The adsorption of phenolic and organotin compounds by clays and cation exchanged clays

Quaternary ammonium exchanged laponites (Quat-laponites) show selectivity in the adsorption of phenols and chlorinated phenols. Strong adsorbate-adsorbent interactions are indicated by adsorption isotherms. Adsorption of phenols and chlorinated phenols by Quat-smectites is greater than that by the Bi Quat-Smectites prepared in this study. It is thought that the quaternary ammonium exchanged smectite components of the Bi Quat-smectites interact with each other (adsorbent-adsorbent interactions) reducing the number of sites available for adsorbate-adsorbent interactions. Solidification/stabilisation studies of 2-chlorophenol show that a blend of ground granulated blast furnace slag and ordinary Portland cement attenuates 2-chlorophenol more effectively than ordinary Portland cement alone. Tetramethyl ammonium- (TMA-) and tetramethyl phosphonium- (TMP-) montmorillonites were exposed to solutions of phenol or chlorinated phenols. TMP- montmorillonite was the better adsorbent and preferentially adsorbed 4-chlorophenol over phenol. Hydration of the interlayer cations occurs to a greater extent in the TMA-montmorillonite than the TMP-montmorillonite restricting interlayer adsorption. Contrary to that observed for phenols and chlorinated phenols, the Quat-smectites were ineffective as adsorbents for triphenyltin hydroxide and bis(tributyltin) oxide at room temperature. Under microwave conditions, only bis(tributyltin) oxide was adsorbed by the quaternary ammonium exchanged smectites. Bis(tributyltin) oxide was adsorbed from ethanol on the surface of the smectite clays at room temperature and under microwave conditions. The adsorbate-adsorbent interactions were weak. Adsorption is accompanied by conversion of bis(tributyltin) oxide to a different tin(IV) species and the release of sodium cations from the montmorillonite interlayer region. Attempts to introduce conditions suitable for charge transfer interactions between synthesised quaternary ammonium compounds and 2,4,6-trichlorophenol are documented. Transition metal complex exchanged clays adsorb 2,4,6-trichlorophenol and phenol. Strong adsorbate-adsorbent interactions (Type I isotherms) occur when the adsorbate is 2,4,6-trichlorophenol and when the adsorbent is [Fe(bipy)3]2+ exchanged montmorillonite or [Co(bipy)3]3+ exchanged montmorillonite. The 2,2'-bipyridyl ligands of the adsorbents are electron rich and the 2,4,6-trichlorophenol is electron deficient. This may have enhanced adsorbate-adsorbent interactions.

The oxidation behaviour of sintered iron

The oxidation behaviour of porous, sintered iron was studied by thermo-gravimetric analysis (TGA), at temperatures between 300oC and 700oC, in a flowing atmosphere of 20% O2/80% N2. Samples for TGA tests were compacted from pure iron powder, at 150MPa to 550MPa, and vacuum sintered at 1120oC. The mass gain of samples during oxidation was recorded continuously for a period of 24 hours. It was found that the oxidation mass gain of PM samples depended on the permeability of the pore structure and the temperature. At low temperatures, the oxidising gas was able to permeate through the pore structure, causing the oxidation of a large active surface area. At high temperatures the active surface area was smaller, because oxygen diffusing into the pore structure, from the external atmosphere, was adsorbed by pore surfaces close to the external surface of the compact. Although the weight of the external oxide scale on compacts increased with increasing oxidation temperature, the absence of oxide in the core porosity in compacts oxidised at higher temperatures resulted in smaller mass gains than were observed for compacts oxidised at lower temperatures. The heat generated by the oxidation of the large active surface areas of porous samples was studied by thermo-calorimetric analysis (TCA). It was determined that this phenomenon could raise the core temperature of samples significantly above the ambient furnace temperature, and affecting the morphology of the oxide scale formed. The effects (on oxidation behaviour at 500oC) of small, elemental alloy additions of Al, Cu, P and Si to pure iron powder were studied. It was found that elements that promote pore rounding during sintering caused a significant reduction in the mass gain rate of the PM alloys, compared to the PM pure iron. The oxidation resistance due to these elements prevented pore closure by oxide growth, so that the active surface area of these PM alloys remained high. The PM alloys were also studied by thermo-mechanical analysis (TMA, dilatometry), to determine their dimensional stability during sintering and subsequent elevated temperature service. The oxidation experiment was augmented with optical and electron microscopy, and X-ray analysis of alloy and scale compositions.

