The development and validation of computational MHD techniques for the modelling of metal production processes

Magnetic fields are used in a number of processes related to the extraction of metals, production of alloys and the shaping of metal components. Computational techniques have an increasingly important role to play in the simulation of such processes, since it is often difficult or very costly to conduct experiments in the high temperature conditions encountered and the complex interaction of fluid flow, heat transfer and magnetic fields means simple analytic models are often far removed from reality. In this paper an overview of the computational activity at the University of Greenwich is given in this area, covering the past ten years. The overview is given from the point of view of the modeller and within the space limitations imposed by the format it covers the numerical methods used, attempts at validation against experiments or analytic procedures; it highlights successes, but also some failures. A broad range of models is covered in the review (and accompanying lecture), used to simulate (a) A-C field applications: induction melting, magnetic confinement and levitation, casting and (b) D-C field applications such as: arc welding and aluminium electroloysis. Most of these processes involve phase change of the metal (melting or solidification), the presence of a dynamic free surface and turbulent flow. These issues affect accuracy and need to be address by the modeller.

Maximising heat transfer efficiency in the cold crucible induction melting process

Induction heating is an efficient method used to melt electrically conductive materials, particularly if melting takes place in a ceramic crucible. This form of melting is particularly good for alloys, as electromagnetic forces set up by the induction coil lead to vigorous stirring of the melt ensuring homogeneity and uniformity in temperature. However, for certain reactive alloys, or where high purity is required, ceramic crucibles cannot be used, but a water-cooled segmented copper crucible is employed instead. Water cooling prevents meltdown or distortion of the metal wall, but much of the energy goes into the coolant. To reduce this loss, the electromagnetic force generated by the coil is used to push the melt away from the walls and so minimise contact with water-cooled surfaces. Even then, heat is lost through the crucible base where contact is inevitable. In a collaborative programme between Greenwich and Birmingham Universities, computer modelling has been used in conjunction with experiments to improve the superheat attainable in the melt for a,number of alloys, especially for y-TiAl intermetallics to cast aeroengine turbine blades. The model solves the discretised form of the turbulent Navier-Stokes, thermal energy conservation and Maxwell equations using a Spectral Collocation technique. The time-varying melt envelope is followed explicitly during the computation using an adaptive mesh. This paper briefly describes the mathematical model used to represent the interaction between the magnetic field, fluid flow, heat transfer and change of phase in the crucible and identifies the proportions of energy used in the melt, lost in the crucible base and in the crucible walls. The role of turbulence is highlighted as important in controlling heat losses and turbulence damping is introduced as a means of improving superheat. Model validation is against experimental results and shows good agreement with measured temperatures and energy losses in the cooling fluid throughout the melting cycle.

Dynamical entanglement transfer for quantum-information networks

A key element in the architecture of a quantum-information processing network is a reliable physical interface between fields and qubits. We study a process of entanglement transfer engineering, where two remote qubits respectively interact with an entangled two-mode continuous-variable (CV) field. We quantify the entanglement induced in the qubit state at the expenses of the loss of entanglement in the CV system. We discuss the range of mixed entangled states which can be obtained with this setup. Furthermore, we suggest a protocol to determine the residual entangling power of the light fields inferring, thus, the entanglement left in the field modes which, after the interaction, are no longer in a Gaussian state. Two different setups are proposed: a cavity-QED system and an interface between superconducting qubits and field modes. We address in detail the practical difficulties inherent in these two proposals, showing that the latter is promising in many aspects.

Entanglement transfer from continuous variables to qubits

We show that two qubits can be entangled by local interactions with an entangled two-mode continuous variable state. This is illustrated by the evolution of two two-level atoms interacting with a two-mode squeezed state. Two modes of the squeezed field are injected respectively into two spatially separate cavities and the atoms are then sent into the cavities to interact resonantly with the cavity field. We find that the atoms may be entangled even by a two-mode squeezed state which has been decohered while penetrating into the cavity.

