Atomistic modeling of Ge damage accumulation, amorphization and solid phase epitaxial regrowth

En los últimos años, el Ge ha ganado de nuevo atención con la finalidad de ser integrado en el seno de las existentes tecnologías de microelectrónica. Aunque no se le considera como un canddato capaz de reemplazar completamente al Si en el futuro próximo, probalemente servirá como un excelente complemento para aumentar las propiedades eléctricas en dispositivos futuros, especialmente debido a su alta movilidad de portadores. Esta integración requiere de un avance significativo del estado del arte en los procesos de fabricado. Técnicas de simulación, como los algoritmos de Monte Carlo cinético (KMC), proporcionan un ambiente atractivo para llevar a cabo investigación y desarrollo en este campo, especialmente en términos de costes en tiempo y financiación. En este estudio se han usado, por primera vez, técnicas de KMC con el fin entender el procesado “front-end” de Ge en su fabricación, específicamente la acumulación de dañado y amorfización producidas por implantación iónica y el crecimiento epitaxial en fase sólida (SPER) de las capas amorfizadas. Primero, simulaciones de aproximación de clisiones binarias (BCA) son usadas para calcular el dañado causado por cada ión. La evolución de este dañado en el tiempo se simula usando KMC sin red, o de objetos (OKMC) en el que sólamente se consideran los defectos. El SPER se simula a través de una aproximación KMC de red (LKMC), siendo capaz de seguir la evolución de los átomos de la red que forman la intercara amorfo/cristalina. Con el modelo de amorfización desarrollado a lo largo de este trabajo, implementado en un simulador multi-material, se pueden simular todos estos procesos. Ha sido posible entender la acumulación de dañado, desde la generación de defectos puntuales hasta la formación completa de capas amorfas. Esta acumulación ocurre en tres regímenes bien diferenciados, empezando con un ritmo lento de formación de regiones de dañado, seguido por una rápida relajación local de ciertas áreas en la fase amorfa donde ambas fases, amorfa y cristalina, coexisten, para terminar en la amorfización completa de capas extensas, donde satura el ritmo de acumulación. Dicha transición ocurre cuando la concentración de dañado supera cierto valor límite, el cual es independiente de las condiciones de implantación. Cuando se implantan los iones a temperaturas relativamente altas, el recocido dinámico cura el dañado previamente introducido y se establece una competición entre la generación de dañado y su disolución. Estos efectos se vuelven especialmente importantes para iones ligeros, como el B, el cual crea dañado más diluido, pequeño y distribuido de manera diferente que el causado por la implantación de iones más pesados, como el Ge. Esta descripción reproduce satisfactoriamente la cantidad de dañado y la extensión de las capas amorfas causadas por implantación iónica reportadas en la bibliografía. La velocidad de recristalización de la muestra previamente amorfizada depende fuertemente de la orientación del sustrato. El modelo LKMC presentado ha sido capaz de explicar estas diferencias entre orientaciones a través de un simple modelo, dominado por una única energía de activación y diferentes prefactores en las frecuencias de SPER dependiendo de las configuraciones de vecinos de los átomos que recristalizan. La formación de maclas aparece como una consecuencia de esta descripción, y es predominante en sustratos crecidos en la orientación (111)Ge. Este modelo es capaz de reproducir resultados experimentales para diferentes orientaciones, temperaturas y tiempos de evolución de la intercara amorfo/cristalina reportados por diferentes autores. Las parametrizaciones preliminares realizadas de los tensores de activación de tensiones son también capaces de proveer una buena correlación entre las simulaciones y los resultados experimentales de velocidad de SPER a diferentes temperaturas bajo una presión hidrostática aplicada. Los estudios presentados en esta tesis han ayudado a alcanzar un mejor entendimiento de los mecanismos de producción de dañado, su evolución, amorfización y SPER para Ge, además de servir como una útil herramienta para continuar el trabajo en este campo. In the recent years, Ge has regained attention to be integrated into existing microelectronic technologies. Even though it is not thought to be a feasible full replacement to Si in the near future, it will likely serve as an excellent complement to enhance electrical properties in future devices, specially due to its high carrier mobilities. This integration requires a significant upgrade of the state-of-the-art of regular manufacturing processes. Simulation techniques, such as kinetic Monte Carlo (KMC) algorithms, provide an appealing environment to research and innovation in the field, specially in terms of time and funding costs. In the present study, KMC techniques are used, for the first time, to understand Ge front-end processing, specifically damage accumulation and amorphization produced by ion implantation and Solid Phase Epitaxial Regrowth (SPER) of the amorphized layers. First, Binary Collision Approximation (BCA) simulations are used to calculate the damage caused by every ion. The evolution of this damage over time is simulated using non-lattice, or Object, KMC (OKMC) in which only defects are considered. SPER is simulated through a Lattice KMC (LKMC) approach, being able to follow the evolution of the lattice atoms forming the amorphous/crystalline interface. With the amorphization model developed in this work, implemented into a multi-material process simulator, all these processes can be simulated. It has been possible to understand damage accumulation, from point defect generation up to full amorphous layers formation. This accumulation occurs in three differentiated regimes, starting at a slow formation rate of the damage regions, followed by a fast local relaxation of areas into the amorphous phase where both crystalline and amorphous phases coexist, ending in full amorphization of extended layers, where the accumulation rate saturates. This transition occurs when the damage concentration overcomes a certain threshold value, which is independent of the implantation conditions. When implanting ions at relatively high temperatures, dynamic annealing takes place, healing the previously induced damage and establishing a competition between damage generation and its dissolution. These effects become specially important for light ions, as B, for which the created damage is more diluted, smaller and differently distributed than that caused by implanting heavier ions, as Ge. This description successfully reproduces damage quantity and extension of amorphous layers caused by means of ion implantation reported in the literature. Recrystallization velocity of the previously amorphized sample strongly depends on the substrate orientation. The presented LKMC model has been able to explain these differences between orientations through a simple model, dominated by one only activation energy and different prefactors for the SPER rates depending on the neighboring configuration of the recrystallizing atoms. Twin defects formation appears as a consequence of this description, and are predominant for (111)Ge oriented grown substrates. This model is able to reproduce experimental results for different orientations, temperatures and times of evolution of the amorphous/crystalline interface reported by different authors. Preliminary parameterizations for the activation strain tensors are able to also provide a good match between simulations and reported experimental results for SPER velocities at different temperatures under the appliance of hydrostatic pressure. The studies presented in this thesis have helped to achieve a greater understanding of damage generation, evolution, amorphization and SPER mechanisms in Ge, and also provide a useful tool to continue research in this field.

