Thèses sur le sujet « Thermic and spectroscopic technique »

AlₓGa₁₋ₓN (x>0.6) based Ultraviolet Light Emitting Diodes (UV LEDs) emit in the UV C range of 200 - 290 nm and suffer from low external quantum efficiencies (EQEs) of less than 3%. This low EQE is representative of a large number of non-radiative recombination events in the multiple quantum well (MQW) layers, which leads to high device temperatures due to self-heating at the device junction. Knowledge of the device temperature is essential to implement and evaluate appropriate thermal management techniques, in order to mitigate optical degradation and lifetime reduction due to thermal overstress. The micro-scale nature of these devices and the presence of large temperature gradients in the multilayered device structure merit the use of several indirect temperature measurement techniques to resolve device temperatures. This work will study UV LEDs with AlₓGa₁₋ₓN active layers, grown on sapphire or AlN growth substrates, and flip-chip mounted onto submounts and package configurations with different thermal properties. Thermal metrology results will be presented for devices with different electrode geometries (i.e., interdigitated and micropixel), for bulk and thinned growth substrates. The body of this work will present a comparative study of optical techniques such as Infrared (IR), micro-Raman and Electroluminescence (EL) spectroscopy for the thermal metrology of UV LEDs. The presence of horizontal and vertical temperature gradients within the device layers will be studied using micro-Raman spectroscopy, while the occurrence of thermal anomalies such as hotspots and shorting paths will be studied using IR spectroscopy. The Forward Voltage (Vf) method, an electrical junction temperature measurement technique, will also be investigated. The Vf method will be applied to the Thermal Resistance Analysis by Induced Transient (TRAIT) procedure, whereby electrical data at short time scales from an operational device will be used to discretize the junction-to- package thermal resistance pathway from the total junction- to-ambient heat path. The TRAIT procedure will be conducted on several LEDs, for comparison. The scope and applicability of each thermal metrology technique will be examined, and the merits and demerits of each technique will be exhibited.

The Upsilon Andromedae system was the first multi-planet system discovered orbiting a main-sequence star. We describe the detection of water vapor in the atmosphere of the innermost non-transiting gas giant ups. And. b by treating the star-planet system as a spectroscopic binary with high-resolution, ground-based spectroscopy. We resolve the signal of the planet's motion and break the mass-inclination degeneracy for this non-transiting planet via deep combined flux observations of the star and the planet. In total, seven epochs of Keck NIRSPEC L band observations, three epochs of Keck NIRSPEC short-wavelength K band observations, and three epochs of Keck NIRSPEC long wavelength K band observations of the ups. And. system were obtained. We perform a multi-epoch cross-correlation of the full data set with an atmospheric model. We measure the radial projection of the Keplerian velocity (K-P = 55 +/- 9 km s(-1)), true mass (M-b = 1.7(-0.24)(+0.33)M(J)), and orbital inclination (i(b) 24 degrees +/- 4 degrees), and determine that the planet's opacity structure is dominated by water vapor at the probed wavelengths. Dynamical simulations of the planets in the ups. And. system with these orbital elements for ups. And. b show that stable, long-term (100 Myr) orbital configurations exist. These measurements will inform future studies of the stability and evolution of the ups. And. system, as well as the atmospheric structure and composition of the hot Jupiter.

We target the thermal emission spectrum of the non-transiting gas giant HD 88133 b with high-resolution near-infrared spectroscopy, by treating the planet and its host star as a spectroscopic binary. For sufficiently deep summed flux observations of the star and planet across multiple epochs, it is possible to resolve the signal of the hot gas giant's atmosphere compared to the brighter stellar spectrum, at a level consistent with the aggregate shot noise of the full data set. To do this, we first perform a principal component analysis to remove the contribution of the Earth's atmosphere to the observed spectra. Then, we use a cross-correlation analysis to tease out the spectra of the host star and HD 88133 b to determine its orbit and identify key sources of atmospheric opacity. In total, six epochs of Keck NIRSPEC L-band observations and three epochs of Keck NIRSPEC K-band observations of the HD 88133 system were obtained. Based on an analysis of the maximum likelihood curves calculated from the multi-epoch cross-correlation of the full data set with two atmospheric models, we report the direct detection of the emission spectrum of the non-transiting exoplanet HD 88133 b and measure a radial projection of the Keplerian orbital velocity of 40 +/- 15 km s(-1), a true mass of 1.02(-0.28)(+0.61) M-J, a nearly face-on orbital inclination of 15(-5)(+60), and an atmosphere opacity structure at high dispersion dominated by water vapor. This, combined with 11 years of radial velocity measurements of the system, provides the most up-to-date ephemeris for HD 88133.

In recent years there has been an increased interest in the use of amorphous materials in the pharmaceutical industry because of their enhanced thermodynamic properties owing to their greater molecular mobility. Pharmaceutically, formulating with an amorphous material can improve the dissolution and bioavailability of a drug. It can also be used in the stabilisation of another formulation component. However, any potential benefits of an amorphous pharmaceutical are counterbalanced by their metastable nature and tendency to recrystallise spontaneously to their, more stable, crystalline state. The work presented here details the development of thermal and spectroscopic characterisation techniques to study pharmaceutical materials in partially and fully amorphous states. This thesis focuses on the characterisation of a single pharmaceutical material, salbutamol sulphate, nevertheless the experimental research involved highlights the complexities of a "real" amorphous material. Throughout this work numerous difficulties were encountered in characterising the amorphous phase. Specifically the close proximity of the decomposition temperature of amorphous salbutamol sulphate to its glass transition temperature proved eventful and differences seen in both the recrystallisation kinetics and physical stability associated with the preparation method were intriguing. In general, the interaction of water with the amorphous phase further complicates its behaviour. Progress was made towards understanding this relationship and this work has identified and detailed several questions and possible future areas of research. Of the newly developed techniques to study amorphous materials, photothermal microspectroscopy was identified as having the potential to differentiate morphological, chemical and physical differences spatially between the amorphous and crystalline forms. Thermally stimulated current spectroscopy was, however, found to be less reliable at determining the relaxation behaviour of the amorphous sample. To conclude, the research carried out and detailed within this thesis used existing and newly developed thermal and spectroscopic characterisation techniques to further our understanding of amorphous materials and their associated complexities.

The Fermi Gamma-ray Space Telescope (Fermi) has focused the intensive multi-wavelength and international observational effort on blazars since it was launched in 2008. Part of this effort involves systematic monitoring of the highly variable polarization of the continuum emission from these objects. These observations are valuable in that they provide direct information on the degree of ordering and orientation on the sky of the magnetic field within the non-thermal emission region(s). Unfortunately, it is not yet possible to measure the polarization of the inverse-Compton continuum, only that of the lower-energy synchrotron emission. The inability to directly compare the polarization of the two dominant continuum sources in blazars is a drawback and leads to more ambiguities in determining their relative locations. There are many compelling examples of strong connections between -ray, X-ray, UV/optical/IR, and radio behavior in blazars that suggest the same region produces much of the observed emission at all wavelengths at least some of the time. However, the wealth of polarization behavior seen relative to flux changes invariably results in a complex situation that is difficult to interpret and model. The long-term blazar monitoring program undertaken at Steward Observatory is designed to primarily obtain accurate optical polarimetry of -ray-bright blazars during the Fermi mission with the goal of gaining important insights into the jet structure and physics of these objects. Data from this program are available to all researchers as soon as reductions are completed. I briefly detail the current status and progress of the program and the data products available. Although the wide variety of polarization behavior in blazars adds another layer of complexity to an already difficult problem, I summarize several important conclusions that can be drawn from the polarization information gathered during the Fermi era.

Trace gases can have a significant impact on the Earth's climate, and the analysis of changes in these gases and an understanding of how much of these changes are a result of human activity is important for understanding global climate change. Methane (CH4) is the second only to CO2 in radiative forcing over the last 200 years, and its concentration in the atmosphere has more than doubled since 1750. Sources and sinks of CH4 have characteristic isotopic effects, which shift the relative concentration of the methane isotopologues. Spectroscopic techniques for of analysis the isotopic composition of methane have been evolving since the early 1990's, and promise real-time, in-situ measurements that would provide unprecedented information on the methane atmospheric cycle. Here we present our development and results of a new optical spectroscopic isotope ratio instrument using cavity ringdown spectroscopy in the near IR region using the ν2+2ν3 overtone band. This region has limited interference from other molecules, and an advantageous juxtaposition of a 13CH4 triplet, and a single 12CH4 peak, allowing near-simultaneous measurement of both isotopologues. We present the results of two datasets showing high linearity over a wide range of isotope ratios, which achieved a precision of ±4 /. We present analysis of the data and consider the effects of temperature and molecular interference.

The work focused on addressing four main objectives. The first objective was to quantify protein and amino acid substitution reactions. Michael addition reactions were used to modify the amino acids and protein. Amino acids alanine, cysteine, and lysine, and protein ovalbumin (OA) were substituted with different concentrations of ethyl vinyl sulfone (EVS). The substituted products were analyzed using Raman spectroscopy and UV-spectroscopy based ninhydrin assay. In case of alanine, Raman and UV results correlated with each other. With cysteine at lower EVS substitutions amine on the main chain was the preferred site while the substitution shifted to thiols at higher substitutions. This could only be discerned using Raman spectroscopy. Lysine has amines on the main chain and side chain while main chain amine was the most reactive site at lower concentrations of EVS while at higher concentrations side chain amines were also substituted. This information could be discerned using Raman spectroscopy only and not UV spectroscopy. In case of protein as observed by Raman and UV spectroscopy the reaction continued at higher concentrations of EVS indicating the participation of glutamine and asparagines at higher substitutions. However, the reaction considerably slowed down at higher EVS substitutions. The second objective of the study was to decrease the glass transition temperature (Tg) of OA through internal plasticization and also study the effects of the substituents on the thermal stability of OA. The hypothesis was by covalently attaching substituents to OA, number of hydrogen bonds can be reduced while increasing the free volume and this would reduce Tg. EVS, acrylic acid (AA), butadiene sulfone (BS) and maleimide (MA) were the four groups used. EVS was the most efficient plasticizer of all the four substituents. The Tg decreased with the increasing concentration of EVS until all of the reactive of groups on OA were used up. Tg decreased slightly with AA and BS while no change was observed with MA. However, the substituents showed exact opposite trend in thermal stability as measured using thermogravimetric analysis (TGA). The thermal stability of MA substituted OA was the highest and that of EVS substituted OA was least. FT-IR spectroscopy results indicated that all four substituents caused structural changes in OA. This implied that there were intermolecular interactions between substituted protein chains in case of AA, BS, and MA. This caused an increase in the thermal stability. EVS on the other hand is a linear chain monomer with a hydrophobic end group and hence could not participate in the intermolecular interactions and hence caused a decrease in Tg. As mentioned above the limitation to this technique is the number of available reactive groups on the protein. However, we successfully demonstrated the feasibility of this method in decreasing Tg of protein. The third objective was to create hydrogels by crosslinking OA with divinyl sulfone (DVS). Protein hydrogels due to their biocompatible nature find applications in drug delivery and tissue engineering. For tissue engineering applications the hydrogels need to be mechanically stable. In this study the protein was substituted with EVS or AA and then crosslinked with DVS. The swelling ratio was measured as a function of pH. All the hydrogels showed the same trend and swelled the least at pH 4.5 which is the isoelectric point of the protein. At basic pH conditions EVS substituted hydrogels swelled the most while AA substituted hydrogels showed least swelling. The static and dynamic moduli of the hydrogels were determined using tensile tester and rheometer respectively. The static modulus values were three times the dynamic modulus. The modulus of the control which is crosslinked OA was least and that of AA substituted OA was highest. The stress relaxation test also showed similar results in which AA substituted OA relaxed the most and the control relaxed the least. FT-IR of the dry hydrogels showed that the amount of hydrogen bonding increased with AA substitution. The hydrophilic AA end groups interacted with each other forming hydrogen bonds. These hydrogen bonds served as additional crosslinks there by increasing the modulus of the hydrogels. EVS on the other hand was incapable of interactions due to the lack of hydrophilic end groups. We were successfully able to create protein hydrogels and control the swelling and mechanical properties by varying the amount of substituted group. The final objective of the study was to create and characterize microstructures from substituted alanine and lysine. Alanine and lysine were substituted with different concentrations of EVS. Bars and fibers were observed for alanine at moderate substitutions while at higher concentrations random structures were observed using scanning electron microscopy (SEM). Lysine formed tubes at moderate EVS substitutions and rosettes at high concentrations of EVS as evidenced by SEM. FT-IR results suggested that instead of carbonyl one of sulfonyl bonded to the available amine in modified amino acids. And only in this case fibers, tubes and rosettes were observed. X-ray diffraction (XRD) results supported this observation. Using these results we hypothesized that the self assembled structures very much depended on the amount of EVS present in the substituted product and sulfonyl forming β-sheet analogs with amine.
Ph. D.

