Theoretical study of correlated systems using hybrid functionals

Diese Arbeit unterstreicht das Potential von Hybridfunktionalen (B3LYP) für die Untersuchung einer großen Bandbreite von Systemen. Durch die Einbeziehung der exakten Hartree-Fock Austauschenergie kann B3LYP für molekulare und kristalline Systeme eingesetzt werden. Zum Beispiel können stark korrelierte Systeme mit B3LYP erfolgreich erforscht werden. Die elektronische Struktur von PAHs wurde mit B3LYP Hybriddichtefunktionalen untersucht. Mit der ∆SCF-Methode wurden Elektronenbindungsenergien bestimmt, welche die mit UPS gewonnenen experimentellen Resultate bestätigen und ergänzen. Symmetrieeigenschaften der molekularen Orbitale wurden analysiert, um eine Zuordnung und Einschätzung der zugehörigen Signalstärke zu ermöglichen. Während σ-artige Orbitale nur schwer durch UPS-Messungen an dünnen Filmen detektiert werden können, bieten Rechnungen eine detaillierte Einsicht in die verborgenen Teile der Spektren.rnWeiterhin wurden π−π-Komplexe untersucht, welche von verschiedenen Donor- und Akzeptor-Molekülen gebildet werden. Die Moleküle basieren auf polyzyklischen, aromatischen Kohlenwasserstoffen. Für Ladungstransferkomplexe finden DFT Rechnungen ein Minimum in der Oberfläche der potentiellen Energie. Diese attraktive Wechselwirkung wird durch Coulombanziehung verursacht. Allerdings ist die Coulombanziehung nicht die stärkste Wechselwirkung in Ladungstransferkomplexen. Die Einbeziehung von van der Waals-Korrekturen verbessert den intermolekularen Abstand und die Bindungsenergie.rnEine Verkleinerung der intermolekularen Abstände führt zu einer großen Verschiebung der HOMO- und LUMO-Energie.rnAus der Klasse der kristallinen korrelierten Systeme wurden Rb4O6 und FeSe untersucht. Im Falle von Rb4O6 führen Ladungsordnung und Korrelationen zu einem isolierenden Grundzustand. Das hypothetische druckabhängige Phasendiagramm wurde untersucht. Eine Erhöhung des Drucks führt zu einer vergrößerten Bandlücke. Bei etwa 75 GPa wird die Bandbreite W größer als der Bandabstand U und das System nimmt einen homogen gemischt valenten Zustand mit teilweise besetzten π−π-Orbitalen an. Für Drücke ab 160 GPa wird W sehr viel größer als U und das System wird metallisch.rnIm Fall von FeSe finden wir eine korrelierte und isolierende Phase bei hohen Drücken, während das System bei niedrigen Drücken supraleitendes Verhalten zeigt. Die Berechnungen der Elektronenstruktur mit dem Hybridfunktional B3LYP führt zum korrekten halbleitenden Grundzustand in der NiAs- und MnP-Struktur von FeSe. Die Rolle der Korrelationen, der Stöchiometrie und der Nähe zum Magnetismus wird besprochen. Im Speziellen wird gezeigt, dass die Phase mit NiAs-Struktur starke lokale Korrelationen aufweist, was zu einem halbleitenden Zustand in einem weiten Druckbereich führt.

Comparison of morphological and rheological conditions between conventional and eversion carotid endarterectomy using computational fluid dynamics - a pilot study

PURPOSE To compare postoperative morphological and rheological conditions after eversion carotid endarterectomy versus conventional carotid endarterectomy using computational fluid dynamics. BASIC METHODS Hemodynamic metrics (velocity, wall shear stress, time-averaged wall shear stress and temporal gradient wall shear stress) in the carotid arteries were simulated in one patient after conventional carotid endarterectomy and one patient after eversion carotid endarterectomy by computational fluid dynamics analysis based on patient specific data. PRINCIPAL FINDINGS Systolic peak of the eversion carotid endarterectomy model showed a gradually decreased pressure along the stream path, the conventional carotid endarterectomy model revealed high pressure (about 180 Pa) at the carotid bulb. Regions of low wall shear stress in the conventional carotid endarterectomy model were much larger than that in the eversion carotid endarterectomy model and with lower time-averaged wall shear stress values (conventional carotid endarterectomy: 0.03-5.46 Pa vs. eversion carotid endarterectomy: 0.12-5.22 Pa). CONCLUSIONS Computational fluid dynamics after conventional carotid endarterectomy and eversion carotid endarterectomy disclosed differences in hemodynamic patterns. Larger studies are necessary to assess whether these differences are consistent and might explain different rates of restenosis in both techniques.

