Performance of five different electrospray ionisation sources in conjunction with rapid monolithic column liquid chromatography and fast MS/MS scanning

The performances of five different ESI sources coupled to a polystyrene-divinylbenzene monolithic column were compared in a series of LC-ESI-MS/MS analyses of Escherichia coli outer membrane proteins. The sources selected for comparison included two different modifications of the standard electrospray source, a commercial low-flow sprayer, a stainless steel nanospray needle and a coated glass Picotip. Respective performances were judged on sensitivity and the number and reproducibility of significant protein identifications obtained through the analysis of multiple identical samples. Data quality varied between that of a ground silica capillary, with 160 total protein identifications, the lowest number of high quality peptide hits obtained (3012), and generally peaks of lower intensity; and a stainless steel nanospray needle, which resulted in increased precursor ion abundance, the highest-quality peptide fragmentation spectra (5414) and greatest number of total protein identifications (259) exhibiting the highest MASCOT scores (average increase in score of 27.5% per identified protein). The data presented show that, despite increased variability in comparative ion intensity, the stainless steel nanospray needle provides the highest overall sensitivity. However, the resulting data were less reproducible in terms of proteins identified in complex mixtures -- arguably due to an increased number of high intensity precursor ion candidates.

Optical fibre sensors with applications in gas and biological sensing

This thesis describes the study of various grating based optical fibre sensors for applications in refractive index sensing. The sensitivity of these sensors has been studied and in some cases enhanced using novel techniques. The major areas of development are as follows. The sensitivity of long period gratings (LPGs) to surrounding medium refractive index (SRI) for various periods was investigated. The most sensitive period of LPG was found to be around 160 µm and this was due to the core mode coupling to a single cladding mode but phase matching at two wavelength locations, creating two attenuation peaks, close to the waveguide dispersion turning point. Large angle tilted fibre gratings (TFGs) have similar behaviour to LPGs, in that they couple to the co-propagating cladding modes. The tilted structure of the index modulation within the core of the fibre gives rise to a polarisation dependency, differing the large angle TFG from a LPG. Since the large angle TFG couple to the cladding mode they are SRI sensitive, the sensitivity to SRI can be further increased through cladding etching using HF acid. The thinning of the cladding layer caused a reordering of the cladding modes and shifted to more SRI sensitive cladding modes as the investigation discovered. In a SRI range of 1.36 to 1.40 a sensitivity of 506.9 nm/URI was achieved for the etched large angle TFG, which is greater than the dual resonance LPG. UV inscribed LPGs were coated with sol-gel materials with high RIs. The high RI of the coating caused an increase in cladding mode effective index which in turn caused an increase in the LPG sensitivity to SRI. LPGs of various periods of LPG were coated with sol-gel TiO2 and the optimal thickness was found to vary for each period. By coating of the already highly SRI sensitive 160µm period LPG (which is a dual resonance) with a sol-gel TiO2, the SRI sensitivity was further increased with a peak value of 1458 nm/URI, which was an almost 3 fold increase compared to the uncoated LPG. LPGs were also inscribed using a femtosecond laser which produced a highly focused index change which was no uniform throughout the core of the optical fibre. The inscription technique gave rise to a large polarisation sensitivity and the ability to couple to multiple azimuthal cladding mode sets, not seen with uniform UV inscribed gratings. Through coupling of the core mode to multiple sets of cladding modes, attenuation peaks with opposite wavelength shifts for increasing SRI was observed. Through combining this opposite wavelength shifts, a SRI sensitivity was achieved greater than any single observed attenuations peak. The maximum SRI achieved was 1680 nm/URI for a femtosecond inscribed LPG of period 400 µm. Three different types of surface plasmon resonance (SPR) sensors with a multilayer metal top coating were investigated in D shape optical fibre. The sensors could be separated into two types, utilized a pre UV inscribed tilted Bragg grating and the other employed a post UV exposure to generate surface relief grating structure. This surface perturbation aided the out coupling of light from the core but also changed the sensing mechanism from SPR to localised surface plasmon resonance (LSPR). This greatly increased the SRI sensitivity, compared to the SPR sensors; with the gold coated top layer surface relief sensor producing the largest SRI sensitivity of 2111.5nm/URI was achieved. While, the platinum and silver coated top layer surface relief sensors also gave high SRI sensitivities but also the ability to produce resonances in air (not previously seen with the SPR sensors). These properties were employed in two applications. The silver and platinum surface relief devices were used as gas sensors and were shown to be capable of detecting the minute RI change of different gases. The calculated maximum sensitivities produced were 1882.1dB/URI and 1493.5nm/URI for silver and platinum, respectively. Using a DFB laser and power meter a cheap alternative approach was investigated which showed the ability of the sensors to distinguish between different gases and flow rates of those gases. The gold surface relief sensor was coated in a with a bio compound called an aptamer and it was able to detect various concentrations of a biological compound called Thrombin, ranging from 1mM to as low as 10fM. A solution of 2M NaCl was found to give the best stripping results for Thrombin from the aptamer and showed the reusability of the sensor. The association and disassociation constants were calculated to be 1.0638×106Ms-1 and 0.2482s-1, respectively, showing the high affinity of the Aptamer to thrombin. This supports existing working stating that aptamers could be alternative to enzymes for chemical detection and also helps to explain the low detection limit of the gold surface relief sensor.

