Current Search: Laser Spectroscopy (x)
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(1 - 16 of 16)
- Title
- Laser Filamentation Interaction with Materials for Spectroscopic Applications.
- Creator
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Weidman, Matthew, Richardson, Martin, Schulzgen, Axel, Christodoulides, Demetrios, Sigman, Michael, University of Central Florida
- Abstract / Description
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Laser filamentation is a non-diffracting propagation regime consisting of an intense core that is surrounded by an energy reservoir. For laser ablation based spectroscopy techniques such as Laser Induced Breakdown Spectroscopy (LIBS), laser filamentation enables the remote delivery of high power density laser radiation at long distances. This work has shown a quasi-constant filament-induced mass ablation along a 35 m propagation distance. The mass ablated was sufficient for the application of...
Show moreLaser filamentation is a non-diffracting propagation regime consisting of an intense core that is surrounded by an energy reservoir. For laser ablation based spectroscopy techniques such as Laser Induced Breakdown Spectroscopy (LIBS), laser filamentation enables the remote delivery of high power density laser radiation at long distances. This work has shown a quasi-constant filament-induced mass ablation along a 35 m propagation distance. The mass ablated was sufficient for the application of laser filamentation as a sampling tool for plasma based spectroscopy techniques. Within the scope of this study, single-shot ablation was compared with multi-shot ablation. The dependence of ablated mass on the number of pulses was observed to have a quasi-linear dependence on the number of pulses, advantageous for applications such as spectroscopy. Sample metrology showed that both physical and optical material properties have significant effects on the filament-induced ablation behavior. A relatively slow filament-induced plasma expansion was observed, as compared with a focused beams. This suggests that less energy was transferred to the plasma during filament-induced ablation. The effects of the filament core and the energy reservoir on the filament-induced ablation and plasma formation were investigated. Goniometric measurements of the filament-induced plasma, along with radiometric calculations, provided the number of emitted photons from a specific atomic transition and sample material.This work has advanced the understanding of the effects of single filaments on the ablation of solid materials and the understanding of filament-induced plasma dynamics. It has laid the foundation for further quantitative studies of multiple filamentation. The implications of this work extend beyond spectroscopy and included any application of filamentation that involves the interaction with a solid material.
Show less - Date Issued
- 2012
- Identifier
- CFE0004616, ucf:49940
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0004616
- Title
- Development of laser spectroscopy for elemental and molecular analysis.
- Creator
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Liu, Yuan, Richardson, Martin, Vanstryland, Eric, Bass, Michael, Sigman, Michael, University of Central Florida
- Abstract / Description
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Laser-Induced Breakdown Spectroscopy (LIBS) and Raman spectroscopy are still growing analytical and sensing spectroscopic techniques. They significantly reduce the time and labor cost in analysis with simplified instrumentation, and lead to minimal or no sample damage. In this dissertation, fundamental studies to improve LIBS analytical performance were performed and its fusion with Raman into one single sensor was explored.On the fundamental side, Thomson scattering was reported for the...
Show moreLaser-Induced Breakdown Spectroscopy (LIBS) and Raman spectroscopy are still growing analytical and sensing spectroscopic techniques. They significantly reduce the time and labor cost in analysis with simplified instrumentation, and lead to minimal or no sample damage. In this dissertation, fundamental studies to improve LIBS analytical performance were performed and its fusion with Raman into one single sensor was explored.On the fundamental side, Thomson scattering was reported for the first time to simultaneously measure the electron density and temperature of laser plasmas from a solid aluminum target at atmospheric pressure. Comparison between electron and excitation temperatures brought insights into the verification of local thermodynamic equilibrium condition in laser plasmas.To enhance LIBS emission, Microwave-Assisted LIBS (MA-LIBS) was developed and characterized. In MA-LIBS, a microwave field extends the emission lifetime of the plasma and stronger time integrated signal is obtained. Experimental results showed sensitivity improvement (more than 20-fold) and extension of the analytical range (down to a few tens of ppm) for the detection of copper traces in soil samples. Finally, laser spectroscopy systems that can perform both LIBS and Raman analysis were developed. Such systems provide two types of complimentary information (-) elemental composition from LIBS and structural information from Raman. Two novel approaches were reported for the first time for LIBS-Raman sensor fusion: (i) an Ultra-Violet system which combines Resonant Raman signal enhancement and high ablation efficiency from UV radiation, and (ii) a Ti:Sapphire laser based NIR system which reduces the fluorescence interference in Raman and takes advantage of femtosecond ablation for LIBS.
Show less - Date Issued
- 2013
- Identifier
- CFE0005105, ucf:50729
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005105
- Title
- Single Mode Wavelength-Tunable Thulium Fiber.
- Creator
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Shin, Dong Jin, Richardson, Martin, Schulzgen, Axel, Amezcua Correa, Rodrigo, University of Central Florida
- Abstract / Description
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Thulium fiber lasers have the broadest emission wavelength bandwidth out of any rare-earth doped fiber lasers. The emission wavelength starts from 1.75(&)#181;m and ends at around 2.15(&)#181;m, covering a vast swath of the eye safe wavelength region and intersecting with a large portion of mid-infrared atmospheric transmission window. Also, thulium fiber lasers provide the highest average output power of any other rare-earth doped fiber lasers in these wavelength regimes, making them...
