The effects of solid contamination in hydraulic fluids on axial piston pumps

The fluids used in hydraulic systems inevitably contain large numbers of small, solid particles, a phenomenon known as 'fluid contamination'. Particles enter a hydraulic system from the environment, and are generated within it by processes of wear. At the same time, particles are removed from the system fluid by sedimentation and in hydraulic filters. This thesis considers the problems caused by fluid contamination, as they affect a manufacturer of axial piston pumps. The specific project aim was to investigate methods of predicting or determining the effects of fluid contamination on this type of pump. The thesis starts with a theoretical analysis of the contaminated lubrication of a slipper-pad bearing. Statistical methods are used to develop a model of the blocking, by particles, of the control capillaries used in such bearings. The results obtained are compared to published, experimental data. Poor correlation between theory and practice suggests that more research is required in this area before such theoretical analysis can be used in industry. Accelerated wear tests have been developed in the U.S.A. in an attempt to predict pump life when operating on contaminated fluids. An analysis of such tests shows that reliability data can only be obtained from extensive test programmes. The value of contamination testing is suggested to be in determining failure modes, and in identifying those pump components which are susceptible to the effects of contamination. A suitable test is described, and the results of a series of tests on axial piston pumps are presented and discussed. The thesis concludes that pump reliability data can only be obtained from field experience. The level of confidence which can be placed in results from normal laboratory testing is shown to be too low for the data to be of real value. Recommendations are therefore given for the ways in which service data should be collected and analysed.

Sonically induced narrowing of the NMR spectra of solids and other novel NMR techniques

A typical liquid state NMR spectrum is composed of a number of discrete absorptions which can be readily interpreted to yield detailed information about the chemical environment of the nuclei found within the sample. The same cannot be said about the spectra of solid samples. For these the absorptions are typically broad, featureless and yield little information directly. This situation may be further exacerbated by the characteristically long T1 values of nuclei bound within a solid lattice which, consequently, require long inter-sequence delays that necessitate lengthy experiments. This work attempts to address both of these inherent problems. Classically, the resolution of the broad-line spectra of solids into discrete resonances has been achieved by imparting to the sample coherent rotation about specific axes in relation to the polarising magnetic field, as implemented in the magic-angle spinning (MAS) [1], dynamic angle spinning (DAS) [2] and double rotation (DOR) [3] NMR experiments. Recently, an alternative method, sonically induced narrowing of the NMR spectra of solids (SINNMR) [4], has been reported which yields the same well resolved solid-state spectra as the classic solid-state NMR experiments, but which achieves the resolution of the broad-line spectra through the promotion of incoherent motion in a suspension of solid particles. The first part of this work examines SINNMR and, in particular, concentrates on ultrasonically induced evaluation, a phenomenon which is thought to be essential to the incoherent averaging mechanism. The second part of this work extends the principle of incoherent motion, implicit in SINNMR, to a new genre of particulate systems, air fluidized beds, and examines the feasibility of such systems to provide well resolved solid state NMR spectra. Samples of trisodium phosphate dodecahydrate and of aluminium granules are examined using the new method with partially resolved spectra being reported in the case of the latter.

Design and construction of an ultrasonic probe for use in a Cryo-Magnet NMR Spectrometer

SINNMR (Sonically Induced Narrowing of the Nuclear Magnetic Resonance spectra of solids), is a novel technique that is being developed to enable the routine study of solids by nuclear magnetic resonance spectroscopy. SINNMR aims to narrow the broad resonances that are characteristic of solid state NMR by inducing rapid incoherent motion of solid particles suspended in a support medium, using high frequency ultrasound in the range 2-10 MHz. The width of the normal broad resonances from solids are due to incomplete averaging of several components of the total spin Hamiltonian caused by restrictions placed on molecular motion within a solid. At present Magic Angle Spinning (MAS) NMR is the classical solid state technique used to reduce line broadening, but: this has associated problems, not least of which is the appearance of many spinning side bands which confuse the spectra. It is hoped that SlNNMR will offer a simple alternative, particularly as it does not reveal spinning sidebands The fundamental question concerning whether the use of ultrasound within a cryo-magnet will cause quenching has been investigated with success, as even under the most extreme conditions of power, frequency and irradiator time, the magnet does not quench. The objective of this work is to design and construct a SINNMR probe for use in a super conducting cryo-magnet NMR spectrometer. A cell for such a probe has been constructed and incorporated into an adapted high resolution broadband probe. It has been proved that the cell is capable of causing cavitation, up to 10 MHz, by running a series of ultrasonic reactions within it and observing the reaction products. It was found that the ultrasound was causing the sample to be heated to unacceptable temperatures and this necessitated the incorporation of temperature stabilisation devices. Work has been performed on the investigation of the narrowing of the solid state 23Na spectrum of tri-sodium phosphate using high frequency ultrasound. Work has also been completed on the signal enhancement and T1 reduction of a liquid mixture and a pure compound using ultrasound. Some preliminary "bench" experiments have been completed on a novel ultrasonic device designed to help minimise sample heating. The concept involves passing the ultrasound through a temperature stabilised, liquid filled funnel that has a drum skin on the end that will enable the passage of ultrasound into the sample. Bench experiments have proved that acoustic attenuation is low and that cavitation in the liquid beyond the device is still possible.