An evaluation of thermal plasmas in pyrometallurgy

The development of reliable, high powered plasma generators has resulted in many plasma processes being proposed as alternatives to existing pyrometallurgical technologies. This work evaluates the advantages and disadvantages of plasma systems by reviewing plasma generators, their integration with reactors and the process economics. Many plasma systems were shown to be technically and economically superior to existing technologies, but some of the plasma system advantages quoted in the literature were found to be impractical because of other system constraints. Process applications were limited by the power inputs available from plasma generators compared to AC electric furnaces. A series of trials were conducted where chromite and steelplant baghouse dusts were smelted in the Tetronics' 2.0 MW transferred arc/open bath reactor to confirm the operating characteristics of the plasma system and its economics. Chromite smelting was technical superior to submerged arc furnace technology, but the economics were unfavourable because of the limited power available from the water-cooled plasma torch and the high electrical energy consumption. A DC graphite electrode plasma furnace using preheated and prereduced chromite concentrates will compete economically with the submerged arc furnace. Ni, Cr and Mo were economically recovered from high alloy content steelplant dusts for recycling. Five Electric Arc Furnace dusts were smelted to produce a non-toxic residue and recover the contained zinc to an enriched zinc oxide product for recycling. It should be possible to condense the zinc vapour directly in a zinc splash condenser to increase the value of the product. Because of the limited power available from plasma generators, plasma processes will be most suitable for treating high and medium value materials such as Au, Pt, Mo, Ni, Ti, V, Cr etc at small production rates, heating metals in tundishes and ladles and remelting superalloy scrap. The treatment of environmentally hazardous waste materials is a particularly interesting application because of the additional financial incentives. Non-transferred arc plasma generators will be used for air and gas preheating in blast furnaces to reduce metallurgical coke consumptions.

Chloride resistance and durability of cement paste and concrete containing metakaolin

Metakaolin (MK), a calcined clay, was included as a partial cement replacement material, at up to 20% by weight of binder, in cement pastes and concrete, and its influence on the resistance to chloride ingress investigated. Reductions in effective chloride diffusion coefficients through hardened cement paste were obtained for binary blends and by combining OPC, MK and a second cement replacement material of pulverised fuel ash or ground granulated blast furnace slag. Steady state oxygen diffusion measurements through hardened cement pastes measured using an electrochemical cell showed that the interaction between charged species and the pore surfaces is a major factor in determining chloride diffusion rate. Rheology of the binder, particularly at high MK replacement levels, was found to have a dramatic influence on the diffusion performance of cement pastes. It was concluded that plasticising admixtures are essential for adequate dispersion of MK in cement pastes. Chloride concentration profile analysis of the concrete cylinders, exposed to sodium chloride solution for one year, was employed to obtain apparent chloride diffusion coefficients for concrete specimens. MK was found to reduce the depth of chloride penetration into concrete when compared with that of unblended mixes. Corrosion rate and corrosion potential measurements were taken on steel bars embedded in concrete exposed to a saline environment under conditions of cyclic wetting and drying. The initiation time for corrosion was found to be significantly longer for MK blended mixes than for plain OPC systems. The aggregate-paste interfacial zone of MK blended systems was investigated by steady state diffusion of chloride ions through mortar containing glass beads as model aggregate. For the model aggregate specimens tested the work confirmed the hypothesis that properties of the bulk paste are the controlling factors in ionic diffusion through mortar.

The durability of glass fibre reinforced cements made with new cementitious matrices

Widespread use of glass fibre reinforced cement (GRC) has been impeded by concerns over its durability. Three degradation mechanisms are proposed - fibre corrosion, Ca(OHh precipitation and matrix densification - although their relative importance is debated. Matrices with reduced alkalinities and Ca(OH)2 contents are being developed; the aim of this study was to investigate their hydration and interaction with alkali-resistant fibres to determine the factors controlling their long-term durability, and assess the relevancy of accelerated ageing. The matrices studied were: OPC/calcium-sulphoaluminate cement plus metakaolin (C); OPC plus metakaolin (M); blast-furnace slag cement plus a micro-silica based additive (D); and OPC (O). Accelerated ageing included hot water and cyclic regimes prior to tensile testing. Investigations included pore solution expression, XRD, DTA/TG, SEM and optical petrography. Bond strength was determined from crack spacings using microstructural parameters obtained from a unique image analysis technique. It was found that, for the new matrices - pore solution alkalinities were lower; Ca(OH)2 was absent or quickly consumed; different hydrates were formed at higher immersion temperatures; degradation under 65°C immersion was an order of magnitude slower, and no interfilamental Ca(OH)2 was observed .It was concluded that: fibre weakening caused by flaw growth was the primary degradation mechanism and was successfully modelled on stress corrosion/static fatigue principles. OPC inferiority was attributed partly to its higher alkalinity but chiefly to the growth of Ca(OH)2 aggravating the degradation; and hot water ageing although useful in model formulation and contrasting the matrices, changed the intrinsic nature of the composites rather than simply accelerating the degradation mechanisms.

