La cellulose étant l'un des biopolymères les plus abondants, elle est employée dans ce travail de thèse sous sa forme nano-fibrille (2 à 5nm de diamètre et plusieurs microns de long) pour préparer des nanomatériaux durables. Les microfibrilles de cellulose (MFC) chargées positivement ou négativement sont assemblées en couches minces dans ces nanomatériaux par la méthode « Layer by Layer » (LbL) par trempage, pulvérisation ou spin assisté. Les différences entre ces films LbL à base de MFC et les films LbL à base de polymères standards sont discutées brièvement et sont reliées à la forme nanofibrillaire de la cellulose. Les MFC réagissent comme des nano-objets anisotropes et rigides. Les films LbL de MFC sont ensuite intégrés à des membranes de séparation, entre la couche polymérique de séparation et le support poreux, pour améliorer le débit à travers ces membranes. Ces films minces sont également déposés sur des aérogels de cellulose pour améliorer la stabilité de ces aérogels en milieu aqueux. Dans les deux applications, les résultats était encouragent et montre une validation de principe. / Cellulose, one of the most abundant biopolymers, is used in this PhD work in its nanofibrillated form, 2-5 nm in diameter and microns long, to prepare sustainable nanomaterials. Both positively and negatively charged microfibrillated celluloses (MFC) are assembled in these nanomaterials using the versatile Layer by Layer (LbL) assembly methods: dipping, spray assisted-deposition and spin-assisted deposition. A brief comparison between the MFC based LbL assembled films and the standard polymeric LbL films is carried out. Thedifferences between the two species are related to the fibrillar form of cellulose. MFC behaves like rigid anisotropic nano-objects. MFC LbL assembled films are then integrated in separation membranes between active polymeric separation layers and a mechanically stable porous support to improve the flux through these membranes. MFC LbL assembled films are also coated on cellulosic aerogels to improve the wet stability of these aerogels. In both cases, results were encouraging and showed a proof of concept.

The purpose of this research project was to design, implement, and evaluate a prototype underwater positioning system which extends the reach of the terrestrial Global Positioning System (GPS) underwater. The GPS does not function underwater because the high-frequency low-power signals used by the GPS are not able to penetrate more than several meters in water. The Underwater Global Positioning System (UGPS), presented in this work, provides underwater position data to an unlimited number of underwater assets, such as autonomous vehicles. The user requirements are discussed and a design is presented that incorporates a topside surface buoy (satellite) and a subsurface receiver. The satellite is responsible for receiving GPS data and relaying the data, via acoustic signals, to the subsurface receiver. The receiver calculates its position using the coded acoustic signals. The implementation of the prototype UGPS satellite and subsurface receiver are discussed in detail; the custom electronics, software, data acquisition systems and mechanical housings are described. The key operating characteristics of the UGPS are investigated both experimentally and through the analysis of a model describing the entire UGPS. Employing the prototype UGPS, a series of sea-trials were performed that provides essential design data for developing the next version of the system. The main characteristics that were experimentally investigated were: the long and short-range accuracy; the repeatability; and the resolution. The experimental data was also employed to confirm the UGPS model performance. The prototype system demonstrated the feasibility of the UGPS concept and showed that a position accuracy of 6.5m should be attainable for an unlimited number of underwater receivers operating within a one square kilometer workspace. The accuracy can be enhanced to sub-meter by employing more accurate GPS receivers in the satellites and using a sound velocity meter to measure the sound velocity profile of the acoustic workspace.

