The imidazole ring offers great potential for a variety of applications including gene delivery vectors, ionic liquids, electromechanical actuators, and novel monomers and polymers. The imidazole ring provides a unique building block for these applications due to its thermal stability, aromatic nature, ability to form ionic salts, and ease of functionalization. Free radical polymerization of 1-vinylimidazole (1-VIm) and free radical copolymerizations with methyl methacrylate (MMA) and n-butyl acrylate (nBA) afforded homopolymers and copolymers with tunable solution and thermal properties. Aqueous SEC provided reproducible and reliable molecular weights for poly(1-VIm) in the absence of polymer aggregates. Analysis of the thermal properties revealed ideal random copolymers with MMA and non-ideal copolymers with nBA. Small angle X-ray scattering determined that the spacing between ionic groups remained constant with increased nonionic comonomer incorporation while the spacing between adjacent polymer backbones increased. Functionalization of 1-VIm with varying length alkyl halides and polymerization prepared a series of imidazolium homopolymers. Anion exchange reactions controlled the thermal and solution properties, and the bromide counteranion quantitatively exchanged to tetrafluoroborate (BF4), trifluoromethanesulfonate (TfO), and bis(trifluoromethanesulfonyl)imide (Tf2N). Thermogravimetric analysis revealed that thermal stability increased with decreased alkyl substituent length and larger counteranion size, and differential scanning calorimetry determined that glass transition temperature (Tg) decreased with increased alkyl substituent length and larger counteranion size. Electrochemical impedance spectroscopy determined the ionic conductivities of the imidazolium homopolymers, and analysis using the Vogel-Fulcher-Tammann equation revealed that the activation energy of ion conduction increased as alkyl substituent length increased. Polymer morphology determined using X-ray scattering also influenced the ionic conductivity. As the alkyl substituent length increased, the spacing between adjacent polymer backbones increased, which decreased the ionic conductivity due to the ion-hopping mechanism of ion conduction. Unsuccessful attempts to control the radical polymerization of 1-VIm led to the investigation of 1-(4-vinylbenzyl)imidazole (VBIm), which is a styrenic-based monomer with excellent propagating radical stability. Triblock copolymers incorporating VBIm monomer into a soft random copolymer center block and reinforcing, hard segment outer blocks provided a template for tuning the properties of the ionomer membranes for electroactive devices. Analysis of the morphology and mechanical properties using small angle X-ray scattering and dynamic mechanical analysis determined microphase separation and optimal mechanical properties for electromechanical transducer fabrication. Testing electromechanical transducers revealed superior performance relative to the benchmark Nafion®. Optimization of triblock copolymer design criteria through varying the comonomer ratio of VBIm and nBA in the soft center block, quaternization reactions, and ionic liquid introduction influenced mechanical properties and ionic conductivity. Higher percentages of VBIm and quaternization of VBIm in the random central block increased Tg and ionic conductivity. IL selectively incorporated into the imidazole-containing phases with no leakage observed for ionic systems, reduced the center block Tg, and increased ionic conductivity. Controlling charge density along poly(1-VIm) through well-defined alkylation reactions with 1-bromobutane provided a potential vector for nonviral gene delivery and polyanion binding. Analysis of DNA and heparin binding using gel electrophoresis revealed a decrease in N/P ratio with increased alkylation percentage. Dynamic light scattering indicated an increase in zeta potential with increasing alkylation percentages, and relatively uniform polyplex sizes in aqueous media. The MTT assay developed cytotoxicity profiles with little toxicity prior to 83% alkylation. Finally, the luciferase expression assay revealed inefficient nucleic acid delivery to multiple cell types. Synthesis of poly(1-VIm) vectors with glutathione conjugates provided an avenue for simultaneous therapeutic gene and anti-oxidant delivery in vitro. Cytotoxicity assays of cells pretreated with glutathione-conjugated poly(1-VIm) prior to oxidative stress showed that higher glutathione conjugation levels improved cell viability. / Ph. D.