Insufficient instrument thermomechanical stability is one of the many roadblocks for achieving 10 cm s(-1) Doppler radial velocity precision, the precision needed to detect Earth-twins orbiting solar-type stars. Highly temperature and pressure stabilized spectrographs allow us to better calibrate out instrumental drifts, thereby helping in distinguishing instrumental noise from astrophysical stellar signals. We present the design and performance of the Environmental Control System (ECS) for the Habitable-zone Planet Finder (HPF), a high-resolution (R = 50,000) fiber-fed near-infrared (NIR) spectrograph for the 10 m Hobby-Eberly Telescope at McDonald Observatory. HPF will operate at 180 K, driven by the choice of an H2RG NIR detector array with a 1.7 mu m cutoff. This ECS has demonstrated 0.6 mK rms stability over 15 days at both 180 and 300 K, and maintained high-quality vacuum (< 10 (7) Torr) over months, during long-term stability tests conducted without a planned passive thermal enclosure surrounding the vacuum chamber. This control scheme is versatile and can be applied as a blueprint to stabilize future NIR and optical high-precision Doppler instruments over a wide temperature range from similar to 77 K to elevated room temperatures. A similar ECS is being implemented to stabilize NEID, the NASA/NSF NN-EXPLORE spectrograph for the 3.5 m WIYN telescope at Kitt Peak, operating at 300 K. A [full SolidWorks 3D-CAD model] and a comprehensive parts list of the HPF ECS are included with this manuscript to facilitate the adaptation of this versatile environmental control scheme in the broader astronomical community.

The nature of the thermal structure of hot Jupiter atmospheres is one of the key questions raised by the characterization of transiting exoplanets over the past decade. There have been claims that many hot Jupiters exhibit atmospheric thermal inversions. However, these claims have been based on broadband photometry rather than the unambiguous identification of emission features with spectroscopy, and the chemical species that could cause the thermal inversions by absorbing stellar irradiation at high altitudes have not been identified despite extensive theoretical and observational effort. Here we present high-precision Hubble Space Telescope WFC3 observations of the dayside thermal emission spectrum of the hot Jupiter HD 209458b, which was the first exoplanet suggested to have a thermal inversion. In contrast to previous results for this planet, our observations detect water in absorption at 6.2 sigma confidence. When combined with Spitzer photometry, the data are indicative of a monotonically decreasing temperature with pressure over the range of 1-0.001 bars at 7.7 sigma confidence. We test the robustness of our results by exploring a variety of model assumptions, including the temperature profile parameterization, presence of a cloud, and choice of Spitzer data reduction. We also introduce a new analysis method to determine the elemental abundances from the spectrally retrieved mixing ratios with thermochemical self-consistency and find plausible abundances consistent with solar metallicity (0.06-10 x solar) and carbon-to oxygen ratios less than unity. This work suggests that high-precision spectrophotometric results are required to robustly infer thermal structures and compositions of extrasolar planet atmospheres and to perform comparative exoplanetology.

La capture de CO2 par adsorption sur des solides poreux (adsorbants) est une alternative prometteuse en raison de sa sélectivité et de sa faible consommation d'énergie. Nous avons étudié l'adsorption in-situ de CO2 sur des adsorbants solides en combinant la spectroscopie infrarouge par réflexion diffuse (DRIFT) avec la thermographie infrarouge afin de mieux comprendre les mécanismes d'interaction CO2-adsorbant et ainsi optimiser sa captation dans des procédés de capture en post-combustion. La thermographie IR est utilisée pour détecter la source de chaleur transitoire provenant de la surface de l'adsorbant au cours de l'adsorption de CO2. Un modèle de transfert de chaleur a été développé afin d'estimer les chaleurs d'adsorption. Un mini réacteur conçu pour la DRIFT nous a permis d'identifier les espèces adsorbées et d'étudier leur évolution sur la surface de l'adsorbant selon la température et l'atmosphère environnante. Enfin, le couplage d'informations provenant des deux approches nous a permis l'investigation haut-débit des paramètres clefs pour le choix des adsorbants les plus performants.

The challenge to defeat diseases starting from a rapid diagnosis has been relighted by the last pandemic due to SARS-CoV-2. The development of biosensors able to recognize molecular adsorption on surfaces plays a crucial role in this issue, allowing for example to detect the presence of disease biomarkers, like specific nucleic acid sequences or antibodies, in solution. Currently, viral RNA detection relies almost exclusively on polymerase chain reaction (PCR), requiring an expensive and complex process, or on fluorescent methods using labels that could interfere with the hybridization process. We exploited spectroscopic ellipsometry (SE) label-free experiments to detect UV-Vis molecular absorptions at the monolayer level in order to develop biosensing platforms. Spectroscopic ellipsometry is a non-perturbative and extremely sensitive method for the analysis of ultrathin molecular films. Changes in polarization of a light beam upon reflection from the sample surface are detected, providing information, both quantitative and molecular-specific, on film thickness and optical properties. In fact, SE difference spectra, obtained as the difference between the spectra acquired after the molecular deposition and the spectra acquired on the bare substrate, clearly show molecular absorption fingerprints in the UV-Vis-NIR spectral range. We focus on an optical DNA-based biosensor, where DNA strands immobilized on gold can detect specific SARS-CoV-2-related RNA sequences through nucleic acid hybridization. DNA-based biosensors are an excellent option to develop micro-nano devices which are reusable thanks to the denaturation property of nucleic acids. DNA self-assembled monolayers are studied in situ and in real time through a multi-technique approach, in order to optimize the experimental protocol and design the cheaper and more efficient biosensor. The tuning of several parameters, like ssDNA immobilization time, concentration of molecular spacer solution and solution ionic strength, allowed us to highlight the subtle interplay of these factors in the DNA self-assembly process. Upon hybridization, changes in film thickness (AFM nanolithography, SE), molecular UV-Vis absorption (SE), coverage (XPS, QCM-D) are detected. In particular, SE allows to recognize the double-helix formation in situ, in a non-destructive and extremely fast way, and to detect DNA hypochromism at the monolayer level, for the first time to our knowledge. In conclusion, an accurate optical SE model, supported by AFM thickness data, allowed us to optically characterize ssDNA and dsDNA films in the whole probed wavelength region, providing a new tool for nucleic acid sequence recognition.

Il mio lavoro `e mirato allo studio delle propriet`a d’accrescimento delle sorgenti protostellari di piccola massa. La ricerca si `e basata sull’uso di due diverse tecniche osservative nel vicino infrarosso: la spettroscopia ad alta risoluzione e l’interferometria. Dall’analisi di spettri VLT/ISAAC (R = 10000) di sei sorgenti protostellari di Classe I, ho determinato la luminosit`a d’accrescimento e il tasso d’accrescimento di massa degli oggetti, facendo uso della luminosit`a delle righe Hi o attraverso la determinazione delle propriet`a stellari degli oggetti, derivate dall’osservazione delle loro righe d’assorbimento fotosferiche. Solamente due oggetti mostrano luminosit`a dominate dall’accrescimento, mentre nelle altre sorgenti solo una piccola frazione della luminosit`a totale risulta dovuta a tale processo, diversamente da quanto aspettato per sorgenti giovani di Classe I nella fase principale di accrescimento. Questo risultato tende quindi a delineare uno scenario in cui gran parte degli oggetti di Classe I sarebbero in realt`a sorgenti che hanno gi`a accumulato la maggior parte della loro massa finale e quindi pi`u evolute rispetto a quanto aspettato. Per le sorgenti che mostrano la presenza di jet protostellari `e stato possibile calcolare il rapporto tra tasso di perdita di massa (derivato da misure spettroscopiche sui jet) e il tasso di accrescimento. I valori osservati si trovano (considerando le ampie incertezze) nell’intervallo 5%-200%, da paragonare ai valori dell’ordine del 10% predetti dai modelli teorici. Nella seconda parte del mio lavoro ho analizzato dati interferometrici acquisiti con AMBER/VLTI, con l’obiettivo di misurare la grandezza della regione di emissione delle righe Hi nella sorgente giovane Z CMa; si vuole cos`ı determinare se queste righe, spesso utilizzate come traccianti del processo d’accrescimento, siano emesse effettivamente dal gas nei flussi di accrescimento o se provengano invece da un vento protostellare. Un semplice modello della sorgente `e stato sviluppato sia per la preparazione delle osservazioni, sia per l’interpretazione delle misure. Sfortunatamente, il rapporto segnale rumore molto basso che caratterizza i dati (dovuto con tutta probabilit`a a problemi tecnici durante le osservazioni) permette solo un’interpretazione di massima delle misure, le quali tenderebbero tuttavia ad indicare che le righe d’emissione dell’idrogeno provengono da un vento protostellare. I metodi adottati per l’analisi dei dati hanno portato allo sviluppo di una procedura di riduzione capace di filtrare segnali spuri dovuti al rivelatore, che contaminano fortemente il segnale interferometrico in osservazioni caratterizzate da flussi molto bassi. Questa procedura sar`a presto inserita nel paccheto software ufficiale per la riduzione dati, distribuito dal consorzio AMBER.
I present a work aiming at studying the accretion properties low mass embedded protostars making use of two observational techniques: near IR high resolution spectroscopy and inteferometry. Through the analysis of VLT/ISAAC near infrared spectra (R = 10000) of a sample of six Class I protostars, I have derived the accretion luminosity and mass accretion rates of the objects, using either the luminosity of Hi lines or determining the stellar properties from detection of the photospheric absorption lines. Only two objects show accretion-dominated luminosities, while in the other sources accretion accounts for only a smal fraction of the total luminosity, in spite of what is commonly expected for Class I stars in the main accretion phase. These findings therefore indicate a scenario where most Class I objects are more evolved than expected and have actually already acquired most of their mass. For sources displaying well developed jet-like structures, the ratio between mass loss (derived from spectral measurements on the jet) and mass accretion rates has been computed; the inferred ratios span (considering the large uncertainties) in the range 5%-200%, to be compared with a 10% value from theoretical models. VLTI/AMBER observations have been analysed in the second part of the work with the aim of measuring the size of the Hi line emission region in the young source Z CMa, thus discriminating between an accretion or wind origin for such emission lines, often used as a tracer for accretion. A simple model of the source has been developed to derive the expected visibility curves needed to plan the observations and interpret them. Unfortunately, the very low signal-to-noise ratio characterising the data, most probably due to technical problems during observations at the VLTI, allows only a tentative interpretation of the measurements, which however tends to indicate a wind origin of the emission. Nevertheless, the methods adopted for the reduction of the AMBER data have led to the development of a reduction procedure able to filter out spurious signals from the detector that heavily bias this kind of very low flux data. This procedure will be soon implemented in the official data reduction software of the instrument.