Indiana University-Purdue University Indianapolis (IUPUI) / In this research thesis, copper indium gallium selenium (CIGS) nanoparticles were synthesized from metal chlorides, functionalized to disperse in water, and further used in layer by layer (LbL) nanoassembly of CIGS films. CIGS nanoparticles were synthesized through the colloidal precipitation in an organic solvent. The peak and average sizes of the synthesized particles were measured to be 68 nm and 75 nm in chloroform, and 30 nm and 115 nm in water, respectively. Two methods were used to disperse the particle in water. In the first method the stabilizing agent oleylamine (OLA) was removed through multiple cleaning processes, and in the second method ligand exchange was performed with polystyrene sulfonate (PSS). Zeta potential of CIGS nanoparticles dispersed in water was measured to be +61 mV. The surface charge of the nanoparticles was reversed by raising the pH of the solution, which was measured to be −43.3 mV at 10.5 pH. In a separate process, the CIGS nanoparticles dispersed in water were coated with PSS. The resulting dispersion was observed to be stable and the surface charge was measured to be −56.9 mV. The LbL deposition process of CIGS nanoparticles was characterized by depositing thin films on quartz crystal microbalance (QCM). LbL depositions was conducted using (i) oppositely charged CIGS nanoparticles, (ii) positively charged CIGS nanoparticles and PSS, and (iii) PSS-coated CIGS (CIGS-PSS) and polyethyleneimine (PEI). The average thickness of each bi-layer of the above mentioned depositions were measured to be 2.2 nm, 1.37 nm, and 10.12 nm, respectively. The results from the QCM have been observed to be consistent with the film thickness results obtained from atomic force microscopy (AFM). Various immersion times versus thickness of the film were also studied. For electrical characterization, the CIGS films were deposited on indium tindioxide (ITO)-coated glass substrates. Current versus voltage (I/V) measurements were carried out for each of the films using the Keithley semiconductor characterization instruments and micromanipulator probing station. It was observed that the conductivity of the films was increased with the deposition of each additional layer. The I/V characteristics were also measured under the light illumination and after annealing to study the photovoltaic and annealing effects. It was observed that under light illumination, the resistivity of a 12-layer CIGS film decreased by 93% to 0.54 MΩ.m, and that of the same number of layers of PSS-coated CIGS and PEI film decreased by 60% to 0.97 MΩ.m under illumination. The resistivity of an 8-layer CIGS and PSS film decreased by 76.4% to 0.1 MΩ.m, and that of the same layers of PSS-coated CIGS and PEI decreased by 87% to 0.07 MΩ.m after annealing. The functionalized nanoparticles and the LbL CIGS films were implemented in the solar cell devices. Several configurations of CIGS films (p-type), and ZnO and CdS films (n-type) were considered. Poly(3,4-ethylenedioxythiophene) (PEDOT), molybdenum (Mo), and ITO were used as back contacts and ITO was used as front contact for all the devices. The devices were characterized the Keithley semiconductor characterization instruments and micromanipulator probing station. For a CIGS and n-ZnO films device with PEDOT as back contact and ITO as front contact, the current density at 0 V and under light illumination was measured to be 60 nA/cm2 and the power density was measured to be 0.018 nW/cm2. For a CIGS and CdS films device with ITO as both back and front contact, the current density at 0 V and under light illumination was measured to be 50 nA/cm2 and the power density was measured to be 0.01 nW/cm2. For a drop-casted CIGS and CdS films device with Mo as back contact and ITO as front contact, the current density of 50 nA/cm2 at 0 V and power density of 0.5 nW/cm2 under light illumination was measured. For the LbL CIGS and chemical bath deposited CdS films device with ITO as both back and front contact, the current density of 0.04 mA/cm2 at 0 V and power density of 1.6 μW/cm2 under light illumination was measured. Comparing to Device-III, an increase by 99% in the power density was observed by using the CIGS LbL film in the device structure. The novel aspects of this research include, (i) functionalization of the CIGS nanoparticles to disperse in water including coating with PSS, (ii) electrostatic LbL deposition of CIGS films using oppositely charged nanoparticles and polymers, and (iii) the utilization of the fabricated LbL CIGS films to develop solar cells. In addition, the n-type cadmium sulfide film (CdS) and zinc oxide (ZnO) buffer layer were also deposited through LbL process after the respective particles were functionalized with PSS coating in separate experiments.

