This work is concerned with mechanical property improvements to poly(ethylene terephthalate), PET, fibers by the addition of layered silicate nanoparticles and by drawing the un-oriented nanocomposite filaments in a second step. No previous studies on PET fibers filled with montmorillonite (MMT) nanoclay examined fiber drawability at temperatures above the glass transition. Therefore, the primary objective of this research was to determine 1) if PET nanocomposite fibers could be drawn to finer diameters and 2) whether drawing imparted improved Young's modulus and tenacity (i.e. strength) relative to un-filled PET fibers. Of equal importance to this work, the subsequent objective was to discern and understand the role of nanoclay in 1) the production of improved or reduced mechanical properties and 2) the ability to draw PET to lower or higher than normal draw ratios. In the first part of this thesis, the improvements in Young's modulus and tenacity of PET fibers filled with various types of organically modified montmorillonite is shown and the method to produce them is discussed. Greater improvements in mechanical properties occurred when the MMT stacks were intercalated with PET. A nominal 1 wt% loading of dimethyl-dehydrogenated tallow quaternary ammonium surface modified MMT in drawn PET fiber showed a 28% and 63% increase in Young's modulus and strength, respectively. Relative to an un-filled PET fiber, these results exceeded the upper-bound of the rule of mixtures estimate. Therefore, both the type of surface modification and concentration of MMT were shown to affect the degree of PET orientation and crystallinity. Furthermore, drawability above Tg and elongation-at-break increased upon the addition of organically modified MMT to un-oriented PET fibers, which was a key distinction of this work from others examining similar systems. Interestingly, the mechanical properties of modulus and tenacity showed a maximum with concentration of alkyl modified clay, but drawability did not show significant variation with increasing nanoclay content. Thermal analysis and Raman spectroscopy was used to examine the role of nanoclay in creating this maximum in mechanical properties. At low loadings, nanoclay was shown to intercalate with PET and enhance amorphous orientation. At higher concentrations of nanoclay the presence of large agglomerates prevented efficient orientation to the fiber axis and acted as stress concentrators to aid in cavitation and failure during testing. Raman spectroscopy showed that the as-spun unfilled PET fibers possessed significantly more trans conformer content of the ethylene glycol moiety than the nanocomposite fibers. The greater gauche content of the nanocomposite fibers delayed crystalline development during non-isothermal DSC scans to higher temperatures was associated with the increased drawability. / Ph. D.

In this study, we will discuss the fabrication detail about the capillary optical fiber and microstructured optical fiber (MOF) from the preform manufacture to the drawing process and apply our capillary optical fiber in a temperature sensor device. First, we discuss the influence of the drawing parameters contribution for the fiber, and we will introduce how to design a preform and discuss how to keep our fibre geometry in drawing process by controlling the drawing parameters. For better fiber products, we need to make some important improvements such as fixing the preform geometry and designing the preform pressure or vacuum input path before the fiber drawing process. In the fiber drawing we want to control the fiber inner diameter and make the interval between three capillary tube disappear. We will solve these problems by different preform making methods or drawing tower hardware design and drawing parameter control. Now we can successfully make single ring hole MOFs by the capillary tube sealed method. But the hole structure is not as good as expectation. We will try to design a pressure and vacuum input device to replace the capillary tube sealed method. And help us to make better and more different MOF structures. We also used our capillary optical fiber to be a temperature sensor. We will describe the principle and the sensing sensitivity of our sensing device in this study. Our temperature sensing device shows a linear relationship between the temperature and operation wavelength, and the sensing sensitivity is 0.038nm/¢XC

A comprehensive experimental study was conducted to determine the limitations in processing conditions for superdrawing. Experimental studies were carried out by uniaxial drawing tests at temperatures from 90 to 120°C and at strain rates ranging from 0.008/s to 0.425/s. Crystallinity and orientation of the drawn samples were evaluated using differential scanning calorimetry and birefringence measurements. This study revealed that increasing temperature from 110°C to 120°C leads to more crystallization at low strain rates (0.001/s), and less crystallization at high strain rates (0.1/s). Furthermore, it was shown for the first time that the mechanism of crystallinity development in PET undergoes a transition at draw temperature of 113°C and strain rate of 0.17/s. A new one-dimensional constitutive model was developed to predict the stress-strain behavior of PET fibers as they are drawn to very large draw ratios (up to 10) over a wide range of temperature (90-120°C) and strain rate (0.008-0.425/s). The model was based on the rubber elasticity theory and non-linear viscoelasticity.