La transformación de las grandes estaciones europeas con la llegada de la Alta Velocidad. El caso de Atocha

La aparición del tren de alta velocidad en Europa en las últimas décadas del siglo XX supuso el resurgir de un medio de transporte en progresivo declive desde la popularización del automóvil y del avión. La decadencia del ferrocarril había supuesto en muchos casos el abandono, o incluso la demolición, de estaciones históricas y el deterioro de su entorno urbano. Como reacción a esa desatención surgió, también en el último cuarto de siglo, una mayor conciencia social preocupada por la conservación del patrimonio construido del ferrocarril. La necesidad de adaptación de las grandes estaciones de ferrocarril para dar servicio al nuevo sistema de transporte, junto con el interés por poner en valor sus construcciones históricas y su céntrico entorno, ha dado como resultado la realización de importantes transformaciones. El objeto de la presente investigación es el estudio de las transformaciones que han sufrido las grandes estaciones europeas del siglo XIX con la llegada del tren de alta velocidad, profundizando de manera especial en el caso más significativo que tenemos en nuestro país: la estación de Atocha. En el ámbito europeo es donde se localizan los ejemplos más relevantes de estaciones que tuvieron gran trascendencia en el siglo XIX y que ahora, con la llegada de la Alta Velocidad, vuelven a recuperar su grandeza. En España, el crecimiento de la Alta Velocidad en los últimos años ha sido extraordinario, hasta situarse como el segundo país del mundo con más kilómetros de líneas de alta velocidad en operación y, en consecuencia, se ha construido un gran número de estaciones adaptadas a este servicio. El caso más notable es el de la estación de Atocha, que desde la llegada del AVE en 1992 hasta el día de hoy, se ha convertido en uno de los complejos ferroviarios más importantes del mundo. El trabajo parte del estudio de otros referentes europeos, como las Gares de París, la estación de St Pancras en Londres y de otras cinco estaciones del centro de Europa –Amsterdam Centraal, Antwerpen Centraal, Köln Hauptbahnhof, Frankfurt (Main) Hauptbahnhof y la Gare de Strasbourg–, para establecer el marco analítico sobre el que se profundiza con la estación de Atocha. El proceso de transformación de la estación de Atocha se ha gestado a través de una serie de proyectos que han ido configurando la estación hasta el momento actual y planteando la previsión de futuro: el proyecto del Plan General de Madrid, el concurso de ideas para el diseño de la estación, la estación de Cercanías, la estación de Alta Velocidad y Largo Recorrido, la ampliación de esta para separar los flujos por niveles, los Estudios Informativos del Nuevo Complejo Ferroviario de la Estación de Atocha y su primera fase de construcción. Estos siete proyectos son objeto de un análisis en tres niveles: análisis cronológico, análisis funcional y análisis formal. La estación de Atocha fue la primera estación histórica europea en sufrir una gran transformación vinculada a la llegada de la Alta Velocidad. Aporta el entendimiento de la estación como un todo y la intermodalidad como sus principales valores, además de la gran mejora urbana que supuso la «operación Atocha», y adolece de ciertas carencias en su desarrollo comercial, vinculadas en parte a la presencia del jardín tropical, y de un pobre espacio en las salas de embarque para los pasajeros de salidas. La estación de Atocha completa su transformación a partir de su renovación funcional, manteniendo la carga simbólica de su historia. De la confrontación del caso de Atocha con otras importantes estaciones europeas resulta la definición de las principales consecuencias de la llegada de la Alta Velocidad a las grandes terminales europeas y la identificación de los elementos clave en su transformación. Las consecuencias principales son: la potenciación de la intermodalidad con otros medios de transporte, el desarrollo comercial no necesariamente destinado a los usuarios de los servicios ferroviarios, y la puesta en valor de la antigua estación y de su entorno urbano. Por su parte, los elementos clave en la transformación de las grandes estaciones tienen que ver directamente con la separación de flujos, el entendimiento de la estación por niveles, la dotación de nuevos accesos laterales y la construcción de una nueva gran cubierta para los nuevos andenes. La preeminencia de unos elementos sobre otros depende del carácter propio de cada estación y de cada país, de la magnitud de la intervención y, también, de la estructura y composición de los equipos encargados del diseño de la nueva estación. En la actualidad, nos encontramos en un momento interesante respecto a las estaciones de Alta Velocidad. Tras el reciente atentado frustrado en el Thalys que viajaba de Ámsterdam a París, se ha acordado establecer controles