Exploring thermal and mechanical properties of selected transition elements under extreme conditions: Experiments at high pressures and high temperatures

Transition metals (Ti, Zr, Hf, Mo, W, V, Nb, Ta, Pd, Pt, Cu, Ag, and Au) are essential building units of many materials and have important industrial applications. Therefore, it is important to understand their thermal and physical behavior when they are subjected to extreme conditions of pressure and temperature. This dissertation presents: • An improved experimental technique to use lasers for the measurement of thermal conductivity of materials under conditions of very high pressure (P, up to 50 GPa) and temperature (T up to 2500 K). • An experimental study of the phase relationship and physical properties of selected transition metals, which revealed new and unexpected physical effects of thermal conductivity in Zr, and Hf under high P-T. • New phase diagrams created for Hf, Ti and Zr from experimental data. • P-T dependence of the lattice parameters in α-hafnium. Contrary to prior reports, the α-ω phase transition in hafnium has a negative dT/dP slope. • New data on thermodynamic and physical properties of several transition metals and their respective high P-T phase diagrams. • First complete thermodynamic database for solid phases of 13 common transition metals was created. This database has: All the thermochemical data on these elements in their standard state (mostly available and compiled); All the equations of state (EoS) formulated from pressure-volume-temperature data (measured as a part of this study and from literature); Complete thermodynamic data for selected elements from standard to extreme conditions. The thermodynamic database provided by this study can be used with available thermodynamic software to calculate all thermophysical properties and phase diagrams at high P-T conditions. For readers who do not have access to this software, tabulated values of all thermodynamic and volume data for the 13 metals at high P-T are included in the APPENDIX. In the APPENDIX, a description of several other high-pressure studies of selected oxide systems is also included. Thermophysical properties (Cp, H, S, G) of the high P-T ω-phase of Ti, Zr and Hf were determined during the optimization of the EoS parameters and are presented in this study for the first time. These results should have important implications in understanding hexagonal-close-packed to simple-hexagonal phase transitions in transition metals and other materials.

An experimental and modelling study of the capture of CO2 from gas mixtures with different techniques, with focus on multicomponent effects.

In the present work, the deviations in the solubility of CO2, CH4, and N2 at 30 °c in the mixed gases (CO2/CH4) and (CO2/N2) from the pure gas behavior were studied using the dual-mode model over a wide range of equilibrium composition and pressure values in two glassy polymers. The first of which was PI-DAR which is the polyimide formed by the reaction between 4, 6-diaminoresorcinol dihydrochloride (DAR-Cl) and 2, 2’-bis-(3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA). The other glassy polymer was TR-DAR which is the corresponding thermally rearranged polymer of PI-DAR. Also, mixed gas sorption experiments for the gas mixture (CO2/CH4) in TR-DAR at 30°c took place in order to assess the degree of accuracy of the dual-mode model in predicting the true mixed gas behavior. The experiments were conducted on a pressure decay apparatus coupled with a gas chromatography column. On the other hand, the solubility of CO2 and CH4 in two rubbery polymers at 30⁰c in the mixed gas (CO2/CH4) was modelled using the Lacombe and Sanchez equation of state at various values of equilibrium composition and pressure. These two rubbery polymers were cross-linked poly (ethylene oxide) (XLPEO) and poly (dimethylsiloxane) (PDMS). Moreover, data about the sorption of CO2 and CH4 in liquid methyl dietahnolamine MDEA that was collected from literature65-67 was used to determine the deviations in the sorption behavior in the mixed gas from that in the pure gases. It was observed that the competition effects between the penetrants were prevailing in the glassy polymers while swelling effects were predominant in the rubbery polymers above a certain value of the fugacity of CO2. Also, it was found that the dual-mode model showed a good prediction of the sorption of CH4 in the mixed gas for small pressure values but in general, it failed to predict the actual sorption of the penetrants in the mixed gas.

Seabed photographs taken along OFOS profiles during POLARSTERN cruise PS96 (ANT-XXXI/2 FROSN)