The transient behaviour of plain concrete at elevated temperatures

This thesis describes an investigation of the effect of elevated temperatures upon the properties of plain concrete containing a siliceous aggregate. A complete stress-strain relationship and creep behaviour are studied. Transient effects (non-steady state) are also examined in order to simulate more realistic conditions. A temperature range of 20-700ºC is used. corresponding to the temperatures generally attained during an actual fire. In order to carry out the requisite tests, a stiff compression testing machine has been designed and built. The overall control of the test rig is provided by a logger/computer system by developing appropriate software, thus enabling the load to be held constant for any period of tlme. Before outlining any details of the development of the testing apparatus which includes an electric furnace and the.associated instrumentation, previous work on properties of both concrete and. steel at elevated temperatures is reviewed. The test programme comprises four series of tests:stress-strain tests (with and without pre-load), transient tests (heating to failure under constant stress) and creep tests (constant stress and constant temperature). Where 3 stress levels are examined: 0.2, 0.4 & 0.6 fc. The experimental results show that the properties of concrete are significantly affected by temperature and the magnitude of the load. The slope of the descending portion branch of the stress-strain curves (strain softening) is found to be temperature dependent. After normalizing the data, the stress-strain curves for different temperatures are represented by a single curve. The creep results are analysed using an approach involving the activation energy which is found to be constant. The analysis shows that the time-dependent deformation is sensibly linear with the applied stress. The total strain concept is shown to hold for the test data within limits.

Pore structure and diffusional properties of hardened cement pastes

This study has investigated the inclusion of pulverised fuel ash (PFA) and blast furnace slag (BFS) into hardened cement pastes (HCP) in retarding the ingress of chloride ions and oxygen molecules from the external environment. The influence of environmental factors such as drying and carbonation on the pore structure and diffusional properties of OPC, OPC/30%PFA and OPC/65%BFS hardened pastes was investigated. Specimens were desorbed from a saturated surface dry condition to a near constant weight at 65% relative humidity (RH) while others were simultaneously exposed to a 65% RH atmosphere and a carbon dioxide atmosphere of up to 5% by volume until there were fully carbonated. The presence of the interfacial zone at the cement paste-aggregate interface was critically reviewed and identified. The influence of the interfacial zone on porosity and chloride ingress in assumed periodic composites of glass bead mortars was also studied. The investigations have demonstrated the following: (a) The use of fly ash and slag in blended cement pastes has resulted in a marked reduction in capillary porosity and rate of chloride ingress. (b) The ratio of oxygen to chloride diffusion coefficients increased from values close to 1 in permeable pastes, to values of around 15 in low-permeability blended fly ash and slag pastes. This supports the view that the diffusion of chloride ions is retarded by the surface charge of the hydrated cement gel in low-permeability pastes. (c) Compared with plain OPC pastes, the carbonation of blended fly ash and slag pastes resulted in a marked increase in the coarse capillary porosity and a corresponding increase in the oxygen and chloride diffusion rates.

Parametric study of the behaviour of reinforced concrete columns in fire

The research is concerned with the application of the computer simulation technique to study the performance of reinforced concrete columns in a fire environment. The effect of three different concrete constitutive models incorporated in the computer simulation on the structural response of reinforced concrete columns exposed to fire is investigated. The material models differed mainly in respect to the formulation of the mechanical properties of concrete. The results from the simulation have clearly illustrated that a more realistic response of a reinforced concrete column exposed to fire is given by a constitutive model with transient creep or appropriate strain effect The assessment of the relative effect of the three concrete material models is considered from the analysis by adopting the approach of a parametric study, carried out using the results from a series of analyses on columns heated on three sides which produce substantial thermal gradients. Three different loading conditions were used on the column; axial loading and eccentric loading both to induce moments in the same sense and opposite sense to those induced by the thermal gradient. An axially loaded column heated on four sides was also considered. The computer modelling technique adopted separated the thermal and structural responses into two distinct computer programs. A finite element heat transfer analysis was used to determine the thermal response of the reinforced concrete columns when exposed to the ISO 834 furnace environment. The temperature distribution histories obtained were then used in conjunction with a structural response program. The effect of the occurrence of spalling on the structural behaviour of reinforced concrete column is also investigated. There is general recognition of the potential problems of spalling but no real investigation into what effect spalling has on the fire resistance of reinforced concrete members. In an attempt to address the situation, a method has been developed to model concrete columns exposed to fire which incorporates the effect of spalling. A total of 224 computer simulations were undertaken by varying the amounts of concrete lost during a specified period of exposure to fire. An array of six percentages of spalling were chosen for one range of simulation while a two stage progressive spalling regime was used for a second range. The quantification of the reduction in fire resistance of the columns against the amount of spalling, heating and loading patterns, and the time at which the concrete spalls appears to indicate that it is the amount of spalling which is the most significant variable in the reduction of fire resistance.