Modelling and measurements on a condensing counter-flow heat exchanger

Experimental investigations and computer modelling studies have been made on the refrigerant-water counterflow condenser section of a small air to water heat pump. The main object of the investigation was a comparative study between the computer modelling predictions and the experimental observations for a range of operating conditions but other characteristics of a counterflow heat exchanger are also discussed. The counterflow condenser consisted of 15 metres of a thermally coupled pair of copper pipes, one containing the R12 working fluid and the other water flowing in the opposite direction. This condenser was mounted horizontally and folded into 0.5 metre straight sections. Thermocouples were inserted in both pipes at one metre intervals and transducers for pressure and flow measurement were also included. Data acquisition, storage and analysis was carried out by a micro-computer suitably interfaced with the transducers and thermocouples. Many sets of readings were taken under a variety of conditions, with air temperature ranging from 18 to 26 degrees Celsius, water inlet from 13.5 to 21.7 degrees, R12 inlet temperature from 61.2 to 81.7 degrees and water mass flow rate from 6.7 to 32.9 grammes per second. A Fortran computer model of the condenser (originally prepared by Carrington[1]) has been modified to match the information available from experimental work. This program uses iterative segmental integration over the desuperheating, mixed phase and subcooled regions for the R12 working fluid, the water always being in the liquid phase. Methods of estimating the inlet and exit fluid conditions from the available experimental data have been developed for application to the model. Temperature profiles and other parameters have been predicted and compared with experimental values for the condenser for a range of evaporator conditions and have shown that the model gives a satisfactory prediction of the physical behaviour of a simple counterflow heat exchanger in both single phase and two phase regions.

A micro gas turbines for UK domestic combined heat and power

Various micro-radial compressor configurations were investigated using one-dimensional meanline and computational fluid dynamics (CFD) techniques for use in a micro gas turbine (MGT) domestic combined heat and power (DCHP) application. Blade backsweep, shaft speed, and blade height were varied at a constant pressure ratio. Shaft speeds were limited to 220 000 r/min, to enable the use of a turbocharger bearing platform. Off-design compressor performance was established and used to determine the MGT performance envelope; this in turn was used to assess potential cost and environmental savings in a heat-led DCHP operating scenario within the target market of a detached family home. A low target-stage pressure ratio provided an opportunity to reduce diffusion within the impeller. Critically for DCHP, this produced very regular flow, which improved impeller performance for a wider operating envelope. The best performing impeller was a low-speed, 170 000 r/min, low-backsweep, 15° configuration producing 71.76 per cent stage efficiency at a pressure ratio of 2.20. This produced an MGT design point system efficiency of 14.85 per cent at 993 W, matching prime movers in the latest commercial DCHP units. Cost and CO2 savings were 10.7 per cent and 6.3 per cent, respectively, for annual power demands of 17.4 MWht and 6.1 MWhe compared to a standard condensing boiler (with grid) installation. The maximum cost saving (on design point) was 14.2 per cent for annual power demands of 22.62 MWht and 6.1 MWhe corresponding to an 8.1 per cent CO2 saving. When sizing, maximum savings were found with larger heat demands. When sized, maximum savings could be made by encouraging more electricity export either by reducing household electricity consumption or by increasing machine efficiency.