The mobility of Nb in rutile-saturated NaCl- and NaF-bearing aqueous fluids from 1-6.5 GPa and 300-800 °C

Rutile (TiO2) is an important host phase for high field strength elements (HFSE) such as Nb in metamorphic and subduction zone environments. The observed depletion of Nb in arc rocks is often explained by the hypothesis that rutile sequesters HFSE in the subducted slab and overlying sediment, and is chemically inert with respect to aqueous fluids evolved during prograde metamorphism in the forearc to subarc environment. However, field observations of exhumed terranes, and experimental studies, indicate that HFSE may be soluble in complex aqueous fluids at high pressure (i.e., >0.5 GPa) and moderate to high temperature (i.e., >300 degrees C). In this study, we investigated experimentally the mobility of Nb in NaCl- and NaF-bearing aqueous fluids in equilibrium with Nb-bearing rutile at pressure-temperature conditions applicable to fluid evolution in arc environments. Niobium concentrations in aqueous fluid at rutile saturation were measured directly by using a hydrothermal diamond-anvil cell (HDAC) and synchrotron X-ray fluorescence (SXRF) at 2.1 to 6.5 GPa and 300-500 degrees C, and indirectly by performing mass loss experiments in a piston-cylinder (PC) apparatus at similar to 1 GPa and 700-800 degrees C. The concentration of Nb in a 10 wt% NaCl aqueous fluid increases from 6 to 11 mu g/g as temperature increases from 300 to 500 degrees C, over a pressure range from 2.1 to 2.8 GPa, consistent with a positive temperature dependence. The concentration of Nb in a 20 wt% NaCl aqueous fluid varies from 55 to 150 mu g/g at 300 to 500 degrees C, over a pressure range from 1.8 to 6.4 GPa; however, there is no discernible temperature or pressure dependence. The Nb concentration in a 4 wt% NaF-bearing aqueous fluid increases from 180 to 910 mu g/g as temperature increases from 300 to 500 degrees C over the pressure range 2.1 to 6.5 GPa. The data for the F-bearing fluid indicate that the Nb content of the fluid exhibits a dependence on temperature between 300 and 500 degrees C at >= 2 GPa, but there is no observed dependence on pressure. Together, the data demonstrate that the hydrothermal mobility of Nb is strongly controlled by the composition of the fluid, consistent with published data for Ti. At all experimental conditions, however, the concentration of Nb in the fluid is always lower than coexisting rutile, consistent with a role for rutile in moderating the Nb budget of arc rocks.

Geochemistry of Ninetyeast Ridge basaltic glasses

The Ninetyeast Ridge (NER), a north-south striking, 5,000 km long, 77 to 43 Ma chain of basaltic submarine volcanoes in the eastern Indian Ocean formed as a hotspot track created by rapid northward migration of the Indian Plate over the Kerguelen hotspot. Based on the major and trace element contents of unaltered basaltic glasses from six locations along the NER, we show that the NER was constructed by basaltic magma derived from at least three geochemically distinct mantle sources: (1) a source enriched in highly incompatible elements relative to primitive mantle like the source of the 29-24 Ma flood basalts in the Kerguelen Archipelago; (2) an incompatible element-depleted source similar to the source of Mid-Ocean Ridge Basalt (MORB) erupted along the currently active Southeast Indian Ridge (SEIR); and (3) an incompatible element-depleted source that is compositionally and mineralogically distinct from the source of SEIR MORB. Specifically, this depleted mantle source was garnet-bearing and had higher Y/Dy and Nb/Zr, but lower Zr/Sm, than the SEIR MORB source. We infer that this third source formed as a garnet-bearing residue created during a previous melting event, perhaps an initial partial melting of the mantle hotspot. Subsequently, this residue partially melted over a large pressure range, from slightly over 3 GPa to less than 1 GPa, and to a high extent (~ 30%) thereby creating relatively high SiO2 and FeO contents in some NER basalts relative to SEIR MORB.

