¡@¡@The purpose of thesis is to study the responses of nanoindentation in fused silica. By experiments the mechanical properties of intrinsic fused silica were obtained. From the finite element simulation the response of material was estimated. Our main work is on simulation. This part includes the effects of different coefficient of friction, different indentation depth, tip rounding, and substrates of thin films. ¡@¡@First, the experimental load¡Vdisplacement curves were obtained through the nanoindentation sensing system. Then, a three-dimensional finite element was successfully modeled through the comparison of the load¡Vdisplacement curves of the experiment and the simulation. The yield stress and the strain-hardness trend of intrinsic fused silica were obtained. ¡@¡@For different coefficient of friction and different tip radii, no significant differences were found through the load¡Vdisplacement curves and von Mises stress distributions. For different indentation depths, varied trends were found through the load¡Vdisplacement curves and von Mises stress distributions. For substrate effect, no significant differences could be found through the normalized hardness. The intrinsic film hardness could be obtained for indentation depth less 20% of the total indentation depth.

Reliable sensing and monitoring systems based on optical fibers operating at high temperatures and in harsh environments are of high demand. One of the limitations of such systems is the devitrification of the fused silica based core and cladding glass at elevated temperatures. Crystallites can nucleate on the surface of the cladding and grow into the core. The formation of these crystalline flaws in the optical fiber causes stress concentration and extrinsic optical scattering and in addition leads to decreased mechanical properties and reduced optical stability. Commercial optical fibers of different compositions and core-cladding design were characterized in this study with respect to crystallization rate under various conditions. The optical stability was monitored with an optical spectrum analyzer. The crystallites were characterized with SEM and optical microscopy. The activation energies of crystallization for High OH and Low OH multimode fibers were estimated by measuring the crystal growth rate at different temperatures. The residual stress resulting from the formation of the crystals, which can lead to decreased mechanical performance of the fibers, was characterized with polarized light optical microscopy. The influence of water vapor in the atmosphere on the crystallization rate was determined. The features induced in the attenuation spectra were consistent with hydroxyl (OH) absorption peak. Spectral features such as thermal emission and hydroxyl absorption bands are discussed. The results obtained in this study can be used for selecting optical fibers for high temperature applications. / Master of Science / Reliable sensing and monitoring systems based on glass optical fibers operating at high temperatures and in harsh environments are in high demand. One of the limitations of such systems is the tendency of glass material to crystallize at elevated temperatures. Crystallites can nucleate on the surface of the fiber and grow inwards, impairing the optical and mechanical properties of the optical fiber. The formation of these crystalline flaws in the optical fiber can decrease the mechanical strength by causing stress concentrations and leading to formation of cracks, and reduce optical stability by causing light to scatter from the crystals. Commercial optical fibers of different compositions and geometry were characterized in this study with respect to crystal growth rate under various conditions, such as different temperatures (400-1350 °C), and different atmospheres (laboratory air and water vapor). The effect of crystals was demonstrated with respect to optical and mechanical performance. The results obtained in this study can be used for selecting optical fibers for high temperature applications.

Konstanz, Univ., Diplomarbeit, 2007.

Pressure measurements are required in various industrial applications, including extremely harsh environments such as turbine engines, power plants and material-processing systems. Conventional sensors are often difficult to apply due to the high temperatures, highly corrosive agents or electromagnetic interference (EMI) noise that may be present in those environments. Fiber optic pressure sensors have been developed for years and proved themselves successfully in such harsh environments. Especially, diaphragm based fiber optic pressure sensors have been shown to possess advantages of high sensitivity, wide bandwidth, high operation temperature, immunity to EMI, lightweight and long life. Static and dynamic pressure measurements at various locations of a gas turbine engine are highly desirable to improve its operation and reliability. However, the operating environment, in which temperatures may exceed 600 °C and pressures may reach 100 psi (690 kPa) with about 1 psi (6.9kPa) variation, is a great challenge to currently available sensors. To meet these requirements, a novel type of fiber optic engine pressure sensor has been developed. This pressure sensor functions as a diaphragm based extrinsic Fabry-Pérot interferometric sensor. One of the unique features of this sensor is the all silica structure, allowing a much higher operating temperature to be achieved with an extremely low temperature dependence. In addition, the flexible nature of the sensor design such as wide sensitivity selection, and passive or adaptive temperature compensation, makes the sensor suitable for a variety of applications An automatically controlled CO₂ laser-based sensor fabrication system was developed and implemented. Several novel bonding methods were proposed and investigated to improve the sensor mechanical ruggedness and reduce its temperature dependence. An engine sensor testing system was designed and instrumented. The system generates known static and dynamic pressures in a temperature-controlled environment, which was used to calibrate the sensor. Several sensor signal demodulation schemes were used for different testing purposes including a white-light interferometry system, a tunable laser based component test system (CTS), and a self-calibrated interferometric-intensity based (SCIIB) system. All of these sensor systems are immune to light source power fluctuations, which offer high reliability and stability. The fiber optic pressure sensor was tested in a F-109 turbofan engine. The testing results prove the sensor performance and the packaging ruggedization. Preliminary laboratory and field test results have shown great potential to meet not only the needs for reliable and precise pressure measurement of turbine engines but also for any other pressure measurements especially requiring high bandwidth and high temperature capability. / Ph. D.