Energy conservation in the steel industry

The last few years have witnessed an unprecedented increase in the price of energy available to industry in the United Kingdom and worldwide. The steel industry, as a major consumer of energy delivered in U.K. (8% of national total and nearly 25% of industrial total) and whose energy costs currently form some 28% of the total manufacturing cost, is very much aware of the need to conserve energy. Because of the complexities of steelmaking processes it is imperative that a full understanding of each process and its interlinking role in an integrated steelworks is understood. An analysis of energy distribution shows that as much as 70% of heat input is dissipated to the environment in a variety of forms. Of these, waste gases offer the best potential for energy conservation. The study identifies areas for and discusses novel methods of energy conservation in each process. Application of these schemes in BSC works is developed and their economic incentives highlighted. A major part of this thesis describes design, development and testing of a novel ceramic rotary regenerator for heat recovery from high temperature waste gases, where no such system is available. The regenerator is a compact, efficient heat exchanger. Application of such a system to a reheating furnace provides a fuel saving of up to 40%. A mathematical model developed is verified on the pilot plant. The results obtained confirm the success of the concept and material selection and outlines the work needed to develop an industrial unit. Last, but not least, the key position of an energy manager in an energy conservation programme is identified and a new Energy Management Model for the BSC is developed.

Flow processes in a radiant tube burner:combusting flow

This paper describes a study of the combustion process in an industrial radiant tube burner (RTB), used in heat treating furnaces, as part of an attempt to improve burner performance. A detailed three-dimensional Computational Fluid Dynamics model has been used, validated with experimental test furnace temperature and flue gas composition measurements. Simulations using the Eddy Dissipation combustion model with peak temperature limitation and the Discrete Transfer radiation model showed good agreement with temperature measurements in the inner and outer walls of the burner, as well as with flue gas composition measured at the exhaust (including NO). Other combustion and radiation models were also tested but gave inferior results in various aspects. The effects of certain RTB design features are analysed, and an analysis of the heat transfer processes within the burner is presented.

The effect of heat treatment on mechanical properties of pulsed Nd:YAG welded thin Ti6Al4V

Pulsed Nd:YAG has been adopted successfully in welding process of thin (0.7 mm) Ti6Al4V. Laser welding of such thin sheet requires a small focal spot, good laser beam quality and fast travel speed, since too much heat generation can cause distortion for thin sheet weld. The microstructures of Ti6Al4V were complex and strongly affected the mechanical properties. These structures include: a´ martensite, metastable ß, Widmanstätten, bimodal, lamellar and equiaxed microstructure. Bimodal and Widmanstätten structures exhibit a good-balance between strength and ductility. The microstructure of pulsed Nd:YAG welded Ti6Al4V was primarily a´ martensite, which showed the lowest ductility but not significantly high strength. A heat treatment at 950 followed by furnace cooling can transform the microstructure in the weld from a´ martensite structure into Widmanstätten structure.

Optical microbubble resonator

We develop a method for fabricating very small silica microbubbles having a micrometer-order wall thickness and demonstrate the first optical microbubble resonator. Our method is based on blowing a microbubble using stable radiative CO2 laser heating rather than unstable convective heating in a flame or furnace. Microbubbles are created along a microcapillary and are naturally opened to the input and output microfluidic or gas channels. The demonstrated microbubble resonator has 370 µm diameter, 2 µm wall thickness, and a Q factor exceeding 10. © 2010 Optical Society of America.

Optical microbubble resonator

We develop a method for fabricating very small silica microbubbles having a micrometer-order wall thickness and demonstrate the first optical microbubble resonator. Our method is based on blowing a microbubble using stable radiative CO2 laser heating rather than unstable convective heating in a flame or furnace. Microbubbles are created along a microcapillary and are naturally opened to the input and output microfluidic or gas channels. The demonstrated microbubble resonator has 370 µm diameter, 2 µm wall thickness, and a Q factor exceeding 10. © 2010 Optical Society of America.

