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A Study of Reaction Sites in AC Electro-Slag Remelting / Reaction Sites in AC Electro-Slag RemeltingGhosh, Debabrata 09 1900 (has links)
<p> The dominant slag-metal reaction site in AC electro-slag
remelting (ESR) has been directly determined by estimating the rate of
sulphur transfer at the electrode tip/slag and metal pool/slag interfaces.
In this investigation, negligible sulphur transfer has been
assumed at the droplet/slag interface, and the basis for such assumption
is discussed. Using a 5.825" diameter mould and CaF2-CaO slags,
it has been established that the electrode tip/slag interface is the
dominant reaction site. Calculations indicate that the pool sulphur
is close to equilibrium with the slag. The importance of all six
reaction sites in AC ESR are discussed. The results indicate the
importance of the slag/atmosphere interface, especially when using slags
of low lime content. Conventonal overall sulphur balances have
been carried out and the results are in agreement with the rates
obtained at the different interfaces, thus indicating internal consistency
of the results. </p> / Thesis / Master of Engineering (MEngr)
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A Theoretical Study on ESR Dating of Geological Faults in Southern CaliforniaBuhay, William M. 12 1900 (has links)
<p> The recent urban sprawl in the tectonically active region of California has prompted palaeoseismologists, to find ways of forecasting potentially hazardous earthquakes on existing
faults. Electron spin resonance (ESR) can be used to date fault gouge from different regions in a fault zone thereby providing a history of fault movements in a particular region. Therefore, an earthquake frequency pattern can be established and the faults can be rated as to their potential danger. </p> <p> ESR dating of fault gouge is based on the premise that the ESR signals of quartz grains in the gouge have been completely reset by movements on the fault. The elapsed time since faulting is recorded by a gradual charge build up in the quartz corresponding to radioactive decay of radionuclides in the fault gouge matrix. The mechanism of zeroing of the ESR
signals in quartz during fault activity is not well understood. In order to better comprehend the zeroing process, the variation of ESR signals, AD and age, with respect to quartz grains size were studied. These parameters are affected by induced stress to a greater extent in the smaller grain
sizes. Therefore, with sufficient stress, the smallest grain sizes (smaller than a critical size) will be totally reset and define a "plateau" of equal age. This plateau criteria is used to define total resetting in a fault gouge sample and only these portions of the samples are used for dating. The establishment of an equal age plateau is confirmed for one of the fault samples collected from Southern California. </p> / Thesis / Master of Science (MS)
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Applications Focused Synthetic Modification on Photoremovable Protecting Groups (PRPG) & Photochemical Analysis on Organic Azides and IsoxazolesThenna Hewa, Kosala R. S. January 2017 (has links)
No description available.
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Multi-Frequenz-ESR spinmarkierter ProteineUrban, Leszek 06 December 2012 (has links)
Die Elektronen-Spin-Resonanz-Spektroskopie (ESR) in Verbindung mit ortsspezifischer Spinmarkierung stellt eine hervorragende Möglichkeit dar, um die Struktur und Dynamik von Proteinen aufzuklären. In dieser Dissertation wurden mit Hilfe der Hochfeld-ESR-Spektroskopie (W-Band, 95 GHz, T=160 K) für dreizehn spinmarkierte Colicin A Proben die Polarität und die Protizität der Umgebung der Spinlabelbindestelle bestimmt. Wasserzugänglichkeiten und Wasserstoffbrückenbindungen zum Spinlabel wurden mittels Puls-ESR Methoden (3-Puls-D-ESEEM und Hahn-Echozerfall) bestimmt und die Ergebnisse mit den Polaritäts- und Protizitätswerten korreliert. Raumtemperaturspektren dieser Proben im X-Band (9.5 GHz), Q-Band (34 GHz) und W-Band (95 GHz) liefern Informationen über die Spinlabelbewegung. Mit Hilfe von Molekulardynamiksimulationen (MD) der spinmarkierten kanalbildenden Domäne von Colicin A konnten die Konformationen (Rotameranalyse) und die Dynamik der Spinlabelseitenketten in den unterschiedlichen Umgebungen charakterisiert werden. Der Vergleich der experimentellen mit den aus MD-Trajektorien berechneten ESR-Spektren liefert die Beiträge der unterschiedlichen Rotamerübergänge, die für die beobachteten Spektrenformen charakteristisch sind.
