Dissertationen zum Thema „Kinetic of transformation“
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1
Massam, Alexandra. „A kinetic model for the transformation of phenol by peroxidase“. Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape8/PQDD_0008/MQ50641.pdf.
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Brandt, Catharine Jane. „Transformation of the kinetic energy of rainfall with variable tree canopies“. Thesis, Royal Holloway, University of London, 1986. http://repository.royalholloway.ac.uk/items/b6beecb7-fb73-4d83-b905-206fccf515d7/1/.
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This thesis defines a physically based model describing the kinetic energy of throughfall from any vegetation canopy. Empirical measurements of the drop-size distribution of rainfall and sub-canopy throughfall were used to develop the model which was tested in the context of splash erosion. Comparisons are made for individual storms between rain falling in the open and through a canopy. Three canopies were used, one oak and two tropical rain forest differing in height. Through each storm raindrop sizes were frequently measured using the paper-staining technique. Kinetic energy/mm/m2 was calculated from the drop sizes, their velocities and amount of rain or throughfall. The velocities were assumed to depend on the height of fall. In the rain forest sites splash cups surrounded by uniform areas of sand were used to measure the material splashed. The oak canopy data was used to examine the validity of a working hypothesis relating qualitatively the size of throughfall drops to the saturation of the canopy. It was confirmed that the canopy changed the drop-size distribution of the rain and consequently changed the kinetic energy/mm/m2. The sequences of drop-size distribution change proposed by the hypothesis were related to the cumulated canopy storage. The tropical rain forest results confirmed these findings and extended them. Although rainfall kinetic energy/mm/m2 may be predicted from rainfall intensity, throughfall kinetic energy/mm/m2 was independent of intensity and the frequency distribution of the energy of throughfall samples was bimodal, with a high energy group which was commonly higher than that of the rainfall. The probability of a thoroughfall sample being in either energy group depended on the cumulated canopy storage or the percentage storm duration elapsed. The relative magnitude of rainfall and throughfall total kinetic energy depended on the saturation of the canopy and on the canopy height and for some storms the throughfall energy was higher than the rainfall. Soil splash increased with increasing kinetic energy. The model predicting throughfall energy requires inputs of canopy height, rainfall intensity and the frequency distribution of energy of discrete samples of throughfall. The model is most sensitive to canopy height.
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Watkins, Claire. „The Transformation of Electricity in my Brain“. VCU Scholars Compass, 2004. http://scholarscompass.vcu.edu/etd/1062.
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This thesis is an exciting and enthralling story about the history of the world as seen through the eyes of Claire Watkins. The story takes place in the dusty corners of her art studio in the old confederate capital, Richmond, Virginia. Ms. Watkins leads her audience through such unsuspecting places as her brain, the life of an African Dung Beetle, the center of an atom and the dark reaches of outer space. The story is inspirational and thought provoking. It will force you to see the world as an interconnected web that weaves your life together with the cosmos. A must read for the summer!"Truly exceptional
a wonderful Thesis
highly recommended!" - Ruby Westcoat"I never thought of the world quite like that
now I see everything in a new and electrifying way." - Timothy Devoe"Once again she proves to be my favorite contemporary artist and author" - Virgil Hale Rhames
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Träff, Annika. „Asymmetric transformation of ß- and γ-functionalized alcohols : Study of combined ruthenium-catalyzed racemization and enzymatic resolution“. Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2011. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-56947.
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The major part of this thesis describes the asymmetric synthesis of β- and γ-amino alcohols through the combination of ruthenium catalyzed racemization and enzymatic kinetic resolution. The dynamic kinetic resolution, DKR, protocol for chlorohydrins was improved by employing Bäckvall’s catalyst, which is a base activated racemization catalyst, in combination with Burkholderia cepacia lipase. These optimized conditions broadened the substrate scope and improved the yields and ee’s of the obtained chlorohydrin acetates. The utility of the method was demonstrated in the synthesis of (S)-salbutamol. In the second part of the thesis, DKR was utilized in the enantio-determining step of the total synthesis of (R)-duloxetine. Optimized DKR conditions, combining Bäckvall’s catalyst together with Candida antarctica lipase B, afforded a β-cyano acetate in high yield and ee. (R)-Duloxetine was accessible through synthetic alterations of the enantioenriched β-cyano acetate in high overall yield. A dynamic kinetic asymmetric transformation, DYKAT, protocol to obtain enantio- and diastereomerically pure γ-amino alcohols was developed. In a first step N-Boc-aminoketones were obtained in high enantiomeric purity through a proline-catalyzed Mannich reaction. Subsequent in situ reduction coupled with a highly efficient DYKAT yielded γ-amino acetates in high dr and ee. The γ-amino alcohols were available through simple hydrolysis/deprotection with retained stereochemistry. In the final part of the thesis a heterogeneous bifunctional catalytic system is reported, which combines the catalytic properties of transition metal-catalyzed racemization with enzymatic acylation. A novel ruthenium-phosphonate complex was synthesized and then covalently anchored to the active site of solid supported Candida antarctica lipase B. The partially inhibited beads proved to be catalytically active both in racemization as well as enzymatic acylation.At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: In press. Paper 3: Epub ahead of print.
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Crouïgneau, Guillaume. „Films de type Ni-Co-Mn-In : élaboration et étude de la transformation magnétostructurale“. Thesis, Université Grenoble Alpes (ComUE), 2015. http://www.theses.fr/2015GREAY048/document.
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Les alliages Heusler de type Ni-Mn-X (X=In, Ga, Sn et Sb) possèdent d'intéressantes propriétés mécaniques, magnétiques et thermiques qui découlent de la transition structurale martensite-austénite. Le couplage de ces propriétés entraîne de potentielles applications dans le domaine des actionneurs, des capteurs ou des refroidisseurs. La fabrication de ces matériaux en films, d'un grand intérêt pour les microsystèmes, reste difficile à maitriser et fait l'objet de ce travail de thèse. Une partie du travail effectué durant cette thèse porte donc sur l'élaboration d'un film de type Ni-Co-Mn-In en utilisant un procédé de co-pulvérisation. L'objectif de la thèse a porté sur l'obtention d'un film présentant une transition structurale et magnétique à température ambiante. Après une étude de la structure et de la microstructure des phases martensite et austénite, les propriétés magnétiques ont été investiguées. Le changement d'état magnétique obtenu pour certains films lors de la transition du premier ordre a entrainé des propriétés magnétocaloriques et d'actionnement intéressantes. Les meilleurs résultats sont obtenus pour un film de composition Ni45,2Co4,7Mn36,2In13,9. La réalisation de mesures de résistivité sous champ magnétique intense constitue un sujet novateur sur des films de ce type. Grâce à ces mesures, une étude de l'irréversibilité et du blocage de la transformation structurale induit par le champ magnétique (kinetic arrest) a été réalisée. La compréhension des phénomènes intervenant dans l'hystérésis thermique et le blocage sous champ magnétique est en effet importante pour les applications basées sur ces matériaux à fort couplage mécanique, magnétique et thermiqueNi-Mn-X (X=In, Ga, Sn and Sb) Heusler type alloys present interesting mechanical, magnetical and thermal properties owing to the martensite-austenite structural transition. Combining these properties induce many potentials applications in the field of actuators, sensors and coolers. Processing these materials into films is of great interest for micro-devices but remains a challenge. It shall be the purpose of this thesis. Part of this thesis shall be dedicated to the development of a Ni-Co-Mn-In Heusler film using a co-sputtering process. The main achievement of the thesis is to have obtained a film exhibiting a structural and magnetic transformation at room temperature. After a study of the structure and microstructure of martensite and austenite phases, magnetic properties are investigated. The evolution of the magnetic state during the first order transformation observed in some films leads to interesting magnetocaloric and activating properties. Optimal results, both in terms of working temperature and functional properties, are obtained for a film with a composition of Ni45,2Co4,7Mn36,2In13,9. Resistivity measurements under high magnetic field are novel on such films. These new measurements have made it possible to study the irreversibility and phase transformation blocking induced by a magnetic field (kinetic arrest). Understanding the physical effect underlying the thermal irreversibility and the blocking by a magnetic field is indeed important for applications based on such materials with strongly coupled mechanical, magnetical and thermal properties
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Venturato, Giulia. „Modelling the Influence of Phase Transformation Kinetics in 22MnB5 Hot Stamping“. Doctoral thesis, Università degli studi di Padova, 2019. http://hdl.handle.net/11577/3424888.
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Sheet metal forming has gained, over the last years, more and more importance since the automotive industry is demanding very specific characteristic for the new generation of components of the car body-in-white. The requirements of more lightness for enhancing the fuel saving is becoming a key factor for the design of new components, but the lightness must be coupled with a high mechanical resistance to grant the passengers’ safety. One of the most effective ways to meet these requirements has been the use of new generations of High Strength Steels (HSS), whose mechanical properties can be enhanced by thermal treatments. Direct hot stamping has represented an effective solution to do that, due to the possibility to shorten the process chain of many sheet metal parts typical of the car body-in-white. Thinner sheets have been used for the manufacturing of many automotive parts, granting the desired lightness and high resistance, to obtain the crashworthiness necessary to protect the passengers of the vehicle. Hot stamping is, nowadays, widely applied in the automotive industry, but the research in this field is still of high interest between the academic environment. This is because the process involves a large series of parameters that have to be accurately understood to enhance the performances and the complexity of the stamped parts. Since the initial heating to the last quenching step, the material undergoes a series of microstructural and mechanical transformations, whose optimization and right timing govern the final characteristic of the final component. In parallel to the industrial development work, a large branch of academic and scientific research is focused on the numerical modelling of the process which reveals of fundamental importance for the process design and optimization.