Noise-immune cavity-enhanced optical heterodyne molecular spectroscopy, NICE-OHMS, is a laser-based spectroscopic detection technique that comprises the concepts of frequency modulation (FM, for reduction of 1/f-noise by detecting the signal at a high frequency) and cavity enhancement (CE, for a prolongation of the optical path length) in a unique way. Properly designed, this gives the technique an intrinsic immunity against the frequency-to-noise conversion that limits many other types of CE techniques. All this gives it an exceptionally high sensitivity for detection of molecular species. Although originally developed for frequency standard purposes in the late 1990s, soon thereafter development of the technique towards molecular spectroscopy and trace gas detection was initiated. This thesis focuses on the further development of Doppler- broadened NICE-OHMS towards an ultra-sensitive detection technique. A number of concepts have been addressed. A few of these are: i) The detection sensitivity of fiber-laser-based NICE- OHMS has been improved to the 10−12 cm−1 range, which for detection of C2H2 corresponds to a few ppt (parts-per-trillion, 1:1012) in gas phase, by improving the locking of the laser to a cavity mode by use of an acousto-optic modulator. ii) It is shown that the system can be realized with a more compact footprint by implementation of a fiber-optic circulator. iii) A systematic and thorough investigation of the experimental conditions that provide maximum signals, referred to as the optimum conditions, e.g. modulation and demodulation conditions and cavity length, has been performed. As a part of this, an expression for the NICE-OHMS line shape beyond the conventional triplet formalism has been proposed and verified. iv) To widen the applicability of NICE-OHMS for detection of pressure broadened signals, also a setup based upon a distributed-feedback (DFB) laser has been realized. v) In this regime, the Voigt profile cannot model signals with the accuracy that is needed for a proper assessment of analyte concentrations. Therefore, the thesis demonstrates the first implementations of line profiles encompassing Dicke narrowing and speed-dependent effects to NICE-OHMS. While such profiles are well-known for absorption, there were no expressions available for their dispersion counterparts. Such expressions have been derived and validated by accompanying experiments. vi) The applicability of the technique for elemental detection, then referred to as NICE-AAS, has been prophesied.
Brusimmun kavitetsförstärkt optisk-heterodyndetekterad molekylärspektroskopi (NICE-OHMS) är en laser-baserad spektroskopisk teknik som förenar frekvensmodulation (för reducring av 1/f-brus genom detektion vid en hög frekvens) och kavitetsförstärkning (KF, för en förlängning av den optiska väglangden) på ett unikt sätt. Korrekt realiserad uppvisar tekniken en inneboende immunitet mot omvandling av frekvensbrus till intensitetsbrus som många andra KF-tekniker är begränsade av. Allt detta ger tekniken en exceptionellt hög känslighet för molekyldetektion. Ursprungligen utvecklad för frekvensstandardändamål i slutet av 1990, har den sedan dess utvecklats för molekylspektroskopi och spårgasdetektering. Denna avhandling fokuserar på vidareutvecklingen av NICE-OHMS mot en tillämpbar, ultrakänslig detektionsteknik. Ett antal koncept har adresserats. Några av dessa är: i) Detektionskänsligheten hos fiberlaserbaserad NICE-OHMS har förbättrats till 10-12 cm-1 området, vilket för detektion av C2H2 i gasfas motsvarar några få ppt (parts per biljon, 1:1012), genom att förbättra låsningen av lasern till en kavitetsmod med hjälp av en akustooptisk modulator. ii) Det har demonstrerats att NICE-OHMS kan realiseras mer kompakt med hjälp av en fiber-kopplad optisk cirkulator. iii) En systematisk och grundlig utredning av de experimentella förhållanden som ger maximala signaler, betecknade de optimala förhållanden, t.ex. modulering och demodulering och kavitetslängden, har utförts. Som ett led i detta har ett uttryck för NICE-OHMS linjeform bortom den konventionella triplett formalismen föreslagits och verifierats. iv) För att bredda tillämpbarheten av NICE-OHMS för detektering av tryckbreddade signaler har även en instrumentering baserad på en distribuerad-återkopplad (eng. distributed feedback, DFB) laser realiserats. v) I detta område kan inte Voigt profilen modellera signalen med den noggrannhet som krävs för en korrekt bedömning av analytkoncentrationer. Därför visar avhandlingen de första implementeringarna i NICE-OHMS av linjeprofiler som inkluderar Dicke avsmalning (eng. Dicke narrowing) och hastighetsberoende effekter (eng. speed-dependent effects). Emedan sådana profiler är välkända för absorption, fanns det inga uttryck för deras dispersiva motparter. Sådana uttryck har därför härletts och validerats av medföljande experiment. vi) Tillämpbarheten av tekniken för detektion av atomer, NICE-AAS, har diskuterats och förutspåtts.

Ytterligare forskningsfinansiär: Kempestiftelserna

Dans le cadre d'un axe d'orientation de la loi Bataille sur la gestion des déchets nucléaires, des expériences ont été menées dans le réacteur à neutrons rapides Phénix. Certaines d'entre elles ont consisté en l'irradiation de plusieurs poudres enrichies en un isotope. Ces irradiations vont permettre, par détermination de la composition élémentaire et isotopique de ces échantillons, d'obtenir des données nucléaires de base afin d'étudier la faisabilité de la transmutation. Un des enjeux du projet provient du fait que de faibles quantités de poudres ont été initialement introduites et en conséquence certains produits issus de l'irradiation sont présents en très faibles quantités (nanogramme). L'objectif de cette étude est le développement de méthodes analytiques innovantes pour l'analyse de ces faibles quantités par spectrométrie de masse à thermo-ionisation, technique dans laquelle l'échantillon est déposé sur un filament métallique en vue de son évaporation, son ionisation et sa séparation en masse. Quatre grands axes d'étude ont ainsi été explorés : i) le développement de méthode d'analyse en consommation totale avec traitement des données obtenues, ii) l'étude des potentialités pour la mesure isotopique de nouveaux systèmes de détecteurs, iii) l'étude des techniques de dépôt de l'échantillon sur le filament afin d'améliorer la robustesse de la technique, et iv) enfin la comparaison des données obtenues avec d'autres techniques de spectrométrie de masse. Ces développements ont permis d'analyser des quantités de l'ordre du nanogramme sur des échantillons issus des expériences d'irradiation avec des incertitudes en adéquation avec les attentes des neutroniciens. Au-delà de l'atteinte des objectifs analytiques, cette étude a permis de proposer une technique de dépôt homogène de l'échantillon sur le filament et qui améliore la robustesse de la méthode pour des quantités déposées de l'ordre du nanogramme. De plus, des premières mesures sur des multiplicateurs d'électrons en consommation totale ont été réalisées et ont permis de mesurer des quantités allant jusqu'à quelques centaines de femtogrammes. Plusieurs échantillons irradiés mais aussi des échantillons naturels d'eaux de rivières ont pu être analysés en utilisant les procédures analytiques mises en place et ont fait l'objet d'une comparaison avec une autre technique analytique la spectrométrie de masse à source plasma et système multicollection
In the framework of the French transmutation project of nuclear wastes, experiments consisted in the irradiation in a fast neutron reactor of few milligrams of isotopically enriched powders. Hence, the isotopic analysis of very small amount of irradiation products is one of the main issues. The aim of this study was to achieve analytical developments in thermal ionization mass spectrometry in order to accurately analyze these samples. Several axes were studied including the new total evaporation method, deposition techniques, electron multiplier potentialities and comparison between different isotope measurement techniques. Results showed that it was possible to drastically decrease the amounts needed for analysis, especially with Eu and Nd, while maintaining an uncertainty level in agreement with the project requirements

L'étude de la dynamique hors équilibre des systèmes fortement corrélés, à l'aide de laser femtoseconde, a révélé une variété de phénomènes sans analogue en physique d'équilibre. Dans cette thèse, nous étudions théoriquement la dynamique hors équilibre des degrés de liberté du réseau et leur signature en spectroscopie pompe-sonde. Nous développons une description microscopique des phonons cohérents displacive excité par le laser. La théorie capture la rétroaction de l'excitation des phonons sur le fluide électronique, qui manque dans la formulation phénoménologique actuelle. Nous montrons que cette rétroaction conduit à une oscillation avec une fréquence qui dépend du temps aux temps courts, même si le mouvement des phonons est harmonique. Pour les temps longs, cette rétroaction apparaît comme une phase résiduelle dans le signal oscillatoire. Nous appliquons la théorie au BaFe2As2, nous expliquons l'origine de la phase du signal oscillatoire rapporté dans des expériences récentes, et nous prédisons que le système oscille avec une fréquence décalé vers le rouge pour les grandes fluences. Notre théorie ouvre également la possibilité d'extraire des informations d'équilibre à partir la dynamique des phonons cohérents. Un autre phénomène intéressant qui a été observé en spectroscopie pompe-sonde est l'oscillation des fluctuations du réseau au double de la fréquence d’un phonon du système étudié. Ces oscillations sont interprétées comme une signature d'états de phonons squeezé macroscopique. Dans ce travail, nous identifions d'autres mécanismes d'oscillations à une fréquence double autre que le squeezing. Nous montrons qu'un quench de la température du bain thermique induite par la pompe, à laquelle le phonon est couplé, ou l'excitation d'un phonon cohérent pour lequel l'anharmonicité cubique est permise par symétrie peut également produire de telles oscillations en spectroscopie sans que le phonon soit dans un état squeezé. Nous concluons que, contrairement à ce qui est communément admis, les oscillations à double fréquence phononique en spectroscopie de bruit ne sont pas nécessairement une signature des phonons squeezés. Nous soulignons ce qui peut être un critère fiable pour identifier un phonon squeezé en utilisant la spectroscopie pompe-sonde
The study of the out of equilibrium dynamics of strongly correlated systems, using ultrafast pulses, uncovered a plethora of phenomena with no analog in equilibrium physics. In this thesis, we theoretically investigate the out of equilibrium dynamics of the lattice degrees of freedom and their signature in pump-probe spectroscopy. We develop a Hamiltonian-based microscopic description of laser pump induced displacive coherent phonons. The theory captures the feedback of the phonon excitation upon the electronic fluid, which is missing in the state-of-the-art phenomenological formulation. We show that this feedback leads to chirping at short timescales, even if the phonon motion is harmonic. At long times, this feedback appears as a finite phase in the oscillatory signal. We apply the theory to BaFe2As2, explain the origin of the phase in the oscillatory signal reported in recent experiments, and we predict that the system will exhibit redshifted chirping at larger fluence. Our theory also opens the possibility to extract equilibrium information from coherent phonon dynamics. Another interesting phenomenon that have been reported in pump-probe spectroscopy is the oscillation of the lattice fluctuations at double phonon frequency. These oscillations are invariably interpreted as a signature of macroscopic squeezed phonon states. In this work, we identify other mechanisms of double phonon frequency oscillations that do not involve squeezing. We show that a pump induced temperature quench of the bath, to which the phonon is coupled to, or exciting a coherent phonon for which cubic anharmonicity is allowed by symmetry can also produce such oscillations in noise spectroscopy without squeezing the phonon state. We conclude that, in contrast with what is commonly believed, double phonon frequency oscillations in noise spectroscopy are not necessarily a signature of macroscopic phonon squeezing. We point out what can be a reliable criterion to identify a squeezed phonon using pump-probe spectroscopy

M dwarfs constitute around 70% of all stars in the local Galaxy. Their multitude together with their long main-sequence lifetimes make them important for studies of global properties of the Galaxy such as the initial mass function or the structure and kinematics of stellar populations. In addition, the exoplanet community is showing an increasing interest for those small, cold stars. However, very few M dwarfs are well characterized, and in the case of exoplanetary systems the stellar parameters have a direct influence on the derived planet properties. Stellar parameters of M dwarfs are difficult to determine because of their low surface temperatures that result in an optical spectrum dominated by molecular lines. Most previous works have therefore relied on empirical calibrations. High-resolution spectrographs operating in the infrared, a wavelength region less affected by molecular lines, have recently opened up a new window for the investigation of M dwarfs. In the two first papers of this thesis we have shown that we can determine the metallicity, and in some cases the effective temperature, using synthetic spectral fitting with improved accuracy. This method is time consuming and therefore not practical or even feasible for studies of large samples of M dwarfs. When comparing our results from the high-resolution studies with available photometric calibrations we find systematic differences. In the third paper we therefore used our sample to determine a new photometric metallicity calibration. Compared to previous calibrations our new photometric calibration shows improved statistical characteristics, and our calibration gives similar results as spectroscopic calibrations. In a comparison with theoretical calculations we find a good agreement of the shapes and slopes of iso-metallicity lines with our empirical relation. Applying the photometric calibration to a sample of M dwarfs with confirmed exoplanets we find a possible giant planet-metallicity correlation for M dwarfs.

