The thesis studies detection of fluorescein for coloration experiments in surface and underground water. The first part of the work deals with the adsorption of fluorescein on active charcoal from water and desorption by means of different desorption solutions. The results of measurements are used for practice of coloration experiments in karst research. In the second part of thesis it is researched the option of automated record of fluorescence concentration and its detection by means of laser induced fluorescence with confocal microscope.

No description available.

<p>This work presents the development and/or application of several laser diagnostics for studying the flame structure of composite propellant flames. These studies include examining the flame structure of novel energetic materials with potential as propellant ingredients, the near-surface flame structure of basic composite propellants, and the global flame structure of propellants containing metal additives.<br></p><p><br></p><p>First, the characterization of the deflagration of various novel energetic cocrystals is presented. The synthesis and development of novel energetic materials is a costly and challenging process. Rather than synthesizing new materials, cocrystallization provides the potential opportunity to achieve improved properties of existing energetic materials. This work presents the characterization of the effect of cocrystallization on the deflagration of a 2:1 molar cocrystal of CL-20 and HMX as well as a 1:1 molar cocrystal of CL-20 and TNT. A hydrogen peroxide (HP) solvate of CL-20 as well as a polycrystalline composite of HMX and ammonium perchlorate (AP) were also studied. A physical mixture of each material was also tested for comparison. The burning rate of each material was measured as a function of pressure. Flame structure during self-deflagration was examined using planar laser-induced fluorescence (PLIF) of CN and OH. The burning rate of the HMX/CL-20 cocrystal and the CL-20/HP solvate closely matched that of CL-20, but the burning rate of the TNT/CL-20 cocrystal was between the burning rate of its coformers. All HMX/AP materials had a higher burning rate than either HMX or AP individually and the burning rate of a physical mixture was found to be a function of particle size. The differences in the burning rate of the physical mixtures and composite crystal of HMX/AP can be explained by changes in the flame structure observed using PLIF. Burning rates and flame structure of the cocrystals were found to closely match those of their respective physical mixtures when smaller particle sizes were used (approx. less than 100 um). The results obtained demonstrate that the deflagration behavior of the coformers is not indicative of the deflagration behavior of the resulting physical mixture or cocrystal. However, changes in the resulting flame structure greatly affect the burning rate.</p><p><br></p><p>Next, PLIF of nitric oxide (NO) was utilized to characterize the near surface flame structure of composite propellants of AP and hydroxyl-terminated polybutadiene (HTPB) containing varying particle sizes of AP burning at 1 atm in air. In all propellants, the NO PLIF signal was strongest close to the burning propellant surface and fell to a non-zero constant value within ~1 mm of the surface where it remained throughout the remainder of the flame. Distinct diffusion-flame-like structure was observed above large individual burning AP particles in the propellant containing a bimodal distribution of 400 and 40 um AP. In contrast, the flame of a propellant containing only fine AP (40 um) behaved like a homogeneous, premixed flame. The flame of the propellant containing a bimodal distribution of 200 and 40 um AP also showed similar behavior to a premixed flame with some heterogeneous structure indicating that, at this pressure, the propellant is approaching a limit where the particle sizing is small enough that the flame behaves like a homogeneous, premixed flame. Additionally, propellants containing aluminum were tested. No significant differences were observed in the NO PLIF behavior between the propellants with and without aluminum suggesting that, at these conditions, the aluminum does not have a significant effect on the AP/HTPB flame structure near the burning surface.</p><p><br></p><p>The effect of aluminum particle size on the temperature of aluminized-composite-propellant flames burning at 1 atm is also presented. In this work, measurements of 1) the temperature of CO (within the flame bath gas) and 2) the temperature of AlO (located primarily within regions surrounding the burning aluminum particles) within aluminized, AP-HTPB-propellant flames were performed as a function of height above the burning propellant surface. Three aluminized propellants with varying aluminum particle size (nominally 31 um, 4.5 um, or 80 nm) and one non-aluminized AP-HTPB propellant were studied while burning in air at 1 atm. A wavelength-modulation-spectroscopy (WMS) diagnostic was utilized to measure temperature and mole fraction of CO via mid-infrared wavelengths and a conventional AlO emission-spectroscopy technique was utilized to measure the temperature of AlO. The bath-gas temperature varied significantly between propellants, particularly within 2 cm of the burning surface. The propellant with the smallest particles (nano-scale aluminum) had the highest average temperatures and far less variation with measurement location. At all measurement locations, the average bath-gas temperature increased as the initial particle size of aluminum in the propellant decreased, likely due to increased aluminum combustion. The results support arguments that larger aluminum particles can act as a heat sink near the propellant surface and require more time and space to ignite and burn completely. On a time-averaged basis, the temperatures measured from AlO and CO agreed within uncertainty at near 2650 K in the nano-aluminum propellant flame, however, AlO temperatures often exceeded CO temperatures by ~250 to 800 K in the micron-aluminum propellant flames. This result suggests that in the flames studied here, and on a time-averaged basis, the micron-aluminum particles burn in the diffusion-controlled combustion regime, whereas the nano-aluminum particles burn within or very close to the kinetically controlled combustion regime.</p><p><br></p><p>The study of the effect of aluminum particle size on the temperature of aluminized, composite-propellant flames was then extended to characterize the same propellants burning at elevated pressures ranging from 1 to 10 atm. A novel mid-infrared scanned-wavelength direct absorption technique was developed to acquire measurements of temperature and CO in particle-laden propellant flames burning at up to 10 atm. The results from the application of this diagnostic are among the very first measurements of gas properties in aluminized composite propellant flames burning at pressures above atmospheric pressure. In all propellants, the flame temperature and combustion efficiency of the propellant flames increased with an increase in pressure. In addition, the propellants with smaller aluminum particle sizes achieved higher flame temperatures as the particles were able to ignite and react faster. However, the propellants containing nano-scale and the smallest micron-scale aluminum powders had similar global flame temperatures suggesting that at some point a decrease in particle size results in minimal gains in the overall flame temperature. The results demonstrate how well measurements of gas properties can be used to understand the behavior of the aluminum particle combustion in the flame.</p><p><br></p><p>Last, the design, development, and application of a laser-absorption-spectroscopy diagnostic capable of providing quantitative, time-resolved measurements of gas temperature and HCl concentration in flames of aluminized, composite propellant flames is presented. This diagnostic utilizes a quantum-well distributed-feedback tunable diode laser emitting near 3.27 um to measure the absorbance spectra of one or two adjacent HCl lines using a scanned-WMS technique which is insensitive to non-absorbing transmission losses caused by metal particulates in the flame. This diagnostic was applied to characterize the spatial and temporal evolution of temperature and/or HCl mole fraction in small-scale flames of AP-HTPB composite propellants containing either an aluminum-lithium alloy or micron-scale aluminum. Experiments were conducted at 1 and 10 atm. At both pressures, the flame temperature of the aluminum-lithium propellant, on a time-averaged basis, was 80 to 200 K higher than that of the aluminum-propellant (depending on location in the flame) indicating more complete combustion. In addition, the mole fraction of HCl in the aluminum-lithium propellant flame reached values 65-70% lower than the conventional aluminum-propellant flame at the highest measurement location in the flame. The measurements at both pressures showed similar trends in the reduction of HCl in the aluminum-lithium propellant flame but at 10 atm this occurred on a length scale an order of magnitude smaller than the flame at atmospheric pressure. The results presented further support that the use of an aluminum-lithium alloy is effective at reducing HCl produced by the propellant flame without compromising performance, thereby making it an attractive additive for solid rocket propellants.</p>

