Dissertations / Theses on the topic 'Activation energy'
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Clarke, Christopher. "Concrete shrinkage prediction using maturity and activation energy." College Park, Md.: University of Maryland, 2009. http://hdl.handle.net/1903/9561.
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Thesis (M.S.) -- University of Maryland, College Park, 2009.Thesis research directed by: by Dept. of Civil and Environmental Engineering. Title from t.p. of PDF. Includes bibliographical references. Published by UMI Dissertation Services, Ann Arbor, Mich. Also available in paper.
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Lin, Yawei. "Spectroscopy of High Energy Ion-neutral Collisions." Thesis, Université d'Ottawa / University of Ottawa, 2011. http://hdl.handle.net/10393/19720.
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This research work focused on studying the emission spectroscopy produced from the high energy ion-molecule collision processes in mass spectrometry. The collision experiments are described and divided into 4 chapters (Chapter 3, 4, 5, 6).N2O+● is an ion of atmospheric importance. In chapter 3 the investigation of the collision between high translational energy (4-8 keV range) N2O+● ions and Helium target gas in mass spectrometry using collision induced emission (CIE) spectroscopy is described.In chapter 4, the collision-induced emission (CIE) spectra from 4-8 keV collisions between projectile He+● ions and CO2 target gas (He+●/CO2) were obtained. In Chapter 5, to probe the validity of this hypothesis, CIE experiments were carried out to observe the photon emissions from keV collisions of a selection of projectile ions with O2 target gas. By studying the resulting CIE spectra, a second potential mechanism came to light, one that involves the nearly isoenergetic O2+. A → X state transition. In chapter 6, neutral hydroxymethylene and formaldehyde were generated by charge exchange neutralization of their respective ionic counterparts and then were reionized and detected as recovery signals in neutralization-reionization mass spectrometry in the modified VG-ZAB mass spectrometer.
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Bien-Aime, Andre J. "Effect of Cement Chemistry and Properties on Activation Energy." Scholar Commons, 2013. http://scholarcommons.usf.edu/etd/4439.
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The objective of this work is to examine the effect of cement chemistry and physical properties on activation energy. Research efforts indicated that time dependent concrete properties such as strength, heat evolution, and thermal cracking are predictable through the concept of activation energy. Equivalent age concept, which uses the activation energy is key to such predictions. Furthermore, research has shown that Portland cement concrete properties are affected by particles size distribution, Blaine fineness, mineralogy and chemical composition. In this study, four Portland cements were used to evaluate different methods of activation energy determination based on strength and heat of hydration of paste and mortar mixtures. Moreover, equivalency of activation energy determined through strength and heat of hydration is addressed. The findings indicate that activation energy determined through strength measurements cannot be used for heat of hydration prediction. Additionally, models were proposed that are capable of predicting the activation energy for heat of hydration and strength. The proposed models incorporated the effect of cement chemistry, mineralogy, and particle size distribution in predicting activation energy.
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Thridandapani, Raghunath Rao. "The Effect of Microwave Energy on Sintering." Diss., Virginia Tech, 2011. http://hdl.handle.net/10919/26864.
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Spent Nuclear Fuel (SNF) is a by-product of existing nuclear reactors; SNF consists of long-lived radioactive actinides which have an average half-life of several thousand years (e.g. Plutonium-239 with a half-life of 24,000 years, and Americium-243 with a half-life of 7,360 years). Several multinational organizations are making an attempt to extract the energetic value out of these nuclear stockpiles in order to minimize the risk of nuclear proliferation and reduce waste volume. The Inert Matrix Fuel (IMF) concept is being considered as an option to reuse the radioactive actinides present in spent nuclear fuel by means of a transmutation process. Due to the volatile nature of these radioactive actinides, it is expected that the high-temperature conventional processing of IMFs will result in a significant loss of material.
This study investigates microwave sintering of inert matrix material (excluding actinide fuel) as an alternative route to conventional processing. It was observed that microwave sintering showed a reduction of 300°C in temperature required for full densification when compared to conventional sintering. The reduction in sintering temperatures did not show any significant variation in the resulting properties (hardness and grain size). While these results satisfy the need for the application, it is important to understand why microwaves enhance the sintering phenomena.
It is speculated (by many researchers) that the electric field associated with microwave energy is enhancing flux leading to accelerated densification during microwave sintering. This study has observed a decrease in the activation energy (for sintering 8YZ) with the increase in the magnitude of the applied electric field.Ph. D.
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Fanfarillo, Michael. "Activation of carbon dioxide and dioxygen in low-energy matrices." Thesis, University of Oxford, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.236314.
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Albright, Eric V. B. "Activation energy of Douglas fir char gasification by carbon dioxide." Thesis, This resource online, 1992. http://scholar.lib.vt.edu/theses/available/etd-10312009-020158/.
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Lasithiotakis, Michail Georgioy. "Irradiated graphite waste - stored energy." Thesis, University of Manchester, 2012. https://www.research.manchester.ac.uk/portal/en/theses/irradiated-graphite-waste--stored-energy(c93c7581-5273-4d30-a05b-2153b4c7cfaf).html.
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The cores of early UK graphite moderated research and production nuclear fission reactors operated at temperatures below 150°C. Due to this low temperature their core graphite contains significant amounts of stored (Wigner) energy that may be released by heating the graphite above the irradiation temperature. This exothermic behavior has lead to a number of decommissioning issues which are related to long term "safe-storage", reactor core dismantling, graphite waste packaging and the final disposal of this irradiated graphite waste. The release of stored energy can be modeled using kinetic models. These models rely on empirical data obtained either from graphite samples irradiated in Material Test Reactors (MTR) or data obtained from small samples obtained from the reactors themselves. Data from these experiments is used to derive activation energies and characteristic functions used in kinetic models. This present research involved the development of an understanding of the different grades of graphite, relating the accumulation of stored energy to reactor irradiation history and an investigation of historic stored energy data. The release of stored energy under various conditions applicable to decommissioning has been conducted using thermal analysis techniques such as Differential Scanning Calorimetry (DSC). Kinetic models were developed, validated and applied, suitable for the study of stored energy release in irradiated graphite components. A potentially valid method was developed, for determining the stored energy content of graphite components and the kinetics of energy release. Another parameter investigated in this study was dedicated in the simulation of irradiation damage using ion irradiation. Ion bombardment of small graphite samples is a convenient method of simulating fast neutron irradiation damage. In order to gain confidence that irradiation damage due to ion irradiation is a good model for neutron irradiation damage the properties and microstructure of various grades of ion irradiated nuclear graphite were also investigated. Raman Spectroscopy was employed to compare the effects of ion bombardment with the reported effects of neutron irradiation on the content of the defects. The changes of the of defect content with thermal annealing of the ion irradiated graphite have been compared with the annealing of neutron irradiated nuclear graphite.
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Bevillon, Emile. "Etude théorique du matériau BaSnO₃, en tant que conducteur protonique pour électrolytes de piles à combustible." Thesis, Châtenay-Malabry, Ecole centrale de Paris, 2009. http://www.theses.fr/2009ECAP0039/document.
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Les travaux effectués ont consisté en une étude théorique du matériau BaSnO3 en tant que matériau conducteur protonique pour électrolytes de piles à combustible. Ces matériaux sont obtenus après un dopage aliovalent préalable qui génère des lacunes d'oxygène sur le sous-réseau d'oxygène du matériau. Ce matériau, placé en milieu humide va s'hydrater, c'est à dire que des molécules d'eau vont se dissocier au sein du matériau. La propriété principale souhaitée pour de tels matériaux est la conductivité protonique. Celle-ci dépend du nombre de porteurs de charges (les hydrogènes ou protons apportés par les molécules d'eau) et de leur mobilité. Ces deux paramètres sont quantifiés par des grandeurs thermodynamiques (l'enthalpies d'hydratation) et cinétiques (énergies d'activation) qui peuvent dépendre très fortement des dopants et de leur concentration. Une étude systématique a donc été entreprise sur ce matériau dopé par Ga, In, Y, Gd, Sm et La sur le site du Sn. Les objectifs étaient, d'une part de déterminer les paramètres clés de la conduction protonique et de les comparer aux données expérimentales, et d'autre part de corréler ces informations énergétiques aux effets structuraux imputables aux dopants, dans le but de comprendre comment ces derniers influencent la conduction. Pour remonter à ces paramètres, des calculs basés sur la Théorie de la Fonctionnelle de la Densité ont été réalisés dans l'approximation GGA-PBE, par l'intermédiaire de deux codes de calculs différents: ABINIT et SIESTA. Les calculs ont été menés à la fois à des concentrations de 12,5% et de 3,7% de dopants et le matériau BaTiO3 a également été étudié. D'intéressants résultats ont étés obtenus, notamment d'un point de vue structural, avec l'analyse des déformations locales aux alentours des dopants. Ont été mis en évidence: i. La stabilisation préférentielle de certaines positions des défauts due aux interactions électrostatiques. ii. L'effet de la concentration des dopants sur les énergies d'interaction entre dopant et défauts (lacune d'oxygène et proton) et iii. Un effet de taille de dopant, perceptible notamment dans le cas des gros dopants, et qui stabilise préférentiellement une autre position que celle favorisée d'un point de vue électrostatiqueThe present work consist in a theoretical study of the BaSnO3 compound as a protonic conductor for fuel cell electrolytes. These materials are obtained after an aliovalent doping stage that will create oxygen vacancies on the oxygen sublattice of the compound. Then, in a moist atmosphere, this lacunar material is going to hydrate: water molecule will be dissociated, creating protonic defects inside of the compound. The main desired property is the protonic conduction, which is due to two major contributions: number of charge careers (hydrogen or proton coming from the hydration reaction) and their mobility, at a given temperature. These two parameters are quantified by a thermodynamic quantity (hydration enthalpy) and a kinetic parameter (activation energy), which are known to be dependant on the dopant concentration. Thus, a systematic study has been done for the material doped Ga, In, Y, Gd, Sm and La on the Sn site. The objectives of this study were, first, to compute the key parameters of the protonic conduction and to compare them to the experimental data, and, in second, to correlate the calculated results to structural effect due to the dopants, in order to understand how they influence the conduction parameters. To determine these parameters, calculations based on the Density Functional Theory in the GGA-PBE form were carried out, using two different codes: ABINIT and SIESTA. Computations were done for dopant concentrations going from 12.5% to 3.7%, the BaTiO3 compound were also studied. Interesting results were also obtained, from a structural point of view, and concerning dopant local environment. Were evidenced: i. Prefential stabilization of defects, relatively to electrostatic interaction considerations. ii. The dopant concentration effect on dopant-defect (oxygen vacancy and proton) interactions. iii. A dopant size effect which acts in particular in the case of big dopants and which stabilize an other defect position than the one favoured by electrostatic considerations
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Amer, Elhadi M. "Thermal analysis and kinetic studies of the decomposition of some high performance polymers." Thesis, University of Salford, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.272943.
