Mathematical modelling of LiFePO4 cathodes

LiFePO4 is a commercially available battery material with good theoretical discharge capacity, excellent cycle life and increased safety compared with competing Li-ion chemistries. It has been the focus of considerable experimental and theoretical scrutiny in the past decade, resulting in LiFePO4 cathodes that perform well at high discharge rates. This scrutiny has raised several questions about the behaviour of LiFePO4 material during charge and discharge. In contrast to many other battery chemistries that intercalate homogeneously, LiFePO4 can phase-separate into highly and lowly lithiated phases, with intercalation proceeding by advancing an interface between these two phases. The main objective of this thesis is to construct mathematical models of LiFePO4 cathodes that can be validated against experimental discharge curves. This is in an attempt to understand some of the multi-scale dynamics of LiFePO4 cathodes that can be difficult to determine experimentally. The first section of this thesis constructs a three-scale mathematical model of LiFePO4 cathodes that uses a simple Stefan problem (which has been used previously in the literature) to describe the assumed phase-change. LiFePO4 crystals have been observed agglomerating in cathodes to form a porous collection of crystals and this morphology motivates the use of three size-scales in the model. The multi-scale model developed validates well against experimental data and this validated model is then used to examine the role of manufacturing parameters (including the agglomerate radius) on battery performance. The remainder of the thesis is concerned with investigating phase-field models as a replacement for the aforementioned Stefan problem. Phase-field models have recently been used in LiFePO4 and are a far more accurate representation of experimentally observed crystal-scale behaviour. They are based around the Cahn-Hilliard-reaction (CHR) IBVP, a fourth-order PDE with electrochemical (flux) boundary conditions that is very stiff and possesses multiple time and space scales. Numerical solutions to the CHR IBVP can be difficult to compute and hence a least-squares based Finite Volume Method (FVM) is developed for discretising both the full CHR IBVP and the more traditional Cahn-Hilliard IBVP. Phase-field models are subject to two main physicality constraints and the numerical scheme presented performs well under these constraints. This least-squares based FVM is then used to simulate the discharge of individual crystals of LiFePO4 in two dimensions. This discharge is subject to isotropic Li+ diffusion, based on experimental evidence that suggests the normally orthotropic transport of Li+ in LiFePO4 may become more isotropic in the presence of lattice defects. Numerical investigation shows that two-dimensional Li+ transport results in crystals that phase-separate, even at very high discharge rates. This is very different from results shown in the literature, where phase-separation in LiFePO4 crystals is suppressed during discharge with orthotropic Li+ transport. Finally, the three-scale cathodic model used at the beginning of the thesis is modified to simulate modern, high-rate LiFePO4 cathodes. High-rate cathodes typically do not contain (large) agglomerates and therefore a two-scale model is developed. The Stefan problem used previously is also replaced with the phase-field models examined in earlier chapters. The results from this model are then compared with experimental data and fit poorly, though a significant parameter regime could not be investigated numerically. Many-particle effects however, are evident in the simulated discharges, which match the conclusions of recent literature. These effects result in crystals that are subject to local currents very different from the discharge rate applied to the cathode, which impacts the phase-separating behaviour of the crystals and raises questions about the validity of using cathodic-scale experimental measurements in order to determine crystal-scale behaviour.

Fast formulas for computing cryptographic pairings

The most powerful known primitive in public-key cryptography is undoubtedly elliptic curve pairings. Upon their introduction just over ten years ago the computation of pairings was far too slow for them to be considered a practical option. This resulted in a vast amount of research from many mathematicians and computer scientists around the globe aiming to improve this computation speed. From the use of modern results in algebraic and arithmetic geometry to the application of foundational number theory that dates back to the days of Gauss and Euler, cryptographic pairings have since experienced a great deal of improvement. As a result, what was an extremely expensive computation that took several minutes is now a high-speed operation that takes less than a millisecond. This thesis presents a range of optimisations to the state-of-the-art in cryptographic pairing computation. Both through extending prior techniques, and introducing several novel ideas of our own, our work has contributed to recordbreaking pairing implementations.