Sodium alanate, or the Na-Al-H system, has been the focus of intense research over the past decade due to its ability to hold almost 5 wt% of hydrogen. In this research, the effective thermal conductivity, k, of a sample of titanium-doped sodium alanate is studied over a range of operating conditions pertinent to practical on-board hydrogen storage. A transient technique employing a platinum hot-wire is used to make the measurements. A cylindrical experimental apparatus was designed with the aide of a finite element model that was used to quantify the cylinder boundary effects. The apparatus dimensions were optimized based on the finite element results with the goal of minimizing measurement uncertainty and temperature rise during testing. Finite element results were also used to predict test times and current requirements. A sample of sodium alanate was obtained and loaded into the experimental apparatus which was enclosed in a pressure vessel with a controlled atmosphere. Effective thermal conductivity was measured as a function of pressure at the fully-hydrided and fully-dehydrided states. The results from the pressure-dependence investigation were compared to an existing study that utilized an alternate measurement technique. The results matched well qualitatively — the effective thermal conductivity was highly dependent on pressure, and was found to be significantly higher in the fully-dehydrided state. However, the results of this study were 20 to 30% lower than the existing available data. Additionally, an exploratory investigation used the PCI technique to study the effect of varying composition between the fully-hydrided state and the intermediate decomposition step at a relatively constant pressure. Effective thermal conductivity did not vary significantly over this range of compositions. / Master of Science

Organic conducting polymers are essential for the development of various electronic devices, including field-effect transistors, light-emitting diodes, solar cells, and thermoelectric devices. Understanding the charge transport mechanisms within these materials, particularly the roles of polarons and bipolarons as charge carriers, is crucial. Despite the recognized importance of these carriers, there are ongoing debates regarding the interpretation of their mid-IR absorption spectral signatures in the 0.3-0.7 eV range. This is mainly due to challenges in applying the conventional mid-gap state model, especially in the context of doped P3HT (poly(3-hexylthiophene)) films. The conventional model predicts a blueshift for the mid-IR P1 band of bipolarons compared to polarons, yet recent experiments reveal both blueshifted and redshifted bands, at elevated oxidation levels, leading to confusion about the true mid-IR spectral hallmark of spinless singlet bipolarons. This thesis aims to resolve these inconsistencies by proposing a Holstein-style model for singlet bipolarons in π-conjugated polymers with nondegenerate ground states. The model incorporates hole hopping, electron−vibration coupling involving the prominent aromatic-quinoidal mode, and Coulombic interactions between (hole) polarons and between polarons and dopant anions. In contrast to the conventional interpretation where bipolaron formation results from self-trapping, our findings indicate that it is primarily driven by attractive electrostatic interactions with dopant anions. Without these anions, two holes would not pair to form singlet bipolarons. More importantly, our results indicate that the observed blueshift at lower oxidation levels signifies the increased localization of Coulombically interacting polarons, whereas at higher oxidation levels, the simultaneous emergence of both redshifted and blueshifted bands is indeed the spectral signature of spinless singlet bipolarons formation. Furthermore, we find that the binding energy of bipolarons in π-stacks of P3HT chains is significantly higher, nearly threefold, than in a single chain, highlighting the profound influence of long-range order and chain stacking on bipolarons formation. This work contributes to resolving the theoretical ambiguities surrounding charge carrier dynamics in organic conjugated polymers and enhances our understanding of their optoelectronic properties. / Chemistry

To date, most two-dimensional conjugated metal–organic frameworks (2D c-MOFs) are based on planar polycyclic aromatic hydrocarbons (PAHs), which limits the ability to introduce additional substituents to control their properties. This thesis introduces a novel monomer ligand derived from highly substituted, core-twisted hexahydroxy-hexa-cata-benzocoronenes (6X-6OH-cHBCs), resulting in a new class of wavy 2D c-MOFs. The structural rigidity and self-complementary nature of the c-HBC ligand makes it a valuable monomer for constructing these novel 2D c-MOFs. Despite the wavy structure, effective conjugation between layers was achieved. This led to the formation of electronically conductive materials, as demonstrated by 6F-cHBC-Cu, which exhibited a conductivity of 1.82∙10-2 S/cm. Furthermore, the wavy motif of the c-HBC ligand promoted extended crystal growth in the z-direction. This was demonstrated by the formation of several micrometer-long single crystals of 6F-cHBC-Cu. The monomers were synthesized through a flexible three-step process, allowing for the incorporation of various substituents or functional groups, thus enabling control over ligand symmetry. This process enabled the synthesis of monomers with diverse symmetries: C6 symmetry (12OH-cHBC), C3 symmetry (6X-6OH-cHBC), and asymmetric monomers (e.g., 3F-6OH-cHBC). This structural variety allowed for systematic investigations into structure-property relationships, offering valuable insights into how monomer design influences the resulting MOF properties. The homologous 6X-cHBC-Cu MOF series (X = H, F, Cl, Br) illustrated that both the electron-withdrawing effect and the size of the substituent significantly impact crystallinity. This in turn enhances fundamental properties such as electronic conductivity, charge carrier mobility, accessible pore size, thermal stability, and morphology. Reactivity trends for the synthesized monomers were also established, showing that strong electron-withdrawing groups like fluorine or hydroxyl directly correlate with enhanced monomer reactivity, optimizing synthetic conditions. Incorporating fluorine into the monomer structure significantly improved the resulting MOF properties, providing a valuable design strategy for future monomers. Finally, this research demonstrated that wavy 2D c-MOFs can rival traditional flat ligands in terms of crystallinity and electronic properties, such as conductivity and charge carrier mobility, thereby expanding the potential for novel 2D c-MOF members.

