Acidic dissolution of iron oxides and regeneration of a ceramic filter medium

The dewatering of iron ore concentrates requires large capacity in addition to producing a cake with low moisture content. Such large processes are commonly energy intensive and means to lower the specific energy consumption are needed. Ceramic capillary action disc filters incorporate a novel filter medium enabling the harnessing of capillary action, which results in decreased energy consumption in comparison to traditional filtration technologies. As another benefit, the filter medium is mechanically and chemically more durable than, for example, filter cloths and can, thus, withstand harsh operating conditions and possible regeneration better than other types of filter media. In iron ore dewatering, the regeneration of the filter medium is done through a combination of several techniques: (1) backwashing, (2) ultrasonic cleaning, and (3) acid regeneration. Although it is commonly acknowledged that the filter medium is affected by slurry particles and extraneous compounds, published research, especially in the field of dewatering of mineral concentrates, is scarce. Whereas the regenerative effect of backwashing and ultrasound are more or less mechanical, regeneration with acids is based on chemistry. The chemistry behind the acid regeneration is, naturally, dissolution. The dissolution of iron oxide particles has been extensively studied over several decades but those studies may not necessarily be directly applicable in the regeneration of the filter medium which has undergone interactions with the slurry components. The aim of this thesis was to investigate if free particle dissolution indeed correlates with the regeneration of the filter medium. For this purpose, both free particle dissolution and dissolution of surface adhered particles were studied. The focus was on acidic dissolution of iron oxide particles and on the study of the ceramic filter medium used in the dewatering of iron ore concentrates. The free particle dissolution experiments show that the solubility of synthetic fine grained iron oxide particles in oxalic acid could be explained through linear models accounting for the effects of temperature and acid concentration, whereas the dissolution of a natural magnetite is not so easily explained by such models. In addition, the kinetic experiments performed both support and contradict the work of previous authors: the suitable kinetic model here supports previous research suggesting solid state reduction to be the reaction mechanism of hematite dissolution but the formation of a stable iron oxalate is not supported by the results of this research. Several other dissolution mechanisms have also been suggested for iron oxide dissolution in oxalic acid, indicating that the details of oxalate promoted reductive dissolution are not yet agreed and, in this respect, this research offers added value to the community. The results of the regeneration experiments with the ceramic filter media show that oxalic acid is highly effective in removing iron oxide particles from the surface of the filter medium. The dissolution of those particles did not, however, exhibit the expected behaviour, i.e. complete dissolution. The results of this thesis show that although the regeneration of the ceramic filter medium with acids incorporates the dissolution of slurry particles from the surface of the filter medium, the regeneration cannot be assessed purely based upon free particle dissolution. A steady state, dependent on temperature and on the acid concentration, was observed in the dissolution of particles from the surface even though the limit of solubility of free iron oxide particles had not been reached. Both the regeneration capacity and efficiency, with regards to the removal of iron oxide particles, was found to be temperature dependent, but was not affected by the acid concentration. This observation further suggests that the removal of the surface adhered particles does not follow the dissolution of free particles, which do exhibit a dependency on the acid concentration. In addition, changes in the permeability and in the pore structure of the filter medium were still observed after the bulk concentration of dissolved iron had reached a steady state. Consequently, the regeneration of the filter medium continued after the dissolution of particles from the surface had ceased. This observation suggests that internal changes take place at the final stages of regeneration. The regeneration process could, in theory, be divided into two, possibly overlapping, stages: (1) dissolution of surface-adhered particles, and (2) dissolution of extraneous compounds from within the pore structure. In addition to the fundamental knowledge generated during this thesis, tools to assess the effects of parameters on the regeneration of the ceramic filter medium are needed. It has become clear that the same tools used to estimate the dissolution of free particles cannot be used to estimate the regeneration of a filter medium unless only a robust characterisation of the order of regeneration efficiency is needed.

