APPLICATION OF FACTOR-ANALYSIS TO CORRECTION OF SPECTRAL OVERLAP INTERFERENCE IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

Correction of spectral overlap interference in inductively coupled plasma atomic emission spectrometry by factor analysis is attempted. For the spectral overlap of two known lines, a data matrix can be composed from one or two pure spectra and a spectrum of the mixture. The data matrix is decomposed into a spectra matrix and a concentration matrix by target transformation factor analysis. The component concentration of interest in a binary mixture is obtained from the concentration matrix and interference from the other component is eliminated. This method is applied to correcting spectral interference of yttrium on the determination of copper and aluminium: satisfactory results are obtained. This method may also be applied to correcting spectral overlap interference for more than two lines. Like other methods of correcting spectral interferences, factor analysis can only be used for additive spectral overlap. Results obtained from measurements on copper/yttrium mixtures with different white noise added show that random errors in measurement data do not significantly affect the results of the correction method.

STUDIES ON INTERFACIAL PHENOMENA OF POLYCRYSTALLINE HG1-XCDXTE THIN-FILM ELECTRODE POLYSULFIDE REDOX SOLUTION

Electrode capacitance and photocurrent spectra of electrodeposited polycrystalline Hg1-xCdxTe thin films of varying (1-x) were measured in polysulfide redox solution, hence the flatband potentional PHI(fb) and the bandgap E(g) of Hg1-xCdxTe thin films obtained. It was of interest to find out that only the location of conduction band E(c) shifts negatively with increasing (1-x) while the valence band E(v), is almost constant. The experimental open circuit photovoltage V0 is smaller than theoretical value V(max) calculated through flatband potential PHI(fb), therefore there is a possibility of promoting the experimental open circuit photovoltage.

Numerical simulation of tides and tidal currents in Liaodong Bay with POM

A three-dimensional ocean circulation model, called Princeton Ocean Model (POM), is employed to simulate tides and tidal currents in Liaodong Bay. The nested grid technique is adopted to improve the computation precision. Computed harmonic constants of M-1, M-2 tides at five tidal gauge stations and surface elevations at two oil platforms are compared with those observed, and show good agreements with them. Based on the calculated results, the co-amplitude and co-phase tag lines of nil and M-2 tidal constituents, the residual current field of M-2 constituent, tidal form, tidal Current ellipse and the moving style of tidal current are given. It is found that diurnal tidal constituents have no amphidromic point whereas semi-diurnal constituents have one in the region of interest. Meanwhile, some meaningful results are concluded and presented, which are conducive to a thorough knowledge of the characteristics of tides and tidal currents in the Liaodong Bay.

Intraseasonal variability of Indian Ocean sea surface temperature during boreal winter: Madden-Julian Oscillation versus submonthly forcing and processes

[ 1] Intraseasonal variability of Indian Ocean sea surface temperature (SST) during boreal winter is investigated by analyzing available data and a suite of solutions to an ocean general circulation model for 1998 - 2004. This period covers the QuikSCAT and Tropical Rainfall Measuring Mission (TRMM) observations. Impacts of the 30 - 90 day and 10 - 30 day atmospheric intraseasonal oscillations (ISOs) are examined separately, with the former dominated by the Madden-Julian Oscillation (MJO) and the latter dominated by convectively coupled Rossby and Kelvin waves. The maximum variation of intraseasonal SST occurs at 10 degrees S - 2 degrees S in the wintertime Intertropical Convergence Zone (ITCZ), where the mixed layer is thin and intraseasonal wind speed reaches its maximum. The observed maximum warming ( cooling) averaged over ( 60 degrees E - 85 degrees E, 10 degrees S - 3 degrees S) is 1.13 degrees C ( - 0.97 degrees C) for the period of interest, with a standard deviation of 0.39 degrees C in winter. This SST change is forced predominantly by the MJO. While the MJO causes a basin-wide cooling ( warming) in the ITCZ region, submonthly ISOs cause a more complex SST structure that propagates southwestward in the western-central basin and southeastward in the eastern ocean. On both the MJO and submonthly timescales, winds are the deterministic factor for the SST variability. Short-wave radiation generally plays a secondary role, and effects of precipitation are negligible. The dominant role of winds results roughly equally from wind speed and stress forcing. Wind speed affects SST by altering turbulent heat fluxes and entrainment cooling. Wind stress affects SST via several local and remote oceanic processes.