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Mereddy, Sandeep Reddy. "Adaptive algorithms for sensor activation in renewable energy-based sensor systems." Thesis, Wichita State University, 2009. http://hdl.handle.net/10057/2505.
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Future sensor networks would comprise of sensing devices with energy harvesting capabilities from renewable energy sources such as solar power. A key research question in such sensor systems is to maximize the asymptotic event detection probability achieved in the system, in the presence of energy constraints and uncertainties. This thesis focuses on the design of adaptive algorithms for sensor activation in the presence of uncertainty in the event phenomena. Ideas from increase/decrease algorithms used in TCP congestion avoidance are applied to design an online and adaptive activation algorithm that varies the subsequent sleep interval according to additive increase and multiplicative decrease based upon the sensor's current energy level. In addition, the proposed algorithm does not depend on global system parameters, or on the degree of event correlations, and hence can easily be deployed in practical scenarios. Through extensive simulations, it is demonstrated that the proposed algorithm not only achieves near-optimal performance, but also exhibits more stability with respect to sensor's energy level and sleep interval variations.Thesis (M.S.)--Wichita State University, College of Engineering, Dept. of Electrical Engineering and Computer Science
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Holdich, Jonathan Peter. "Assessment of Gαq-coupled receptor activation using fluorescence resonance energy transfer." Thesis, University of Cambridge, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.612154.
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Schmidt, Julian C. "PARP Activation, NAD+ Depletion, and Energy Dysregulation following Traumatic Brain Injury." Thesis, The University of Arizona, 2019. http://pqdtopen.proquest.com/#viewpdf?dispub=13422970.
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Traumatic brain injury (TBI) is characterized by a sudden concussive (direct force or shock wave) blow to the head, in which traumatic biomechanical forces are transferred throughout the head and neck. Damage to neural tissue occurs due to rapid acceleration and deceleration forces of the brain, culminating upon impact of the brain with the interior of the skull. At the molecular level, TBI generates a host of physiological responses, which manifest in many different ways. The focus of this thesis will be on the trajectory that progresses through 1) brain acceleration forces, 2) force-induced DNA damage in neurons and glia, 3) activation of DNA repair mechanisms (specifically, poly ADP-ribose polymerase (PARP)), 4) nicotinamide adenine dinucleotide (NAD +) depletion via PARP assembly, 5) the effect of NAD + depletion on energy metabolism, and 6) the potential value of an NAD+ modulator (nicotinamide riboside chloride, NR-Cl) in modulating this effect. Pathologically, reactive oxygen species (ROS) and other free radicals are generated following TBI. The generation of these radicals leads to DNA damage in affected regions of the brain. In response to DNA damage, PARP, a molecule responsible for initiating DNA repair, is activated and begins to polymerize. The assembly of PARP is directly dependent upon nicotinamide adenine dinucleotide (NAD+) cannibalization, in which the ADP-ribosyl subunit of NAD+ is used to build the large poly ADP-ribose (PAR) polymer. One PAR assembly can consume up to 200 ADP-ribose subunits derived from NAD+. This leads to depleted cellular NAD + and diminished energy metabolism, the severity of which is dependent upon the extent of injury and degree of PARP activation. In this thesis, I will summarize the molecular mechanisms associated with PARP activation, NAD + depletion, energy dysregulation, and the potential value of NR-Cl as a potential therapeutic agent in mild and moderate TBI.
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Brown, Ashley Kaye. "Investigating the Effect of Energy Substrates and LPS-activation on the In Vitro Energy Metabolism of BV-2, RAW264.7 and VM-M3 Cells." Thesis, Boston College, 2016. http://hdl.handle.net/2345/bc-ir:106811.
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Thesis advisor: Thomas N. SeyfriedTwo major metabolic phenomena observed in cancer cells include the Warburg effect and Crabtree effect. The Crabtree effect is the in vitro inhibition of respiration by glucose. The influence of glucose on the oxygen consumption rate (OCR) and extracellular acidification rate (ECAR) of tumorigenic RAW264.7 and VM-M3 macrophage cells, as well as non-tumorigenic BV-2 microglia cells, was studied using the Seahorse XF96 extracellular flux analyzer. RAW264.7, VM-M3, and BV-2 cells incubated in glucose medium displayed a significantly lower OCR and higher ECAR compared to cells incubated in no glucose medium. Furthermore, when glucose medium was added to the RAW264.7 and BV-2 cells in real-time using the Seahorse XF96 injection ports, a rapid decrease in OCR and increase and ECAR was observed. Therefore, RAW264.7, VM-M3, and BV-2 cells display a robust Crabtree effect in vitro, as assessed by OCR and ECAR. Additionally, it is important to consider the Crabtree effect when studying in vitro energy metabolism of all cell and tissue types. It was also found that the elimination of the Crabtree effect through glucose deprivation resulted in dynamic cardiolipin (CL) fatty acid changes in VM-M3 cells. VM-M3 cells incubated in 10 mM glucose medium for four hours displayed a short-chain, saturated (immature) CL fatty acid composition, while VM-M3 cells incubated in no glucose media for four hours displayed long-chain, unsaturated (mature) CL fatty acid composition. Cardiolipin (CL) is a phospholipid highly enriched in the inner mitochondrial membrane. Mature, long-chain, unsaturated CL molecular species are involved in maintaining mitochondrial function and membrane integrity. Overall, these data suggest that CL fatty acid composition may function as a structural component of the Crabtree effect in vitro. The Warburg effect, or aerobic glycolysis, is the observation that tumor cells consume less oxygen and more glucose than normal, untransformed cells in the presence of oxygen. It has been shown that immune cells display a Warburg effect upon activation by changing their core metabolism from oxidative phosphorylation to glycolysis. In this study, it was observed that both RAW264.7 macrophage cells and BV-2 microglia cells display a significantly lower OCR and higher ECAR following LPS-activation. However, this observation is dependent on the concentration of LPS. Therefore, these data suggest that both RAW264.7 and BV-2 cells display a LPS concentration-dependent change in metabolism from oxidative phosphorylation to glycolysis upon LPS-activation in vitro. The in vitro lipid profiles that resulted from the Crabtree effect and the LPS-activated Warburg effect were also studied in the RAW264.7 cell line. The lipids phosphatidylserine (PS) and cardiolipin (CL) displayed the most robust changes in the RAW264.7 cells. Both PS and CL have been shown to be associated with cellular respiration
Thesis (MS) — Boston College, 2016
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Biology
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Mitchell, Nathan. "Eyring Activation Energy Analysis of Acetic Anhydride Hydrolysis in Acetonitrile Cosolvent Systems." Digital Commons @ East Tennessee State University, 2018. https://dc.etsu.edu/etd/3430.
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Acetic anhydride hydrolysis in water is considered a standard reaction for investigating activation energy parameters using cosolvents. Hydrolysis in water/acetonitrile cosolvent is monitored by measuring pH vs. time at temperatures from 15.0 to 40.0 °C and mole fraction of water from 1 to 0.750. This work utilizes a temperature controlled water bath and a Vernier glass-body pH probe with Vernier Logger Pro 3.10.1 software for automated data collection. Data analysis is used to determine observed kinetic rate constants under the assumption that hydrolysis is a pseudo-first-order reaction. Eyring plots were used to compare activation energy parameters under iso-mole fraction conditions. The hydrolysis reaction of acetic anhydride was enthalpically stabilized and entropically destabilized at mole fractions of acetonitrile greater than 0.17 and the reverse occurred at mole fractions less than 0.17. Activation enthalpy and entropy result in the reaction being less favorable to form products as mole fraction of acetonitrile increased.
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ZECCA, CHRISTIAN. "Towards the organic actor: neuroplastic training for the dynamic activation of presence energy." Doctoral thesis, Università degli studi di Genova, 2018. http://hdl.handle.net/11567/929875.
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Mohammad, Shafiei Adel. "An Energy-Efficient Target Tracking Protocol Using Wireless Sensor Networks." Thesis, Université d'Ottawa / University of Ottawa, 2015. http://hdl.handle.net/10393/32384.
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Target tracking using Wireless Sensor Networks (WSNs) has drawn lots of attentions
after the recent advances of wireless technologies. Target tracking aims at locating
one or several mobile objects and depicting their trajectories over time. The applications
of Object Tracking Sensor Networks (OSTNs) include but not limited to environmental
and wildlife monitoring, industrial sensing, intrusion detection, access control, traffic
monitoring, patient monitoring in the health-related studies and location awareness in
the battle eld. One of the most rewarding applications of target tracking is wildlife
monitoring. Wildlife monitoring is used to protect the animals which are endangered
to extinction. Road safety applications are another popular usage of wildlife monitoring
using WSNs.
In this thesis, the issues and challenges of energy-efficient wildlife monitoring and
target tracking using WSNs are discussed. This study provides a survey of the proposed
tracking algorithms and analyzes the advantages and disadvantages of these algorithms. Some of the tracking algorithms are proposed to increase the energy e ciency of the tracking algorithm and to prolong the network lifetime; while, other algorithms aim at improving the localization accuracy or decreasing the missing rate. Since improving the energy efficiency of the system provides more alive sensors over time to locate the target; it helps to decrease the missing rate as the network ages. Thus, this study proposes to adjust the sensing radius of the sensor nodes in real-time to decrease the sensing energy consumption and prolong the network lifetime.
The proposed VAriable Radius Sensor Activation (VARSA) mechanism for target
tracking using wireless sensor networks tackles the energy consumption issues due to
resource constraints of the WSNs. VARSA reduces the radio covered area of each sensor node to only cover the Area of Interest (AoI) which is the location of the target in tracking applications. Thus, VARSA aims at decreasing the sensing energy consumption which leads to encreasing the network life time. In addition, VARSA decreases the missing rate over time as it provides more alive sensors to detect the target compared to previous activation algorithms as the network ages. VARSA is compared to PRediction-based Activation (PRA) and Periodic PRediction-based Activation (PPRA) algorithms which are two of the most promising algorithms proposed for sensor activation. The simulation results show that VARSA outperforms PRA and PPRA. VARSA prolongs the lifetime of the network and decreases the missing rate of the target over time.
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Zeman, Vojtěch. "Kinetika fotochromních reakcí v tenkých polymerních filmech." Master's thesis, Vysoké učení technické v Brně. Fakulta chemická, 2008. http://www.nusl.cz/ntk/nusl-216218.