Liquid-phase adsorption of n-paraffins on type 5A molecular sieves

As a basis for the commercial separation of normal paraffins a detailed study has been made of factors affecting the adsorption of binary liquid mixtures of high molecular weight normal paraffins (C12, C16, and C20) from isooctane on type 5A molecular sieves. The literature relating to molecular sieve properties and applications, and to liquid-phase adsorption of high molecular weight normal paraffin compounds by zeolites, was reviewed. Equilibrium isotherms were determined experimentally for the normal paraffins under investigation at temperatures of 303oK, 323oK and 343oK and showed a non-linear, favourable- type of isotherm. A higher equilibrium amount was adsorbed with lower molecular weight normal paraffins. An increase in adsorption temperature resulted in a decrease in the adsorption value. Kinetics of adsorption were investigated for the three normal paraffins at different temperatures. The effective diffusivity and the rate of adsorption of each normal paraffin increased with an increase in temperature in the range 303 to 343oK. The value of activation energy was between 2 and 4 kcal/mole. The dynamic properties of the three systems were investigated over a range of operating conditions (i.e. temperature, flow rate, feed concentration, and molecular sieve size in the range 0.032 x 10-3 to 2 x 10-3m) with a packed column. The heights of adsorption zones calculated by two independent equations (one based on a constant width, constant velocity and adsorption zone and the second on a solute material balance within the adsorption zone) agreed within 3% which confirmed the validity of using the mass transfer zone concept to provide a simple design procedure for the systems under study. The dynamic capacity of type 5A sieves for n-eicosane was lower than for n-hexadecane and n-dodecane corresponding to a lower equilibrium loading capacity and lower overall mass transfer coefficient. The values of individual external, internal, theoretical and experimental overall mass transfer coefficient were determined. The internal resistance was in all cases rate-controlling. A mathematical model for the prediction of dynamic breakthrough curves was developed analytically and solved from the equilibrium isotherm and the mass transfer rate equation. The experimental breakthrough curves were tested against both the proposed model and a graphical method developed by Treybal. The model produced the best fit with mean relative percent deviations of 26, 22, and 13% for the n-dodecane, n-hexadecane, and n-eicosane systems respectively.

Gas distribution in shallow packed beds

Packed beds have many industrial applications and are increasingly used in the process industries due to their low pressure drop. With the introduction of more efficient packings, novel packing materials (i.e. adsorbents) and new applications (i.e. flue gas desulphurisation); the aspect ratio (height to diameter) of such beds is decreasing. Obtaining uniform gas distribution in such beds is of crucial importance in minimising operating costs and optimising plant performance. Since to some extent a packed bed acts as its own distributor the importance of obtaining uniform gas distribution has increased as aspect ratios (bed height to diameter) decrease. There is no rigorous design method for distributors due to a limited understanding of the fluid flow phenomena and in particular of the effect of the bed base / free fluid interface. This study is based on a combined theoretical and modelling approach. The starting point is the Ergun Equation which is used to determine the pressure drop over a bed where the flow is uni-directional. This equation has been applied in a vectorial form so it can be applied to maldistributed and multi-directional flows and has been realised in the Computational Fluid Dynamics code PHOENICS. The use of this equation and its application has been verified by modelling experimental measurements of maldistributed gas flows, where there is no free fluid / bed base interface. A novel, two-dimensional experiment has been designed to investigate the fluid mechanics of maldistributed gas flows in shallow packed beds. The flow through the outlet of the duct below the bed can be controlled, permitting a rigorous investigation. The results from this apparatus provide useful insights into the fluid mechanics of flow in and around a shallow packed bed and show the critical effect of the bed base. The PHOENICS/vectorial Ergun Equation model has been adapted to model this situation. The model has been improved by the inclusion of spatial voidage variations in the bed and the prescription of a novel bed base boundary condition. This boundary condition is based on the logarithmic law for velocities near walls without restricting the velocity at the bed base to zero and is applied within a turbulence model. The flow in a curved bed section, which is three-dimensional in nature, is examined experimentally. The effect of the walls and the changes in gas direction on the gas flow are shown to be particularly significant. As before, the relative amounts of gas flowing through the bed and duct outlet can be controlled. The model and improved understanding of the underlying physical phenomena form the basis for the development of new distributors and rigorous design methods for them.

