Theoretical investigation of mechanisms of formation and interaction of nanoparticles

In this thesis an investigation into theoretical models for formation and interaction of nanoparticles is presented. The work presented includes a literature review of current models followed by a series of five chapters of original research. This thesis has been submitted in partial fulfilment of the requirements for the degree of doctor of philosophy by publication and therefore each of the five chapters consist of a peer-reviewed journal article. The thesis is then concluded with a discussion of what has been achieved during the PhD candidature, the potential applications for this research and ways in which the research could be extended in the future. In this thesis we explore stochastic models pertaining to the interaction and evolution mechanisms of nanoparticles. In particular, we explore in depth the stochastic evaporation of molecules due to thermal activation and its ultimate effect on nanoparticles sizes and concentrations. Secondly, we analyse the thermal vibrations of nanoparticles suspended in a fluid and subject to standing oscillating drag forces (as would occur in a standing sound wave) and finally on lattice surfaces in the presence of high heat gradients. We have described in this thesis a number of new models for the description of multicompartment networks joined by a multiple, stochastically evaporating, links. The primary motivation for this work is in the description of thermal fragmentation in which multiple molecules holding parts of a carbonaceous nanoparticle may evaporate. Ultimately, these models predict the rate at which the network or aggregate fragments into smaller networks/aggregates and with what aggregate size distribution. The models are highly analytic and describe the fragmentation of a link holding multiple bonds using Markov processes that best describe different physical situations and these processes have been analysed using a number of mathematical methods. The fragmentation of the network/aggregate is then predicted using combinatorial arguments. Whilst there is some scepticism in the scientific community pertaining to the proposed mechanism of thermal fragmentation,we have presented compelling evidence in this thesis supporting the currently proposed mechanism and shown that our models can accurately match experimental results. This was achieved using a realistic simulation of the fragmentation of the fractal carbonaceous aggregate structure using our models. Furthermore, in this thesis a method of manipulation using acoustic standing waves is investigated. In our investigation we analysed the effect of frequency and particle size on the ability for the particle to be manipulated by means of a standing acoustic wave. In our results, we report the existence of a critical frequency for a particular particle size. This frequency is inversely proportional to the Stokes time of the particle in the fluid. We also find that for large frequencies the subtle Brownian motion of even larger particles plays a significant role in the efficacy of the manipulation. This is due to the decreasing size of the boundary layer between acoustic nodes. Our model utilises a multiple time scale approach to calculating the long term effects of the standing acoustic field on the particles that are interacting with the sound. These effects are then combined with the effects of Brownian motion in order to obtain a complete mathematical description of the particle dynamics in such acoustic fields. Finally, in this thesis, we develop a numerical routine for the description of "thermal tweezers". Currently, the technique of thermal tweezers is predominantly theoretical however there has been a handful of successful experiments which demonstrate the effect it practise. Thermal tweezers is the name given to the way in which particles can be easily manipulated on a lattice surface by careful selection of a heat distribution over the surface. Typically, the theoretical simulations of the effect can be rather time consuming with supercomputer facilities processing data over days or even weeks. Our alternative numerical method for the simulation of particle distributions pertaining to the thermal tweezers effect use the Fokker-Planck equation to derive a quick numerical method for the calculation of the effective diffusion constant as a result of the lattice and the temperature. We then use this diffusion constant and solve the diffusion equation numerically using the finite volume method. This saves the algorithm from calculating many individual particle trajectories since it is describes the flow of the probability distribution of particles in a continuous manner. The alternative method that is outlined in this thesis can produce a larger quantity of accurate results on a household PC in a matter of hours which is much better than was previously achieveable.

The effect of prolonged reading on visual functions and reading performance in students with low vision