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 verre de silice (SiO₂) est un des matériaux les plus couramment utilisés dans notre société moderne. Il est notamment employé dans des structures à haut niveau de risque, telles que les verrières d'engins spatiaux ou les protections d'équipements optiques. Cette thèse est effectuée dans le cadre du projet ANR GLASS, qui a pour objectif de faire évoluer les moyens servant à en étudier le comportement sous chargement dynamique (hautes pressions et hautes vitesses de déformations). Elle est focalisée sur l'étude expérimentale de la silice dans ce domaine, afin notamment de permettre un dialogue efficace entre expériences et simulations. Pour cela, la silice est impactée par une impulsion laser de haute puissance, générant une onde de choc qui se propage dans le matériau. Une première étude faite avec des résultats de mesures in situ de la propagation d'ondes de choc dans le verre permet d'obtenir des points de l'équation d'état du matériau. Ensuite, des mesures de spectroscopie Raman sont effectuées sur les échantillons impactés pour observer les modifications permanentes de leur structure atomique. Elles mettent en évidence une densification du matériau et la relaxation thermique du verre dans les zones ayant subi les plus hautes pressions lors du choc. Cet effet est causé par l'importante élévation de température pendant le chargement. Ces résultats montrent une bonne correspondance avec des études numériques effectuées dans le cadre du projet ANR. Enfin, des mesures de microtomographie aux rayons X montrent l'existence de nombreuses fissures à l'intérieur de l'échantillon. Des simulations numériques de peridynamic, une formulation spécialisée dans l'étude de l'endommagement, fournissent un scénario possible pour leur formation. / Fused silica (SiO₂) is one of the most commonly used materials in our modern society. Among other uses, it is the main component of highly critical structures like spacecraft windows or shields for optical equipments. This PhD thesis is done within the context of the ANR GLASS project, whose objective is to model the behavior of silica glass from the atomic cluster to the whole structure under dynamic loading (high pressures and high strain rates). Its main objective is to conduct an experimental study of this material in this loading domain to enable an efficient dialog between experiments and simulations. To this end, samples of fused silica are impacted with high-power laser impulses, generating a shockwave that propagates in the material. A first study is done with in situ results of shockwave propagation in fused silica, giving some data of the equation of state. Subsequently, Raman spectroscopy is used to observe the atomic structure modifications of shocked samples. These measurements show that silica glass is densified in the shocked area, and also that the zones where the highest pressures were applied are subjected to thermal relaxation. This last effect is caused by the important temperature increase during the shock loading. All these results are in accordance with those of numerical simulations performed within the ANR project. Finally, X-Ray microtomography highlight complex fracture patterns inside some of the shocked samples. Numerical simulations using peridynamic formulation, a method specialized to study fracture patterns, provide a possible scenario for the formation and propagation of these cracks.

Evaluation of solid-phase microextraction as an alternative official method for analysis of polymers migration. The objective this study was to compaire the official methods with solid-phase microextraction (SPME)for the analysis of compounds migrating from cross-linked polyethylene into water. A medium polarity polydimethylsiloxane/divinylbenzene (PDMS/DVB)was proved most efficient for the SPME extraction. However, when applied to water samples in contact with polyethylene, SPME proved to be immensely more sensitive and have a greater extraction range than liquid-liquid extraction (LLE). It was proved the migration of Phenol, 2,4-bis(1,1-dimethylethyl). Concentration of this compound 0,6-0,15mg/l.It was proved the migration of Cyclohexadiene-1,4-dione, 2,6-bis(1,1-dimethylethyl).

