Langmuir-Blodgett assembly of colloidal crystals combined with controlled infiltration of conducting metal oxides

Colloidal photonic crystals (PhCs) possess a periodic dielectric structure which gives rise to a photonic band gap (PBG) and offer great potential in the ability to modify or control light at visible wavelengths. Although the refractive index contrast between the void or infill and the matrix material is paramount for photonics applications, integration into real optoelectronics devices will require a range of added functionalities such as conductivity. As such, colloidal PhCs can be used as templates to direct infiltration of other functional materials using a range of deposition strategies. The work in this thesis seeks to address two challenges; first to develop a reproducible strategy based on Langmuir-Blodgett (LB) deposition to assemble high quality colloidal PhCs based on silica with precise film thickness as most other assembly methods suffer from a lack of reproducibility thickness control. The second is to investigate the use of LBdeposited colloidal PhCs as templates for infiltration with conducting metal oxide materials using vapor phase deposition techniques. Part of this work describes the synthesis and assembly of colloidal silica spheres with different surface chemical functionalities at the air-water interface in preparation for LB deposition. Modification of surface funtionality conferred varying levels of hydrophobicity upon the particles. The behaviour of silica monolayer films at the air-water interface was characterised by Brewster Angle Microscopy and surface pressure isotherms with a view to optimising the parameters for LB deposition of multilayer colloidal PhC films. Optical characterisation of LB-fabricated colloidal PhCs indicated high quality photonic behaviour, exhibiting a pseudo PBG with a sharp Bragg diffraction peak in the visible region and reflectance intensities greater than 60%. Finally the atomic layer deposition (ALD) of nominally undoped ZnO and aluminium “doped” ZnO (Al-doped ZnO) inside the pores of a colloidal PhC assembled by the LB technique was carried out. ALD growth in this study was performed using trimethyl aluminium (TMA) and water as precursors for the alumina and diethyl zinc (DEZn) and water for the ZnO. The ZnO:Al films were grown in a laminate mode, where DEZn pulses were substituted for TMA pulses in the sequences with a Zn:Al ratio 19:1. The ALD growth of ZnO and ZnO:Al in colloidal PhCs was shown to be highly conformal, tuneable and reproducible whilst maintaining excellent photonic character. Furthermore, at high levels of infiltration the opal composite films demonstrated significant conductivity.

Deposition of silver nanoparticles in geochemically heterogeneous porous media: predicting affinity from surface composition analysis.

The transport of uncoated silver nanoparticles (AgNPs) in a porous medium composed of silica glass beads modified with a partial coverage of iron oxide (hematite) was studied and compared to that in a porous medium composed of unmodified glass beads (GB). At a pH lower than the point of zero charge (PZC) of hematite, the affinity of AgNPs for a hematite-coated glass bead (FeO-GB) surface was significantly higher than that for an uncoated surface. There was a linear correlation between the average nanoparticle affinity for media composed of mixtures of FeO-GB and GB collectors and the relative composition of those media as quantified by the attachment efficiency over a range of mixing mass ratios of the two types of collectors, so that the average AgNPs affinity for these media is readily predicted from the mass (or surface) weighted average of affinities for each of the surface types. X-ray photoelectron spectroscopy (XPS) was used to quantify the composition of the collector surface as a basis for predicting the affinity between the nanoparticles for a heterogeneous collector surface. A correlation was also observed between the local abundances of AgNPs and FeO on the collector surface.

Simulation of 2-D metal cutting by means of a distributed algorithm

Temperature distributions involved in some metal-cutting or surface-milling processes may be obtained by solving a non-linear inverse problem. A two-level concept on parallelism is introduced to compute such temperature distribution. The primary level is based on a problem-partitioning concept driven by the nature and properties of the non-linear inverse problem. Such partitioning results to a coarse-grained parallel algorithm. A simplified 2-D metal-cutting process is used as an example to illustrate the concept. A secondary level exploitation of further parallel properties based on the concept of domain-data parallelism is explained and implemented using MPI. Some experiments were performed on a network of loosely coupled machines consist of SUN Sparc Classic workstations and a network of tightly coupled processors, namely the Origin 2000.

Computational modelling of metal extrusion and forging processes

The computational modelling of extrusion and forging processes is now well established. There are two main approaches: Lagrangian and Eulerian. The first has considerable complexities associated with remeshing, especially when the code is parallelised. The second approach means that the mould has to be assumed to be entirely rigid and this may not be the case. In this paper, a novel approach is described which utilises finite volume methods on unstructured meshes. This approach involves the solution of free surface non-Newtonian fluid flow equations in an Eulerian context to track the behaviour of the workpiece and its extrusion/forging, and the solution of the solid mechanics equations in the Lagrangian context to predict the deformation/stress behaviour of the die. Test cases for modelling extrusion and forging problems using this approach will be presented.

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.