Show moreThulium fiber lasers have the broadest emission wavelength bandwidth out of any rare-earth doped fiber lasers. The emission wavelength starts from 1.75(&)#181;m and ends at around 2.15(&)#181;m, covering a vast swath of the eye safe wavelength region and intersecting with a large portion of mid-infrared atmospheric transmission window. Also, thulium fiber lasers provide the highest average output power of any other rare-earth doped fiber lasers in these wavelength regimes, making them uniquely suited for applications such as remote sensing. At the moment, high power beam propagation of continuous wave laser through the atmosphere in the mid-infrared range is yet to be investigated anywhere. In particular, the effects of atmospheric water vapors on the thulium fiber laser propagation are unknown and are of great research interest. This dissertation identifies the stringent requirements in constructing a high power, single frequency, wavelength tunable, continuous wave thulium fiber laser with the aim of using it to study various atmospheric transmission effects. A fine spectral control scheme using diffraction gratings is explored and improvements are made. Moreover, a fiber numerical simulation model is presented and is used for designing and implementing the thulium fiber laser system. The current limitations of the implemented system are discussed and an improved system is proposed. This will lay the foundation for the future high power atmospheric propagation studies.
Show less - Date Issued
- 2018
- Identifier
- CFE0007372, ucf:52084
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007372
- Title
- LASER PLASMA RADIATION STUDIES FOR DROPLET SOURCES IN THE EXTREME ULTRAVIOLET.
- Creator
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Kamtaprasad, Reuvani, Richardson, Martin, University of Central Florida
- Abstract / Description
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The advancement of laboratory based Extreme Ultraviolet (EUV) radiation has escalated with the desire to use EUV as a source for semiconductor device printing. Laser plasmas based on a mass-limited target concept, developed within the Laser Plasma Laboratory demonstrate a much needed versatility for satisfying rigorous source requirements. This concept produces minimal debris concerns and allows for the attainment of high repetition rates as well as the accommodation of various laser and...
Show moreThe advancement of laboratory based Extreme Ultraviolet (EUV) radiation has escalated with the desire to use EUV as a source for semiconductor device printing. Laser plasmas based on a mass-limited target concept, developed within the Laser Plasma Laboratory demonstrate a much needed versatility for satisfying rigorous source requirements. This concept produces minimal debris concerns and allows for the attainment of high repetition rates as well as the accommodation of various laser and target configurations. This work demonstrates the generation of EUV radiation by creating laser plasmas from mass-limited targets with indium, tin, and antimony doped droplets. Spectral emission from the laser plasmas is quantified using a flat-field spectrometer. COWAN code oscillator strength predications for each of the dopants were convolved with narrow Gaussian functions creating synthetic spectra for the EUV region between 10 nm - 20 nm. A preliminary comparison was made between the theoretical spectra and experimental results. From this comparison, ion stage transitions for each of the hot dense plasmas generated were assessed.
Show less - Date Issued
- 2010
- Identifier
- CFE0003168, ucf:48597
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0003168
- Title
- High Temperature Shock Tube Ignition Studies of CO2 Diluted Mixtures.
- Creator
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Pryor, Owen, Vasu Sumathi, Subith, Kapat, Jayanta, Kassab, Alain, University of Central Florida
- Abstract / Description
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Energy demand is expected to grow by 20% over the next 10 years. In order to account for this increase in energy consumption new and novel combustion techniques are required to mitigate the effects of pollution and fossil fuel dependency. Oxy-fuel combustion in supercritical carbon dioxide (sCO2) cycles can increase plant efficiencies up to 52% and reduce pollutants such as NOX and CO2 by 99%. Supercritical engine cycles have demonstrated electricity costs of $121/MWh, which is competitive in...
Show moreEnergy demand is expected to grow by 20% over the next 10 years. In order to account for this increase in energy consumption new and novel combustion techniques are required to mitigate the effects of pollution and fossil fuel dependency. Oxy-fuel combustion in supercritical carbon dioxide (sCO2) cycles can increase plant efficiencies up to 52% and reduce pollutants such as NOX and CO2 by 99%. Supercritical engine cycles have demonstrated electricity costs of $121/MWh, which is competitive in comparison to conventional coal ($95.60/MWh) and natural gas power plants ($128.4/MWe). This increase in efficiency is mainly driven by the near-liquid density of the working fluid (sCO2), in the super critical regime, before entering the turbine for energy extraction of the high pressure and high density sCO2 gas. In addition, supercritical CO2 engine cycles produce near-zero air emissions since CO2, a product of combustion, is the working fluid of the system which can be regenerated to the combustor. The predictive accuracy and lack of combustion models in highly CO2 diluted mixtures and at high pressures is one the major limitations to achieving optimum design of super critical engine combustors. Also, most natural gas mechanisms and validation experiments have been conducted at low pressures (typically less than 40 atm) and not in CO2 diluted environment. Thus experimental data is important for the development of modern combustion systems from work focusing on supercritical carbon dioxide cycles to rotational detonation engines. This thesis presents the design of the shock tube and two optical diagnostic techniques for measuring ignition delay times and species time histories using a shock tube in CO2 diluted mixtures.Experimental data for ignition delay times and species time-histories (CH4) were obtained in mixtures diluted with CO2. Experiments were performed behind reflected shockwaves from temperatures of 1200 to 2000 K for pressures ranging from 1 to 11 atm. Ignition times were obtained from emission and laser absorption measurements. Current experimental data were compared with the predictions of detailed chemical kinetic models (available from literature) that will allow for accurate design and modeling of combustion systems.