THE EFFECTIVE DIFFUSIVITY OF CLOVE(Eugenia caryophyllus) ESSENTIAL OIL IN PRESSURIZED CO2

The effective diffusivity of clove essential oil in subcritical liquid CO2 was estimated. The experimental apparatus employed was a fixed-bed extractor. The fixed bed was formed with grounded (mesh -32 + 65) and compacted clove buds which were considered a solid element. The effective diffusion coefficient was evaluated by fitting the experimental concentration profile to the unsteady state mass balance equation for unidirectional diffusion in a finite solid medium. The diffusion coefficient was related to the concentration of oil in the solid by an exponential function. The estimated values of the effective diffusion coefficient varied from 3.64 to 5.22x10-10 m2/s. The average relative errors were lower than 3.1%.

The Macroeconomic Effects of Infrequent Information with Adjustment Costs

In the last decade, the potential macroeconomic effects of intermittent large adjustments in microeconomic decision variables such as prices, investment, consumption of durables or employment – a behavior which may be justified by the presence of kinked adjustment costs – have been studied in models where economic agents continuously observe the optimal level of their decision variable. In this paper, we develop a simple model which introduces infrequent information in a kinked adjustment cost model by assuming that agents do not observe continuously the frictionless optimal level of the control variable. Periodic releases of macroeconomic statistics or dividend announcements are examples of such infrequent information arrivals. We first solve for the optimal individual decision rule, that is found to be both state and time dependent. We then develop an aggregation framework to study the macroeconomic implications of such optimal individual decision rules. Our model has the distinct characteristic that a vast number of agents tend to act together, and more so when uncertainty is large. The average effect of an aggregate shock is inversely related to its size and to aggregate uncertainty. We show that these results differ substantially from the ones obtained with full information adjustment cost models.

Étude structurale et fonctionnelle du canal potassium dépendant du voltage KvAP

Les canaux ioniques dépendants du voltage sont responsables de l'initiation et de la propagation des potentiels d'action dans les cellules excitables. De nombreuses maladies héréditaires (channelopathies) sont associées à un contrôle défectueux du voltage par ces canaux (arythmies, épilepsie, etc.). L’établissement de la relation structure-fonction exacte de ces canaux est donc crucial pour le développement de nouveaux agents thérapeutiques spécifiques. Dans ce contexte, le canal procaryote dépendant du voltage et sélectif au potassium KvAP a servi de modèle d’étude afin d’approfondir i) le processus du couplage électromécanique, ii) l’influence des lipides sur l’activité voltage-dépendante et iii) l’inactivation de type closed-state. Afin de pallier à l’absence de données structurales dynamiques du côté cytosolique ainsi que de structure cristalline dans l’état fermé, nous avons mesuré le mouvement du linker S4-S5 durant le gating par spectroscopie de fluorescence (LRET). Pour ce faire, nous avons utilisé une technique novatrice du contrôle de l’état conformationnel du canal en utilisant les lipides (phospholipides et non phospholipides) au lieu du voltage. Un modèle dans l’état fermé a ainsi été produit et a démontré qu’un mouvement latéral modeste de 4 Å du linker S4-S5 est suffisant pour mener à la fermeture du pore de conduction. Les interactions lipides - canaux jouent un rôle déterminant dans la régulation de la fonction des canaux ioniques mais ne sont pas encore bien caractérisées. Nous avons donc également étudié l’influence de différents lipides sur l’activation voltage - dépendante de KvAP et mis en évidence deux sites distincts d’interactions menant à des effets différents : au niveau du senseur de voltage, menant au déplacement de la courbe conductance-voltage, et du côté intracellulaire, influençant le degré de la pente de cette même courbe. Nous avons également démontré que l’échange de lipides autour de KvAP est extrêmement limité et affiche une dépendance à l’état conformationnel du canal, ne se produisant que dans l’état ouvert. KvAP possède une inactivation lente particulière, accessible depuis l'état ouvert. Nous avons étudié les effets de la composition lipidique et de la température sur l'entrée dans l'état inactivé et le temps de récupération. Nous avons également utilisé la spectroscopie de fluorescence (quenching) en voltage imposé afin d'élucider les bases moléculaires de l’inactivation de type closed-state. Nous avons identifié une position à la base de l’hélice S4 qui semble impliquée à la fois dans le mécanisme responsable de ce type d'inactivation et dans la récupération particulièrement lente qui est typique du canal KvAP.