de identidad y equipajes en todas las estaciones de la red europea de alta velocidad, lo que implicará modificaciones importantes en las grandes estaciones que, probablemente, tomarán el modelo de la estación de Atocha como referencia. ABSTRACT The emergence of the high speed train in Europe in the last few decades of the 20th century represented the resurgence of a means of transport in progressive decline since the popularization of the car and the airplane. The railway decay brought in many cases the abandonment, or even the demolition, of historical stations and the deterioration of its urban environment. In response to that neglect, a greater social awareness towards the preservation of the railway built heritage raised up, also in the last quarter-century. The need for adaptation of the great railway stations to serve the new transport system, along with the interest in enhancing the historical buildings and its central locations, had resulted in important transformations. The subject of current investigation is the study of the transformations that the great 19th century European stations have experienced with the arrival of the high speed rail, deepening in particular in the most significant case we have in Spain: Atocha railway station. At European level is where the most relevant examples of stations which have had a great significance in the 19th century and now, with the arrival of the high speed train, have regain their greatness, are located. In Spain, the growth of the high speed rail over the past few years has been outstanding. Today is the second country in the world with the longest high speed rail network in operation and, therefore, with a great number of new stations adapted to this service. The most remarkable case is Atocha station. Since the arrival of the AVE in 1992, the station has become one of the world's most important railway hub. The research starts with the study of other European reference points, as the Gares of Paris, St Pancras station in London and five other stations of Central Europe –Amsterdam Centraal, Antwerpen Centraal, Köln Hauptbahnhof, Frankfurt (Main) Hauptbahnhof y la Gare de Strasbourg–, to establish the analytical framework that will be deepen with Atocha station. The transformation process of Atocha station has been created through a number of projects that have forged the station to date and have raised the sights in the future: the project of the General Urban Development Plan, the ideas competition for the station design, the Suburban train station, the High Speed and Long Distance station, its enlargement in order to separate passenger flows in different levels, the 'Masterplans' for the new Atocha transport hub and its first phase of construction. These seven projects are under scrutiny at three levels: chronological analysis, functional analysis and formal analysis. Atocha station was the first European historical station to undergo a great transformation tied to the arrival of the high speed rail. It brings the understanding of the station as a whole and the intermodality as its greatest values, besides the great urban improvement of the 'Atocha operation', and suffers from certain shortcomings in its commercial development, partly linked to the presence of the tropical garden, and from a poor space in the departure lounges. Atocha station completes its transformation on the basis of its functional renewal, keeping the symbolic charge of its history. The confrontation of Atocha case with the great European stations results in the definition of the principal consequences of the high speed rail arrival to the great European terminals and the identification of the key elements in its transformation. The principal consequences are: the empowering of the intermodality with other means of transport, of the commercial development, not necessarily intended for railway services users, and the enhancement of the old station and its urban environment. On the other hand, the key elements in the transformation of the great stations are directly related with the separation of passenger flows, the understanding of the station in different levels, the placement of new lateral accesses and the construction of a new deck over the new platforms. The pre-eminence of some elements over the others depends on the particular nature of each station and each country, on the scale of the intervention and also in the structure and composition of the teams in charge of the new station design. Nowadays, this is an interesting time concerning the high speed rail stations. After the recent foiled terrorist attempt in the Thalys train travelling from Amsterdam to Paris, it was agreed to establish passenger and luggage controls in every European high speed rail station. This will mean important changes in these great stations, which probably will take Atocha station's model as a reference.

