965 resultados para Diffusion Processes


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Energy prices are highly volatile and often feature unexpected spikes. It is the aim of this paper to examine whether the occurrence of these extreme price events displays any regularities that can be captured using an econometric model. Here we treat these price events as point processes and apply Hawkes and Poisson autoregressive models to model the dynamics in the intensity of this process.We use load and meteorological information to model the time variation in the intensity of the process. The models are applied to data from the Australian wholesale electricity market, and a forecasting exercise illustrates both the usefulness of these models and their limitations when attempting to forecast the occurrence of extreme price events.

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Airborne particles have been shown to be associated with a wide range of adverse health effects, which has led to a recent increase in medical research to gain better insight into their health effects. However, accurate evaluation of the exposure-dose-response relationship is highly dependent on the ability to track actual exposure levels of people to airborne particles. This is quite a complex task, particularly in relation to submicrometer and ultrafine particles, which can vary quite significantly in terms of particle surface area and number concentrations. Therefore, suitable monitors that can be worn for measuring personal exposure to these particles are needed. This paper presents an evaluation of the metrological performance of six diffusion charger sensors, NanoTracer (Philips Aerasense) monitors, when measuring particle number and surface area concentrations, as well as particle number distribution mean when compared to reference instruments. Tests in the laboratory (by generating monodisperse and polydisperse aerosols) and in the field (using natural ambient particles) were designed to evaluate the response of these devices under both steady-state and dynamics conditions. Results showed that the NanoTracers performed well when measuring steady state aerosols, however they strongly underestimated actual concentrations during dynamic response testing. The field experiments also showed that, when the majority of the particles were smaller than 20 nm, which occurs during particle formation events in the atmosphere, the NanoTracer underestimated number concentration quite significantly. Even though the NanoTracer can be used for personal monitoring of exposure to ultrafine particles, it also has limitations which need to be considered in order to provide meaningful results.

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Packaged software is pre-built with the intention of licensing it to users in domestic settings and work organisations. This thesis focuses upon the work organisation where packaged software has been characterised as one of the latest ‘solutions’ to the problems of information systems. The study investigates the packaged software selection process that has, to date, been largely viewed as objective and rational. In contrast, this interpretive study is based on a 21⁄2 year long field study of organisational experiences with packaged software selection at T.Co, a consultancy organisation based in the United Kingdom. Emerging from the iterative process of case study and action research is an alternative theory of packaged software selection. The research argues that packaged software selection is far from the rationalistic and linear process that previous studies suggest. Instead, the study finds that aspects of the traditional process of selection incorporating the activities of gathering requirements, evaluation and selection based on ‘best fit’ may or may not take place. Furthermore, even where these aspects occur they may not have equal weight or impact upon implementation and usage as may be expected. This is due to the influence of those multiple realities which originate from the organisational and market environments within which packages are created, selected and used, the lack of homogeneity in organisational contexts and the variously interpreted characteristics of the package in question.

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This paper aims to contribute to an understanding of what actually takes place during consulting engagements. It draws on data collected from a qualitative case study of eight engagements by a niche consultancy in Australia to describe how consultants actively engage boundary crossing processes to address knowledge boundaries encountered during formal interactions with clients. While consultants actively managed knowledge boundary processes during interactions, by applying techniques such as evoking an ‘ideal state’ for clients, the engagements also yielded many missed opportunities for knowledge transformation.

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Mathematical descriptions of birth–death–movement processes are often calibrated to measurements from cell biology experiments to quantify tissue growth rates. Here we describe and analyze a discrete model of a birth–death-movement process applied to a typical two–dimensional cell biology experiment. We present three different descriptions of the system: (i) a standard mean–field description which neglects correlation effects and clustering; (ii) a moment dynamics description which approximately incorporates correlation and clustering effects, and; (iii) averaged data from repeated discrete simulations which directly incorporates correlation and clustering effects. Comparing these three descriptions indicates that the mean–field and moment dynamics approaches are valid only for certain parameter regimes, and that both these descriptions fail to make accurate predictions of the system for sufficiently fast birth and death rates where the effects of spatial correlations and clustering are sufficiently strong. Without any method to distinguish between the parameter regimes where these three descriptions are valid, it is possible that either the mean–field or moment dynamics model could be calibrated to experimental data under inappropriate conditions, leading to errors in parameter estimation. In this work we demonstrate that a simple measurement of agent clustering and correlation, based on coordination number data, provides an indirect measure of agent correlation and clustering effects, and can therefore be used to make a distinction between the validity of the different descriptions of the birth–death–movement process.

