Large quantities of particulate solids and fluids are stored in cylindrical metal shell silos and tanks with a vertical axis. Such metal silos and tanks are often required to be elevated above ground level to permit trains, trucks or conveying systems to be placed beneath a hopper from which the solid or fluid is withdrawn. Elevated silos must be supported, and access requirements often mean that the supports must be local (either on columns or supported from an elevated floor system). The connection of a local support to an elevated cylindrical metal silo shell is a longstanding difficult problem in shell analysis, and most designs are based on simple ideas using past experiences of successes and failures. Smaller silo structures are often supported on local brackets attached to the side of the shell, but very few investigations of the behaviour or strength of such an arrangement have ever been made. This thesis presents a comprehensive investigation into the behaviour of a cylindrical steel shell that is discretely supported on several brackets, each rigidly connected to a stiff column or floor. The study has been conducted within the framework of the European Standard for Shell Structures (EN1993-1-6, 2006), which requires that the two reference strengths of the small displacement theory plastic collapse resistance and the linear bifurcation critical elastic resistance should both be evaluated to establish the context in which more sophisticated analyses are judged, and to provide a rapid means of producing reliable but simple design information. Therefore this thesis begins with a thorough investigation of the predictions of these two reference strengths for these structures, discovering the challenges inherent in this methodology and finally developing equations that can be used in hand calculations intended for the simple evaluation of the reference strengths for a wide variety of geometries. The influence of geometric nonlinearity is next explored, both with and without geometric imperfections. The results pose some interesting questions concerning the relative importance of geometric nonlinearity and geometric imperfections in shell buckling problems where the stress field is far from uniform. In the final part of the investigation, analyses are conducted that include both material and geometric nonlinearity with and without geometric imperfections. The results of these analyses are presented and analysed in the context of interaction capacity curves. Following this extensive parametric investigation using linear and nonlinear analyses of all kinds, design recommendations are formulated so that bracket supports of this type can be used on thin cylindrical shells of any thickness and with any bracket dimensions necessary to transmit the loads. Finally, proposals are made for key future research investigations.

No description available.

No description available.

This investigation has been concerned with the behaviour of solid internal lubricant during mixing, compaction, ejection, dewaxing and sintering of iron powder compacts. Zinc stearate (0.01%-4.0%) was added to irregular iron powder by admixing or precipitation from solution. Pressure/density relationships, determined by continuous compaction, and loose packed densities were used to show that small additions of zinc stearate reduced interparticle friction during loose packing and at low compaction pressures. Large additions decreased particle/die-wall friction during compaction and ejection but also caused compaction inhibition. Transverse rupture strengths were determined on compacts containing various stearate based lubricants and it was found that green strength was reduced by the interposition of a thin lubricant layer within inter~particle contacts. Only materials much finer than the iron powder respectively) were able to form such layers. Investigations were undertaken to determine the effect of the decomposition of these lubricants on the development of mechanical properties in dewaxed or sintered compacts. Physical and chemical influences on tensile strength were observed. Decomposition of lubricants was associated with reductions of strength caused by the physical effects of pressure increases and removal of lubricant from interparticle contacts. There were also chemical effects associated with the influence of gaseous decomposition products and solid residues on sintering mechanisms. Thermogravimetry was used to study the decomposition behaviour of various lubricants as free compounds and within compacts. The influence of process variables such as atmosphere type, flow-rate and compact density were investigated. In a reducing atmosphere the decomposition of these lubricants was characterised by two stages. The first involved the rapid decomposition of the hydrocarbon radical. The second, higher temperature, reactions depended on lubricant type and involved solid residues. The removal of lubricant could also markedly affect dimensional change.