Metodología de análisis estadístico de roturas en redes de distribución de agua

La presente Tesis plantea una metodología de análisis estadístico de roturas de tubería en redes de distribución de agua, que analiza la relación entre las roturas y la presión de agua y que propone la implantación de una gestión de presiones que reduzca el número de roturas que se producen en dichas redes. Las redes de distribución de agua se deterioran y una de sus graves consecuencias es la aparición de roturas frecuentes en sus tuberías. Las roturas llevan asociados elevados costes sociales, económicos y medioambientales y es por ello por lo que las compañías gestoras del agua tratan de reducirlas en la medida de lo posible. Las redes de distribución de agua se pueden dividir en zonas o sectores que facilitan su control y que pueden ser independientes o aislarse mediante válvulas, como ocurre en las redes de países más desarrollados, o pueden estar intercomunicados hidráulicamente. La implantación de una gestión de presiones suele llevarse a cabo a través de las válvulas reductoras de presión (VPR), que se instalan en las cabeceras de estos sectores y que controlan la presión aguas abajo de la misma, aunque varíe su caudal de entrada. Los métodos más conocidos de la gestión de presiones son la reducción de presiones, que es el control más habitual, el mantenimiento de la presión, la prevención y/o alivio de los aumentos repentinos de presión y el establecimiento de un control por alturas. A partir del año 2005 se empezó a reconocer el efecto de la gestión de presiones sobre la disminución de las roturas. En esta Tesis, se sugiere una gestión de presiones que controle los rangos de los indicadores de la presión de cabecera que más influyan en la probabilidad de roturas de tubería. Así, la presión del agua se caracteriza a través de indicadores obtenidos de la presión registrada en la cabecera de los sectores, debido a que se asume que esta presión es representativa de la presión de operación de todas las tuberías porque las pérdidas de carga son relativamente bajas y las diferencias topográficas se tienen en cuenta en el diseño de los sectores. Y los indicadores de presión, que se pueden definir como el estadístico calculado a partir de las series de la presión de cabecera sobre una ventana de tiempo, pueden proveer la información necesaria para ayudar a la toma de decisiones a los gestores del agua con el fin de reducir las roturas de tubería en las redes de distribución de agua. La primera parte de la metodología que se propone en esta Tesis trata de encontrar los indicadores de presión que influyen más en la probabilidad de roturas de tuberías. Para conocer si un indicador es influyente en la probabilidad de las roturas se comparan las estimaciones de las funciones de distribución acumulada (FDAs) de los indicadores de presiones, considerando dos situaciones: cuando se condicionan a la ocurrencia de una rotura (suceso raro) y cuando se calculan en la situación normal de operación (normal operación). Por lo general, las compañías gestoras cuentan con registros de roturas de los años más recientes y al encontrarse las tuberías enterradas se complica el acceso a la información. Por ello, se propone el uso de funciones de probabilidad que permiten reducir la incertidumbre asociada a los datos registrados. De esta forma, se determinan las funciones de distribución acumuladas (FDAs) de los valores del indicador de la serie de presión (situación normal de operación) y las FDAs de los valores del indicador en el momento de ocurrencia de las roturas (condicionado a las roturas). Si las funciones de distribución provienen de la misma población, no se puede deducir que el indicador claramente influya en la probabilidad de roturas. Sin embargo, si se prueba estadísticamente que las funciones proceden de la misma población, se puede concluir que existe una relación entre el indicador analizado y la ocurrencia de las roturas. Debido a que el número de valores del indicador de la FDA condicionada a las roturas es mucho menor que el número de valores del indicador de la FDA incondicional a las roturas, se generan series aleatorias a partir de los valores de los indicadores con el mismo número de valores que roturas registradas hay. De esta forma, se comparan las FDAs de series aleatorias del indicador con la FDA condicionada a las roturas del mismo indicador y se deduce si el indicador es influyente en la probabilidad de las roturas. Los indicadores de presión pueden depender de unos parámetros. A través de un análisis de sensibilidad y aplicando un test estadístico robusto se determina la situación en la que estos parámetros dan lugar a que el indicador sea más influyente en la probabilidad de las roturas. Al mismo tiempo, los indicadores se pueden calcular en función de dos parámetros de cálculo que se denominan el tiempo de anticipación y el ancho de ventana. El tiempo de anticipación es el tiempo (en horas) entre el final del periodo de computación del indicador de presión y la rotura, y el ancho de ventana es el número de valores de presión que se requieren para calcular el indicador de presión y que es múltiplo de 24 horas debido al comportamiento cíclico diario de la presión. Un análisis de sensibilidad de los parámetros de cálculo explica cuándo los indicadores de presión influyen más en la probabilidad de roturas. En la segunda parte de la metodología se presenta un modelo de diagnóstico bayesiano. Este tipo de modelo forma parte de los modelos estadísticos de prevención de roturas, parten de los datos registrados para establecer patrones de fallo y utilizan el teorema de Bayes para determinar la probabilidad de fallo cuando se condiciona la red a unas determinadas características. Así, a través del teorema de Bayes se comparan la FDA genérica del indicador con la FDA condicionada a las roturas y se determina cuándo la probabilidad de roturas aumenta para ciertos rangos del indicador que se ha inferido como influyente en las roturas. Se determina un ratio de probabilidad (RP) que cuando es superior a la unidad permite distinguir cuándo la probabilidad de roturas incrementa para determinados intervalos del indicador. La primera parte de la metodología se aplica a la red de distribución de la Comunidad de Madrid (España) y a la red de distribución de Ciudad de Panamá (Panamá). Tras el filtrado de datos se deduce que se puede aplicar la metodología en 15 sectores en la Comunidad de Madrid y en dos sectores, llamados corregimientos, en Ciudad de Panamá. Los resultados demuestran que en las dos redes los indicadores más influyentes en la probabilidad de las roturas son el rango de la presión, que supone la diferencia entre la presión máxima y la presión mínima, y la variabilidad de la presión, que considera la propiedad estadística de la desviación típica. Se trata, por tanto, de indicadores que hacen referencia a la dispersión de los datos, a la persistencia de la variación de la presión y que se puede asimilar en resistencia de materiales a la fatiga. La segunda parte de la metodología se ha aplicado a los indicadores influyentes en la probabilidad de las roturas de la Comunidad de Madrid y se ha deducido que la probabilidad de roturas aumenta para valores extremos del indicador del rango de la presión y del indicador de la variabilidad de la presión. Finalmente, se recomienda una gestión de presiones que limite los intervalos de