Show less - Date Issued
- 2016
- Identifier
- CFE0006165, ucf:51141
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006165
- Title
- Characterization and Application of Isolated Attosecond Pulses.
- Creator
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Chini, Michael, Chang, Zenghu, Saha, Haripada, Chow, Lee, Schulzgen, Axel, University of Central Florida
- Abstract / Description
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Tracking and controlling the dynamic evolution of matter under the influence of external fields is among the most fundamental goals of physics. In the microcosm, the motion of electrons follows the laws of quantum mechanics and evolves on the timescale set by the atomic unit of time, 24 attoseconds. While only a few time-dependent quantum mechanical systems can be solved theoretically, recent advances in the generation, characterization, and application of isolated attosecond pulses and few...
Show moreTracking and controlling the dynamic evolution of matter under the influence of external fields is among the most fundamental goals of physics. In the microcosm, the motion of electrons follows the laws of quantum mechanics and evolves on the timescale set by the atomic unit of time, 24 attoseconds. While only a few time-dependent quantum mechanical systems can be solved theoretically, recent advances in the generation, characterization, and application of isolated attosecond pulses and few-cycle femtosecond lasers have given experimentalists the necessary tools for dynamic measurements on these systems. However, pioneering studies in attosecond science have so far been limited to the measurement of free electron dynamics, which can in most cases be described approximately using classical mechanics. Novel tools and techniques for studying bound states of matter are therefore desired to test the available theoretical models and to enrich our understanding of the quantum world on as-yet unprecedented timescales.In this work, attosecond transient absorption spectroscopy with ultrabroadband attosecond pulses is presented as a technique for direct measurement of electron dynamics in quantum systems, demonstrating for the first time that the attosecond transient absorption technique allows for state-resolved and simultaneous measurement of bound and continuum state dynamics. The helium atom is the primary target of the presented studies, owing to its accessibility to theoretical modeling with both ab initio simulations and to model systems with reduced dimensionality. In these studies, ultrafast dynamics (-) on timescales shorter than the laser cycle (-) are observed in prototypical quantum mechanical processes such as the AC Stark and ponderomotive energy level shifts, Rabi oscillations and electromagnetically-induced absorption and transparency, and two-color multi-photon absorption to (")dark(") states of the atom. These features are observed in both bound states and quasi-bound autoionizing states of the atom. Furthermore, dynamic interference oscillations, corresponding to quantum path interferences involving bound and free electronic states of the atom, are observed for the first time in an optical measurement. These first experiments demonstrate the applicability of attosecond transient absorption spectroscopy with ultrabroadband attosecond pulses to the study and control of electron dynamics in quantum mechanical systems with high fidelity and state selectivity. The technique is therefore ideally suited for the study of charge transfer and collective electron motion in more complex systems.The transient absorption studies on atomic bound states require ultrabroadband attosecond pulses ? attosecond pulses with large spectral bandwidth compared to their central frequency. This is due to the fact that the bound states in which we are interested lie only 15-25 eV above the ground state, so the central frequency of the pulse should lie in this range. On the other hand, the bandwidth needed to generate an isolated 100 as pulse exceeds 18 eV (-) comparable to or even larger than the central frequency. However, current methods for characterizing attosecond pulses require that the attosecond pulse spectrum bandwidth is small compared to its central frequency, known as the central momentum approximation. We therefore explore the limits of attosecond pulse characterization using the current technology and propose a novel method for characterizing ultrabroadband attosecond pules, which we term PROOF (phase retrieval by omega oscillation filtering). We demonstrate the PROOF technique with both simulated and experimental data, culminating in the characterization of a world-record-breaking 67 as pulse.
Show less - Date Issued
- 2012
- Identifier
- CFE0004781, ucf:49802
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0004781
- Title
- Quantitative Line Assignment in Optical Emission Spectroscopy.
- Creator
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Chappell, Jessica, Baudelet, Matthieu, Hernandez, Florencio, Campiglia, Andres, Ni, Liqiang, Sigman, Michael, University of Central Florida
- Abstract / Description
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Quantitative elemental analysis using Optical Emission Spectroscopy (OES) starts with a high level of confidence in spectral line assignment from reference databases. Spectral interferences caused by instrumental and line broadening decrease the resolution of OES spectra creating uncertainty in the elemental profile of a sample for the first time. An approach has been developed to quantify spectral interferences for individual line assignment in OES. The algorithm calculates a statistical...
Show moreQuantitative elemental analysis using Optical Emission Spectroscopy (OES) starts with a high level of confidence in spectral line assignment from reference databases. Spectral interferences caused by instrumental and line broadening decrease the resolution of OES spectra creating uncertainty in the elemental profile of a sample for the first time. An approach has been developed to quantify spectral interferences for individual line assignment in OES. The algorithm calculates a statistical interference factor (SIF) that combines a physical understanding of plasma emission with a Bayesian analysis of the OES spectrum. It can be used on a single optical spectrum and still address individual lines. Contrary to current methods, quantification of the uncertainty in elemental profiles of OES, leads to more accurate results, higher reliability and validation of the method. The SIF algorithm was evaluated for Laser-Induced Breakdown Spectroscopy (LIBS) on samples with increasing complexity: from silicon to nickel spiked alumina to NIST standards (600 glass series and nickel-chromium alloy). The influence of the user's knowledge of the sample composition was studied and showed that for the majority of spectral lines this information is not changing the line assignment for simple compositions. Nonetheless, the amount of interference could change with this information, as expected. Variance of the SIF results for NIST glass standard was evaluated by the chi-square hypothesis test of variance showing that the results of the SIF algorithm are very reproducible.