This thesis describes the synthesis and characterisation of group I and group II nitride materials as potential hydrogen stores. New synthetic routes as well as the development of conventional methods were employed to synthesise binary and ternary nitrides. Ball milling of single phase α-Li3N and of commercial Li3N was performed to induce a phase transformation in order to synthesise β-Li3N which adopts a hexagonal crystal structure (space group P63/mmc). The beta polymorph was initially characterised by PXD and subsequently by a variable temperature PND experiment, which demonstrated that the phase transformation to α-Li3N began at 600 K. Due to the fact that β-Li3N exhibits the same magnitude of Li+ conductivity as α-Li3N and that lithium ion diffusion is thought to be an important factor in the hydrogen storage potential of the solid, a further PND investigation to study the interaction of D2 gas with β-Li3N was performed. At lower temperatures, negative thermal expansion can be observed; this expands following similar trends known for α-Li3N and commercial Li3N. In agreement with the behaviour of Li3N reported in the literature, Li3N reacts with D2 at higher temperatures resulting in the formation of LiND2 and LiD. The phase behaviour in the complex Li-N-H system is still being debated despite significant research in this area. This work has focussed on lithium nitride hydride, which has been reported as a minority phase during the hydrogenation of Li3N. Li4ND was prepared by both conventional means and by a novel synthesis using microwaves; the product was characterised by PXD and PND. During both conventional and microwave syntheses, tetragonal Li4ND (space group I-4) and a new high temperature cubic polymorph formed (space group Fm-3m) where N3-, D- and (ND)2- are disordered across the anti-fluorite anion sites. With regard to providing further evidence for the proposition of a new reaction pathway upon hydrogenation of Li3N, Li4ND and Li2ND were reacted in-situ during a PND investigation forming a solid solution and resulting in synthesis of a cubic ‘quasi-imide’ phase. The ‘quasi-imide’ phase was refined against a modified cubic Li2ND starting model. The presence of D+ and D- ensured that charge balance was maintained. As the stoichiometry increases, the anion distribution changes; the occupancy of N3- and N from (ND)2- on the 4a site increases as does the occupancy of protonic D from (ND)2- on the 192l site. A ternary nitride, LiCaN (space group Pnma), was prepared by both conventional and novel (via microwaves) means. Optimization of the reaction parameters was the initial focus of the investigation in order to synthesise single phase LiCaN. Firstly, a PND study was performed in order to ascertain accurate Li positions and ensure the material was perfectly stoichiometric as made. In order to compare the Li-Ca-N system with reports on the Li-Mg-N system in which both Mg-rich and Li-rich phases as well as stoichiometric LiMgN have been synthesised, attempts were made to synthesise nonstoichiometric Li-Ca-N compounds. This system was investigated by PND.

The work outlined in this thesis was sponsored, in part, by Anglo American and concerns the development of new technologies to achieve the concentration and separation of base metal values in chloride hydrometallurgical circuits. New processes for the production of zinc, cobalt and nickel aim to use solvent extraction to achieve the separation of metal values in highly concentrated acid chloride feeds containing iron and this thesis involves new extractants for potential use in these circuits. Anion exchange solvent extraction was chosen as the most practical approach and so a range of new reagents are described which remove zinc(II), cobalt(II) and iron(III) chlorometallates from acid chloride solutions via the reaction: nL(org) + nH+ + MClx n- [(LH)nMClx](org) Chapter 1 reviews the literature which concerns base metal chloride hydrometallurgy, presents a range of commercial processes and discusses the chemistry which underpins them. This chapter also outlines the new Anglo American circuits and the general approach to the design of base metal chlorometallate extractants. In Chapter 2, the analytical methods are discussed. These methods include the solvent extraction experiments that were used to define the behaviour of the new ligands and the techniques that were employed to examine the interactions between an extractant and a chlorometallate anion. Chapter 3 presents a series of five new amido-functionalised pyridine reagents that were designed to investigate the affect of hydrogen bond donor functionality on the extraction of zinc, cobalt and iron chlorometallates. The pyridine nitrogen atom is sterically hindered in the new reagents to suppress formation of inner-sphere complexes. Solvent extraction performance was found to vary considerably with hydrogen bond donor functionality and ligand structure. The ligand 2-(4,6-di-tertbutylpyridin- 2-yl)-N,N’-dihexylmalonamide (L2) was the strongest and most efficient extractant in this series and this was attributed to a ‘proton chelate’ six-membered ring interaction between the malonamide oxygens and the protonated pyridine nitrogen that resulted in a pre-organised array of N-H and C-H donors that could interact favourably with the chlorometallate anion. Chapter 4 explores a series of six new tertiary amine-based ligands which contain varying amido-functionality, e.g. 3-(di-2-ethylhexylamino)-N-hexylpropanamide (MAA). Zinc, cobalt and iron chlorometallate extraction studies show the amide and malonamide-functionalised ligands are notably stronger than the tertiary alkylamine control, tris-2-ethylhexylamine (TEHA). Platinum(IV) extraction is also discussed, showing that some of the new reagents are more efficient than the tren-based ligands previously described,{Bell Katherine, 2008 #93} which were the most efficient known. The enhanced extraction performance of the new ‘MAA-type’ ligands was again attributed to the formation of a ‘proton chelate’ six-membered ring forming [(LH)2MCl4] assemblies in the organic phase. Conditions have been identified which would allow separation of Fe(III), Co(II) and Zn(II) in circuits which use the ‘MAAtype’ reagents. Chapter 5 explores a series of three new malonamide reagents which contain varying alkyl-chain functionality, e.g. N,N’-dimethylhexylpentadecylmalonamide (M1), which are thought to extract chlorometallate anions via protonation of the carbonyl oxygens. Zinc, cobalt and iron chlorometallate extraction studies demonstrate that the malonamide ligands show high efficiency and selectivity for iron over zinc and cobalt. Performance as chlorometallate extractants was found to vary considerably with ligand structure and hydrogen bond donor functionality in all three ligand series, with a number of ligands showing potential for commercial application. Analysis of anion-host interactions suggests that chlorometallate binding in the organic phase probably proceeds via an array of both N-H and C-H weak hydrogen bonding interactions between the extractant and the outer-sphere of the metallate complex.