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Simulation numérique du procédé de refusion sous laitier électroconducteur / A comprehensive model of the electroslag remelting processWeber, Valentine 27 February 2008 (has links)
Le procédé de refusion sous laitier électroconducteur (Electro Slag Remelting ou ESR) est aujourd’hui largement utilisé pour la production d’alliages métalliques à haute valeur ajoutée, comme les aciers spéciaux ou les superalliages base nickel. La modélisation mathématique et la simulation numérique du procédé ESR présentent un grand intérêt puisque les études expérimentales sur installations industrielles sont coûteuses et souvent difficiles à mettre en oeuvre. Ainsi, afin d’améliorer la compréhension et la maîtrise de la conduite d’une refusion, un modèle prédictif a été développé dans le cadre de cette étude. Il décrit les transferts couplés de chaleur et de quantité de mouvement lors de la croissance et de la solidification d’un lingot, en géométrie axisymétrique. La résolution des équations est basée sur une approche de type volumes finis. Le modèle tient compte de l’effet Joule dans le laitier résistif, des forces électromagnétiques et de la turbulence éventuelle de l’écoulement des phases liquides. La zone pâteuse est traitée comme un milieu poreux. Le modèle permet notamment de prédire la formation de la peau de laitier solide qui entoure le laitier et le lingot. Par ailleurs, il offre l’avantage de simuler le comportement du lingot et du laitier après la coupure finale du courant.Le développement s’est accompagné d’une importante étape de validation. Quatre refusions à l’échelle industrielle ont ainsi été réalisées à l’aciérie des Ancizes (Aubert&Duval). Les observations expérimentales ont ensuite été confrontées aux résultats du calcul. La comparaison a montré que le modèle peut être utilisé afin de prédire le comportement du procédé, à condition d’accorder une attention particulière à l’estimation des propriétés thermophysiques du métal, et surtout du laitier. Enfin, afin d’illustrer l’utilisation du modèle comme support à la compréhension du procédé, nous avons étudié l’influence de la variation de paramètres opératoires tels que la profondeur d’immersion de l’électrode, le taux de remplissage ou la pression de l’eau de refroidissement. / Electro Slag Remelting (ESR) is widely used for the production of high-value-added alloys such as special steels or nickel-based superalloys. Because of high trial costs and complexity of the process, trial-and-error based approaches are not well suitable for fundamental studies and optimization of the process.Consequently, a transient-state numerical model which accounts for electromagnetic phenomena and coupled heat and momentum transfers in an axisymmetrical geometry has been developed. The model simulates the continuous growth of the electroslag remelted ingot through a mesh-splitting method. In addition, solidification of the metal and slag is modelled by an enthalpy-based technique. A turbulence model is implemented to compute the motion of liquid phases (slag and metal), while the mushy zone is described as a porous medium whose permeability varies with the liquid fraction, thus enabling an accurate calculation of solid/liquid interaction. The coupled partial differential equations are solved using a finite-volume technique.Computed results are compared to experimental observation of 4 industrial remelted ingots fully dedicated to the model validation step. Pool depth and shape are particularly investigated in order to validate the model. Comparison shows that the model can be used as a predictive tool to analyse the process behavior. Nevertheless, it is necessary to pay a particular attention to the estimation of the thermophysical properties of metal and especially slag.These results provide valuable information about the process performance and influence of operating parameters. In this way, we present some examples of model use as a support to analyse the influence of operating parameters. We have studied the variation of electrode immersion depth, fill ratio and water pressure in the cooling circuit.