Show less - Date Issued
- 2018
- Identifier
- CFE0007564, ucf:52575
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007564
- Title
- LASER INDUCED BREAKDOWN SPECTROSCOPY FOR DETECTION OF ORGANIC RESIDUES: IMPACT OF AMBIENT ATMOSPHERE AND LASER PARAMETERS.
- Creator
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Brown, Christopher, Richardson, Martin, University of Central Florida
- Abstract / Description
-
Laser Induced Breakdown Spectroscopy (LIBS) is showing great potential as an atomic analytical technique. With its ability to rapidly analyze all forms of matter, with little-to-no sample preparation, LIBS has many advantages over conventional atomic emission spectroscopy techniques. With the maturation of the technologies that make LIBS possible, there has been a growing movement to implement LIBS in portable analyzers for field applications. In particular, LIBS has long been considered the...
Show moreLaser Induced Breakdown Spectroscopy (LIBS) is showing great potential as an atomic analytical technique. With its ability to rapidly analyze all forms of matter, with little-to-no sample preparation, LIBS has many advantages over conventional atomic emission spectroscopy techniques. With the maturation of the technologies that make LIBS possible, there has been a growing movement to implement LIBS in portable analyzers for field applications. In particular, LIBS has long been considered the front-runner in the drive for stand-off detection of trace deposits of explosives. Thus there is a need for a better understanding of the relevant processes that are responsible for the LIBS signature and their relationships to the different system parameters that are helping to improve LIBS as a sensing technology. This study explores the use of LIBS as a method to detect random trace amounts of specific organic materials deposited on organic or non-metallic surfaces. This requirement forces the limitation of single-shot signal analysis. This study is both experimental and theoretical, with a sizeable component addressing data analysis using principal components analysis to reduce the dimensionality of the data, and quadratic discriminant analysis to classify the data. In addition, the alternative approach of 'target factor analysis' was employed to improve detection of organic residues on organic substrates. Finally, a new method of characterizing the laser-induced plasma of organics, which should lead to improved data collection and analysis, is introduced. The comparison between modeled and experimental measurements of plasma temperatures and electronic density is discussed in order to improve the present models of low-temperature laser induced plasmas.
Show less - Date Issued
- 2011
- Identifier
- CFE0003708, ucf:48843
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0003708
- Title
- TOWARDS DIRECT WRITING OF 3-D PHOTONIC CIRCUITS USING ULTRAFAST LASERS.
- Creator
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Zoubir, Arnaud, Richardson, Martin, University of Central Florida
- Abstract / Description
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The advent of ultrafast lasers has enabled micromachining schemes that cannot be achieved by other current techniques. Laser direct writing has emerged as one of the possible routes for fabrication of optical waveguides in transparent materials. In this thesis, the advantages and limitations of this technique are explored. Two extended-cavity ultrafast lasers were built and characterized as the laser sources for this study, with improved performance over existing systems. Waveguides are...
Show moreThe advent of ultrafast lasers has enabled micromachining schemes that cannot be achieved by other current techniques. Laser direct writing has emerged as one of the possible routes for fabrication of optical waveguides in transparent materials. In this thesis, the advantages and limitations of this technique are explored. Two extended-cavity ultrafast lasers were built and characterized as the laser sources for this study, with improved performance over existing systems. Waveguides are fabricated in oxide glass, chalcogenide glass, and polymers, these being the three major classes of materials for the telecommunication industry. Standard waveguide metrology is performed on the fabricated waveguides, including refractive index profiling and mode analysis. Furthermore, a finite-difference beam propagation method for wave propagation in 3D-waveguides is proposed. The photo-structural modifications underlying the changes in the material optical properties after exposure are investigated. The highly nonlinear processes of the light/matter interaction during the writing process are described using a free electron model. UV/visible absorption spectroscopy, photoluminescence spectroscopy and Raman spectroscopy are used to assess the changes occurring at the atomic level. Finally, the impact of laser direct writing on nonlinear waveguide applications is discussed.
Show less - Date Issued
- 2004
- Identifier
- CFE0000236, ucf:46252
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0000236
- Title
- Intracavity Laser Absorption Spectroscopy using Quantum Cascade Laser and Fabry-Perot Interferometer.
- Creator
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Medhi, Gautam, Peale, Robert, Ishigami, Marsahir, Chernyak, Leonid, Delfyett, Peter, University of Central Florida
- Abstract / Description
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Intracavity Laser Absorption Spectroscopy (ICLAS) at IR wavelengths offers an opportunity for spectral sensing of low vapor pressure compounds. We report here an ICLAS system design based on a quantum cascade laser (QCL) at THz (69.9 ?m) and IR wavelengths (9.38 and 8.1 ?m) with an open external cavity. The sensitivity of such a system is potentially very high due to extraordinarily long effective optical paths that can be achieved in an active cavity. Sensitivity estimation by numerical...