Column switching-back flushing technique for the analysis of aromatic compounds in gasoline

A simple method, based on the technique of capillary column switching-back flushing, has been developed for the detailed analysis of aromatic compounds in gasoline. The sample was first separated on a 30-m long OV-2330 polar precolumn and then backflushed onto a nonpolar analytical column. The early eluting components from the precolumn and the components of interest (aromatic compounds plus heavier compounds) eluting from the analytical column are all directed to the same flame ionization detection system through a T piece, which permits the quantitative analysis of aromatic hydrocarbons in gasoline by a normalization method using correcting factors. The switching time window of the method is +/-5 s, resulting in easier operation and higher reliability. The reproducibility of the quantitative analysis was less than or equal to3% RSD for real gasoline samples. (C) 2002 Elsevier Science B.V. All rights reserved.

Syntax-Based Analytic Reading of Musical Scores

As part of a larger research project in musical structure, a program has been written which "reads" scores encoded in an input language isomorphic to music notation. The program is believed to be the first of its kind. From a small number of parsing rules the program derives complex configurations, each of which is associated with a set of reference points in a numerical representation of a time-continuum. The logical structure of the program is such that all and only the defined classes of events are represented in the output. Because the basis of the program is syntactic (in the sense that parsing operations are performed on formal structures in the input string), many extensions and refinements can be made without excessive difficulty. The program can be applied to any music which can be represented in the input language. At present, however, it constitutes the first stage in the development of a set of analytic tools for the study of so-called atonal music, the revolutionary and little understood music which has exerted a decisive influence upon contemporary practice of the art. The program and the approach to automatic data-structuring may be of interest to linguists and scholars in other fields concerned with basic studies of complex structures produced by human beings.

Time-dependent wavepacket approach to the influence of intense fields on the population of molecular excited states

The influence of laser-field parameters, such as intensity and pulse width, on the population of molecular excited state is investigated by using the time-dependent wavepacket method. For a two-state system in intense laser fields, the populations in the upper and lower states are given by the wavefunctions obtained by solving the Schrodinger equation through split-operator scheme. The calculation shows that both the laser intensity and the pulse width have a strong effect on the population in molecular excited state, and that as the common feature of light-matter interaction (LMI), the periodic changing of the population with the evolution time in each state can be interpreted by Rabi oscillation and area-theorem. The results illustrate that by controlling these two parameters, the needed population in excited state of interest can be obtained, which provides the foundation of light manipulation of molecular processes. (C) 2005 Elsevier B.V. All rights reserved.

Resolution prediction and optimization of temperature programme in comprehensive two-dimensional gas chromatography

A model is developed for predicting the resolution of interested component pair and calculating the optimum temperature programming condition in the comprehensive two-dimensional gas chromatography (GC x GC). Based on at least three isothermal runs, retention times and the peak widths at half-height on both dimensions are predicted for any kind of linear temperature-programmed run on the first dimension and isothermal runs on the second dimension. The calculation of the optimum temperature programming condition is based on the prediction of the resolution of "difficult-to-separate components" in a given mixture. The resolution of all the neighboring peaks on the first dimension is obtained by the predicted retention time and peak width on the first dimension, the resolution on the second dimension is calculated only for the adjacent components with un-enough resolution on the first dimension and eluted within a same modulation period on the second dimension. The optimum temperature programming condition is acquired when the resolutions of all components of interest by GC x GC separation meet the analytical requirement and the analysis time is the shortest. The validity of the model has been proven by using it to predict and optimize GC x GC temperature programming condition of an alkylpyridine mixture. (c) 2005 Elsevier B.V. All rights reserved.