Analysis of some Stochastic models in inventories and Queues

The thesis entitled Analysis of Some Stochastic Models in Inventories and Queues. This thesis is devoted to the study of some stochastic models in Inventories and Queues which are physically realizable, though complex. It contains a detailed analysis of the basic stochastic processes underlying these models. In this thesis, (s,S) inventory systems with nonidentically distributed interarrival demand times and random lead times, state dependent demands, varying ordering levels and perishable commodities with exponential life times have been studied. The queueing system of the type Ek/Ga,b/l with server vacations, service systems with single and batch services, queueing system with phase type arrival and service processes and finite capacity M/G/l queue when server going for vacation after serving a random number of customers are also analysed. The analogy between the queueing systems and inventory systems could be exploited in solving certain models. In vacation models, one important result is the stochastic decomposition property of the system size or waiting time. One can think of extending this to the transient case. In inventory theory, one can extend the present study to the case of multi-item, multi-echelon problems. The study of perishable inventory problem when the commodities have a general life time distribution would be a quite interesting problem. The analogy between the queueing systems and inventory systems could be exploited in solving certain models.

Intrinsic channel closing in strong-field single ionization of H2

Die Ionisation von H2 in intensiven Laserpulsen wird mit Hilfe der numerischen Integration der zeitabhängigen Schrödingergleichung für ein Einelektronenmodell untersucht, das die Vibrationsbewegung berücksichtigt. Die Spektren der kinetischen Elektronenenergie hängen stark von der Vibrationsquantenzahl des erzeugten H2+ Ions ab. Für bestimmte Vibrationszustände ist die Ausbeute der Elektronen in der Mitte des Plateaus stark erhöht. Der Effekt wird "channel closings" zugeschrieben, die in Atomen durch Variation der Laserintensität beobachtet wurden. The ionization of H2 in intense laser pulses is studied by numerical integration of the time-dependent Schrödinger equation for a single-active-electron model including the vibrational motion. The electron kinetic energy spectra in high-order above-threshold ionization are strongly dependent on the vibrational quantum number of the created H2+ ion. For certain vibrational states, the electron yield in the mid-plateau region is strongly enhanced. The effect is attributed to channel closings, which were previously observed in atoms by varying the laser intensity.

Multiple vacancy inclusive probabilities for the scattering system 16 MeV S{^16+} on Ar

To evaluate single and double K-shell inclusive charge transfer probabilities in ion-atom collisions we solve the time-dependent Dirac equation. By expanding the timedependent wavefunction in a set of molecular basis states the time-dependent equation reduces to a set of coupled-channel equations. The energy eigenvalues and matrix elements are taken from self-consistent relativistic molecular many-electron Dirac-Fock-Slater calculations. We present many-electron inclusive probabilities for different final configurations as a function of impact parameter for single and double K-shell vacancy production in collisions of bare S on Ar.

Tomographic imaging of molecular orbitals in length and velocity form

Recently Itatani et al. [Nature 432, 876 (2004)] introduced the new concept of molecular orbital tomography, where high harmonic generation (HHG) is used to image electronic wave functions. We describe an alternative reconstruction form, using momentum instead of dipole matrix elements for the electron recombination step in HHG. We show that using this velocity-form reconstruction, one obtains better results than using the original length-form reconstruction. We provide numerical evidence for our claim that one has to resort to extremely short pulses to perform the reconstruction for an orbital with arbitrary symmetry. The numerical evidence is based on the exact solution of the time-dependent Schrödinger equation for 2D model systems to simulate the experiment. Furthermore we show that in the case of cylindrically symmetric orbitals, such as the N2 orbital that was reconstructed in the original work, one can obtain the full 3D wave function and not only a 2D projection of it. Vor kurzem führten Itatani et al. [Nature 432, 876 (2004)] das Konzept der Molelkülorbital-Tomographie ein. Hierbei wird die Erzeugung hoher Harmonischer verwendet, um Bilder von elektronischen Wellenfunktionen zu gewinnen. Wir beschreiben eine alternative Form der Rekonstruktion, die auf Impuls- statt Dipol-Matrixelementen für den Rekombinationsschritt bei der Erzeugung der Harmonischen basiert. Wir zeigen, dass diese "Geschwindigkeitsform" der Rekonstruktion bessere Ergebnisse als die ursprüngliche "Längenform" liefert. Wir zeigen numerische Beweise für unsere Behauptung, dass man zu extrem kurzen Laserpulsen gehen muss, um Orbitale mit beliebiger Symmetrie zu rekonstruieren. Diese Ergebnisse basieren auf der exakten Lösung der zeitabhängigen Schrödingergleichung für 2D-Modellsysteme. Wir zeigen ferner, dass für zylindersymmetrische Orbitale wie das N2-Orbital, welches in der oben zitierten Arbeit rekonstruiert wurde, das volle 3D-Orbital rekonstruiert werden kann, nicht nur seine 2D-Projektion.