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Rôle du système ZraPSR dans le stress de l’enveloppe et la résistance aux antimicrobiens chez la bactérie Escherichia coli / Role of the ZraPSR system in envelope stress and antimicrobial resistance in Escherichia coliRome, Kevin Josué 18 December 2017 (has links)
Les bactéries ont réussi à coloniser toutes les niches écologiques de la planète. Le passage d’un environnement à un autre s’accompagne de la fluctuation de nombreux paramètres environnementaux aboutissant à un stress cellulaire. Directement en contact avec le milieu environnant, l’enveloppe bactérienne est la première barrière contre ces stress extracellulaires. Toute rupture de son intégrité aura des conséquences délétères pour la cellule. Parmi les mécanismes permettant aux bactéries de détecter les changements de conditions environnementales, il existe des systèmes spécifiques appelés ESR (Envelope Stress Response). Ces systèmes maintiennent l’intégrité membranaire en réparant les dommages de l’enveloppe. Ce travail de thèse s’inscrit dans l’étude des mécanismes intrinsèques de résistance chez les bactéries, par la caractérisation d’un nouvel ESR d’E. coli : le système ZraPSR (Zinc Resistance Associated Protein Sensor Regulator). ZraPSR est un système à deux composants, composé d’un senseur ZraS, d’un régulateur transcriptionnel ZraR et d’une protéine périplasmique accessoire ZraP. La cascade ZraS-R est activée par des concentrations élevées en Zn et Pb. Ce travail a montré que ZraP établit un rétrocontrôle négatif sur la cascade de signalisation ZraSR par un mécanisme nécessitant sa métallation. Malgré une induction en présence de métaux, nous avons montré que le système ZraPSR ne possède aucun rôle dans l’homéostasie métallique. A contrario, en réponse à des signaux de stress, ZraSR va contribuer à la résistance intrinsèque à certains antimicrobiens. De plus, l’étude du régulon de ZraR a permis de commencer à entrevoir les mécanismes sous-jacents de réponse aux stress antimicrobiens médiée par ZraPSR. Cette réponse intègre des signaux de l’état physiologique de la cellule par l’intermédiaire de régulateurs globaux du métabolisme aboutissant à une réponse optimale. Le système ZraPSR semble donc être un nouveau mécanisme de résistance-croisée aux stress environnementaux. / Bacteria succeed in colonizing all the ecological niches on earth. Transition from one environment to another comes along with the fluctuation in numerous environmental parameters wich induce cellular stress. Directly in contact with the surrounding environment, the bacterial envelope is the first barrier against these extracellular stresses. Any break of its integrity will have deleterious consequences for the cell. Among mechanisms allowing bacteria to detect environmental changes, specific systems called ESR (Envelope Stress Response) have been studied. Such systems maintain membrane integrity by repairing envelope damages. This work takes part in the study of the intrinsic mechanisms of antimicrobial resistance in bacteria, by the characterization of a new ESR of E. coli: the ZraSR (Zinc Resistance Associated Protein Sensor Regulator) system. ZraPSR is a two-component system consisting of a ZraS sensor, a ZraR transcriptional regulator and a ZraP accessory periplasmic protein. The ZraS-R cascade is activated by high concentrations of Zn and Pb. In this study, we showed that ZraP establishes a negative feedback on the ZraSR pathway by a mechanism requiring its metallation. Despite the observed induction in the presence of metals, we showed that the ZraPSR system is not required for metal homeostasis. Whereas, in response to stress signals, ZraSR contribute to intrinsic resistance to certain antimicrobials. Futhermore, the study of the ZraR regulon allowed us to begin glimpsing the underlying mechanisms of antimicrobial stress response mediated by ZraPSR. This response incorporates signals from the physiological state of the cell through global regulators of the metabolism leading to an optimal response. The ZraPSR system seems to be a new cross-resistance mechanism to environmental stresses.