Eliminating False Matches for the Projective Registration of Free-Form Surfaces with Small Translational Motions

Liu, Yonghuai. Eliminating False Matches for the Projective Registration of Free-Form Surfaces with Small Translational Motions. IEEE Transactions on Systems, Man and Cybernetics, Part B: Cybernetics, vol. 35, no. 3, pp. 607-624, 2005.

History repeats itself: The failure of rational choice models in corporate governance

Marnet, Oliver, 'History repeats itself: The failure of rational choice models in corporate governance', Critical Perspectives on Accounting (2005) 18(2) pp.191-210 RAE2008

Characterization of Network-Wide Anomalies in Traffic Flows

Detecting and understanding anomalies in IP networks is an open and ill-defined problem. Toward this end, we have recently proposed the subspace method for anomaly diagnosis. In this paper we present the first large-scale exploration of the power of the subspace method when applied to flow traffic. An important aspect of this approach is that it fuses information from flow measurements taken throughout a network. We apply the subspace method to three different types of sampled flow traffic in a large academic network: multivariate timeseries of byte counts, packet counts, and IP-flow counts. We show that each traffic type brings into focus a different set of anomalies via the subspace method. We illustrate and classify the set of anomalies detected. We find that almost all of the anomalies detected represent events of interest to network operators. Furthermore, the anomalies span a remarkably wide spectrum of event types, including denial of service attacks (single-source and distributed), flash crowds, port scanning, downstream traffic engineering, high-rate flows, worm propagation, and network outage.

Inference and Labeling of Metric-Induced Network Topologies

The development and deployment of distributed network-aware applications and services over the Internet require the ability to compile and maintain a model of the underlying network resources with respect to (one or more) characteristic properties of interest. To be manageable, such models must be compact, and must enable a representation of properties along temporal, spatial, and measurement resolution dimensions. In this paper, we propose a general framework for the construction of such metric-induced models using end-to-end measurements. We instantiate our approach using one such property, packet loss rates, and present an analytical framework for the characterization of Internet loss topologies. From the perspective of a server the loss topology is a logical tree rooted at the server with clients at its leaves, in which edges represent lossy paths between a pair of internal network nodes. We show how end-to-end unicast packet probing techniques could b e used to (1) infer a loss topology and (2) identify the loss rates of links in an existing loss topology. Correct, efficient inference of loss topology information enables new techniques for aggregate congestion control, QoS admission control, connection scheduling and mirror site selection. We report on simulation, implementation, and Internet deployment results that show the effectiveness of our approach and its robustness in terms of its accuracy and convergence over a wide range of network conditions.

Comparison of deterministic, stochastic and fuzzy logic uncertainty modelling for capacity extension projects of DI/WFI pharmaceutical plant utilities with variable/dynamic demand

The last 30 years have seen Fuzzy Logic (FL) emerging as a method either complementing or challenging stochastic methods as the traditional method of modelling uncertainty. But the circumstances under which FL or stochastic methods should be used are shrouded in disagreement, because the areas of application of statistical and FL methods are overlapping with differences in opinion as to when which method should be used. Lacking are practically relevant case studies comparing these two methods. This work compares stochastic and FL methods for the assessment of spare capacity on the example of pharmaceutical high purity water (HPW) utility systems. The goal of this study was to find the most appropriate method modelling uncertainty in industrial scale HPW systems. The results provide evidence which suggests that stochastic methods are superior to the methods of FL in simulating uncertainty in chemical plant utilities including HPW systems in typical cases whereby extreme events, for example peaks in demand, or day-to-day variation rather than average values are of interest. The average production output or other statistical measures may, for instance, be of interest in the assessment of workshops. Furthermore the results indicate that the stochastic model should be used only if found necessary by a deterministic simulation. Consequently, this thesis concludes that either deterministic or stochastic methods should be used to simulate uncertainty in chemical plant utility systems and by extension some process system because extreme events or the modelling of day-to-day variation are important in capacity extension projects. Other reasons supporting the suggestion that stochastic HPW models are preferred to FL HPW models include: 1. The computer code for stochastic models is typically less complex than a FL models, thus reducing code maintenance and validation issues. 2. In many respects FL models are similar to deterministic models. Thus the need for a FL model over a deterministic model is questionable in the case of industrial scale HPW systems as presented here (as well as other similar systems) since the latter requires simpler models. 3. A FL model may be difficult to "sell" to an end-user as its results represent "approximate reasoning" a definition of which is, however, lacking. 4. Stochastic models may be applied with some relatively minor modifications on other systems, whereas FL models may not. For instance, the stochastic HPW system could be used to model municipal drinking water systems, whereas the FL HPW model should or could not be used on such systems. This is because the FL and stochastic model philosophies of a HPW system are fundamentally different. The stochastic model sees schedule and volume uncertainties as random phenomena described by statistical distributions based on either estimated or historical data. The FL model, on the other hand, simulates schedule uncertainties based on estimated operator behaviour e.g. tiredness of the operators and their working schedule. But in a municipal drinking water distribution system the notion of "operator" breaks down. 5. Stochastic methods can account for uncertainties that are difficult to model with FL. The FL HPW system model does not account for dispensed volume uncertainty, as there appears to be no reasonable method to account for it with FL whereas the stochastic model includes volume uncertainty.

