Design and development of a time of flight fast scattering spectrometer : a quantitative surface analysis technique and a new approach towards the experimental investigation of the surface particle interactions

A new surface analysis technique has been developed which has a number of benefits compared to conventional Low Energy Ion Scattering Spectrometry (LEISS). A major potential advantage arising from the absence of charge exchange complications is the possibility of quantification. The instrumentation that has been developed also offers the possibility of unique studies concerning the interaction between low energy ions and atoms and solid surfaces. From these studies it may also be possible, in principle, to generate sensitivity factors to quantify LEISS data. The instrumentation, which is referred to as a Time-of-Flight Fast Atom Scattering Spectrometer has been developed to investigate these conjecture in practice. The development, involved a number of modifications to an existing instrument, and allowed samples to be bombarded with a monoenergetic pulsed beam of either atoms or ions, and provided the capability to analyse the spectra of scattered atoms and ions separately. Further to this a system was designed and constructed to allow incident, exit and azimuthal angles of the particle beam to be varied independently. The key development was that of a pulsed, and mass filtered atom source; which was developed by a cyclic process of design, modelling and experimentation. Although it was possible to demonstrate the unique capabilities of the instrument, problems relating to surface contamination prevented the measurement of the neutralisation probabilities. However, these problems appear to be technical rather than scientific in nature, and could be readily resolved given the appropriate resources. Experimental spectra obtained from a number of samples demonstrate some fundamental differences between the scattered ion and neutral spectra. For practical non-ordered surfaces the ToF spectra are more complex than their LEISS counterparts. This is particularly true for helium scattering where it appears, in the absence of detailed computer simulation, that quantitative analysis is limited to ordered surfaces. Despite this limitation the ToFFASS instrument opens the way for quantitative analysis of the 'true' surface region to a wider range of surface materials.

The design of a high pressure solvent extraction process using liquid ammonia as solvent

The literature on the potential use of liquid ammonia as a solvent for the extraction of aromatic hydrocarbons from mixtures with paraffins, and the application of reflux, has been reviewed. Reference is made to extractors suited to this application. A pilot scale extraction plant was designed comprising a Scm. diameter by 12Scm. high, 50 stage Rotating Disc Contactor with 2 external settlers. Provision was made for operation with, or without, reflux at a pressure of 10 bar and ambient temperature. The solvent recovery unit consisted of an evaporator, compressor and condenser in a refrigeration cycle. Two systems were selected for study, Cumene-n-Heptane-Ammonia and Toluene-Methylcyclohexane-Ammonia. Equlibrium data for the first system was determined experimentally in a specially-designed, equilibrium bomb. A technique was developed to withdraw samples under pressure for analysis by chromatography and titration. The extraction plant was commissioned with a kerosine-water system; detailed operating procedures were developed based on a Hazard and Operability Study. Experimental runs were carried out with both ternary ammonia systems. With the system Toluene-Methylcyclohexane-Ammonia the extraction plant and the solvent recovery facility, operated satisfactorily, and safely,in accordance with the operating procedures. Experimental data gave reasonable agreement with theory. Recommendations are made for further work with plant.

Design and characterization of zeolite membranes for fluid separation

Experimental and theoretical methods have been used to study zeolite structures, properties and applications as membranes for separation purposes. Thin layers of silicalite-1 and Na-LTA zeolites have been synthesised onto carbon-graphite supports using a hydrothermal synthesis procedure. The separation behaviour of the composite membranes was characterized by gas permeation studies of pure, binary and ternary mixtures of methane, ethane and propane. The influence of temperature and feed gas mixture composition on the separation and selectivity performance of the membranes was also investigated. It was found that the silicalite-1 composite membranes synthesised onto the 4 hour oxidized carbon-graphite supports showed the most promising separation behaviour of all the composite membranes investigated. Molecular simulation methods were used to gain an understanding of how hydrocarbon molecules behave both within the pores and on the surfaces of silicalite-1, mordenite and LTA zeolites. Molecular dynamic simulations were used to investigate the influence of temperature and molecular loadings on the diffusional behaviour of hydrocarbons in zeolites. Both hydroxylated (surface termination with hydroxyl groups) and non-hydroxylated silicalite-1 and Na-mordenite surfaces were generated. For both zeolites the most stable surfaces correspond to the {010} surface. For the silicalite-1 {010} surface the adsorption of hydrocarbons and molecular water onto the hydroxylated surface showed a favourable exothermic adsorption process compared to adsorption on the non-hydroxylated surface. With the Na-mordenite {010} surface the adsorption of hydrocarbons onto both the hydroxylated and non-hydroxylated surfaces had a combination of favourable and non-favourable adsorption energies, while the adsorption of molecular water onto both types of surface was found to be a favourable adsorption process.