Show moreIntracavity Laser Absorption Spectroscopy (ICLAS) at IR wavelengths offers an opportunity for spectral sensing of low vapor pressure compounds. We report here an ICLAS system design based on a quantum cascade laser (QCL) at THz (69.9 ?m) and IR wavelengths (9.38 and 8.1 ?m) with an open external cavity. The sensitivity of such a system is potentially very high due to extraordinarily long effective optical paths that can be achieved in an active cavity. Sensitivity estimation by numerical solution of the laser rate equations for the THz QCL ICLAS system is determined. Experimental development of the external cavity QCL is demonstrated for the two IR wavelengths, as supported by appearance of fine mode structure in the laser spectrum. The 8.1 ?m wavelength exhibits a dramatic change in the output spectrum caused by the weak intracavity absorption of acetone. Numerical solution of the laser rate equations yields a sensitivity estimation of acetone partial pressure of 165 mTorr corresponding to ~ 200 ppm. The system is also found sensitive to the humidity in the laboratory air with an absorption coefficient of just 3 x 10-7 cm-1 indicating a sensitivity of 111 ppm. Reported also is the design of a compact integrated data acquisition and control system. Potential applications include military and commercial sensing for threat compounds such as explosives, chemical gases, biological aerosols, drugs, banned or invasive organisms, bio-medical breath analysis, and terrestrial or planetary atmospheric science.
Show less - Date Issued
- 2011
- Identifier
- CFE0004137, ucf:49040
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0004137
- Title
- EXTREME ULTRAVIOLET SPECTRAL STREAK CAMERA.
- Creator
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Szilagyi, John, Richardson, Martin, University of Central Florida
- Abstract / Description
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The recent development of extreme ultraviolet (EUV) sources has increased the need for diagnostic tools, and has opened up a previously limited portion of the spectrum. With ultrafast laser systems and spectroscopy moving into shorter timescales and wavelengths, the need for nanosecond scale imaging of EUV is increasing. EUVÂÂÂÂ's high absorption has limited the number of imaging options due...
Show moreThe recent development of extreme ultraviolet (EUV) sources has increased the need for diagnostic tools, and has opened up a previously limited portion of the spectrum. With ultrafast laser systems and spectroscopy moving into shorter timescales and wavelengths, the need for nanosecond scale imaging of EUV is increasing. EUVÂÂÂÂ's high absorption has limited the number of imaging options due to the many atomic resonances in this spectrum. Currently EUV is imaged with photodiodes and X-ray CCDs. However photodiodes are limited in that they can only resolve intensity with respect to time and X-ray CCDs are limited to temporal resolution in the microsecond range. This work shows a novel approach to imaging EUV light over a nanosecond time scale, by using an EUV scintillator to convert EUV to visible light imaged by a conventional streak camera. A laser produced plasma, using a mass-limited tin based target, provided EUV light which was imaged by a grazing incidence flat field spectrometer onto a Ce:YAG scintillator. The EUV spectrum (5 nm-20 nm) provided by the spectrometer is filter by a zirconium filter and then converted by the scintillator to visible light (550 nm) which can then be imaged with conventional optics. Visible light was imaged by an electron image tube based streak camera. The streak camera converts the visible light image to an electron image using a photocathode, and sweeps the image across a recording medium. The streak camera also provides amplification and gating of the image by the means of a micro channel plate, within the image tube, to compensate for low EUV intensities. The system provides 42 ns streaked images of light with a temporal resolution of 440 ps at a repetition rate of 1 Hz. Upon calibration the EUV streak camera developed in this work will be used in future EUV development.
Show less - Date Issued
- 2010
- Identifier
- CFE0003558, ucf:48905
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0003558
- Title
- Shock Tube and Mid-infrared Laser Absorption Measurements of Ignition Delay Times and Species Time-histories.
- Creator
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Koroglu, Batikan, Vasu Sumathi, Subith, Kapat, Jayanta, Kassab, Alain, Peale, Robert, University of Central Florida
- Abstract / Description
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Energy consumption has increased dramatically as the world advances and becomes more industrialized. Over the next twenty five years, the U.S. Department of Energy expects the energy demand to increase by 29% with majority of the new energy coming from natural gas (methane). Another promising fuel source for power generation and transportation is the biofuels. The biofuel use in the US is shown to have increased substantially in the last decade. There are serious environmental concerns...