Entre: de repente, sin fin, lo innombrable

Etiquetamos para reducir nuestra incertidumbre; clasificamos en base a términos opuestos para poder entender. El universo y el espacio construido en particular, se explican desde una arquitectónica dual: dentro – fuera, arriba – abajo, derecha – izquierda, día – noche, hombre – mujer. Lo que nos diferencia como grupo, raza o género, distinguiendo los modos de vivir, las ideologías y las teorías, es la relación que establecemos entre los términos opuestos: entre lo individual y lo colectivo, lo privado y lo público, la imaginación y la realidad, la identidad y la otredad, el orden y el caos, el deseo y la saciedad. El afán clasificatorio dicotómico de la realidad que la modernidad lleva a su extremo, hiere la vida: la mutua exclusión de los opuestos elimina la distancia, el espacio-tiempo entre ambos, que es donde la vida se sitúa. La concepción dual que rige nuestro conocimiento contamina también la relación entre los arquitectos y la sociedad, siendo la causa del ambiente tóxico que envuelve al habitante que ya no se identifica con los lugares que habita. Puede que sea oportuno pasar del pensamiento binario a una lógica de lo intersticial que abandone la dualidad para instalarse en el Entre; los arquitectos serían mediadores entre el poder y la vida, sintiendo el Entre como el transcurso de la vida y la potencia de interacción: los lugares ambiguos e intermedios, es donde sucede el encuentro entre los términos, entre arquitectos y habitantes, entre la imaginación y la realidad, entre tú y yo. ABSTRACT We label to reduce our uncertainty; we classify based on opposites to understand. The universe and all constructed space in particular, are explained from a dual architecture: inside - out, up - down, right - left, day - night, male - female, black - white. What differentiate us as a group, race, gender, distinguishing the lifestyles, ideologies and theories, is how we draw the relation between the opposites: between the individual and the collective, private and public, imagination and reality , identity and otherness, order and disorder, desire and satiety. The dichotomous classification of reality that modernity carried to its extreme, hurts life: the mutual exclusion of opposites eliminates the distance, the space-time between the two, which is where life is located. The dual conception that governs our knowledge has also contaminated the relationship between architect and society, being the cause of the toxic environment that surrounds the inhabitant who no longer identify himself with the places he inhabit. It may be appropriate pass from binary thinking to a logic of the interstitial which abandon duality to settle in Between; architect then will be the mediator between authorities and life, sensing the Between as a flowing of life a potency of interaction rather than a separation between the extremes; ambiguous, in –between, places are where the encounter between opposites happens, between the architect and the inhabitant, between imagination and reality, between you and me.