Preterm birth (PTB) results in over 15 million early births annually and is the leading cause of neonatal deaths. There are no clinical methods currently available to evaluate risk of PTB at early stages in pregnancy; thus, a rapid diagnostic to analyze PTB risk would be beneficial. Microfluidic immunoaffinity extraction is a promising platform for preparing complex samples, such as maternal serum with PTB risk biomarkers. 3D printed microfluidic devices have advantages over conventional microfluidic systems including simple fabrication and potential for iterative optimization to improve designs. In this work, I developed immunoaffinity monoliths in 3D printed microfluidic devices modified with antibodies to enrich PTB biomarkers from human blood serum. I retained and eluted a peptide PTB biomarker in both buffer and blood serum using an immunoaffinity column. An additional three PTB biomarkers were also successfully extracted either from buffer or blood serum on single-antibody columns. Both polyclonal and monoclonal antibodies to PTB biomarkers were characterized by dot blots, biolayer interferometry, and surface plasmon resonance to determine their specificity and dissociation constants. I created multiplexed immunoaffinity columns to simultaneously enrich three PTB biomarkers from depleted human blood serum in a single extraction. This is the first demonstration of multiplexed immunoaffinity columns for PTB biomarkers in a 3D printed microfluidic device. My work is a key step towards the future development of 3D printed microfluidic devices for rapid PTB testing.