Phase estimation receiver for full-field detection: a novel receiver structure for electronic dispersion compensation of metropolitan area networks

The development of ultra high speed (~20 Gsamples/s) analogue to digital converters (ADCs), and the delayed deployment of 40 Gbit/s transmission due to the economic downturn, has stimulated the investigation of digital signal processing (DSP) techniques for compensation of optical transmission impairments. In the future, DSP will offer an entire suite of tools to compensate for optical impairments and facilitate the use of advanced modulation formats. Chromatic dispersion is a very significant impairment for high speed optical transmission. This thesis investigates a novel electronic method of dispersion compensation which allows for cost-effective accurate detection of the amplitude and phase of the optical field into the radio frequency domain. The first electronic dispersion compensation (EDC) schemes accessed only the amplitude information using square law detection and achieved an increase in transmission distances. This thesis presents a method by using a frequency sensitive filter to estimate the phase of the received optical field and, in conjunction with the amplitude information, the entire field can be digitised using ADCs. This allows DSP technologies to take the next step in optical communications without requiring complex coherent detection. This is of particular of interest in metropolitan area networks. The full-field receiver investigated requires only an additional asymmetrical Mach-Zehnder interferometer and balanced photodiode to achieve a 50% increase in EDC reach compared to amplitude only detection.

