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A long-period grating is obtained by introducing a periodic refractive index modulation in the core of a hydrogen-sensitized germanosilicate fiber. The phase-matching condition causes light from the fundamental guided mode to couple to discrete, forward-propagating cladding modes. These cladding modes attenuate rapidly on propagation and result in loss bands at distinct wavelengths in the grating transmission spectrum. We present a comprehensive analysis of the spectral modulation provided by long-period gratings. An analytical model is developed to predict the location of the resonance bands as functions of the grating period and the parameters of the host fiber. These gratings with small insertion loss and negligible back-ret1ection are shown to possess two different regions of operation, namely, normal and anomalous. The fabrication and high temperature annealing of these devices is detailed, and a novel method to obtain these gratings without employing ultra-violet radiation is presented. Long-period gratings are proposed as simple yet versatile optical fiber sensors. It is demonstrated that external temperature and axial strain introduce large spectral shifts in the resonance bands. A theoretical evaluation of the sensitivity reveals a strong dependence on the properties of the optical fiber, the grating periodicity, the order of the cladding mode, the writing and annealing conditions, and the index of refraction of the surrounding medium. Temperature-insensitive and strain-insensitive long-period gratings written in standard optical fibers are studied for their sensing characteristics. Long period grating-based refractive index sensors are obtained without etching the cladding of the fiber. It is demonstrated that long-period grating sensors can be implemented with simple demodulation schemes. Applications of these devices to structural health monitoring and biochemical sensing are presented. Finally, long-period gratings are demonstrated as effective sensors that can be used to separate temperature and axial strain acting simultaneously on the fiber. Strain-insensitive gratings are used to extend the dynamic range of the system in the presence of non-linearities and cross-sensitivities. / Ph. D.

Biosensors are detection devices that couple biological recognition elements to physiochemical transducers to generate quantifiable signals. Immunosensors are biosensors that use antibodies as the recognition element. The highly specific nature of antibody-antigen binding is exploited to create immunosensors that are sensitive to analytes in complex mixtures and demonstrate a rapid response. Fiber optical immunosensors based on long-period gratings have limited sensitivity at the refractive index of ordinary aqueous solutions (~1.33). A composite film was designed to raise the local refractive index of the sensor, thus increasing sensitivity. Titanium dioxide deposition raised the refractive index of the sensor to ~1.42. Bovine serum albumin was immobilized onto a dextran hydrogel and attached to the LPG element via reductive amination. The thickness of the hydrogel was estimated to be 500 nm using Environmental Scanning Electron Microscopy. The affinity film was probed by an evanescent wave to detect changes in refractive index due to the binding of anti-BSA IgG. Under these conditions, the sensor yielded a signal ratio of approximately 10-4 refractive index units per nm signal. Reproducible binding was shown over multiple exposures, with no cross reactivity for non-specific antibodies and other proteins. Anti-BSA IgG (20 µg/mL) in whole serum was recycled through the fiber holder with an accompanying peak wavelength shift that averaged 2 nm on an Optical Spectrum Analyzer with a noise level of 0.1 nm. The BSA affinity film was regenerated 50 times and showed a baseline shift of -1.3 nm. / Master of Science

Carbon dioxide sequestration is one of many mitigation tools available to help reduce carbon dioxide emissions while other disposal/repurposing methods are being investigated. Geologic sequestration is the most stable option for long-term storage of carbon dioxide (CO2), with significant CO2 trapping occurring through mineralization within the first 20-50 years. A fiber optic based monitoring system has been proposed to provide real time concentrations of CO2 at various points throughout the geologic formation. The proposed sensor is sensitive to the refractive index (RI) of substances in direct contact with the sensing component. As RI is a measurement of light propagating through a bulk medium relative to light propagating through a vacuum, the extraction of the effects of any specific component of that medium to the RI remains very difficult. Therefore, a requirement for a selective barrier to be able to prevent confounding substances from being in contact with the sensor and specifically isolate CO2 is necessary. As such a method to evaluate the performance of the selective element of the sensor was investigated. Polybenzimidazole (PBI) and VTEC polyimide (PI) 1388 are high performance polymers with good selectivity for CO2 used in high temperature gas separations. These polymers were spin coated onto a glass substrate and cured to form ultra-thin (>10 μm) membranes for gas separation. At a range of pressures (0.14 –0.41 MPa) and a set temperature of 24.2±0.8 °C, intrinsic permeabilities to CO2 and nitrogen (N2) were investigated as they are the gases of highest prevalence in underground aquifers. Preliminary RI testing for proof of concept has yielded promising results when the sensor is exposed exclusively to CO2 or N2. However, the use of both PBI and VTEC PI in these trials resulted in CO2 selectivities of 0.72 to 0.87 and 0.33 to 0.63 respectively, for corresponding feed pressures of 0.14 to 0.41 MPa. This indicates that both of the polymers are more selective for N2 and should not be used in CO2 sensing applications as confounding gas permeants, specifically N2, will interfere with the sensing element. / Graduate / 0428 / 0495 / 0542 / ben.t.davies@gmail.com