The present work stands in the framework of the researches in the field of the hot stamping process. The material investigated in this work is the AluSi® pre-coated quenchable steel 22MnB5, well known with the commercial name of Usibor 1500P®. The complete characterization of this material aims to fill the lack in literature about testing in hot condition the material flow stress of all the microstructural phases, proposing a fitting model capable to describe the mechanical behaviour in the FE models. The formability in hot conditions is studied as well, analysing the effect of the temperature and microstructure on the resultant Forming Limit Curve (FLC). The phase transformation kinetics was studied, confirming the literature and giving the motivation for this work. Finally, the damage criterion Generalized Incremental Stress-State dependent damage MOdel (GISSMO) was calibrated. The whole experimental activity was coupled with numerical simulations, for the necessary data analysis and calibration.
The work presented in this thesis has been carried out at the DII laboratories of the University of Padova, from October 2016 to September 2019 under the supervision of Prof. Andrea Ghiotti. This work was carried out within the framework of the University Research Project “Advanced CAE method to predict failure and material properties in hot forming” ref. 2014-4050 URP Award developed in cooperation with Ford Motor Company GMBH.La deformazione di lamiere sta guadagnando, negli ultimi anni, sempre più importanza dal momento che l’industria automobilistica sta richiedendo caratteristiche molto specifiche per la nuova generazione di componenti per la scocca. Le richieste di leggerezza per aumentare il risparmio di carburante sta diventando un fattore chiave per il design di nuovi componenti, ma la leggerezza deve necessariamente essere accoppiata con l’alta resistenza meccanica per garantire la sicurezza dei passeggeri. Uno dei metodi più efficaci per incontrare tali richieste è stato l’utilizzo della nuova generazione di acciai alto resistenziali (HSS), le cui proprietà meccaniche possono essere migliorate grazie ai trattamenti termici. Lo stampaggio a caldo diretto rappresenta una soluzione efficace per questo scopo, grazie alla possibilità di accorciare la catena di processo di molti componenti metallici della scocca dell’auto. Lamiere più sottili vengono impiegate per la produzione di molte parti dell’auto, garantendo le desiderate leggerezza e alta resistenza, per ottenere la resistenza agli urti necessaria a proteggere i passeggeri del veicolo. Lo stampaggio a caldo è, oggigiorno, ampiamente applicato nell’industria automobilistica, ma la ricerca in questo campo è ancora di alto interesse nell’ambiente accademico. Questo è dovuto al fatto che lo stampaggio a caldo coinvolge un’ampia serie di parametri che devono essere accuratamente compresi per migliorare il potenziale del processo e la complessità delle parti stampate. A partire dal primo stage di riscaldamento all’ultima fase di tempra, il materiale subisce una serie di trasformazioni microstrutturali e meccaniche, la cui ottimizzazione e il loro corretto timing controlla le caratteristiche finali del componente. Parallelamente al lavoro di ricerca sperimentale, una grande branca della ricerca è volta allo studio delle simulazioni numeriche che sono di fondamentale importanza per simulare il processo e ottimizzarne ogni step. Il presente lavoro si inquadra nella ricerca nell’ambito dello stampaggio a caldo. Il materiale studiato in questo lavoro è l’acciaio temprabile 22MnB5 rivestito da AluSi®, conosciuto commercialmente con il nome di Usibor 1500 P®. La completa caratterizzazione del materiale ha come scopo di coprire le mancanze nella letteratura nell’ambito dei test ad alta temperatura sulla reologia di tutte le microstrutture, proponendo un modello di fitting per rappresentare i dati nei modelli FE. La formabilità ad alta temperatura è altresì soggetto di studio, analizzando gli effetti della temperatura e della microstruttura nella risultante curva limite di formabilità (FLC). La cinetica di trasformazione di fase è stata oggetto di studio, confermando i dati presentati in letteratura e fornendo le basi per questo lavoro. Infine, il nuovo modello di danneggiamento Generalized Incremental Stress-State dependent damage MOdel (GISSMO) è stato calibrato. L’intera attività sperimentale è stata affiancata alle simulazioni numeriche, per la necessità dell’analisi e calibrazione dei dati. Il lavoro presentato in questa tesi è stato portato avanti nei laboratori del Dipartimento di Ingegneria Industriale, DII, dell’università di Padova, da ottobre 2016 a settembre 2019 sotto la supervisione del prof. Andrea Ghiotti. Questo lavoro è parte del progetto di ricerca dell’Università chiamato “Advanced CAE method to predict failure and material properties in hot forming” ref. 2014-4050 URP Award, sviluppato in collaborazione con Ford Motor Company GMBH.
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Moscu, Corcodel Alina. „Structural transformation under reaction conditions of supported PtSn nanoparticles characterized by in situ DRIFTS and kinetic modeling“. Thesis, Lyon 1, 2015. http://www.theses.fr/2015LYO10177.
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La réaction d’oxydation sélective du CO par O2 en présence d’un excès d’hydrogène (PROX) est considérée comme une étape de purification essentielle de l’H2 à utiliser dans des piles à combustible. L’objectif de cette thèse est de mieux comprendre le mécanisme de cette réaction sur des catalyseurs bimétallique s à base de Pt et Sn. Des catalyseurs modèles Pt et Pt-Sn ont été synthétisés en deux étapes : (i) formation de nanoparticules (NP) métalliques colloïdales en suspension suivi par ( ii) l’imprégnation de ces particules sur des supports. L’adsorption du CO suivit par spectroscopie FT-IR en réflexion diffuse (DRIFTS) a été utilisée pour caractériser ces solides après une réduction permettant de reformer des phases d’alliage PtSn. L’analyse DRIFTS permet de caractériser la nature des sites de Pt présents, soit dans l’alliage, soit dans des phases pures de Pt. La chaleur d’adsorption du CO sur la phase d’alliage a été mesurée par DRIFTS, pour la première fois, et apparait bien plus faible que celle sur le Pt seul. De manière surprenante, la ségrégation de l’alliage en présence de CO/H 2 à des températures inférieur es à 175°C a été mise en évidence. Des mesures in situ DRIFTS de la réaction d’oxydation préférentielle du CO (PROX) indiquent que l’alliage se transforme rapidement en Pt et SnOx de par la présence de l’O2. Aucune indication de la présence d’alliage n’a jamais pu être obtenue sous PROX, indiquant que les meilleures propriétés catalytiques associés aux phases Pt-Sn sont dues à leur habilité à générer une nouvelle phase active Pt+SnOx lors de leur ségrégation. Un modèle microcinétique du PROX sur Pt+SnOx a été développé sur la base de ceux pertinents à l’oxydation du CO et PROX sur Pt seul, permettant une modélisation satisfaisante des données. Ce travail montre l’intérêt du couplage des méthodes spectroscopiques et cinétiques pour la compréhension de la structure des catalyseurs « au travail » et des mécanismes de réactions complexesThe selective oxidation of CO in the presence of a large excess of H2 (PROX) is considered as a crucial step in the purification of H 2 to be used in low-temperature fuel cells, which are clean sources of energy. The objective of this thesis was to better understand the reaction mechanisms taking place over promising catalysts based on Pt and Sn. Model Pt-Sn catalysts were prepared by a two-step method: (i) synthesis of metallic nanoparticules (NP) in a colloidal suspension followed by (ii) the deposition of these NPs onto a support. The first step of the method enabled to produce well-controlled Pt-Sn NPs in terms of size and composition. However, the NPs were partly destroyed during the deposition step followed by calcination, due to the reoxidation of Sn. The adsorption of CO followed by diffuse reflectance spectroscopy (DRIFTS) was used to characterize the nature of these solids following a reduction, which was able to regenerate an alloyed phase. The DRIFTS analysis enabled to discriminate between Pt in an alloyed phase and Pt on monometallic surfaces. The heat of CO adsorption measured by DRIFTS appeared to be much lower than that associated with the pure Pt phase. Surprinsingly, a segregation of Pt and Sn was observed under a CO/H2 mixture below 175°C. In situ analysis by DRIFTS of the PROX reaction indicated that the Pt-Sn alloy rapidly decomposed in the presence of O2, forming an intimate mixture of Pt and SnOx. No evidence of the presence of Pt -Sn alloyed phases could be obtained under PROX conditions, suggesting that the superior catalytic activity of the Pt –Sn materials were related to the Pt+SnOx mixture. A detailed PROX microkinetic model was developed over Pt+SnOx, based on those relevant to CO oxidation and PROX over pure Pt. This work epitomises the benefits in combining in situ spectroscopic study with kinetic modelling to better understand the structure of catalysts “at work” and reaction mechanisms
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Shiraiwa, Manabu [Verfasser]. „Kinetic modeling and experiments on gas uptake and chemical transformation of organic aerosol in the atmosphere / Manabu Shiraiwa“. Mainz : Universitätsbibliothek Mainz, 2011. http://d-nb.info/1025263596/34.