This dissertation presents the first reported identification and analyses of the phase relations in the YBa2Cu3O7-x (YBCO)-SiO2 system at elevated temperatures. In this regard, a rigorous characterization study of the reaction phases within YBCO glass fibers, heat-treated YBCO+SiO2 pellets, rapid thermally annealed YBCO+SiO2 rods and rapid thermally annealed YBCO powder inside a fused silica tube is provided. These analyses are based on a vast set of generated novel results obtained using energy dispersive spectroscopy analyses on an environmental scanning electron microscope, X-Ray diffraction analyses, Raman spectroscopy, X-ray photoelectron spectroscopy analyses and a cross-polarized light study. First, original drawings of YBCO into glass fibers using the molten-core approach on a fiber draw tower in air and oxygen atmospheres are presented and analyzed. The performed analyses reveal the occurrence of reactions between the YBCO core and the silica cladding in as-drawn fibers as well as after additional heat-treatments. A detailed analysis and characterization of the occurring dissolution and diffusion based reaction processes is, then, provided along with the identification of the arising phase separation. Moreover, in order to analyze drawing YBCO glass fibers at lower temperatures, the use of borosilicate as the preform material is also investigated. This varied set of experiments and associated analyses reveal that the as-drawn YBCO fibers contain an amorphous core and that cuprite (Cu2O) is the first phase to crystallize out of the amorphous silicate matrix upon heat-treatment. Furthermore, the obtained results demonstrate the dissolution of the fused silica cladding into Si4+ and O2- ions and their subsequent diffusion into the molten YBCO core, leading to phase separation due to an occurring miscibility gap in the YBCO-SiO2 system as well as to silicate formation and amorphization of the YBCO core. This, as a result, prohibits the formation of the superconductive YBCO (Y-123) phase upon annealing. In addition, heat-treatment analyses show that higher temperatures or prolonged dwelling times at lower temperatures lead to the formation of barium copper and yttrium barium silicates. The analysis focusing on the use of borosilicate as the preform material reveals that drawing at lower temperatures reduces the dissolution and diffusion based reactions, but does not prevent them. Furthermore, the analysis on YBCO glass fibers with a fused silica cladding drawn in oxygen atmosphere shows that a higher oxygen content increases the dissolution of the fused silica cladding into its ions and their subsequent diffusion into the molten YBCO core. In addition, the performed heat-treatments on YBCO+SiO2 pellets in air and oxygen atmospheres demonstrate the gradual decomposition of the Y-123 phase with an increase in SiO2 content. Moreover, the rapid thermal annealing experiments with a subsequent quenching step on YBCO+SiO2 rods and on YBCO powder inserted inside a fused silica tube show the decomposition of the Y-123 phase and the formation of phases similar to the phases obtained in the YBCO glass fiber study, thus corroborating the results thereof. In summary, this dissertation enables the determination of the phase relations and reaction processes within the YBCO-SiO2 system, the identification of the direct effects of the silicon content on the Y-123 phase decomposition, as well as a rigorous characterization of the dissolution and diffusion based reactions within the YBCO-SiO2 glass-clad fiber system. The generated results and drawn conclusions build a fundamental understanding of phase relations in the YBCO-SiO2 system, which enables a definite assessment of the feasibility of manufacturing long-scale purely superconductive YBCO glass fibers using the molten-core approach and introduces advanced contributions to general glass-clad fiber systems manufactured using this method. / Doctor of Philosophy / This dissertation provides the first reported identification and analysis of the phase relations in the YBa2Cu3O7-x (YBCO)-SiO2 system at high temperatures. In this regard, a thorough characterization study of the reaction phases within YBCO glass fibers drawn using the molten-core approach on a fiber draw tower is provided. In addition, heat-treatment analyses considering YBCO+SiO2 pellets, rapid thermally annealed YBCO+SiO2 rods and rapid thermally annealed YBCO powder inside a fused silica tube are performed to gain further fundamental insights. The performed analyses are based on a wide set of characterization methods including energy dispersive spectroscopy on an environmental scanning electron microscope, X-Ray diffraction analyses, Raman spectroscopy, X-ray photoelectron spectroscopy and a cross-polarized light study. Our experimental results and performed analyses identify the phase relations and reaction processes within the YBCO-SiO2 system at elevated temperatures, demonstrate the direct effects of the silicon content on the superconductive YBCO phase decomposition, enable drawing definite conclusions regarding the feasibility of manufacturing long-scale purely superconductive YBCO glass fibers using the molten-core approach, and, characterize the dissolution and diffusion based reactions occurring within the YBCO-SiO2 glass-clad fiber system. In a nutshell, this dissertation provides a fundamental understanding of phase relations in the YBCO-SiO2 glass-clad system as well as key insights covering general glass-clad fibers drawn using the molten-core approach, paving the way for improved glass-clad fiber manufacturing using this method.