This dissertation presents a fibre-optic sensing approach to provide continuous measurements of CO2 concentration at discrete points under typical conditions of geological CO2 storage. Carbon capture and storage is considered to have potential for a large-scale reduction in CO2 emissions in a relatively short period of time while other solutions to replace fossil fuels are being investigated. One significant drawback of carbon capture and storage is the possibility of long-term CO2 leakage. Therefore, the development of reliable technology for monitoring, verification, and accounting of geological CO2 storage is critical to fulfill safety regulations and achieve public acceptance. The major limitations of current technology include relatively low resolutions, high costs, and the lack of continuous monitoring for long periods of time. To address these limitations, two types of fibre-optic sensors are investigated, namely long period gratings and Mach-Zehnder interferometers. The sensing principle for CO2 detection is based on the sensitivity of these sensors to the refractive index of the medium that surrounds the fibre. Fibre-optic sensors are attractive for downhole applications due to the possibility of fabricating inexpensive high resolution devices that are able to operate in harsh environments over long periods of time. This dissertation focuses on increasing the refractive index sensitivity of long period gratings and Mach-Zehnder interferometers by applying coatings that have a high refractive index. The dip-coating method is used to coat long period gratings with polystyrene, and the sensitivity at low refractive indices is increased by tuning coating thickness. The results show that long period gratings coated with polystyrene are able to detect CO2 in gaseous and aqueous media. This work reports the first measurement of CO2 dissolution in water at high pressure with a fibre-optic sensor. Additionally, atomic layer deposition is investigated to coat long period gratings and Mach-Zehnder interferometers with hafnium oxide. The study of this coating technique aims to address the main limitation of the dip-coating method: the challenge to achieve precise control over coating thickness. The results show that atomic layer deposition is suitable to maximize the sensitivity of long period gratings and Mach-Zehnder interferometers at a target refractive index. / Graduate / 0548 / 0752 / 0799 / luismelo@uvic.ca

Besides attenuation, dispersion is the major limiting factor in high data rate fiber optical transmission systems. Dispersion compensation techniques have to be deployed in order to increase the data bandwidth or the reach of fiber optical links. Typically fixed value dispersion compensators are used. However at channel bit rates of 40 GBit/s and beyond adjustable residual dispersion compensator modules (DCM) are needed to guarantee an error free transmission under changing environmental conditions. In this thesis dispersion techniques were investigated which exploit the special propagation properties of higher order modes in custom-designed optical fibers. After a short introduction of state-of-the-art dispersion techniques and their parameters (chapter 2) the modeling and calculation of propagation properties of a particular mode in an optical fiber with an arbitrary, rotation-symmetric refractive index profile is shown (chapter 3). A converter from the fundamental mode and back is needed in order to exploit the propagation properties of a higher order mode (HOM). In this work long-period gratings (LPG) were considered as mode converters (chapter 4) as they can excite selective and nearly lossless a higher order mode. The modeling und calculation of these gratings, based on the fiber calculation of chapter 3, is presented in the first part of chapter 4. Afterwards the manufacturing methods developed during this work are introduced. The spectral properties of realized long-period gratings are discussed and the influence of such factors as strain and temperature on tuning the mode conversion is shown. A dispersion compensator type utilizing only the waveguide dispersion of a certain mode in a custom few mode fiber (FMF) is the subject of chapter 5. The working principle, the fiber design process and first measurements of a realized HOM-DCM with almost completely coupling FMF-LPG are presented. Subsequently the principle of a novel dispersion compensator with an arbitrary dispersion function for a higher or the fundamental mode is explained. In chapter 6 another type of dispersion compensator is investigated consisting of equally distributed long-period gratings along an optical fiber. The fiber pieces between the gratings create a certain time delay between the fundamental mode and the considered higher order mode. It is shown in simulations and in an experiment, that by tuning the mode conversion of each grating and the optical phase relation between the two signal paths in each fiber piece this finite impulse filter structure is so adjusted to function as a tunable residual dispersion compensator.

There is currently a great interest in the field of porous organosilica materials because of the high surface areas (> 1000 m²/g) and narrow pore size distributions which are beneficial for applications such as chromatography, chiral catalysis, sensing or selective adsorption. Periodic mesoporous organosilicas (PMOs) represent an interesting class of hybrid silica materials because of the wide variety of bridging organic groups which can be incorporated within the precursors [(OR)3Si-R-Si(OR)3] giving rise to materials with exceptional properties. We have synthesized and characterized various aromatic PMOs composed of supporting structural monomers (phenylene- or biphenylenebridged) and functional stilbene monomers (cis and trans) (1, 2). The effect of the different synthetic procedures and varying amounts of functional stilbene monomer on the properties of the materials was examined. The functional transstilbene component was determined to be well distributed in a phenylene-bridged PMO using P123 as a pore template from TEM techniques with Os staining. The trans-stilbene linkers were completely transformed to aryl aldehydes through ozonolysis with dimethylsulfide workup. Further transformation of the carbonyl functionality to an aryl imine showed a moderate level of success. Enantiomeric forms of a novel, chiral PMO precursor (CM) were synthesized and incorporated into biphenylene-bridged PMOs. Under basic pH conditions templated with C18TMACl, although very low levels of CM are incorporated, enantiomeric forms of chiral, porous materials are obtained as was verified by distinct mirror-image circular dichroism spectra. Powder XRD patterns suggest that a tightly packed asymmetric biphenylene arrangement may be necessary for the optical activity. Preliminary results using these materials as a chiral chromatographic phase are promising. Finally, a thin film morphology of an ethane-bridged PMO incorporating a thiol ligand, (3-mercaptopropyl)trimethoxysilane, was prepared on a fibre optic cable and used as a component in a heavy-metal sensing application. / Thesis (Ph.D, Chemistry) -- Queen's University, 2011-03-11 17:24:48.997