The research presented in this dissertation is focused on the construction of complex molecular structures on planar gold and silicon dioxide surfaces using a variety of surface modification techniques, along with thorough surface characterization at each modification step. The dissertation is structured into six separate chapters. In Chapter 1, an introduction to the importance and implications of molecular level surface modification, commonly employed surface modification methods, and available surface characterization techniques is presented. Chapter 2 shows applications of novel methodologies for the functionalization of gold surfaces using alkane dithiol self-assembled monolayers and thiol-ene click chemistry. The resulting functionalized gold substrates demonstrate higher chemical stability than alkanethiol self-assembled monolayers alone and allow spatially controlled functionalization of gold surfaces with light. In Chapter 3, work on tunable hydrophobic surfaces is presented. These surfaces are prepared using a combination of organosilane chemistry, layer-by-layer polyelectrolyte deposition, and thiol-ene chemistry. These hydrophobic surfaces demonstrate high mechanical and chemical stability, even at low pH (1.68). The pinning of water droplets could be tuned on them by the extent of their thermal treatment. Comprehensive surface characterization using X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), spectroscopic ellipsometry, atomic force microscopy, and water contact angles was carried out on the molecular assemblies prepared on gold and silicon dioxide surfaces. Chapters 4 and 5 are focused on the application, data interpretation, and enhancement in sensitivity of different surface characterization methods. In Chapter 4, XPS, ToF-SIMS, and principal components analysis are used to probe a real world corrosion-type problem. This systemic study showed the destruction of a protective coating composed of a nitrilotris(methylene)triphosphonic acid by a low-intensity fluorine plasma. In Chapter 5, enhancement in ToF-SIMS signals is shown via bismuth metal deposition. These surfaces are also probed by spectroscopic ellipsometry using the interference enhancement method. Finally, Chapter 6 concludes this dissertation by describing possible future work.

[EN] Fiber grating sensors and devices have demonstrated outstanding capabilities in both telecommunications and sensing areas, due to their well-known advantageous characteristics. Therefore, one of the most important motivations lies in the potential of customized fiber gratings to be suitably employed for improving the interrogation process of optical fiber sensors and systems. This Ph.D. dissertation is focused on the study, design, fabrication and performance evaluation of customized fiber Bragg gratings (FBGs) and long period gratings (LPGs) with the double aim to present novel sensing technologies and to enhance the response of existing sensing systems. In this context, a technique based on time-frequency domain analysis has been studied and applied to interrogate different kind of FBGs-based sensors. The distribution of the central wavelength along the sensing structures has been demonstrated, based on a combination of frequency scanning of the interrogating optical pulse and optical time-domain reflectometry (OTDR), allowing the detection of spot events with good performance in terms of measurand resolution. Moreover, different customized FBGs have been interrogated using a technology inspired on the operation principle of microwave photonics (MWP) filters, enabling the detection of spot events using radio-frequency (RF) devices with modest bandwidth. The sensing capability of these technological platforms has been fruitfully employed for implementing a large scale quasi-distributed sensor, based on an array of cascaded FBGs. The potentiality of LPGs as fiber optic sensors has also been investigated in a new fashion, exploiting the potentials of MWP filtering techniques. Besides, a novel approach for simultaneous measurements based on a half-coated LPG has been proposed and demonstrated. Finally, the feasibility of FBGs as selective wavelength filters has been exploited in sensing applications; an alternative approach to improve the response and performance of Brillouin distributed fiber sensors has been studied and validated via experiments. The performance of the reported sensing platforms have been analyzed and evaluated so as to characterize their impact on the fiber sensing field and to ultimately identify the use of the most suitable technology depending on the processing task to be carried out and on the final goal to reach. / [ES] Los sensores y dispositivos en fibra basados en redes de difracción han mostrado excepcionales capacidades en el ámbito de las telecomunicaciones y del sensado, gracias a sus excelentes propiedades. Entre las motivaciones más estimulantes destaca la posibilidad de fabricar redes de difracción ad-hoc para implementar y/o mejorar las prestaciones de los sensores fotónicos. Esta tesis doctoral se ha enfocado en el estudio, diseño, fabricación y evaluación de las prestaciones de redes de difracción de Bragg (FBGs) y de redes de