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Phenomenology And Experimental Observations In High Temperature Ternary InterdiffusionElliott, Abby Lee 01 January 2004 (has links)
A new method to extract composition dependent ternary interdiffusion coefficients from a single diffusion couple experiment is presented. The calculations involve direct determination of interdiffusion fluxes from experimental concentration profiles and local integration and differentiation of Onsager's formalism. This new technique was applied to concentration profiles obtained from selected semi-infinite, single-phase diffusion couple experiments in the Cu-Ni-Zn, Fe-Ni-Al, and Ni-Cr-Al systems. These couples exhibit features such as uphill diffusion and zero flux planes. The interdiffusion coefficients from the new technique along with coefficients reported from other methods are graphed as functions of composition. The coefficients calculated from the new technique are consistent with those determined from Boltzmann-Matano analysis and an alternate analysis based on the concept of average ternary interdiffusion coefficients. The concentration profiles generated from the error function solutions using the calculated interdiffusion coefficients are in good agreement with the experimental profiles including those exhibiting uphill diffusion. The new technique is checked for accuracy and consistency by back-calculating known interdiffusion coefficients; in this exercise, the new method accurately predicts constant diffusivity. After rigorous verification, the new technique is applied to previously unexamined couples in the Ni-Pt-Al system. With Ni as the dependent component, the main coefficients are shown to be relatively constant and the cross coefficients are negative. The interdiffusion coefficient representing the contribution of the concentration gradient of Pt to the interdiffusion flux of Al is relatively large for couples whose Al content is low, indicating that Pt has a significant effect on Al when Al concentration is low. Another important aspect of analyzing diffusional interactions is the movement of single and multi-phase boundaries within a diffusion couple. Phase boundaries for an n-component system are newly classified and boundary movement is analyzed in terms of degrees of freedom. Experimental evidence of a category 2:1 boundary is presented with a solid-to-solid semi-infinite diffusion couple in the Fe-Ni-Al system with two single-phase terminal alloys. The diffusion path for this couple surprisingly passes through the vertex of the equilibrium tie triangle on the phase diagram to exhibit three phase equilibria in a ternary system. Here is shown for the first time experimental verification of this phenomenon.
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Accurate Measurements and Modeling of the PpT Behavior of Pure Substances and Natural Gas-Like Hydrocarbon MixturesMantilla, Ivan 2012 August 1900 (has links)
The scale of the energy business today and a favorable and promising economic environment for the production of natural gas, requires study of the thermophysical behavior of fluids: sophisticated experimentation yielding accurate, new volumetric data, and development and improvement of thermodynamic models. This work contains theoretical and experimental contributions in the form of 1) the revision and update of a field model to calculate compressibility factors starting from the gross heating value and the mole fractions of diluents in natural gas mixtures; 2) new reference quality volumetric data, gathered with state of the art techniques such as magnetic suspension densimetry and isochoric phase boundary determinations; 3) a rigorous first-principles uncertainty assessment for density measurements; and 4) a departure technique for the extension of these experimental data for calculating energy functions. These steps provide a complete experimental thermodynamic characterization of fluid samples.
A modification of the SGERG model, a standard virial-type model for prediction of compressibility factors of natural gas mixtures, matches predictions from the master GERG-2008 equation of state, using least squares routines coded at NIST. The modification contains new values for parametric constants, such as molecular weights and the universal gas constant, as well as a new set of coefficients.
A state-of-the-art high-pressure, single-sinker magnetic suspension densimeter is used to perform density measurements over a wide range of temperatures and pressures. This work contains data on nitrogen, carbon dioxide, and a typical residual gas mixture (95% methane, 4% ethane, and 1% propane). Experimental uncertainty results from a rigorous, first-principles estimation including composition uncertainty effects.
Both low- and high-pressure isochoric apparatus are used to perform phase boundary measurements. Isochoric P-T data can determine the phase boundaries. Combined with density measurements, isochoric data provides isochoric densities. Further mathematical treatment, including noxious volume and thermal expansion corrections, and isothermal integration, leads to energy functions and thus to a full thermodynamic characterization.
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COOLING RATE CONTROLLED RELAXATION AND THE ASSOCIATED CHEMICAL AND STRUCTURAL RESPONSES IN SINGLE CRYSTAL HETEROSTRUCTURES WITH VOLATILE CATIONSFarghadany, Elahe, Dr 23 May 2022 (has links)
No description available.
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Darstellung und Verwendung von Nucleolipiden zur Lipophilisierung von Nucleinsäuren sowie deren Wechselwirkung und Duplex-Bildung an horizontalen Lipid-Bilayers und Phasengrenzen zur Entwicklung einer neuartigen RNA/DNA-Analytik / Synthesis and Application of Nucleolipids for the Lipophilization of Nucleic Acids and Their Interaction and Duplex Formation at Horizontal Lipid-Bilayers and Phase Boundaries for the Development of a Novel RNA/DNA AnalyticsWerz, Emma 17 February 2016 (has links)
Ziel der vorgestellten Arbeit war die Synthese von Nucleolipiden zur Lipophilisierung von Oligonucleotiden sowie deren Untersuchung im Hinblick auf ihre Wechselwirkung und Duplex-Bildung an horizontalen Lipidmembranen und verschiedenen Phasengrenzen zur Entwicklung eines neuartigen Bio-Chips für die RNA/DNA-Analyse.
Mit der Synthese N(3)-prenylierter und 2’,3’-O-ketalisierter Pyrimidinbasen Uridin und Methyluridin wurden Nucleolipid-Bausteine dargestellt, die auch als terminale Kopfgruppen eines Oligonucleotid-Dodecamers den lipophilen Charakter dieser Oligonucleotid-Sequenz erhöhten. Für den Einsatz solcher LONs (Lipo-Oligonucleotide) in einer vereinfachten RNA/DNA-Analytik wurde eine Vielzahl von Lipo-Oligonucleotiden mit diversen Nucleolipid-Kopfgruppen synthetisiert und auf ihr Einlagerungsverhalten in künstliche Lipid-Bilayer untersucht. Fluoreszenz-spektroskopische Untersuchungen zeigten, dass alle Lipo-Oligonucleotide in der Lage sind, sich in künstliche Lipid-Bilayer einzulagern. Abhängig von der Struktur, der Länge und der Anzahl der C-Atom-Ketten dieser lipophilen Anker-Bausteine wurden die Geschwindigkeit und die Festigkeit der Verankerung im Lipid-Bilayer beeinflusst.
Des Weiteren wurde die Hybridisierung von LONs mit komplementären Oligomeren an Lipidmembranen untersucht. Es konnte gezeigt werden, dass die im Bilayer verankerten Lipo-Oligonucleotide mit komplementären Oligomeren DNA-Duplexe bilden. Die hybridisierte DNA wurde nicht nur über einen kovalent gebundenen Cy5-Fluorophor am Gegenstrang nachgewiesen, sondern auch über den DNA-Interkalator SYBR Green I (SG).
Am Beispiel von zwei Lipo-Oligonucleotiden (LON 20 und 23), die sich schnell und fest in der Bilayermembran verankern, konnte eine spontane Akkumulation dieser LONs an CHCl3/H2O sowie H2O/n-Decan Grenzflächen direkt nach der Probenzugabe beobachtet werden. Diese und andere Ergebnisse stützen den Einsatz von Lipo-Oligonucleotiden als Ziel-Oligomere in einem neuartigen RNA/DNA-Nachweisverfahren an Phasengrenzen.
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