En años recientes se han realizado esfuerzos para incrementar la compresión de los fenómenos asociados al flujo bifásico líquido - gas, para lo cual se han establecido modelos matemáticos que intentan reflejar el comprotamiento del flujo, como es el caso del modelo de los Dos Fluídos. Una causa de la complejidad que representa el modelado es la transferencia de masa, momento y energía entre fases debida a la interacción entre fases. Actualmente los modelos de cálculo empleados en CFD y en códigos termohidraúlicos confían en correlaciones experimentales altamente dependientes del régimen de flujo para determinar el área interfacial, sin embargo este procedimiento no refleja la naturaleza física y se presentan irregularidades en la zona de la interfase debidas a fenómenos de transporte no descritos por estos modelos. En este sentido se ha propuesto recientemente una teoría de transporte de area interfacial que parece ser una solución viable al problema de la obtención de ecuaciones constitutivas del area interfacial y con ella, el cierre del modelo. Esta ecuación consta de términos convectivos y temporales que pueden ser resueltos analíticamente, por otro lado contiene términos fuente y sumidero que representan la creación y destrucción de burbujas que aún no han sido completamente modelados; para la comprension de dichos términos es requerida información experimental, misma que este trabajo intenta generar mediante la obtención de una base de datos experimentales que aporten información útil para el modelado de sistemas bifásicos. Para la obtención de la base de datos fue necesario diseñar, construir e instrumentar una instalación experimental que permitiera la formación de flujos bifásicos agua-aire con velocidades superficiales de fase líquida y gas similares a las existentes en los actuales reactores nucleares. El sistema de formación de mezcla bifásica que se diseñó y construyó permite la obtención de varios regímenes de flujo, en su funcionamiento emplea medio / Méndez Díaz, S. (2008). Medida experimental de la concentración de área interfacial en flujos bifásicos finalmente dispersos y en transición [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/3301

Very few stone sculptures conserve their original polychromy nowadays so the exceptional condition presented by the oil paint film of the Tomb of Chancellor Villaespesa in the Cathedral of Tudela (Spain) here presented as case study suggested that both the chemical-mineral composition of the oil paint films and of the lithotypes chosen for the artists to be in contact with the polichromy, could be responsible for their unexpected durability. When the mechanisms governing these painted structures stability are not understood properly, conservation materials and methods and even environmental conditions can have a dramatic effect in their performance and compromise their stability in the long term. In this study, mock-ups simulating different oil paint layers on the sandstone of the case study have been prepared. Mock-ups with the same oil paint films on other substrates have been made for comparison purpose. After four years of natural ageing, the aggregation of lead and calcium carboxylates have been identified and characterized on some mock-ups by means of the combined use of UV-VIS light microscopy, SEM-EDX and micro FT-IR spectroscopy. pH and conductivity have been measured and monitorized both in the mock-ups and the case study. Saponification reactions, ionomer formation and carboxylate aggregation in lead white or minium oil paint films contributed to make them less acidic, less ionized, less hydrolyzed and less soluble after ageing sandstone or on pine wood at room environmental conditions for four years. The same given paint films became more acid and more ionized after ageing on a glass slide. Understanding the properties of such films, the chemical-physical mechanisms governing their adhesive and cohesive forces, and their surface pH is not easy. Mineral assemblages as well as the availability of ions in the substrate of a given oil paint film containing lead white or minium play a fundamental role in the eventual formation, migration and aggregation of lead and calcium carboxylates not only at their surface but also within the substrate-film interface. Furthermore, monitoring surface pH and conductivity as well as understanding solubility issues and the adhesion forces existing between soils, the paint layer and the substrate is needed when designing any conservation strategy to minimize risks and to preserve the balance acquired by these artworks in time. / Muy pocas esculturas pétreas conservan su policromía original. El excepcional estado en el se mantienen las películas pictóricas al óleo del caso de estudio de esta tesis doctoral (el Sepulcro de Villaespesa de la catedral de