This dissertation has focused on the solid-state characterization of different co-crystal system as well as the effect of co-crystallization of these systems on pharmaceutical dosage form performance. Urea/ 2-MB, caffeine/ malonic acid, caffeine/ oxalic acid and theophylline/ malonic acid co-crystals were prepared using co-grinding- and co-precipitation techniques. In addition, the synthesis of co-crystals through two novel methods has been demonstrated. This includes compaction and convection mixing. The solid-state characterization of the co-crystals has been carried out using XRPD, Raman spectroscopy, DSC, TGA, hot-stage microscopy and SEM. After preparation of co-crystals, tablets have been produced from co-ground-, co-precipitated-, and physical mixtures using Compaction Studies Press (Kaleva), and the data were recorded to compare between the different mixtures, regarding compactibilty, compressibility and deformational properties. The DSC results showed that the physical mixtures of all systems, formed co-crystals during heating process. For systems of urea/ 2-MB, caffeine/ malonic acid and theophylline/ malonic acid, the co-ground mixture produced tablets with higher tensile strength compared with either co-precipitated or physical mixture. However, for caffeine/ oxalic acid system, the tensile strengths of compacts produced from the physical mixture were greater than those obtained from either co-ground or co-precipitated mixtures. The Heckel data suggested that urea/ 2-MB, caffeine/ malonic acid and theophylline/ malonic acid systems are Type 1 materials, as an extensive linearity during compression was indicative of a plastic deformation mechanism, while the caffeine/ oxalic acid system was Type 2 materials. However, the co-precipitated mixture of urea/ 2-MB system was the least compressible, as it possessed the greatest value of yield pressure (85 MPa) and the highest elastic recovery (7.42%). The co-precipitated mixture of both of caffeine/ malonic acid and theophylline/ malonic acid systems was the most compressible with small yield pressure values of (44 & 80 MPa) and elastic recovery of (7.2% & 6.56%), respectively. The co-ground mixture of caffeine/ oxalic acid possessed the highest value of yield pressure (166 MPa) and thus the lowest compressibility among other mixtures. Furthermore, the addition of microcrystalline cellulose and α-lactose monohydrate has affected the crystallinity as well as the tableting properties of the co-crystals. After the addition of excipients, the tensile strength of compacts was about 2 times higher than any other mixture. Finally, urea/ 2-MB and caffeine/ malonic acid co-crystals were successfully synthesized through convection mixing and compaction.

This dissertation has focused on the solid-state characterization of different co-crystal system as well as the effect of co-crystallization of these systems on pharmaceutical dosage form performance. Urea/ 2-MB, caffeine/ malonic acid, caffeine/ oxalic acid and theophylline/ malonic acid co-crystals were prepared using co-grinding- and co-precipitation techniques. In addition, the synthesis of co-crystals through two novel methods has been demonstrated. This includes compaction and convection mixing. The solid-state characterization of the co-crystals has been carried out using XRPD, Raman spectroscopy, DSC, TGA, hot-stage microscopy and SEM. After preparation of co-crystals, tablets have been produced from co-ground-, co-precipitated-, and physical mixtures using Compaction Studies Press (Kaleva), and the data were recorded to compare between the different mixtures, regarding compactibilty, compressibility and deformational properties. The DSC results showed that the physical mixtures of all systems, formed co-crystals during heating process. For systems of urea/ 2-MB, caffeine/ malonic acid and theophylline/ malonic acid, the co-ground mixture produced tablets with higher tensile strength compared with either co-precipitated or physical mixture. However, for caffeine/ oxalic acid system, the tensile strengths of compacts produced from the physical mixture were greater than those obtained from either co-ground or co-precipitated mixtures. The Heckel data suggested that urea/ 2-MB, caffeine/ malonic acid and theophylline/ malonic acid systems are Type 1 materials, as an extensive linearity during compression was indicative of a plastic deformation mechanism, while the caffeine/ oxalic acid system was Type 2 materials. However, the co-precipitated mixture of urea/ 2-MB system was the least compressible, as it possessed the greatest value of yield pressure (85 MPa) and the highest elastic recovery (7.42%). The co-precipitated mixture of both of caffeine/ malonic acid and theophylline/ malonic acid systems was the most compressible with small yield pressure values of (44 & 80 MPa) and elastic recovery of (7.2% & 6.56%), respectively. The co-ground mixture of caffeine/ oxalic acid possessed the highest value of yield pressure (166 MPa) and thus the lowest compressibility among other mixtures. Furthermore, the addition of microcrystalline cellulose and α-lactose monohydrate has affected the crystallinity as well as the tableting properties of the co-crystals. After the addition of excipients, the tensile strength of compacts was about 2 times higher than any other mixture. Finally, urea/ 2-MB and caffeine/ malonic acid co-crystals were successfully synthesized through convection mixing and compaction.
Islamic University of Omdurman and the Ministry of Higher Education in Sudan

Le DNA topoisomerasi sono enzimi che catalizzano il rilassamento del DNA durante importanti processi che includono la replicazione del DNA, la trascrizione, la ricombinazione e la segregazione cromosomica. In questo progetto ho analizzato le proprietà strutturali del dominio N-terminale dello enzima umano e in secondo momento ho comparato l’effetto dell’Acido eicosapentaenoico coniugato (cEPA) sull’attività della topoisomerasi umana e di quella appartenente alla L. donovani. La struttura tridimensionale dell’enzima umano è stata risolta in assenza del dominio N-terminale e quindi le sue caratteristiche strutturali sono ad oggi sconosciute. Durante lo svolgimento di questa tesi di dottorato il dominio N-terminale della topoisomerasi IB è stato espresso, purificato e caratterizzato attraverso tecniche spettroscopiche. Gli spettri CD ottenuti in funzione della concentrazione e del pH indicano che il dominio non presenta struttura secondaria. La proteina è probabilmente in uno stato detto “natively unfolded” dato anche che la sua curva di denaturazione è indicativa di una trnsizione non-cooperativa. Prove di una struttura parzialmente foldata vengono dallo spettro di fluorescenza dell’ ANS, la cui intensità aumenta in presenza del dominio. Un’indicazione di struttura parzialmente organizzata del dominio viene anche dalla fluorescenza intrinseca dei triptofani che è centrata a 350 nm nello stato nativo e slitta a 354 nm nella proteina completamente denaturata. Nonostante il basso grado di struttura, confermato anche da un’analisi bioinformatica, il dominio lega con alta efficienza il DNA, suggerendo che l’assenza di una struttura definita ha il significato funzionale di permettere al dominio di essere disponibile per l’interazione con diversi partners molecolari. La topoisomerasi umana è inibita da numerosi composti e tra questi il meglio caratterizzato è la camptotecina, che essendo un efficiente stabilizzatore dei “topoisomerase cleavable complex”, è stata largamente utilizzata come agente antitumorale. L’acido eicosapentaenoico coniugato (cEPA) è stato visto avere proprietà antitumorali che sono state ascritte alla sua capacità di inibire le DNA topoisomerasi e DNA polimerasi. In questo studio è stato dimostrato che il cEPA inibisce l’ attività catalitica della topoisomerasi IB umana, ma diversamente dalla camptotecina non stabilizza I “cleavable complex”, indicando un differente meccanismo di azione. Il cEPA inibisce la topoisomerasi impedendo il cleavage del DNA come dimostrato usando oligonucleotidi specifici come substrati, ed è in grado di prevenire la stabilizzazione dei “cleavable complex” da parte della camptotecina. La Preincubazione dell’inibitore con l’enzima è necessaria per ottenere un’inibizione completa. Tecniche simulative di “Molecular docking” indicano che il sito di legame preferenziale del cEPA è vicino al sito attivo dell’enzima, dove il gruppo carbossilico del cEPA interagisce fortemente con i residui carichi positivamente K443 e K587. Questi risultati indicano che il cEPA non impedisce il legame al DNA ma inibisce il cleavage del DNA, legandosi a una regione vicina al sito attivo della topoisomerasi. Anche l’effetto del cEPA sulla topoisomerasi proveniente da L. donovani è stato studiato dimostrando un efficienza di inibizione più alta di quella per l’enzima umano. Il cEPA mostra anche un’attività contro le cellule promastigoti della L. donovani ( EC50= 22.7 μg/ml) mentre non ha effetto contro i macrofagi murini ( IC50 > 600 μg/ml). risultati indicano che la topoisomerasi I di L. donovani può esssere considerata un interessante target molecolare e che l’acido eicosapentaenoico coniugato (cEPA) può essere preso in considerazione come possibile composto specifico contro la Leishmaniosi.
DNA topoisomerases are enzymes that catalyze the relaxation of supercoiled DNA during important processes including DNA replication, transcription, recombination and chromosome segregation. In this work I have investigated the structural properties of the N-terminal domain of the human enzyme and I have compared the effect of conjugated eicosapentaenoic acid (cEPA) on the activity of human and L. donovani topoisomerase. The 3D structure of the human enzyme has been solved in absence of the N-terminal domain and so nothing is known on its structural feature. In this thesis, the N-terminal domain of human topoisomerase IB has been expressed, purified and characterized by spectroscopic techniques. CD spectra as a function of concentration and pH indicate that the domain does not possess any defined secondary structure. The protein is probably in a natively unfolded state since its denaturation curve is indicative of a non-cooperative transition. Evidence of a partially folded structure comes from the fluorescence spectrum of ANS, whose intensity increase in presence of the domain. Indication of a partial structural arrangement of the domain comes also from the endogenous fluorescence of tryptophans that is centred at 350 nm in the native and shifts to 354 nm in the fully denaturated protein. Interestingly despite the poor degree of structural organization, as also confirmed by a predictive approach, the domain efficiently binds DNA, suggesting that the absence of a defined 3D structure has a functional meaning that permits the domain to be available for the interaction with different molecular partners. Human topoisomerase has been shown to be inhibited by several compounds and among these the best characterized one is camptothecin that, being an efficient stabilizer of the topoisomerase cleavable complex, is widely used as antitumor agent. Conjugated eicosapentaenoic acid (cEPA) has been recently found to have antitumor effects, ascribed to its ability to inhibit DNA topoisomerases and DNA polymerases. Here it is shown that cEPA inhibits the catalytic activity of human topoisomerase I, but unlike camptothecin it does not stabilize the cleavable complex, indicating a different mechanism of action. cEPA inhibits topoisomerase by impeding the catalytic cleavage of the DNA substrate as demonstrated using specific oligonucleotide substrates, and prevents the stabilization of the cleavable complex by camptothecin. Preincubation of the inhibitor with the enzyme is required to obtain complete inhibition. Molecular docking simulations indicate that the preferred cEPA binding site is proximal to the active site with the carboxylic group strongly interacting with the positively charged K443 and K587. Taken together the results indicate that cEPA does not prevent DNA binding but inhibits DNA cleavage, binding in a region close to the topoisomerase active site. The effect of cEPA on L. donovani topoisomerase has been also investigated showing an inhibitory efficiency higher than that displayed for the corresponding human enzyme. Moreover cEPA shows a strong antiprotozoal activity against L. donovani promastigotes ( EC50= 22.7 μg/ml) whilst it has no effect against murine macrophages ( IC50 > 600 μg/ml). Taken together the results indicate that L. donovani topoisomerase I can be considered an interesting molecular target and that conjugated eicosapentaenoic acid can be taken in consideration as a possible lead compound against leishmaniasis.