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Moyano, Garcia Iván. „Controllability of of some kinetic equations, of parabolic degenerated equations and of the Schrödinger equation via domain transformation“. Thesis, Université Paris-Saclay (ComUE), 2016. http://www.theses.fr/2016SACLX062/document.
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Ce mémoire présente les travaux réalisés au cours de ma thèse dans le but d'étudier la contrôlabilité de quelques équations aux dérivées partielles. La première partie de cette thèse est consacrée à l'étude de la contrôlabilité de quelques équations cinétiques en différents régimes. Dans un régime collisionnel, nous étudions la contrôlabilité de l'équation de Kolmogorov, un modèle de type Fokker-Planck cinétique, posée dans l'espace de phases $R^d times R^d$. Nous obtenons la contrôlabilité à zéro de cette équation grâce à l'utilisation d'une inégalité spectrale associée à l'opérateur Laplacien dans tout l'espace. Dans un régime non-collisionnel, nous étudions la contrôlabilité de deux systèmes de couplage fluide-cinétique, les systèmes de Vlasov-Stokes et de Vlasov-Navier-Stokes, comportant des non-linéarités dues au terme de couplage. Dans ces cas, l'approche repose sur la méthode du retour.Dans la deuxième partie nous étudions la contrôlabilité d'une famille d'équations paraboliques dégénérées 1-D par la méthode de platitude, qui permet la constructions de contrôles explicites. La troisième partie porte sur le problème de la contrôlabilité de l'équation de Schrödinger par la forme du domaine, c'est-à-dire, en utilisant le domaine comme variable de contrôle. Nous obtenons un résultat de ce type dans le cas du disque unité bidimensionnel. Nos méthodes sont basées sur un résultat de contrôle exact local autour d'une certaine trajectoire, obtenu grâce au théorème d'inversion localeThis memoir presents the results obtained during my PhD, whose goal is the study of the controllability of some Partial Differential Equations.The first part of this thesis is concerned with the study of the controllability of some kinetic equations undergoing different regimes. Under a collisional regime, we study the controllability of the Kolmogorov equation, a particular case of kinetic Fokker-Planck equation, in the phase space $R^d times R^d$. We obtain the null-controllability of this equation thanks to the use of a spectral inequality associated to the Laplace operator in the whole space. Under a non-collisional regime, we study the controllability of two fluid-kinetic models, the Vlasov-Stokes system and the Vlasov-Navier-Stokes system, which exhibe nonlinearities due to the coupling terms. In those cases, the strategy relies on the Return method.In the second part, we study the controllability of a family of 1-D degenerate parabolic equations by the flatness method, which allows the construction of explicit controls.The third part is focused on the problem of the controllability of the Schrödinger equation via domain deformations, i.e., using the domain as a control. We obtain a result of this kind in the case of the two-dimensional unit disk, for radial data. Our methods are based on a local exact controllability result around a certain trajectory, obtained thanks to the Inverse Mapping theorem
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Cluff, Stephen Roy. „Characterization and Modeling of the Martensite Transformation in Advanced High-Strength Steels“. BYU ScholarsArchive, 2019. https://scholarsarchive.byu.edu/etd/9051.
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Multiple studies on the microstructures of advanced high-strength steels are presented here that seek to add to the already substantial body of knowledge on martensite in steel. These studies seek to gain additional insight into the role that the martensite transformation has on the observed mechanical properties of modern steels. Crystallographic Reconstruction of Parent Austenite Twin Boundaries in a Lath Martensitic Steel The study of post-transformation microstructures and their properties can be greatly enhanced by studying their dependence on the grain boundary content of parent microstructures. Recent work has extended the crystallographic reconstruction of parent austenite in steels to include the reconstruction of special boundaries, such as annealing twins. These reconstructions present unique challenges, as twinned austenite grains share a subset of possible daughter variant orientations. This gives rise to regions of ambiguity in a reconstruction. A technique for the reconstruction of twin boundaries is presented here that is capable of reconstructing 60 degree <1 1 1> twins, even in the case where twin regions are comprised entirely of variants that are common between the twin and the parent. This technique is demonstrated in the reconstruction of lath martensitic steels. The reconstruction method utilizes a delayed decision-making approach, where a chosen orientation relationship is used to define all possible groupings of daughter grains into possible parents before divisive decisions are made. These overlapping, inclusive groupings (called clusters) are compared to each other individually using their calculated parent austenite orientations and the topographical nature of the overlapping region. These comparisons are used to uncover possible locations of twin boundaries present in the parent austenite. This technique can be applied to future studies on the dependence of post-transformation microstructures on the special grain boundary content of parent microstructures. Coupling Kinetic Monte Carlo and Implicit Finite Element Methods for Predicting the Strain Path Sensitivity of the Mechanically Induced Martensite Transformation The kinetic Monte Carlo method is coupled with a finite-element solver to simulate the nucleation of martensite inside the retained austenite regions of a TRIP (transformation induced plasticity) assisted steel. Nucleation kinetics are expressed as a function of load path and kinematic coupling between retained austenite regions. The model for martensite nucleation incorporates known elements of the kinetics and crystallography of martensite. The dependence of martensite transformation on load path is simulated and compared to published experimental results. The differences in transformation rates of retained austenite are shown to depend on load path through the Magee effect. The effects of average nearest neighbor distance between austenite grains is shown to affect the rate at which martensite nucleates differently depending on load path. Ductility and Strain Localization of Advanced High-Strength Steel in the Presence of a Sheared Edge The localization of strain in the microstructures of DP 980 and TBF 980 is quantified and compared. Of particular interest is the difference in final elongation observed for both materials in the presence of a sheared edge. Scanning electron micrographs of etched microstructures near the sheared edge are gathered for both materials at varying amounts of macroscopic strain. These micrographs are used to generate strain maps using digital image correlation. A two point statistical measure for strain localization is developed that utilizes strain map data to quantify the degree to which strain localizes around the hard phase of both materials. The DP steel exhibits higher strain localization around the martensite phase. Reasons for differences in strain localization and shear banding between the two materials are suggested, and the role played by the mechanically induced martensite transformation is speculated.
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Xiong, Wei. „Thermodynamic and Kinetic Investigation of the Fe-Cr-Ni System Driven by Engineering Applications“. Doctoral thesis, KTH, Termodynamisk modellering, 2012. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-96707.
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This work is a thermodynamic and kinetic study of the Fe-Cr-Ni system as the core of stainless steels. The Fe-Cr, Fe-Ni and Cr-Ni systems were studied intensively using both computational and experimental techniques, including CALPHAD (CALculation of PHAse Diagrams), phase field simulation, ab initio modeling, calorimetry, and atom probe tomography. The purpose of this thesis is to reveal the complexity of the phase transformations in the Fe-Cr-Ni system via the integrated techniques. Due to the importance of the binary Fe-Cr system, it was fully reassessed using the CALPHAD technique by incorporating an updated description of the lattice stability for Fe down to zero kelvin. The improved thermodynamic description was later adopted in a phase field simulation for studying the spinodal decomposition in a series of Fe-Cr binary alloys. Using atom probe tomography and phase field simulation, a new approach to analyze the composition amplitude of the spinodal decomposition was proposed by constructing an amplitude density spectrum. The magnetic phase diagram of the Fe-Ni system was reconstructed according to the results from both ab initio calculations and reported experiments. Based on the Inden-Hillert-Jarl magnetic model, the thermodynamic reassessment of the Fe-Ni system demonstrated the importance of magnetism in thermodynamic and kinetic investigations. Following this, the current magnetic model adopted in the CALPHAD community was further improved. Case studies were performed showing the advantages of the improved magnetic model. Additionally, the phase equilibria of the Fe-Cr-Ni ternary were discussed briefly showing the need of thermodynamic and kinetic studies at low temperatures. The “low temperature CALPHAD” concept was proposed and elucidated in this work showing the importance of low temperature thermodynamics and kinetics for designing the new generation of stainless steels.QC 20120612
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Dussol, Damien. „Étude expérimentale et modélisation cinétique de la transformation d’éthanol en butadiène“. Thesis, Lyon, 2019. http://www.theses.fr/2019LYSE1221/document.