los indicadores influyentes en la probabilidad de roturas que incrementen dicha probabilidad. La metodología propuesta puede aplicarse a otras redes de distribución y puede ayudar a las compañías gestoras a reducir el número de fallos en el sistema a través de la gestión de presiones. This Thesis presents a methodology for the statistical analysis of pipe breaks in water distribution networks. The methodology studies the relationship between pipe breaks and water pressure, and proposes a pressure management procedure to reduce the number of breaks that occur in such networks. One of the manifestations of the deterioration of water supply systems is frequent pipe breaks. System failures are one of the major challenges faced by water utilities, due to their associated social, economic and environmental costs. For all these reasons, water utilities aim at reducing the problem of break occurrence to as great an extent as possible. Water distribution networks can be divided into areas or sectors, which facilitates the control of the network. These areas may be independent or isolated by valves, as it usually happens in developing countries. Alternatively, they can be hydraulically interconnected. The implementation of pressure management strategies is usually carried out through pressure-reducing valves (PRV). These valves are installed at the head of the sectors and, although the inflow may vary significantly, they control the downstream pressure. The most popular methods of pressure management consist of pressure reduction, which is the common form of control, pressure sustaining, prevention and/or alleviation of pressure surges or large variations in pressure, and level/altitude control. From 2005 onwards, the effects of pressure management on burst frequencies have become more widely recognized in the technical literature. This thesis suggests a pressure management that controls the pressure indicator ranges most influential on the probability of pipe breaks. Operating pressure in a sector is characterized by means of a pressure indicator at the head of the DMA, as head losses are relatively small and topographical differences were accounted for at the design stage. The pressure indicator, which may be defined as the calculated statistic from the time series of pressure head over a specific time window, may provide necessary information to help water utilities to make decisions to reduce pipe breaks in water distribution networks. The first part of the methodology presented in this Thesis provides the pressure indicators which have the greatest impact on the probability of pipe breaks to be determined. In order to know whether a pressure indicator influences the probability of pipe breaks, the proposed methodology compares estimates of cumulative distribution functions (CDFs) of a pressure indicator through consideration of two situations: when they are conditioned to the occurrence of a pipe break (a rare event), and when they are not (a normal operation). Water utilities usually have a history of failures limited to recent periods of time, and it is difficult to have access to precise information in an underground network. Therefore, the use of distribution functions to address such imprecision of recorded data is proposed. Cumulative distribution functions (CDFs) derived from the time series of pressure indicators (normal operation) and CDFs of indicator values at times coincident with a reported pipe break (conditioned to breaks) are compared. If all estimated CDFs are drawn from the same population, there is no reason to infer that the studied indicator clearly influences the probability of the rare event. However, when it is statistically proven that the estimated CDFs do not come from the same population, the analysed indicator may have an influence on the occurrence of pipe breaks. Due to the fact that the number of indicator values used to estimate the CDF conditioned to breaks is much lower in comparison with the number of indicator values to estimate the CDF of the unconditional pressure series, and that the obtained results depend on the size of the compared samples, CDFs from random sets of the same size sampled from the unconditional indicator values are estimated. Therefore, the comparison between the estimated CDFs of random sets of the indicator and the estimated CDF conditioned to breaks allows knowledge of if the indicator is influential on the probability of pipe breaks. Pressure indicators depend on various parameters. Sensitivity analysis and a robust statistical test allow determining the indicator for which these parameters result most influential on the probability of pipe breaks. At the same time, indicators can be calculated according to two model parameters, named as the anticipation time and the window width. The anticipation time refers to the time (hours) between the end of the period for the computation of the pressure indicator and the break. The window width is the number of instantaneous pressure values required to calculate the pressure indicator and is multiple of 24 hours, as water pressure has a cyclical behaviour which lasts one day. A sensitivity analysis of the model parameters explains when the pressure indicator is more influential on the probability of pipe breaks. The second part of the methodology presents a Bayesian diagnostic model. This kind of model belongs to the class of statistical predictive models, which are based on historical data, represent break behavior and patterns in water mains, and use the Bayes’ theorem to condition the probability of failure to specific system characteristics. The Bayes’ theorem allows comparing the break-conditioned FDA and the unconditional FDA of the indicators and determining when the probability of pipe breaks increases for certain pressure indicator ranges. A defined probability ratio provides a measure to establish whether the probability of breaks increases for certain ranges of the pressure indicator. The first part of the methodology is applied to the water distribution network of Madrid (Spain) and to the water distribution network of Panama City (Panama). The data filtering method suggests that the methodology can be applied to 15 sectors in Madrid and to two areas in Panama City. The results show that, in both systems, the most influential indicators on the probability of pipe breaks are the pressure range, which is the difference between the maximum pressure and the minimum pressure, and pressure variability, referred to the statistical property of the standard deviation. Therefore, they represent the dispersion of the data, the persistence of the variation in pressure and may be related to the fatigue in material resistance. The second part of the methodology has been applied to the influential indicators on the probability of pipe breaks in the water distribution network of Madrid. The main conclusion is that the probability of pipe breaks increases for the extreme values of the pressure range indicator and of the pressure variability indicator. Finally, a pressure management which limits the ranges of the pressure indicators influential on the probability of pipe breaks that increase such probability is recommended. The methodology presented here is general, may be applied to other water distribution networks, and could help water utilities reduce the number of system failures through pressure management.