The thesis deals with research of pulse compression of the acoustic signal in terms of applications in civil engineering. Based on the study and analysis of these methods, automated measuring equipment for non-destructive testing with pseudorandom sequence of maximum length and automated signal analysis, have been designed and implemented. In a single test cycle are obtained three parameters that characterize the linear and nonlinear behavior of the sample. A nonlinear parameter, Time of Flight of ultrasonic wave in the sample is further in the work compared with the conventional pulse measuring, and spectral analysis is compared with the method impact-echo. Functionality and optimization of the testing method was performed on a total of three sets of test pieces made of various building materials. The experiments proved simple result interpretation, and high sensitivity to structural damage associated with temperature loading. The results were correlated with conventional nondestructive methods and by destructive testing was measured change in compressive strength and flexural strength. This work also includes continual measurement of fundamental frequency influenced by moisture on a mortar sample. Use of pulse compression signal is in the civil engineering quite unusual. Only in recent years this topic is discussed in scientific articles with increasing frequency. Great potential lies in the association of three test methods into a single. Beneficial is high test speed and measurement reproducibility, but also theoretical possibility of testing massive test elements.

Ruthenium und sein elektrisch leitfähiges Rutheniumdioxid sind viel versprechende Kandidaten als Elektrodenmaterial in MIM (Metall-Isolator-Metall-)Kondensatoren mit Dielektrika hoher Permittivität der nächsten Generation von DRAM-Speichern, als Metall-Gate-Elektroden in p-Kanal-MOS-Transistoren mit Dielektrika hoher Permittivität, oder als Keimschicht für das direkte elektrochemische Abscheiden von Kupfer-Verbindungsleitungen. Die ALD (Atomic Layer Deposition) wächst Materiallagen mit weniger als einem Zehntel Nanometer Dicke, indem sie gasförmige Reaktanden abwechselnd, getrennt durch spülende Pulse, in die Reaktionskammer einleitet. Dadurch wird mit jeder zyklischen Wiederholung idealerweise selbstbeendender Gas-Festkörper-Reaktionen stets die gleiche Materialmenge abgeschieden, bis eine gewünschte Schichtdicke erreicht ist. Wie sich die Oberfläche aufgrund der Materialabscheidung während der ALD verändert, kann mit der in-situ SE (Spektroskopische Ellipsometrie) beobachtet werden. Die Ellipsometrie misst die Änderung eines Polarisationszustands bzgl. Amplitude und Phase, nachdem ein einfallender Lichtstrahl von einer (schichtbedeckten) Oberfläche reflektiert und/ oder durch diese transmittiert wurde. Die ellipsometrischen Daten stehen im direkten Zusammenhang mit optischen Materialparametern und sind somit physikalisch interpretierbar – oder sie werden in eindimensionale strukturelle Größen, wie die Schichtdicke übersetzt. In dieser Arbeit wurden Schichten aus Ruthenium und Rutheniumdioxid aus dem Präkursor ECPR, [(Ethylcyclopentadienyl)(Pyrrolyl)Ruthenium(II)], und molekularem Sauerstoff per ALD gewachsen. Die chemischen Teilreaktionen wurden während der ALD von Ruthenium und Rutheniumoxid auf frisch abgeschiedenen Schichtoberflächen per in-situ SE, on-site QMS (Quadrupol-Massenspektrometrie) und XPS (Röntgen-Photoelektronenspektroskopie) ohne Vakuumunterbrechung untersucht. Weiterhin wurden Experimente zum Schichtwachstum auf frisch abgeschiedenen Schichten sowie einer Ausgangssubstratoberfläche per in-situ und Echtzeit SE durchgeführt, wobei die folgenden Prozessparameter variiert wurden: die jeweilige Reaktanden Dosis, die Spülpulsdauern, die Substrattemperatur und der Prozessdruck
Ruthenium and its conductive dioxide are promising candidates as electrodes in MIM (metal-insulator-metal) capacitors with high-k dielectrics of next generation DRAM (dynamic random access memory) devices, as metal-gate electrodes in pMOS-Transistors with high-k dielectrics, and as seed layer for direct electrochemical plating of copper interconnects. ALD (atomic layer deposition) grows material layers with less than a tenth of a nanometer thickness, pulsing gaseous reactants alternately into the reaction chamber, separated by purging pulses. Hence, every cyclic recurrence of ideally self-limiting gas-solid reactions deposits a fixed material amount, until the desired film thickness is achieved. So, the surface’s chemical composition changes through material deposition during ALD, observable by in-situ SE (spectroscopic ellipsometry). Ellipsometry measures the polarization state’s change in amplitude and phase, reflecting an incident light beam from and/ or transmitting it through a (film covered) surface. The ellipsometric data can be directly related to optical material parameters and are thus physically interpretable – or they are translated into one-dimensional structural values, like film thickness. In this work, ruthenium and ruthenium dioxide films were grown from ECPR, [(ethylcyclopentadienyl)(pyrrolyl)ruthenium(II)], and molecular oxygen. Reaction mechanisms during the ALD of ruthenium and ruthenium dioxide were studied on the as-deposited film surface by in-situ SE, on-site QMS (quadrupole mass spectrometry), as well as XPS (x-ray photoelectron spectroscopy) without vacuum break. Additionally, film growth experiments were performed on the as-deposited film and the initial substrate surface by in-situ and real-time SE, varying the process parameters: reactant doses, purging times, substrate temperature and total pressure

[EN] The test for determining the resonance frequencies has traditionally been used to investigate the mechanical integrity of concrete cores, to assess the conformity of concrete constituents in different accelerated durability tests, and to ascertain constitutive properties such as the elastic modulus and the damping factor. This nondestructive technique has been quite appealed for evaluation of mechanical properties in all kinds of durability tests. The damage evolution is commonly assessed from the reduction of dynamic modulus which is produced as a result of any cracking process. However, the mechanical behavior of concrete is intrinsically nonlinear and hysteretic. As a result of a hysteretic stress-strain behavior, the elastic modulus is a function of the strain. In dynamic tests, the nonlinearity of the material is manifested by a decrease of the resonance frequencies, which is inversely proportional to the excitation amplitude. This phenomenon is commonly referred as fast dynamic effect. Once the dynamic excitation ceases, the material undergoes a relaxation process whereby the elastic modulus is restored to that at rest. This phenomenon is termed as slow dynamics. These phenomena (fast and slow dynamics) find their origin in the internal friction of the material. Therefore, in cement-based materials, the presence of microcracks and interfaces between its constituents plays an important role in the material nonlinearity. In the context of the assessment of concrete durability, the damage evolution is based on the increase of hysteresis, as a result of any cracking process. In this thesis three different nondestructive techniques are investigated, which use impacts for exciting the resonant frequencies. The first technique consists in determining the resonance frequencies over a range of impact forces. The technique is termed Nonlinear Impact Resonant Acoustic Spectroscopy (NIRAS). It consists in ascertaining the downward resonant frequency shift that the material undergoes upon increasing excitation amplitude. The second technique consists in investigating the nonlinear behavior by analyzing the signal corresponding to a single impact. This is, to determine the instantaneous frequency, amplitude and attenuation variations corresponding to a single impact event. This technique is termed as Nonlinear Resonant Acoustic Single Impact Spectroscopy (NSIRAS). Two techniques are proposed to extract the nonlinear behavior by analyzing the instantaneous frequency variations and attenuation over the signal ring down. The first technique consists in discretizing the frequency variation with time through a Short-Time Fourier Transform (STFT) based analysis. The second technique consists of a least-squares fit of the vibration signals to a model that considers the frequency and attenuation variations over time. The third technique used in this thesis can be used for on-site evaluation of structures. The technique is based on the Dynamic Acousto- Elastic Test (DAET). The variations of elastic modulus as derived through NIRAS and NSIRAS techniques provide an average behavior and do not allow derivation of the elastic modulus variations over one vibration cycle. Currently, DAET technique is the only one capable to investigate the entire range of nonlinear phenomena in the material. Moreover, unlike other DAET approaches, this study uses a continuous wave source as probe. The use of a continuous wave allows investigation of the relative variations of the elastic modulus, as produced by an impact. Moreover, the experimental configuration allows one-sided inspection.
[ES] El ensayo de determinación de las frecuencias de resonancia ha sido tradicionalmente empleado para determinar la integridad mecánica de testigos de hormigón, en la evaluación de la conformidad de mezclas de hormigón en diversos ensayos de durabilidad, y en la terminación de propiedades constitutivas como son el módulo elástico y el factor de amortiguamiento. Esta técnica no destructiva ha sido ampliamente apelada para la evaluación de las propiedades mecánicas en todo tipo de ensayos de durabilidad. La evolución del daño es comúnmente evaluada a partir de la reducción del módulo dinámico, producido como resultado de cualquier proceso de fisuración. Sin embargo, el comportamiento mecánico del hormigón es intrínsecamente no lineal y presenta histéresis. Como resultado de un comportamiento tensión-deformación con histéresis, el módulo elástico depende de la deformación. En ensayos dinámicos, la no linealidad del material se manifiesta por una disminución de las frecuencias de resonancia, la cual es inversamente proporcional a la amplitud de excitación. Este fenómeno es normalmente denominado como dinámica rápida. Una vez la excitación cesa, el material experimenta un proceso de relajación por el cual, el módulo elástico es restaurado a aquel en situación de reposo. Este fenómeno es denominado como dinámica lenta. Estos fenómenos ¿dinámicas rápida y lenta¿ encuentran su origen en la fricción interna del material. Por tanto, en materiales basados en cemento, la presencia de microfisuras y las interfaces entre sus constituyentes juegan un rol importante en la no linealidad mecánica del material. En el contexto de evaluación de la durabilidad del hormigón, la evolución del daño está basada en el incremento de histéresis, como resultado de cualquier proceso de fisuración. En esta tesis se investigan tres técnicas diferentes las cuales utilizan el impacto como medio de excitación de las frecuencias de resonancia. La primera técnica consiste en determinar las frecuencias de resonancia a diferentes energías de impacto. La técnica es denominada en inglés: Nonlinear Impact Resonant Acoustic Spectroscopy (NIRAS). Ésta consiste en relacionar el detrimento que el material experimenta en sus frecuencias de resonancia, con el aumento de la amplitud de la excitación. La segunda técnica consiste en investigar el comportamiento no lineal mediante el análisis de la señal correspondiente a un solo impacto. Ésta consiste en determinar las propiedades instantáneas de frecuencia, atenuación y amplitud. Esta técnica se denomina, en inglés, Nonlinear Single Impact Resonant Acoustic Spectroscopy (NSIRAS). Se proponen dos técnicas de extracción del comportamiento no lineal mediante el análisis de las variaciones instantáneas de frecuencia y atenuación. La primera técnica consiste en la discretización de la variación de la frecuencia con el tiempo, mediante un análisis basado en Short-Time Fourier Transform (STFT). La segunda técnica consiste en un ajuste por mínimos cuadrados de las señales de vibración a un modelo que considera las variaciones de frecuencia y atenuación con el tiempo. La tercera técnica empleada en esta tesis puede ser empleada para la evaluación de estructuras in situ. La técnica se trata de un ensayo acusto-elástico en régimen dinámico. En inglés Dynamic Acousto-Elastic Test (DAET). Las variaciones del módulo elástico obtenidas mediante los métodos NIRAS y NSIRAS proporcionan un comportamiento promedio y no permiten derivar las variaciones del módulo elástico en un solo ciclo de vibración. Actualmente, la técnica DAET es la única que permite investigar todo el rango de fenómenos no lineales en el material. Por otra parte, a diferencia de otras técnicas DAET, en este estudio se emplea como contraste una onda continua. El uso de una onda continua permite investigar las variaciones relativas del módulo elástico, para una señal transito
[CAT] L'assaig de determinació de les freqüències de ressonància ha sigut tradicionalment empleat per a determinar la integritat mecànica de testimonis de formigó, en l'avaluació de la conformitat de mescles de formigó en diversos assajos de durabilitat, i en la terminació de propietats constitutives com són el mòdul elàstic i el factor d'amortiment. Esta tècnica no destructiva ha sigut àmpliament apel·lada per a l'avaluació de les propietats mecàniques en tot tipus d'assajos de durabilitat. L'evolució del dany és comunament avaluada a partir de la reducció del mòdul dinàmic, produït com resultat de qualsevol procés de fisuración. No obstant això, el comportament mecànic del formigó és intrínsecament no lineal i presenta histèresi. Com resultat d'un comportament tensió-deformació amb histèresi, el mòdul elàstic depén de la deformació. En assajos dinàmics, la no linealitat del material es manifesta per una disminució de les freqüències de ressonància, la qual és inversament proporcional a l'amplitud d'excitació. Este fenomen és normalment denominat com a dinàmica ràpida. Una vegada l'excitació cessa, el material experimenta un procés de relaxació pel qual, el mòdul elàstic és restaurat a aquell en situació de repòs. Este fenomen és denominat com a dinàmica lenta. Estos fenòmens --dinámicas ràpida i lenta troben el seu origen en la fricció interna del material. Per tant, en materials basats en ciment, la presència de microfissures i les interfícies entre els seus constituents juguen un rol important en la no linealitat mecànica del material. En el context d'avaluació de la durabilitat del formigó, l'evolució del dany està basada en l'increment d'histèresi, com resultat de qualsevol procés de fisuración. En esta tesi s'investiguen tres tècniques diferents les quals utilitzen l'impacte com a mitjà d'excitació de les freqüències de ressonància. La primera tècnica consistix a determinar les freqüències de ressonància a diferents energies d'impacte. La tècnica és denominada en anglés: Nonlinear Impact Resonant Acoustic Spectroscopy (NIRAS). Esta consistix a relacionar el detriment que el material experimenta en les seues freqüències de ressonància, amb l'augment de l'amplitud de l'excitació. La segona tècnica consistix a investigar el comportament no lineal per mitjà de l'anàlisi del senyal corresponent a un sol impacte. Esta consistix a determinar les propietats instantànies de freqüència, atenuació i amplitud. Esta tècnica es denomina, en anglés, Nonlinear Single Impact Resonant Acoustic Spectroscopy (NSIRAS). Es proposen dos tècniques d'extracció del comportament no lineal per mitjà de l'anàlisi de les variacions instantànies de freqüència i atenuació. La primera tècnica consistix en la discretización de la variació de la freqüència amb el temps, per mitjà d'una anàlisi basat en Short-Time Fourier Transform (STFT). La segona tècnica consistix en un ajust per mínims quadrats dels senyals de vibració a un model que considera les variacions de freqüència i atenuació amb el temps. La tercera tècnica empleada en esta tesi pot ser empleada per a l'avaluació d'estructures in situ. La tècnica es tracta d'un assaig acusto-elástico en règim dinàmic. En anglés Dynamic Acousto-Elastic Test (DAET). Les variacions del mòdul elàstic obtingudes per mitjà dels mètodes NIRAS i NSIRAS proporcionen un comportament mitjà i no permeten derivar les variacions del mòdul elàstic en un sol cicle de vibració. Actualment, la tècnica DAET és l'única que permet investigar tot el rang de fenòmens no lineals en el material. D'altra banda, a diferència d'altres tècniques DAET, en este estudi s'empra com contrast una ona contínua. L'ús d'una ona contínua permet investigar les variacions relatives del mòdul elàstic, per a un senyal transitori. A més, permet la inspecció d'elements per mitjà de l'accés per una sola cara.
Eiras Fernández, JN. (2016). Studies on nonlinear mechanical wave behavior to characterize cement based materials and its durability [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/71439
TESIS
Premiado