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Le butadiène est une molécule d’intérêt industriel qui peut être produite par le procédé dit Ostromislensky, avec l’éthanol en tant que matière première. Cette étude a pour objectif de développer un modèle cinétique pour expliquer la transformation d’un mélange éthanol/acétaldéhyde en butadiène, dans le cadre de la seconde étape de ce procédé. Le modèle cinétique est basé sur un schéma réactionnel et un modèle de réacteur. Le schéma proposé comprend la voie de Gorin Jones, communément acceptée dans la littérature, et une toute nouvelle voie impliquant un intermédiaire buténone. Les étapes clés ont été étudiées spécifiquement via des tests dédiés. Le schéma décrit aussi les étapes amenant aux principaux produits secondaires. Il a été validé à partir d’une base de données expérimentale, générée en amont de l’étude sur une unité de type gaz/solide, lit fixe, isobare (3 bara) et isotherme, avec un catalyseur Ta2O5 SiO2. L’influence des conditions opératoires sur l’effluent a été observée pour trois ratios éthanol/acétaldéhyde et sur des gammes de PPH (1,1 à 8,1 g·gcata 1·h-1) et de températures (320 à 370 °C). Le réacteur (piston dispersif sans limitations diffusionnelles) intégrant des lois cinétiques d’ordre, a été modélisé à l’état permanent via un solveur LSODE. Les paramètres cinétiques ont été estimés via un optimiseur Levenberg Marquardt à partir de la base de données expérimentale. Le modèle cinétique obtenu, basé sur un schéma réactionnel inédit, est en capacité de représenter et de prédire les débits des composés principaux et les tendances et ordre de grandeurs des débits des composés minoritaires selon les effets de PPH, de charge et de température, excepté dans certaines conditions opératoires limites isoléesButadiene is a molecule of industrial interest that can be produced by the so-called Ostromislensky process, with ethanol as raw material. This study aims to develop a kinetic model to explain the transformation of an ethanol/acetaldehyde mixture into butadiene, as part of the second step of this process. The kinetic model is based on a reaction scheme and a reactor model. The proposed scheme includes the commonly accepted Gorin Jones pathway and a new pathway involving a butenone intermediate. The key steps were specifically studied via dedicated experiments. The scheme describes also steps leading to by products. It was validated from an experimental database, generated upstream of the study on a gas / solid type unit, fixed bed, isobaric (3 bara) and isothermal, with a Ta2O5 SiO2 catalyst. The influence of the operating conditions on the effluent was observed for three ethanol/acetaldehyde ratios and over ranges of PPH (1.1 to 8.1 g·gcata 1·h-1) and temperatures (320 to 370 °C). The reactor (plug flow without diffusional limitations) integrating kinetic laws of order, was modeled in the permanent state via a solver LSODE. Kinetic parameters were estimated via a Levenberg Marquardt optimizer from the experimental database. The kinetic model obtained, based on a brand new reaction scheme, is able to represent and predict the flow rates of the main compounds and the trends and orders of magnitude of the flow rates of the minority compounds according to the effects of PPH, charge and temperature, except under certain isolated operating conditions
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Swarts, Andrew John. „Novel transition metal complexes based on N,N and N,P ligands as catalysts for ethylene transformation reactions“. Thesis, Stellenbosch : Stellenbosch University, 2014. http://hdl.handle.net/10019.1/86330.
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Santos, Alan Silva dos. „Transformation de composés modèles soufrés et oléfiniques représentatifs d'une essence de FCC. Approche expérimentale et théorique“. Thesis, Poitiers, 2017. http://www.theses.fr/2017POIT2276/document.
Annotation:
Une des voies privilégiées pour réduire la teneur en soufre dans les essences commerciales est l'hydrodésulfuration sélective (HDS) des essences issues du procédé de FCC. Une essence étant composée d'un mélange de composés soufrés (1000 ppm) et d'oléfines (20-40%pds). Il est important de comprendre leur transformation de manière à améliorer l'HDS tout en minimisant l'hydrogénation (HYD) des oléfines. Par conséquent, la transformation de plusieurs molécules modèles soufrées (2-méthylthiophène, 3-méthylthiophène et le benzothiophène) et oléfiniques (hex-1-ène, 4-méthylpent-1-ène, 3,3-diméthylbut-1-ène et 2,3-diméthylbut-2-ène) a été étudiée dans les conditions opératoires d'HDS. Par une approche expérimentale couplée à de la modélisation cinétique, nous avons établi une échelle de réactivité entre les composés soufrés d'une part et les oléfines d'autre part. Le benzothiophène est le composé le plus réactif, mais aussi celui qui est le plus inhibiteur pour la transformation des autres composés soufrés. Concernant les oléfines, l'hex-1-ène est la plus réactive par rapport aux autres oléfines ramifiées. Lorsque ces composés sont en mélange, on constate des inhibitions mutuelles plus au moins conséquentes selon la structure des composés modèles. Ces effets qui résultent de compétitions à l'adsorption entre les molécules à la surface du catalyseur ont été modélisés et quantifiés (constantes cinétique et d'adsorption) à partir d'un modèle unique en considérant le formalisme de Langmuir-HinshelwoodA preferred route to reduce the sulfur content on the commercial gasoline is the selective hydrodesulfurization (HDS) process of FCC gasoline. A typical gasoline is composed by a mixture of sulfur (1000 ppm) and olefins (20-40%wt) compounds. Therefore, it is important to understand their transformation in order to improve the HDS and minimizing the olefin hydrogenation (HYD). Consequently, the transformation of various sulfur (2-methylthiophene, 3-methylthiophene and benzothiophene) and olefins (hex-1-ene, 4-methylpent-1-ene, 3,3-dimethylbut-1-ene and 2,3-dimethylbut-2-ene) has been studied under HDS operating conditions.By experimental and theoretical (kinetic modeling) approaches, a reactivity scale has been established between the sulfur compounds on one hand and olefins compounds on the other hand. The benzothiophene is the most reactive compound. However it is the most inhibitor compound for the transformation of others sulfur compounds. Regarding the olefins, the hex-1-ene is the most reactive compound among the others branched compounds. A mutual inhibition has been observed when those compounds are studied in mixture according with their structures. These effects result from competitive adsorption between the molecules on the catalyst surface. These results could be modeled and quantified (adsorption and kinetic constants) from a unique model considering the Langmuir-Hinshelwood formalism
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Na, Dong-Yeop NA. „Electromagnetic Particle-in-Cell Algorithms on Unstructured Meshes for Kinetic Plasma Simulations“. The Ohio State University, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=osu1543398838970791.
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Liu, Rong. „Enzymes as catalysts in synthesis of enantiomerically pure building blocks : secondary alcohols bearing two vicinal stereocenters“. Doctoral thesis, Stockholm : Chemical Science and Engineering, KTH, 2005. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-424.
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Brownie, Barbara Kay. „The behaviours of fluid characterforms in temporal typography“. Thesis, University of Hertfordshire, 2012. http://hdl.handle.net/2299/9037.
Annotation:
This thesis identifies and characterises a particular kind of temporal typography in which verbal forms exhibit behaviours that have been identified by Eduardo Kac as ‘fluid’ , and fluctuate between the verbal and pictorial or abstract. A typology will be constructed which identifies the various behaviours by which fluidity is exhibited, and provides terminology for their analysis, accompanied by analysis of how these behaviours address the relationship between the commonly distinct paradigms of verbal and pictorial signs. The work identifies the distinction between fluidity and other forms of kineticism, and explores the various behaviours exhibited in fluid artefacts. When addressing local kineticism, gaps in existing research are filled by employing terms and observations from other fields. For example, Kac offers the term ‘fluid’ in description of his holographic poetry, which exhibits behaviours much like those presented in some examples of screenbased temporal typography. This thesis proposes that Kac’s term, ‘fluid’, may be adopted in order to differentiate significant local change in verbal forms from the various other kinds of kineticism observable in temporal typography. Fluid behaviours are identified in examples including Martin Lambie Nairn and MPC’s Channel 4 idents, the credit sequences of Kyle Cooper, and the typographic animations of practitioners including Komnios Zervos and Dan Waber. This thesis demonstrates that the existing discourse surrounding temporal typography has been held back by a failure to make distinguish between global kineticism (effecting layout) and local kineticism (effecting individual characters). The distinction between the global and the local is considered vital in studies of perceptual organisation, particularly Gestalt psychology. By providing a coherent typology, and consistent terminology, this study has the potential to positively influence understanding and analysis of fluid characterforms.
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Feng, Zhiyao. „The Deformation-induced Martensitic Phase Transformation in Low Chromium Iron Nitrides at Cryogenic Temperatures“. Case Western Reserve University School of Graduate Studies / OhioLINK, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=case1526306156203016.
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Monassier, Antoine [Verfasser], Fritz Elmar [Akademischer Betreuer] Kühn und Jean-Marie [Akademischer Betreuer] Basset. „Kinetic and mechanistic studies on the transformation of carbon dioxide by molecular catalysts / Antoine Monassier. Gutachter: Jean-Marie Basset ; Fritz Elmar Kühn. Betreuer: Fritz Elmar Kühn“. München : Universitätsbibliothek der TU München, 2012. http://d-nb.info/1031550437/34.
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Lu, Chang-Tsan. „Atomistic Study of Motion of Twin Boundaries: Nucleation, Initiation of Motion, and Steady Kinetics“. Research Showcase @ CMU, 2013. http://repository.cmu.edu/dissertations/297.
Annotation:
The materials that exhibit martensite transformation have very important applications in engineering, and the microstructures of the materials play a key role foraffecting their mechanical behavior in macroscope. Therefore many attentions havebeen drawn for studying the related problems. This work focuses on the motion oftwin boundaries. Three questions are being asked: how is a twin boundary is nucleated in a homogenous (untwinned) material? After the twin boundary is nucleated,how is its motion initiated? How fast does it move? This study provides an atomisticunderstanding for these three questions.
Linear stability analysis is firstly applied to capture the initiation of motion of atwin boundary. When a twin boundary is about to move, the lowest eigenvalue of thesystem Hessian drops to zero. And the corresponding eigenvector predicts accuratelythe way in which the twin boundary is going to move. The same idea is applied toinvestigate how motion of an irrational twin boundary is initiated. Atomic modelsof irrational twin boundaries are constructed by employment of continuum models,provided that the point group of rotations which relate two variants is extended toany rotations in plane. The zero eigenvectors reveal the complicated behavior ofmotion of irrational twin boundaries.