difracción de periodo largo (LPGs) personalizadas con el fin de desarrollar nuevas plataformas de detección y a la vez mejorar la respuesta y las prestaciones de los sensores fotónicos ya existentes. En este contexto, una técnica basada en el análisis tiempofrecuencia se ha estudiado e implementado para la interrogación de sensores en fibra basados en varios tipos y modelos de FBGs. Se ha analizado la distribución de la longitud de onda central a lo largo de la estructura de sensado, gracias a una metodología que conlleva el escaneo en frecuencia del pulso óptico incidente y la técnica conocida como reflectometria óptica en el dominio del tiempo (OTDR). De esta manera se ha llevado a cabo la detección de eventos puntuales, alcanzando muy buenas prestaciones en términos de resolución de la magnitud a medir. Además, se han interrogado varias FBGs a través de una técnica basada en el principio de operación de los filtros de fotónica de microondas (MWP), logrando así la detección de eventos puntuales usando dispositivos de radio-frecuencia (RF) caracterizados por un moderado ancho de banda. La capacidad de sensado de estas plataformas tecnológicas ha sido aprovechada para la realización de un sensor quasi-distribuido de gran alcance, formado por una estructura en cascada de muchas FBGs. Por otro lado, se han puesto a prueba las capacidades de las LPGs como sensores ópticos según un enfoque novedoso; para ello se han aprovechados las potencialidades de los filtros de MWP. Asimismo, se ha estudiado y demostrado un nuevo método para medidas simultáneas de dos parámetros, basado en una LPG parcialmente recubierta por una película polimérica. Finalmente, se ha explotado la viabilidad de las FBGs en cuanto al filtrado selectivo en longitud de onda para aplicaciones de sensado; para ello se ha propuesto un sistema alternativo para la mejora de la respuesta y de las prestaciones de sensores ópticos distribuidos basados en el scattering de Brillouin. En conclusión, se han analizado y evaluado las prestaciones de las plataformas de sensado propuestas para caracterizar su impacto en el ámbito de los sistemas de detección por fibra y además identificar el uso de la tecnología más adecuada dependiendo de la tarea a desarrollar y del objetivo a alcanzar. / [CA] Els sensors i dispositius en fibra basats en xarxes de difracció han mostrat excepcionals capacitats en l'àmbit de les telecomunicacions i del sensat, gràcies a les seus excel¿lents propietats. Entre les motivacions més estimulants destaca la possibilitat de fabricar xarxes de difracció ad-hoc per a implementar i/o millorar les prestacions de sensors fotònics. Esta tesi doctoral s'ha enfocat en l'estudi, disseny, fabricació i avaluació de les prestacions de xarxes de difracció de Bragg (FBGs) i de xarxes de difracció de període llarg (LPGs) personalitzades per tal de desenvolupar noves plataformes de detecció i al mateix temps millorar la resposta i les prestacions dels sensors fotònics ja existents. En este context, una tècnica basada en l'anàlisi temps-freqüència s'ha estudiat i implementat per a la interrogació de sensors en fibra basats en diversos tipus i models de FBGs. S'ha analitzat la distribució de la longitud d'ona central al llarg de l'estructura de sensat, gràcies a una metodologia que comporta l'escaneig en freqüència del pols òptic incident i la tècnica coneguda com reflectometria òptica en el domini del temps (OTDR). D'esta manera s'ha dut a terme la detecció d'esdeveniments puntuals, aconseguint molt bones prestacions en termes de resolució de la magnitud a mesurar. A més, s'han interrogat diverses FBGs a través d'una tècnica basada en el principi d'operació dels filtres de fotònica de microones (MWP), aconseguint així la detecció d'esdeveniments puntuals utilitzant dispositius de ràdio-freqüència (RF) caracteritzats per un moderat ample de banda. La capacitat de sensat d'aquestes plataformes tecnològiques ha sigut aprofitada per a la realització d'un sensor quasi-distribuït a llarga escala, format per una estructura en cascada de moltes FBGs. D'altra banda, s'han posat a prova les capacitats de les LPGs com a sensors òptics segons un enfocament nou; per a això s'han aprofitat les potencialitats dels filtres de MWP. Així mateix, s'ha estudiat i demostrat un nou mètode per a mesures simultànies de dos paràmetres, basat en una LPG parcialment recoberta per una pel¿lícula polimèrica. Finalment, s'ha explotat la viabilitat de les FBGs pel que fa al filtrat selectiu en longitud d'ona per a aplicacions de sensat; per això s'ha proposat un sistema alternatiu per a la millora de la resposta i de les prestacions de sensors òptics distribuïts basats en el scattering de Brillouin. S'han analitzat i avaluat les prestacions de les plataformes de sensat propostes per a caracteritzar el seu impacte en l'àmbit dels sistemes de detecció per fibra i a més identificar l'ús de la tecnologia més adequada depenent de la tasca a desenvolupar i de l'objectiu a assolir. / Ricchiuti, AL. (2016). Design and fabrication of customized fiber gratings to improve the interrogation of optical fiber sensors [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/66343 / Premios Extraordinarios de tesis doctorales