Realistic many electron coupled channel calculations in heavy ion scattering

The time dependent Dirac equation which describes a heavy ion-atom collision system is solved via a set of coupled channel equations with energy eigenvalues and matrix elements which are given by a selfconsistent field many electron calculation. After a brief discussion of the theoretical approximations and the connection of the many particle with the one particle interpretation we discuss first results for the systems F{^8+} - Ne and F{^6+} - Ne. The resulting P(b) curves for the creation of a Ne K-hole are in good agreement with the experimental results.

Electron-Nuclear Correlation in Laser-Driven Diatomic Molecules

The interaction of short intense laser pulses with atoms/molecules produces a multitude of highly nonlinear processes requiring a non-perturbative treatment. Detailed study of these highly nonlinear processes by numerically solving the time-dependent Schrodinger equation becomes a daunting task when the number of degrees of freedom is large. Also the coupling between the electronic and nuclear degrees of freedom further aggravates the computational problems. In the present work we show that the time-dependent Hartree (TDH) approximation, which neglects the correlation effects, gives unreliable description of the system dynamics both in the absence and presence of an external field. A theoretical framework is required that treats the electrons and nuclei on equal footing and fully quantum mechanically. To address this issue we discuss two approaches, namely the multicomponent density functional theory (MCDFT) and the multiconfiguration time-dependent Hartree (MCTDH) method, that go beyond the TDH approximation and describe the correlated electron-nuclear dynamics accurately. In the MCDFT framework, where the time-dependent electronic and nuclear densities are the basic variables, we discuss an algorithm to calculate the exact Kohn-Sham (KS) potentials for small model systems. By simulating the photodissociation process in a model hydrogen molecular ion, we show that the exact KS potentials contain all the many-body effects and give an insight into the system dynamics. In the MCTDH approach, the wave function is expanded as a sum of products of single-particle functions (SPFs). The MCTDH method is able to describe the electron-nuclear correlation effects as the SPFs and the expansion coefficients evolve in time and give an accurate description of the system dynamics. We show that the MCTDH method is suitable to study a variety of processes such as the fragmentation of molecules, high-order harmonic generation, the two-center interference effect, and the lochfrass effect. We discuss these phenomena in a model hydrogen molecular ion and a model hydrogen molecule. Inclusion of absorbing boundaries in the mean-field approximation and its consequences are discussed using the model hydrogen molecular ion. To this end, two types of calculations are considered: (i) a variational approach with a complex absorbing potential included in the full many-particle Hamiltonian and (ii) an approach in the spirit of time-dependent density functional theory (TDDFT), including complex absorbing potentials in the single-particle equations. It is elucidated that for small grids the TDDFT approach is superior to the variational approach.

Input constraints handling in an MPC/feedback linearization scheme

The combination of model predictive control based on linear models (MPC) with feedback linearization (FL) has attracted interest for a number of years, giving rise to MPC+FL control schemes. An important advantage of such schemes is that feedback linearizable plants can be controlled with a linear predictive controller with a fixed model. Handling input constraints within such schemes is difficult since simple bound contraints on the input become state dependent because of the nonlinear transformation introduced by feedback linearization. This paper introduces a technique for handling input constraints within a real time MPC/FL scheme, where the plant model employed is a class of dynamic neural networks. The technique is based on a simple affine transformation of the feasible area. A simulated case study is presented to illustrate the use and benefits of the technique.