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Funkcionalne i antioksidativne osobine tropa cvekle (Beta vulgaris) / Functional and antioxidant characteristics of beetroot pomace (Beta vulgaris)Vulić Jelena 04 September 2012 (has links)
<p>Etanolni ekstrakti tropa odabranih sorti cvekle (Detroit, Cardeal-F1, Egipatska, Bikor i Kestrel) prečišćeni su primenom ekstrakcije na čvrstoj fazi (SPE). Sadržaj ukupnih<br />fenolnih jedinjenja, flavonoida i betalaina u prečišćenim ekstraktima određeni su spektrofotometrijskim metodama. HPLC analizom utvrđen je kvalitativni i kvantitativni sastav fenolnih jedinjenja i betalaina ekstrakata tropa odabranih sorti cvekle. ESR spektroskopijom ispitana je antiradikalska aktivnost ekstrakata topa cvekle na stabilne DPPH i reaktivne superoksid anjon i hidroksil radikale.<br />Spektrofotometrijski je određena antioksidativna aktivnost na DPPH radikale i redukciona sposobnost po Oyaizu u ekstraktima odabranih sorti cvekle. Ispitana je in vitro<br />antiproliferativna aktivnost frakcija ekstrakata, njihovim delovanjem na rast tri histološki različite humane ćelijske linije: MCF-7 (adenokarcinom dojke), HeLa (epitelni karcinom cerviksa)i MRC-5 (fetalni fibroblastni karcinom pluća). U završnoj fazi rada određena je antimikrobna aktivnost ekstrakata tropa odabranih sorti cvekle.</p> / <p> Beetroot (Detroit, Cardeal-F1, Egipatska, Bikor i Kestrel)<br /> pomace ethanol extracts were purified using solid phase<br /> extraction (SPE). Contents of total phenols, flavonoids and<br /> betalains in purified extracts were determined by spectrophotometric<br /> methods. HPLC analysis were used for quantitative<br /> and qualitative characterization of phenolic compounds<br /> and betalains in investigated extracts. ESR spectroscopy<br /> was used for investigation of antiradical activity of<br /> beetroot pomace extracts on stable DPPH and reactive<br /> superoxide anion and hydroxyl radicals. Antioxidant activity<br /> was determined spectrophotometrically on DPPH radicals<br /> and reducing power according to Oyaizu in the beetroot pomace<br /> extracts. Antiproliferative activity of investigated extracts<br /> was determined in vitro, testing their influence on the<br /> growth of three histologically different human cell lines:<br /> MCF-7 (breast adenocarcinoma), HeLa (cervix epithelioid<br /> carcinoma) and MRC-5 (fetal lung). Also, antimicrobial activity<br /> of beetroot pomace extracts was determined.</p>
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Antiradikalska i antiproliferativna aktivnost ekstrakata odabranih biljaka iz familija rosaceae i ericaceae / Antiradical and antiproliferative activity of selected plantextracts from Rosaceae and Ericaceae familyTumbas Vesna 14 June 2010 (has links)
<p>Acetonski ekstrakti bobičastog voća iz familija Ericaceae<br />(borovnica,<em> Vaccinium myrtillus</em> L., i brusnica, <em>Vaccinium<br />macrocarpon</em> L.) i Rosaceae (šipak, <em>Rosa canina</em> L., i glog,<br /><em>Crataegus oxyacantha</em> L.) prečišćeni su i frakcionisani<br />primenom ekstrakcije na čvrstoj fazi (SPE). Sadržaj ukupnih<br />polifenolnih jedinjenja, flavonoida i antocijana u prečišćenim<br />ekstraktima određeni su spektrofotometrijskim metodama.<br />HPLC analizom utvrđen je kvalitativni i kvantitativni<br />sastav frakcija ekstrakata ispitivanih bobica. ESR spektroskopijom<br />ispitana je antiradikalska aktivnost frakcija ekstrakata<br />bobica na stabilne DPPH<sup>●</sup> i reaktivne superoksid anjon i<br />hidroksil radikale. ESR spektroskopijom ispitano je i<br />prisustvo slobodnih radikala antioksidanata nastalih tokom<br />reakcije frakcija ekstrakata bobica sa superoksid anjon<br />radikalima. U završnoj fazi rada ispitana je<em> in vitro</em><br />antiproliferativna aktivnost frakcija ekstrakata bobica, njihovim<br />delovanjem na rast tri histološki različite humane ćelijske<br />linije: HeLa (epitelni karcinom cerviksa), HT-29 (adenokarcinom<br />debelog creva) i MCF-7 (adenokarcinom dojke).</p> / <p>Acetone extracts of berries form Ericaceae (bilberry, <em>Vaccinium<br />myrtillus</em> L., and cranberry, <em>Vaccinium macrocarpon</em><br />L.) and Rosaceae (rose hip, <em>Rosa canina</em> L., and hawthorn,<br /><em>Crataegus oxyacantha </em>L.) families were purified and fractionated<br />using solid phase extraction (SPE). Contents of total<br />polyphenols, flavonoids and anthocyanins in purified extracts<br />were determined by spectrophotometric methods.