Metal ion levels post unilateral primary Exeter total hip replacement

There has been much discussion and controversy in the media recently regarding metal toxicity following large head metal on metal (MoM) total hip replacement (THR). Patients have been reported as having hugely elevated levels of metal ions with, at times, devastating systemic, neurolgical and/or orthopaedic sequelae. However, no direct correlation between metal ion level and severity of metallosis has yet been defined. Normative levels of metal ions in well functioning, non Cobalt-Chrome hips have also not been defined to date. The Exeter total hip replacement contains no Cobalt-Chrome (Co-Cr) as it is made entirely from stainless steel. However, small levels of these metals may be present in the modular head of the prosthesis, and their effect on metal ion levels in the well functioning patient has not been investigated. We proposed to define the “normal” levels of metal ions detected by blood test in 20 well functioning patients at a minimum 1 year post primary Exeter total hip replacement, where the patient had had only one joint replaced. Presently, accepted normal levels of blood Chromium are 10–100 nmol/L and plasma Cobalt are 0–20 nmol/L. The UK Modern Humanities Research Association (MHRA) has suggested that levels of either Cobalt or Chromium above 7 ppb (equivalent to 135 nmol/L for Chromium and 120 nmol/L for Cobalt) may be significant. Below this level it is indicated that significant soft tissue reaction and tissue damage is less likely and the risk of implant failure is reduced. Hips were a mixture of cemented and hybrid procedures performed by two experienced orthopaedic consultants. Seventy percent were female, with a mixture of head sizes used. In our cohort, there were no cases where the blood Chromium levels were above the normal range, and in more than 70% of cases, levels were below recordable levels. There were also no cases of elevated plasma Cobalt levels, and in 35% of cases, levels were negligible. We conclude that the implantation with an Exeter total hip replacement does not lead to elevation of blood metal ion levels.

Safety enhancement of water-filled road safety barrier using interaction of composite materials

Road safety barriers are used to redirect traffic at roadside work-zones. When filled with water, these barriers are able to withstand low to moderate impact speeds up to 50kmh-1. Despite this feature, Portable Water-filled barriers (PWFB) face challenges such as large lateral displacements, tearing and breakage during impact; especially at higher speeds. This study explores the use of composite action to enhance the crashworthiness of PWFBs and enable their usage at higher speeds. Initially, energy absorption capability of water in PWFB is investigated. Then, composite action of the PWFB with the introduction of steel frame is considered to evaluate its enhanced impact performance. Findings of the study show that the initial height of the impact must be lower than the free surface level of water in a PWFB in order for the water to provide significant crash energy absorption. In general, an impact of a road barrier with 80% filled is a good estimation. Furthermore, the addition of a composite structure greatly reduces the probability of tearing by decreasing the strain and impact energy transferred to the shell container. This allows the water to remain longer in the barrier to absorb energy via inertial displacements and sloshing response. Information from this research will aid in the design of new generation roadside safety structures aimed to increase safety in modern roadways.