Tudela, Navarra, España) sugiere que tanto la composición químico-mineral de la roca seleccionada por sus escultores como la composición de las películas pictóricas al óleo con las que se policromó dicha piedra, podrían ser responsables de su inesperada durabilidad. En el transcurso de esta tesis doctoral se prepararon probetas con distintas películas pictóricas al óleo sobre la arenisca del caso de estudio. Para hacer un análisis comparativo también se prepararon probetas con las mismas películas sobre otros soportes. Se monitorizó el pH y la conductividad el caso de estudio así como de todas probetas. A través del uso combinado de microscopía óptica, SEM-EDX y micro espectroscopía FT-IR se estudió la formación y envejecimiento de las películas al óleo identificó y se caracterizó la agregación de carboxilatos de calcio y plomo en algunas de las películas pictóricas al óleo con pigmentos de plomo. En aquellas películas al óleo con albayalde o minio que envejecieron durante cuatro años sobre substratos de arenisca y madera de pino, las reacciones de saponificación, la formación de ionómeros y la agregación de carboxilatos contribuyeron a generar estratos pictóricos menos ácidos, menos ionizados, menos hidrolizados y menos solubles. Dichas películas pictóricas se tornaron más ácidas e ionizadas tras envejecer, en las mismas condiciones medioambientales, sobre vidrio de microscopio. La comprensión de los mecanismos físico-químicos que gobiernan no solo el pH y la conductividad sino también las fuerzas adhesivas y cohesivas de estas películas a lo largo del tiempo, no es sencilla. Tanto los agregados minerales como la disponibilidad de iones que presentan sus substratos juegan un papel fundamental en la eventual formación, migración y agregación de carboxilatos de calcio y plomo no solo en su superficie, sino también en la interfase substrato-película pictórica. Cuando los mecanismos que gobiernan los equilibrios físico-químicos de estos sistemas pictóricos no se comprenden adecuadamente, los materiales y métodos empleados en su conservación así como las condiciones medioambientales en las que se mantienen pueden tener un efecto dramático en el comportamiento de estos sistemas pictóricos y comprometer su estabilidad a largo plazo. / Molt poques escultures pètries conserven la seua policromia original. L'excepcional estat de conservación en que es conserven les policromies del cas d'estudi d'aquesta Tesi Doctoral (el Sepulcre de Villaespesa de la catedral de Tudela, Navarra, Espanya) sugereix que tant la composició química-mineral i la porositat de les roques seleccionades pels artistes com la composició de les pel·lícules pictòriques a l'oli que van preparar per a policromar la pedra, podrien ser responsables de la seua inesperada durabilitat. Quan els mecanismes que governen els seus equilibris fisicoquímics no han estat compresos adequadament, els materials i mètodes emprats en la seua conservació així com les condicions mediambientals en què es mantenen poden tinder un efecte dramatic al comportament d'aquests sistemes pictòrics i comprometre la seua estabilitat a llarg termini. En aquesta tesi es van preparar provetes amb diferents pel·lícules pictòriques a l'oli sobre l'arenisca emprada en el cas d'estudi. També es van preparar provetes amb les mateixes pel·lícules sobre altres suports per fer una anàlisi comparatiu. Després de quatre anys d'envelliment natural, es va identificar i caracteritzar l'agregació de carboxilats de calci i plom en algunes de les provetes a través de l'ús combinat de microscòpia òptica, SEM-EDX i micro espectroscòpia FT-IR. També es monitarizaren el pH i la conductivitat de les provetes així com del cas d'estudi. En aquelles pel·lícules a l'oli amb blanc de plom o mini que van envellir durant quatre anys sobre substrats de gres i fusta de pi, les reaccions de saponificació, la formació de ionómeros i l'agregació de carboxilats van contribuir a generar estrats pictòrics menys àcids, menys ionitzats, menys hidrolitzats i menys solubles. Aquestes pel·lícules pictòriques es van tornar més àcides i ionitzades després envellir, en les mateixes condicions mediambientals, sobre vidre de microscopi. La comprensió dels mecanismes fisicoquímics que governen el seu pH i la seua conductivitat així com les forces adhesives i cohesives d'aquestes pel·lícules al llarg del temps no és senzilla. Tant els agregats minerals com la disponibilitat de ions que presenten els seus substrats juguen un paper fonamental en l'eventual formació, migració i agregació de carboxilats de calci i plom no només en la seua superfície, sinó també en la interfase substrat-pel·lícula pictòrica. / Aguado Guardiola, E. (2017). Estudio del rol de los agregados minerales en la formación, envejecimiento y conservación de películas pictóricas al óleo [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/90462