The problem of nonuniqueness of kinetic relations proposed by Schwetlick andZimmer is solved in a thermoelasticity framework. By calculating the net heat fluxcrossing the phase boundary which is carried by the phonons, a unique kinetic relationcan be determined. Finally, a nonlocal criterion for nucleation of twin boundariesis proposed. By checking the stiffness of each unit cell evaluated with respect to asingle variable that represents the displacement along the unit cell diagonal direction,locations and the orientations of nucleated twin boundaries can be predicted.
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Іваненко, Тетяна, und Михайло Опалєв. „Інноваційні шрифтові експерименти як засіб самовираження“. Thesis, Київський національний університет технологій та дизайну, 2018. https://er.knutd.edu.ua/handle/123456789/10387.
Annotation:
Розглянуто експериментальні прийоми у шрифтовому дизайні як соціокультурне явище та рефлексію на майбутнє. Результати дослідження побудовані на прикладі як професійних шрифтових проектів, так і роботах дизайнерів та художників, що не спеціалізуються на шрифтовій справі. Розглянуто прийоми трансформації морфологічних структур акцидентного шрифту, а також сучасні технічні прийоми виконання авторського задуму.The experimental techniques in the font design are considered as a socio-cultural phenomenon and reflection for the future. The results of the study are based on an example of professional font projects, as well asworks by designers and artists who do not specialize in typeface design. Techniques of transformation of the morphological structures of the accident font, as well as modern technical methods of execution of the author's plan, are considered.
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Mercier, Géraldine. „Equipo 57. Un art expérimental collectif au service d’une transformation de la société, entre l’Espagne franquiste et l’Europe (1957-1966)“. Thesis, Paris 4, 2017. http://www.theses.fr/2017PA040200.
Annotation:
Dans une Espagne étouffée par la dictature de Francisco Franco qui tente de réintégrer la scène artistique internationale en promouvant à l’étranger certains artistes abstraits informels, la position de collectif d’artistes abstraits géométriques Equipo 57 est singulière. Désireux de découvrir un monde libre et assoiffés de savoir, les jeunes artistes Juan Serrano, José Duarte, Agustín Ibarrola et Ángel Duart se rencontrent à Paris en 1957. Partageant les mêmes affinités pour l’art construit, les avant-gardes russes et la même volonté de rénovation de la vie culturelle espagnole, ils décident de former une équipe de travail et de discussion. De retour à Cordoue, rejoints par Juan Cuenca, les cinq membres du collectif élaborent la théorie de l’Interactivité de l’espace plastique qui sous-tend leurs créations, où l’individualité de chacun est gommée au profit de l’oeuvre collective. À la recherche d’un art qui puisse se réintégrer dans la vie quotidienne tout en questionnant la responsabilité de l’artiste, Equipo 57 emploie un langage rationnel et objectif qui s’exprime aussi bien dans le champ de la peinture, de la sculpture que du design. Il tente ainsi de conjuguer recherches formelles et engagement social. Cette première étude monographique en français propose d’analyser le parcours d’Equipo 57, depuis sa formation à Paris en 1957 jusqu’à dissolution officielle en 1966, en le confrontant au contexte socioculturel de l’Espagne franquiste et de l’Europe occidentale au tournant des années cinquante et soixanteIn the 1950s, as Francisco Franco’s dictatorship tries to reintegrate its stifled country’s art scene onto the world stage by promoting certain Spanish abstract expressionists abroad, the position of Equipo 57, a collective of geometrical abstractionists, is unique. Eager to discover the free world, and thirsty for knowledge, the young artists Juan Serrano, José Duarte, Agustín Ibarrola and Ángel Duart meet in Paris in 1957. Sharing the same affinity for constructivist art and the Russian avant-garde, and united in their desire to renew Spanish cultural life, they decide to form a team of work and discussion. Upon their return to Cordoba, where they are joined by Juan Cuenca, the five members of the team elaborate a theory of the Interactivity of plastic space which guides their creation. The individuality of each member is thus erased for the good of the collective work. Aiming for an art that is able to enter into everyday life while questioning the responsibility of the artist, Equipo 57 uses a rational and objective language which takes form in painting, sculpture and design. They try to combine formal experiments as well as socio-political engagement. This premier monographic study in French aims to analyze the career of Equipo 57, from its inception in Paris in 1957 to its official dissolution in 1966. The group’s existence will be confronted with its sociocultural context in Franco’s Spain and Western Europe at the turn of the decade of the 1950s and 1960s
23
Wang, Bincheng. „Ultrahigh Density Magnetic Recording Media: Quantitative Kinetic Experiments and Models of the A1 to L10 Phase Transformation in FePt and Related Ternary Alloy Films“. Research Showcase @ CMU, 2011. http://repository.cmu.edu/dissertations/72.
Annotation:
L10 ordered FePt continues to be of interest for ultrahigh density magnetic recording media, in particular, heat assisted magnetic recording (HAMR) media. However, when deposited at room temperature, the alloy film forms in the chemically disordered A1 state, requiring a post-deposition anneal at high temperatures or for long times, or deposition onto heated substrates at temperature ≥ 400 °C to form the ordered L10 phase. It has been of interest to identify ternary alloying additions that can reduce the post deposition annealing or the elevated deposition temperatures, and to examine the impact of deposition at elevated temperatures on the transformation kinetics.
Binary and ternary alloy films were sputter deposited from elemental targets at nominally room temperature at two different thicknesses of 1 micron and 500 nm. The latter films were used for composition analysis using energy dispersive X-ray spectrometry (EDS). The transformation from the A1 phase to the L10 phase was studied by differential scanning calorimetry (DSC) using freestanding micron-thick films. The kinetic ordering temperature (KOT), defined as the peak temperature of the DSC trace at a heating rate of 40 °C/min, was used to evaluate the impact of alloy composition and alloying additions on the ordering transformation
The nine ternary alloying elements and composition ranges are: 0.0 - 2.6 at.% Mg, 0.7 – 12.2 at.% V, 2.2 – 16.3 at.% Mn, 1.6 – 21.5 at.% Ni, 1.3 – 17.3 at.% Cu, 0.0 – 16.7 at.% Ag, 1.9 – 13.8 at.% Au, 1.2 – 12.9 at.% B and 1.4 at.% C. Compared with binary FePt, Cu additions have no impact on the (KOT), whereas all the other additions except C result in an increase of KOT. Additional experiments are necessary to better evaluate the impact of C additions. Elevated temperature deposition experiments showed that higher deposition temperatures result in faster transformation only for binary films with > 46 at.% Pt.
The time-temperature-transformation (TTT) and isothermal transformation curves for binary FePt and ternary Fe46.7Cu2.4Pt50.9 films were calculated using the Michaelsen- Dahms (MD), k2(T), k2(T)N(T) and a new continuous nucleation model, k2(T)N(T,t). The model that most closely agrees with all available experimental data is the k2(T) model.
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Svärd, Michael. „Structural, Kinetic and Thermodynamic Aspects of the Crystal Polymorphism of Substituted Monocyclic Aromatic Compounds“. Doctoral thesis, KTH, Teknisk strömningslära, 2011. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-33836.