Does Leaf Position within a Canopy Affect Acclimation of Photosynthesis to Elevated CO2?1 : Analysis of a Wheat Crop under Free-Air CO2 Enrichment

Previous studies of photosynthetic acclimation to elevated CO2 have focused on the most recently expanded, sunlit leaves in the canopy. We examined acclimation in a vertical profile of leaves through a canopy of wheat (Triticum aestivum L.). The crop was grown at an elevated CO2 partial pressure of 55 Pa within a replicated field experiment using free-air CO2 enrichment. Gas exchange was used to estimate in vivo carboxylation capacity and the maximum rate of ribulose-1,5-bisphosphate-limited photosynthesis. Net photosynthetic CO2 uptake was measured for leaves in situ within the canopy. Leaf contents of ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco), light-harvesting-complex (LHC) proteins, and total N were determined. Elevated CO2 did not affect carboxylation capacity in the most recently expanded leaves but led to a decrease in lower, shaded leaves during grain development. Despite this acclimation, in situ photosynthetic CO2 uptake remained higher under elevated CO2. Acclimation at elevated CO2 was accompanied by decreases in both Rubisco and total leaf N contents and an increase in LHC content. Elevated CO2 led to a larger increase in LHC/Rubisco in lower canopy leaves than in the uppermost leaf. Acclimation of leaf photosynthesis to elevated CO2 therefore depended on both vertical position within the canopy and the developmental stage.