The thesis deals with the modification of salicylaldoxime-based reagents used in hydrometallurgical extraction, addressing rational ligand design to tune copper(II) extractant strengths and also the development of reagents which are capable of transporting transition metal salts. Chapter 1 reviews current solvent extractant technology for metal recovery, including the limited knowledge of the effect of substituents on extractive efficacy. Advances in leaching technology have led to systems wherein increases in process efficiency could be obtained using reagents which can transport both a transition metal cation and its attendant anion(s), and the potential advantages of metal salt extractants are discussed. The problems encountered when trying to extract hydrophilic anions selectively into organic media are also considered. Chapter 2 discusses techniques used in industry to tune reagent properties, many of which depend on the importance of H-bonding in non-polar solvents. Synthesis of a series of 5-alkyl-3-X-2-hydroxybenzaldehyde oximes (X = a range of substituents) is described and copper extraction experiments are reported. 3-Substitution is found to alter reagent strength by two orders of magnitude, with 3-bromo-5-tert-butyl-2- hydroxybenzaldehyde oxime the strongest extractant. An analysis of X-ray structures of several ligands and copper(II) complexes is given in an attempt to establish whether trends in the solid state structures can account for variations in extractant strength. A more detailed analysis of the hydrogen bonding in salicylaldoximato copper(II) complexes and ligand dimers is carried out in Chapter 3, with the aim of defining how substituent effects could be used to design reagents with appropriate extractive behaviour. 3-X-2-Hydroxybenzaldehyde oximes with no 5-alkyl substituent are synthesised and subjected to a detailed study by X-ray crystallography and computational techniques, which, alongside evidence provided by CID-MS experiments, suggest that the dominant substituent effect in determining extractant strength is the ability to “buttress” the pseudomacrocyclic hydrogen bonding motif involving the oximic hydrogen and phenolic oxygen. Ligands with 3-substituents capable of accepting H-bonds were found to be stronger extractants than those which could not, and the steric hindrance afforded by bulky substituents made 3,5-di-tert-butyl-2-hydroxybenzaldehyde oxime the weakest extractant. Ligand acidity is also noted to have a significant effect on reagent strength, with electronwithdrawing substituents lowering the pKa of the phenolic proton and increasing extractive efficacy. Chapter 4 focuses on metal salt extraction, and the development of selective, robust and hydrolytically stable reagents. Six novel extractants, based on a salicylaldoxime scaffold with a pendant dialkylaminomethyl arm, are described. Only 5-tert-butyl-3- dihexylaminomethyl-2-hydroxybenzaldehyde oxime and 3-tert-butyl-5- dihexylaminomethyl-2-hydroxybenzaldehyde oxime have sufficient solubility to be effective reagents. The former extracts CuCl2 and ZnCl2 in a highly efficient manner, with one mole of metal salt extracted per mole of ligand, twice the expected capacity. X-ray structure determination of complexes of the related ligand 5-tertbutyl- 2-hydroxy-3-piperidin-1-ylmethylbenzaldehyde oxime defines the binding mode, with the chloride anions bound to the inner sphere of the metal cations. Loading and stripping experiments show it to be an extractant with potential commercial application. Cation and anion selectivity of the two extractants defined above is the focus of Chapter 5, which begins with an overview of techniques and attempts to attenuate the Hofmeister bias, the main factor in the selective extraction of hydrophilic anions into organic media. pH loading profiles show the 3- dihexylaminomethyl isomer to be an effective CuCl2 and CuSO4 extractant, but the cation extractive efficacy of the 5-isomer is hampered by the 3-tert-butyl group. Both ligands are found to be selective for Cl- > SO4 2-, following the Hofmeister bias. Further information on anion binding is provided by solid state structures of copper salt complexes, showing that in all cases the copper(II) cation interacts in some way with the anion. Cation extraction is affected significantly by the anion present, with FeIII selectively extracted against CuII in the presence of SO4 2- which is consistent with cation-anion interactions having great influence on the overall stability of the ligand-metal salt assembly.

No description available.

No description available.

No description available.