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The thesis is aimed to the study of spiropyrane behavior in polymeric matrix of poly(N-vinylkarbazole) (PVK) and poly[2-methoxy-5-(3´,7´-dimethyloctyloxy)-1,4-fenylenvinylene)] (MDMO-PPV). The photochromic transformation of spiropyrane to its isomeric merocyanine form (SPMC) was studied by absorption and emission spectroscopy. It was found, that photochromic reaction is markedly dependent on the environment. In the PVK polymer, which don’t absorb in the visible region, a high yield of photochromic reaction was achieved. Both, absorption and emission spectrums were observed for this system. From the measurement of time dependencies of the fotochromic reaction, the activation energy of the reverse reaction was determined. A different behavior, particularly in emissive spectrums, was found for the MDMO-PPV polymer doped with spiropyrane. Instead of formation of new band of merocyanine, decrease of the polymer fluorescence was observed. Subsequently, we studied the interaction between the polymeric matrix and the photochromic spiropyrane using fluorescence quenching method. On the basis of energy transfer theory, a critical radius of the fluorescence quenching sphere in solution and in solid was determined.
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Guangliang, Chen. "The Dissociation of Metalloporphyrin Anions." Thesis, Université d'Ottawa / University of Ottawa, 2015. http://hdl.handle.net/10393/32517.
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ESI-MS spectra of Ni(II), Co(III), Mg(III), and Fe(II) porphyrin solutions in methanol show porphyrin monomer species with different charge states, such as [Ni(II)TPPS+H]3-, [Co(III)TPPS]3-, [Mn(III)TPPS]3-, [Mn(III)TPPS+H]2-, [Fe(II)TPPS+H]3-, and [Fe(II)TPPS+2H]2- ions. Collision-induced dissociation (CID) of these monomer species produced primarily losses of neutral SO3 and SO2. The mechanisms, in which these dissociation pathways took place, were investigated by the means of DFT calculations of the corresponding dissociation of neutral and ionized benzenesulfonate (B3-LYP/6-31+G(2d, p) level) and porphyrin monomer (B3-LYP/6-31+G(2d, p)+LANL2DZ//PM7 level). RRKM fitting of the CID breakdown curves showed that the activation energies of the reactions that experience a loss of SO2 from [Co(III)TPPS]3- and [Mn(III)TPPS]3- were similar, but of a lower magnitude than those for a loss of SO3. On the other hand, for [Ni(II)TPPS+H]3- and [Fe(II)TPPS+2H]2-, the activation energies of the reaction leading to a loss of SO2 were also similar, but this time were larger than those leading to SO3 loss. These results are consistent with a mechanism by which the SO2 loss starts with -C6H4SO3-, while the SO3 loss has to begin with -C6H4SO3H. To lose this SO3, extra energy is required for [Co(III)TPPS]3- and [Mn(III)TPPS]3- in order for them to overcome the barrier of H transfer from the porphyrin ring to -SO3-, but this is irrelevant when it comes to [Ni(II)TPPS+H]3- and [Fe(II)TPPS+2H]2- since the C6H4SO3H moiety already exists. In addition, the reaction of [Fe(II)TPPS+H]3- losing H leads to a unique dissociation mechanism.
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Alexander, Rebecca. "Energy landscape of defects in body-centered cubic metals." Thesis, Université Paris-Saclay (ComUE), 2016. http://www.theses.fr/2016SACLX072/document.
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Les matériaux composants les réacteurs nucléaires subissent des conditions d’irradiationsévères, donnant lieu à des modifications de leurs propriétés mécaniques. Le vieillissement de cesmatériaux soulève des questions aussi importantes que celles liées à la sécurité des centrales existantes etaux futurs réacteurs à fission et à fusion. Dans plusieurs situations les matériaux de structure cristallinecubique centrée CC sont utilisés ayant pour base le fer, le tungstène, le vanadium et le tantale. Lescollisions entre les particules irradiantes et les atomes constituants les matériaux engendrent des défautsponctuels dont la migration mène à la formation d’amas responsables du vieillissement. Dans cette thèsenous avons étudié les propriétés énergétiques des défauts ponctuels dans les métaux CC citésprécédemment à l’échelle atomique. La modélisation des défauts ponctuels à l’échelle atomique peut êtreréalisée avec différentes méthodes se différenciant uniquement par la qualité de la description del’interaction entre atomes. Les études utilisant des interactions atomiques exactes, type ab initio,nécessitent des calculs lourds rendant impossible l’étude directe des amas de grandes tailles. Avec lamodélisation des interactions atomiques via les potentiels semi-empiriques on réduit la fiabilité et lecaractère prédictif du calcul. Ceux-ci permettent toutefois de réaliser une étude des amas en fonction deleur taille. Dans cette thèse nous avons développé un modèle énergétique original pour les boucles dedislocation ainsi que pour les amas interstitiels tridimensionnels de type C15. Le modèle obtenu est sanslimite de taille et peut être paramétré entièrement par les calculs ab initio. Afin de tester sa robustessepour les grandes tailles d’amas nous avons également paramétré ce modèle par rapport à des calculs enpotentiels semi-empiriques et comparé les prédictions du modèle aux simulations atomiques. Grâce ànotre développement nous avons pu déterminer : (i) la stabilité relative des boucles de dislocationd’interstitiels d’après leur vecteur de Burgers. (ii) La stabilité des amas C15 par rapport aux amas de typeboucle. Nous avons montré que les amas de type C15 étaient plus stables lorsqu’ils impliquent moins de41 interstitiels dans le fer. (iii) Dans le Ta nous avons pu mettre en évidence la même stabilité jusqu’à 20interstitiels. Les expériences dans le fer irradié montrent qu’en fonction de la température d’irradiation, ilse forme des boucles de dislocation très mobiles de vecteur de Burgers ½<111> ou immobiles ayant unvecteur de Burgers <100>. Les mécanismes de formation sous irradiation en fonction de la température,des amas de type <100> étaient une question restée sans explication théorique depuis 50 ans. Dans cettethèse, grâce à la précision de notre modèle énergétique, nous avons pu tester plusieurs théories.Notamment nous avons montré que les amas C15 constituent un catalyseur dans la formation des boucles<100>. Les clusters C15 peuvent se former, par germination, directement dans le processus d’irradiation.Ces clusters sont immobiles et peuvent croitre. A partir d’une certaine taille les amas C15 se dissocienten boucles ½ <111> ou <100>. Nous avons étendu notre modèle au calcul d’énergie libre de formationdes défauts permettant ainsi des prédictions à température finie que nous avons comparées auxsimulations atomiques. Les lois établies dans cette thèse en utilisant notre modéle pour calculer l’énergielibre de formation en fonctions de la taille des amas, ont été ensuite utilisées dans une simulation dedynamique d’amas. Nous avons ainsi pu prédire avec un très bon accord expérience-théorie laconcentration des amas d’interstitiels en fonction de leurs tailles au cours du murissement d’Oswald postirradiationdans un échantillon de Fer sous atmosphère d’Hélium. Le succès d’une telle approche nouspermet d’espérer étendre ce type d’étude à des matériaux plus complexesThe structural materials in nuclear reactors are subjected to severe irradiation conditions,leading to changes in their mechanical properties. The aging of these materials raises important issuessuch as those related to the safety of existing plants and future reactors. In many cases, materials withbody-centered cubic bcc crystal structure are used with iron, tungsten, vanadium and tantalum as basemetal. Collisions between irradiating particles and atoms constituting materials generate point defectswhose migration leads to the formation of clusters responsible for aging. In this thesis, we studied theenergetic properties of point defects in the bcc metals mentioned above at the atomic scale. Modelingpoint defects at the atomic scale can be achieved with different methods that differ only in the quality ofthe description of the interaction between atoms. Studies using accurate atomic interactions such ab initiocalculations are computationally costly making it impossible to directly study clusters of large sizes. Themodeling of atomic interactions using semi-empirical potentials reduces the reliability of predictivecalculations but allow calculations for large-sized clusters. In this thesis we have developed a uniqueenergy model for dislocation loops as well as for three-dimensional interstitial cluster of type C15. Theresulting model has no size limit and can be set entirely by ab initio calculations. To test its robustness forlarge sizes of clusters we also set this model with semi-empirical potentials calculations and comparedthe predictions of the model to atomic simulations. With our development we have determined: (i) Therelative stability of interstitial dislocation loops according to their Burgers vectors. (ii) The stability of theclusters C15 compared to the type of cluster loop. We showed that the C15 type clusters are more stablewhen they involve less than 41 interstitials in iron. (iii) In Ta we were able to show the same stability till20 interstitials. The experiments involving iron show that depending on the irradiation temperature,highly mobile dislocation loops of Burgers vector ½ <111> or loops with Burgers vector <100> areformed. Considering formation mechanisms under irradiation as a function of temperature, formation ofthe <100>-type clusters lacked an acceptable theoretical explanation for about 50 years. In this thesis, theaccuracy of our energy model enabled validation of several theories proposed in the last 50 years. Inparticular we have shown that the formation of loops <100> at high temperatures can be formed fromC15 clusters which may be created directly in the irradiation process. These clusters are immobile andcan grow. Beyond a certain size, the C15 clusters dissociate into loops ½ <111> or <100>. We haveextended our model to free energy calculation of defect formation allowing for finite temperaturepredictions which is further compared to atomic simulations. The laws established in this thesis using ourmodel to calculate the free energy of formation of the cluster size functions were then used in a clusterdynamics simulation. On comparison with experiments involving post-irradiation Oswald ripening in asample of iron exposed to an atmosphere of helium, our energy model showed significant improvementsover older energy laws, such as the capillary law widely-used in multiscale computation cluster dynamicsor Monte Carlo kinetics. We conclude that the new laws established from our calculations are essential topredict the concentration of dislocation loop under irradiation, depending on their sizes. The success ofsuch an approach encourages extension of a similar study in more complex materials
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Pena, Jenny Juliana. "Study of chars prepared from biomass wastes : material and energy recovery." Thesis, Ecole nationale supérieure Mines-Télécom Atlantique Bretagne Pays de la Loire, 2018. http://www.theses.fr/2018IMTA0104.