Annotation:
This work concerns the interrelationship between thermodynamic, kinetic and structural aspects of crystal polymorphism. It is both experimental and theoretical, and limited with respect to compounds to substituted monocyclic aromatics. Two polymorphs of the compound m-aminobenzoic acid have been experimentally isolated and characterized by ATR-FTIR spectroscopy, X-ray powder diffraction and optical microscopy. In addition, two polymorphs of the compound m-hydroxybenzoic acid have been isolated and characterized by ATR-FTIR spectroscopy, high-temperature XRPD, confocal Raman, hot-stage and scanning electron microscopy. For all polymorphs, melting properties and specific heat capacity have been determined calorimetrically, and the solubility in several pure solvents measured at different temperatures with a gravimetric method. The solid-state activity (ideal solubility), and the free energy, enthalpy and entropy of fusion have been determined as functions of temperature for all solid phases through a thermodynamic analysis of multiple experimental data. It is shown that m-aminobenzoic acid is an enantiotropic system, with a stability transition point determined to be located at approximately 156°C, and that the difference in free energy at room temperature between the polymorphs is considerable. It is further shown that m-hydroxybenzoic acid is a monotropic system, with minor differences in free energy, enthalpy and entropy. 1393 primary nucleation experiments have been carried out for both compounds in different series of repeatability experiments, differing with respect to solvent, cooling rate, saturation temperature and solution preparation and pre-treatment. It is found that in the vast majority of experiments, either the stable or the metastable polymorph is obtained in the pure form, and only for a few evaluated experimental conditions does one polymorph crystallize in all experiments. The fact that the polymorphic outcome of a crystallization is the result of the interplay between relative thermodynamic stability and nucleation kinetics, and that it is vital to perform multiple experiments under identical conditions when studying nucleation of polymorphic compounds, is strongly emphasized by the results of this work. The main experimental variable which in this work has been found to affect which polymorph will preferentially crystallize is the solvent. For m-aminobenzoic acid, it is shown how a significantly metastable polymorph can be obtained by choosing a solvent in which nucleation of the stable form is sufficiently obstructed. For m-hydroxybenzoic acid, nucleation of the stable polymorph is promoted in solvents where the solubility is high. It is shown how this partly can be rationalized by analysing solubility data with respect to temperature dependence. By crystallizing solutions differing only with respect to pre-treatment and which polymorph was dissolved, it is found that the immediate thermal and structural history of a solution can have a significant effect on nucleation, affecting the predisposition for overall nucleation as well as which polymorph will preferentially crystallize. A set of polymorphic crystal structures has been compiled from the Cambridge Structural Database. It is found that statistically, about 50% crystallize in the crystallographic space group P21/c. Furthermore, it is found that crystal structures of polymorphs tend to differ significantly with respect to either hydrogen bond network or molecular conformation. Molecular mechanics based Monte Carlo simulated annealing has been used to sample different potential crystal structures corresponding to minima in potential energy with respect to structural degrees of freedom, restricted to one space group, for each of the polymorphic compounds. It is found that all simulations result in very large numbers of predicted structures. About 15% of the predicted structures have excess relative lattice energies of <=10% compared to the most stable predicted structure; a limit verified to reflect maximum lattice energy differences between experimentally observed polymorphs of similar compounds. The number of predicted structures is found to correlate to molecular weight and to the number of rotatable covalent bonds. A close study of two compounds has shown that predicted structures tend to belong to different groups defined by unique hydrogen bond networks, located in well-defined regions in energy/packing space according to the close-packing principle. It is hypothesized that kinetic effects in combination with this structural segregation might affect the number of potential structures that can be realized experimentally. The experimentally determined crystal structures of several compounds have been geometry-optimized (relaxed) to the nearest potential energy minimum using ten different combinations of common potential energy functions (force fields) and techniques for assigning nucleus-centred point charges used in the electrostatic description of the energy. Changes in structural coordinates upon relaxation have been quantified, crystal lattice energies calculated and compared with experimentally determined enthalpies of sublimation, and the energy difference before and after relaxation computed and analysed. It is found that certain combinations of force fields and charge assignment techniques work reasonably well for modelling crystal structures of small aromatics, provided that proper attention is paid to electrostatic description and to how the force field was parameterized. A comparison of energy differences for randomly packed as well as experimentally determined crystal structures before and after relaxation suggests that the potential energy function for the solid state of a small organic molecule is highly undulating with many deep, narrow and steep minima.QC 20110527
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Dupont, Anthony. „Cinétiques de transformations de produits pharmaceutiques sous broyage“. Electronic Thesis or Diss., Université de Lille (2022-....), 2022. https://pepite-depot.univ-lille.fr/LIBRE/EDSMRE/2022/2022ULILR020.pdf.
Annotation:
L'objectif de cette thèse, est d'améliorer la compréhension des mécanismes microscopiques fondamentaux qui gouvernent les transformations de phases induites directement à l'état solide par broyage mécanique. Trois problèmes essentiels ont été plus particulièrement abordés : (i) Nous avons évalué l'influence de la température de broyage sur la vitesse d'amorphisation effective d'un matériau cristallin. (ii) Nous avons déterminé l'influence des caractères monotrope et énantiotrope sur les mécanismes de transformations polymorphiques sous broyage. (iii) Nous avons montré que les transformations polymorphiques sous broyage ne sont pas directes mais qu'elles font, au contraire, intervenir un mécanisme d'amorphisation transitoire. Notre stratégie a consisté à étudier ces différents problèmes par une analyse fine des cinétiques de transformations qui sont le reflet direct des mécanismes physiques qui les gouvernent. Pour cela, nous avons étudié en détail les cinétiques transformations d'états physiques de plusieurs composés judicieusement choisis. Il s'agit notamment de l'hydrochlorothiazide, du sorbitol, de la glycine et de leurs mélanges. Les investigations ont principalement été menées par diffraction des rayons X et par analyse enthalpique différentielle (DSC). De plus, certains mécanismes de transformation mis en évidence expérimentalement ont pu être modélisés et validés par simulations numériques. En résumé, l'ensemble de nos travaux indiquent que, d'une manière générale, les transformations sous broyage semblent résulter systématiquement d'une compétition entre un mécanisme d'amorphisation dû aux chocs mécaniques et un mécanisme de recristallisation dont la nature dépend à la fois de la température de broyage et des spécificités cristallines du matériauThe objective of this thesis is to improve the understanding of the fundamental microscopic mechanisms that govern the phase transformations induced directly in the solid state by mechanical milling. In particular, three key issues have been addressed: (i) We evaluated the influence of the milling temperature on the effective amorphization rate of a crystalline material. (ii) We determined the influence of monotropic and enantiotropic characters on the mechanisms of polymorphic transformations under milling. (iii) We have shown that the polymorphic transformations under milling are not direct but involve, on the contrary, a transient amorphization mechanism. Our strategy consisted in studying these different problems through a detailed analysis of the transformation kinetics which are the direct reflection of the physical mechanisms that govern them. For this purpose, we have studied in detail the transformation kinetics of physical states of several carefully chosen compounds. These include hydrochlorothiazide, sorbitol, glycine and their mixtures. The investigations were mainly carried out by X-ray diffraction and differential scanning calorimetry (DSC). Moreover, some experimentally demonstrated transformation mechanisms could be modelled and validated by numerical simulations. In summary, all our work indicates that, in general, the transformations under milling seem to result systematically from a competition between an amorphization mechanism due to mechanical shocks and a recrystallization mechanism whose nature depends on both the milling temperature and the crystalline specificities of the material
26
Kempen, Antoine. „Solid state phase transformation kinetics“. [S.l.] : [s.n.], 2002. http://deposit.ddb.de/cgi-bin/dokserv?idn=964251191.
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Kempen, Antonius Theodorus Wilhelmus. „Solid state phase transformation kinetics“. Stuttgart : Max-Planck-Institut für Metallforschung, 2001. http://www.bsz-bw.de/cgi-bin/xvms.cgi?SWB9795832.
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Garnier, Thomas. „Transfert d'échelle dans la modélisation thermodynamique et cinétique des alliages“. Phd thesis, Université Paris Sud - Paris XI, 2012. http://tel.archives-ouvertes.fr/tel-00784326.
Annotation:
La prédiction des microstructures représente un enjeu majeur pour l'étude des processus de vieillissement des alliages métalliques, en particulier sous irradiation. Les résultats des calculs ab initio de structure électronique peuvent être utilisés pour paramétrer les méthodes cinétiques de Monte Carlo Atomique et permettent ainsi de simuler quantitativement la diffusion des atomes et l'évolution de la microstructure qui en résulte. Cette méthode est cependant limitée par le temps de calcul qu'elle exige. Les simulations mésoscopiques évitent cet écueil, mais souffrent généralement de ne pouvoir être paramétrées sur les résultats obtenus aux échelles inférieures, limitant ainsi leur pouvoir de prédiction. Dans ce travail, une méthode de simulation appelée Monte Carlo cellulaire cinétique a été développée pour relier les échelles atomiques et mésoscopiques tout en conservant la nature discrète des atomes. Une procédure de paramétrisation basée sur les simulations Monte Carlo à l'échelle atomique a été établie. Elle permet de reproduire quantitativement les propriétés macroscopiques d'équilibre des alliages indépendamment de la taille des cellules utilisées. Une application à l'alliage fer-cuivre est présentée. Afin de décrire les propriétés cinétiques à ces échelles, un outil générique de calcul de la matrice d'Onsager dans les alliages a été mis en place. Il est fondé sur la theorie du Champ Moyen Auto-Cohérent. Les résultats obtenus sur des cinétiques de diffusion et de précipitation dans un alliage modèle sont présentés et validés par une comparaison systématique avec des simulations Monte Carlo à l'échelle atomique.
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Sheikh, Kharisha S. „Kinetics of 2, 4, 6-Trinitrotoluene Reduction by Pseudomonas Putida“. Ohio University / OhioLINK, 2006. http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1156790187.
30
Mohapatra, Goutam. „Phase transformation kinetics the role of stress /“. [S.l. : s.n.], 2006. http://nbn-resolving.de/urn:nbn:de:bsz:93-opus-28837.
31
Lewis, Ryan D. „Everted Sanctuaries: Increments of Silence“. Ohio University / OhioLINK, 2013. http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1366374561.
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Wu, Hsiu-Jean. „The kinetics of solvent-mediated phase transformations“. Diss., The University of Arizona, 1990. http://hdl.handle.net/10150/184981.
Annotation:
The objectives of this work are to characterize and model the solvent-mediated phase transformation process of theophylline anhydrous crystals to the monohydrate crystals in an aqueous system. In order to model the transformation, the following processes are taken into account: (1) the dissolution kinetics of theophylline anhydrous crystals, (2) the kinetics of the formation of theophylline monohydrate nuclei, and (3) the growth kinetics of the monohydrate crystals. The driving forces for the above processes are determined from the concentration of theophylline in the solution and the solubilities of theophylline anhydrous and monohydrate. The solubilities of theophylline anhydrous and the monohydrate, and these three distinct processes along with the overall transformation phenomena were investigated in the present study. By using theophylline as a model compound we have gained some understanding of the kinetics of the solvent-mediated phase transformation between the metastable anhydrous form and the stable hydrated form of an organic compound and we were able to model the transformation process. By identifying the mechanisms for nucleation, growth of the hydrate form and the dissolution of the anhydrous form one can predict and control the transformation process. The growth kinetics of thymine monohydrate crystals at various temperatures are also investigated in the present study.