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The aim of this paper is examine how firms renew their organisational capabilities based on micro organisational processes. Organisational capability development literature points to firms’ failure in capability renewal process. To overcome this inefficiency, it is proposed to integrate dynamic capability and ambidexterity perspectives by studying knowledge integration within product innovation. In this relation, applying micro perspective in studying technology diffusion within Iranian Auto industry revealed micro co-evolutionary relationships between knowledge integration within product innovation and capability development. Furthermore, based on near decomposability principals, the analysis suggested relationships among modularity of product architecture, modularity of organisational modularity and modularity of industry architecture in downstream and upstream value chain. Based on these micro-macro co evolutionary effects, capability development process underlying successful corporate entrepreneurship may be verified.

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Sugarcane bagasse is an abundant and sustainable resource, generated as a by-product of sugarcane milling. The cellulosic material within bagasse can be broken down into glucose molecules and fermented to produce ethanol, making it a promising feedstock for biofuel production. Mild acid pretreatment hydrolyses the hemicellulosic component of biomass, thus allowing enzymes greater access to the cellulosic substrate during saccharification. A particle-scale mathematical model describing the mild acid pretreatment of sugarcane bagasse has been developed, using a volume averaged framework. Discrete population-balance equations are used to characterise the polymer degradation kinetics, and diffusive effects account for mass transport within the cell wall of the bagasse. As the fibrous material hydrolyses over time, variations in the porosity of the cell wall and the downstream effects on the reaction kinetics are accounted for using conservation of volume arguments. Non-dimensionalization of the model equations reduces the number of parameters in the system to a set of four dimensionless ratios that compare the timescales of different reaction and diffusion events. Theoretical yield curves are compared to macroscopic experimental observations from the literature and inferences are made as to constraints on these “unknown” parameters. These results enable connections to be made between experimental data and the underlying thermodynamics of acid pretreatment. Consequently, the results suggest that data-fitting techniques used to obtain kinetic parameters should be carefully applied, with prudent consideration given to the chemical and physiological processes being modeled.

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The mean action time is the mean of a probability density function that can be interpreted as a critical time, which is a finite estimate of the time taken for the transient solution of a reaction-diffusion equation to effectively reach steady state. For high-variance distributions, the mean action time under-approximates the critical time since it neglects to account for the spread about the mean. We can improve our estimate of the critical time by calculating the higher moments of the probability density function, called the moments of action, which provide additional information regarding the spread about the mean. Existing methods for calculating the nth moment of action require the solution of n nonhomogeneous boundary value problems which can be difficult and tedious to solve exactly. Here we present a simplified approach using Laplace transforms which allows us to calculate the nth moment of action without solving this family of boundary value problems and also without solving for the transient solution of the underlying reaction-diffusion problem. We demonstrate the generality of our method by calculating exact expressions for the moments of action for three problems from the biophysics literature. While the first problem we consider can be solved using existing methods, the second problem, which is readily solved using our approach, is intractable using previous techniques. The third problem illustrates how the Laplace transform approach can be used to study coupled linear reaction-diffusion equations.

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Monte Carlo simulations were used to investigate the relationship between the morphological characteristics and the diffusion tensor (DT) of partially aligned networks of cylindrical fibres. The orientation distributions of the fibres in each network were approximately uniform within a cone of a given semi-angle (θ0). This semi-angle was used to control the degree of alignment of the fibres. The networks studied ranged from perfectly aligned (θ0 = 0) to completely disordered (θ0 = 90°). Our results are qualitatively consistent with previous numerical models in the overall behaviour of the DT. However, we report a non-linear relationship between the fractional anisotropy (FA) of the DT and collagen volume fraction, which is different to the findings from previous work. We discuss our results in the context of diffusion tensor imaging of articular cartilage. We also demonstrate how appropriate diffusion models have the potential to enable quantitative interpretation of the experimentally measured diffusion-tensor FA in terms of collagen fibre alignment distributions.

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Construction contracts often provide that the decision of an independent certifier is final and binding. The effect of a contractual term like this has been debated in the courts over time. This paper considers the binding nature of certificates in the context of traditional construction contract arrangements and also considers the implications for more complex contracts like those entered into to facilitate public private partnerships. This article considers the response of the courts and the drafting implications and argues that a different focus would be advantageous.

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The ability of metals to store or trap considerable amounts of energy, and thus exist in a non-equilibrium or metastable state, is very well known in metallurgy; however, such behaviour, which is intimately connected with the defect character of metals, has been largely ignored in noble metal surface electrochemistry. Techniques for generating unusually high energy surface states for gold, and the unusual voltammetric responses of such states, are outlined. The surprisingly high (and complex) electrocatalytic activity of gold in aqueous media is attributed to the presence of a range of such non-equilibrium states as the vital entities at active sites on conventional gold surfaces. The possible relevance of these ideas to account for the remarkable catalytic activity of oxide-supported gold microparticles is briefly outlined.