The contributions of nonlinear absorption processes to laser-induced damage of three selected groups of transparent dielectrics were investigated. The studied materials were irradiated and non-irradiated fused silica, doped and undoped fluorozirconate glass and cubic zirconia stabilized with yttria. The laser-induced damage thresholds, prebreakdown transmission, and nonlinear absorption processes were studied for several specimens of each group. Experimental measurements were performed at wavelengths of 1064 nm and 532 nm using nanosecond and picosecond Nd:YAG laser pulses. In the irradiated fused silica and fluorozirconate glasses, we found that there is a correlation between the damage thresholds at wavelength λ and the linear absorption of the studied specimens at λ/2. In other words, the laser-induced breakdown is related to the probability of all possible two-photon transitions. The results are found to be in excellent agreement with a proposed two-photon-initiated electron avalanche breakdown model. In this model, the initial "seed" electrons for the formation of an avalanche are produced by two-photon excitations of E' centers and metallic impurity levels which are located within the bandgaps of irradiated Si02 and fluorozirconate glasses, respectively. Once the initial electrons are liberated in the conduction band, a highly absorbing plasma is formed by avalanche impact ionization. The resultant heating causes optical damage. In cubic zirconia, we present direct experimental evidence that significant energy is deposited in the samples at wavelength 532 nm prior to electron avalanche formation. The mechanism is found to be due to formation of color centers (F+ or F° centers) by the two-photon absorption process. The presence of these centers was directly shown by transmission measurements. The two-photon absorption (2PA) process was independently investigated and 2PA coefficients obtained. The accumulated effects of the induced centers on the nonlinear absorption measurements were also considered and the 2PA coefficients were measured using short pulses where this effect is negligible. At room temperature, the color centers slowly diffuse out of the irradiated region. The density of these centers was monitored as a function of time. The initial distribution of the centers was assumed to have a Gaussian profile. For this model the diffusion equation was solved exactly and the diffusion constant obtained.

La structuration laser femtoseconde en trois dimensions rencontre un intérêt grandissant du fait de sa facilité de mise en œuvre et des nombreuses applications qu’elle peut couvrir dans le domaine des composants photoniques. Des structures telles que des guides d’onde, des réseaux de diffraction, des mémoires optiques ou des cristaux photoniques peuvent être fabriquées grâce à cette technique. Son emploi sur des verres oxydes est prometteur car ces derniers présentent des avantages certains ; ils sont très résistants au flux et au vieillissement, leur composition chimique peut être changée facilement afin de s’adapter à un cahier des charges précis. On les retrouve déjà dans les amplificateurs Raman, les fibres optiques, les lasers à fibres, etc… Le travail de cette thèse s’articule autour de deux grands axes. Le premier axe consiste à caractériser les propriétés optiques linéaires et non-linéaires de matériaux vitreux massifs afin d’optimiser leur composition en vue d’une application particulière. Dans ce contexte, les propriétés optiques non-linéaires, leurs origines physiques (électronique et nucléaire) ainsi que leurs temps de réponse caractéristiques (de quelques femtosecondes à quelques centaines de picosecondes) sont décrits dans le cadre de l’approximation de Born-Oppenheimer. Ainsi, la silice fondue et plusieurs verres sodo-borophosphates contenant différentes concentrations en oxyde de niobium ont été étudiés. Les résultats montrent que les propriétés optiques non-linéaires dans la silice fondue sont majoritairement d’origine électronique, alors que dans les verres sodo-borophosphates, la contribution d’origine nucléaire peut devenir prépondérante lorsque la concentration en oxyde de niobium dépasse 30%. Le second axe s’articule autour de la structuration des matériaux. Trois échantillons commerciaux de silice fondue présentant des conditions de fabrication différentes (donc des taux d’impuretés distincts) et irradiés avec un laser femtoseconde proche infrarouge ont été étudiés. Les défauts induits par laser ont été identifiés au moyen de plusieurs techniques de spectroscopie. Elles ont montré la formation de centres colorés ainsi qu’une densification au niveau de la zone irradiée. Leurs propriétés optiques linéaire (indice de réfraction) et non-linéaire (susceptibilité du troisième ordre) ont été mesurées. De plus, la structuration de la silice fondue à l’échelle sub-micrométrique sous forme de « nano-réseaux » est observée et la biréfringence de forme induite par ces structures est discutée. En plus des échantillons de silice fondue, plusieurs verres oxydes présentant des compositions chimiques très distinctes ont été étudiés. Un verre sodo-borophosphate contenant de l’oxyde de niobium exhibe des micro-craquelures et des nano-crystallites après irradiation. Un verre silicate contenant ou non de l’argent dévoile des structures en anneau fluorescentes ou en « nano-réseaux ». Un verre zinc phosphate contenant de l’argent présente lui aussi des structures en anneau fluorescentes, d’une taille de l’ordre de 80 nm, bien inférieure à la limite de diffraction. Des techniques pompe-sonde sous microscope ont été mises en œuvre sur ce dernier verre pour étudier l’interaction laser-verre. Le mécanisme d’absorption de l’énergie lumineuse pour ce verre est l’absorption à quatre photons. La densité d’électrons libres générée est de l’ordre de 1017 cm-3, ce qui permet de conclure qu’un gaz d’électrons plutôt qu’un plasma se forme pendant l’irradiation laser. / Three-dimensional femtosecond laser structuring has a growing interest because of its ease of implementation and the numerous possible applications in the domain of photonic components. Structures such as waveguides, diffraction gratings, optical memories or photonic crystals can be fabricated thanks to this technique. Its use with oxide glasses is promising because of several advantages; they are resistant to flux and ageing, their chemical composition can easily be changed to fit the well-defined requirements of an application. They can already be found in Raman amplifiers, optical fibers, fiber lasers, and other devices. This thesis is based on two axes. The first axis consists in characterizing the linear and nonlinear optical properties of bulk vitreous materials in order to optimize their composition with a particular application in view. Within this context, the nonlinear optical properties, their physical origins (electronic and nuclear) as well as their characteristic response times (from a few femtoseconds to a few hundreds of picoseconds) are described within the Born-Oppenheimer approximation. Fused silica and several sodium-borophosphate glasses containing different concentrations in niobium oxide have been studied. Results show that the nonlinear optical properties of fused silica are mainly from electronic origin, whereas in the sodium-borophosphate glasses, the contribution from nuclear origin becomes predominant when the concentration of niobium oxide exceeds 30%. The second axis is based on the structuring of materials. Three commercially available fused silica samples presenting different fabrication conditions (therefore distinct impurity levels) and irradiated with a near infrared femtosecond laser have been studied. The laser induced defects have been identified by means of several spectroscopic techniques. They show the formation of color centers as well as a densification inside the irradiated area. Their linear refractive index and nonlinear third-order susceptibility properties have been measured. Moreover, the structuring of fused silica at the subwavelength scale into “nanogratings” is observed and the form of birefringence induced by these structures is discussed. In addition to the fused silica samples, several oxide glasses presenting very distinct chemical compositions have been studied. A sodium-borophosphate glass containing niobium oxide exhibits micro-cracks and nano-crystallites following irradiation. A silicate glass with or without a silver component reveals fluorescent rings or “nanograting” structures. A zinc phosphate glass containing silver also presents fluorescent ring structures, with a size of the order of 80 nm, well below the diffraction limit. Pump-probe microscope techniques have been performed on this glass to investigate the laser-glass interaction. The absorption mechanism is determined to be four-photon absorption. The generated free electron density is ~ 1017 cm-3, which suggests the conclusion that an electron gas rather than a plasma is formed during the laser irradiation.