Robust image hash functions using higher order spectra

Robust hashing is an emerging field that can be used to hash certain data types in applications unsuitable for traditional cryptographic hashing methods. Traditional hashing functions have been used extensively for data/message integrity, data/message authentication, efficient file identification and password verification. These applications are possible because the hashing process is compressive, allowing for efficient comparisons in the hash domain but non-invertible meaning hashes can be used without revealing the original data. These techniques were developed with deterministic (non-changing) inputs such as files and passwords. For such data types a 1-bit or one character change can be significant, as a result the hashing process is sensitive to any change in the input. Unfortunately, there are certain applications where input data are not perfectly deterministic and minor changes cannot be avoided. Digital images and biometric features are two types of data where such changes exist but do not alter the meaning or appearance of the input. For such data types cryptographic hash functions cannot be usefully applied. In light of this, robust hashing has been developed as an alternative to cryptographic hashing and is designed to be robust to minor changes in the input. Although similar in name, robust hashing is fundamentally different from cryptographic hashing. Current robust hashing techniques are not based on cryptographic methods, but instead on pattern recognition techniques. Modern robust hashing algorithms consist of feature extraction followed by a randomization stage that introduces non-invertibility and compression, followed by quantization and binary encoding to produce a binary hash output. In order to preserve robustness of the extracted features, most randomization methods are linear and this is detrimental to the security aspects required of hash functions. Furthermore, the quantization and encoding stages used to binarize real-valued features requires the learning of appropriate quantization thresholds. How these thresholds are learnt has an important effect on hashing accuracy and the mere presence of such thresholds are a source of information leakage that can reduce hashing security. This dissertation outlines a systematic investigation of the quantization and encoding stages of robust hash functions. While existing literature has focused on the importance of quantization scheme, this research is the first to emphasise the importance of the quantizer training on both hashing accuracy and hashing security. The quantizer training process is presented in a statistical framework which allows a theoretical analysis of the effects of quantizer training on hashing performance. This is experimentally verified using a number of baseline robust image hashing algorithms over a large database of real world images. This dissertation also proposes a new randomization method for robust image hashing based on Higher Order Spectra (HOS) and Radon projections. The method is non-linear and this is an essential requirement for non-invertibility. The method is also designed to produce features more suited for quantization and encoding. The system can operate without the need for quantizer training, is more easily encoded and displays improved hashing performance when compared to existing robust image hashing algorithms. The dissertation also shows how the HOS method can be adapted to work with biometric features obtained from 2D and 3D face images.

Effects of air pollution exposure on adult bicycle commuters : an investigation of respiratory health, motorised traffic proximity and the utility of commute re-routing