<br />HPLC analysis were used for quantitative and qualitative<br />characterization of investigated berry extracts fractions. ESR<br />spectroscopy was used for investigation of antiradical activity<br />of berry extracts fractions on stable DPPH<sup>●</sup> and<br />reactive superoxide anion and hydroxyl radicals. The<br />presence of antioxidant free radicals formed during reaction<br />of investigated berry extracts fractions with superoxide<br />anion radicals was also investigated by ESR. Antiprolixferative<br />activity of investigated berry extracts fractions was<br />determined<em> in vitro</em>, testing their influence on the growth of<br />three histologically different human cell lines: HeLa (cervix<br />epithelioid carcinoma), HT-29 (colon adenocarcinoma) i<br />MCF-7 (breast adenocarcinoma).</p>
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Phase Transitions And Relaxation Processes In Water And Glycerol-Water Binary Liquid Mixtures : Spin Probe ESR SudiesBanerjee, Debamalya 08 1900 (has links)
A liquid Cooled below its normal freezing temperature is known as a supercooled liquid. On further cooling, supercooled liquids crystallize to thermodynamically stable, ordered structures. Alternatively, if the cooling rate is fast enough, the crystallization may be avoided altogether. Below a particular temperature during rapid cooling the liquid will solidify into a disordered, amorphous phase -also known as the glassy phase of matter. This particular temperature is termed the ”glass transition temperature” (Tg). Unlike a crystalline solid, a glass is neither a thermodynamically stable phase nor does it possess long range molecular ordering. Very slow structural relaxation (in the time scale of ∼ 100 s) is always present in the glassy phase. Thus, this phase is often referred to as a metastable phase of matter. Experimental and theoretical studies related to the behavior of supercooled liquids are the subject matter of many investigations for the last few decades [1]. These studies find their applications in diverse fields such as geology, cryopreservation, glaciology and atmospheric science. However, properties of supercooled liquids and the corresponding amorphous phase are not completely understood at present, particularly for hydrogen bonded (H-bonded) systems. This thesis concerns both the crystallization and the glass formation process of H-bonded systems. The systems of interest are water, the commonly accepted universal solvent, and the aqueous binary mixture of glycerol and water.
The technique of molecular probing is often used to study the cooperativety and rotational diffusion of supercooled liquids and for determination of the glass transition temperature. For the present set of work, a molecular probe technique called spin probe ESR is extensively used. Electron paramagnetic resonance or electron spin resonance (EPR/ESR) measures the electronic energy level separation and is well known for the high sensitivity. All of the systems studied in the present set of work are diamagnetic. This issue is circumvented by dissolving paramagnetic spin probe molecules, which are usually organic free radicals with one N-O group, into the systems. Spin probes are added in very low concentrations (~10-3M) to minimize the effect on the host system and also to avoid mutual interactions between them. The unpaired electron delocalized in the direction of the N-O bond serves as the paramagnetic center required for an ESR experiment. The splitting of electron energy level due to the external magnetic field (Zeeman splitting) can give rise to resonance absorption of energy if exposed to a microwave of appropriate frequency. There is also a magnetic coupling (hyperfine) between the spin of the unpaired electron and nuclear spin of the nearby nitrogen atom. The hyperfine coupling splits each electron energy levels, to the first order, symmetrically into three levels. The transitions between these levels -subject to appropriate selection rules -give rise to the ESR spectrum [2]. The spectral shape in a magnetic field sweep ESR experiment appears complex if randomly oriented spin probes are dispersed in an amorphous or polycrystalline solid matrix. The high degree of mobility in probe molecules, present in a liquid solution, can average out the individual anisotropy of magnetic tensors to get a spectrum of three equally spaced liens. Experiments can be performed spanning a spin probe reorientation timescale of 10-7-10-12 s typically in the temperature range of 4.2 -300K.