Los modelos numéricos son herramientas fundamentales para realizar predicciones de muchos problemas enfrentados por ingenieros geotécnicos y geoambientales. Sin embargo, para que estos modelos puedan realizar predicciones confiables, los parámetros de entrada del modelo deben ser estimados considerando el efecto escala. En este contexto, esta tesis se concentra en las reglas del cambio de escala de los parámetros de flujo y transporte de masa en un suelo tropical a través de estudios numéricos, de laboratorio y de campo. Esta está organizada en cuatro partes. Primero, la heterogeneidad, correlación y correlación cruzada entre los parámetros de transporte de solutos (dispersividad, ¿, y coeficiente de partición, Kd) y las propiedades del suelo fueron estudiadas en detalle. En esta parte fue verificado que la conductividad hidráulica (K) y los parámetros de transporte de solutos son altamente heterogéneos, mientras que las propiedades del suelo no lo son. La correlación espacial de ¿ y K con variables estadísticamente significativas fue estudiada. Este resultado probablemente podrá mejorar la estimación en casos de estudios de pequeña escala debido a que solo fue observada correlaciones de hasta 2,5 m. Este estudio fue un primer intento de evaluar la variación espacial en el coeficiente de correlación de los parámetros de transporte de un soluto reactivo y de un no reactivo, indicando las variables más relevantes y aquella que debería ser incluida en estudios futuros. En la segunda parte, el efecto escala en K, dispersividad y coeficiente de partición de potasio y clorito fue estudiado experimentalmente a través de experimentos de laboratorio y de campo. El objetivo de esta parte fue contribuir a la discusión sobre el efecto escala en K, ¿ y Kd, y entender como estos parámetros se comportan con el cambio de escala de medición. La dispersividad tiende a aumentar con la altura de la muestra de manera exponencial. El coeficiente de partición tiende a aumentar con la altura, el diámetro y el volumen de la muestra. Estas diferencias encontradas en los parámetros de acuerdo con la escala de medición deben ser considerados cuando estos valores sean usados posteriormente como datos de entrada de modelos numéricos; de otra manera, las respuestas pueden ser malinterpretadas. Tercero, análisis estocásticos tridimensionales de cambio de escala de la conductividad hidráulica fueron realizados usando los métodos de promedios simples y de Laplace con piel para una variedad de tamaños de bloques usando mediciones reales de K. En esta parte son demostrados los errores que pueden ser introducidos al usar métodos determinísticos de cambio de escala usando promedios simples de las mediciones de K sin llevar en consideración la correlación espacial. La aplicación muestra que la heterogeneidad de K puede ser incorporada en la práctica diaria del modelador geotécnico. Los aspectos que considerar durante un proceso de cambio de escala también son discutidos. Finalmente, la dependencia del exponente de la norma-p como función del tamaño del bloque fue analizada. En la última parte, una aplicación de cambio de escala estocástico del coeficiente de dispersión hidrodinámica D y del factor de retardo R fue realizada usando datos reales con el objetivo de reducir la falta de casos de investigación experimental de cambio de escala de parámetros de transporte de solutos reactivos. El cambio de escala de D fue realizado usando el método de macrodispersión. El método de promedio simple de norma-p fue usado para realizar el cambio de escala de R. Una buena propagación de incertidumbres fue alcanzada. Métodos simples de cambio de escala pueden ser introducidos en la práctica del modelaje usando programas comerciales de transporte y conseguir reproducir el transporte en escala gruesa, pero puede requerir correcciones con el objetivo de reducir el efecto de suavizado de la heterogeneidad causado por el / Numerical models are becoming fundamental tools to predict a range of complex problems faced by geotechnical and geo-environmental engineers. However, to render the model reliable for future predictions, the model input parameters must be determined with consideration of the scale effects. In this context, this thesis focuses on upscaling of water flow and mass transport in a tropical soil by means of numerical, laboratory and field studies. This thesis is organized in four parts. First, the heterogeneity, correlation and cross-correlation between solute transport parameters (dispersivity, ¿, and partition coefficient, Kd) and soil properties were studied in detail. In this part, it was verified that the hydraulic conductivity (K) and solute transport parameters are highly heterogeneous, while soil properties not. Spatial correlation of ¿, K, and statistically significant variables were