The morphology of spray-dried particles

Samples of Various industrial or pilot plant spray-dried materials were obtained from manufacturers together with details of drying conditions and feed concentrations. The samples were subjected to qualitative and semi-quantitative examination to identify structural and morphological features. The results were related to measured bulk physical properties and to drying conditions. Single particles were produced in a convective drying process Analogous to spray drying, in which different solids or mixtures of solids were dried from solutions, slurries or pastes as single suspended droplets. The localized chemical and physical structures were analysed and in some cases the retention of volatiles monitored. The results were related to experimental conditions, viz.; air temperature, initial solids concentration and the degree of feed aeration. Three distinct categories of particle morphology were identified, i.e.; crystalline, skin-forming and agglomerate. Each category is evidence of a characteristic drying behaviour which is dependent on initial solids concentration. the degree of feed aeration, and drying temperature. Powder flow ability, particle and bulk density, particle-size, particle friability, and the retention of volatiles bear a direct relationship to morphological structure. Morphologies of multicomponent mixtures were complex, but the respective migration rates of the solutes were dependent on drying temperature. Gas-film heat and SDSS transfer coefficients of single pure liquid droplets were also measured over a temperature range of 50•C to 200•C under forced convection. Balanced transfer rates were obtained attributed to droplet instability or oscillation within the airflow, demonstrated in associated work with single free-flight droplets. The results are of relevance to drier optimisation and to the optimisation of product characteristics, e.g.; particle strength and essential volatiles-retention, in convective drying.

A study on the flow characteristics of an industrial radiant tube burner

The thesis presents an experimentally validated modelling study of the flow of combustion air in an industrial radiant tube burner (RTB). The RTB is used typically in industrial heat treating furnaces. The work has been initiated because of the need for improvements in burner lifetime and performance which are related to the fluid mechanics of the com busting flow, and a fundamental understanding of this is therefore necessary. To achieve this, a detailed three-dimensional Computational Fluid Dynamics (CFD) model has been used, validated with experimental air flow, temperature and flue gas measurements. Initially, the work programme is presented and the theory behind RTB design and operation in addition to the theory behind swirling flows and methane combustion. NOx reduction techniques are discussed and numerical modelling of combusting flows is detailed in this section. The importance of turbulence, radiation and combustion modelling is highlighted, as well as the numerical schemes that incorporate discretization, finite volume theory and convergence. The study first focuses on the combustion air flow and its delivery to the combustion zone. An isothermal computational model was developed to allow the examination of the flow characteristics as it enters the burner and progresses through the various sections prior to the discharge face in the combustion area. Important features identified include the air recuperator swirler coil, the step ring, the primary/secondary air splitting flame tube and the fuel nozzle. It was revealed that the effectiveness of the air recuperator swirler is significantly compromised by the need for a generous assembly tolerance. Also, there is a substantial circumferential flow maldistribution introduced by the swirier, but that this is effectively removed by the positioning of a ring constriction in the downstream passage. Computations using the k-ε turbulence model show good agreement with experimentally measured velocity profiles in the combustion zone and proved the use of the modelling strategy prior to the combustion study. Reasonable mesh independence was obtained with 200,000 nodes. Agreement was poorer with the RNG  k-ε and Reynolds Stress models. The study continues to address the combustion process itself and the heat transfer process internal to the RTB. A series of combustion and radiation model configurations were developed and the optimum combination of the Eddy Dissipation (ED) combustion model and the Discrete Transfer (DT) radiation model was used successfully to validate a burner experimental test. The previously cold flow validated k-ε turbulence model was used and reasonable mesh independence was obtained with 300,000 nodes. The combination 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. The inner tube wall temperature predictions validated the experimental measurements in the largest portion of the thermocouple locations, highlighting a small flame bias to one side, although the model slightly over predicts the temperatures towards the downstream end of the inner tube. NOx emissions were initially over predicted, however, the use of a combustion flame temperature limiting subroutine allowed convergence to the experimental value of 451 ppmv. With the validated model, the effectiveness of certain RTB features identified previously is analysed, and an analysis of the energy transfers throughout the burner is presented, to identify the dominant mechanisms in each region. The optimum turbulence-combustion-radiation model selection was then the baseline for further model development. One of these models, an eccentrically positioned flame tube model highlights the failure mode of the RTB during long term operation. Other models were developed to address NOx reduction and improvement of the flame profile in the burner combustion zone. These included a modified fuel nozzle design, with 12 circular section fuel ports, which demonstrates a longer and more symmetric flame, although with limited success in NOx reduction. In addition, a zero bypass swirler coil model was developed that highlights the effect of the stronger swirling combustion flow. A reduced diameter and a 20 mm forward displaced flame tube model shows limited success in NOx reduction; although the latter demonstrated improvements in the discharge face heat distribution and improvements in the flame symmetry. Finally, Flue Gas Recirculation (FGR) modelling attempts indicate the difficulty of the application of this NOx reduction technique in the Wellman RTB. Recommendations for further work are made that include design mitigations for the fuel nozzle and further burner modelling is suggested to improve computational validation. The introduction of fuel staging is proposed, as well as a modification in the inner tube to enhance the effect of FGR.