Hydrogen bonding and collective proton modes in clusters and periodic layers of squaric acid: A density functional study

Hydrogen bonding in clusters and extended layers of squaric acid molecules has been investigated by density functional computations. Equilibrium geometries, harmonic vibrational frequencies, and energy barriers for proton transfer along hydrogen bonds have been determined using the Car-Parrinello method. The results provide crucial parameters for a first principles modeling of the potential energy surface, and highlight the role of collective modes in the low-energy proton dynamics. The importance of quantum effects in condensed squaric acid systems has been investigated, and shown to be negligible for the lowest-energy collective proton modes. This information provides a quantitative basis for improved atomistic models of the order-disorder and displacive transitions undergone by squaric acid crystals as a function of temperature and pressure. (C) 2001 American Institute of Physics.

Light tunneling via resonant surface plasmon polariton states and the enhanced transmission of periodically nanostructured metal films: An analytical study

An analytical treatment of optical transmission through periodically nanosructured metal films capable of supporting surface-plasmon polaritons is presented. The optical properties of such metal films are governed by surface polariton behavior in a periodic surface structure forming a surface polaritonic crystal. Due to different configurations of the electromagnetic field of surface polariton modes, only states of even Brillouin zones are responsible for the optical transmission enhancement at normal incidence. The transmission enhancement is related to photon tunneling via resonant states of surface polariton Bloch modes in which the energy buildup takes place. Surface polariton states of at least one of the film interfaces contribute to the transmission resonance which occurs due to tunnel coupling between photons and surface polaritons on the opposite interfaces. Under double-resonance conditions, resonant tunneling between surface polariton states of both interfaces is achieved, which leads to further enhancement of the transmission efficiency. The double-resonance conditions occur not only in the case of a film in symmetric environment but can also be engineered for a film on a substrate. Light tunneling via surface polariton states can take place directly through a structured metal film and does not necessarily require holes in a film.

Catalytic Role of Metal Oxides in Gold-Based Catalysts: A First Principles Study of CO Oxidation on TiO2 Supported Au

CO oxidation on TiO2 supported Au has been studied using density functional theory calculations. Important catalytic roles of the oxide have been identified: (i) CO oxidation occurs at the interface between Au and the oxide with a very small barrier; and (ii) O-2 adsorption at the interface is the key step in the reaction. The physical origin of the oxide promotion effect has been further investigated: The oxide enhances electron transfer from the Au to the antibonding states of O-2, giving rise to (i) strong ionic bonding between the adsorbed O-2, Au, and the Ti cation; and (ii) a significant activation of O-2 towards CO oxidation.

Experimental investigation into the temperature and heat transfer distribution around air-cooled cylinders

This paper describes an experimental investigation into the surface heat transfer coefficient of finned metal cylinders in a free air stream. Ten cylinders were tested with four different fin pitches and five different fin lengths. The cylinders and their fins were designed to be representative of those found on a motorcycle engine with an external cylinder diameter of 100 mm and fin lengths of 10 to 50 mm. The fins of each cylinder were gravity die cast in aluminum allow. Each cylinder was electrically heated and mounted in a wind tunnel which subjected it to a range of air speeds between 2 and 20 m/s. The surface heat transfer coefficient, h, was found primarily to be a function of the air speed and the fin separation, with fin length having a lesser effect. In addition to the determination of an overall heat transfer coefficient, the distribution of cooling around the circumference of each cylinder was also studied. Not surprisingly, the cooling was found to be greatest on the front of the cylinder, which was the side first impinged by the air stream. The cooling of the rear of the cylinder was better than might have been expected and this is quantified.