Full textAbstract:
L'objectif de la thèse est d'étudier la valorisation des chars de biomasse. Dans ce contexte de transition énergétique, les biomasses sélectionnées sont les écales de sarrasin et de millet, assez pu étudiées jusqu'à maintenant, produites localement pour contribuer au développement de l'économie circulaire et qui ne compromettent pas une filière de valorisation connue. Dans ce travail, la valorisation matière est abordée à travers la réutilisation de ces résidus dans des procédés d'épuration catalytique de syngaz ou dépuration de biogaz pour lesquels les polluants sont respectivement les goudrons et le sulfure d'hydrogène. Des bilans énergétiques relatifs à la production de ces chars ont été établis et des indicateurs d'efficacité énergétiques ont été calculés. Pour ce faire, les chars ont été produits à 500 °C puis caractérisés par des analyses chimiques et physiques. Afin de leur conférer de meilleures propriétés poreuses nécessaires pour les applications d'épuration de gaz en lit fixe, des activations ont été réalisées à 850 °C avec du CO₂ ou de la vapeur d'eau. Les écales de sarrasin se révèlent être une biomasse assez classique et la particularité des écales de millet est de présenter des taux élevés en silicium. Si les chars de pyrolyse ont montré une efficacité faible dans l'épuration des gaz, l'activation leur ouvre de nouvelles potentialités, notamment pour les écales de sarrasin qui s'apparentent alors à des charbons actifs. Les chars des écales de sarrasin démontrent leur intérêt lorsqu'ils sont activés à la vapeur d'eau pour la purification du syngaz et ils conservent leur pouvoir calorifique (PCI) que permet d'envisager une valorisation énergétique par gazéification. Ces résultats montrent également qu'en fonction de la nature de la biomasse et du type d'activation, les objectifs de valorisation matière et énergie sont parfois incompatiblesThe aim of the thesis is to study the valorization of chars prepared from biomass wastes. In this context of energy transition, the selected biomasses are the buckwheat and millet husks since they are barely studied until now. In addition these wastes are produced locally, contribute to the developement of the circular economy and to not compromise a known value chain. In this word, material recovery is approcached through the reuse of these residues in syngaz and biogas cleaning processus in order to remove key pollutants such as tars and hydrogen sulfide, respectively. Energy balances form the prodution fo these chars have been established and energy efficiency indicators have been calculated. The chars were produced at 500 °C and then characterized by chemical and physical analysis. In order to provide them porous properties necessary for fixed-bed gas cleaning applications, activations were carried out at 850 °C with CO₂ or steam. Buckwheat husks turn out to be a fairly conventional biomass and the particularity of millet husks is to have high levels of silicon. If pyrolysis chars have shown a low efficiency in the purification of gases, activation opens up new potential for them, especially for materials from buckwheat husks, which are similar to activated carbons. When activated with steam these chars show interesting efficiency for the purification of syngas and they conserve their calorific value (LHV) which makes it possible to consider an energy recovery through gasification. Results from this study also show that depending on the nature of biomass and type of activation, the material valorization and energy recovery are sometimes incompatible
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Vancea, Anisoara. "Energy and electron transfer on titania-silica binary oxides." Thesis, Loughborough University, 2013. https://dspace.lboro.ac.uk/2134/12152.
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Steady state reflectance and emission characteristics of anthracene adsorbed on silica gel and titania-silica mixed oxides have been investigated as a function of sample loading. Titania-silica mixed oxides with 1, 3, 5 and 10 wt. % TiO2 were prepared by two different methods: a dropwise method and a sol-gel route. Ground state diffuse reflectance and fluorescence emission spectra of anthracene adsorbed on titania-silica surfaces show a dependence on titania content. The absorption peaks of anthracene are difficult to resolve at higher titania content due to the increasing red-shift of the titania absorption edge. The absorption edge of titania is shifted to longer wavelengths and the band gap energy decreases with increasing the titania loading. Diffuse reflectance laser flash photolysis at 355 nm produces both the triplet and radical cation of anthracene and gives relevant information regarding the photochemical transients and the kinetics details of the surface photochemical processes. Energy dependence studies confirm the monophotonic nature of the triplet production, whereas the anthracene radical cation is formed by monophoton or multiphoton ionisation in the mixed titania-silica systems. Energy and electron transfer reactions of anthracene co-adsorbed with azulene as electron donor on silica sol-gel and titania-silica mixed oxides prepared by the sol-gel method with different titania content have been studied using the time-resolved diffuse reflectance laser flash photolysis technique. The fluorescence of excited anthracene adsorbed on silica sol-gel is quenched by the addition of azulene, while co-adsorption of azulene on titania-silica mixed oxides resulted in a decrease in the fluorescence intensity of the adsorbed anthracene due to the formation, at the same time, of anthracene radical cation and Ti3+ species on the titania-silica surface. Triplet-triplet energy transfer from the excited anthracene to ground state azulene and electron transfer from azulene to the anthracene radical cation have been investigated using a time-resolved diffuse reflectance laser flash photolysis technique following laser excitation at 355 nm. Bimolecular rate constants for energy and electron transfer between anthracene and azulene have been obtained. Kinetic analysis of the decay of the anthracene triplet state and radical cation show that the kinetic parameters depend on the titania content of the sample and the azulene concentration. This indicates that the rate of energy and electron transfer reactions increases as a function of azulene concentration and decreases with increasing titania content in titania-silica mixed oxides, whereas the observed rate of reaction on silica sol-gel is predominantly governed by the rate of diffusion of azulene. Electron transfer reactions in a ternary system using azulene for hole transfer between 9-anthracenecarboxylic acid radical cation as electron acceptor and perylene as electron donor were also studied in order to demonstrate the mobility of radical cations on the silica sol-gel and titania-silica surfaces. The co-adsorption of azulene as a molecule shuttle with 9-anthracenecarboxylic acid and perylene on both silica sol-gel and titania-silica systems has been shown to enhance the rate of electron transfer in this ternary system. Activation energies for energy and electron transfer on photoinduced bimolecular and termolecular processes on silica sol-gel and titania-silica mixed oxides have been measured. In bimolecular anthracene / azulene systems, at higher azulene loadings, the activation energies and the pre-exponential factors on titania-silica surfaces are the same for both energy and electron transfer and are comparable with the parameters extracted for azulene diffusion on silica Davisil suggesting that azulene diffuses across the silica Davisil and titania-silica mixed oxides surfaces, while at lower azulene loadings, ion-electron recombination dominates and the activation energy extracted is for this process. In a ternary 9-anthracenecarboxylic acid / azulene / perylene system, the activation energy for perylene diffusion is higher than that observed for the anthracene / azulene system, reflecting the lower mobility of the perylene molecule. In this study, a series of titania-silica samples with different loadings of titania (1 10 wt. %) prepared by the sol-gel method and also the pure TiO2 P25 Degussa have been used to study the photocatalytic degradation of 4-chlorophenol in aqueous solution under UV light irradiation. The absorption peak of 4-chlorophenol at 280 nm decreases with increasing titania content and finally disappeared suggesting that titania has a positive influence on the degradation of 4-chlorophenol. The investigated titania-silica mixed oxides prepared by the sol-gel method are less efficient photocatalysts for the degradation of 4-chlorophenol than TiO2 P25.
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Oparah, Irene A. "Photosynthetic acclimation to temperature of four Eucalyptus species and Sequoia sempervirens." Thesis, University of Canterbury. School of Forestry, 2012. http://hdl.handle.net/10092/7531.
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The 3-PG physiological/mensurational hybrid model is a useful forest management tool capable of producing accurate growth results across a number of parameterised species. The temperature data used in the model are the average maximum and minimum values for photosynthesis above the compensation point (Landsberg and Sands 2011). There is a minimum temperature below which positive net CO₂ exchange will not occur, a maximum temperature above which it will not occur and an optimum temperature at which it is maximised. These parameters are used in the 3-PG physiological model of forest production. However, a species’ photosynthetic response to short-term variation may differ from one season to another as species acclimate to temperatures over periods of a few weeks.
In this study, acclimation responses of four species of eucalypt and Sequoia sempervirens to long-term temperatures were studied over a wide range of short-term temperature changes in order to identify the minimum, optimum and maximum temperatures of CO₂ assimilation for physiological/mensurational hybrid modelling, and also to identify the sites for which the species would be best suited. In order to achieve the aims of this study, a growth chamber experiment was established.
Seedlings of four eucalypt species and Sequoia sempervirens were grown at base-line day/night temperatures of 30/16, 22/12 and 10/5ºC in controlled environment chambers for three months and leaf gas exchange measurements were made of the species at seven short-term temperature levels (5, 10, 15, 20, 25, 30 and 35ºC). The optimum and the maximum temperatures for net photosynthesis increased with an increase in base-line temperature for all species. The highest optimum temperature and net photosynthetic rates recorded were in plants grown at 30/16ºC and the lowest were in those grown at 10/5ºC.
The maximum rate of net CO₂ assimilation increased with the temperature at which plants were grown partly because of acclimation in key photosynthetic processes in the Calvin cycle. Responses of maximal carboxylation rate (Vcmax) and also the maximal light-driven electron flux (Jmax) to short-term temperature change varied with base-line temperature for all species studied. Net photosynthesis and photosynthetic parameters measured did not vary significantly with effects of nitrogen, phosphorus and their interaction (p = 0.1468). The ratio of Jmax to Vcmax decreased with increasing leaf temperatures for all species (p < 0.001).
These results indicate that the species studied will adapt to long-run changes in temperature, and the parameters obtained from these studies can be used for models that simulate the physiology and growth of the species.
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Madakasira, Sreenivas. "Performance analysis of an adaptive algorithm for sensor activation in renewable energy based sensor systems." Thesis, Wichita State University, 2010. http://hdl.handle.net/10057/3698.
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Linear increase-decrease algorithms have applicability in various fields of research. For instance,
transmission control protocol (TCP) congestion control mechanism employs an additive
increase and multiplicative decrease (AIMD) algorithm to vary the congestion window size dynamically
at the sender. Recently, an adaptive algorithm for sensor activation in renewable energy
based systems was proposed. This activation algorithm is designed in such a way that the sensor
dynamically computes its sleep interval according to additive increase and multiplicative decrease,
based on its current energy level. The objective is to maximize the asymptotic event detection
probability achieved in the system in the presence of uncertainties and energy constraints. This
thesis provides a simple, but accurate model to compute the performance of the algorithm for a
single sensor scenario. By means of the proposed model, the performance of the algorithm is
evaluated and is validated with that of the results obtained from simulations. A Markov Chain is
used to analyze the system for a single sensor scenario. Furthermore, the AIMD based algorithm
is extended towards a distributed implementation in a network with multiple sensors and multiple
event processes. Through extensive simulations, it is shown that the proposed algorithm performs
better than other algorithms in this scenario. In addition, the proposed algorithm is completely
localized, which makes it extremely suitable for distributed deployment.Thesis (M.S.)--Wichita State University, College of Engineering, Dept. of Electrical Engineering and Computer Science Engineering.
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Afolaju, Wasiu ALOWONLE Mr, and SCOTT Dr Dane. "Hydrolysis of Acetic Anhydride in Water/Tetrahydrofuran Co-solvent Systems Using Eyring Activation Energy Analysis." Digital Commons @ East Tennessee State University, 2019. https://dc.etsu.edu/asrf/2019/schedule/52.