Blind separation of auditory event-related brain responses into independent components

Averaged event-related potential (ERP) data recorded from the human scalp reveal electroencephalographic (EEG) activity that is reliably time-locked and phase-locked to experimental events. We report here the application of a method based on information theory that decomposes one or more ERPs recorded at multiple scalp sensors into a sum of components with fixed scalp distributions and sparsely activated, maximally independent time courses. Independent component analysis (ICA) decomposes ERP data into a number of components equal to the number of sensors. The derived components have distinct but not necessarily orthogonal scalp projections. Unlike dipole-fitting methods, the algorithm does not model the locations of their generators in the head. Unlike methods that remove second-order correlations, such as principal component analysis (PCA), ICA also minimizes higher-order dependencies. Applied to detected—and undetected—target ERPs from an auditory vigilance experiment, the algorithm derived ten components that decomposed each of the major response peaks into one or more ICA components with relatively simple scalp distributions. Three of these components were active only when the subject detected the targets, three other components only when the target went undetected, and one in both cases. Three additional components accounted for the steady-state brain response to a 39-Hz background click train. Major features of the decomposition proved robust across sessions and changes in sensor number and placement. This method of ERP analysis can be used to compare responses from multiple stimuli, task conditions, and subject states.

RNA analysis by ion-pair reversed-phase high performance liquid chromatography

Ion-pair reversed-phase high performance liquid chromatography (IP RP HPLC) is presented as a new, superior method for the analysis of RNA. IP RP HPLC provides a fast and reliable alternative to classical methods of RNA analysis, including separation of different RNA species, quantification and purification. RNA is stable under the analysis conditions used; degradation of RNA during the analyses was not observed. The versatility of IP RP HPLC for RNA analysis is demonstrated. Components of an RNA ladder, ranging in size from 155 to 1770 nt, were resolved. RNA transcripts of up to 5219 nt were analyzed, their integrity determined and they were quantified and purified. Purification of mRNA from total RNA is described, separating mouse rRNA from poly(A)+ mRNA. IP RP HPLC is also suitable for the separation and purification of DIG-labeled from unlabeled RNA. RNA purified by IP RP HPLC exhibits improved stability.

GE models and algorithms for condensed phase equilibrium data regression in ternary systems: limitations and proposals

Phase equilibrium data regression is an unavoidable task necessary to obtain the appropriate values for any model to be used in separation equipment design for chemical process simulation and optimization. The accuracy of this process depends on different factors such as the experimental data quality, the selected model and the calculation algorithm. The present paper summarizes the results and conclusions achieved in our research on the capabilities and limitations of the existing GE models and about strategies that can be included in the correlation algorithms to improve the convergence and avoid inconsistencies. The NRTL model has been selected as a representative local composition model. New capabilities of this model, but also several relevant limitations, have been identified and some examples of the application of a modified NRTL equation have been discussed. Furthermore, a regression algorithm has been developed that allows for the advisable simultaneous regression of all the condensed phase equilibrium regions that are present in ternary systems at constant T and P. It includes specific strategies designed to avoid some of the pitfalls frequently found in commercial regression tools for phase equilibrium calculations. Most of the proposed strategies are based on the geometrical interpretation of the lowest common tangent plane equilibrium criterion, which allows an unambiguous comprehension of the behavior of the mixtures. The paper aims to show all the work as a whole in order to reveal the necessary efforts that must be devoted to overcome the difficulties that still exist in the phase equilibrium data regression problem.

Spin separation in digital ferromagnetic heterostructures

In a study of the ferromagnetic phase of a multilayer digital ferromagnetic semiconductor in the mean-field and effective-mass approximations, we find the exchange interaction to have the dominant energy scale of the problem, effectively controlling the spatial distribution of the carrier spins in the digital ferromagnetic heterostructures. In the ferromagnetic phase, the majority-spin and minority-spin carriers tend to be in different regions of the space (spin separation). Hence, the charge distribution of carriers also changes noticeably from the ferromagnetic to the paramagnetic phase. An example of a design to exploit these phenomena is given here.