Dynamic simulation of chemical processes

This thesis describes the design and implementation of an interactive dynamic simulator called DASPRII. The starting point of this research has been an existing dynamic simulation package, DASP. DASPII is written in standard FORTRAN 77 and is implemented on universally available IBM-PC or compatible machines. It provides a means for the analysis and design of chemical processes. Industrial interest in dynamic simulation has increased due to the recent increase in concern over plant operability, resiliency and safety. DASPII is an equation oriented simulation package which allows solution of dynamic and steady state equations. The steady state can be used to initialise the dynamic simulation. A robust non linear algebraic equation solver has been implemented for steady state solution. This has increased the general robustness of DASPII, compared to DASP. A graphical front end is used to generate the process flowsheet topology from a user constructed diagram of the process. A conversational interface is used to interrogate the user with the aid of a database, to complete the topological information. An original modelling strategy implemented in DASPII provides a simple mechanism for parameter switching which creates a more flexible simulation environment. The problem description generated is by a further conversational procedure using a data-base. The model format used allows the same model equations to be used for dynamic and steady state solution. All the useful features of DASPI are retained in DASPII. The program has been demonstrated and verified using a number of example problems, Significant improvements using the new NLAE solver have been shown. Topics requiring further research are described. The benefits of variable switching in models has been demonstrated with a literature problem.

Managing uncertainty in complex stochastic models: design and emulation of a Rabies model

In this paper we present a novel method for emulating a stochastic, or random output, computer model and show its application to a complex rabies model. The method is evaluated both in terms of accuracy and computational efficiency on synthetic data and the rabies model. We address the issue of experimental design and provide empirical evidence on the effectiveness of utilizing replicate model evaluations compared to a space-filling design. We employ the Mahalanobis error measure to validate the heteroscedastic Gaussian process based emulator predictions for both the mean and (co)variance. The emulator allows efficient screening to identify important model inputs and better understanding of the complex behaviour of the rabies model.

Improved production of industrially relevant recombinant proteins: application of multi-factorial design of experiments and scalable process modelling

The work described in this thesis focuses on the use of a design-of-experiments approach in a multi-well mini-bioreactor to enable the rapid establishments of high yielding production phase conditions in yeast, which is an increasingly popular host system in both academic and industrial laboratories. Using green fluorescent protein secreted from the yeast, Pichia pastoris, a scalable predictive model of protein yield per cell was derived from 13 sets of conditions each with three factors (temperature, pH and dissolved oxygen) at 3 levels and was directly transferable to a 7 L bioreactor. This was in clear contrast to the situation in shake flasks, where the process parameters cannot be tightly controlled. By further optimisating both the accumulation of cell density in batch and improving the fed-batch induction regime, additional yield improvement was found to be additive to the per cell yield of the model. A separate study also demonstrated that improving biomass improved product yield in a second yeast species, Saccharomyces cerevisiae. Investigations of cell wall hydrophobicity in high cell density P. pastoris cultures indicated that cell wall hydrophobin (protein) compositional changes with growth phase becoming more hydrophobic in log growth than in lag or stationary phases. This is possibly due to an increased occurrence of proteins associated with cell division. Finally, the modelling approach was validated in mammalian cells, showing its flexibility and robustness. In summary, the strategy presented in this thesis has the benefit of reducing process development time in recombinant protein production, directly from bench to bioreactor.

