asilant cadascun dels components per a poder extraure i pesar el refrigerant i així conéixer que quantitat hi havia en cada zona. Amb les dades recollides, s'ha pogut observar diferències entre la predicció de càrrega de refrigerant i la mesura experimentalment, i també s'ha trobat alguna de les causes d'aqueixa discrepància, podent així corregir el model. Per a això, s'ha desenvolupat un model de compressor i al model existent de bescanviadors de calor se li ha afegit un volum mort de refrigerant. Amb aquests canvis la predicció ha millorat notablement i en l'actualitat es pot utilitzar per a conéixer una aproximació del refrigerant necessari. / [EN] Due to the climate crisis, there is a need to find alternative energy sources for space heating, cooling, and domestic hot water (DHW) production. Heat pumps are an excellent alternative to substitute current boilers to reduce gas emissions. A liquid source heat pump is highly recommended in new buildings with access to land or water due to its significant advantages. The main problem with this technology is that it uses a refrigerant inside, and there is no refrigerant with good performance, cheap and safe to handle. The near future trend in heat pumps used for space heating is to use pure refrigerants such as natural refrigerants and HFOs. These refrigerants (except CO2) have safety issues (flammability or toxicity); consequently, a maximum amount of refrigerant is allowed without considering extra safety measures. This PhD presents an experimental work with a ground source heat pump (GSHP) with a low R290 refrigerant amount. This experimental campaign is helpful to know the current achievable performance derived from the limitation of refrigerant amount, to develop refrigerant charge reduction strategies and to improve existing simulation software based on refrigerant charge prediction. The experimental campaign was divided into two parts to focus separately on normal annual behaviour and refrigerant charge reduction strategies. In each test campaign, performance data was recorded during the test, and the refrigerant charge amount in each component was extracted and weighed after the end of each test. The installation had the tools to acquire data from the vapour compression circuit, isolate the components, and extract and weigh the refrigerant to know how much refrigerant was inside each section. With the data collected, it was observed that the differences in refrigerant charge prediction in the components with the software used were significant, and some causes of these differences have been identified, correcting the prediction model. So, a compressor model has been developed, and a dead volume has been added to the refrigerant charge calculation in heat exchangers. With these changes, the refrigerant prediction has greatly improved in the model used and could be a reliable approximation. / Gracias a la Universitat Politècnica de València por brindarme la financiación y los medios a través del programas “Ayudas para movilidad de estudiantes de Doctorado de la Universitat Politècnica de València” y “Programa de Ayudas de investigación y Desarrollo” (PAID-01-17) / Sánchez-Moreno Giner, L. (2023). Research about Refrigerant Charge in Domestic Heat Pumps [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/196786