NMR spectroscopy in the presence of ultrasound and other perturbations

The work described in this thesis has been concerned with exploring the potential uses of ultrasound in Nuclear Magnetic Resonance (NMR) spectroscopy, The NMR spectra of liquids provide detailed structural information that may be deduced from the chemical shifts and spin-spin coupling, that are evident in the narrow resonances, arising from some of the nuclear broadening interactions being reduced to zero. In the solid state, all of the nuclear broadening interactions are present and broad lines in the NMR spectrum are observed. Current techniques employed to reduce the line widths in solids are based on coherent averaging techniques such as MAS NMR1,2 which can remove first order interactions. Recently DOR3 and DAS4 have become available to remove higher order interactions. SINNMR (Sonically Induced Narrowing of the NMR spectra of solids) has been reported by Homer et al5 and developed by Homer and Howard6 to reduce the line widths of solids. The basis of their work is the proposal that a colloidal suspension of solid particles can be made to move like large molecules by using ultrasonic agitation. The advantage of the technique is that the particles move incoherently removing all of the nuclear interactions responsible for broad lines. This thesis describes work on the extension of SINNMR by showing that the line width of 27AI and 11B for the glass Na20/B203/AI203 can be reduced by placing solid particles in a colloidal suspension. Further line width reduction is possible by applying ultrasound, at 2 MHz, of sufficient intensity. It is proposed that a cavitation field is responsible for imparting sufficient rotational motion to the solid particles to partially average the nuclear interactions responsible for broad lines. Rapid stirring of the colloidal suspension generates turbulent flow, however, the motion is insufficient to narrow the line widths for 27AI in the glass. Investigations of sonochemical reactions for in situ rate measurements by NMR have been made. 8y using the Weissler reaction7, it has been shown that ultrasonic cavitation is possible up to 10MHz. Preliminary studies have been carried out into the rate of ultrasonic polymerisation of methylmethacrylate by NMR. Long range order in liquid crystals can imposed when they are aligned in the presence a magnetic field. The degree of alignment can be monitored by NMR using, for example a deuterated solute added to the liquid crystal8. Ultrasonic streaming can then be employed to deflect the directors of the liquid crystal from their equilibrium position, resulting in a change In the NMR spectrum. The angle of deflection has been found for the thermotropic liquid crystal (I35) to be ca, 35° and for the lyotropic (ZLI-1167) to be ca, 20°, Mechanical stirring can used to re- orientate the liquid crystal but was found to give a smaller deflection, In a separate study, that did not use ultrasound, it has been found that the signal to noise ratio of 13C NMR signals can be enhanced by rapidly stirring a Iiquid. Accelerating the diffusion of nuclei out of the coil region enables M0 to be re-established more rapidly than the normal relaxation process. This allows the pulse repetition rate to be reduced without saturating the spin system. The influence of varying the relaxation delay, acquisition time and inter-pulse delay have been studied and parameters optimised. By studying cholesterol the technique was found to be most effective for nuclei with long relaxation times, such as quaternary carbon sites. Key Worde: NMR, Ulf.rasciund, 1,.lqi.fi!:l cryllltalt!h SCll1C1otlemlstryl I!r1hano~d algnflllf

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.