Show moreEnergy consumption has increased dramatically as the world advances and becomes more industrialized. Over the next twenty five years, the U.S. Department of Energy expects the energy demand to increase by 29% with majority of the new energy coming from natural gas (methane). Another promising fuel source for power generation and transportation is the biofuels. The biofuel use in the US is shown to have increased substantially in the last decade. There are serious environmental concerns associated with greenhouse (e.g. carbon-dioxide) and toxic gas emissions (e.g. nitrogen oxides and aldehydes such as propanal) due to deriving energy from natural gas and biofuel combustion. In this doctoral study, a shock tube experimental setup was designed, assembled, and tested in order to study the ignition as well as thermal decomposition characteristics of two types of fuels: methane (the major natural gas component, which is also a major intermediate during higher order hydrocarbon ignition and pyrolysis) and propanal (an oxygenated hydrocarbon found in the exhaust emissions of biofuels). A laser diagnostics using semi-conductor type laser diodes in the infrared region for measurements of methane and propanal gas concentrations was developed and used with the shock tube. This diagnostics also enabled the interference-free detection of methane during the course of propanal pyrolysis. The experimental measurements highlighted the areas in which refinement of reaction kinetic models was required. The current research provided information on the ignition delay times as well as concentration time-histories of fuels (e.g. propanal or methane) and intermediates (e.g. methane). The knowledge gained during this doctoral study is vital for the accurate modeling of emissions due to combustion of fuels. The dissertation discusses the details of the four following items: 1) design, assembly, and testing of a shock tube setup as well as a laser diagnostics apparatus for studying ignition characteristics of fuels and associated reaction rates, 2) measurements of methane and propanal infrared spectra at room and high temperatures using a Fourier Transformed Infrared Spectrometer (FTIR) and a shock tube , 3) measurements of ignition delay times and reaction rates during propanal thermal decomposition and ignition, and 4) investigation of ignition characteristics of methane during its combustion in carbon-dioxide diluted bath gas. The main benefit and application of this work is the experimental data which can be used in future studies to constrain reaction mechanism development.
Show less - Date Issued
- 2016
- Identifier
- CFE0006533, ucf:51382
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006533
- Title
- Shock Tube Investigations of Novel Combustion Environments Towards a Carbon-Neutral Future.
- Creator
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Barak, Samuel, Vasu Sumathi, Subith, Kapat, Jayanta, Ahmed, Kareem, University of Central Florida
- Abstract / Description
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Supercritical carbon dioxide (sCO2) cycles are being investigated for the future of power generation. These cycles will contribute to a carbon-neutral future to combat the effects of climate change. These direct-fired closed cycles will produce power without adding significant pollutants to the atmosphere. For these cycles to be efficient, they will need to operate at significantly higher pressures (e.g., 300 atm for Allam Cycle) than existing systems (typically less than 40 atm). There is...
Show moreSupercritical carbon dioxide (sCO2) cycles are being investigated for the future of power generation. These cycles will contribute to a carbon-neutral future to combat the effects of climate change. These direct-fired closed cycles will produce power without adding significant pollutants to the atmosphere. For these cycles to be efficient, they will need to operate at significantly higher pressures (e.g., 300 atm for Allam Cycle) than existing systems (typically less than 40 atm). There is limited knowledge on combustion at these pressures or at the high dilution of carbon dioxide. Nominal fuel choices for gas turbines include natural gas and syngas (mixture of CO and H2). Shock tubes study these problems in order to understand the fundamentals and solve various challenges. Shock tube experiments have been studied by the author in the sCO2 regime for various fuels including natural gas, methane and syngas. Using the shock tube to take measurements, pressure and light emissions time-histories measurements were taken at a 2-cm axial location away from the end wall. Experiments for syngas at lower pressure utilized high-speed imaging through the end wall to investigate the effects of bifurcation. It was found that carbon dioxide created unique interactions with the shock tube compared to tradition bath gasses such as argon. The experimental results were compared to predictions from leading chemical kinetic mechanisms. In general, mechanisms can predict the experimental data for methane and other hydrocarbon fuels; however, the models overpredict for syngas mixtures. Reaction pathway analysis was evaluated to determine where the models need improvements. A new shock tube has been designed and built to operate up to 1000 atm pressures for future high-pressure experiments. Details of this new facility are included in this work. The experiments in this work are necessary for mechanism development to design an efficient combustor operate these cycles.
Show less - Date Issued
- 2019
- Identifier
- CFE0007781, ucf:52359
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007781
- Title
- NEW DEVELOPMENTS ON HIGH-RESOLUTION LUMINESCENCE SPECTROSCOPY AND THEIR APPLICATION TO THE DIRECT ANALYSIS OF ORGANIC POLLUTANTS IN ENVIRONMENTAL SAMPLES.
- Creator
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yu, shenjiang, Campiglia, Andres, University of Central Florida
- Abstract / Description
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Polycyclic aromatic compounds (PACs), which comprise a complex class of condensed multi-ring benzenoid compounds, are important environmental pollutants originating from a wide variety of natural and anthropogenic sources. PACs are generally formed during incomplete combustion of pyrolisis of organic matter containing carbon and hydrogen. Because combustion of organic materials is involved in countless natural processes or human activities, PACs are omnipresent and abundant pollutants in air,...