Critical slip and time dependence in sea ice friction

Recent research into sea ice friction has focussed on ways to provide a model which maintains much of the clarity and simplicity of Amonton's law, yet also accounts for memory effects. One promising avenue of research has been to adapt the rate- and state- dependent models which are prevalent in rock friction. In such models it is assumed that there is some fixed critical slip displacement, which is effectively a measure of the displacement over which memory effects might be considered important. Here we show experimentally that a fixed critical slip displacement is not a valid assumption in ice friction, whereas a constant critical slip time appears to hold across a range of parameters and scales. As a simple rule of thumb, memory effects persist to a significant level for 10 s. We then discuss the implications of this finding for modelling sea ice friction and for our understanding of friction in general.

Flexibility of representational states in working memory

The relationship between working memory (WM) and attention is a highly interdependent one, with evidence that attention determines the state in which items in WM are retained. Through focusing of attention, an item might be held in a more prioritized state, commonly termed as the focus of attention (FOA). The remaining items, although still retrievable, are considered to be in a different representational state. One means to bring an item into the FOA is to use retrospective cues (‘retro-cues’) which direct attention to one of the objects retained in WM. Alternatively, an item can enter a privileged state once attention is directed towards it through bottom-up influences (e.g. recency effect) or by performing an action on one of the retained items (‘incidental’ cueing). In all these cases, the item in the FOA is recalled with better accuracy compared to the other items in WM. Far less is known about the nature of the other items in WM and whether they can be flexibly manipulated in and out of the FOA. We present data from three types of experiments as well as transcranial magnetic stimulation to early visual cortex to manipulate the item inside FOA. Taken together, our results suggest that the context in which items are retained in WM matters. When an item remains behaviourally relevant, despite not being inside the FOA, re-focusing attention upon it can increase its recall precision. This suggests that a non-FOA item can be held in a state in which it can be later retrieved. However, if an item is rendered behaviourally unimportant because it is very unlikely to be probed, it cannot be brought back into the FOA, nor recalled with high precision. Under such conditions, some information appears to be irretrievably lost from WM. These findings, obtained from several different methods, demonstrate quite considerable flexibility with which items in WM can be represented depending upon context. They have important consequences for emerging state-dependent models of WM.

Enhanced long-range forecast skill in boreal winter following stratospheric strong vortex conditions

There has been a great deal of recent interest in producing weather forecasts on the 2–6 week sub-seasonal timescale, which bridges the gap between medium-range (0–10 day) and seasonal (3–6 month) forecasts. While much of this interest is focused on the potential applications of skilful forecasts on the sub-seasonal range, understanding the potential sources of sub-seasonal forecast skill is a challenging and interesting problem, particularly because of the likely state-dependence of this skill (Hudson et al 2011). One such potential source of state-dependent skill for the Northern Hemisphere in winter is the occurrence of stratospheric sudden warming (SSW) events (Sigmond et al 2013). Here we show, by analysing a set of sub-seasonal hindcasts, that there is enhanced predictability of surface circulation not only when the stratospheric vortex is anomalously weak following SSWs but also when the vortex is extremely strong. Sub-seasonal forecasts initialized during strong vortex events are able to successfully capture the associated surface temperature and circulation anomalies. This results in an enhancement of Northern annular mode forecast skill compared to forecasts initialized during the cases when the stratospheric state is close to climatology. We demonstrate that the enhancement of skill for forecasts initialized during periods of strong vortex conditions is comparable to that achieved for forecasts initialized during weak events. This result indicates that additional confidence can be placed in sub-seasonal forecasts when the stratospheric polar vortex is significantly disturbed from its normal state.

Approach to Equilibrium for a Class of Random Quantum Models of Infinite Range

We consider random generalizations of a quantum model of infinite range introduced by Emch and Radin. The generalizations allow a neat extension from the class l (1) of absolutely summable lattice potentials to the optimal class l (2) of square summable potentials first considered by Khanin and Sinai and generalised by van Enter and van Hemmen. The approach to equilibrium in the case of a Gaussian distribution is proved to be faster than for a Bernoulli distribution for both short-range and long-range lattice potentials. While exponential decay to equilibrium is excluded in the nonrandom l (1) case, it is proved to occur for both short and long range potentials for Gaussian distributions, and for potentials of class l (2) in the Bernoulli case. Open problems are discussed.