This thesis broadly describes the construction of two kinds of spectroscopic set-ups to analyze properties of various materials. In the first part, construction of a Raman spectrometer and a high-throughput in-vivo detection for early plant abiotic stress responses is described. Following which, the set-up is modified into a microscope employed to study Murine blood components with samples varying in age. Initial Raman set-up is also improvised using a polarizer in order to gain deeper understanding of the vibrational and rotational bonds in water. The second part of the thesis explains the construction of a laser-induced fluorescence (LIF) sensor module. Performance testing and experiments were carried out with the sensor module to monitor stress in vegetation and fruits and also detect toxins found in corn and carcinogenic compounds in gasoline. The module was further mounted to an unmanned aerial vehicle for field surveys and preliminary testing in flight is described.

No description available.

No description available.

The purpose of this dissertation is to — on occasion very literally — shine a light on processes that occur in non-thermal plasmas containing CO2, mostly for CO2 conversion. In particular, the focus lies on the transient behaviour of these discharges: how do these systems evolve over time before they settle in a (non-thermal) equilibrium. In addition to that, it analyses trends in the field of plasma-catalytic CO2 conversion as a whole to evaluate the current state-of-the-art, but also presents a new platform for the community to contribute and collaborate on, to facilitate cross-comparison between disparate experiments. The first part consists of experiments performed on: (a) an atmospheric pressure nanosecond repetitively pulsed (NRP) discharge for CO2 conversion, and (b) a test bed system for a remote CCP plasma source for plasma-enhanced atomic layer deposition (PE-ALD) of trimethylaluminium (TMA). The common theme in these experiments is a focus on the application of time-resolved, in situ diagnostics to study transient behaviour in the systems under investigation. The main diagnostics employed for such measurements are optical emission spectroscopy (OES) and laser induced fluorescence (LIF), which can provide complementary results when used in conjunction. In particular, this work presents the following results: A study of the evolution of emission from an NRP discharge (using OES), establishing both electron densities (by Stark broadening of atomic oxygen and carbon lines) and gas temperatures (by the N2 second positive system) as the discharge evolves from a breakdown phase to a spark phase. It furthermore explores the changes to these properties when operating in burst mode, where a subsequent pulse experiences a memory effect from the preceding one, which has been shown to be conducive to efficient conversion in literature. A study into the effect on energy efficiency of CO2 conversion by alternating the power modulation in an NRP discharge. Crucially, using CET-LIF (collisional energy transfer LIF) and OES it is shown that while power deposition to the discharge occurs in the order of 100 ns in the discharge, CO2 dissociation occurs on a timescale beyond a microsecond. This indicates that instead of direct electron impact, molecular-excitation kinetics play an important role under these conditions for CO2 dissociation. By shortening the time between pulses in a burst (down to 33 us in the work), these mechanisms can be further enhanced, by prolonging the quasi-‘metastable’ state of the system. The application of LIF in a PE-ALD process plasma along with OES, where diffusion profiles were measured close to the substrate surface with local time-resolved measurements of the OH ground state density. These indicate that the investigated surface reactions finish on a timescale of 100 ms, faster than would be indicated by OES which effectively measures emission from the bulk plasma after diffusion of reaction products away from the surface. The second part of this work is an open access database on plasma(-catalytic) CO2 conversion that is instrumental in identifying and verifying trends in experimental data, but also stresses the importance of rigorous reporting of essential parameters in literature. The approach in literature is diverse: some studies focus more on a mechanistic understanding of the fundamental processes, whilst others already focus on process tailoring and optimization for industrial applications. Trends observed in earlier review papers are observed as well and can now be trivially reproduced. The database platform (https://db.co2pioneer.eu) is put forward as a new tool for the community to easily cross-compare and contextualize experimental outcomes and strongly encourages new contributions. Based on the 196 papers included at the time of publication, a number of observations and recommendations can already be made. Chief among those is a clear and present need in the field for a more fundamental understanding of plasma-catalysis interaction, to develop techniques and criteria that are properly suited to test the synergy of both, rather than relying on methods from e.g. traditional thermal-catalysis. Also in this instance, local, time-resolved diagnostics may play a key role, but their implementation will be challenging.