33
Riehm, Derek J. „Kinetics of the pearlite to austenite reversion transformation“. Thesis, University of British Columbia, 1990. http://hdl.handle.net/2429/29739.
Annotation:
The pearlite-to-austenite reversion transformation kinetics under isothermal and continuous
heating conditions in a eutectoid plain-carbon steel have been measured, using a dilatometric technique on a Gleeble 1500 Thermomechanical Simulator. The isothermal data was characterized in terms of the transformation start time at temperature for the onset of the P→ γ transformation, and in terms of the Avrami parameters n and b. Under the assumption that the P→ γ transformation was additive, the Scheil equation was applied to the measured isothermal transformation start data to predict the onset of the transformation on continuous heating, and the isothermal phase transformation kinetics were used to predict the continuous heating kinetics.
It was found that the kinetic model significantly underpredicted the transformation start time during continuous heating. This was attributed to the large experimental error inherent in the estimation of the isothermal transformation start time, t[formula omitted].
The model's continuous heating kinetic predictions were excellent at low heating rates, but it tended to overpredict the kinetics at higher heating rates. The problem was traced to an observed difference between the measured temperature and the programmed temperature
during the high heating rate tests. When the model was modified to incorporate the actual temperature profile, its prediction of the kinetics was considerably improved. Thus the austenite reversion transformation was concluded to be experimentally additive.
An average Avrami n value of 2.2 suggested that austenite was nucleating on pearlite colony corners and edges. This conclusion was verified with optical and scanning electron microscopy.
Previously published data, which indicated that the pearlite-to-austenite transformation
is isokinetic, was found to be based on questionable assumptions. Metallographic information suggests, however, that the nucleation sites are saturated early in the reaction.
Furthermore, the isothermal austenite formation data generated in this work was found to meet the effective site saturation criterion for additivity, implying that the austenitization process would be expected to be additive.
The effect of starting microstructure was evaluated by performing isothermal and continuous heating tests on two different pearlitic microstructures. It was found that, in agreement with published results, the transformation rate varied in inverse proportion with the pearlite spacing and colony size.Applied Science, Faculty of
Materials Engineering, Department of
Graduate
34
Gehringer, Paul. „Transformations: An Arts Center for Narrows, Virginia“. Thesis, Virginia Tech, 1999. http://hdl.handle.net/10919/36253.
Annotation:
What is the role of mechanisms and change in architecture? How does a building relate to the people in and around it? How might architecture interact with people, not as an object, but as a participant in a dialogue?Master of Architecture
35
Bogár, Krisztián. „Synthetic transformations via metal- and enzyme-catalyzed dynamic kinetic resolution /“. Stockholm : Department of Organic Chemistry, Stockholm University, 2007. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-6876.
36
Bauer, Rico [Verfasser]. „Solid-solid phase transformation kinetics / vorgelegt von Rico Bauer“. Stuttgart : Max-Planck-Inst. für Metallforschung, 2010. http://d-nb.info/100971175X/34.
37
Jones, Stephen John. „Modelling inclusion potency and simultaneous transformation kinetics in steels“. Thesis, University of Cambridge, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.245152.
38
Bray, Helen Jane. „Kinetics of high-temperature transformations of clay minerals“. Thesis, University of Cambridge, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.249204.
39
Fan, Frank Yongzhen. „Kinetics of phase transformations in lithium-sulfur batteries“. Thesis, Massachusetts Institute of Technology, 2017. http://hdl.handle.net/1721.1/111247.
Annotation:
Thesis: Ph. D., Massachusetts Institute of Technology, Department of Materials Science and Engineering, 2017.This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.
Cataloged from student-submitted PDF version of thesis.
Includes bibliographical references (pages 139-150).
Sulfur is a promising positive electrode for lithium batteries with the potential to create the step-change improvement in energy density and cost needed for the widespread adoption of electric vehicles and renewable energy. However, lithium-sulfur batteries suffer from a number of challenges, among them poor rate capability resulting in part from a complex dissolution-precipitation mechanism which produces electronically insulating end members S₈ and Li₂S. Few studies have heretofore been performed on rate-limiting mechanisms in Li-S batteries, which must be elucidated in order to inform rational design of electrodes with high capacity and rate capability. Polysulfide solutions, intermediates in the electrochemical reduction of sulfur, are used for the first time to make an efficient, high energy density flow battery, enabled by a novel flow battery architecture using a percolating network of nanoscale conductive carbon. An extensive experimental study of exchange current density for redox of higher order polysulfide solutions and their ionic conductivity has been conducted. The type and amount of electrolyte solvent has been found to influence both of these. The second portion of this thesis characterizes the kinetics of Li₂S electrodeposition, which is responsible for three-quarters of the theoretical capacity of the sulfur cathode. Kinetics are found to be highly dependent on solvent choice in a manner similar to exchange current density. Furthermore, electrodeposition kinetics are found to slow considerably at the low electrolyte/sulfur ratios which are needed for high energy density and low cost. Materials such as conductive oxides can serve as nucleation promoters and help solve this challenge. The morphology of precipitates is found to be dependent on discharge rate, with large, discrete particles forming at low rates. A model was for describing 3-D electrodeposition of Li₂S under the influence of a soluble redox mediator which enables efficient utilization of conductive surface area and prevents passivation of conductive carbon with insulating Li₂S.
by Frank Yongzhen Fan.
Ph. D.
40
Alves, Margot. „Carbon dioxide and vegetable oil for the synthesis of bio-based polymer precursors“. Thesis, Bordeaux, 2016. http://www.theses.fr/2016BORD0129/document.
Annotation:
Bien que thermodynamiquement et cinétiquement stable, le dioxyde de carbone est une molécule qui peut être convertie en carbonates cycliques à cinq ou six atomes respectivement au départ d’époxydes ou d’oxétanes moyennant l’utilisation d’un catalyseur approprié. Ces carbonates cycliques sont utilisés comme solvants verts, électrolytes pour les batteries au lithium ou comme intermédiaires pour la synthèse de polymères. Cependant, les performances catalytiques doivent être améliorées en particulier pour lecouplage du CO2 avec les huiles végétales époxydées ou les oxétanes. Dans ce contexte, nous avons développé un nouveau catalyseur homogène bicomposant organique composé d’un sel d’ammonium jouant le rôle de catalyseur et d’un co-catalyseur fluoré simple ou double donneur de liaison hydrogène. Dans un premier temps, l’efficacité de ces nouveaux catalyseurs a été évaluée et optimisée pour le couplage entre un époxyde terminal et le CO2 via des études cinétiques par spectroscopie FTIR ou Raman in-situ sous pression. Ces études ont démontré que l’utilisation combinée de sels d’ammonium et d’alcools fluorés induit un effet synergique permettant la fixation rapide et sélective du CO2 sur les époxydes modèles et les huiles végétales époxydées dans des conditions douces et sans solvant. L’utilisation de cette plateforme catalytique performante a ensuite été exploitée pour la synthèse d’oligocarbonates hydroxyles téléchéliques au départ d’oxétanes nettement moins réactifs que les époxydes. Ces oligocarbonates ont finalement été valorisés pour la synthèse de polyuréthanes CO2-sourcés par extension de chaines en présence de diisocyanates. En complément de ces travaux, une compréhension fine des mécanismes réactionnels a été réalisée via calculs DFT qui ont mis en évidence que l’efficacité catalytique de ces catalyseurs était liée à la stabilisation multiple des intermédiaires et états de transition par liaisons hydrogènes. A ce jour, via une étude comparative, nous avons mis en évidence que ce système catalytique bicomposant constitue un des catalyseurs organiques les plus performants pour le couplage du CO2 et d’époxydes et le seul système organique permettant la conversion d’oxétanes en synthons d’intérêtAlthough it is a thermodynamically and kinetically stable molecule, carbon dioxide can beconverted into five- and six-membered cyclic carbonates by coupling with epoxides or oxetanes, respectively, using appropriate catalysts. Cyclic carbonates are used as green solvents, electrolytes for Liion batteries or intermediates for the synthesis of polymers. However, the catalytic performance must be further enhanced in particular for the coupling of CO2 with epoxidized vegetable oils or oxetanes. In this context, we developed a new highly efficient bicomponent homogeneous organocatalyst composed of anammonium salt as the catalyst and fluorinated single or double hydrogen bond donors as co-catalysts. First,a screening of onium-based catalysts and hydrogen-bond donors was performed. Performances of thecatalysts and optimization of the reaction was realized through detailed kinetics studies using in-situ FTIR/Raman spectroscopy under pressure. We demonstrated that fluorinated alcohols showed unexpected co-catalytic activity due to synergisms between the onium salt and fluorinated co-catalysts enabling the fast and selective addition of CO2 on to model epoxides and epoxidized vegetable oils under solvent-free and mild experimental conditions. The use of this powerful dual catalyst was then extended to the first organocatalytic coupling of CO2 with less reactive oxetanes to produce hydroxyl telechelic oligocarbonates that were used asprecursor of CO2-based polyurethanes by chain-extension with a diisocyanate. In addition, a fine comprehension of the mechanisms was investigated by DFT calculations highlighting that the co-catalytic performance of the onium salt/fluorinated alcohol binary catalyst arose from the strong stabilization of the intermediates and transitions states by hydrogen-bonding. To date, through comparative studies, we evidenced that this new catalyst is one
41
Lihammar, Richard. „Enzyme- and Transition Metal-Catalyzed Asymmetric Transformations : Application of Enzymatic (D)KR in Enantioselective Synthesis“. Doctoral thesis, Stockholms universitet, Institutionen för organisk kemi, 2014. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-108351.