A mixed Eulerian-Lagrangian approach for metal extrusion

In this paper a mixed Eulerian-Lagrangian approach for the modelling metal extrusion processes is presented. The approach involves the solution of non-Newtonian fluid flow equations in an Eulerian context, using a free-surface algorithm to track the behaviour of the workpiece and its extrusion. The solid mechanics equations associated with the tools are solved in Lagangrian context. Thermal interactions between the workpiece are modelled and a fluid-structure interaction technique is employed to model the effect of the fluid traction load imposed by the workpiece on the tools. Two extrusion test cases are investigated and the results obtained show the potential of the model with regard to representing the physics of the process and the simulation time.

Dynamic model for metal cleanness evaluation by melting in a cold crucible

Melting of metallic samples in a cold crucible causes inclusions to concentrate on the surface owing to the action of the electromagnetic force in the skin layer. This process is dynamic, involving the melting stage, then quasi-stationary particle separation, and finally the solidification in the cold crucible. The proposed modeling technique is based on the pseudospectral solution method for coupled turbulent fluid flow, thermal and electromagnetic fields within the time varying fluid volume contained by the free surface, and partially the solid crucible wall. The model uses two methods for particle tracking: (1) a direct Lagrangian particle path computation and (2) a drifting concentration model. Lagrangian tracking is implemented for arbitrary unsteady flow. A specific numerical time integration scheme is implemented using implicit advancement that permits relatively large time-steps in the Lagrangian model. The drifting concentration model is based on a local equilibrium drift velocity assumption. Both methods are compared and demonstrated to give qualitatively similar results for stationary flow situations. The particular results presented are obtained for iron alloys. Small size particles of the order of 1 μm are shown to be less prone to separation by electromagnetic field action. In contrast, larger particles, 10 to 100 μm, are easily “trapped” by the electromagnetic field and stay on the sample surface at predetermined locations depending on their size and properties. The model allows optimization for melting power, geometry, and solidification rate.

Manufacturing of uniformly-sized silicon particles for solar cell from molten metal jet by electromagnetic pinch force

Spherical silicon solar cells are expected to serve as a technology to reduce silicon usage of photovoltaic (PV) power systems[1, 2, 3]. In order to establish the spherical silicon solar cell, a manufacturing method of uniformly sized silicon particles of 1mm in diameter is required. However, it is difficult to mass-produce the mono-sized silicon particles at low cost by existent processes now. We proposed a new method to generate liquid metal droplets uniformly by applying electromagnetic pinch force to a liquid metal jet[4]. The electromagnetic force was intermittently applied to the liquid metal jet issued from a nozzle in order to fluctuate the surface of the jet. As the fluctuation grew, the liquid jet was broken up into small droplets according to a frequency of the intermittent electromagnetic force. Firstly, a preliminary experiment was carried out. A single pulse current was applied instantaneously to a single turn coil around a molten gallium jet. It was confirmed that the jet could be split up by pinch force generated by the current. And then, electromagnetic pinch force was applied intermittently to the jet. It was found that the jet was broken up into mono-sized droplets in the case of a force frequency was equal to a critical frequency[5], which corresponds to a natural disturbance wave length of the jet. Numerical simulations of the droplet generation from the liquid jet were then carried out, which consisted of an electromagnetic analysis and a fluid flow calculation with a free surface of the jet. The simulation results were compared with the experiments and the agreement between the two was quite good.

General rules for predicting where a catalytic reaction should occur on metal surfaces: A density functional theory study of C-H and C-O bond breaking/making on flat, stepped, and kinked metal surfaces

To predict where a catalytic reaction should occur is a fundamental issue scientifically. Technologically, it is also important because it can facilitate the catalyst's design. However, to date, the understanding of this issue is rather limited. In this work, two types of reactions, CH4 CH3 + H and CO C + 0 on two transition metal surfaces, were chosen as model systems aiming to address in general where a catalytic reaction should occur. The dissociations of CH4 - CH3 + H and CO --> C + O and their reverse reactions on flat, stepped, and kinked Rh and Pd surfaces were studied in detail. We find the following: First, for the CH4 Ch(3) + H reaction, the dissociation barrier is reduced by similar to0.3 eV on steps and kinks as compared to that on flat surfaces. On the other hand, there is essentially no difference in barrier for the association reaction of CH3 + H on the flat surfaces and the defects. Second, for the CO C + 0 reaction, the dissociation barrier decreases dramatically (more than 0.8 eV on Rh and Pd) on steps and kinks as compared to that on flat surfaces. In contrast to the CH3 + H reaction, the C + 0 association reaction also preferentially occurs on steps and kinks. We also present a detailed analysis of the reaction barriers in which each barrier is decomposed quantitatively into a local electronic effect and a geometrical effect. Our DFT calculations show that surface defects such as steps and kinks can largely facilitate bond breaking, while whether the surface defects could promote bond formation depends on the individual reaction as well as the particular metal. The physical origin of these trends is identified and discussed. On the basis of our results, we arrive at some simple rules with respect to where a reaction should occur: (i) defects such as steps are always favored for dissociation reactions as compared to flat surfaces; and (ii) the reaction site of the association reactions is largely related to the magnitude of the bonding competition effect, which is determined by the reactant and metal valency. Reactions with high valency reactants are more likely to occur on defects (more structure-sensitive), as compared to reactions with low valency reactants. Moreover, the reactions on late transition metals are more likely to proceed on defects than those on the early transition metals.