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This study determines the activation energy parameters for the hydrolysis of acetic anhydride in water/tetrahydrofuran solutions. These values are needed for studies to quantify the effect of the bulk electrostatic environment solvent-solute interactions on the hydrolysis reaction rate. Hydrolysis of an acetic anhydride with water or under basic conditions yields acetic acid. The current study is based on simple hydrolysis of acetic anhydride which produces acetic acid decreasing the pH over time. Simple hydrolysis is monitored by measuring pH versus time at temperatures ranging from 20.0 to 35.0 oC and mole fraction of water ranging from 0.75 to 1.00. Measuring pH over time has advantages over other methods such as conductivity, UV-vis spectroscopy, temperature scanning, FTIR, calorimeter as it is simple, inexpensive and reproducible. Experimental results were used to determine activation enthalpy and entropy for hydrolysis of acetic anhydride using tetrahydrofuran as the co-solvent. These values were determined using the Eyring rate equation under iso-mole fraction and isothermal conditions. Analysis was performed to determine if the activation enthalpy and entropy are temperature dependent. Eyring plots are expected to be linear for iso-mole fractions and isothermal conditions of tetrahydrofuran.
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Smith, Lori Lyn. "Effectiveness of low energy collisional activation methods for automated peptide sequencing by tandem mass spectrometry." Diss., The University of Arizona, 2003. http://hdl.handle.net/10150/280450.
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The relative efficiencies of low energy (< 100 eV) collisional activation techniques were determined for peptide sequencing by tandem mass spectrometry (MS/MS). Tryptic peptides were fragmented using either collision induced dissociation (CID) or surface induced dissociation (SID) to generate spectral databases. Statistical analysis of the resulting fragment ions and success rates for automated peptide sequencing by publicly available algorithms provided a measure of the value of sequencing information content of CID and SID MS/MS spectra. Typical success rates were determined for automated sequencing by SEQUEST¹⁻³, MS-Tag⁴, Mascot's⁵ MS/MS Ion Search and Sequence Query using low energy CID spectra. The ability of an algorithm to match peptide sequences to raw MS/MS data directly depended on various factors including the mass spectrometer from which the spectra were acquired, the precursor ion charge state, and the mass accuracy and resolution available in the spectra. Statistical analysis demonstrated the presence of similar fragment ions in SID and CID spectra. A lack of long contiguous ion series in SID spectra prevented automated sequencing using conventional approaches. Thus, "patchwork peptide sequencing"⁶, an unconventional method to derive specific sequence criteria for unknown peptides from SID spectra, was performed. Submitting this information to Mascot's Sequence Query allowed database searching strategies to achieve automated peptide sequencing with SID spectra. Some aspects of gas phase ion chemistry were explored for the unexpected formation of fragment ions from cleavage C-terminal to proline residues. Semi-empirical calculations suggest the most stable structure for valineprolyl-b₂ ion is a diketopiperazine, although the MS/MS/MS fragmentation pattern for VP-b₂ is indicative of an oxazalone structure. Support for a diketopiperazine structure is provided by similar fragmentation patterns for VP-b₂ and a synthetic diketopiperazine VP, and prevention of the formation of VP-b₂ by acetylation of the free N-terminus. Substitution of N-methyl alanine for proline produces a b₂ ion that fragments by loss of a portion of the valine residue, consistent with an oxazalone structure. However, theoretical calculations suggest the N-methyl alanine-containing b₂ ion is a diketopiperazine. The differences in fragmentation patterns indicate that the gas phase ion structures for the proline- and N-methyl alanine-containing b₂ ions are different, although stability calculations suggest otherwise.
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Lücken, Jana. "Transformations of Energy-Related Small Molecules at Dinuclear Complexes." Doctoral thesis, Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2020. http://hdl.handle.net/21.11130/00-1735-0000-0005-1563-4.
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Yang, Yang. "Investigation of vanadium-containing oxide systems : CALPHAD and experiments." Doctoral thesis, KTH, Termodynamisk modellering, 2016. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-197292.
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Fundamental studies on thermodynamic properties of vanadium-containing oxides systems are essential to understand practical vanadium metallurgical process. The CALPHAD technique is here applied to the thermodynamic modelling of the V-O, Ca-V-O and Ti-V-O systems. The compound energy formalism is used for all the solution phases. All optimization processes and calculations are performed using the Thermo-Calc software package. The present work attempts to develop a self-consistent thermodynamic database of all phases in the studied systems. The obtained datasets can be used to calculate thermodynamic properties, stable as well as metastable phase equilibria and driving forces for oxidation etc. Steelmaking slag is an important secondary source for vanadium extraction. The phase relationships and vanadium distribution in the CaO-SiO2-MgO-V2O3-Al2O3 synthetic slags, whose compositions were chosen based on the relevance to the steel producers, are also studied. Phase equilibria in the temperature range of 1773 to 1823 K at oxygen partial pressure of 10-10 bar and 0.21 bar were characterized. An investigation of the volatilization of vanadium oxide was also carried out in the present work. Isothermal evaporation of vanadium pentoxide in the temperature range between 1723 and 1873 K was investigated by Thermogravimetric Analysis under different oxygen partial pressures, viz. oxygen, air or CO2. The Arrhenius activation energy for the evaporation reaction in various atmospheres was calculated from the experimental results. A mathematical model was developed to describe the kinetics of the evaporation process. Evaporation coefficients and enthalpies in various atmospheres were also estimated. The present results may have some implications in recovering vanadium from different vanadium-bearing sources.QC 20161202
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Olowoyo, Samson. "Kinetics and Activation Energy Parameters for Hydrolysis of Acetic Anhydride in a Water-Acetone Cosolvent System." Digital Commons @ East Tennessee State University, 2018. https://dc.etsu.edu/etd/3409.
Full textAbstract:
The hydrolysis of acetic anhydride is a widely-studied liquid phase reaction studied since 1906. Different approaches have been used to study the kinetics of this reaction. Approaches used by researchers have involved the use of sophisticated experimental set-ups. In this work, the pH technique has been adopted which involves the use of a pH meter to monitor the hydrolysis reaction. Analysis of the hydrolysis reaction has been performed for water/acetone cosolvent systems over a range of temperatures and mole fractions. Eyring analysis was performed under isomole fraction conditions and activation enthalpy, entropy, and Gibbs free energy for hydrolysis of acetic anhydride have been determined.
The isomole fraction Eyring plots are linear, because, activation enthalpy and entropy are independent of temperature under these conditions. Activation free Gibbs energy increases with increasing temperature at a constant water mole fraction, while it decreases with increasing water mole fraction at constant temperature.
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Shestakov, A. F. "Telomeres of Tetrafluoroethylene - Advanced Materials to Create Superhydrophobic Coatings and Optical Fiber with Low Attenuation Coefficient." Thesis, Sumy State University, 2013. http://essuir.sumdu.edu.ua/handle/123456789/35479.
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The paper describes formation of telomers of tetrafluoroethylene (TFE), which are very interesting in-termediate materials of different purposes, by radiation polymerization. In some cases there are formed long chained oligomers suitable for creation of superhydrophobic coatings. In such systems formation of gels is observed under low TFE content. Quantum chemical analysis allows to reveal the factors that are responsible for this phenomenon. In the case of solvents with appropriate cyclic structure, short chain oli-gomers, which have low C-H bonds content, are raw materials for fluoropolymers suitable for manufactur-ing optical fibers. The work is aimed to predict which types of materials are formed under polymerization conditions. For these purposes the generalized Polany-Semenov rule is used. Its parameters found by DFT calculations can be recommended for practical applications in the molecular design of new fluorine-containing polymers.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35479
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Lin, Xi. "The Kinetic and Mechanism of The Oxygen Reduction Reaction on Pt, Au, Cu, PtCu/C and CuAu/C in Alkaline Media." The Ohio State University, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=osu1471874766.
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Mendiratta, Neeraj K. "Kinetic Studies of Sulfide Mineral Oxidation and Xanthate Adsorption." Diss., Virginia Tech, 2000. http://hdl.handle.net/10919/27545.
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Sulfide minerals are a major source of metals; however, certain sulfide minerals, such as pyrite and pyrrhotite, are less desirable. Froth flotation is a commonly used separation technique, which requires the use of several reagents to float and depress different sulfide minerals. Xanthate, a thiol collector, has gained immense usage in sulfide minerals flotation. However, some sulfides are naturally hydrophobic and may float without a collector.
Iron sulfides, such as pyrite and pyrrhotite, are few of the most abundant minerals, yet economically insignificant. Their existence with other sulfide minerals leads to an inefficient separation process as well as environmental problems, such as acid mine drainage during mining and processing and SO2 emissions during smelting process. A part of the present study is focused on understanding their behavior, which leads to undesired flotation and difficulties in separation. The major reasons for the undesired flotation are attributed to the collectorless hydrophobicity and the activation with heavy metal ions.
To better understand the collectorless hydrophobicity of pyrite, Electrochemical Impedance Spectroscopy (EIS) of freshly fractured pyrite electrodes was used to study the oxidation and reduction of the mineral. The EIS results showed that the rate of reaction increases with oxidation and reduction. At moderate oxidizing potentials, the rate of reaction is too slow to replenish hydrophilic iron species leaving hydrophobic sulfur species on the surface. However, at higher potentials, iron species are replaced fast enough to depress its flotation. Effects of pH and polishing were also explored using EIS.
Besides collectorless hydrophobicity, the activation of pyrrhotite with nickel ions and interaction with xanthate ions makes the separation more difficult. DETA and SO2 are commonly used as pyrrhotite depressants; however, the mechanism is not very well understood. Contact angle measurements, cyclic voltammetry and Tafel studies have been used to elucidate the depressing action of DETA and SO2. It was observed that DETA and SO2 complement each other in maintaining lower pulp potentials and removing polysulfides. DETA also helps in deactivating pyrrhotite. Therefore, the combined use of DETA and SO2 leads to the inhibition of both the collectorless flotation and the adsorption of xanthate.
The adsorption of xanthate on sulfide minerals is a mixed-potential mechanism, i.e., the anodic oxidation of xanthate requires a cathodic counterpart. Normally, the cathodic reaction is provided by the reduction of oxygen. However, oxygen can be replaced by other oxidants. Ferric ions are normally present in the flotation pulp. Their source could be either iron from the grinding circuit or the ore itself. The galvanic studies were carried out to test the possibility of using ferric ions as oxidants and positive results were obtained.