In chapter one we have given a brief overview of the supercooled liquids and the phase transitions related to the present work. Particular emphasis has been given to the dynamical features of the supercooled liquid close to its glass transition temperature and their classification based on the degree of ’fragility’ [3]. Brief general introductions of the systems studied in each of the following chapters are also provided. Then, the details of ESR spectroscopy and a quantum mechanical picture of the method of spin probe ESR have been discussed [4]. A separate section has been devoted to the numerical and analytical methods used to analyze the spectrum to extract information related to the spin probe dynamics [5]. The chapter concludes with a description of the ESR spectrometer.
In chapter two we have studied the glass transition and dynamics of the supercooled water by the method of spin probe ESR. The vitrification has been done by direct exposure of the bulk water sample, doped with the spin probe TEMPOL, to the liquid helium flow. The vitrified matrix turns into the ultraviscous liquid above the putative glass transition temperature of ~136 K which further transforms to cubic ice (Ic) above TX ~150 K. The supercooled fraction of water, along with the spin probes which are treated as impurities by the crystallized surroundings, remain trapped inside the veins or triple junctions of the ice grains which serve as the interfacial reservoir of impurities in a polycrystalline ice matrix. The spectra for the entire temperature range have been analyzed with the help of in-depth computation by modelling the reorientation of TEMPOL in terms of the jump angle θs and the rotational correlation time τ [5]. This model, based on a homogeneous mobility scenario of the spin probe, works nicely except in the temperature range of 140-180 K. Dynamical heterogeneity (DH) is apparent in this temperature range and a more mobile (fast) component, as compared to the one corresponding to the very slow dynamics of TEMPOL at lower temperatures (slow), is observed. The relative weight of the fast and the slow component changes with temperature and above ~180 K the entire spectrum changes into the motionally narrowed triplet. The temperature dependence of the slow component of τ shows a change in slope at a temperature close to the putative glass transition temperature of water. The fast component of τ exhibits a fragile, i.e. non-Arrhenius character at high temperature with a crossover to a strong, i.e. Arrhenius behavior below ~225 K, close to the hypothesized fragile-to-strong crossover (FSC) for water at TFSC ~228 K. The breakdown of the Debye-Stokes-Einstein (DSE) law is observed when the τ values are combined with the available viscosity data of water to evaluate the DSE ratio, paralleling the SE breakdown which has recently been observed in nanoconfined water [6].
The dynamical heterogeneity is thought to be closely associated with the static structural heterogeneities of supercooled water. The existence of large scale structural fluctuations spanning a range of low-and high-density phases of liquid water have been associated with the heterogeneous dynamics sensed by TEMPOL. Motivated by the Arrhenius like behavior of the slow component, it has been identified with the low density liquid (LDL). The fragile nature of the fast component at high temperature may be identified with that of the high density liquid (HDL) which is the predominant fraction in liquid or weakly supercooled water [6].
Chapter three reports the studies on freezing and dynamics of the supercooled water trapped inside the veins of a polycrystalline ice matrix by dissolving spin probes TEMPO and TEMPOL into it. When a millimolar spin probe aqueous solution is cooled below the freezing point of water, the spin probes -driven by the mechanism described above migrate to the liquid environment inside the ice veins. Local concentration of the probe molecules inside the veins can go up to 1-10 M [7]. Bulk crystallization is evident in differential scanning calorimetry (DSC) studies whereas the liquid environment of the spin probe below the bulk freezing is confirmed by its narrow triplet ESR spectrum. A sudden collapse of this narrow triplet into a single broad line indicates the freezing of the trapped water fraction which usually happens well below the DSC freezing point for both the probes. The spin probe detected freezing point of this interstitial water is found to be largely dependent on the properties and the amount of the dissolved probe molecules. An explanation is sought in terms of the ’destructuring effect’ on the tetrahedral ordering of the water H-bond network by both the high local concentration of the spin probes and the hydrogen bond strength, formed between the water and the spin probe molecules through the polar groups of the latter [8, 9]. These two factors are thought to play important roles in determining the reorientational dynamics of the spin probe molecules, as well. The rotational correlation times of the two probes exhibit a crossover owing to the different mobility of their salvation shells in the more ordered supercooled water. The observed relaxation behavior of this confined water using the probe TEMPO, which has little effect on water H-bond network, is found in agreement with the previous experimental investigations on water confined in a nanochannel [10].