Factors governing the adsorption of ethanol on spherical activated carbons

Ethanol adsorption on different activated carbons (mostly spherical ones) was investigated covering the relative pressure range from 0.001 to 1. Oxygen surface contents of the ACs were modified by oxidation (in HNO3 solution or air) and/or by thermal treatment in N2. To differentiate the concomitant effects of porosity and oxygen surface chemistry on ethanol adsorption, different sets of samples were used to analyze different relative pressure ranges (below 1000 ppmv concentration and close to unity). To see the effect of oxygen surface chemistry, selected samples having similar porosity but different oxygen contents were studied in the low relative pressure range. At low ethanol concentration (225 ppmv) adsorption is favored in oxidized samples, remarking the effect of the oxidizing treatment used (HNO3 is more effective than air) and the type of oxygen functionalities created (carboxyl and anhydride groups are more effective than phenolic, carbonyl and derivatives). To analyze the high relative pressure range, spherical and additional ACs were used. As the relative pressure of ethanol increases, the effect of oxygen-containing surface groups decreases and microporosity becomes the most important variable affecting the adsorption of ethanol.

Multicomponent adsorption on activated carbons under supercritical conditions

Adsorption of binary mixtures onto activated carbon Norit R1 for the system nitrogen-methane-carbon dioxide was investigated over the pressure range up to 15 MPa. A new model is proposed to describe the experimental data. It is based on the assumption that an activated carbon can be characterized by the distribution function of elements of adsorption volume (EAV) over the solid-fluid potential. This function may be evaluated from pure component isotherms using the equality of the chemical potentials in the adsorbed phase and in the bulk phase for each EAV. In the case of mixture adsorption a simple combining rule is proposed, which allows determining the adsorbed phase density and its composition in the EAV at given pressure and compositions of the bulk phase. The adsorbed concentration of each adsorbate is the integral of its density over the set of EAV. The comparison with experimental data on binary mixtures has shown that the approach works reasonably well. In the case of high-pressure binary mixture adsorption, when only total amount adsorbed was measured, the proposed model allows reliably determining partial amounts of the adsorbed components. (C) 2004 Elsevier Inc. All rights reserved.

Cooperative and competitive adsorption of ethylene, ethane, nitrogen and argon on graphitized carbon black and in slit pores

In this paper we investigate the mixture adsorption of ethylene, ethane, nitrogen and argon on graphitized thermal carbon black and in slit pores by means of the Grand Canonical Monte Carlo simulations. Pure component adsorption isotherms on graphitized thermal carbon black are first characterized with the GCMC method, and then mixture simulations are carried out over a wide range of pore width, temperature, pressure and composition to investigate the cooperative and competitive adsorption of all species in the mixture. Results of mixture simulations are compared with the experimental data of ethylene and ethane (Friederich and Mullins, 1972) on Sterling FTG-D5 (homogeneous carbon black having a BET surface area of 13 m(2)/g) at 298 K and a pressure range of 1.3-93 kPa. Because of the co-operative effect, the Henry constant determined by the traditional chromatography method is always greater than that obtained from the volumetric method.

Grand canonical Monte Carlo simulation study of methane adsorption at an open graphite surface and in slitlike carbon pores at 273 K

Grand canonical Monte Carlo (GCMC) simulation was used for the systematic investigation of the supercritical methane adsorption at 273 K on an open graphite surface and in slitlike micropores of different sizes. For both considered adsorption systems the calculated excess adsorption isotherms exhibit a maximum. The effect of the pore size on the maximum surface excess and isosteric enthalpy of adsorption for methane storage at 273 K is discussed. The microscopic detailed picture of methane densification near the homogeneous graphite wall and in slitlike pores at 273 K is presented with selected local density profiles and snapshots. Finally, the reliable pore size distributions, obtained in the range of the microporosity, for two pitch-based microporous activated carbon fibers are calculated from the local excess adsorption isotherms obtained via the GCMC simulation. The current systematic study of supercritical methane adsorption both on an open graphite surface and in slitlike micropores performed by the GCMC summarizes recent investigations performed at slightly different temperatures and usually a lower pressure range by advanced methods based on the statistical thermodynamics.