Progetto di un convertitore full-bridge phase-shifted isolato a commutazione risonante

L'evoluzione della tecnologia allo stato solido e il fiorire di nuove applicazioni determinano una forte spinta verso la miniaturizzazione dei convertitori elettronici di potenza. Questa riduzione di pesi ed ingombri è particolarmente sentita anche in quei convertitori di media potenza che necessitano di un trasformatore d'isolamento. In quest'ambito assume importante rilievo l'utilizzo di una architettura circuitale a ponte intero e di tecniche in grado di spingere la frequenza di commutazione il più in alto possibile. Questa tesi si propone quindi di studiare a fondo il funzionamento dei convertitori DC/DC isolati di tipo Full-Bridge e pilotati con la tecnica di modulazione Phase-Shifted che ben si presta all'impiego di commutazioni risonanti del tipo Zero-Voltage-Switching. L'analisi teorica sarà corroborata da simulazioni condotte su LTspice e sarà orientata all'individuazione di una metodologia di progetto generale per questo tipo di convertitori. Al fine di formalizzare meglio il progetto si è individuata una possibile applicazione nell'alimentazione di un DC-bus per telecomunicazioni (48 Volt DC sostenuti da batterie) a partire da una fonte di energia fotovoltaica quale una stringa di pannelli operanti con tensioni variabili da 120 a 180 Volt DC. Per questo particolare tipo di applicazione in discesa può avere senso l'impiego di un rettificatore del tipo a duplicazione di corrente, che quindi si provvederà a studiare e ad implementare a secondario del trasformatore d'isolamento. Infine particolare cura sarà dedicata alla parte di controllo che si ha intenzione di integrare all'interno di LTspice così da riuscire a simulare il comportamento dinamico del convertitore e verificare quanto predetto in via teorica mediante l'impiego della procedura che utilizza il K-Factor per la realizzazione della rete compensatrice.

The Contribution of the Activation Entropy to the Gas-Phase Stability of Modified Nucleic Acid Duplexes

Tricyclo-DNA (tcDNA) is a sugar-modified analogue of DNA currently tested for the treatment of Duchenne muscular dystrophy in an antisense approach. Tandem mass spectrometry plays a key role in modern medical diagnostics and has become a widespread technique for the structure elucidation and quantification of antisense oligonucleotides. Herein, mechanistic aspects of the fragmentation of tcDNA are discussed, which lay the basis for reliable sequencing and quantification of the antisense oligonucleotide. Excellent selectivity of tcDNA for complementary RNA is demonstrated in direct competition experiments. Moreover, the kinetic stability and fragmentation pattern of matched and mismatched tcDNA heteroduplexes were investigated and compared with non-modified DNA and RNA duplexes. Although the separation of the constituting strands is the entropy-favored fragmentation pathway of all nucleic acid duplexes, it was found to be only a minor pathway of tcDNA duplexes. The modified hybrid duplexes preferentially undergo neutral base loss and backbone cleavage. This difference is due to the low activation entropy for the strand dissociation of modified duplexes that arises from the conformational constraint of the tc-sugar-moiety. The low activation entropy results in a relatively high free activation enthalpy for the dissociation comparable to the free activation enthalpy of the alternative reaction pathway, the release of a nucleobase. The gas-phase behavior of tcDNA duplexes illustrates the impact of the activation entropy on the fragmentation kinetics and suggests that tandem mass spectrometric experiments are not suited to determine the relative stability of different types of nucleic acid duplexes.

PVT behaviour of fluids with potential models optimised for phase equilibria

NPT and NVT Monte Carlo simulations are applied to models for methane and water to predict the PVT behaviour of these fluids over a wide range of temperatures and pressures. The potential models examined in this paper have previously been presented in the literature with their specific parameters optimised to fit phase coexistence data. The exponential-6 potential for methane gives generally good prediction of PVT behaviour over the full range of temperature and pressures studied with the only significant deviation from experimental data seen at high temperatures and pressures. The NSPCE water model shows very poor prediction of PVT behaviour, particularly at dense conditions. To improve this. the charge separation in the NSPCE model is varied with density. Improvements for vapour and liquid phase PVT predictions are achieved with this variation. No improvement was found in the prediction of the oxygen-oxygen radial distribution by varying charge separation under dense phase conditions. (C) 2004 Elsevier B.V. All rights reserved.