This study is the first to investigate the effect of prolonged reading on reading performance and visual functions in students with low vision. The study focuses on one of the most common modes of achieving adequate magnification for reading by students with low vision, their close reading distance (proximal or relative distance magnification). Close reading distances impose high demands on near visual functions, such as accommodation and convergence. Previous research on accommodation in children with low vision shows that their accommodative responses are reduced compared to normal vision. In addition, there is an increased lag of accommodation for higher stimulus levels as may occur at close reading distance. Reduced accommodative responses in low vision and higher lag of accommodation at close reading distances together could impact on reading performance of students with low vision especially during prolonged reading tasks. The presence of convergence anomalies could further affect reading performance. Therefore, the aims of the present study were 1) To investigate the effect of prolonged reading on reading performance in students with low vision 2) To investigate the effect of prolonged reading on visual functions in students with low vision. This study was conducted as cross-sectional research on 42 students with low vision and a comparison group of 20 students with normal vision, aged 7 to 20 years. The students with low vision had vision impairments arising from a range of causes and represented a typical group of students with low vision, with no significant developmental delays, attending school in Brisbane, Australia. All participants underwent a battery of clinical tests before and after a prolonged reading task. An initial reading-specific history and pre-task measurements that included Bailey-Lovie distance and near visual acuities, Pelli-Robson contrast sensitivity, ocular deviations, sensory fusion, ocular motility, near point of accommodation (pull-away method), accuracy of accommodation (Monocular Estimation Method (MEM)) retinoscopy and Near Point of Convergence (NPC) (push-up method) were recorded for all participants. Reading performance measures were Maximum Oral Reading Rates (MORR), Near Text Visual Acuity (NTVA) and acuity reserves using Bailey-Lovie text charts. Symptoms of visual fatigue were assessed using the Convergence Insufficiency Symptom Survey (CISS) for all participants. Pre-task measurements of reading performance and accuracy of accommodation and NPC were compared with post-task measurements, to test for any effects of prolonged reading. The prolonged reading task involved reading a storybook silently for at least 30 minutes. The task was controlled for print size, contrast, difficulty level and content of the reading material. Silent Reading Rate (SRR) was recorded every 2 minutes during prolonged reading. Symptom scores and visual fatigue scores were also obtained for all participants. A visual fatigue analogue scale (VAS) was used to assess visual fatigue during the task, once at the beginning, once at the middle and once at the end of the task. In addition to the subjective assessments of visual fatigue, tonic accommodation was monitored using a photorefractor (PlusoptiX CR03™) every 6 minutes during the task, as an objective assessment of visual fatigue. Reading measures were done at the habitual reading distance of students with low vision and at 25 cms for students with normal vision. The initial history showed that the students with low vision read for significantly shorter periods at home compared to the students with normal vision. The working distances of participants with low vision ranged from 3-25 cms and half of them were not using any optical devices for magnification. Nearly half of the participants with low vision were able to resolve 8-point print (1M) at 25 cms. Half of the participants in the low vision group had ocular deviations and suppression at near. Reading rates were significantly reduced in students with low vision compared to those of students with normal vision. In addition, there were a significantly larger number of participants in the low vision group who could not sustain the 30-minute task compared to the normal vision group. However, there were no significant changes in reading rates during or following prolonged reading in either the low vision or normal vision groups. Individual changes in reading rates were independent of their baseline reading rates, indicating that the changes in reading rates during prolonged reading cannot be predicted from a typical clinical assessment of reading using brief reading tasks. Contrary to previous reports the silent reading rates of the students with low vision were significantly lower than their oral reading rates, although oral and silent reading was assessed using different methods. Although the visual acuity, contrast sensitivity, near point of convergence and accuracy of accommodation were significantly poorer for the low vision group compared to those of the normal vision group, there were no significant changes in any of these visual functions following prolonged reading in either group. Interestingly, a few students with low vision (n =10) were found to be reading at a distance closer than their near point of accommodation. This suggests a decreased sensitivity to blur. Further evaluation revealed that the equivalent intrinsic refractive errors (an estimate of the spherical dioptirc defocus which would be expected to yield a patient’s visual acuity in normal subjects) were significantly larger for the low vision group compared to those of the normal vision group. As expected, accommodative responses were significantly reduced for the low vision group compared to the expected norms, which is consistent with their close reading distances, reduced visual acuity and contrast sensitivity. For those in the low vision group who had an accommodative error exceeding their equivalent intrinsic refractive errors, a significant decrease in MORR was found following prolonged reading. The silent reading rates however were not significantly affected by accommodative errors in the present study. Suppression also had a significant impact on the changes in reading rates during prolonged reading. The participants who did not have suppression at near showed significant decreases in silent reading rates during and following prolonged reading. This impact of binocular vision at near on prolonged reading was possibly due to the high demands on convergence. The significant predictors of MORR in the low vision group were age, NTVA, reading interest and reading comprehension, accounting for 61.7% of the variances in MORR. SRR was not significantly influenced by any factors, except for the duration of the reading task sustained; participants with higher reading rates were able to sustain a longer reading duration. In students with normal vision, age was the only predictor of MORR. Participants with low vision also reported significantly greater visual fatigue compared to the normal vision group. Measures of tonic accommodation however were little influenced by visual fatigue in the present study. Visual fatigue analogue scores were found to be significantly associated with reading rates in students with low vision and normal vision. However, the patterns of association between visual fatigue and reading rates were different for SRR and MORR. The participants with low vision with higher symptom scores had lower SRRs and participants with higher visual fatigue had lower MORRs. As hypothesized, visual functions such as accuracy of accommodation and convergence did have an impact on prolonged reading in students with low vision, for students whose accommodative errors were greater than their equivalent intrinsic refractive errors, and for those who did not suppress one eye. Those students with low vision who have accommodative errors higher than their equivalent intrinsic refractive errors might significantly benefit from reading glasses. Similarly, considering prisms or occlusion for those without suppression might reduce the convergence demands in these students while using their close reading distances. The impact of these prescriptions on reading rates, reading interest and visual fatigue is an area of promising future research. Most importantly, it is evident from the present study that a combination of factors such as accommodative errors, near point of convergence and suppression should be considered when prescribing reading devices for students with low vision. Considering these factors would also assist rehabilitation specialists in identifying those students who are likely to experience difficulty in prolonged reading, which is otherwise not reflected during typical clinical reading assessments.