Flowback of solids through distribution plates of gas fluidized beds and associated phenomena

This work is concerned with a study of certain phenomena related to the performance and design of distributors in gas fluidized beds with particular regard to flowback of solid particles. The work to be described is divided into two parts. I. In Part one, a review of published material pertaining to distribution plates, including details from the patent specifications, has been prepared. After a chapter on the determination of the incipient fluidizing velocity, the following aspects of multi-orifice distributor plates in gas fluidized beds have been studied: (i) The effect of the distributor on bubble formation related to the way in which even distribution of bubbles on the top surface of the fluidized bed is obtained, e.g. the desirable pressure drop ratio ?PD/?PB for the even distribution of gas across the bed. Ratios of distributor pressure drop ?PD to bed pressure drop at which stable fluidization occurs show reasonable agreement with industrial practice. There is evidence that larger diameter beds tend to be less stable than smaller diameter beds when these are operated with shallow beds. Experiments show that in the presence of the bed the distributor pressure drop is reduced relative to the pressure drop without the bed, and this pressure drop in the former condition is regarded as the appropriate parameter for the design of the distributor. (ii) Experimental measurements of bubble distribution at the surface has been used to indicate maldistribution within the bed. Maldistribution is more likely at low gas flow rates and with distributors having large fractional free area characteristics (i.e. with distributors having low pressure drops). Bubble sizes obtained from this study, as well as those of others, have been successfully correlated. The correlation produced implies the existence of a bubble at the surface of an orifice and its growth by the addition of excess gas from the fluidized bed. (iii) For a given solid system, the amount of defluidized particles stagnating on the distributor plate is influenced by the orifice spacing, bed diameter and gas flow rate, but independent of the initial bed height and the way the orifices are arranged on the distributor plate. II. In Part two, solids flowback through single and multi-orifice distributors in two-dimensional and cylindrical beds of solids fluidized with air has been investigated. Distributors equipped with long cylindrical nozzles have also been included in the study. An equation for the prediction of free flowback of solids through multi-orifice distributors has been derived. Under fluidized conditions two regimes of flowback have been differentiated, namely Jumping and weeping. Data in the weeping regime have been successfully correlated. The limiting gas velocity through the distributor orifices at which flowback is completely excluded is found to be indepnndent of bed height, but a function of distributor design and physical properties of gas and solid used. A criterion for the prediction of this velocity has been established. The decisive advantage of increasing the distributor thickness or using nozzles to minimize solids flowback in fluidized beds has been observed and the opportunity taken to explore this poorly studied subject area. It has been noted, probably for the first time, that with long nozzles, there exists a critical nozzle length above which uncontrollable downflow of solids occurs. A theoretical model for predicting the critical length of a bundle of nozzles in terms of gas velocity through the nozzles has been set up. Theoretical calculations compared favourably with experiments.