Bicycle commuting has the potential to be an effective contributing solution to address some of modern society’s biggest issues, including cardiovascular disease, anthropogenic climate change and urban traffic congestion. However, individuals shifting from a passive to an active commute mode may be increasing their potential for air pollution exposure and the associated health risk. This project, consisting of three studies, was designed to investigate the health effects of bicycle commuters in relation to air pollution exposure, in a major city in Australia (Brisbane). The aims of the three studies were to: 1) examine the relationship of in-commute air pollution exposure perception, symptoms and risk management; 2) assess the efficacy of commute re-routing as a risk management strategy by determining the exposure potential profile of ultrafine particles along commute route alternatives of low and high proximity to motorised traffic; and, 3) evaluate the feasibility of implementing commute re-routing as a risk management strategy by monitoring ultrafine particle exposure and consequential physiological response from using commute route alternatives based on real-world circumstances; 3) investigate the potential of reducing exposure to ultrafine particles (UFP; < 0.1 µm) during bicycle commuting by lowering proximity to motorised traffic with real-time air pollution and acute inflammatory measurements in healthy individuals using their typical, and an alternative to their typical, bicycle commute route. The methods of the three studies included: 1) a questionnaire-based investigation with regular bicycle commuters in Brisbane, Australia. Participants (n = 153; age = 41 ± 11 yr; 28% female) reported the characteristics of their typical bicycle commute, along with exposure perception and acute respiratory symptoms, and amenability for using a respirator or re-routing their commute as risk management strategies; 2) inhaled particle counts measured along popular pre-identified bicycle commute route alterations of low (LOW) and high (HIGH) motorised traffic to the same inner-city destination at peak commute traffic times. During commute, real-time particle number concentration (PNC; mostly in the UFP range) and particle diameter (PD), heart and respiratory rate, geographical location, and meteorological variables were measured. To determine inhaled particle counts, ventilation rate was calculated from heart-rate-ventilation associations, produced from periodic exercise testing; 3) thirty-five healthy adults (mean ± SD: age = 39 ± 11 yr; 29% female) completed two return trips of their typical route (HIGH) and a pre-determined altered route of lower proximity to motorised traffic (LOW; determined by the proportion of on-road cycle paths). Particle number concentration (PNC) and diameter (PD) were monitored in real-time in-commute. Acute inflammatory indices of respiratory symptom incidence, lung function and spontaneous sputum (for inflammatory cell analyses) were collected immediately pre-commute, and one and three hours post-commute. The main results of the three studies are that: 1) healthy individuals reported a higher incidence of specific acute respiratory symptoms in- and post- (compared to pre-) commute (p < 0.05). The incidence of specific acute respiratory symptoms was significantly higher for participants with respiratory disorder history compared to healthy participants (p < 0.05). The incidence of in-commute offensive odour detection, and the perception of in-commute air pollution exposure, was significantly lower for participants with smoking history compared to healthy participants (p < 0.05). Females reported significantly higher incidence of in-commute air pollution exposure perception and other specific acute respiratory symptoms, and were more amenable to commute re-routing, compared to males (p < 0.05). Healthy individuals have indicated a higher incidence of acute respiratory symptoms in- and post- (compared to pre-) bicycle commuting, with female gender and respiratory disorder history indicating a comparably-higher susceptibility; 2) total mean PNC of LOW (compared to HIGH) was reduced (1.56 x e4 ± 0.38 x e4 versus 3.06 x e4 ± 0.53 x e4 ppcc; p = 0.012). Total estimated ventilation rate did not vary significantly between LOW and HIGH (43 ± 5 versus 46 ± 9 L•min; p = 0.136); however, due to total mean PNC, accumulated inhaled particle counts were 48% lower in LOW, compared to HIGH (7.6 x e8 ± 1.5 x e8 versus 14.6 x e8 ± 1.8 x e8; p = 0.003); 3) LOW resulted in a significant reduction in mean PNC (1.91 x e4 ± 0.93 x e4 ppcc vs. 2.95 x e4 ± 1.50 x e4 ppcc; p ≤ 0.001). Commute distance and duration were not significantly different between LOW and HIGH (12.8 ± 7.1 vs. 12.0 ± 6.9 km and 44 ± 17 vs. 42 ± 17 mins, respectively). Besides incidence of in-commute offensive odour detection (42 vs. 56 %; p = 0.019), incidence of dust and soot observation (33 vs. 47 %; p = 0.038) and nasopharyngeal irritation (31 vs. 41 %; p = 0.007), acute inflammatory indices were not significantly associated to in-commute PNC, nor were these indices reduced with LOW compared to HIGH. The main conclusions of the three studies are that: 1) the perception of air pollution exposure levels and the amenability to adopt exposure risk management strategies where applicable will aid the general population in shifting from passive, motorised transport modes to bicycle commuting; 2) for bicycle commuting at peak morning commute times, inhaled particle counts and therefore cardiopulmonary health risk may be substantially reduced by decreasing exposure to motorised traffic, which should be considered by both bicycle commuters and urban planners; 3) exposure to PNC, and the incidence of offensive odour and nasopharyngeal irritation, can be significantly reduced when utilising a strategy of lowering proximity to motorised traffic whilst bicycle commuting, without significantly increasing commute distance or duration, which may bring important benefits for both healthy and susceptible individuals. In summary, the findings from this project suggests that bicycle commuters can significantly lower their exposure to ultrafine particle emissions by varying their commute route to reduce proximity to motorised traffic and associated combustion emissions without necessarily affecting their time of commute. While the health endpoints assessed with healthy individuals were not indicative of acute health detriment, individuals with pre-disposing physiological-susceptibility may benefit considerably from this risk management strategy – a necessary research focus with the contemporary increased popularity of both promotion and participation in bicycle commuting.