Tafel studies were carried out to measure the activation energies for the adsorption of ethylxanthate on several sulfide minerals. Pyrite, pyrrhotite (pure and nickel activated), chalcocite and covellite were studied in 10-4 M ethylxanthate solution at pH 6.8 at temperatures in the range of 22 â 30 0C. The Tafel studies showed that xanthate adsorbs as dixanthogen (X2) on pyrite and pyrrhotite, nickel dixanthate (NiX2) on nickel-activated pyrrhotite and cuprous xanthate (CuX) on both chalcocite and covellite. However, the mechanism for xanthate adsorption on each mineral is different. The free energy of reaction estimated from the activation energies are in good agreement with thermodynamically calculated ones.Ph. D.
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Aquino, Fl?via de Medeiros. "S?ntese, caracteriza??o e cin?tica da decomposi??o t?rmica dos materiais cer?micos PrMO3 (M = Ni ou Co)." Universidade Federal do Rio Grande do Norte, 2010. http://repositorio.ufrn.br:8080/jspui/handle/123456789/12690.
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In this work have been studied the preparation, characterization and kinetic study of decomposition of the polymerizing agent used in the synthesis under non-isothermal condition ceramics PrMO3 of general formula (M = Co and Ni). These materials were obtained starting from the respective metal nitrates, as a cations source, and making use of gelatin as polymerizing agent. The powders were calcined at temperatures of 500?C, 700?C and 900?C and characterized by X-ray Diffraction (XRD), Thermogravimetric Analysis (TG / DTG/ DTA), Infrared Spectroscopy (FTIR), Temperature Programmed Reduction (TPR) and Scanning Electron Microscopy (SEM). The perovskite phase was detected in all the X-rays patterns. In the infrared spectroscopy observed the oxide formation as the calcination temperature increases with the appearance of the band metal - oxygen. The images of SEM revealed uniform distribution for the PrCoO3 and particles agglomerated as consequence of particle size for PrNiO3. From the data of thermal analysis, the kinetics of decomposition of organic matter was employed using the kinetics methods called Model Free Kinetics and Flynn and Wall, in the heating ratios 10, 20 and 30? C.min-1 between room temperature and 700?C. Finally, been obtained the values of activation energy for the region of greatest decomposition of organic matter in samples that were determined by the degree of conversion (α)
Neste trabalho foi realizado a prepara??o, caracteriza??o e um estudo cin?tico da decomposi??o t?rmica do agente polimerizante utilizado na s?ntese sob condi??o n?o isot?rmica de materiais cer?micos de f?rmula geral PrMO3 (M = Co ou Ni). Esses materiais foram obtidos partindo dos respectivos nitratos met?licos, como fonte de c?tions, e fazendo uso da gelatina como agente polimerizante. Os p?s-obtidos foram calcinados a temperaturas de 500?C, 700?C e 900?C e caracterizados pelas t?cnicas de Difra??o de Raios X (DRX), An?lise Termogravim?trica (TG/DTG/DTA), Espectroscopia na regi?o do infravermelho (FTIR), Redu??o ? Temperatura Programada (RTP) e Microscopia Eletr?nica de Varredura (MEV). A fase perovsquita foi evidenciada em todos os difratogramas de raios X para os materiais de PrCoO3 e PrNiO3. Nos espectros de FTIR foi observado a forma??o do ?xido na medida em que a temperatura de calcina??o aumenta com o aparecimento da banda referente ? liga??o Metal Oxig?nio. As imagens do MEV evidenciaram distribui??o uniforme para o PrCoO3 e part?culas aglomeradas em consequ?ncia do tamanho da part?cula para o PrNiO3. Com os dados da an?lise t?rmica, o estudo ci-n?tico da decomposi??o da mat?ria org?nica foi empregado utilizando-se os m?todos cin?ticos denominados Model Free Kinetics e Flynn e Wall, nas raz?es de aquecimento 10, 20 e 30?C.min-1 entre a temperatura ambiente e 700?C. Foram obtidos os valores das energias de ativa??o para a regi?o de maior decomposi??o da mat?ria org?nica nas amostras que foram determinadas como uma fun??o do grau de convers?o (α)
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Kopecký, Jan. "Určení kinetických parametrů reakcí pomocí DSC měření." Master's thesis, Vysoké učení technické v Brně. Fakulta strojního inženýrství, 2018. http://www.nusl.cz/ntk/nusl-378413.
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The master thesis deals with DSC measurments a calculation of kinetic parameters. In the theoretical part, iron alotropy is briefly described, followed by a description of the DSC analysis itself. The thesis also includes division and derivation of isoconversional methods for calculating the activation energy. In the experimental part, a series of measurments is perfomed on pure iron prepared by Cold Spray method. In the paper the influence of deformation on the Curie temperature of the magnetic transformation in -Fe and transformation > is investigated. The activation energy is calculated for transformation > for different degrees of deformation. The degree of deformation is monitored by channeling contrast.
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Zhang, Hongtu. "Activation of Small Molecule and Organic Substrates by Tris(Phosphinoamide) Zr/Co Heterobimetallic Complexes." The Ohio State University, 2020. http://rave.ohiolink.edu/etdc/view?acc_num=osu1594900050962052.
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Ríos, Quiroga Luis Carlos [UNESP]. "Avaliação da relação entre a energia de ativação e a energia útil para diferentes misturas de etanol e gasolina aplicados a motores de ignição por centelha." Universidade Estadual Paulista (UNESP), 2016. http://hdl.handle.net/11449/146676.
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Asociación Universitaria Iberoamericana de Postgrado (AIUP)
A aplicação do etanol como combustível ou como aditivo misturado à gasolina é muito importante para a maioria dos países que procuram reduzir a dependência dos combustíveis fósseis e mitigar os gases de efeito estufa. O uso cada vez maior de misturas de etanol e gasolina torna cada vez mais relevante o conhecimento de suas propriedades físicas e químicas, de forma a favorecer uma melhor compreensão do efeito do teor de etanol na mistura com a gasolina no desempenho do motor. Esta tese tem por objetivo avaliar se existe, ou não, uma relação entre a energia de ativação da mistura de etanol e gasolina, obtida pelas técnicas de análise térmica, e a energia útil obtida em testes de motor. Foram utilizadas diferentes percentagem de etanol na mistura de etanol-gasolina denominadas por E0 (gasolina pura), E5 (5% v/v etanol), E10, E15, E20, E25, E30, E50 e E75. O estudo cinético foi realizado em um sistema simultâneo TG (termogravimetria) e DTA (análise térmica diferencial) com a metodologia para ensaios não isotérmicos para obter a energia de ativação. Alem de utilizar a análise do sinergismo, entre os componentes das misturas, como ferramenta para avaliar o efeito do teor de etanol na mistura com a gasolina. A energia útil dos combustíveis foi obtida nos testes de dinamômetro no motor monocilíndrico padrão de ciclo Otto com seis taxas de compressão diferentes. Na análise dos dados verificou-se que existe sinergismo nas misturas com teor de etanol entre 5% e 30%. Estas misturas também foram as que apresentaram melhores resultados na potência, para taxas de compressão entre 6:1 a 7:1. Os resultados da análise térmica mostram que as misturas com baixo conteúdo de etanol (até 30%) apresentam maior volatilidade e, possivelmente, esta é característica que melhora a combustão nos motores de ciclo Otto.
The use of ethanol as fuel or as an additive blended with gasoline is very important for most countries which aim to reduce the heavy dependence on fossil fuels and mitigate greenhouse gases emission. An increased use of ethanol and gasoline blends has placed great relevance on acquiring knowledge about their physical and chemical properties. Thus, knowledge of such properties favors a better understanding of the effect of the percentage of ethanol/gasoline blends on engine performance. This thesis aims to assess whether there is or not a relationship between the activation energy of the mixture of ethanol and gasoline, obtained by thermal analysis techniques, and the useful energy obtained in engine tests. They used different percentage of ethanol in the ethanol-gasoline blends denoted by E0 (pure gas), E5 (5% v/v ethanol), E10, E15, E20, E25, E30, E50 and E75. A kinetic study has been conducted through a simultaneous TG (thermogravimetry) and DTA (differential thermal analysis) by following the methodology of non-isothermal tests to obtain the activation energies of the tested mixtures. Was used the synergism analyze, between the components of the mixtures, as a tool to evaluate the effect of ethanol content in the gasoline mixture. The useful energy fuel was obtained by dynamometer tests to Otto cycle single cylinder standard engine with six different compression rates. In the data analysis was found that synergism exists in mixtures with ethanol content between 5% to 30%. These mixtures also showed the best power results for compression ratios of 6:1 to 7:1. The thermal analysis results showed that mixtures with low ethanol content (to 30%) exhibit higher volatility and, possibly, this characteristic improves combustion in Otto cycle engines.
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Seaton, Robert Leonard. "The influence of temperature and composition on the activation energy for creep in binary aluminum lithium alloys." Thesis, Monterey, California: Naval Postgraduate School, 1990. http://hdl.handle.net/10945/27666.
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Approved for public release; distribution is unlimited.With the fast pace of technology in the aerospace industry, there are increasing demands for higher strength and stiffness in structural materials but with reduced weight and improved formability. Aluminum alloys have been widely used in the construction of aerospace vehicles because of their high strength to weight ratio, forming characteristics and corrosion resistance. An investigation was conducted to determine the temperature and composition dependence on the activation energy for creep of A1-0.5wt.pct.lithium, A1-1.Owt.pct.Li, and A1-2. Owt.pc+.Li alloys. A series of isothermal tests were conducted utilizing constant true stress creep tests, with nominal temperatures ranging from 300 C to 500 C. Temperature cycling tests involved a range of 10 C for each test. Experimental results indicate all three alloys behave as a class II alloy (pure metal class) with a stress exponent, n, approximately equal to 5. In addition, subgrain formation was observed in association with the primary stage of creep. The activation energy for creep of the A1-0.5wt.pct.Li and A1-1.Owt.pct.Li alloys was observed to b essentially the same as that for pure Aluminum.
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Seaton, Robert L. "The influence of temperature and composition on the activation energy for creep in binary aluminum lithium alloys." Monterey, California : Naval Postgraduate School, 1990. http://handle.dtic.mil/100.2/ADA242299.
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Thesis (M.S. in Mechanical Engineering)--Naval Postgraduate School, December 1990.Thesis Advisor(s): McNelley, Terry R. ; Kalu, Peter N. "December 1990." Description based on title screen as viewed on April 2, 2010. DTIC Identifier(s): Aluminum alloys, lithium, creep, binary alloys, strength weight ratio, stress tests, stress strain relations, microstructure, aerospace craft, isothermal tests, theses. Author(s) subject terms: Temperature, composition, activation energy, creep binary aluminum lithium alloys. Includes bibliographical references (p. 89-90). Also available in print.