studied, and it would probably improve the estimation only in a small-scale study, since the spatial correlation were only observed up to 2.5 m. This study was a first attempt to evaluate the spatial variation in the correlation coefficient of transport parameters of a reactive and a nonreactive solute, indicating the more relevant variables and the one that should be included in future studies. In the second part, scale effect on K, dispersivity and partition coefficient of potassium and chloride is studied experimentally by means of laboratory and field experiments. The purpose of was to contribute to the discussion about scale effects on K, ¿ and Kd and understanding how these parameters behave with the change in the scale of measurement. Results shows that K increases with scale, regardless of the method of measurement. Dispersivity trends to increases exponentially with the sample height. Partition coefficient, tend to increase with sample length, diameter and volume. These differences in the parameters according to the scale of measurement must be considered when these observations are later used as input to numerical models, otherwise the responses can be misrepresented. Third, stochastic analysis of three-dimensional hydraulic conductivity upscaling was performed using a simple average and the Laplacian-with-skin methods for a variety of block sizes using real K measurements. In this part it was demonstrated the errors that can be introduced by using a deterministic upscaling using simple averages of the measured K without accounting for the spatial correlation. The application shows that K heterogeneity can be incorporated in the daily practice of the geotechnical modeler. The aspects to consider when performing the upscaling were also discussed. Finally, the dependence of the exponent of the p-norm as a function of the block size was analyzed. In the last part, an application of stochastic upscaling of hydrodynamic dispersion coefficient (D) and retardation factor (R) was performed using real data aiming to reduce the lack in experimental upscaling of reactive solute transport research. Upscaling of D was done using macrodispersion method. Simple average method based on p-norm was used to perform R upscaling. A good propagation of the uncertainties was achieved. Simple upscaling methods can be incorporated to the modeling practice using commercial transport codes and properly reproduce de transport at coarse scale but may require corrections to reduce smoothing of the heterogeneity caused by the upscaling procedure. / Els models numèrics s'estan constituint en eines fonamentals per a realitzar prediccions d'una àmplia gamma de problemes enfrontats per enginyers geotècnics i geoambientales. No obstant açò, perquè aquests models puguen realitzar prediccions fiables, els paràmetres d'entrada del model han de considerar l'efecte escala. En aquest context, aquesta tesi es concentra en les regles del canvi d'escala dels paràmetres de flux i transport de massa en un sòl tropical a través d'estudis numèrics, de laboratori i de camp. Aquesta tesi està organitzada en quatre parts. Primer, l'heterogeneïtat, correlació i correlació creuada entre els paràmetres de transport de soluts (dispersivitat, ¿, i coeficient de partició, Kd) i les propietats del sòl van ser estudiades detalladament. En aquesta part va ser verificat que la conductivitat hidràulica (K) i els paràmetres de transport de soluts són altament heterogenis, mentre que les propietats del sòl no ho són. La correlació espacial de ¿ i K amb variables estadísticament significatives va ser estudiada. Aquest resultat probablement podrà millorar l'estimació en casos d'estudis de xicoteta escala a causa que solament va ser observada correlacions de fins a 2,5 m. Aquest estudi va ser un primer intent d'avaluar la variació espacial en el coeficient de correlació dels paràmetres de transport d'un solut reactiu i d'un no reactiu, indicant les variables més rellevants i aquelles que haurien de ser inclosas en estudis futurs. En la segona part, l'efecte escala en K, dispersivitat i coeficient de partició de potassi i clorito va ser estudiat experimentalment a través d'experiments de laboratori i de camp. L'objectiu d'aquesta part va ser contribuir a la discussió sobre l'efecte escala en K, ¿ i Kd, i entendre com aquests paràmetres es comporten amb el canvi d'escala de mesurament. La dispersivitat tendeix a augmentar amb l'altura de la mostra, és a dir, amb la longitud del transport, de manera exponencial. El coeficient de partició tendeix a augmentar amb l'altura, el diàmetre i el volum de la mostra. Aquestes diferències en els paràmetres d'acord amb l'escala de mesurament han de ser considerats quan aquests valors siguen usats posteriorment com a dades d'entrada de models numèrics; d'una altra manera, les respostes poden