Material Synthesis and Characterization on Low-Dimensional Cobaltates

In this thesis, results of the investigation of a new low-dimensional cobaltates Ba2-xSrxCoO 4 are presented. The synthesis of both polycrystalline and single crystalline compounds using the methods of conventional solid state chemical reaction and floating-zone optical furnace is first introduced. Besides making polycrystalline powders, we successfully, for the first time, synthesized large single crystals of Ba2CoO4. Single crystals were also obtained for Sr doped Ba2-xSrxCoO 4. Powder and single crystal x-ray diffraction results indicate that pure Ba2CoO4 has a monoclinic structure at room temperature. With Sr doping, the lattice structure changes to orthorhombic when x ≥ 0.5 and to tetragonal when x = 2.0. In addition, Ba2CoO4 and Sr2CoO4, have completely different basic building blocks in the structure. One is CoO4 tetrahedron and the later is CoO6 octahedron, respectively. Electronic and magnetic properties were characterized and discussed. The magnetic susceptibility, specific heat and thermal conductivity show that Ba2CoO4 has an antiferromagnetic (AF) ground state with an AF ordering temperature TN = 25 K. However, the magnitude of the Néel temperature TN is significantly lower than the Curie-Weiss temperature (:&thetas;: ∼ 110 K), suggesting either reduced-dimensional magnetic interactions and/or the existence of magnetic frustration. The AF interaction persists in all the samples with different doping concentrations. The Néel temperature doesn't vary much in the monoclinic structure regime but decreases when the system enters orthorhombic. Magnetically, Ba2CoO4 has an AF insulating ground state while Sr2CoO4 has a ferromagnetic (FM) metallic ground state. Neutron powder refinement results indicate a magnetic structure with the spin mostly aligned along the a-axis. The result from a μ-spin rotation/relaxation (μ+SR) experiment agrees with our refinement. It confirms the AF order in the ab -plane. We also studied the spin dynamics and its anisotropy in the AF phase. The results from inelastic neutron scattering show that spin waves have a clear dispersion along a-axis but not along c-axis, indicating spin anisotropy. This work finds the strong spin-lattice coupling in this novel complex material. The interplay between the two degrees of freedom results an interesting phase diagram. Further research is needed when large single crystal samples are available.

Site specific growth of metal catalyzed silica nanowires for biological and chemical sensing

In this research the integration of nanostructures and micro-scale devices was investigated using silica nanowires to develop a simple yet robust nanomanufacturing technique for improving the detection parameters of chemical and biological sensors. This has been achieved with the use of a dielectric barrier layer, to restrict nanowire growth to site-specific locations which has removed the need for post growth processing, by making it possible to place nanostructures on pre-pattern substrates. Nanowires were synthesized using the Vapor-Liquid-Solid growth method. Process parameters (temperature and time) and manufacturing aspects (structural integrity and biocompatibility) were investigated. Silica nanowires were observed experimentally to determine how their physical and chemical properties could be tuned for integration into existing sensing structures. Growth kinetic experiments performed using gold and palladium catalysts at 1050°C for 60 minutes in an open-tube furnace yielded dense and consistent silica nanowire growth. This consistent growth led to the development of growth model fitting, through use of the Maximum Likelihood Estimation (MLE) and Bayesian hierarchical modeling. Transmission electron microscopy studies revealed the nanowires to be amorphous and X-ray diffraction confirmed the composition to be SiO2 . Silica nanowires were monitored in epithelial breast cancer media using Impedance spectroscopy, to test biocompatibility, due to potential in vivo use as a diagnostic aid. It was found that palladium catalyzed silica nanowires were toxic to breast cancer cells, however, nanowires were inert at 1μg/mL concentrations. Additionally a method for direct nanowire integration was developed that allowed for silica nanowires to be grown directly into interdigitated sensing structures. This technique eliminates the need for physical nanowire transfer thus preserving nanowire structure and performance integrity and further reduces fabrication cost. Successful nanowire integration was physically verified using Scanning electron microscopy and confirmed electrically using Electrochemical Impedance Spectroscopy of immobilized Prostate Specific Antigens (PSA). The experiments performed above serve as a guideline to addressing the metallurgic challenges in nanoscale integration of materials with varying composition and to understanding the effects of nanomaterials on biological structures that come in contact with the human body.