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Rai, Chaudhuri Anjana. "Electronic structure and bond energy trends in silicon-hydrogen and germanium-hydrogen bond activation by transition metals." Diss., The University of Arizona, 1989. http://hdl.handle.net/10150/184731.
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The electronic structure factors that control Si-H and Ge-H bond activation by transition metals are investigated by means of photoelectron spectroscopy. Molecular orbital calculations are also used to gain additional insight into the orbital interactions involved in bond activation. The complexes studied have the general molecular formula (η⁵-C₅R'₅)Mn(CO)(L)HER₃, where R' is H or CH₃, L is CO or PMe₃, E is Si or Ge and R is Ph or Cl. These compounds are interesting models for catalysts in industrial processes like hydrosilation. The compounds display different stages of interaction and "activation" of the E-H bonds with the metal. One purpose is to measure the degree of Mn, Si, H 3-center-2-electron bonding in these complexes. The three-center interaction can be tuned by changing the substituents on Si, methylating the cyclopentadienyl ring, changing the ligand environment around the metal and substituting Si with Ge. The degree of activation is measured by observing the shifts in the metal and ligand ionizations relative to starting materials and free ligand in the photoelectron spectrum. Changing the substituent on Si extensively changes the degree of activation. Photoelectron spectral studies on (η⁵-C₅H₅)Mn(CO)₂HSiPh₃ show this to be a Mn(I) system. Progressive methylation of the cyclopentadienyl ring increases the electron richness at the metal center with no substantial effect on the degree of activation. Substitution on the metal (PMe₃ for CO) is less able to control the electronic structure factors of activation than the substitution on the Si atom. The magnitude of Ge-H bond activation is found to be of the same order as the Si-H bond activation for analogous compounds as found by studying (η⁵-C₅H₅)Mn(CO)₂HGePh₃, (η⁵-CH₃C₅H₄)Mn(CO)₂HGePh₃ and (η⁵- C₅(CH₃)₅)Mn(CO)₂HGePh₃ complexes by photoelectron spectroscopy. The photoelectron spectra of CpFe(CO)₂SiCl₃ and CpFe(CO)₂SiMe₃ were measured to study the electron charge shift from the metal to the ligand in these complexes as compared to CpMn(CO)₂HSiR₃ complexes. The photoelectron spectroscopic studies include numerous perturbations of the ligand and metal center to observe the extent of bond interaction and remain one of the best techniques to detect activation products.
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Parks, William. "Force activation of I domain containing and lacking integrins on live cells." Thesis, Georgia Institute of Technology, 2010. http://hdl.handle.net/1853/42695.
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Cellular adhesion plays a crucial role in the biological function of cells, allowing them to communicate and signal, as well as physically anchor, by enabling them to adhere to either other cells or the extra cellular matrix (ECM). This process is regulated by several factors including intrinsic bond kinetics, internal cellular signaling, environment, force exerted on the bond, and force history of the bond. Concerning the force and force history dependence, the observation of catch bonds in integrin binding has asked as more questions than it has answered.
To explore the force and force history dependence this process, each bond was loaded to a peak force before relaxing to a much lower force that was held for the duration of the measurement. Two different integrins were studied, both of which have in previous works exhibited a catch bond. Furthermore, the effects of different metal ion conditions and an allosteric antagonist were also studied to elucidate the conformational effects on force priming of integrin. What was observed was that I domain, or αA domain, possessing integrin, whether tested against its more active or less active binding state, changed very little in terms of off rate once the priming force was applied. However in the I domain, or αA domain, lacking integrin, the observed off rate changed as well. It seems that force priming is capable of causing integrin to bind in a stronger manner regardless of the other conditions used to either activate or inhibit binding. However the way in which the binding is strengthened depends on the receptors structure.
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Ekström, Erik. "Effect of texture and blasting pressure on residual stress and surface modifications in wet sand blasted α-Al2O3 coating." Thesis, Linköpings universitet, Institutionen för fysik, kemi och biologi, 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:liu:diva-122508.
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Recently, wet sand blasting on coated cutting tool inserts has drawn interest to the tooling industry due to its positive effects on cutting performance and tool life. This performance boost has partly been attributed to the buildup of compressive residual stresses in the coating during the blasting process. However, the mechanism of forming residual stresses in ceramic coatings during sand blasting is not fully understood. This work utilize x-ray diffraction as the main tool to study the formation and relaxation of residual stresses after wet sand blasting and annealing on 001, 012 and 110 textured α-Al2O3 coatings. To minimize the influence of stress gradients in the samples, all stress measurements were set up with a fixed analysis depth of 2 µm. Sand blasting was made with an alumina based slurry at 2, 3.2 and 4 bar pressure and the anneal was done at temperatures from 400 to 1000 °C for 2 hours or more. The coating hardness was evaluated by nanoindentation. Finally, the activation energy for the relaxation of residual stresses was estimated using the Zener-Wert-Avrami function. The results reveal the highest compressive residual stress with up to -5.3 GPa for the 012 texture while the stresses for the 001 and 110 textures peaked at -3.1 and -2.0 GPa, respectively. Further, a hardness gradient was present after blasting of the 001 and 012 textured samples indicating a higher stress at the surface of the coating. The 110 textured sample is the most brittle resulting in flaking of the coating during sand blasting. The different deformation mechanisms are related to difference in active slip planes between coatings with different textures. Both the stress and hardness decreased after heat treatment and the activation energy for stress relaxation was found to be as 1.1 ± 0.3 eV, 1.9 ± 0.2 eV and 1.2 ± 0.1 eV for the 001, 012 and 110 textures, respectively.
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Zou, Yiming. "The Effect of Various Dopants on Diamond Growth : A Combined Experimental & Theoretical Approach." Doctoral thesis, Uppsala universitet, Institutionen för kemi - Ångström, 2016. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-271491.
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Diamond is a unique material with many exceptional properties. It has therefore been proven to be an important material for many applications. Moreover, the introduction of dopant species into the gas phase during the CVD growth process has been shown to strongly influence not only the properties and morphology of diamond, but also the growth rate. The purpose with the theoretical part of the present study has been to support and explain the experimental observations regarding the effect of various dopants (nitrogen, phosphorous, sulphur, and boron) on the diamond growth rate. Commonly observed H-terminated diamond surfaces [(111), (110) and (100)-2×1], were thereby carefully investigated using density functional theory under periodic boundary conditions. Based on the assumption that the hydrogen abstraction reaction is the growth rate-limiting step, both the thermodynamic and kinetic aspects of the diamond growth process were found to be severely affected by various dopants. More specifically, the results showed that nitrogen and phosphorous dopants (positioned within the 2nd, 3rd or 4th carbon layer) will cause an enhancement in the growth rate (as compared with non-doped situations). On the other hand, any growth rate improvement does only occur when positioning boron in the 2nd, and sulphur in the 4th, atomic carbon layer. With boron, and sulphur, positioned within the other atomic carbon layers, the growth rates were observed to decrease. In addition, the main purpose with the experimental part of the present study has been to investigate the effect of one specific dopant precursor (TMB) on the boron-doped diamond growth process. The result has shown that the increasing mass flow of TMB will not affect the mechanism of the HFCVD growth process of boron doped diamond. However, a linear boron carrier concentration in the diamond film vs. mass flow rate of TMB was observed.
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Gudavalli, Ravi Krishna. "Effect of pH and temperature on the carbonate promoted dissolution of sodium meta-autunite." FIU Digital Commons, 2012. http://digitalcommons.fiu.edu/etd/773.
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Release of uranium from Na-autunite, an artificial mineral created as a result of polyphosphate injection in the subsurface at the DOE Hanford Site, takes place during slow dissolution of the mineral structure. Stability information of the uranyl-phosphate phases is limited to conditions involving pH, temperature, and a few aqueous organic materials. The carbonate ion, which creates very strong complexes with uranium, is the predominant ion in the groundwater composition.
The polyphosphate technology with the formation of autunite was identified as the most feasible remediation strategy to sequester uranium in contaminated groundwater and soil in situ. The objectives of the experimental work were (i) to quantify the effect of bicarbonate on the stability of synthetic sodium meta-autunite created as a result of uranium stabilization through polyphosphate injection, (ii) calculate the kinetic rate law parameters of the uranium release from Na-autunite during dissolution, and (iii) to compare the process parameters with those obtained for natural calcium meta-autunite.
Experiments were conducted using SPTF apparatus, which consists of syringe pumps for controlling flow rate, Teflon reactors and a heating/cooling system. 0.25 grams of synthetic Na-autunite was placed in the reactor and buffer solutions with varying bicarbonate concentrations (0.0005 to 0.003 M) at different pH (6 - 11) were pumped through the reactors. Experiments were conducted at four different temperatures in the range of 5 - 60oC.
It was concluded that the rate of release of uranium from synthetic Na-autunite is directly correlated to the bicarbonate concentration. The rate of release of uranium increased from 1.90 x 10-12 at pH 6 to 2.64 x 10-10 (mol m-2 s-1) at pH 11 at 23oC over the bicarbonate concentration range tested. The activation energy values were invariant with the change in the bicarbonate concentration; however, pH is shown to influence the activation energy values. Uranyl hydroxides and uranyl carbonates complexes helped accelerate the dissolution of autunite mineral.
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Demková, Eva. "Polypropylen s řízenou dobou života." Master's thesis, Vysoké učení technické v Brně. Fakulta chemická, 2017. http://www.nusl.cz/ntk/nusl-295673.
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The master´s thesis is focused on the characterization of degradation process of polypropylene and polypropylene with statistic copolymer into which manganese (II) stearate and cobalt (II) stearates were added at 0.05, 0.10 and 0.20 wt.% loadings. The aim of the thesis was to prepare the controlled life-time polypropylene. The degradation was studied at varying temperatures and prodegradant loadings. The prodegradants were synthetized and characterized using the FTIR and DSC techniques. Thermooxidation of the tested samples induced the changes in crystallinity, melting points and melt-flow indexes. Tensile strength and other mechanical properties were determined by means of the tensile test. The carbonyl index was determined using FTIR, the thermooxidation stability test was used to determine the activation energies of reactions. The changes in morphology of degraded samples were observed by SEM analysis.
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Orford, Dennis. "Fry drying and pyrolysis of municipal solid waste." Thesis, Queensland University of Technology, 2021. https://eprints.qut.edu.au/207758/1/Dennis_Orford_Thesis.pdf.