In this thesis, a joint experimental and theoretical investigation of the vector properties that describe the inelastic scattering of a diatomic radical with an atomic collision partner is presented. A particular emphasis is placed on those correlations that include the final rotational angular momentum, j', of the radical. The depolarisation of both NO(A) and OH(A) brought about through collisions with krypton has been studied, providing a measure of the j-j' correlation, where j is the initial rotational angular momentum associated with the diatom. The total depolarisation cross- sections for both collisional disorientation and disalignment have been measured using quantum beat spectroscopy, and modelled theoretically using quasi-classical trajectory (QCT) calculations. The agreement between experiment and theory for NO(A)-Kr is excellent, but is not observed for OH(A)-Kr under thermal conditions. This has been attributed to the importance of electronic quenching in OH(A)-Kr. The depolarisation cross-sections have also been determined at a higher collision energy for OH(A)-Kr where electronic quenching is less significant, and the experimental results are in better agreement with those obtained theoretically. The NO(A)-Kr depolarisation cross-sections fall with increasing rotational quantum number, N, whereas for OH(A)-Kr, they exhibit less of an N dependence. This trend is mirrored in the elastic depolarisation cross-sections, which have also been determined experimentally for OH(A)-Kr. The significantly attractive and anisotropic nature of the OH(A)-Kr potential energy surface (PES) accounts for these observations. The j-j' correlation is extended to include the initial (relative) velocity (k) in a new theoretical treatment of the k-j-j' correlation. The formalism developed is used with the results from the QCT calculations for NO(A)-Kr and OH(A)-Kr to provide further insight into the mechanism of depolarisation in the two systems. Collisions of NO(A) with krypton do not cause significant depolarisation due to their impulsive nature, and the projection of j onto the kinematic apse is conserved. In contrast, collisions of OH(A) with krypton effectively randomise the direction of j, again showing the influence of the anisotropic and attractive nature of the PES. However, the projection of j onto the kinematic apse is still conserved. The inelastic scattering of NO(X) with argon and krypton has also been investigated, using a crossed molecular beam apparatus. The initial Λ-doublet state of the NO(X) was selected using hexapole focussing, and the products of the collision detected using velocity mapped ion imaging. The state to state differential cross-sections (equivalent to the k-k' correlation, where k' is the final relative velocity) have been measured for collisions which conserve the initial spin-orbit level of the NO(X) with krypton. The same parity dependent effects were seen as have been observed previously for NO(X)-Ar. The collision induced alignment (equivalent to the k-k'-j' correlation) of NO(X) as a result of scattering with argon has also been determined experimentally. The results can be explained classically by considering the conservation of the projection of j onto the kinematic apse.

L'étude décrite dans cette thèse porte sur l'injection ponctuelle d'une solution saline au sein d'une cellule dite de Hele-Shaw, afin de caractériser le comportement dispersif d'un polluant en milieu poreux. L'approche expérimentale employée est basée sur l'implémentation originale d'un dispositif de Fluorescence Induite par Laser (LIF) dans la cellule. La mise en place d'un protocole de mesure efficace permet de mener une analyse quantitative des résultats expérimentaux. En outre, en appliquant la méthode des moments, il est possible de caractériser avec précision le comportement dispersif de la zone de mélange de la solution injectée. Parallèlement aux expériences, à l'aide du code numérique FRIPE, les injections ont été simulées numériquement. L'analyse quantitative a été appliquée à ces dernières. Une comparaison poussée des résultats expérimentaux et numériques a donc été effectuée, du point de vue qualitatif mais aussi sur l'expression de la dispersion du panache de la zone de mélange de la solution / The study described in this thesis is about punctual injection of a saline solution inside a "Hele-Shaw cell" in order to characterize the dispersive behavior of a pollutant in porous media. The chosen experimental approach is based on the setup of an original Laser Induced Fluorescence (LIF) in the Hele-Shaw cell. The setting of the experimental apparatus allows quantitative data reduction of the experimental results. Moreover the "Moments Method" studied precisely the solution mixing dispersive behavior. Using the numerical code FRIPE the same injections have been simulated. The same quantitative data reductions have been applied to the numerical results. This led to an extensive comparison of the numerical and the experimental results, qualitatively but also of the dispersion in the mixing area of the injected solution