Le développement de nouvelles fibres optiques en silice repose sur l’insertion des ions luminescents (ions de terres rares) dans des nanoparticules diélectriques. Dans ce contexte, la taille des particules est un paramètre clef qu’il convient de contrôler afin de bénéficier des nouvelles propriétés. Pour répondre à cet impératif, l’objectif de cette thèse était double. Premièrement, dans un objectif de structuration, il a été important d’étudier l’évolution des caractéristiques du matériau au cours de la fabrication, et deuxièmement, l’évolution des propriétés de luminescence avec les caractéristiques du matériau. La première partie de ce manuscrit décrit les différents types d’évolution des nanoparticules qui ont été observées au cours de ce travail de thèse. La réaction chimique de nanoparticules avec la matrice en silice est abordée dans l’étude du dopage par des nanoparticules de LaF3. Une observation originale de l’allongement et de la fragmentation de particules durant l’étirage en fibre optique est présentée. L’évolution thermodynamique des particules au cours de l’étirage, ainsi que l’influence des paramètres de l’étirage sont abordées. Enfin, la seconde partie de ce manuscrit se focalise sur le lien entre le matériau et ses propriétés spectroscopiques (Tm3+, Er3+). Les résultats montrent notamment que l’ajout de lanthane dans les fibres optiques dopées aux ions thulium augmente les pertes optiques, mais permet aussi d’augmenter la durée de vie du niveau 3H4 du Tm3+ jusqu’à un record de 58 μs pour une fibre transparente (pertes inférieures à 0,1 dB.m−1). Ces résultats confirment ainsi la nécessité d’un compromis sur la taille des particules et l’importance de ces travaux sur leurs possibilités de structuration. / The development of new silica-based optical fibers is relies on the insertion of luminescent ions (rare-earth ions) in dielectric nanoparticles. In this context, particle size is a key parameter that should be controlled in order to benefit from the new properties. To reach this goal, the objective of this thesis was twofold. Firstly, it was important to understand, to engineer its structuration, the evolution of the characteristics of the material during its fabrication process, and secondly, the evolution of the spectroscopic properties with the characteristics of the material. The first part of this manuscript describes the different types of evolution of the nanoparticles that were observed during this thesis work. The chemical reaction of nanoparticles with the silica matrix is discussed in the study of LaF3-nanoparticles doping. Also, an original observation of the elongation and the break-up of particles during the fiber drawing are presented. The thermodynamic evolution of the particles during the fabrication process as well as the influence of its parameters are discussed. Finally, the second part of this manuscript focuses on the link between the material and its spectroscopic properties (Tm3+, Er3+). In particular, the addition of lanthanum in the Tm3+-doped fibers increased the optical losses, but also enabled the increase of the lifetime of the 3H4 level up to a record in silica of 58 μs (optical losses below 0,1 dB.m−1). These results highlight the need for a compromise on particle size and the importance of this work on structuring possibilities.