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Semi-conducting phase I CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane), which is of considerable interest as a switching device for memory storage materials, can be electrocrystallized from CH3CN via two distinctly different pathways when TCNQ is reduced to TCNQ˙− in the presence of [Cu(MeCN)4]+. The first pathway, identified in earlier studies, occurs at potentials where TCNQ is reduced to TCNQ˙− and involves a nucleation–growth mechanism at preferred sites on the electrode to produce arrays of well separated large branched needle-shaped phase I CuTCNQ crystals. The second pathway, now identified at more negative potentials, generates much smaller needle-shaped phase I CuTCNQ crystals. These electrocrystallize on parts of the surface not occupied in the initial process and give rise to film-like characteristics. This process is attributed to the reduction of Cu+[(TCNQ˙−)(TCNQ)] or a stabilised film of TCNQ via a solid–solid conversion process, which also involves ingress of Cu+via a nucleation–growth mechanism. The CuTCNQ surface area coverage is extensive since it occurs at all areas of the electrode and not just at defect sites that dominate the crystal formation sites for the first pathway. Infrared spectra, X-ray diffraction, surface plasmon resonance, quartz crystal microbalance, scanning electron microscopy and optical image data all confirm that two distinctly different pathways are available to produce the kinetically-favoured and more highly conducting phase I CuTCNQ solid, rather than the phase II material.

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Unlike the case with other divalent transition metal M\[TCNQ](2)(H(2)O)(2) (M = Fe, Co, Ni) analogues, the electrochemically induced solid-solid phase interconversion of TCNQ microcrystals (TCNQ = 7,7,8,8-tetracyanoquinodimethane) to Mn\[TCNQ](2)(H(2)O)(2) occurs via two voltammetrically distinct, time dependent processes that generate the coordination polymer in nanofiber or rod-like morphologies. Careful manipulation of the voltammetric scan rate, electrolysis time, Mn(2+)((aq)) concentration, and the method of electrode modification with solid TCNQ allows selective generation of either morphology. Detailed ex situ spectroscopic (IR, Raman), scanning electron microscopy (SEM), and X-ray powder diffraction (XRD) characterization clearly establish that differences in the electrochemically synthesized Mn-TCNQ material are confined to morphology. Generation of the nanofiber form is proposed to take place rapidly via formation and reduction of a Mn-stabilized anionic dimer intermediate, \[(Mn(2+))(TCNQ-TCNQ)(2)(*-)], formed as a result of radical-substrate coupling between TCNQ(*-) and neutral TCNQ, accompanied by ingress of Mn(2+) ions from the aqueous solution at the triple phase TCNQ/electrode/electrolyte boundary. In contrast, formation of the nanorod form is much slower and is postulated to arise from disproportionation of the \[(Mn(2+))(TCNQ-TCNQ)(*-)(2)] intermediate. Thus, identification of the time dependent pathways via the solid-solid state electrochemical approach allows the crystal size of the Mn\[TCNQ](2)(H(2)O)(2) material to be tuned and provides new mechanistic insights into the formation of different morphologies.

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The creation of electrocatalysts based on noble metals has received a significant amount of research interest due to their extensive use as fuel cell catalysts and electrochemical sensors. There have been many attempts to improve the activity of these metals through creating nanostructures, as well as post-synthesis treatments based on chemical, electrochemical, sonochemical and thermal approaches. In many instances these methods result in a material with active surface states, which can be considered to be adatoms or clusters of atoms on the surface that have a low lattice co-ordination number making them more prone to electrochemical oxidation at a wide range of potentials that are significantly less positive than those of their bulk metal counterparts. This phenomenon has been termed pre-monolayer oxidation and has been reported to occur on a range of metallic surfaces. In this work we present findings on the presence of active sites on Pd that has been: evaporated as a thin film; electrodeposited as nanostructures; as well as commercially available Pd nanoparticles supported on carbon. Significantly, advantage is taken of the low oxidation potential of these active sites whereby bimetallic surfaces are created by the spontaneous deposition of Ag from AgNO3 to generate Pd/Ag surfaces. Interestingly this approach does not increase the surface area of the original metal but has significant implications for its further use as an electrode material. It results in the inhibition or promotion of electrocatalytic activity which is highly dependent on the reaction of interest. As a general approach the decoration of active catalytic materials with less active metals for a particular reaction also opens up the possibility of investigating the role of the initially present active sites on the surface and identifying the degree to which they are responsible for electrocatalytic activity.

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We investigate the physical origins of etching observed during Ti diffusion. The relationship between observed etch depth and water vapor content in the annealing environment is quantified. The dynamics of the etching process are also identified. It is discovered that water vapor content is essential for etching and that there is a characteristic delay before etching is observed. From these observations we can conclude that the process is electrochemical in nature with ionic defects diffusing into the Ti strip from the lithium niobate and these defects catalyzing the dissociation of water into reactive ions.