SOMMARIO Gli incendi interessano vaste aree di superficie terrestre, più di ogni altro fattore naturale di disturbo. Essi sono un fattore ecologico primario nella formazione e nell’evoluzione degli ecosistemi forestali. Gli incendi hanno un forte impatto sulla sostanza organica del suolo, sulla sua abbondanza ma anche sulla sua composizione, che può subire profonde alterazioni. Durante la combustione hanno luogo reazioni che portano alla neo-formazione di composti aromatici, più o meno condensati, ad elevata recalcitranza. Nonostante gli studi intrapresi da tempo sul tema, ad oggi rimangono molte incertezze sui cambiamenti indotti dagli incendi sulla quantità, composizione e recalcitranza della sostanza organica del suolo. Gli obbiettivi di questa ricerca sono stati: (i) attestare l’impatto, nel brevissimo periodo, che hanno due fuochi di differente intensità sulla composizione e la quantità della sostanza organica del suolo; (ii) valutare l’applicazione complementare di tecniche spettroscopiche e termiche nello studio dei cambiamenti indotti da un incendio sulla sostanza organica del suolo; (iii) stimare, sul lungo periodo, l’effetto che ha un’elevata frequenza degli incendi sulla composizione e la permanenza della sostanza organica del suolo. Le analisi svolte in questa tesi hanno prodotto diversi dati utili, contribuendo alla comprensione dell’impatto degli incendi sulla sostanza organica del suolo. Per questo studio sono stati selezionati diversi siti forestali che, recentemente o in passato, sono stati percorsi da uno o più incendi. I primi due siti studiati sono stati Orentano (Italia) e Mount Gordon (Australia). Questi due siti sono stati paragonati per mettere in risalto l’effetto di incendi di differente intensità sulla quantità e sulla composizione della sostanza organica del suolo. I risultati sono stati analizzati cercando di trovare un indice di facile utilizzo in grado di definire sinteticamente l’intensità dell’incendio percepita al livello del suolo e il grado di deterioramento di quest’ultimo. Lo studio dei principali componenti della lettiera, come gli zuccheri e la lignina, e la composizione della sostanza organica totale rilevata con analisi all’NMR, non hanno fornito alcun parametro utile a risalire al grado di intensità dell’incendio a cui il suolo è stato soggetto. A Roccastrada, Toscana, è stato analizzato un suolo bruciato utilizzando contemporaneamente tecniche termiche e spettroscopiche contraddistinte dall’essere rapide e relativamente economiche. In questo modo è stato possibile caratterizzare efficacemente alcuni importanti cambiamenti della composizione della sostanza organica del suolo indotti dal passaggio del fuoco. Il passaggio del fuoco ha comportato una significativa riduzione della frazione organica, meno resistente alla degradazione biochimica, ed un relativo arricchimento di quella più recalcitrante. In più, il passaggio del fuoco ha portato alla formazione di composti contenenti azoto re-arrangiati in strutture relativamente resistenti alla degradazione. Infine è stata analizzata una sequenza climatica/altitudinale di suoli sull’Etna per valutare l’effetto di lungo termine degli incendi sulla composizione e la stabilità della sostanza organica del suolo. Sull’Etna, alle altitudini meno elevate, dove la frequenza degli incendi è maggiore, il tempo di residenza della frazione stabile della sostanza organica, carbone compreso, si è rivelato minore che alle quote superiori, mentre è stato rilevato un accumulo della frazione meno resistente e più facilmente degradabile. Ciononostante, in alcuni casi il carbone (macroscopico) contribuiva significativamente allo stock di carbonio totale nell’intero profilo del suolo, con tempi di permanenza stimati, con la tecnica del radiocarbonio, fino a 1400-1500 anni. Quindi un’elevata frequenza degli incendi sembra avere un “potere ringiovanente” sulla sostanza organica, rimuovendo, dalla superficie dei suoli in maniera non selettiva, parte della frazione con elevati tempi di residenza e biologicamente più recalcitrante. SUMMARY Fire affects more land surfaces than any other natural disturbance. It is a major driving factor in forest ecosystems formation and evolution. It has a strong impact on soil organic matter, primarily by changing its abundance. Also, soil organic matter composition is substantially affected by fire. During the combustion, many reactions take place, leading to the formation of thermally-condensed aromatic compounds characterised by high recalcitrance. However, there are still many uncertainties and contrasting results dealing with fire-induced changes in soil organic matter abundance, composition and recalcitrance. The aims of this study were: (i) assessing the immediate impact of two wildfires of different severity on soil organic matter composition and abundance; (ii) evaluating the complementary application of thermal and spectroscopic techniques to assess fire-induced changes to soil organic matter; (iii) estimating the long-term effect of a high fire frequency on soil organic matter composition and stability. This investigation provided useful information and contributes to the understanding of the overall impact of fire on soil organic matter. To carry out this study, we selected some forest sites that have been affected by one or more recent or past wildfires. Two sites, Orentano (Italy) and Mount Gordon (Australia), were contrasted to highlight the effect of wildfires of different severity on soil organic matter abundance and composition. The results were further analysed to find a possible reliable index of fire severity in soil, eventually useful to define the damage degree of soil quality or charring degree of necromass. Biogeochemical parameters, such as soil sugar and lignin contents and composition, as well as the black carbon spectroscopic properties, did not result useful for this purpose. At Roccastrada, Tuscany, Italy, the soil of a burnt pine forest was investigated by using a set of thermal and spectroscopic – rapid and cheap – techniques, that efficaciously characterised some important fire-induced changes in soil organic matter composition. They provided indications also on the burning temperatures occurred in soil. Fire produced a substantial reduction in the most labile organic fraction and a relative enrichment in recalcitrant organic matter. Additionally, the fire led to the formation of nitrogen-bearing compounds characterised by a fairly resistant structure. A topo-climosequence on Mt. Etna was finally analysed for estimating the long-term effect of wildfires on soil organic matter composition and stability. The residence time of the stable soil organic matter fraction – charcoal included – decreased from high to lower elevations, where fire frequency is higher. At lower elevations, labile organic matter, more easily degradable, accumulated in the mineral soil. Macroscopic charcoal fragments were present in significant amounts in the soil profile, showing radiocarbon ages up to 1400-1500 years. High fire frequency resulted to act as a powerful rejuvenating factor to soil organic matter, removing part of the very old, biologically recalcitrant organic matter from the surface horizons.

碩士
國立臺灣海洋大學
光電科學研究所
93
We have determined the complex conductivity and the refractive indices of GaN and InGaN/GaN MQWs LED by terahertz time-domain spectroscopy. Frequency dependent electron dynamics, power absorption and dispersion are obtained over the frequency range from 0.1 to 3.0THz. The index of refraction of the GaN film varies from 10.0 to 2.6. The power absorption of the GaN film varies from 62mm-1 to 230mm-1.The real conductivity of the GaN film varies from 19.2/Ωcm to 13.4/Ωcm. The transmission measurements of the GaN film are fit by simple Drude model. We obtain the plasma frequency and the carrier damping rate of the GaN film are 11.64THz and 3.92THz, respectively. The index of refraction of the InGaN/GaN MQWs LED varies from 11.0 to 2.9. The power absorption of the InGaN/GaN MQWs LED varies from 65mm-1 to 252mm-1. The real conductivity of the InGaN/GaN MQWs LED varies from 23.2/Ωcm to 12.4/Ωcm. The transmission measurements of the InGaN/GaN MQWs LED are fit by simple Drude model. We obtain the plasma frequency and the carrier damping rate of the InGaN/GaN MQWs LED are 11.31THz and 3.08THz, respectively.

碩士
國立清華大學
物理學系
91
We use mode-locked Ti:Sapphire Laser, wavelength 800nm, after being chirped pulse amplification and splitted, the power of per pulse is 12.8GW, pulse width 130fs, to pump insulated GaAs witch biased by DC voltage, and generate THz pulse with pulse width 5ps.We can get the time-domain spectroscopy of THz by electro-optic sampling. We let the THz signal pass through Ba2(Ti1-xSnx)9O20 x=0，0.024 sintered 4hrs and calculate the dielectric constant by effective-medium theory, and we compare the result with the dielectric constant at microwave range (4GHz). After that, we get several conclusions：1.The dielectric constants of the powdered samples are similar to sintered samples (about 39.5 and 38). 2.At the rage 0.1THz~0.6THz (besides 0.2TH), we also get the result that the Q values of x=0.024 are higher. 3.The power absorption coefficients of x=0 and 0.024 are different obviously, this may be caused by sintered or not. Application of THz Time-domain Spectroscopic Technique in Powdered Samples

A 3D wavelet based encoding spectroscopic method (WE-SI) is investigated and implemented on a 3 Tesla Siemens Scanner. Compared to CSI, the proposed method is able to reduce acquisition time, and preserves the spatial metabolite distribution. As expected, a decrease in Signal to Noise Ratio (SNR) is noticed in WE-SI data compared to CSI. The dissertation explores important physical principles in MRI and spectroscopic imaging as a background, following by introduction of the wavelet encoding theory and comparison to Fourier encoding.