Modeling of adsorption in finite cylindrical pores by means of density functional theory

Adsorption of argon at its boiling point infinite cylindrical pores is considered by means of the non-local density functional theory (NLDFT) with a reference to MCM-41 silica. The NLDFT was adjusted to amorphous solids, which allowed us to quantitatively describe argon adsorption isotherm on nonporous reference silica in the entire bulk pressure range. In contrast to the conventional NLDFT technique, application of the model to cylindrical pores does not show any layering before the phase transition in conformity with experimental data. The finite pore is modeled as a cylindrical cavity bounded from its mouth by an infinite flat surface perpendicular to the pore axis. The adsorption of argon in pores of 4 and 5 nm diameters is analyzed in canonical and grand canonical ensembles using a two-dimensional version of NLDFT, which accounts for the radial and longitudinal fluid density distributions. The simulation results did not show any unusual features associated with accounting for the outer surface and support the conclusions obtained from the classical analysis of capillary condensation and evaporation. That is, the spontaneous condensation occurs at the vapor-like spinodal point, which is the upper limit of mechanical stability of the liquid-like film wetting the pore wall, while the evaporation occurs via a mechanism of receding of the semispherical meniscus from the pore mouth and the complete evaporation of the core occurs at the equilibrium transition pressure. Visualization of the pore filling and empting in the form of contour lines is presented.

A new strategy for selecting and evaluating physical solvents for gas absorption

This work describes how the physical properties of a solvent affect the design variables of a physical gas absorption process. The role of every property in determining the capital and the running cost of a process has been specified. Direct mathematical relationships have been formulated between every item of capital or running cost and the properties which are related to that item. The accuracy of the equations formulated has been checked by comparing their outcome with some actual design data. A good agreement has been found. The equations formulated may be used to evaluate on the basis of economics any suggested new solvents. A group of solvents were selected for evaluation. Their physical properties were estimated or collected as experimental data. The selected ones include three important solvents, the first is polyethylene glycol dimethyl ether (Selexol) which represents the currently most successful one, The other two solvents are acetonyl acetone (B2) and n-formyl morpholine which have been suggested previously as potential credible alternatives to the current ones. The important characteristics of: acetonyl acetone are its high solubility and its low viscosity, while the n-formyl morpholine is characterised by its low vapour pressure and its high selectivity. It was found that acetonyl acetone (B2) is the most attractive solvent for commercial applications particularly for process configurations that:include heat exchangers and strippers. The effect of the process configuration on the selected solvent was investigated in detail and it was found that there is no universal solvent which is the best for any process configuration, but that there is a best solvent for a given process configuration. In previous work, acetonyl acetone was suggested as a commercially promising physical solvent. That suggestion was not fully based on experimental measurement of all the physical properties. The viscosity of acetonyl acetone and its solubility at 1 atm were measured but the vapour pressure and the solubility of C02 and CH4 at high pressure were predicted. In this work, the solubilities of C02, CH4 and C3H8 in acetenyl acetone were measured for a partial pressure range of (2 ~ 22) bar at 25°C, The vapour pressure of this solvent was also measured, and the Antoine equation was formulated from tbe experimental data. The experimental data were found to be not In agreement with the predicted ones, so acetonyl acetone was re-evaluated according to the experimental data. It was found that this solvent can be recommended for further trials in a pilot plant study or for small scale commercial units.

Liquid-phase alcohol promoted methanol synthesis from CO2 and H2

Methanol is an important and versatile compound with various uses as a fuel and a feedstock chemical. Methanol is also a potential chemical energy carrier. Due to the fluctuating nature of renewable energy sources such as wind or solar, storage of energy is required to balance the varying supply and demand. Excess electrical energy generated at peak periods can be stored by using the energy in the production of chemical compounds. The conventional industrial production of methanol is based on the gas-phase synthesis from synthesis gas generated from fossil sources, primarily natural gas. Methanol can also be produced by hydrogenation of CO2. The production of methanol from CO2 captured from emission sources or even directly from the atmosphere would allow sustainable production based on a nearly limitless carbon source, while helping to reduce the increasing CO2 concentration in the atmosphere. Hydrogen for synthesis can be produced by electrolysis of water utilizing renewable electricity. A new liquid-phase methanol synthesis process has been proposed. In this process, a conventional methanol synthesis catalyst is mixed in suspension with a liquid alcohol solvent. The alcohol acts as a catalytic solvent by enabling a new reaction route, potentially allowing the synthesis of methanol at lower temperatures and pressures compared to conventional processes. For this thesis, the alcohol promoted liquid phase methanol synthesis process was tested at laboratory scale. Batch and semibatch reaction experiments were performed in an autoclave reactor, using a conventional Cu/ZnO catalyst and ethanol and 2-butanol as the alcoholic solvents. Experiments were performed at the pressure range of 30-60 bar and at temperatures of 160-200 °C. The productivity of methanol was found to increase with increasing pressure and temperature. In the studied process conditions a maximum volumetric productivity of 1.9 g of methanol per liter of solvent per hour was obtained, while the maximum catalyst specific productivity was found to be 40.2 g of methanol per kg of catalyst per hour. The productivity values are low compared to both industrial synthesis and to gas-phase synthesis from CO2. However, the reaction temperatures and pressures employed were lower compared to gas-phase processes. While the productivity is not high enough for large-scale industrial operation, the milder reaction conditions and simple operation could prove useful for small-scale operations. Finally, a preliminary design for an alcohol promoted, liquid-phase methanol synthesis process was created using the data obtained from the experiments. The demonstration scale process was scaled to an electrolyzer unit producing 1 Nm3 of hydrogen per hour. This Master’s thesis is closely connected to LUT REFLEX-platform.