Optimal design for correlated processes with input-dependent noise

Optimal design for parameter estimation in Gaussian process regression models with input-dependent noise is examined. The motivation stems from the area of computer experiments, where computationally demanding simulators are approximated using Gaussian process emulators to act as statistical surrogates. In the case of stochastic simulators, which produce a random output for a given set of model inputs, repeated evaluations are useful, supporting the use of replicate observations in the experimental design. The findings are also applicable to the wider context of experimental design for Gaussian process regression and kriging. Designs are proposed with the aim of minimising the variance of the Gaussian process parameter estimates. A heteroscedastic Gaussian process model is presented which allows for an experimental design technique based on an extension of Fisher information to heteroscedastic models. It is empirically shown that the error of the approximation of the parameter variance by the inverse of the Fisher information is reduced as the number of replicated points is increased. Through a series of simulation experiments on both synthetic data and a systems biology stochastic simulator, optimal designs with replicate observations are shown to outperform space-filling designs both with and without replicate observations. Guidance is provided on best practice for optimal experimental design for stochastic response models. © 2013 Elsevier Inc. All rights reserved.

The Experience Software-based Design of Virtual Medical Intrascopy Systems for Simulation Study

The questions of software-based design of “virtual” technical systems are considered as facility of imitation experiment for educational purposes. These virtual systems are usable for analysis of medical intrascopy systems functioning. The virtual educational technical systems allow guarantee the goodness technical training of bioengineers.

A simulation analysis of spoke-terminals operating in LTL Hub-and-Spoke freight distribution systems

DUE TO COPYRIGHT RESTRICTIONS ONLY AVAILABLE FOR CONSULTATION AT ASTON UNIVERSITY LIBRARY AND INFORMATION SERVICES WITH PRIOR ARRANGEMENT The research presented in this thesis is concerned with Discrete-Event Simulation (DES) modelling as a method to facilitate logistical policy development within the UK Less-than-Truckload (LTL) freight distribution sector which has been typified by “Pallet Networks” operating on a hub-and-spoke philosophy. Current literature relating to LTL hub-and-spoke and cross-dock freight distribution systems traditionally examines a variety of network and hub design configurations. Each is consistent with classical notions of creating process efficiency, improving productivity, reducing costs and generally creating economies of scale through notions of bulk optimisation. Whilst there is a growing abundance of papers discussing both the network design and hub operational components mentioned above, there is a shortcoming in the overall analysis when it comes to discussing the “spoke-terminal” of hub-and-spoke freight distribution systems and their capabilities for handling the diverse and discrete customer profiles of freight that multi-user LTL hub-and-spoke networks typically handle over the “last-mile” of the delivery, in particular, a mix of retail and non-retail customers. A simulation study is undertaken to investigate the impact on operational performance when the current combined spoke-terminal delivery tours are separated by ‘profile-type’ (i.e. retail or nonretail). The results indicate that a potential improvement in delivery performance can be made by separating retail and non-retail delivery runs at the spoke-terminal and that dedicated retail and non-retail delivery tours could be adopted in order to improve customer delivery requirements and adapt hub-deployed policies. The study also leverages key operator experiences to highlight the main practical implementation challenges when integrating the observed simulation results into the real-world. The study concludes that DES be harnessed as an enabling device to develop a ‘guide policy’. This policy needs to be flexible and should be applied in stages, taking into account the growing retail-exposure.

A simulation conceptual modelling procedure for SCM applications

Purpose – The purpose of this paper is to outline a seven-phase simulation conceptual modelling procedure that incorporates existing practice and embeds a process reference model (i.e. SCOR). Design/methodology/approach – An extensive review of the simulation and SCM literature identifies a set of requirements for a domain-specific conceptual modelling procedure. The associated design issues for each requirement are discussed and the utility of SCOR in the process of conceptual modelling is demonstrated using two development cases. Ten key concepts are synthesised and aligned to a general process for conceptual modelling. Further work is outlined to detail, refine and test the procedure with different process reference models in different industrial contexts. Findings - Simulation conceptual modelling is often regarded as the most important yet least understood aspect of a simulation project (Robinson, 2008a). Even today, there has been little research development into guidelines to aid in the creation of a conceptual model. Design issues are discussed for building an ‘effective’ conceptual model and the domain-specific requirements for modelling supply chains are addressed. The ten key concepts are incorporated to aid in describing the supply chain problem (i.e. components and relationships that need to be included in the model), model content (i.e. rules for determining the simplest model boundary and level of detail to implement the model) and model validation. Originality/value – Paper addresses Robinson (2008a) call for research in defining and developing new approaches for conceptual modelling and Manuj et al., (2009) discussion on improving the rigour of simulation studies in SCM. It is expected that more detailed guidelines will yield benefits to both expert (i.e. avert typical modelling failures) and novice modellers (i.e. guided practice; less reliance on hopeful intuition)