ser malament interpretades. Tercer, anàlisis estocàstiques tridimensionals de canvi d'escala de la conductivitat hidràulica van ser realitzats usant els mètodes de mitjanes simples i de Laplace amb pell per a una varietat de grandàries de blocs usant mesuraments reals de K. En aquesta part són demostrats els errors que poden ser introduïts en usar mètodes determinístics de canvi d'escala usant mitjanes simples dels mesuraments de K sense tindre en consideració la correlació espacial. L'aplicació mostra que l'heterogeneïtat de K pot ser incorporada en la pràctica diària del modelador geotècnic. Els aspectes a considerar durant un procés de canvi d'escala també són discutits. Finalment, la dependència de l'exponent de la norma-p com a funció de la grandària del bloc va ser analitzada. En l'última part, una aplicació de canvi d'escala estocàstic del coeficient de dispersió hidrodinámica D i del factor de retard R va ser realitzada usant dades reals amb l'objectiu de reduir la falta de casos de recerca experimental de canvi d'escala de paràmetres de transport de soluts reactius. El canvi d'escala de D va ser realitzat usant el mètode de macrodispersió. El mètode de mitjana simple de norma-p va ser usat per a realitzar el canvi d'escala de R. Una bona propagació d'incerteses va ser aconseguida. Mètodes simples de canvi d'escala poden ser introduïts en la pràctica de la modelació usant programes comercials de transport i aconseguir reproduir el transport en escala gruixuda, però pot requerir correccions amb l'objectiu de reduir l'efecte de suavitzat de l'heterogeneïtat causat pel procés de canvi d'escala. / Almeida De Godoy, V. (2018). Upscaling of water flow and mass transport in a tropical soil: numerical, laboratory and field studies [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/102405

Electrochemical energy storage has been widely used in various areas, including new energy sources, auto industry, and information technology. However, the performance of current electrochemical energy storage devices does not meet the requirements of these areas that include both high energy and power density, fast recharge time, and long lifetime. One solution to meet consumer demands is to discover new materials that can substantially enhance the performance of electrochemical energy storage devices. In this dissertation we report four transition metal materials systems with potential applications in electrochemical energy storage. Nanoscale and nanostructured materials are expected to play important roles in energy storage devices because of their enhanced and sometimes unique physical and chemical properties. Studied here is the comparative electrochemical cation insertion into a nanostructured vanadium oxide, a promising electrode material candidate, for the alkali metal ions Li+, Na+ and K+ and the organic ammonium ion, in aqueous electrolyte solutions. Observed are the distinctive insertion processes of the different ions, which yield a correlation between physical degradation of the material and a reduction of the calculated specific charge. The results reveal the potential of this nanostructured vanadium oxide material for energy storage. Vanadium based electrochemical systems are of general interest, and as models for vanadium based solid-state electrochemical processes, the solution state and the solid-state electrochemical properties of two cryolite-type compounds, (NH4)3VxGa1-xF6, and Na3VF6, are studied. The electrochemical behavior of (NH4)3VxGa1-xF6 explored the possibility of using this material as an electrolyte for solid state energy storage systems. Zeolite-like materials have large surface to volume ratios, with ions and neutral species located in the nanometer sized pores of the 3-dimensional framework, potentially yielding high energy density storage capabilities. Yet the insulating nature of known zeolite-like materials has limited their use for electrical energy storage. Studied here are two vanadium based zeolite-like structures, the oxo-vanadium arsenate [(As6V15O51)-9]∞, and the oxo-vanadium phosphate [(P6V15O51)-9]∞, where the former shows electronic conduction in the 3-dimensional framework. Mixed electronic and ionic conductivity, from the framework and from the cations located within the framework, respectively, is measured in the oxo-vanadium arsenate, and allows the use of this material in electrochemical double-layer capacitor configuration for energy storage. By contrast, the oxo-vanadium phosphate shows ionic conduction only. Lastly, a new strontium manganese vanadate with a layered structure exhibiting mixed protonic and electronic conductivity is studied. The various transition metal compounds and materials systems experimentally studied in this thesis showcase the importance of novel materials in future energy storage schemes. / Ph. D.