Growth of C36-films on diamond surface through molecular dynamics simulation

In this paper, the initial stage of films assembled by energetic C36 fullerenes on diamond (001)–(2 × 1) surface at low-temperature was investigated by molecular dynamics simulation using the Brenner potential. The incident energy was first uniformly distributed within an energy interval 20–50 eV, which was known to be the optimum energy range for chemisorption of single C36 on diamond (001) surface. More than one hundred C36 cages were impacted one after the other onto the diamond surface by randomly selecting their orientation as well as the impact position relative to the surface. The growth of films was found to be in three-dimensional island mode, where the deposited C36 acted as building blocks. The study of film morphology shows that it retains the structure of a free C36 cage, which is consistent with Low Energy Cluster Beam Deposition (LECBD) experiments. The adlayer is composed of many C36-monomers as well as the covalently bonded C36 dimers and trimers which is quite different from that of C20 fullerene-assembled film, where a big polymerlike chain was observed due to the stronger interaction between C20 cages. In addition, the chemisorption probability of C36 fullerenes is decreased with increasing coverage because the interaction between these clusters is weaker than that between the cluster and the surface. When the incident energy is increased to 40–65 eV, the chemisorption probability is found to increased and more dimers and trimers as well as polymerlike-C36 were observed on the deposited films. Furthermore, C36 film also showed high thermal stability even when the temperature was raised to 1500 K.

Molecular dynamics study of ‘contact epitaxy’ in Ag clusters supported on a copper (001) surface

In this paper, the formation of heteroepitaxial interfacial layers was investigated by molecular dynamics simulation of soft silver particles landing on the (001) surface of single-crystal copper. In our simulations, the clusters Ag13, Ag55, Ag147 and Ag688 were chosen as projectiles. A small cluster will rearrange into an f.c.c. structure when it is supported on the substrate, due to the large value of its surface/volume ratio. Contact epitaxy appeared in large clusters. The characteristic structure of an epitaxial layer in large silver cluster shows the 〈111〉 direction to be the preferential orientation of heteroepitaxial layers on the surface because of the lattice mismatch between the cluster and the substrate. This was confirmed by studying soft landing events in other systems (Au/Cu and Al/Ni).

Virtual birding : extending an environmental pastime into the virtual world for citizen science

This paper investigates engaging experienced birders, as volunteer citizen scientists, to analyze large recorded audio datasets gathered through environmental acoustic monitoring. Although audio data is straightforward to gather, automated analysis remains a challenging task; the existing expertise, local knowledge and motivation of the birder community can complement computational approaches and provide distinct benefits. We explored both the culture and practice of birders, and paradigms for interacting with recorded audio data. A variety of candidate design elements were tested with birders. This study contributes an understanding of how virtual interactions and practices can be developed to complement existing practices of experienced birders in the physical world. In so doing this study contributes a new approach to engagement in e-science. Whereas most citizen science projects task lay participants with discrete real world or artificial activities, sometimes using extrinsic motivators, this approach builds on existing intrinsically satisfying practices.

Proteomics science and society :the role of knowledge translation in moving towards clinical applications

Gaining support for proteomics science requires effective knowledge translation. Knowledge translation (KT) processes turn the evidence generated by scientific discovery into recommendations for clinical applications, funding priorities, and policy/regulatory reforms. Clinicians, regulators, and funders need to understand why emerging proteomics knowledge is relevant, and what are the potential applications of that knowledge. A lack of clarity remains about what KT means.

Impact of information on intentions to vaccinate in a potential epidemic : Swine-origin Influenza A (H1N1)

Vaccination campaigns to prevent the spread of epidemics are successful only if the targeted populations subscribe to the recommendations of health authorities. However, because compulsory vaccination is hardly conceivable in modern democracies, governments need to convince their populations through efficient and persuasive information campaigns. In the context of the swine-origin A (H1N1) 2009 pandemic, we use an interactive study among the general public in the South of France, with 175 participants, to explore what type of information can induce change in vaccination intentions at both aggregate and individual levels. We find that individual attitudes to vaccination are based on rational appraisal of the situation, and that it is information of a purely scientific nature that has the only significant positive effect on intention to vaccinate.