Show morePolycyclic aromatic compounds (PACs), which comprise a complex class of condensed multi-ring benzenoid compounds, are important environmental pollutants originating from a wide variety of natural and anthropogenic sources. PACs are generally formed during incomplete combustion of pyrolisis of organic matter containing carbon and hydrogen. Because combustion of organic materials is involved in countless natural processes or human activities, PACs are omnipresent and abundant pollutants in air, soil, and water. Chemical analysis of PACs is of great environmental and toxicological importance. Many of them are highly suspect as etiological agents in human cancer. Because PACs carcinogenic properties strongly depend on molecular structure and differ significantly from isomer to isomer, it is of paramount importance to determine the most toxic isomers even if they are present at much lower concentrations than their less toxic isomers. Gas chromatography (GC), high-resolution GC, and high-performance liquid chromatography (HPLC) are the basis for standard PACs identification and determination. Many cases exist where GC, HPLC, and even HR-GC have not been capable to provide unambiguous isomer identification. The lack of reliable analytical data has lead to serious errors in environmental and toxicological studies. This dissertation deals with the development of novel instrumentation and analytical methods for the analysis of PACs in environmental samples. The developed methodology is based on two well-known high-resolution luminescence techniques, namely Shpol'skii Spectroscopy (SS) and Fluorescence Line Narrowing Spectroscopy (FLNS). Although these two techniques have long been recognized for their capability in providing direct determination of target PACs in complex environmental samples, several reasons have hampered their widespread use for the problem at hand. These include inconvenient sample freezing procedures; questions about signal reproducibility; lengthy spectral acquisition, which might cause severe sample degradation due to prolonged excitation; broadband fluorescence background that degrades quality of spectra, precision of measurements and detection limits; solvent constrains imposed by the need of optically transparent media; and, most importantly, the lack of selectivity and sensitivity for unambiguous determination of closely related PACs metabolites. This dissertation presents significant advances on all fronts. The analytical methodology is then extended to the analysis of fluoroquinolones (FQs) in aqueous samples. FQs are one of the most powerful classes of antibiotics currently used for the treatment of urinary tract infections. Their widespread use in both human and animal medicine has prompted their appearance in aquatic systems. The search for a universal method capable to face this new environmental challenge has been centered on HPLC. Depending on the FQ and its concentration level, successful determination has been accomplished with mass spectrometry, room-temperature fluorescence (RTF) or UV absorption spectrometry. Unfortunately, no single detection mode has shown the ability to detect all FQ at the concentration ratios found in environmental waters. We provide a feasible alternative based on FLNS. On the instrumentation side, we present a single instrument with the capability to collect multidimensional data formats in both the fluorescence and the phosphorescence time domains. We demonstrate the ability to perform luminescence measurements in highly scattering media by comparing the precision of measurements in optically transparent solvents (Shpol'skii solvents) to those obtained in "snow-like" matrixes and solid samples. For decades, conventional low-temperature methodology has been restricted to optically transparent media. This restriction has limited its application to organic solvents that freeze into a glass. In this dissertation, we remove this limitation with the use of cryogenic fiber-optic probes. Our final efforts deal with low-temperature absorption measurements. Recording absorption spectra via transmittance through frozen matrixes is a challenging task. The main reason is the difficulty to overcome the strong scattering light reaching the detector. This is particularly true when thick samples are necessary for recording absorption spectra of weak oscillators. In the case of strongly fluorescent compounds, additional errors in absorbance measurements arise from the emission reaching the detector, which might have comparable intensity to that of the transmitted light. We present a fundamentally different approach to low-temperature absorption measurements as the sought-for-information is the intensity of laser excitation returning from the frozen sample to the intensified-charge coupled device (ICCD). Laser excitation is collected with the aid of a cryogenic fiber optic probe. The feasibility of our approach is demonstrated with single-site and multiple-site Shpol'skii systems. 4.2K absorption spectra show excellent agreement to their literature counterparts recorded via transmittance with closed cycle cryogenators. Fluorescence quantum yields measured at room-temperature compare well to experimental data acquired in our lab via classical methodology. Similar agreement is observed between 77K fluorescence quantum yields and previously reported data acquired with classical methodology. We then extend our approach to generate original data on fluorescence quantum yields at 4.2K.
Show less - Date Issued
- 2006
- Identifier
- CFE0001456, ucf:47039
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0001456
- Title
- Novel Developments on the Extraction and Analysis of Polycyclic Aromatic Hydrocarbons in Environmental Samples.
- Creator
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Wilson, Walter, Campiglia, Andres, Belfield, Kevin, Rex, Matthew, Harper, James, Hoffman, Jay, University of Central Florida
- Abstract / Description
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This dissertation focuses on the development of analytical methodology for the analysis of polycyclic aromatic hydrocarbons (PAHs) in water samples. Chemical analysis of PAHs is of great environmental and toxicological importance. Many of them are highly suspect as etiological agents in human cancer. Among the hundreds of PAHs present in the environment, the U.S. Environmental Protection Agency (EPA) lists sixteen as "Consent Decree" priority pollutants. Their routine monitoring in...