Modificação da pasta kraft de eucalipto para novas aplicações

Este trabalho constou num estudo da modificação da pasta kraft de eucalipto, utilizando uma técnica de processamento por alta pressão hidrostática com o intuito de melhorar a sua performance para novas aplicações tal como o papel tissue ou o papel para embalagens. Para tal pretendia-se melhorar algumas propriedades da pasta com a utilização da técnica de alta pressão hidrostática. Realizou-se um estudo preliminar onde se submeteu uma pasta branqueada A, não refinada, a um tratamento hiperbárico (TH) numa gama de pressões de 5000-8000 bar. Para uma pressão de 6000 bar constatou-se uma melhoria de cerca de 16 % no alongamento percentual na rotura, 17 % na resistência à tração, 27 % no índice de rebentamento e cerca de 19 % no índice de rasgamento. Posteriormente, e tendo em conta os resultados positivos verificados na pasta A, estudou-se o efeito do TH numa pasta branqueada B variando a consistência de tratamento (1,5% ou 3%) e o tempo de processamento (5 ou 10 minutos). Foi estudado também o efeito do TH quando aplicado antes e após a refinação da pasta. A pasta branca foi submetida à refinação num moinho PFI entre 1000 e 3000 rotações. Os resultados obtidos mostram que o TH realizado a menores consistências apresenta um efeito mais significativo nas propriedades físico-mecânicas de pastas e que o efeito é distinto quando o processamento é aplicado antes e depois da refinação, tendo-se registado melhoramentos das propriedades mecânicas apenas quando o TH ocorre após a refinação. A pasta kraft foi também modificada com anidrido alquenil succínico (ASA). A modificação da pasta de celulose com ASA resultou numa diminuição das propriedades mecânicas e para além disso não gerou qualquer alteração na termoplasticidade do material, no entanto registou-se um aumento na resistência à molhabilidade. Concluiu-se que o TH conduz a alterações ao nível de propriedades mecânicas e estruturais da pasta de interesse para a aplicação em papéis tissue no caso da pasta B. Para além disso a modificação da pasta com ASA resultou em alterações de interesse particular para papéis de embalagem.

Low-pressure planar magnetron discharge for surface deposition and nanofabrication

Current-voltage characteristics of the planar magnetron are studied experimentally and by numerical simulation. Based on the measured current-voltage characteristics, a model of the planar magnetron discharge is developed with the background gas pressure and magnetic field used as parameters. The discharge pressure was varied in a range of 0.7-1.7 Pa, the magnetic field of the magnetron was of 0.033-0.12 T near the cathode surface, the discharge current was from 1 to 25 A, and the magnetic field lines were tangential to the substrate surface in the region of the magnetron discharge ignition. The discharge model describes the motion of energetic secondary electrons that gain energy by passing the cathode sheath across the magnetic field, and the power required to sustain the plasma generation in the bulk. The plasma electrons, in turn, are accelerated in the electric field and ionize effectively the background gas species. The model is based on the assumption about the prevailing Bohm mechanism of electron conductivity across the magnetic field. A criterion of the self-sustained discharge ignition is used to establish the dependence of the discharge voltage on the discharge current. The dependence of the background gas density on the current is also observed from the experiment. The model is consistent with the experimental results. © 2010 American Institute of Physics.