Technoeconomic modelling of coal conversion processes for liquid fuel production

Since the oil crisis of 1973 considerable interest has been shown in the production of liquid fuels from alternative sources. In particular processes utilizing coal as the feedstock have received considerable interest. These processes can be divided into direct and indirect liquefaction and pyrolysis. This thesis describes the modelling of indirect coal liquefaction processes for the purpose of performing technical and economic assessment of the production of liquid fuels from coal and lignite, using a variety of gasification and synthesis gas liquefaction technologies. The technologies were modeled on a 'step model' basis where a step is defined as a combination of individual unit operations which together perform a significant function on the process streams, such as a methanol synthesis step or a gasification and physical gas cleaning step. Sample results of the modelling, covering a wide range of gasifiers, liquid synthesis processes and products are presented in this thesis. Due to the large number of combinations of gasifier, liquid synthesis processes, products and economic sensitivity cases, a complete set of results is impractical to present in a single publication. The main results show that methanol is the cheapest fuel to produce from coal followed by fuel alcohol, diesel from the Shell Middle Distillate Synthesis process,gasoline from Mobil Methanol to Gasoline (MTG) process, diesel from the Mobil Methanol Olefins Gasoline Diesel (MOGD) process and finally gasoline from the same process. Some variation in production costs of all the products was shown depending on type of gasifier chosen and feedstock.

Formation of droplets from the liquid wall film passing through the inlet port of a spark ignition engine

The available literature has been surveyed to determine the parameters affecting fuelling requirements of spark ignition engines and their relation to engine performance and emissions. Theories and experiment relating to two phase and multi-component flows have also been examined and the techniques employed in the measurement of droplet sizes and liquid wall films have been reviewed. Following preliminary steady flow visualisation experiments to examine the trajectories of droplets discharging from the valve port an extensive practical investigation of the spectrum of droplet sizes formed by the break up of the wall film has produced results which have been correlated in terms of the important fuel and airflow parameters. It is concluded that the Sauter mean diameter of droplets formed by the break up of the wall film will vary between 70 and 150 m, depending on the operating conditions of the engine. The spectra of droplet sizes measured show that a significant proportion of the total mass of the wall film breaks into drops which will be too large to burn completely and, by comparison with measurements of unburned hydrocarbon emissions from engines supplied with a homogeneous mixture of air and gaseous hydrocarbons, it is concluded that the droplets from the wall film are likely to increase emissions by 50%.

Development of multiphase and multiscale mathematical models for thermal spray process

High velocity oxyfuel (HVOF) thermal spraying is one of the most significant developments in the thermal spray industry since the development of the original plasma spray technique. The first investigation deals with the combustion and discrete particle models within the general purpose commercial CFD code FLUENT to solve the combustion of kerosene and couple the motion of fuel droplets with the gas flow dynamics in a Lagrangian fashion. The effects of liquid fuel droplets on the thermodynamics of the combusting gas flow are examined thoroughly showing that combustion process of kerosene is independent on the initial fuel droplet sizes. The second analysis copes with the full water cooling numerical model, which can assist on thermal performance optimisation or to determine the best method for heat removal without the cost of building physical prototypes. The numerical results indicate that the water flow rate and direction has noticeable influence on the cooling efficiency but no noticeable effect on the gas flow dynamics within the thermal spraying gun. The third investigation deals with the development and implementation of discrete phase particle models. The results indicate that most powder particles are not melted upon hitting the substrate to be coated. The oxidation model confirms that HVOF guns can produce metallic coating with low oxidation within the typical standing-off distance about 30cm. Physical properties such as porosity, microstructure, surface roughness and adhesion strength of coatings produced by droplet deposition in a thermal spray process are determined to a large extent by the dynamics of deformation and solidification of the particles impinging on the substrate. Therefore, is one of the objectives of this study to present a complete numerical model of droplet impact and solidification. The modelling results show that solidification of droplets is significantly affected by the thermal contact resistance/substrate surface roughness.