A peculiar metal-rich star, HD 135485

Local thermodynamic equilibrium (LTE) absolute and differential abundances are presented for a peculiar metal-rich B-type star, HD 135485. These suggest that HD 135485 has a general enrichment of similar to0.5 dex in all the metals observed (C, N, O, Ne, Mg, Al, Si, P, S, Cl, Ar, Sc, Ti, Cr, Mn, Fe and Sr), except for nickel. The helium enhancement and hence hydrogen deficiency can account for less than or equal to 0.2 dex of this enhancement of metals, with the additional enhancement probably being representative of the progenitor gas. However, some of the metals appear to have greater enhancements, which may have occurred during the star's evolution. The significantly larger nitrogen abundance coupled with a modest helium enhancement observed in HD 135485 indicates that carbon- nitrogen (CN) processed material has possibly contaminated the stellar surface. Neon and carbon enhancements may indicate that helium core flashes have also occurred in HD 135485. Some of the iron-group elements (viz. Mn and Ni) appear to have similar abundance patterns to that of silicon Ap stars, but it is uncertain how these abundance patterns formed if they were not present in the progenitor gas. From a kinematical investigation it is unclear whether this star formed in a metal-rich region as implied by its chemical composition. From its position in the Hertzsprung-Russell diagram, HD 135485 would appear to be an evolved star lying close to or on the horizontal branch.

Effects of tip structure on the generation of metal clusters by an STM tip: a way to control the orientation of nanocrystallites?

The role of the crystalline orientation of the STM tip in the generation of metal clusters is studied by atom dynamics simulations. When a (111) facet is facing the surface, the process is accompanied by a perturbation of the surface stronger than that observed for more open tip structures. This implies a technological application: the possibility of orienting a nanocrystallite deposited on a tip according to the changes observed in the force on the tip.

Optical bistability in nonlinear surface-plasmon polaritonic crystals

Nonlinear optical transmission through periodically nanostructured metal films (surface-plasmon polaritonic crystals) has been studied. The surface polaritonic crystals have been coated with a nonlinear polymer. The optical transmission of such nanostructures has been shown to depend on the control-light illumination conditions. The resonant transmission exhibits bistable behavior with the control-light intensity. The bistability is different at different resonant signal wavelengths and for different wavelengths of the control light. The effect is explained by the strong sensitivity of the surface-plasmon mode resonances at the signal wavelength to the surrounding dielectric environment and the electromagnetic field enhancement due to plasmonic excitations at the controlled light wavelengths.

Relevance of heterometallic binding energy for metal underpotential deposition

We present first-principles calculations for a number of metals adsorbed on several different metallic substrates. Some of these systems are very relevant in electrochemistry, especially in the field of underpotential deposition phenomena. The present studies reveal the existence of a relationship between the excess binding energy and the surface energy difference between substrate and adsorbate. Comparisons with experimental underpotential shifts show that excess binding energies are systematically underestimated. By analyzing experimental information on different systems, we conclude that this discrepancy between our vacuum calculations and experiments carried out in an electrolytic solution is likely to be due to anion adsorption and/or solvent effects.

Monte Carlo simulation of properties of monolayers and metal islands adsorbed on metallic (111) surfaces

To obtain the surface stress changes due to the adsorption of metal monolayers onto metallic surfaces, a new model derived from thermodynamic considerations is presented. Such a model is based on continuum Monte Carlo simulations with embedded atom method potentials in the canonical ensemble, and it is extended to consider the behavior on different islands adsorbed onto (111) substrate surfaces. Homoepitaxial and heteroepitaxial systems are studied. Pseudomorphic growth is not observed for small metal islands with considerable positive misfit with the substrate. Instead, the islands become compressed upon increase of their size. A simple model is proposed to interpolate between the misfits of atoms in small islands and the pseudomorphic behavior of the monolayer.

On the generation of metal clusters with the electrochemical scanning tunneling microscope

In the present work we consider two aspects of the deposition of metal clusters on an electrode surface. The formation of such clusters with the tip of a scanning tunneling microscope is simulated by atom dynamics. Subsequently the stability of these clusters is investigated by Monte Carlo simulations in a grand-canonical ensemble. In particular, the following systems were considered explicitly: Pd clusters on Au(111), Cu on Au(111), Ag on Au(111), Pb on Au(111) and Cu on Ag(111). The analysis of the results obtained for the different systems leads to the conclusion that optimal systems for nanostructuring are those where the metals participating have similar cohesive energies and negative heats of alloy formation. In this respect, the system Cu-Pd(111) is predicted as a good candidate for the formation of stable clusters. (c) 2005 Elsevier B.V. All rights reserved.