Preparation and characterisation of ceria particles

Cerium dioxide (ceria) nanoparticles have been the subject of intense academic and industrial interest. Ceria has a host of applications but academic interest largely stems from their use in the modern automotive catalyst but it is also of interest because of many other application areas notably as the abrasive in chemical-mechanical planarisation of silicon substrates. Recently, ceria has been the focus of research investigating health effects of nanoparticles. Importantly, the role of non-stoichiometry in ceria nanoparticles is implicated in their biochemistry. Ceria has well understood non-stoichiometry based around the ease of formation of anion vacancies and these can form ordered superstructures based around the fluorite lattice structure exhibited by ceria. The anion vacancies are associated with localised or small polaron states formed by the electrons that remain after oxygen desorption. In simple terms these electrons combine with Ce4+ states to form Ce3+ states whose larger ionic radii is associated with a lattice expansion compared to stoichiometric CeO2. This is a very simplistic explanation and greater defect chemistry complexity is suggested by more recent work. Various authors have shown that vacancies are mobile and may result in vacancy clustering. Ceria nanoparticles are of particular interest because of the high activity and surface area of small particulates. The sensitivity of the cerium electronic band structure to environment would suggest that changes in the properties of ceria particles at nanoscale dimensions might be expected. Notably many authors report a lattice expansion with reducing particle size (largely confined to sub-10 nm particles). Most authors assign increased lattice dimensions to the presence of a surface stable Ce2O3 type layer at low nanoparticle dimensions. However, our understanding of oxide nanoparticles is limited and their full and quantitative characterisation offers serious challenges. In a series of chemical preparations by ourselves we see little evidence of a consistent model emerging to explain lattice parameter changes with nanoparticle size. Based on these results and a review of the literature it is worthwhile asking if a model of surface enhanced defect concentration is consistent with known cerium/cerium oxide chemistries, whether this is applicable to a range of different synthesis methods and if a more consistent description is possible. In Chapter one the science of cerium oxide is outlined including the crystal structure, defect chemistry and different oxidation states available. The uses and applications of cerium oxide are also discussed as well as modelling of the lattice parameter and the doping of the ceria lattice. Chapter two describes both the synthesis techniques and the analytical methods employed to execute this research. Chapter three focuses on high surface area ceria nano-particles and how these have been prepared using a citrate sol-gel precipitation method. Changes to the particle size have been made by calcining the ceria powders at different temperatures. X-ray diffraction methods were used to determine their lattice parameters. The particles sizes were also assessed using transmission electron microscopy (TEM), scanning electron microscopy (SEM), and BET, and, the lattice parameter was found to decrease with decreasing particle size. The results are discussed in light of the role played by surface tension effects. Chapter four describes the morphological and structural characterization of crystalline CeO2 nanoparticles prepared by forward and reverse precipitation techniques and compares these by powder x-ray diffraction (PXRD), nitrogen adsorption (BET) and high resolution transmission electron microscopy (HRTEM) analysis. The two routes give quite different materials although in both cases the products are essentially highly crystalline, dense particulates. It was found that the reverse precipitation technique gave the smallest crystallites with the narrowest size dispersion. This route also gave as-synthesised materials with higher surface areas. HRTEM confirmed the observations made from PXRD data and showed that the two methods resulted in quite different morphologies and surface chemistries. The forward route gives products with significantly greater densities of Ce3+ species compared to the reverse route. Data are explained using known precipitation chemistry and kinetic effects. Chapter five centres on the addition of terbia to ceria and has been investigated using XRD, XRF, XPS and TEM. Good solid solutions were formed across the entire composition range and there was no evidence for the formation of mixed phases or surface segregation over either the composition or temperature range investigated. Both Tb3+ and Tb4+ ions exist within the solution and the ratios of these cations are consistent with the addition of Tb8O15 to the fluorite ceria structure across a wide range of compositions. Local regions of anion vacancy ordering may be visible for small crystallites. There is no evidence of significant Ce3+ ion concentrations formed at the surface or in the bulk by the addition of terbia. The lattice parameter of these materials was seen to decrease with decreasing crystallite size. This is consistent with increased surface tension effects at small dimension. Chapter six reviews size related lattice parameter changes and surface defects in ceria nanocrystals. Ceria (CeO2) has many important applications, notably in catalysis. Many of its uses rely on generating nanodimensioned particles. Ceria has important redox chemistry where Ce4+ cations can be reversibly reduced to Ce3+ cations and associated anion vacancies. The significantly larger size of Ce3+ (compared with Ce4+) has been shown to result in lattice expansion. Many authors have observed lattice expansion in nanodimensioned crystals (nanocrystals), and these have been attributed to the presence of stabilized Ce3+ -anion vacancy combinations in these systems. Experimental results presented here show (i) that significant, but complex changes in the lattice parameter with size can occur in 2-500 nm crystallites, (ii) that there is a definitive relationship between defect chemistry and the lattice parameter in ceria nanocrystals, and (iii) that the stabilizing mechanism for the Ce3+ -anion vacancy defects at the surface of ceria nanocrystals is determined by the size, the surface status, and the analysis conditions. In this work, both lattice expansion and a more unusual lattice contraction in ultrafine nanocrystals are observed. The lattice deformations seen can be defined as a function of both the anion vacancy (hydroxyl) concentration in the nanocrystal and the intensity of the additional pressure imposed by the surface tension on the crystal. The expansion of lattice parameters in ceria nanocrystals is attributed to a number of factors, most notably, the presence of any hydroxyl moieties in the materials. Thus, a very careful understanding of the synthesis combined with characterization is required to understand the surface chemistry of ceria nanocrystals.