In chapter four, the glass transition, relaxation and the free volume of the glycerol-water (G-W) system are studied over the glycerol concentration range of 5 -85 mol% with TEMPO as the spin probe. G-W mixture is intrinsically inhomogeneous due to the well established phase segregation below a critical glycerol concentration of 40 mol%. In the inhomogeneous regime the water molecules tend to form cooperative domains besides the mesoscopic G-W mixture [11]. Samples are quenched by rapid cooling down to 4.2 K inside the spectrometer cryostat. Spectra were recorded on slow heating of the sample in the temperature range of 130 -305 K. The glass transition temperature is correlated to the sharp transition of the extrema separation of the ESR spectrum. The glass transition temperatures are found to follow a concentration dependence which is closely associated to the mesoscopic inhomogeneities of the G-W system. The steady enhancement in fragility of the G-W system with the addition of water is evident from the temperature dependence of the spin probe correlation time τ for the entire concentration range. In the temperature range of 283 -303 K, the DSE law is followed i.e. the spin probe reorientation process is found to be strongly coupled to the system viscosity. In this regime, the τ values have been used along with the available viscosity data to calculate the effective volume V of the spin probe for the entire concentration range. The spin probe effective volume is a measure of the available free volume of the host matrix. A drastic change in the quantity is seen in the vicinity of the 40 mol% glycerol concentration owing to a similar structural change of the matrix due to the formation of mesoscopic scale inhomogeneities below the critical concentration [12].
The thesis concludes with a discussion about the possible future directions of research.
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High-field electron spin resonance in low-dimensional spin systemsOzerov, Mykhaylo 14 June 2011 (has links) (PDF)
Due to recent progress in theory and the growing number of physical realizations, low-dimensional quantum magnets continue to receive a considerable amount of attention. They serve as model systems for investigating numerous physical phenomena in spin systems with cooperative ground states, including the field-induced evolution of the ground-state properties and the corresponding rearrangement of their low-energy excitation spectra. This work is devoted to systematic studies of recently synthesized low-dimensional quantum spin systems by means of multi-frequency high-field electron spin resonance (ESR) investigations. In the spin- 1/2 chain compound (C6H9N2)CuCl3 [known as (6MAP)CuCl3] the striking incompatibility with a simple uniform S = 1/2 Heisenberg chain model employed previously is revealed. The observed ESR mode is explained in terms of a recently developed theory, revealing the important role of the alternation and next-nearest-neighbor interactions in this compound. The excitations spectrum in copper pyrimidine dinitrate [PM·Cu(NO3)2(H2O)2]n, an S = 1/2 antiferromagnetic chain material with alternating g-tensor and Dzyaloshinskii-Moriya interaction, is probed in magnetic fields up to 63 T. To study the high field behavior of the field-induced energy gap in this material, a multi-frequency pulsed-field ESR spectrometer is built. Pronounced changes in the frequency-field dependence of the magnetic excitations are observed in the vicinity of the saturation field, B ∼ Bs = 48.5 T. ESR results clearly indicate a transition from the soliton-breather to a spin-polarized state with magnons as elementary excitations. Experimental data are compared with results of density matrix renormalization group calculations; excellent agreement is found. ESR studies of the spin-ladder material (C5H12N)2CuBr4 (known as BPCB) completes the determination of the full spin Hamiltonian of this compound. ESR results provide a direct evidence for a pronounced anisotropy in this compound, that is in contrast to fully isotropic spin-ladder model employed previously for BPCB. Our observations can be of particular importance for describing the rich temperature-field phase diagram of this material. The frequency-field diagram of magnetic excitations in the quasi-two dimensional S = 1/2 compound [Cu(C4H4N2)2(HF2)]PF6 in the AFM-ordered state is studied. The AFM gap is observed directly. Using high-field magnetization and ESR results, parameters of the effective spin-Hamiltonian (exchange interaction, anisotropy and g-factor) are obtained and compared with those estimated from thermodynamic properties of this compound.
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