Annotation:
Dynamic kinetic resolution (DKR) is a powerful method for obtaining compounds with high optical purity. The process relies on the combination of a kinetic resolution with an in situ racemization. In this thesis, a combination of an immobilized hydrolase and a transition metal-based racemization catalyst was employed in DKR to transform racemic alcohols and amines into enantioenriched esters and amides, respectively. In the first part the DKR of 1,2-amino alcohols with different rings sizes and N-protecting groups is described. We showed that the immobilization method used to support the lipase strongly influenced the stereoselectivity of the reaction. The second part deals with the DKR of C3-functionalized cyclic allylic alcohols affording the corresponding allylic esters in high yields and high ee’s. The protocol was also extended to include carbohydrate derivatives, leading to inversion of a hydroxyl substituted chiral center on the carbohydrate. The third part focuses on an improved method for obtaining benzylic primary amines. By using a novel, recyclable catalyst composed of Pd nanoparticles on amino-functionalized mesocellular foam, DKR could be performed at 50 °C. Moreover, Lipase PS was for the first time employed in the DKR of amines. In the fourth part DKR was applied in the total synthesis of Duloxetine, a compound used in the treatment of major depressive disorder. By performing a six-step synthesis, utilizing DKR in the enantiodetermining step, Duloxetine could be isolated in an overall yield of 37% and an ee >96%. In the final part we investigated how the enantioselectivty of reactions catalyzed by Candida Antarctica lipase B for δ-substituted alkan-2-ols are influenced by water. The results showed that the enzyme displays much higher enantioselectivity in water than in anhydrous toluene. The effect was rationalized by the creation of a water mediated hydrogen bond in the active site that helps the enzyme form enantiodiscriminating binding modes.At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 3: Manuscript.
42
Leslie, Daniel C. „Transformation of UV-Filtering Agents in the Presence of Aqueous Chlorine: Kinetics and Transformation Products“. University of Akron / OhioLINK, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=akron1306282546.
43
Kherrouba, Nabil. „Étude expérimentale et modélisation des cinétiques de transformation de phase dans un alliage de titane“. Thesis, Lorient, 2017. http://www.theses.fr/2017LORIS449/document.
Annotation:
L’objectif de cette thèse est l’étude expérimentale et la modélisation des évolutions microstructurale et des cinétiques de transformation de phase α + β → β → αII dans l’alliage de titane Ti-6Al-4V dans des conditions isothermes et non-isothermes. Dans cette optique, diverses techniques ont été utilisées (DSC, MEB, microscopie optique, résistivité électrique in-situ et DRX). L’équation de KM-JMA a été utilisée pour décrire les cinétiques de transformation de phase en conditions isothermes. Une approche basée sur le principe d’additivité est proposée pour adapter l’équation de KM-JMA pour les transformations de phases non-isothermes et est comparée à celle utilisant la notion de temps fictif. Les paramètres de cinétique de transformation de phase (n, k et Q) sont ainsi déterminés et interprétés sur la base des résultats de l’analyse métallographique réalisée. Les mécanismes des différentes transformations de phase ont été discutés en tenant compte de l’analyse microstructurale et des paramètres de cinétiques déterminés. Enfin la cinétique de transformation de phase βm → αII en condition isotherme a été simulée à l’aide du logiciel MatCalc et modélisée en utilisant la théorie de germination – croissance ainsi que l’équation de KM-JMAThe aim of this thesis is to experimentally study and to model the kinetics of α + β → β → αII phase transformations in Ti-6Al-4V alloy for isothermal and non-isothermal conditions. To this purpose, several technics have been performed (DSC, SEM, optical microscopy, in-situ electrical resistivity and XRD). The KM-JMA equation has been used to describe the kinetics of phase transformations during isothermal holdings. An approach based on the additivity rule has been developed to adapt the KM-JMA equation to non-isothermal phase transformations and is compared to the one using the fictitious time. Kinetics parameters (n, k and Q) have been determined using this approach and discussed based on the microstructural analysis. Mechanisms of the α + β → β → α phase transformations have been discussed by considering the microstructural analysis and the kinetics parameters already determined. Finally, the βm → αII phase transformation kinetics in isothermal conditions has been simulated with the MatCalc software and modelled using both the nucleation – growth theory and the KM-JMA equation
44
CUNHA, CECILIO A. da. „Estudo da cinetica da transformacao de fase no estado solido UAL-3+AL-UAL-4“. reponame:Repositório Institucional do IPEN, 1986. http://repositorio.ipen.br:8080/xmlui/handle/123456789/9862.
Annotation:
Made available in DSpace on 2014-10-09T12:32:12Z (GMT). No. of bitstreams: 0Made available in DSpace on 2014-10-09T14:10:36Z (GMT). No. of bitstreams: 1 02364.pdf: 3622835 bytes, checksum: 6196cd6738513d9951eb29446742874f (MD5)
Dissertacao (Mestrado)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP
45
Okutman, Tas Didem. „Microbial Reductive Transformation of Pentachloronitrobenzene“. Diss., Georgia Institute of Technology, 2006. http://hdl.handle.net/1853/10520.
Annotation:
Pentachloronitrobenzene (PCNB) is an organochlorine fungicide used either as seed dressing or for soil treatment. Research was conducted to investigate the microbial reductive transformation of PCNB with cultures developed from a contaminated estuarine sediment. The biotransformation of PCNB to pentachloroaniline (PCA) occurred under all electron accepting conditions tested. Sequential dechlorination of PCA to di- and in some cases to mono-chlorinated anilines occurred under fermentative/methanogenic conditions. Based on the use of inhibitors, methanogens were not involved in the sequential dechlorination of PCA. Based on 16S rRNA gene analysis, among five known dechlorinating bacterial groups tested, only Dehalococcoides was detected in the mixed culture. The sequential dechlorination of PCA was simulated using a branched-chain Michaelis-Menten kinetic model. The dechlorination rate (k) of the chlorinated anilines ranged from 0.25 to 1.19 uM/day and the half-saturation coefficient (KC) ranged from 0.11 to 1.72 uM at an incubation temperature of 22C and pH 6.90.1. Incubation at different temperature and pH values resulted in significant differences in the biotransformation rate and extent of PCNB in the fermentative/methanogenic enrichment culture. Incubation at 35C resulted in significantly different product distribution. The effect of temperature on the PCA dechlorination rate was modeled using an Arrhenius relationship. Dechlorination of PCA and methanogenesis were not observed in cultures amended with completely bioavailable iron sources until all Fe3+ was reduced to Fe2+. In contrast, PCA dechlorination took place at the same time with iron reduction in the same mixed, methanogenic culture amended with a less bioavailable iron source (FeOOH). PCA was sequentially dechlorinated to dichloroanilines in cultures amended with low nitrate concentrations, whereas partial dechlorination of PCA to tetrachloroanilines was observed in cultures amended with high initial nitrate concentrations due to the accumulation of reduced nitrogen species (e.g., NO, N2O). A semi-empirical molecular model (MOPAC/AM1) was used to estimate the thermodynamic and electronic properties of all chlorinated aniline congeners. These values were used to predict the sequential PCA dechlorination pathway and compare to experimentally observed dechlorination reactions. The results of this study have significant environmental implications relative to the fate and transport of PCNB, PCA and its dechlorination products in subsurface systems.
46
Baumann, Wolfgang [Verfasser]. „Phase-transformation kinetics of TiCr2 laves phases / vorgelegt von Wolfgang Baumann“. Stuttgart : Max-Planck-Inst. für Metallforschung, 2010. http://d-nb.info/1007316489/34.
47
Mohapatra, Goutam [Verfasser]. „Phase transformation kinetics : the role of stress / vorgelegt von Goutam Mohapatra“. Stuttgart : Max-Planck-Inst. für Metallforschung, 2006. http://d-nb.info/995372578/34.
48
Rheingans, Bastian [Verfasser], und Eric Jan [Akademischer Betreuer] Mittemeijer. „Kinetics of phase transformations / Bastian Rheingans. Betreuer: Eric Jan Mittemeijer“. Stuttgart : Universitätsbibliothek der Universität Stuttgart, 2015. http://d-nb.info/107952553X/34.
49
Bos, Cornelis. „Atomistic simulation of interface controlled solid state phase transformations“. [S.l. : s.n.], 2005. http://nbn-resolving.de/urn:nbn:de:bsz:93-opus-25279.
50
Kuroda, Yukio. „Kinetics of deformation-induced transformation of dispersed austenite in two alloy systems“. Thesis, Massachusetts Institute of Technology, 1987. http://hdl.handle.net/1721.1/52893.