The objective of this study was to determine the photothermal and photochemical tissue response to carbon nanotube inclusion in laser therapy using experimental and computational methods. In this study, we specifically considered varying types and concentrations (0.01-1 mg/ml) of carbon nanotubes (CNTs), e.g., multi-walled carbon nanotubes (MWNTs), single-walled carbon nanotubes (SWNTs), and single-walled carbon nanohorns (SWNHs). In order to determine the photothermal effect of CNT inclusion, the thermal conductivity and optical properties of tissue representative phantoms with CNT inclusion were measured. Thermal conductivity of tissue phantoms containing CNTs was measured using the hot wire probe method. For identical CNT concentrations, phantoms containing MWNTs had the highest thermal conductivity. Optical properties (absorption and reduced scattering coefficients) of solutions and tissue phantoms containing carbon nanotubes were measured with spectrophotometry and determined by the inverse adding doubling (IAD) method. Inclusion of CNTs in phantoms increased light absorption with minimal effect on scattering and anisotropy. Light absorption of MWNTs was found to be higher than SWNTs and SWNHs. The photochemical response to laser irradiation (wavelength 1064 nm) of CNTs was measured with spin-trap electron paramagnetic resonance (EPR) spectroscopy. Only SWNHs appeared to produce significant levels of ROS production in response to laser excitation in the presence of NADH. We detected the predominant presence of trapped hydroxyl radical (•OH) with a trace of the trapped super oxide (O2•-) radical. These free radicals are highly reactive and could be utilized to cause targeted toxicity to cancer cells. The distribution of CNTs at the cellular level, in phantoms, and in kidney tumors was measured using transmission electron microscopy (TEM) imaging. Samples were imaged following various time periods (2-48h) of incubation and CNTs were observed inside the cell cytoplasm, nucleus, vacuole, and outside cells for the above mentioned time periods. CNTs in phantoms and tumor tissue were randomly and uniformly distributed in the entire volume. Computational model geometries were developed based on CNTs distribution in cells, tissue phantoms, and kidney tumor tissue. In the computational part of this research the temperature response to laser irradiation alone or with CNT inclusion was determined using Penne's bioheat equation which was solved by finite element methods. Experimentally measured thermal conductivity and absorption and reduced scattering coefficients were used as input parameters in Penne's bioheat equation. The accuracy of the model predicted temperature distribution was determined by comparing it to experimentally measured temperature in tissue phantoms and kidney tumors following CNT inclusion and laser therapy. The model determined temperature distribution was in close correspondence with the experimentally measured temperature. Our computational model can predict the effectiveness of laser cancer therapy by predicting the transient temperature distribution. / Ph. D.

Chlorinated ethenes are considered one of the most prevalent sources of groundwater contamination in developed countries. Natural attenuation of chlorinated ethenes is possible through the process of microbial reductive dechlorination. Reductive dechlorination can occur in contaminated aquifers where there are sufficient amounts of organic carbon and reducing redox conditions to support dechlorinating microorganisms. Natural organic carbon (NOC) from dissolved aquifer sediment is thought to be the source of fermentable compounds needed to produce molecular hydrogen that functions as the primary electron donor for reductive dechlorination. Therefore, in an anaerobic aquifer, the production of molecular hydrogen from the fermentation of NOC drives the reductive dechlorination process. The variability and distribution of potential bioavailable organic carbon (PBOC) at a site is relatively unknown and any potential relationships between PBOC and the physical properties of the aquifer sediment have not been evaluated. Exploring relationships between the grain size of aquifer sediment PBOC may help to determine the feasibility of natural attenuation as a long-term remediation strategy at chlorinated ethene-contaminated sites. Because hydraulic conductivity is directly related to aquifer sediment grain size, zones of high hydraulic conductivity may promote greater microbial activity or biodegradation because of the increased availability of PBOC and nutrient flux. To determine potential relationships between PBOC and aquifer sediment grain size, two experiments were performed. PBOC was measured for 106 sediment samples impacted by chlorinated solvent contamination from an anaerobic type II site through a multiple liquid extraction process (Rectanus et al. 2007). Grain size distributions for each of the 106 sediment samples were determined by conducting sieve analyses. The results of both experiments were compared to explore relationships between PBOC and sediment grain size and to evaluate spatial distribution of both in the surficial aquifer. / Master of Science