Raman microscopy holds potential advantages over spectroscopic techniques like nuclear magnetic resonance and infrared spectroscopy. These include minimum sample preparation and fast measurement times. When used as an imaging technique (Raman microscopy) the spatial resolution is an additional advantage over infrared microscopy. The aspects of sample preparation and measurement times have been exploited to quantify the comonomer content in ethylene/1-olefin copolymers. In the thesis the aspect of spatial resolution has been explored for crosslinked ethylene/vinyl acetate (EVA) laminates and welds between polypropylene (PP). The results are summarized in the following: Quantifying the comonomer content in ethylene-1-olefin copolymers is important to develop structure property↔relationships and unambiguously identify samples. Nuclear magnetic resonance spectroscopy has been widely used for this purpose, but quantitative measurements require significant amounts of sample, therefore limiting its scope for cases, where measurements are limited by the amount of sample available, such as liquid chromatography or forensics. In this study, experimental protocols for Raman spectroscopy have been developed to quantify the comonomer content in copolymers of ethylene and even numbered 1-olefins, ranging from 1-hexene to 1-octadecene. With increasing comonomer content the spectra reflect the combined effect of the decrease in ethylene content, the associated changes in the phase composition of polyethylene and the scattering from the comonomer sequences. The band ensemble characteristic for the comonomer itself cannot be used for quantification alone since the intensity of the spectra is affected by the sample focus and the spectral acquisition time. Therefore an internal standard for normalizing the intensity of the band ensemble is required, and the intensity of the band at 1295 cm-1 in the C-C twisting region was found to be appropriate for this purpose. This method has also been extended for determining the comonomer content of a cyclic olefin copolymer (ethylene/norbornene) having low crystallinity where the bands arising due to scattering from the comonomer sequences start dominating. Hence, the Raman spectra of copolymers of ethylene with 1-olefins ranging from 1-butene to 1-octadecene and the cyclic norbornene have been analyzed and a method has been developed to quantify the comonomer content. Due to the minimal sample preparation, fast spectral acquisition time and its non-destructive nature, the Raman spectroscopic approach holds potential for quality control. A strong need for such a technique also exists in liquid chromatography where the amounts of sample acquired are regularly very small. EVA resins are widely used as encapsulant for photovoltaic modules and the degree of crosslinking plays a critical role in the cell efficiency. A crucial question when developing processproperty relationships for the process of encapsulation is, how the degree of crosslinking, XC, is spatially distributed i.e., identifying inhomogeneities in the latter. Techniques such as DSC, FT-IR spectroscopy and Soxhlet extraction have been previously used for this purpose. Yet, all these approaches lack spatial resolution per se, as they are limited to bulk differences in XC, and local inhomogeneities are averaged out. In the investigations it could be shown that the sensitivity of FT-IR and DSC analysis, which is based on analyzing the amount of residual crosslinker, limits their applicability. In the present study a method based on Raman microscopy has been developed to study local variations in crosslinking of EVA laminates using model sheets crosslinked between Teflon sheets. The intensity of the respective νCH2 vibration at 2934 cm-1 and the νCH3 vibration at 2885 cm-1 reflect the transformation of the methyl groups of the VA comonomer into methylene bridges as a consequence of crosslinking, and thus the conversion. Yet, this information is of relative nature, and to translate it into absolute values, a calibration was carried out using a non-crosslinked EVA sample and the results from Soxhlet extraction for a highly crosslinked sample as reference points. The developed method has then been applied to study crosslinking inhomogeneities in EVA/glass laminates. In this case the quantification of crosslinking yielded significantly higher values for XCR compared to the model EVA laminates. This can be explained by differences in the cooling pattern of the glass laminate, leading to the formation of multiple crosslinks, which are then recorded by Raman spectroscopy. This demonstrates the limitations for transferring results from a model system to the real process. PP is widely used to produce pipes for civil engineering and construction. However processing of PP regularly leads to anisotropies induced in the melt due to shearing which in the solidified product embody themselves in the form of variations in the degree of crystallinity (Xc), the chain orientation and the polymorphic composition. The spatial variations induced in the polymer morphology have been identified and analyzed through the Raman spectrum of the α- and β-polymorph of PP. Changes in the form of band shifts distinct for the specific polymorph (β polymorph at 809 and 841 cm-1) have been seen and a new method has been developed which can selectively ascertain the presence of the α polymorph in PP plates. A method for qualitatively determining the differences in the crystallinity across the spherulites has been developed using the shift in the position of the band at 2954cm-1. This method has been used to compare the crystallinity profiles for both polymorphs. PP welds show a large impact of the processing conditions on the morphology and thereby act as weak spots susceptible to rupture under application of load. Measurements using techniques such as DSC and FT-IR microscopy are limited to the high step width in measurements and intricate changes across the weld seams are averaged out. These were investigated with Raman microscopy and a gradient of ~18 % in the degree of crystallinity was seen to be present in narrow channels across the weld seams. The effect of the welding on the morphology was also investigated and the cooling time in the weld core region favored the formation of the β-polymorph, which was identified and profiled using spectral band shifts. A binate weld system of a PP homopolymer (PP-H) and a propylene copolymer with ethylene (PP-R) was investigated to study these morphological variations occurring across the welds comprising of two different materials. The crystallinity in the PP-R region of the weld core was affected more in this case and no formation of the β-polymorph was observed in the weld core region from PP-H. The weld core belonging to PP-H, however, showed a similar profile as observed for the previous sample. Using Raman microscopy it was also possible to map the spatial distribution of the two polymers and a clear boundary separating them was observed, indicating that no intercalation of the two components takes place upon welding. The above work shows the prospects of utilizing Raman microscopy for characterization of plastic materials. The experimental protocols can be implemented in quality control of ethylene/1-olefins copolymers with regard to comonomer content. The homogeneity of crosslinking in EVA modules impacting the solar cell behavior can for the first time be determined at a μm level. The impact of the processing parameters on the morphology and crystallinity of PP welded materials have been analyzed and analytical information which could not be retrieved previously can now be accessed easily.

博士
靜宜大學
應用化學系
104
The substituent effect on azo-hydrazone tautomerization of 1-aryldiazo-2-naphthalenol is studied by means of NMR and MS analysis. Among the 13C chemical shifts, the C(2) of this series compound is the most sensitive to the variation in the nature of substituent on the phenyl ring. Therefore, the variation in the chemical shifts of C(2) is used to probe the substituent effect by using the substituent chemical shifts and free energy vs. Hammett’s constant (σ+). Both methods give a negative correlation slope, which are ρ=-8.74 and ρ=-1.38 , indicating the electron-withdrawing groups favor the hydrazone tautomer form. The effect on the chemical shifts of C(2) of 1-phenyldiazo-2-naphthalenol in ten solvents can be classified as the solvent with a proton-donor, proton-acceptor and arenes system. The substituent with electron-donating character is more sensitive to the nature of solvent and it favors the azo form. Free energy obtained from the dynamic NMR technique indicates the tautomerization favors the hydrazone-form for the substituent with electron-withdrawing character. The relaxation time of carbon are slight affected by the size of substituents. In the viscosity study, an inverse-law relationship between relaxation times and viscosity was observed. An electron-ionization (EI) mass spectra of a series of 1-aryldiazo-2-naphthalenol was obtained for studying the substituent effect on the fragmentation. The correlation between the ratio, molecular ion and fragment ion, and Hammett’s constants is applied to examine the effect of the substituent on the fragmentation. The negative correction between the ratio, Imolecular ion/(I171amu + I143amu + I115amu), and Hammett’s constants, which is ρ=-0.778, indicates an electron-withdrawing group destabilized the molecular ion. An unusual long-range hydrogen transfer demonstrates an important role in the fragmentation process.

abstract: Interpreting the petrogenesis of materials exposed on the surface of planets and asteroids is fundamental to understanding the origins and evolution of the inner Solar System. Temperature, pressure, fO2, and bulk composition directly influence the petrogenetic history of planetary surfaces and constraining these variables with remote sensing techniques is challenging. The integration of remote sensing data with analytical investigations of natural samples, lab-based spectroscopy, and thermodynamic modelling improves our ability to interpret the petrogenesis of planetary materials. A suite of naturally heated carbonaceous chondrite material was studied with lab-based spectroscopic techniques, including visible near-infrared and Fourier transform infrared reflectance spectroscopy. Distinct mineralogic, and thus spectroscopic, trends are observed with increasing degree of thermal metamorphism. Characterization of these spectral trends yields a set of mappable parameters that will be applied to remotely sensed data from the OSIRIS-REx science payload. Information about the thermal history of the surface of the asteroid Bennu will aid in the selection of a sampling site, ensuring OSIRIS-REx collects a pristine regolith sample that has not experienced devolatilization of primitive organics or dehydration of phyllosilicates. The evolution of mafic magma results in distinct major element chemical trends. Mineral assemblages present in evolved volcanic rocks are indicators of these processes. Using laboratory spectroscopic analyses of a suite of evolved volcanic rocks from the Snake River Plain, Idaho, I show that these evolutionary trends are reflected in the spectral signatures of ferromagenesian and feldspar minerals. The Athena science package on the Mars Exploration Rover Spirit allows for the in situ investigation of bulk chemistry, texture, and mineralogy on the surface of Mars. Using the bulk composition of the Irvine and Backstay volcanic rocks, thermodynamic modeling was performed to further constrain the formation conditions of Martian volcanics. Irvine and Backstay compositions exhibit dramatic variations in modal mineralogy with changing fO2. Using these results, I show that the observed Mini-TES spectra of Irvine and Backstay can be adequately reproduced, and additional constraints can be placed on their primary fO2.
Dissertation/Thesis
Doctoral Dissertation Geological Sciences 2018