Demonstration of the spatial separation of the entangled quantum sidebands of an optical field

Quantum optics experiments on bright beams are based on the spectral analysis of field fluctuations and typically probe correlations between radio-frequency sideband modes. However, the extra degree of freedom represented by this dual-mode picture is generally ignored. We demonstrate the experimental operation of a device which can be used to separate the quantum sidebands of an optical field. We use this device to explicitly demonstrate the quantum entanglement between the sidebands of a squeezed beam.

Fringe spacing and phase of interfering matter waves

We experimentally investigate the outcoupling of atoms from Bose-Einstein condensates using two radio-frequency (rf) fields in the presence of gravity. We show that the fringe separation in the resulting interference pattern derives entirely from the energy difference between the two rf fields and not the gravitational potential difference between the two resonances. We subsequently demonstrate how the phase and polarization of the rf radiation directly control the phase of the matter wave interference and provide a semiclassical interpretation of the results.

Separation of n-paraffins by selective adsorption

A study has been undertaken of the vapor-phase adsorptive separation of n-alkanes from Kuwait kerosene (Kuwait National Petroleum Company, heavy kerosene) using zeolite molecular sieves. Due to the shortage of information on the adsorption of multicomponent systems in the open literature, the present investigation was initiated to study the effect of feed flowrate, temperature, and zeolite particle size on the height of mass transfer zone (MTZ) and the dynamic capacity of the adsorbent for multicomponent n-alkanes adsorption on a fixed-bed of zeolite type-5A. The optimum operating conditions for separation of the n-alkanes has been identified so that the effluent would also be of marketable quality. The effect of multicycle adsorption-desorption stages on the dynamic behaviour of zeolite using steam as a desorbing agent has been studied and compared with n-pentane and n-hexane as desorbing agents. The separation process comprised one cycle of adsorption using a fixed-bed of zeolite type-5A. The bed was fed with vaporized kerosene until saturation had been achieved whereby the n-alkanes were adsorbed and the denormalized material eluted. The process of adsorption-desorption was carried out isobarically at one atmosphere. A mathematical model has been developed to predict the breakthrough time using the method of characteristics. The results were in a reasonable agreement with the experimental values. This model has also been utilized to develop the equilibrium isotherm. Optimum operating conditions were achieved at a feed flowrate of 33.33 x 10-9 m3/s, a temperature of 643 K, and a particle size of (1.0 - 2.0) x 10-3 m. This yielded an HMTZ value and a dynamic capacity of 0.206 m and 9.6S3 x 10-2 kg n-alkanes/kg of zeolite respectively. These data will serve as a basis for design of a commercial plant. The purity of liquid-paraffin product desorbed using steam was 83.24 wt%. The dynamic capacity was noticed to decrease sharply with the cycle number, without intermediate reactivation of zeolite, while it was kept unchanged by intermediate reactivation. Normal hexane was found to be the best desorbing agent, the efficiency of which was mounted to 88.2%.

Bioreaction and separation in preparative batch chromatographic columns : the hydrology of lactose to yield glucose,galactose and oligosaccharides