Darbe pristatomi eksperimentiniai bei teoriniai rezultatai, susiję su skaidriųjų terpių lūžio rodiklio pokyčio indukavimu. Parodoma, kad lydytą kvarcą veikiant Yb:KGV lazerine sistema generuojamais impulsais, jame galima sukurti modifikuoto lūžio rodiklio sritis. Šios sritys pasižymi dvejopu šviesos lūžimu, atsirandančiu dėl medžiagos tūryje besiformuojančių nanogardelių, o modifikuotų sričių vienalytiškumas priklauso nuo akumuliacinių efektų. Pakitusio lūžio rodiklio sritis taip pat galima formuoti ir ličio niobato kristale. Priklausomai nuo spinduliuotės parametrų, šiame kristale galima įrašyti stabilius modifikuoto lūžio rodiklio darinius, o taip pat ir nestabilias modifikacijas, atsirandančias dėl fotorefrakcinio reiškinio. Pastarąjį efektą galima panaudoti daugkartiniam informacijos įrašymui. Pademonstruoti efektyvūs fotoniniai elementai, tūrinės Brego gardelės, įrašytos tiek lydyto kvarco, tiek ličio niobato kristalo tūryje. Pateikiama metodika, skirta lazerio indukuoto lūžio rodiklio pokyčiui nustatyti matuojant Brego gardelių difrakcinius efektyvumus. Taip pat tyrinėjama kaip modifikuoti dariniai lemia superkontinuumo ir šviesos gijos formavimosi reiškinius lydytame kvarce. / The study on refractive index modification of transparent materials with ultrashort laser pulses is presented in this dissertation. Based on experimental data it was demonstrated, that using ultrashort pulses, generated with Yb:KGW laser system, it is possible to produce modified refractive index zones in the fused silica glass, that possess birefringence. This effect is caused by nanogratings that form in the bulk of the material. Homogeneity of the modified zones is determined by the accumulation effects, mainly the number of pulses that affect each area. Refractive index variations can be created also in crystalline material such as lithium niobate. Depending on the writing pulse parameters different types of modifications can be created: permanent modification that is caused by crystal amorphization and non-stable modifications that originate from the photorefractive properties of the crystal. Latter modifications can be used for three-dimensional, rewritable data recording. Highly efficient photonic elements, such as volume Bragg gratings, recorded in fused silica and lithium niobate crystal are demonstrated. The technique allowing the evaluation of refractive index change applying Bragg gratings is described. Also modification influence on nonlinear processes that appear in fused silica such as filament formation and supercontinuum generation is experimentally investigated.