Show moreThis dissertation focuses on the development of analytical methodology for the analysis of polycyclic aromatic hydrocarbons (PAHs) in water samples. Chemical analysis of PAHs is of great environmental and toxicological importance. Many of them are highly suspect as etiological agents in human cancer. Among the hundreds of PAHs present in the environment, the U.S. Environmental Protection Agency (EPA) lists sixteen as "Consent Decree" priority pollutants. Their routine monitoring in environmental samples is recommended to prevent human contamination risks.A primary route of human exposure to PAHs is the ingestion of contaminated water. The rather low PAH concentrations in water samples make the analysis of the sixteen priority pollutants particularly challenging. Current EPA methodology follows the classical pattern of sample extraction and chromatographic analysis. The method of choice for PAHs extraction and pre-concentration is solid-phase extraction (SPE). PAHs determination is carried out via high-performance liquid chromatography (HPLC) or gas chromatography/mass spectrometry (GC/MS). When HPLC is applied to highly complex samples, EPA recommends the use of GC/MS to verify compound identification and to check peak-purity of HPLC fractions. Although EPA methodology provides reliable data, the routine monitoring of numerous samples via fast, cost effective and environmentally friendly methods remains an analytical challenge. Typically, 1 L of water is processed through the SPE device in approximately 1 h. The rather large water volume and long sample processing time are recommended to reach detectable concentrations and quantitative removal of PAHs from water samples. Chromatographic elution times of 30 (-) 60 min are typical and standards must be run periodically to verify retention times. If concentrations of targeted PAHs are found to lie outside the detector's response range, the sample must be diluted (or concentrated), and the process repeated. In order to prevent environmental risks and human contamination, the routine monitoring of the sixteen EPA-PAHs is not sufficient anymore. Recent toxicological studies attribute a significant portion of the biological activity of PAH contaminated samples to the presence of high molecular weight (HMW) PAHs, i.e. PAHs with MW ? 300. Because the carcinogenic properties of HMW-PAHs differ significantly from isomer to isomer, it is of paramount importance to determine the most toxic isomers even if they are present at much lower concentrations than their less toxic isomers. Unfortunately, established methodology cannot always meet the challenge of specifically analyzing HMW-PAHs at the low concentration levels of environmental samples. The main problems that confront classic methodology arise from the relatively low concentration levels and the large number of structural isomers with very similar elution times and similar, possibly even virtually identical, fragmentation patterns. This dissertation summarizes significant improvements on various fronts. Its first original component deals with the unambiguous determination of four HMW-PAHs via laser-excited time-resolved Shpol'skii spectroscopy (LETRSS) without previous chromatographic separation. The second original component is the improvement of a relatively new PAH extraction method - solid-phase nanoextraction (SPNE) - which uses gold nanoparticles as extracting material for PAHs. The advantages of the improved SPNE procedure are demonstrated for the analysis of EPA-PAHs and HMW-PAHs in water samples via GC/MS and LETRSS, respectively.
Show less - Date Issued
- 2014
- Identifier
- CFE0005443, ucf:50384
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005443
- Title
- Analysis of Benzopyrenes and Benzopyrene Metabolites by Fluorescence Spectroscopy Techniques.
- Creator
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Al-Farhani, Bassam, Campiglia, Andres, Harper, James, Zou, Shengli, Frazer, Andrew, Lee, Woo Hyoung, University of Central Florida
- Abstract / Description
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Polycyclic aromatic hydrocarbons (PAHs) are some of the most common and toxic pollutants encountered worldwide. Presently, monitoring is restricted to sixteen PAHs, but it is well understood that this list omits many toxic PAHs. Among the (")forgotten(") PAHs, isomers with molecular weight 302 are of particular concern due to their high toxicological properties. The chromatographic analysis of PAHs with MW 302 is challenged by similar retention times and virtually identical mass fragmentation...
Show morePolycyclic aromatic hydrocarbons (PAHs) are some of the most common and toxic pollutants encountered worldwide. Presently, monitoring is restricted to sixteen PAHs, but it is well understood that this list omits many toxic PAHs. Among the (")forgotten(") PAHs, isomers with molecular weight 302 are of particular concern due to their high toxicological properties. The chromatographic analysis of PAHs with MW 302 is challenged by similar retention times and virtually identical mass fragmentation patterns.The first original component of this dissertation evolves from a high-resolution spectroscopic approach specifically developed to fulfil this gap. Herein, 4.2 K Laser-Excited Time-Resolved Shpol'skii Spectroscopy (4.2K LETRSS) is applied to the analysis of HMW-PAHs in a complex coal tar standard reference material (SRM 1597a). The spectral and lifetime information obtained with LETRSS provide the required selectivity for the unambiguous determination of PAH isomers in the high-performance liquid chromatography (HPLC) fractions. Complete LETRSS analysis is possible with microliters of HPLC fractions and organic solvent. The excellent analytical figures of merit associated to its non-destructive nature, which provides ample opportunity for further analysis with other instrumental methods, makes this approach a unique alternative for the analysis of isomers of HMW-PAHs in complex environmental samples.The second original component of this dissertation focuses on the development of screening methodology for the routine analysis of PAH metabolites in urine samples. It explores the room-temperature fluorescence (RTF) properties of 3-hydroxy-benzo[a]pyrene, benzo[a]pyrene-trans-9,10-dihydrodiol, benzo[a]pyrene-r-7,t-8,c-9-tetrahydrotriol and benzo[a]pyrene-r-7,t-8,c-9,c-10-tetrahydrotetrol previously extracted with octadecyl-silica membranes. RTF measurements from extraction membranes are carried out with the aid of fiber optic probe that eliminates the need for manual optimization of signal intensities. Relative standard deviations varying from 2.07% (benzo[a]pyrene-r-7,t-8,c-9-tetrahydrotriol) to 8.55% (3-hydroxy-benzo[a]pyrene) were obtained with a straightforward procedure. Analytical recoveries from human urine samples varied from 87.54 (&)#177; 3.11% (3-hydroxy-benzo[a]pyrene) to 99.77 (&)#177; 2.48% (benzo[a]pyrene-r-7,t-8,c-9,c-10-tetrahydrotetrol). The excellent analytical figures of merit and the simplicity of the experimental procedure demonstrate the potential of Solid phase extraction-RTF for screening biomarkers of PAH exposure in numerous urine samples.
Show less - Date Issued
- 2016
- Identifier
- CFE0006520, ucf:51363
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006520