Elasto-plastic impact of fine particles and fragmentation of small agglomerates

Surface deposition of dense aerosol particles is of major concern in the nuclear industry for safety assessment. This study presents theoretical investigations and computer simulations of single gas-born U3O8 particles impacting with the in-reactor surface and the fragmentation of small agglomerates. A theoretical model for elasto-plastic spheres has been developed and used to analyse the force-displacement and force-time relationships. The impulse equations, based on Newton's second law, are applied to govern the tangential bouncing behaviour. The theoretical model is then incorporated into the Distinct Element Method code TRUBAL in order to perform computer simulated tests of particle collisions. A comparison of simulated results with both theoretical predictions and experimental measurements is provided. For oblique impacts, the results in terms of the force-displacement relationship, coefficients of restitution, trajectory of the impacting particle, and distribution of kinetic energy and work done during the process of impact are presented. The effects of Poisson's ratio, friction, plastic deformation and initial particle rotation on the bouncing behaviour are also discussed. In the presence of adhesion an elasto-plastic collision model, which is an extension to the JKR theory, is developed. Based on an energy balance equation the critical sticking velocity is obtained. For oblique collisions computer simulated results are used to establish a set of criteria determining whether or not the particle bounces off the target plate. For impact velocities above the critical sticking value, computer simulated results for the coefficients of restitution and rebound angles of the particle are presented. Computer simulations of fracture/fragmentation resulting from agglomerate-wall impact have also been performed, where two randomly generated agglomerates (one monodisperse, the other polydisperse), each consisting of 50 primary particles are used. The effects of impact angle, local structural arrangements close to the impact point, and plastic deformation at the contacts on agglomerate damage are examined. The simulated results show a significant difference in agglomerate strength between the two assemblies. The computer data also shows that agglomerate damage resulting from an oblique impact is determined by the normal velocity component rather than the impact speed.

Investigating the molecular structures of solid dispersions by the simulated annealing method

Knowledge of the molecular structures of solid dispersions is vital, yet, despite thousands of reports in this area, it remains unclear. The aim of this research is to investigate the molecular structure of solid dispersions with hot melt preparation method by the simulated annealing method. Simulation results showed linear polymer chains form the random coils under heat and the drug molecules stick on the surface of polymer coils, while drug molecules are dispersed molecularly but irregularly within the amorphous low molecular weight carriers. This research presents more reasonable molecular images of solid dispersions than the existed theory.

Gas-liquid-solid flow modelling in a bubble column

An alternative approach to the modelling of solid-liquid and gas-liquid-solid flows for a 5:1 height to width aspect ratio bubble column is presented here. A modified transport equation for the volume fraction of a dispersed phase has been developed for the investigation of turbulent buoyancy driven flows (Chem. Eng. Proc., in press). In this study, a modified transport equation has been employed for discrete phase motion considering both solid-liquid and gas-liquid-solid flows. The modelling of the three-phase flow in a bubble column was achieved in the following case: injecting a slug of solid particles into the column for 10 s at a velocity of 0.1 m s-1 and then the gas phase flow was initiated with a superficial gas velocity of 0.02 cm s-1. © 2003 Elsevier B.V. All rights reserved.

Lagrangian and Eulerian descriptions of inertial particles in random flows

We study how the spatial distribution of inertial particles evolves with time in a random flow. We describe an explosive appearance of caustics and show how they influence an exponential growth of clusters due to smooth parts of the flow, leading in particular to an exponential growth of the average distance between particles. We demonstrate how caustics restrict applicability of Lagrangian description to inertial particles.

Optimising the nanoporous architecture of solid acid and base catalysts for biodiesel synthesis

Dwindling oil reserves and growing concerns over CO2 emissions and associated climate change are driving the utilisation of renewable feedstocks as alternative, sustainable fuel sources. While rising oil prices are improving the commercial feasibility of biodiesel production, many current processes still employ homogeneous acid and/or base catalysts to transform plant or algae oil into the fatty acid methyl ester (FAME) components of biodiesel. Fuel purification requires energy intensive aqueous quench and neutralization steps, thus the rational design of new high activity catalysts is required to deliver biodiesel as a major player in the 21st century sustainable energy portfolio. Advances in the development of heterogeneous catalysts for biodiesel synthesis require catalysts with pore architectures designed to improve the accessibility of bulky viscous reactants typical of plant oils. Here we discuss how improvements to active site accessibility and catalyst activity in transesterification or esterification reactions can be achieved either by designing hierarchical pore networks or by pore expansion and use of interconnected pore architectures.