Continual scaling of devices and on-chip wiring has brought significant challenges for materials and processes beyond the 32-nm technology node in microelectronics. Recently, three-dimensional (3-D) integration with through-silicon vias (TSVs) has emerged as an effective solution to meet the future interconnect requirements. Among others, thermo-mechanical reliability is a key concern for the development of TSV structures used in die stacking as 3-D interconnects. In this dissertation, thermal stresses and interfacial reliability of TSV structures are analyzed by combining analytical and numerical models with experimental measurements. First, three-dimensional near-surface stress distribution is analyzed for a simplified TSV structure consisting of a single via embedded in a silicon (Si) wafer. A semi-analytic solution is developed and compared with finite element analysis (FEA). For further study, the effects of anisotropic elasticity in Si and metal plasticity in the via on the stress distribution and deformation are investigated. Next, by micro-Raman spectroscopy and bending beam technique, experimental measurements of the thermal stresses in TSV structures are conducted. The micro-Raman measurements characterize the local distribution of the near-surface stresses in Si around TSVs. On the other hand, the bending beam technique measures the average stress and viii deformation in the TSV structures. To understand the elastic and plastic behavior of TSVs, the microstructural evolution of the Cu vias is analyzed using focused ion beam (FIB) and electron backscattering diffraction (EBSD) techniques. To study the impacts of the thermal stresses on interfacial reliability of TSV structures, an analytical solution is developed for the steady-state energy release rate as the upper bound of the driving force for interfacial delamination. The effect of crack length and wafer thickness on the energy release rate is studied by FEA. Furthermore, to model interfacial crack nucleation, an analytical approach is developed by combining a shear lag model with a cohesive interface model. Finally, the effects of structural designs and the variation of the constituent materials on TSV reliability are investigated. The steady state solutions for the energy release rate are developed for various TSV designs and via materials (Al, Cu, Ni, and W) to evaluate the interfacial reliability. The parameters for TSV design optimization are discussed from the perspectives of interfacial reliability.
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Lines in the mid- to far-infrared wavelength range, less affected by dust extinction than optical lines, are ideally suited to study the physical processes taking place in the dust-hidden regions in galaxies, where heavily obscured star formation and accretion onto supermassive black-holes at their nuclei take place. These tools are fundamental for the study of local galaxies, but become of paramount importance to probe galaxies at the “Cosmic Noon”, at redshift z1-3, when the peak of star formation activity has taken place and most of the baryonic mass in galaxies has been assembled. One of the main goals of this Thesis is to provide reliable calibrations of mid- to far-IR ionic fine structure lines, H2 molecular lines and PAH (polycyclic aromatic hydrocarbon features), that will be used in the near and mid term to derive crucial information on the physics driving galaxy evolution. Based on these calibrations I identify the best spectroscopic measurements for the star formation rate and the black hole accretion rate in galaxies. This is done by comparing the marginal correlation of the different line luminosities versus the total IR luminosity for three samples of galaxies in the local Universe: star-forming galaxies, active galactic nuclei, and low-metallicity dwarf galaxies. For the most commonly observed fine-structure lines in the far-IR, I compare the calibrations derived from local galaxies to the existing ALMA observations of high redshift galaxies, finding an excellent agreement. These calibrations will be exploited for distant galaxies by present and future ground-based facilities observing in the millimeter and sub-millimeter range, and for galaxies in the nearby Universe through mid-IR spectroscopic observations with the upcoming James Webb Space Telescope (JWST). The second goal of this Thesis is to design future spectro-photometric surveys that will be able to address the most challenging problems that limit our current understanding of the galaxy evolution: the co-evolution of star formation and black hole accretion, the build-up of heavy elements and the chemical evolution of galaxies, and the feedback from active galactic nuclei. Using my calibration of the mid- to far-IR lines as a basis, I have simulated deep spectro -photometric surveys covering large cosmological volumes over extended fields (1–15 deg2) with an imaging spectrometer covering the mid-IR spectral range (17–36m interval), following the study case of the SPace Infrared telescope for Cosmology and Astrophysics (SPICA). A SPICA-like mission would be able to provide an unobscured three-dimensional view of galaxy evolution back to an age of the universe of less than 3 Gyrs. This survey strategy would produce a full census of the Star Formation Rate in the Universe, using PAH bands and fine-structure ionic lines, reaching the characteristic knee of the galaxy luminosity function, where the bulk of the population is distributed, at any redshift up to z3.5. Deep follow-up pointed spectroscopic observations with grating spectrometers onboard the satellite, from mid- to far-IR spectral range, would also measure the Black Hole Accretion Rate from high-ionisation fine-structure lines down to the knee of their luminosity function. Moreover, other two relevant goals of IR spectroscopic observations from space are the studies of feedback from AGN/starburst galaxies and of the metallicity evolution. While at the present time the SPICA mission will not be further developed, a similar study on galaxy evolution can be partially addressed by the ALMA telescope in the mm/sub-mm range, and the James Webb Space Telescope (JWST) in the mid-IR. These facilities, while unable to perform wide-field blind surveys, will allow to study the processes that led to the Cosmic Noon,using the ALMA telescope to observe galaxies at redshift above z3, and the late evolution of galaxies after their peak activity, with JWST observing local galaxies up to redshift z1.

Ce mémoire présente une recherche détaillée et une analyse des étoiles naines blanches hybrides chimiquement stratifiées dans le Sloan Digital Sky Survey (SDSS). Une seule étoile stratifiée, PG 1305-017, était connue avant notre recherche. L'objectif principal est de confirmer l'existence de plusieurs nouvelles étoiles stratifiées. Pour ce faire, il a fallu dans un premier temps développer une nouvelle génération de modèles d'atmosphère à partir de ceux de Bergeron et al. (1991) et Tremblay & Bergeron (2009). Nous y avons ajouté l'opacité de toutes les raies d'hélium et les calculs nécessaires pour tenir compte de la stratification chimique de l'atmosphère, où une mince quantité d’hydrogène flotte en équilibre diffusif au-dessus d’une enveloppe massive d’hélium. En parallèle, nous avons aussi calculé des modèles standards, chimiquement homogènes. Ensuite, nous avons sélectionné des naines blanches chaudes (Teff > 30,000 K) de type spectral hybride (traces d'hélium et d'hydrogène) parmi les ~38,000 naines blanches répertoriées dans le SDSS. Un total de 52 spectres d'étoile a été retenu dans notre échantillon final. La technique spectroscopique, c'est-à-dire l'ajustement des raies spectrales des modèles sur un spectre observé, a été appliquée à toutes les étoiles de notre échantillon. Nous avons ainsi mesuré la température effective, la gravité de surface et la composition chimique de l'atmosphère de ces étoiles. Par l'ajustement simultané de modèles stratifiés et homogènes, nous avons aussi pu déterminer si les étoiles étaient stratifiées ou non. Nous identifions ainsi 14 naines blanches stratifiées. Nous tirons de ces résultats plusieurs conclusions sur les processus physiques expliquant la présence d'hélium dans l'atmosphère.
We present a detailed research and analysis of chemically stratified hybrid white dwarf stars in the Sloan Digital Sky Survey (SDSS). Only one stratified star, PG 1305-017, was known before our analysis. The main objective is to confirm the existence of several new stratified stars. To do so, we initially had to develop a new generation of model atmospheres from those of Bergeron et al. (1991) and Tremblay & Bergeron (2009). We added the opacity of all the helium lines and the necessary calculations to account for the chemical stratification of the atmosphere, where a thin hydrogen layer floats in diffusive equilibrium on top of a more massive helium layer. In parallel, we also calculated a grid of standard models, which are chemically homogeneous. Then, we selected hot white dwarfs (Teff > 30,000 K) with a hybrid spectral type (traces of helium and hydrogen) from the ~38,000 white dwarfs listed in the SDSS. A total of 52 spectra were retained in our final sample. The spectroscopic technique, i.e. the fit of model spectra to an observed spectrum, was applied to all stars in our sample. Thereby, we have measured the effective temperature, the surface gravity and the chemical composition of these stars. By simultaneously fitting stratified and homogeneous models, we have also been able to determine if the stars were stratified or not. We identify 14 stratified white dwarfs. From these results, we draw several conclusions on the physical processes explaining the presence of helium in the atmosphere.

Thesis (PhD.(Chemistry)--University of Pretoria, 2008.
On title page: Submitted in partial fulfilment of the degree Philosophiae Doctor in Chemistry in the faculty of Natural and Agricultural Sciences of the University of Pretoria. Includes bibliographical index.

Hydrogen peroxide (H2O2) is extensively used in a broad range of industrial and medical applications, such as aseptic processing of food and pharmaceuticals, disinfection, water treatment plants, and decontamination of industrial effluents. H2O2 is believed to be responsible for chemical degradation of polymer membranes in Polymer-Electrolyte-Membrane (PEM) fuel cells. Therefore, a versatile H2O2 sensor that functions in different environments with different conditions is of practical importance in various fields. This dissertation presents the fabrication of a fiber-optic H2O2 sensing probe (optrode) and its H2O2 sensing behavior in different conditions. An H2O2 optrode is fabricated using chemical deposition of Prussian blue (PB) onto the tip of a multimode optical fiber. Sensing tests are performed in aqueous solutions at a constant pH and different concentrations of H2O2. Sensing features of the optrode (i.e. repeatability, durability, and reproducibility) are assessed by performing multiple sensing tests with several optrodes. The results show the prepared optrode is able to detect concentrations of H2O2 in aqueous solutions at a constant pH of 4 and the optrode features a repeatable and durable response at this condition. The functionality of optrodes at different pH values is further investigated by performing additional sensing experiments. These experiments are carried out in aqueous solutions with different concentrations of H2O2 at different pH values (i.e. pH 2-7). The sensor detects the presence of H2O2 at a range of pH values. Sensing behavior of optrodes toward detection and measurement of H2O2 concentrations is studied at the pH value corresponding to an operating PEM fuel cell (i.e. pH 2). The optrode is able to detect concentrations of H2O2 at this condition with a repeatable and durable response. The stability of PB films, prepared through different conditions, is investigated to address the stability of optrodes at elevated temperatures. PB films are first deposited onto the glass slides through three different chemical processes, and then at different synthesis temperatures. The PB films are left in Phosphate-Buffer-Solutions (PBS) with pH 2 and at elevated temperatures for a day. Finally, PB films are characterized using Fourier transform infrared spectroscopy (FTIR) to analyze their stability following PBS processing at operating temperatures and pH value corresponding to an operating PEM fuel cell (i.e. 80 °C and pH 2). The results of these experiments illustrate the PB films prepared through the single-source precursor (SSP) technique and at synthesis temperatures above 60 °C remain stable after the PBS processing. The proposed optrode shows reliable sensing behavior toward detection and measurement of H2O2 concentrations in aqueous solutions at different conditions. The prepared optrode has the potential for being developed and used in different industrial and medical fields, as well as an operating PEM fuel cell, to detect and measure H2O2 concentrations.
Graduate
0794
0548
0485
hakbarik@uvic.ca

Ce mémoire présente une exploitation additionnelle du catalogue LSPM comportant deux grandes parties, soit la poursuite du relevé des naines blanches à l'intérieur d'un rayon de 40 pc et l'étude de la contrepartie SDSS de ce catalogue. La première consiste à utiliser les critères basés sur des diagrammes de mouvements propres réduits établis dans des travaux antérieurs afin de dresser une liste de candidates naines blanches. Quelques modifications quant à l'ordre de priorité ainsi que le critère basé sur les magnitudes photographiques seront apportées. Une approche de moindres carrés non-linéaire appliquée aux magnitudes observées dans les systèmes photométriques disponibles permet ensuite de déterminer la distance des objets sélectionnés par comparaison avec les plus récents modèles de naines blanches disponibles. Un second critère est appliqué en se basant sur la qualité de l'ajustement résultant de la procédure. Ceci mènera à l'identification de 31 nouvelles naines blanches, dont 11 situées vraisemblablement à moins de 40 pc. Une nouvelle liste de candidates a aussi pu être établie pour la poursuite du relevé. La seconde partie consiste à utiliser tous les objets du 7e relevé du SDSS identifiés dans le catalogue LSPM pour l'étude statistique des naines blanches, essentiellement via la détermination de leur fonction de luminosité. Pour ce faire, un critère basé sur les diagrammes de mouvements propres réduits sera encore une fois utilisé. La distance des objets sélectionnés sera déterminée selon la même procédure, mais cette fois en ne se limitant pas à 40 pc. La méthode de pondération selon le volume observable (1/v_max) est utilisée afin de compenser pour le biais introduit par la sensibilité du catalogue à la magnitude. Cependant, d'autres facteurs viennent influencer la détermination de la fonction de luminosité et une analyse de ceux-ci est finalement présentée.
We present an additional exploitation of the Lépine \& Shara Proper Motion catalog (LSPM) divided in two main parts: a follow up and some improvements on the census or northern white dwarfs within 40 pc of the Sun and a study of the SDSS white dwarfs component in the LSPM survey. The former consists in the use of criteria previously established in order to create a list of white dwarf candidates with an associated priority. The priority order has been enriched and one of the criteria has been slightly modified. We then use a non-linear least square method to the observed magnitudes in each available photometric system simultaneously in order to determine the atmospheric parameters and, in particular, the distance of each white dwarf candidate. This approach allows a second criteria to be applied on our sample based on the goodness of the fit. This will lead us to the identification of 31 new white dwarfs, from which 11 are likely to remain within 40 pc of the Sun. A new list of 340 candidates has also been established for eventual observations. The latter consists in the use of all the objects from the 7th data release of the SDSS that have a counterpart in the LSPM catalog to elaborate a statistical study of white dwarfs, in this case by calculating the white dwarf luminosity function. To do so, one of the same criterion mentioned above will be used to make a first selection of presumed white dwarfs. Afterwards, the distance will be determined by the same least-square method, but without any restriction on the distance. To balance the effect due to the sensibility in magnitude of the survey, we used a ponderation method based on the maximum observable volume (1/v_max). However, other factors come to affect our results and the last part of this work concentrates on their identification.