Semi-analytic method of contact modelling

An algorithm to improve the accuracy and stability of rigid-body contact force calculation is presented. The algorithm uses a combination of analytic solutions and numerical methods to solve a spring-damper differential equation typical of a contact model. The solution method employs the recently proposed patch method, which especially suits the spring-damper differential equations. The resulting semi-analytic solution reduces the stiffness of the differential equations, while performing faster than conventional alternatives.

Re-conceptualising IS function's support performance : a preliminary model

While IS function has gained widespread attention for over two decades, there is little consensus among information systems (IS) researchers and practitioners on how best to evaluate IS function's support performance. This paper reports on preliminary findings of a larger research effort proceeds from a central interest in the importance of evaluating IS function's support in organisations. This study is the first that attempts to re-conceptualise and conceive evaluate IS function's support as a multi- dimensional formative construct. We argue that a holistic measure for evaluating evaluate IS function's support should consist of dimensions that together assess the variety of the support functions and the quality of the support services provided to end-users. Thus, the proposed model consists of two halves, "Variety" and "Quality" within which resides seven dimensions. The Variety half includes five dimensions: Training; Documentation; Data- related Support, Software-related Support; and Hardware-related Support. The Quality half includes two dimensions: IS Support Staff and Support Services Performance. The proposed model is derived using a directed content analysis of 83 studies; from top IS outlets, employing the characteristics of the analytic theory and consistent with formative construct development procedures.

Novel analytical and numerical methods for solving fractional dynamical systems

During the past three decades, the subject of fractional calculus (that is, calculus of integrals and derivatives of arbitrary order) has gained considerable popularity and importance, mainly due to its demonstrated applications in numerous diverse and widespread fields in science and engineering. For example, fractional calculus has been successfully applied to problems in system biology, physics, chemistry and biochemistry, hydrology, medicine, and finance. In many cases these new fractional-order models are more adequate than the previously used integer-order models, because fractional derivatives and integrals enable the description of the memory and hereditary properties inherent in various materials and processes that are governed by anomalous diffusion. Hence, there is a growing need to find the solution behaviour of these fractional differential equations. However, the analytic solutions of most fractional differential equations generally cannot be obtained. As a consequence, approximate and numerical techniques are playing an important role in identifying the solution behaviour of such fractional equations and exploring their applications. The main objective of this thesis is to develop new effective numerical methods and supporting analysis, based on the finite difference and finite element methods, for solving time, space and time-space fractional dynamical systems involving fractional derivatives in one and two spatial dimensions. A series of five published papers and one manuscript in preparation will be presented on the solution of the space fractional diffusion equation, space fractional advectiondispersion equation, time and space fractional diffusion equation, time and space fractional Fokker-Planck equation with a linear or non-linear source term, and fractional cable equation involving two time fractional derivatives, respectively. One important contribution of this thesis is the demonstration of how to choose different approximation techniques for different fractional derivatives. Special attention has been paid to the Riesz space fractional derivative, due to its important application in the field of groundwater flow, system biology and finance. We present three numerical methods to approximate the Riesz space fractional derivative, namely the L1/ L2-approximation method, the standard/shifted Gr¨unwald method, and the matrix transform method (MTM). The first two methods are based on the finite difference method, while the MTM allows discretisation in space using either the finite difference or finite element methods. Furthermore, we prove the equivalence of the Riesz fractional derivative and the fractional Laplacian operator under homogeneous Dirichlet boundary conditions – a result that had not previously been established. This result justifies the aforementioned use of the MTM to approximate the Riesz fractional derivative. After spatial discretisation, the time-space fractional partial differential equation is transformed into a system of fractional-in-time differential equations. We then investigate numerical methods to handle time fractional derivatives, be they Caputo type or Riemann-Liouville type. This leads to new methods utilising either finite difference strategies or the Laplace transform method for advancing the solution in time. The stability and convergence of our proposed numerical methods are also investigated. Numerical experiments are carried out in support of our theoretical analysis. We also emphasise that the numerical methods we develop are applicable for many other types of fractional partial differential equations.