Science fiction

Few science fiction films have been made in Australia by Australians for Australian audiences, with most of the handful of locally-produced films made since the mid-1990s. Yet there has always been a solid Australian audience for non-Australian science fiction films and a strong international niche audience for the genre. While Australia has provided below-the-line crews and heads of departments (cinematographers, production designers, and so on) for many non-Australian science fiction films produced domestically, few Australian film directors have specialised in the genre. This is somewhat surprising considering that Alex Proyas achieved a degree of international success for his gothic science fiction film Dark City (1998), and George Miller achieved international fame following the worldwide success of Mad Max II (1981). Although the science fiction element of Mad Max II is tenuous – and even more so in the case of the original Mad Max (George Miller, 1979) – Miller is credited with creating a new (sub)genre which incorporates science fiction elements and has been widely imitated internationally: the dystopian, post-apocalyptic movie. Nevertheless, Australia has only produced a small number of science fiction movies. In addition to the above films, key titles include: Mad Max Beyond Thunderdome (George Miller, 1985), Shirley Thompson versus the Aliens (Jim Sharman, 1972), The Time Guardian (Brian Hannant, 1987), The Chain Reaction (Ian Barry, 1980) and, more recently, Knowing (Alex Proyas, 2009), Daybreakers (Michael and Peter Spierig, 2009), and Iron Sky (Timo Vuorensola, 2012).

Post-genomic science & society : Getting our fangs into omics science and its implications

Genomics and genetic findings have been hailed with promises of unlocked codes and new frontiers of personalized medicine. Despite cautions about gene hype, the strong cultural pull of genes and genomics has allowed consideration of genomic personhood. Populated by the complicated records of mass spectrometer, proteomics, which studies the human protein, has not achieved either the funding or the popular cultural appeal proteomics scientists had hoped it would. While proteomics, being focused on the proteins that actually indicate and create disease states, has a more direct potential for clinical applications than genomic risk predictions, culturally, it has not provided the material for identity creation. In our ethnographic research, we explore how proteomic scientists attempting to shape an appeal to personhood through which legitimacy may be defined.

BWW ontology as a lens on IS design theory: Extending the design science research roadmap

The Design Science Research Roadmap (DSR-Roadmap) [1] aims to give detailed methodological guidance to novice researchers in Information Systems (IS) DSR. Focus group evaluation, one phase of the overall study, of the evolving DSR-Roadmap revealed that a key difficulty faced by both novice and expert researchers in DSR, is abstracting design theory from design. This paper explores the extension of the DSR-Roadmap by employing IS deep structure ontology (BWW [2-4]) as a lens on IS design to firstly yield generalisable design theory, specifically 'IS Design Theory' (ISDT) elements [5]. Consideration is next given to the value of BWW in the application of the design theory by practitioners. Results of mapping BWW constructs to ISDT elements suggest that the BWW is promising as a common language between design researchers and practitioners, facilitating both design theory and design implementation

The design science research roadmap : in progress evaluation

Although Design Science Research (DSR) is now an accepted approach to research in the Information Systems (IS) discipline, consensus on the methodology of DSR has yet to be achieved. Lack of a comprehensive and detailed methodology for Design Science Research (DSR) in the Information System (IS) discipline is a main issue. Prior research (the parent-study) aimed to remedy this situation and resulted in the DSR-Roadmap (Alturki et al., 2011a). Continuing empirical validation and revision of the DSR-Roadmap strives towards a methodology with appropriate levels of detail, integration, and completeness for novice researchers to efficiently and effectively conduct and report DSR in IS. The sub-study reported herein contributes to this larger, ongoing effort. This paper reports results from a formative evaluation effort of the DSR-Roadmap conducted using focus group analysis. Generally, participants endorsed the utility and intuitiveness of the DSR-Roadmap, while also suggesting valuable refinements. Both parent-study and sub-study make methodological contributions. The parent-study is the first attempt of utilizing DSR to develop a research methodology showing an example of how to use DSR in research methodology construction. The sub-study demonstrates the value of the focus group method in DSR for formative product evaluation.