Importance of electronegativity differences and surface structure in molecular dissociation reactions at transition metal surfaces

The dissociative adsorption of N-2 has been studied at both monatomic steps and flat regions on the surfaces of the 4d transition metals from Zr to Pd. Using density functional theory (DFT) calculations, we have determined and analyzed the trends in both straight reactivity and structure sensitivity across the periodic table. With regards to reactivity, we find that the trend in activation energy (Ea) is determined mainly by a charge transfer from the surface metal atoms to the N atoms during transition state formation, namely, the degree of ionicity of the N-surface bond at the transition state. Indeed, we find that the strength of the metal-N bond at the transition state (and therefore the trend in Ea) can be predicted by the difference in Mulliken electronegativity between the metal and N. Structure sensitivity is analyzed in terms of geometric and electronic effects. We find that the lowering of Ea due to steps is more pronounced on the right-hand side of the periodic table. It is found that for the early transition metals the geometric and electronic effects work in opposition when going from terrace to step active site. In the case of the late 4d metals, however, these effects work in combination, producing a more marked reduction in Ea.

Softened C-H modes of adsorbed methyl and their implications for dehydrogenation: An ab initio study

To investigate the softening of CH vibrational frequencies and their implications for dehydrogenation of adsorbed hydrocarbons, an issue of scientific and technological importance, density functional theory calculations have been performed on the chemisorption and dehydrogenation of CH3 on Cu(111) and Pt(111) surfaces. By comparing these results with those of Ni(111) we find that the CH bonds of the adsorbate, when close enough, interact with metal atoms of the surface. It is this interaction and its associated lengthening and weakening of CH bonds that is the physical origin of mode softening. We rule out the possibility of a relationship between the mere presence of mode softening and dehydrogenation. We do show, however, that there is a clear relationship between the extent to which a surface can induce mode softening and the activation energy to dehydrogenation. In addition, periodic trends concerning the extent of mode softening are reproduced. (C) 2001 American Institute of Physics.

Task-specific ionic liquid for solubilizing metal oxides

Protonated betaine bis(trifluoromethylsulfonyl) imide is an ionic liquid with the ability to dissolve large quantities of metal oxides. This metal-solubilizing power is selective. Soluble are oxides of the trivalent rare earths, uranium(VI) oxide, zinc(II) oxide, cadmium( II) oxide, mercury( II) oxide, nickel( II) oxide, copper(II) oxide, palladium(II) oxide, lead(II) oxide, manganese( II) oxide, and silver( I) oxide. Insoluble or very poorly soluble are iron(III), manganese(IV), and cobalt oxides, as well as aluminum oxide and silicon dioxide. The metals can be stripped from the ionic liquid by treatment of the ionic liquid with an acidic aqueous solution. After transfer of the metal ions to the aqueous phase, the ionic liquid can be recycled for reuse. Betainium bis( trifluoromethylsulfonyl) imide forms one phase with water at high temperatures, whereas phase separation occurs below 55.5 degrees C ( temperature switch behavior). The mixtures of the ionic liquid with water also show a pH-dependent phase behavior: two phases occur at low pH, whereas one phase is present under neutral or alkaline conditions. The structures, the energetics, and the charge distribution of the betaine cation and the bis( trifluoromethylsulfonyl) imide anion, as well as the cation-anion pairs, were studied by density functional theory calculations.