Within the context of the overall ecological working programme Dynamics of Antarctic Marine Shelf Ecosystems (DynAMo) of the PS96 (ANT-XXXI/2) cruise of RV "Polarstern" to the Weddell Sea (Dec 2015 to Feb 2016), seabed imaging surveys were carried out along drift profiles by means of the Ocean Floor Observation System (OFOS) of the Alfred Wegener Institute, Helmholtz Centre for Polar and Marine Research (AWI) Bremerhaven. The setup and mode of deployment of the OFOS was similar to that described by Bergmann and Klages (2012, doi:10.1016/j.marpolbul.2012.09.018). OFOS is a surface-powered gear equipped with two downward-looking cameras installed side-by-side: one high-resolution, wide-angle still camera (CANON® EOS 5D Mark III; lens: Canon EF 24 f/1.4L II, f stop: 13, exposure time: 1/125 sec; in-air view angles: 74° (horizontal), 53° (vertical), 84° (diagonal); image size: 5760 x 3840 px = 21 MPix; front of pressure resistant camera housing consisting of plexiglass dome port) and one high-definition color video camera (SONY® FCB-H11). The system was vertically lowered over the stern of the ship with a broadband fibre-optic cable, until it hovers approximately 1.5 m above the seabed. It was then towed after the slowly sailing ship at a speed of approximately 0.5 kn (0.25 m/s). The ship's Global Acoustic Positioning System (GAPS), combining Ultra Short Base Line (USBL), Inertial Navigation System (INS) and satellite-based Global Positioning System (GPS) technologies, was used to gain highly precise underwater position data of the OFOS. During the profile, OFOS was kept hanging at the preferred height above the seafloor by means of the live video feed and occasional minor cable-length adjustments with the winch to compensate small-scale bathymetric variations in seabed morphology. Information on water depth and height above the seafloor were continuously recorded by means of OFOS-mounted sensors (GAPS transponder, Tritech altimeter). Three lasers, which are placed beside the still camera, emit parallel beams and project red light points, arranged as an equilateral triangle with a side length of 50 cm, in each photo, thus providing a scale that can be used to calculate the seabed area depicted in each image and/or measure the size of organisms or seabed features visible in the image. In addition, the seabed area depicted was estimated using altimeter-derived height above seafloor and optical characteristics of the OFOS still camera. In automatic mode, a seabed photo, depicting an area of approximately 3.45 m**2 (= 2.3 m x 1.5 m; with variations depending on the actual height above ground), was taken every 30 seconds to obtain series of "TIMER" stills distributed at regular distances along the profiles that vary in length depending on duration of the cast. At a ship speed of 0.5 kn, the average distance between seabed images was approximately 5 m. Additional "HOTKEY" photos were taken from interesting objects (organisms, seabed features, such as putative iceberg scours) when they appeared in the live video feed (which was also recorded, in addition to the stills, for documentation and possible later analysis). If any image from this collection is used, please cite the reference as given above.

Caracterización fenotípica y bases moleculares de los pacientes con eosinofilia esofágica respondedora a fármacos inhibidores de la bomba de protones

La esofagitis eosinofílica (EEo) es una enfermedad esofágica alérgica de creciente incidencia. Afecta a niños y adultos jóvenes, principalmente hombres (razón 3:1), encontrándose enfermedades atópicas subyacentes (asma y/o rinoconjuntivitis estacional, dermatitis atópica, alergia alimentaria) en el 80%-90% de los casos. Los primeros criterios diagnósticos para la EEo, publicados en el año 2007, se basaban en la conjunción de tres criterios mayores: datos clínicos (síntomas de disfunción esofágica), datos histológicos (infiltración epitelial esofágica por eosinófilos > 15 eos/cga) y ausencia de respuesta a inhibidores de la bomba de protones (IBP) o pHmetría esofágica normal. Sin embargo, la gran mayoría de los pacientes con síntomas de disfunción esofágica e inflamación esofágica eosinofílica eran diagnosticados de EEo sin confirmación de la respuesta a IBP o realización de pHmetría. Por tanto, existía un riesgo evidente de infraestimación de la respuesta a IBP en estos pacientes. Este incumplimiento de las premisas diagnósticas de consenso no sólo impedía cuantificar el porcentaje de pacientes que eran respondedores a IBP, sino que hacía que pacientes potencialmente respondedores a IBP recibieran otros tratamientos específicos para la EEo (corticoides tópicos, dietas de eliminación), los cuales, comparados con los IBP, provocan mayor cantidad de efectos adversos o podían limitar notablemente la calidad de vida de los pacientes. Inmediatamente después de la publicación de las primeras recomendaciones diagnósticas en el año 2007, se comunicaron pequeñas series retrospectivas de pacientes pediátricos con eosinofilia esofágica sintomática que alcanzaron remisión completa con IBP, tanto con pHmetría normal como patológica. Por tanto, estas series iniciales comenzaron cuestionar el papel diagnóstico de la pHmetría y su capacidad para predecir la respuesta a IBP...

Annotated record and chemical composition of Mn deposits from R/V Mahi Cruise Abyssal Hills 69 stations

A University of Hawaii oceanographic cruise, Abyssal Hills 69, with the R/V Mahi, was carried out to study the association of manganese nodules with an abyssal hill. Manganese nodules from three dredge hauls on an abyssal hill located at 36°W and 157°W exhibited differences in morphology and composition between stations only three miles apart. The morphology of the nodules suggests that nodules from a single site have similar morphologies because they began growth at the same time, probably because of a volcanic event. Differences in morphology between stations indicate a local supply of elements. Atomic absorption analysis for manganese, iron, cobalt, nickel, and copper revealed that nodules nearest to a probable fault line and source of volcanism have a, lower manganese to iron ratio than nodules farther removed. This finding supports the theory that volcanism contributes to the formation of some nodules. Additional evidence showing association with volcanism consists of volcanic nuclei in nodules, crusts formed on layers of volcanic ash, and basalt encrusted to various degrees. The variation in cobalt, nickel, and copper contents Gt the nodules from a single dredge is two-to threefold, but iron content is more uniiorm. Four of the six cores from the area increased in manganese concentration with depth, suggesting that diffusion is concentrating manganese in the upper zone of the sediments or in nodules. The author concludes that volcanism is contributing to the formation of nodules by supplying nuclei and transition elements, but is not necessary for the formation of manganese nodules.