The initial aim of this project was to improve the performance of a chromatographic bioreactor-separator (CBRS). In such a system, a dilute enzyme solution is pumped continuously through a preparative chromatographic column, while pulses of substrate are periodically injected on to the column. Enzymic reaction and separation are therefore performed in a single unit operation. The chromatographic columns used were jacketed glass columns ranging from 1 to 2 metres long with an internal diameter of 1.5 cm. Linking these columns allowed 1, 2, 3 and 4 metre long CBRS systems to be constructed. The hydrolysis of lactose in the presence of β~galactosidase was the reaction of study. From previous work at Aston University, there appeared to be no difficulties in achieving complete lactose hydrolysis in a CBRS. There did, however, appear to be scope for improving the separative performance, so this was adopted as an initial goal. Reducing the particle size of the stationary phase was identified as a way of achieving this improvement. A cation exchange resin was selected which had an average particle size of around half that previously used when studying this reaction. A CBRS system was developed which overcame the operational problems (such as high pressure drop development) associated with use of such a particle size. A significant improvement in separative power was achieved. This was shown by an increase in the number of theoretical plates (N) from about 500 to about 3000 for a 2 metre long CBRS, coupled with higher resolution. A simple experiment with the 1 metre column showed that combined bioreaction and separation was achievable in this system. Having improved the separative performance of the system, the factors affecting enzymic reaction in a CBRS were investigated; including pulse volume and the degree of mixing between enzyme and substrate. The progress of reaction in a CBRS was then studied. This information was related to the interaction of reaction and separation over the reaction zone. The effect of injecting a pulse over a length of time as in CBRS operation was simulated by fed batch experiments. These experiments were performed in parallel with normal batch experiments where the substrate is mixed almost instantly with the enzyme. The batch experiments enabled samples to be taken every minute and revealed that reaction is very rapid. The hydrodynamic characteristics of the two injector configurations used in CBRS construction were studied using Magnetic Resonance Imaging, combined with hydrodynamic calculations. During the optimisation studies, galactooligosaccharides (GOS) were detected as intermediates in the hydrolysis process. GOS are valuable products with potential and existing applications in food manufacture (as nutraceuticals), medicine and drug targeting. The focus of the research was therefore turned to GOS production. A means of controlling reaction to arrest break down of GOS was required. Raising temperature was identified as a possible means of achieving this within a CBRS. Studies were undertaken to optimise the yield of oligosaccharides, culminating in the design, construction and evaluation of a Dithermal Chromatographic Bioreactor-separator.

Combined bioreaction and separation in a simulated counter-current chromatographic bioreactor-separator system

The objective of this work has been to investigate the principle of combined bioreaction and separation in a simulated counter-current chromatographic bioreactor-separator system (SCCR-S). The SCCR-S system consisted of twelve 5.4cm i.d x 75cm long columns packed with calcium charged cross-linked polystyrene resin. Three bioreactions, namely the saccharification of modified starch to maltose and dextrin using the enzyme maltogenase, the hydrolysis of lactose to galactose and glucose in the presence of the enzyme lactase and the biosynthesis of dextran from sucrose using the enzyme dextransucrase. Combined bioreaction and separation has been successfully carried out in the SCCR-S system for the saccharification of modified starch to maltose and dextrin. The effects of the operating parameters (switch time, eluent flowrate, feed concentration and enzyme activity) on the performance of the SCCR-S system were investigated. By using an eluent of dilute enzyme solution, starch conversions of up to 60% were achieved using lower amounts of enzyme than the theoretical amount required by a conventional bioreactor to produce the same amount of maltose over the same time period. Comparing the SCCR-S system to a continuous annular chromatograph (CRAC) for the saccharification of modified starch showed that the SCCR-S system required only 34.6-47.3% of the amount of enzyme required by the CRAC. The SCCR-S system was operated in the batch and continuous modes as a bioreactor-separator for the hydrolysis of lactose to galactose and glucose. By operating the system in the continuous mode, the operating parameters were further investigated. During these experiments the eluent was deionised water and the enzyme was introduced into the system through the same port as the feed. The galactose produced was retarded and moved with the stationary phase to be purge as the galactose rich product (GalRP) while the glucose moved with the mobile phase and was collected as the glucose rich product (GRP). By operating at up to 30%w/v lactose feed concentrations, complete conversions were achieved using only 48% of the theoretical amount of enzyme required by a conventional bioreactor to hydrolyse the same amount of glucose over the same time period. The main operating parameters affecting the performance of the SCCR-S system operating in the batch mode were investigated and the results compared to those of the continuous operation of the SCCR-S system. . During the biosynthesis of dextran in the SCCR-S system, a method of on-line regeneration of the resin was required to operate the system continuously. Complete conversion was achieved at sucrose feed concentrations of 5%w/v with fructose rich. products (FRP) of up to 100% obtained. The dextran rich products were contaninated by small amounts of glucose and levan formed during the bioreaction. Mathematical modelling and computer simulation of the SCCR-S. system operating in the continuous mode for the hydrolysis of lactose has been carried out. .