Nonlinear dynamics and chaos simulation system analysis for improved design

Small errors proved catastrophic. Our purpose to remark that a very small cause which escapes our notice determined a considerable effect that we cannot fail to see, and then we say that the effect is due to chance. Small differences in the initial conditions produce very great ones in the final phenomena. A small error in the former will produce an enormous error in the latter. When dealing with any kind of electrical device specification, it is important to note that there exists a pair of test conditions that define a test: the forcing function and the limit. Forcing functions define the external operating constraints placed upon the device tested. The actual test defines how well the device responds to these constraints. Forcing inputs to threshold for example, represents the most difficult testing because this put those inputs as close as possible to the actual switching critical points and guarantees that the device will meet the Input-Output specifications. ^ Prediction becomes impossible by classical analytical analysis bounded by Newton and Euclides. We have found that non linear dynamics characteristics is the natural state of being in all circuits and devices. Opportunities exist for effective error detection in a nonlinear dynamics and chaos environment. ^ Nowadays there are a set of linear limits established around every aspect of a digital or analog circuits out of which devices are consider bad after failing the test. Deterministic chaos circuit is a fact not a possibility as it has been revived by our Ph.D. research. In practice for linear standard informational methodologies, this chaotic data product is usually undesirable and we are educated to be interested in obtaining a more regular stream of output data. ^ This Ph.D. research explored the possibilities of taking the foundation of a very well known simulation and modeling methodology, introducing nonlinear dynamics and chaos precepts, to produce a new error detector instrument able to put together streams of data scattered in space and time. Therefore, mastering deterministic chaos and changing the bad reputation of chaotic data as a potential risk for practical system status determination. ^

Developing an enhanced model for combined heat and air infiltration energy simulation

The need for efficient, sustainable, and planned utilization of resources is ever more critical. In the U.S. alone, buildings consume 34.8 Quadrillion (1015) BTU of energy annually at a cost of $1.4 Trillion. Of this energy 58% is utilized for heating and air conditioning. ^ Several building energy analysis tools have been developed to assess energy demands and lifecycle energy costs in buildings. Such analyses are also essential for an efficient HVAC design that overcomes the pitfalls of an under/over-designed system. DOE-2 is among the most widely known full building energy analysis models. It also constitutes the simulation engine of other prominent software such as eQUEST, EnergyPro, PowerDOE. Therefore, it is essential that DOE-2 energy simulations be characterized by high accuracy. ^ Infiltration is an uncontrolled process through which outside air leaks into a building. Studies have estimated infiltration to account for up to 50% of a building's energy demand. This, considered alongside the annual cost of buildings energy consumption, reveals the costs of air infiltration. It also stresses the need that prominent building energy simulation engines accurately account for its impact. ^ In this research the relative accuracy of current air infiltration calculation methods is evaluated against an intricate Multiphysics Hygrothermal CFD building envelope analysis. The full-scale CFD analysis is based on a meticulous representation of cracking in building envelopes and on real-life conditions. The research found that even the most advanced current infiltration methods, including in DOE-2, are at up to 96.13% relative error versus CFD analysis. ^ An Enhanced Model for Combined Heat and Air Infiltration Simulation was developed. The model resulted in 91.6% improvement in relative accuracy over current models. It reduces error versus CFD analysis to less than 4.5% while requiring less than 1% of the time required for such a complex hygrothermal analysis. The algorithm used in our model was demonstrated to be easy to integrate into DOE-2 and other engines as a standalone method for evaluating infiltration heat loads. This will vastly increase the accuracy of such simulation engines while maintaining their speed and ease of use characteristics that make them very widely used in building design.^