Quintus Curtius before his sources: the episode of Alexander and the Scythians on the Tanais

Quintus Curtius found in his sources a speech where a Scythian censured Alexander, followed by the King’s reply. Curtius drastically abridged this second discourse in order to highlight the criticism of the Macedonian. The Scythian’s words have a striking rhetorical language and some allusions taken from Greek literature, in addition to possible indirect references to Caligula. Curtius declares that he follows his source word-for-word aiming to justify these inconsistencies, but also trying to hide the manipulations he has done to achieve his own narrative purposes.

Stochastic Modeling of Reversible Biochemical Reaction-Diffusion Systems and High-Resolution Shock-Capturing Methods for Fluid Interfaces

Thesis (Ph.D.)--University of Washington, 2016-08

Mixing performance evaluation of additive manufactured milli-scale reactors

The mixing performance of three passive milli-scale reactors with different geometries was investigated at different Reynolds numbers. The effects of design and operating characteristics such as mixing channel shape and volume flow rate were investigated. The main objective of this work was to demonstrate a process design method that uses on Computational Fluid Dynamics (CFD) for modeling and Additive Manufacturing (AM) technology for manufacture. The reactors were designed and simulated using SolidWorks and Fluent 15.0 software, respectively. Manufacturing of the devices was performed with an EOS M-series AM system. Step response experiments with distilled Millipore water and sodium hydroxide solution provided time-dependent concentration profiles. Villermaux-Dushman reaction experiments were also conducted for additional verification of CFD results and for mixing efficiency evaluation of the different geometries. Time-dependent concentration data and reaction evaluation showed that the performance of the AM-manufactured reactors matched the CFD results reasonably well. The proposed design method allows the implementation of new and innovative solutions, especially in the process design phase, for industrial scale reactor technologies. In addition, rapid implementation is another advantage due to the virtual flow design and due to the fast manufacturing which uses the same geometric file formats.

Study on the inhibitory effects of native medicinal plants on growth and aflatoxin production by toxigenic Aspergilli isolated from rainbow trout feed

In the present study, natural occurrence of fungi and aflatoxin B1 (AFB1) in pellet feed and feed ingredients used for rainbow trout was investigated with emphasis to Aspergillus section Flavi members and medicinal plants inhibitory to Aspergillus growth and/or AF production. The feed samples were cultured on the standard isolation media including dichloran rosebengal chloramphenicol agar (DRCA) and Aspergillus flavus/parasiticus agar (AFPA) for 2 weeks at 28 °C. Identification of fungal isolates was implemented based on the macro- and microscopic morphological criteria. AFs were detected using high performance liquid chromatography (HPLC). Based on the results obtained, a total of 109 fungal isolates were identified of which Aspergillus was the prominent genus (57.0%), followed by Penicillium (12.84%), Absidia (11.01%) and Pseudallscheria (10.10%). The most frequent Aspergillus species was A. flavus (60.66%) isolated from all the feed ingredients as well as pellet feed. Among 37 A. flavus isolates, 19 (51.35%) were able to produce AFB1 on yeast extract-sucrose (YES) broth in the range of 10.2 to 612.8 [tg/g fungal dry weight. HPLC analyses of trout feed showed that pellet feed and all feed ingredients tested except gluten were contaminated with different levels of AFB1 in the range of 1.83 to 67.35 lig/kg. In order to finding natural inhibitors of fungal growth and/or AF production, essential oils (EOs) and extracts of 49 medicinal plants were studied against an aflatoxin-producing A. parasiticus using a microbioassay technique. The EOs was analyzed by gas chromatography/mass spectrometry (GC/MS). Based on the results obtained, Achillea millefolium sub sp. elborsensis, Ferula gummosa, Mentha spicata, Azadirachta indica, Conium maculatum and Artemisia dracunculus remarkably inhibited A. parasiticus growth without affecting AF production by the fungus. Besides of Thymus vulgaris and Citrus aurantifolia, the EO of Foeniculum vulgare significantly inhibited both fungal growth (-70.0%) and AFs B1 and G1 (-99.0%) production. The EO of Carum carvi and ethyl acetate extract of Platycladus orientalis suppressed AFs B1 and G1 by more than 90.0%, without any obvious effect on fungal growth. The IC50 values of bioactive plants for AFs B1 and G1 were determined in the ranges of 90.6 to 576.2 and 2.8 to 61.9 µg/ml, respectively. Overall, results of the present study indicate the importance of AF contamination of trout feed as a risk factor for fish farming and thus, an urgent necessity for constant monitoring of trout feed for any unacceptable levels of AF contamination. Likewise, antifungal activities of bioactive plants introduced here would be an important contribution to explain the use of these plants as effective antimicrobial candidates to protect feeds from toxigenic fungus growth and subsequent AF contamination.