TRANSIENT RESONANCE RAMAN AND RAMAN SPECTROELECTROCHEMICAL STUDIES OF CUI COMPLEXES WITH POLYPYRIDYL LIGANDS

Studies by laser flash photolysis, transient Raman spectroscopy, and Raman and UV-vis spectroelectrochemistry are described in which the techniques have been used in parallel to compare the lowest energy charge-transfer excited states of Cu (1) complexes ([Cu(L)2]+ and [ (PPh3)2Cu(L)]+ [L = 2,2'-biquinoline (BIQ) or 6,7-dihydro-5,8-dimethyldibenzo[b,j] [1,10]-phenanthroline (DMCH)) with the species produced by electrochemical reduction in the same group of complexes. Transient resonance Raman spectra for the metal-to-ligand charge-transfer (MLCT) states of [Cu(DMCH)2]+ (1), [Cu(BIQ)2]+ (2), [Cu(DMCH)(PPh3)2]+ (3), and [Cu(BIQ)(PPh3)2]+ (4) are compared with the resonance Raman spectra of the same group of complexes following one-electron electrochemical reduction of the DMCH and BIQ ligands. The UV-vis and resonance Raman evidence suggests that the electrochemical reduction of the [Cu(I)L2]+ species proceeds according to the sequence [LCu(I)L]+ -->e- [LCu0L] -->e- [L.-Cu(I)L.-]-. Several features assignable to modes of the electrochemically generated DMCH.-and BIQ'- radical anions exhibit a close correspondence in both frequency and relative intensity with counterparts in the spectra of the MLCT states of 1 and 2. A notable exception is a band near 1590 cm-1 in the spectra of the electrochemically reduced species which occurs some 15 cm-1 lower in the corresponding spectra of the excited-state species. It is suggested that the shift may reflect the change in oxidation state of the metal center from Cu(I) to Cu(II) which occurs as a result of charge-transfer excitation.

Dipolar emission in trench metal-insulator-metal waveguides for short-scale plasmonic communications: numerical optimization

Here we consider the numerical optimization of active surface plasmon polariton (SPP) trench waveguides suited for integration with luminescent polymers for use as highly localized SPP source devices in short-scale communication integrated circuits. The numerical analysis of the SPP modes within trench waveguide systems provides detailed information on the mode field components, effective indices, propagation lengths and mode areas. Such trench waveguide systems offer extremely high confinement with propagation on length scales appropriate to local interconnects, along with high efficiency coupling of dipolar emitters to waveguided plasmonic modes which can be close to 80%. The large Purcell factor exhibited in these structures will further lead to faster modulation capabilities along with an increased quantum yield beneficial for the proposed plasmon-emitting diode, a plasmonic analog of the light-emitting diode. The confinement of studied guided modes is on the order of 50 nm and the delay over the shorter 5 μm length scales will be on the order of 0.1 ps for the slowest propagating modes of the system, and significantly less for the faster modes.

Conserved histidine of metal transporter AtNRAMP1 is crucial for optimal plant growth under manganese deficiency at chilling temperatures

Manganese (Mn) is an essential nutrient required for plant growth, in particular in the process of photosynthesis. Plant performance is influenced by various environmental stresses including contrasting temperatures, light or nutrient deficiencies. The molecular responses of plants exposed to such stress factors in combination are largely unknown. 

Screening of 108 Arabidopsis thaliana (Arabidopsis) accessions for reduced photosynthetic performance at chilling temperatures was performed and one accession (Hog) was isolated. Using genetic and molecular approaches, the molecular basis of this particular response to temperature (GxE interaction) was identified. 

Hog showed an induction of a severe leaf chlorosis and impaired growth after transfer to lower temperatures. We demonstrated that this response was dependent on the nutrient content of the soil. Genetic mapping and complementation identified NRAMP1 as the causal gene. Chlorotic phenotype was associated with a histidine to tyrosine (H239Y) substitution in the allele of Hog NRAMP1. This led to lethality when Hog seedlings were directly grown at 4 degrees C. 

Chemical complementation and hydroponic culture experiments showed that Mn deficiency was the major cause of this GxE interaction. For the first time, the NRAMP-specific highly conserved histidine was shown to be crucial for plant performance.

Nanoscale detection of metal-labeled copolymers in patchy polymersomes

We report the synthesis of polymersome-forming block copolymers using two different synthetic routes based on Atom Transfer Radical Polymerization (ATRP) and Reversible Addition Fragmentation chain Transfer (RAFT) polymerization, respectively. Functionalization with 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) allowed the block copolymer chains to be labelled with electron-dense metal ions (e.g. indium). The resulting metal-conjugated copolymers can be visualized by transmission electron microscopy with single chain resolution, hence enabling the study of polymer/polymer immiscibility and phase separation on the nano-scale.