This dissertation demonstrates the first of its kind distributed magnetic field sensor based on a fiber optic distributed acoustic sensing (DAS) scheme. Ferromagnetic nickel and Metglas® were dispersed internally within a fiber optic preform and then drawn on an in-house fiber optic draw tower to lengths in the kilometers. Due to the close proximity of the ferromagnetic metals and fiber optic core, the magnetostrictive strain response of the ferromagnetic materials when exposed to a magnetic field would perturbate within the fiber cladding and transfer that strain, internally, to the fiber optic core. Strain resulting from the magnetostrictive effect allows the DAS based sensor to accurately translate strain into readable magnetic field data. Due to the high sensitivity seen in this sensor design, multiparameter sources, acoustic and magnetic fields, were tested and validated and a three dimensional magnetic-field vector sensor was proposed. Numerical analysis of the novel sensor design was first implemented using COMSOL Multiphysics, where inputs such as magnetostrictive element shape, size, distance, and number were first investigated. Upon optimizing system constraints, the sensor design was further modified such that single mode operation was consistent across multiple fiber draws while retaining high strain transfer from the ferromagnetic elements to the fiber optic core. Ferromagnetic material selection was evaluated as a function of the saturation magnetostriction constants and a total of 4 modules were used to fully characterize the complex physics involved in this sensor design. All fabrication and testing were performed in-house using a full scale 3-story fiber draw tower and custom environmental testing stations to imitate naturally occurring events such as magnetic or acoustic point sources. A unique stacking method was used to embed ferromagnetic nickel and Metglas® into a fiber optic preform which when combined with a custom fiber draw process resulted in consistent multi-material fibers drawn to lengths of 1-km. In-house testing facilities included different types of electromagnetic generators, in addition to a soil test bed, and an outdoor test bed which allowed 100 meters of fiber to be tested simultaneously. All tested sensors demonstrated high strain transfer capabilities on the order of 0.01-10 μϵ depending on the materials used, ferromagnetic rod number, and core to metal spacing. Due to the sensitivity of the system the difference between AC and DC was distinct, and directional magnetostriction was studied. Transverse and longitudinal magnetic wave propagation was controlled through a solenoid and rectangular Helmholtz coil, both built in-house. A three-dimensional magnetic field vector sensor was proposed due to the success of the magnetic field sensor, and a design was proposed and initially tested to validate direction as a function of field strength and distance. To summarize, this dissertation explores the first fully distributed magnetic field sensor using DAS based techniques and one of the first multi-material fiber draw processes which can produce consistent single mode fiber up to 1-km. Due to extensive FEA modeling, multiple iterations of the magnetic sensor were fully characterized and an equation describing the relationship between sensor design and strain transfer has been created and validated experimentally. Multi-parameter tests including acoustic and magnetic fields were implemented and an algorithm was developed to separate the mixed signals. Finally, a test was performed to demonstrate the feasibility of sensing magnetic fields directionally. Cumulative results demonstrate a high-quality sensor alternative to current designs which may surpass other magnetic sensors due to innate multi-parameter capabilities, in addition to the inexpensive production cost and extremely long operating lengths. / Doctor of Philosophy / This dissertation demonstrates the first of its kind distributed magnetic field sensor based on a fiber optic distributed acoustic sensing (DAS) scheme. Ferromagnetic nickel and Metglas® were dispersed internally within a fiber optic preform and then drawn on an in-house fiber optic draw tower to lengths in the kilometers. Due to the close proximity of the ferromagnetic metals and fiber optic core, the magnetostrictive strain response of the ferromagnetic materials when exposed to a magnetic field would perturbate within the fiber cladding and transfer that strain, internally, to the fiber optic core. Strain resulting from the magnetostrictive effect allows the DAS based sensor to accurately translate strain into readable magnetic field data. Due to the high sensitivity seen in this sensor design, multiparameter sources, acoustic and magnetic fields, were tested and validated and a three dimensional magnetic-field vector sensor was proposed. Numerical evaluation of the sensing structure was perused before experimental testing using COMSOL Multiphysics. Experimental and numerical evaluations were compared and showed a high degree of certainty which allowed expedited design modifications. Sensor characterization included scanning electron microscopy, and electron diffraction spectroscopy, which provided insight into material composition and fiber polishing quality. Due to the high-quality results attained in the combined acoustic and magnetic field tests, a final design was proposed to gather magnetic field data as a vector, showing both magnitude and direction. The 3D magnetic field vector sensor was partially validated based on a test which compared intensity with distance and a design and methodology was proposed to fully test and characterize this design. To summarize, a novel magnetic field sensor, capable of multi-parameter sensing, was proposed and tested experimentally and numerically resulting in a robust and highly sensitive design. The work presented here provides some of the first insights into multi-material fiber fabrication, an equation which provides an estimated relationship between magnetostrictive strain transfer onto a fiber optic core and the perceived DAS based sensor results, as well as a first of its kind multi-parameter distributed acoustic and magnetic field sensor.