A process for the management of physical infrastructure

Physical infrastructure assets are important components of our society and our economy. They are usually designed to last for many years, are expected to be heavily used during their lifetime, carry considerable load, and are exposed to the natural environment. They are also normally major structures, and therefore present a heavy investment, requiring constant management over their life cycle to ensure that they perform as required by their owners and users. Given a complex and varied infrastructure life cycle, constraints on available resources, and continuing requirements for effectiveness and efficiency, good management of infrastructure is important. While there is often no one best management approach, the choice of options is improved by better identification and analysis of the issues, by the ability to prioritise objectives, and by a scientific approach to the analysis process. The abilities to better understand the effect of inputs in the infrastructure life cycle on results, to minimise uncertainty, and to better evaluate the effect of decisions in a complex environment, are important in allocating scarce resources and making sound decisions. Through the development of an infrastructure management modelling and analysis methodology, this thesis provides a process that assists the infrastructure manager in the analysis, prioritisation and decision making process. This is achieved through the use of practical, relatively simple tools, integrated in a modular flexible framework that aims to provide an understanding of the interactions and issues in the infrastructure management process. The methodology uses a combination of flowcharting and analysis techniques. It first charts the infrastructure management process and its underlying infrastructure life cycle through the time interaction diagram, a graphical flowcharting methodology that is an extension of methodologies for modelling data flows in information systems. This process divides the infrastructure management process over time into self contained modules that are based on a particular set of activities, the information flows between which are defined by the interfaces and relationships between them. The modular approach also permits more detailed analysis, or aggregation, as the case may be. It also forms the basis of ext~nding the infrastructure modelling and analysis process to infrastructure networks, through using individual infrastructure assets and their related projects as the basis of the network analysis process. It is recognised that the infrastructure manager is required to meet, and balance, a number of different objectives, and therefore a number of high level outcome goals for the infrastructure management process have been developed, based on common purpose or measurement scales. These goals form the basis of classifYing the larger set of multiple objectives for analysis purposes. A two stage approach that rationalises then weights objectives, using a paired comparison process, ensures that the objectives required to be met are both kept to the minimum number required and are fairly weighted. Qualitative variables are incorporated into the weighting and scoring process, utility functions being proposed where there is risk, or a trade-off situation applies. Variability is considered important in the infrastructure life cycle, the approach used being based on analytical principles but incorporating randomness in variables where required. The modular design of the process permits alternative processes to be used within particular modules, if this is considered a more appropriate way of analysis, provided boundary conditions and requirements for linkages to other modules, are met. Development and use of the methodology has highlighted a number of infrastructure life cycle issues, including data and information aspects, and consequences of change over the life cycle, as well as variability and the other matters discussed above. It has also highlighted the requirement to use judgment where required, and for organisations that own and manage infrastructure to retain intellectual knowledge regarding that infrastructure. It is considered that the methodology discussed in this thesis, which to the author's knowledge has not been developed elsewhere, may be used for the analysis of alternatives, planning, prioritisation of a number of projects, and identification of the principal issues in the infrastructure life cycle.

Differences in the performance of safety performance functions estimated for total crash count and for crash count by crash type

In recent years the development and use of crash prediction models for roadway safety analyses have received substantial attention. These models, also known as safety performance functions (SPFs), relate the expected crash frequency of roadway elements (intersections, road segments, on-ramps) to traffic volumes and other geometric and operational characteristics. A commonly practiced approach for applying intersection SPFs is to assume that crash types occur in fixed proportions (e.g., rear-end crashes make up 20% of crashes, angle crashes 35%, and so forth) and then apply these fixed proportions to crash totals to estimate crash frequencies by type. As demonstrated in this paper, such a practice makes questionable assumptions and results in considerable error in estimating crash proportions. Through the use of rudimentary SPFs based solely on the annual average daily traffic (AADT) of major and minor roads, the homogeneity-in-proportions assumption is shown not to hold across AADT, because crash proportions vary as a function of both major and minor road AADT. For example, with minor road AADT of 400 vehicles per day, the proportion of intersecting-direction crashes decreases from about 50% with 2,000 major road AADT to about 15% with 82,000 AADT. Same-direction crashes increase from about 15% to 55% for the same comparison. The homogeneity-in-proportions assumption should be abandoned, and crash type models should be used to predict crash frequency by crash type. SPFs that use additional geometric variables would only exacerbate the problem quantified here. Comparison of models for different crash types using additional geometric variables remains the subject of future research.