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23861号 / 工博第4948号 / 新制||工||1773(附属図書館) / 京都大学大学院工学研究科都市社会工学専攻 / (主査)教授 清野 純史, 教授 三村 衛, 准教授 古川 愛子 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

abstract: Biological membranes are critical to cell sustainability by selectively permeating polar molecules into the intracellular space and providing protection to the interior organelles. Biomimetic membranes (model cell membranes) are often used to fundamentally study the lipid bilayer backbone structure of the biological membrane. Lipid bilayer membranes are often supported using inorganic materials in an effort to improve membrane stability and for application to novel biosensing platforms. Published literature has shown that a variety of dense inorganic materials with various surface properties have been investigated for the study of biomimetic membranes. However, literature does not adequately address the effect of porous materials or supports with varying macroscopic geometries on lipid bilayer membrane behavior. The objective of this dissertation is to present a fundamental study on the synthesis of lipid bilayer membranes supported by novel inorganic supports in an effort to expand the number of available supports for biosensing technology. There are two fundamental areas covered including: (1) synthesis of lipid bilayer membranes on porous inorganic materials and (2) synthesis and characterization of cylindrically supported lipid bilayer membranes. The lipid bilayer membrane formation behavior on various porous supports was studied via direct mass adsorption using a quartz crystal microbalance. Experimental results demonstrate significantly different membrane formation behaviors on the porous inorganic supports. A lipid bilayer membrane structure was formed only on SiO2 based surfaces (dense SiO2 and silicalite, basic conditions) and gamma-alumina (acidic conditions). Vesicle monolayer adsorption was observed on gamma-alumina (basic conditions), and yttria stabilized zirconia (YSZ) of varying roughness. Parameters such as buffer pH, surface chemistry and surface roughness were found to have a significant impact on the vesicle adsorption kinetics. Experimental and modeling work was conducted to study formation and characterization of cylindrically supported lipid bilayer membranes. A novel sensing technique (long-period fiber grating refractometry) was utilized to measure the formation mechanism of lipid bilayer membranes on an optical fiber. It was found that the membrane formation kinetics on the fiber was similar to its planar SiO2 counterpart. Fluorescence measurements verified membrane transport behavior and found that characterization artifacts affected the measured transport behavior. / Dissertation/Thesis / Ph.D. Chemical Engineering 2011

Besides attenuation, dispersion is the major limiting factor in high data rate fiber optical transmission systems. Dispersion compensation techniques have to be deployed in order to increase the data bandwidth or the reach of fiber optical links. Typically fixed value dispersion compensators are used. However at channel bit rates of 40 GBit/s and beyond adjustable residual dispersion compensator modules (DCM) are needed to guarantee an error free transmission under changing environmental conditions. In this thesis dispersion techniques were investigated which exploit the special propagation properties of higher order modes in custom-designed optical fibers. After a short introduction of state-of-the-art dispersion techniques and their parameters (chapter 2) the modeling and calculation of propagation properties of a particular mode in an optical fiber with an arbitrary, rotation-symmetric refractive index profile is shown (chapter 3). A converter from the fundamental mode and back is needed in order to exploit the propagation properties of a higher order mode (HOM). In this work long-period gratings (LPG) were considered as mode converters (chapter 4) as they can excite selective and nearly lossless a higher order mode. The modeling und calculation of these gratings, based on the fiber calculation of chapter 3, is presented in the first part of chapter 4. Afterwards the manufacturing methods developed during this work are introduced. The spectral properties of realized long-period gratings are discussed and the influence of such factors as strain and temperature on tuning the mode conversion is shown. A dispersion compensator type utilizing only the waveguide dispersion of a certain mode in a custom few mode fiber (FMF) is the subject of chapter 5. The working principle, the fiber design process and first measurements of a realized HOM-DCM with almost completely coupling FMF-LPG are presented. Subsequently the principle of a novel dispersion compensator with an arbitrary dispersion function for a higher or the fundamental mode is explained. In chapter 6 another type of dispersion compensator is investigated consisting of equally distributed long-period gratings along an optical fiber. The fiber pieces between the gratings create a certain time delay between the fundamental mode and the considered higher order mode. It is shown in simulations and in an experiment, that by tuning the mode conversion of each grating and the optical phase relation between the two signal paths in each fiber piece this finite impulse filter structure is so adjusted to function as a tunable residual dispersion compensator.