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This research investigated sustainable resource recovery from unsorted urban, industrial and agricultural waste using fry drying and pyrolytic distillation process methods. Thermogravimetric analysis and Fourier Transform Infrared Spectroscopy were used to identify and quantify linkages between feedstock composition, process chemistry and likely end products. Distributed activation energy modelling was used as an initial step towards development of an accurate kinetic process model. It was postulated that sequential pyrolytic distillation technology be developed to create circular economies, reverse environmental pollution, recycle primary resources and produce carbon negative biofuels to replace fossil fuels such as coal, oil and gas.
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Nogueira, Paulo Alberto. "Influência da temperatura na dinâmica oscilatória de um sistema químico homogêneo aberto." Universidade de São Paulo, 2011. http://www.teses.usp.br/teses/disponiveis/75/75131/tde-16092011-155351/.
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As reações químicas genericamente referidas como reações de Belousov-Zhabotinsky (BZ) têm sido bastante utilizadas como paradigmas de complexidade em sistemas químicos homogêneos. Apesar dos avanços consideráveis realizados no estudo de tais sistemas, aspectos como o papel do fluxo de reagentes e da temperatura na dinâmica oscilatória ainda são pouco entendidos. O presente trabalho consiste na investigação experimental do efeito destes dois parâmetros em duas variantes da reação de BZ. Após alguns testes iniciais com o sistema bromato/hipofosfito-acetona/manganês-ferroína, a maioria dos experimentos foi feita com o sistema bromato/ácido oxálico-acetona/cério. A evolução temporal do sistema foi estudada a diferentes temperaturas e em condições de batelada e de fluxo por meio do monitoramento simultâneo do potencial de um eletrodo de platina e espectrofotometricamente na região do UV-vis. A discussão foi baseada na energia de ativação em regime oscilatório, Eω. Para o sistema com dois catalisadores não foram observadas oscilações nas condições de fluxo. Para o sistema com cério, em batelada, com Ce4+ é observado que Eω aumenta conforme o sistema evolui para o estado de equilíbrio termodinâmico. Com Ce3+, em batelada, Eω manteve-se praticamente constante e em fluxo, o valor de Eω foi menor do que o valor observado para o sistema em batelada.The chemical reactions usually referred to as the Belousov-Zhabotinsky (BZ) reactions have been extensively employed as paradigms of complexity in homogeneous chemical systems. In spite of the considerable advance in the study of such systems, aspects such as the role played by the flux of reactants and temperature on the oscillatory dynamics are still poorly understood. The present work consists of the experimental investigation of the effect of these two parameters on two variants of the BZ reaction. After some initial tests with the bromate/hipophosphite-acetone/manganese-ferroin, most of the experiments were carried with the bromate/oxalic acid-acetone/cerium system. The time-evolution of the system was followed at different temperatures and under batch and flow conditions by means of potentiometric and spectrophotometric (UV-vis region) approaches. The discussion was based on the activation energy under oscillatory regime, Eω. For the two-catalyst system, no oscillations were observed under flow conditions. For the cerium-catalyzed system operated in batch, when Ce4+ is used, it is observed that Eω increases as the system evolves to the thermodynamic equilibrium. With Ce3+, the Eω under batch conditions remained virtually constant and in flow, the value of Eω was lower than the value observed for the batch system.
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Leiva, Cecilia Rocío Morales. "O emprego da termogravimetria na determinação da energia de ativação no processo de combustão de óleos combustíveis." Universidade de São Paulo, 2005. http://www.teses.usp.br/teses/disponiveis/18/18135/tde-30092005-094638/.
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Neste trabalho, determinou-se a energia de ativação (Ea) no processo de combustão de três óleos combustíveis cedidos pela PetrobrásCenpes e denominados por A, B e C. Empregou-se análise termogravimétrica (TG) utilizando um sistema Shimadzu 51H e, para todas as amostras observaram-se três regiões oxidativas distintas identificadas como, oxidação à baixa temperatura (LTO), depósito de combustível (FD) e oxidação à alta temperatura (HTO). As energias de ativação foram determinadas como uma função do grau de conversão ('alfa') e temperatura na região LTO e utilizando-se dois métodos cinéticos, denominados ASTM E 1641 (Flynn eWall) e Model Free Kinetics de Vyazovkin. Empregaram-se as seguintes razões de aquecimento: 2,5; 5,0; 10,0; 15,0 e 20,0°C por min entre a temperatura ambiente e 600°C. As demais condições experimentais foram: massa da amostra de aproximadamente 20 mg, suporte de amostra de alumínio e gás de arraste ar sintético com vazão de 100 mL/min. Os valores de Ea encontrados foram os mesmos para ambos os métodos cinéticos: 44 ± 7% kJ/mol ('alfa'=0,1 a 0,9) para amostra A. Para a amostra B os valores de Ea foram em média de 48 ± 4% kJ/mol ('alfa'=0,1 a 0,5) e 66 ± 16% kJ/mol ('alfa'=0,5 a 0,9) e, para a amostra C os valores de Ea foram em média de 58 ± 4% kJ/mol ('alfa'=0,1 a 0,5) e 65 ± 5% kJ/mol ('alfa'=0,5 a 0,9). Conclui-se que a Ea pode ser usada como um parâmetro adequado para apontar uma tendência de comportamento e para caracterizar diferentes óleos sob processo de combustãoIn this work activation energies (Ea) in the combustion of three fuels oils were determined through thermogravimetry. The oil samples, here named A, B and C were supplied by Petrobras-Cenpes. The thermogravimetric experiments were performed in a Shimadzu TGA-51H analyzer. In all the combustion experiments three distinct oxidation regions were observed, identified as low temperature oxidation (LTO), fuel deposition (FD) and high temperature oxidation (HTO). Activation energies were determined as a function of conversion degree ('alfa') and temperature for LTO region, following two different procedures, namely Model Free Kinetics and ASTM E 1641. Transient experiments were performed from room temperature up to 600°C, at heating rates of 2.5, 5.0, 10.0, 15.0 and 20.0°C for min. Samples of 20.0 ± 0.5 mg and aluminum crucibles were used. The reacting atmosphere was synthetic air, which was continuously blown over the samples, throughout the analyzer furnace, at a volumetric rate of 100 mL/min. The activation energies resulted equal for both considered methods. For oil A, the activation energy resulted 44 ± 7% kJ/mol ('alfa'=0.1 to 0.9). For oil B it resulted in average 48 ± 4% kJ/mol ('alfa'=0.1 to 0.5) and 66 ± 16% kJ/mol ('alfa'=0.5 to 0.9). For oil C the activation energy resulted 58 ± 3% kJ/mol ('alfa'=0.1 to 0.5) e 65 ± 5% kJ/mol ('alfa'=0.5 to 0.9). It is concluded that the oxidation activation energy is a suitable parameter concerning to point out a tendency of behavior and characterizing different oils under combustion process
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Pourghahramani, Parviz. "Effects of grinding variables on structural changes and energy conversion during mechanical activation using line profile analysis (LPA) /." Luleå : Luleå tekniska universitet/Chemical Engineering and Geosciences/Mineral Processing, 2006. http://epubl.ltu.se/1402-1757/2006/19/index.html.
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Acharya, Ananta R. "Indium Nitride Surface Structure, Desorption Kinetics and Thermal Stability." Digital Archive @ GSU, 2013. http://digitalarchive.gsu.edu/phy_astr_diss/62.
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Unique physical properties such as small effective mass, high electron drift velocities, high electron mobility and small band gap energy make InN a candidate for applications in high-speed microelectronic and optoelectronic devices. The aim of this research is to understand the surface properties, desorption kinetics and thermal stability of InN epilayers that affect the growth processes and determine film quality as well as device performance and life time. We have investigated the structural properties, the surface desorption kinetics, and the thermal stability using Auger electron spectroscopy (AES), x-ray diffraction (XRD), Raman spectroscopy, atomic force microscopy (AFM), high resolution electron energy loss spectroscopy (HREELS), and temperature programmed desorption (TPD). Investigations on high pressure chemical vapor deposition (HPCVD)-grown InN samples revealed the presence of tilted crystallites, which were attributed to high group V/III flux ratio and lattice mismatch. A study of the thermal stability of HPCVD-grown InN epilayers revealed that the activation energy for nitrogen desorption was 1.6±0.2 eV, independent of the group V/III flux ratio. Initial investigations on the ternary alloy In0.96Ga0.04N showed single-phase, N-polar epilayers using XRD and HREELS, while a thermal desorption study revealed an activation energy for nitrogen desorption of 1.14 ± 0.06 eV.
HREELS investigations of atomic layer epitaxy (ALE)-grown InN revealed vibrational modes assigned to N-N vibrations. The atomic hydrogen cleaned InN surface also exhibited modes assigned to surface N-H without showing In-H species, which indicated N-polar InN. Complete desorption of hydrogen from the InN surface was best described by the first-order desorption kinetics with an activation energy of 0.88 ± 0.06 eV and pre-exponential factor of (1.5 ± 0.5) ×105 s-1.
Overall, we have used a number of techniques to characterize the structure, surface bonding configuration, thermal stability and hydrogen desorption kinetics of InN and In0.96Ga0.04N epilayers grown by HPCVD and ALE. High group V/III precursors ratio and lattice mismatch have a crucial influence on the film orientation. The effects of hydrogen on the decomposition add to the wide variation in the activation energy of nitrogen desorption. Presence of surface defects lowers the activation energy for hydrogen desorption from the surface.
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Vargun, Elif. "Polymerization And Characterization Of 2-hydroxyethyl Acrylate." Master's thesis, METU, 2003. http://etd.lib.metu.edu.tr/upload/1225010/index.pdf.
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Poly(2-Hydroxyethyl acrylate), PHEA, is used as hydrophilic polymeric gels which have been studied because of its great importance for agricultural or biomedical applications. Biomedical applications of hydrogels include soft contact lenses, artificial corneas, soft tissue substitutes and burn dressings. In this study, it was aimed to synthesis the polymers with well-defined molecular weights, polydispersities and cahin topologies. Bulk, solution and atom transfer radical polymerization (ATRP) techniques at different temperatures were examined. The polymerization in bulk form was carried in vacuum and in open atmosphere. The polymerization curves showed autoacceleration mechanism. The polymers obtained were insoluable in most common solvents because of having high molecular weights and are crosslinked. So in order to overcome this problem, 2-hydroxyethyl acrylate was polymerized by solution and ATRP methods. The activation energy for bulk polymerization was found from Arrhenius plot. The polymer was characterized by FT-IR, DSC, TGA, 1H and 13C NMR techniques, Tensile tests were also examined for PHEA.
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Xu, Juan. "Hydro-dechlorination of Ortho-substituted PCB Congeners Widespread in the Environment: Effects of Triethylamine and Mild Reaction Conditions." University of Cincinnati / OhioLINK, 2020. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1613745571433659.
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