Evaluation of remote sensing for the detection of landfill gas and leachate in an urban environment

The technique of remote sensing provides a unique view of the earth's surface and considerable areas can be surveyed in a short amount of time. The aim of this project was to evaluate whether remote sensing, particularly using the Airborne Thematic Mapper (ATM) with its wide spectral range, was capable of monitoring landfill sites within an urban environment with the aid of image processing and Geographical Information Systems (GIS) methods. The regions under study were in the West Midlands conurbation and consisted of a large area in what is locally known as the Black Country containing heavy industry intermingled with residential areas, and a large single active landfill in north Birmingham. When waste is collected in large volumes it decays and gives off pollutants. These pollutants, landfill gas and leachate (a liquid effluent), are known to be injurious to vegetation and can cause stress and death. Vegetation under stress can exhibit a physiological change, detectable by the remote sensing systems used. The chemical and biological reactions that create the pollutants are exothermic and the gas and leachate, if they leave the waste, can be warmer than their surroundings. Thermal imagery from the ATM (daylight and dawn) and thermal video were obtained and used to find thermal anomalies on the area under study. The results showed that vegetation stress is not a reliable indicator of landfill gas migration, as sites within an urban environment have a cover too complex for the effects to be identified. Gas emissions from two sites were successfully detected by all the thermal imagery with the thermal ATM being the best. Although the results were somewhat disappointing, recent technical advancements in the remote sensing systems used in this project would allow geo-registration of ATM imagery taken on different occasions and the elimination of the effects of solar insolation.

Ground cracking and frost heaving associated with chilled gas pipeline operations in Britain

This thesis investigates the soil-pipeline interactions associated with the operation of large-diameter chilled gas pipelines in Britain, these are frost/pipe heave and ground cracking. The investigation was biased towards the definition of the mechanism of ground cracking and, the parameters which influence its generation and subsequent development, especially its interaction with frost heave. The study involved a literature review, questionnaire, large-scale test and small-scale laboratory model experiments. The literature review concentrated on soil-pipeline interactions and frost action, with frost/pipe heave often reported but ground cracking was seldom reported. A questionnaire was circulated within British Gas to gain further information on these interactions. The replies indicated that if frost/pipe heave was reported, ground cracking was also likely to be observed. These soil-pipeline interactions were recorded along 19% of pipelines in the survey and were more likely along the larger diameter, higher flow pipelines. A large-scale trial along a 900 mm pipeline was undertaken to assess the soil thermal, hydraulic and stress regimes, together with pipe and ground movements. Results indicated that cracking occurred intermittently along the pipeline during periods of rapid frost/pipe heave and ground movement and, that frozen annulus growth produced a ground surface profile was approximated by a normal probability distribution curve. This curve indicates maximum tensile strain directly over the pipe centre. Finally a small-scale laboratory model was operated to further define the ground cracking mechanism. Ground cracking was observed at small upward ground surface movement, and with continued movement the ground crack increased in width and depth. At the end of the experiments internal soil failure planes slanting upwards and away from the frozen annulus were noted. The suggested mechanism for ground cracking involved frozen annulus growth producing tensile strain in the overlying unfrozen soil, which when sufficient produced a crack.

Gas-metal reactions and porosity in the inert gas arc welding of copper

A study has been made of the effects of welding and material variables on the occurrence of porosity in tungsten inert gas arc welding of copper. The experiments were based on a statistical design and variables included, welding current, welding speed, arc atmosphere composition, inert gas flow rate, weld preparation, and base material. The extent of weld metal porosity was assessed by density measurement and its morphology by X-ray radiography and metallography. In conjunction with this the copper-steam reaction has been investigated under conditions of controlled atmosphere arc melting. The welding experiments have shown that the extent of steam porosity is increased by increased water vapour content of the arc atmosphere, increased oxygen content of the base material and decreased welding speed. The arc melting experiments have shown that the steam reaction occurs in the body of the weld pool and proceeds to an apparent equi1ibrium state appropriate to to its temperature, the hydrogen and oxygen being supplied by the dissociation of water vapour in the arc atmosphere. It has been shown conclusively that nitrogen porosity can occur in the tungsten inert gas arc welding of copper and that this porosity can be eliminated by using filler wires containing small amounts of aluminum and titanium. Since it has been shown to be much more difficult to produce sound butt welds than melt runs it has been concluded that the porosity associated with joint fit up is due to nitrogen entrained into tho arc atmosphere. Clearly atmospheric entrainment would also, to a much lesser extent, involve water vapour. From a practical welding point of view it has thus been postulated that use of a filler wire containing small amounts of aluminum and/or titanium would eliminate both forms of porosity since these elements are both strongJy deoxidising and denitriding.