User-web interactions : how wholistic/analytic web users search the web?

User-Web interactions have emerged as an important research in the field of information science. In this study, we examine extensively the Web searching performed by general users. Our goal is to investigate the effects of users’ cognitive styles on their Web search behavior in relation to two broad components: Information Searching and Information Processing Approaches. We use questionnaires, a measure of cognitive style, Web session logs and think-aloud as the data collection instruments. Our study findings show wholistic Web users tend to adopt a top-down approach to Web searching, where the users searched for a generic topic, and then reformulate their queries to search for specific information. They tend to prefer reading to process information. Analytic users tend to prefer a bottom-up approach to information searching and they process information by scanning search result pages.

Improving governance : practical methods and an analytic framework for the enhancement of democracy

Seven endemic governance problems are shown to be currently present in governments around the globe and at any level of government as well (for example municipal, federal). These problems have their roots traced back through more than two thousand years of political, specifically ‘democratic’, history. The evidence shows that accountability, transparency, corruption, representation, campaigning methods, constitutionalism and long-term goals were problematic for the ancient Athenians as well as modern international democratisation efforts encompassing every major global region. Why then, given the extended time period humans have had to deal with these problems, are they still present? At least part of the answer to this question is that philosophers, academics and NGOs as well as MNOs have only approached these endemic problems in a piecemeal manner with a skewed perspective on democracy. Their works have also been subject to the ebbs and flows of human history which essentially started and stopped periods of thinking. In order to approach the investigation of endemic problems in relation to democracy (as the overall quest of this thesis was to generate prescriptive results for the improvement of democratic government), it was necessary to delineate what exactly is being written about when using the term ‘democracy’. It is common knowledge that democracy has no one specific definition or practice, even though scholars and philosophers have been attempting to create a definition for generations. What is currently evident, is that scholars are not approaching democracy in an overly simplified manner (that is, it is government for the people, by the people) but, rather, are seeking the commonalities that democracies share, in other words, those items which are common to all things democratic. Following that specific line of investigation, the major practiced and theoretical versions of democracy were thematically analysed. After that, their themes were collapsed into larger categories, at which point the larger categories were comparatively analysed with the practiced and theoretical versions of democracy. Four democratic ‘particles’ (selecting officials, law, equality and communication) were seen to be present in all practiced and theoretical democratic styles. The democratic particles fused with a unique investigative perspective and in-depth political study created a solid conceptualisation of democracy. As such, it is argued that democracy is an ever-present element of any state government, ‘democratic’ or not, and the particles are the bodies which comprise the democratic element. Frequency- and proximity-based analyses showed that democratic particles are related to endemic problems in international democratisation discourse. The linkages between democratic particles and endemic problems were also evident during the thematic analysis as well historical review. This ultimately led to the viewpoint that if endemic problems are mitigated the act may improve democratic particles which might strengthen the element of democracy in the governing apparatus of any state. Such may actively minimise or wholly displace inefficient forms of government, leading to a government specifically tailored to the population it orders. Once the theoretical and empirical goals were attained, this thesis provided some prescriptive measures which government, civil society, academics, professionals and/or active citizens can use to mitigate endemic problems (in any country and at any level of government) so as to improve the human condition via better democratic government.

Corrupt police networks : uncovering hidden relationship patterns, functions and roles

This article applies social network analysis techniques to a case study of police corruption in order to produce findings which will assist in corruption prevention and investigation. Police corruption is commonly studied but rarely are sophisticated tools of analyse engaged to add rigour to the field of study. This article analyses the ‘First Joke’ a systemic and long lasting corruption network in the Queensland Police Force, a state police agency in Australia. It uses the data obtained from a commission of inquiry which exposed the network and develops hypotheses as to the nature of the networks structure based on existing literature into dark networks and criminal networks. These hypotheses are tested by entering the data into UCINET and analysing the outcomes through social network analysis measures of average path distance, centrality and density. The conclusions reached show that the network has characteristics not predicted by the literature.