Multicomponent charge transport in electrolyte solutions

The work presented in this thesis investigates the mathematical modelling of charge transport in electrolyte solutions, within the nanoporous structures of electrochemical devices. We compare two approaches found in the literature, by developing onedimensional transport models based on the Nernst-Planck and Maxwell-Stefan equations. The development of the Nernst-Planck equations relies on the assumption that the solution is infinitely dilute. However, this is typically not the case for the electrolyte solutions found within electrochemical devices. Furthermore, ionic concentrations much higher than those of the bulk concentrations can be obtained near the electrode/electrolyte interfaces due to the development of an electric double layer. Hence, multicomponent interactions which are neglected by the Nernst-Planck equations may become important. The Maxwell-Stefan equations account for these multicomponent interactions, and thus they should provide a more accurate representation of transport in electrolyte solutions. To allow for the effects of the electric double layer in both the Nernst-Planck and Maxwell-Stefan equations, we do not assume local electroneutrality in the solution. Instead, we model the electrostatic potential as a continuously varying function, by way of Poisson’s equation. Importantly, we show that for a ternary electrolyte solution at high interfacial concentrations, the Maxwell-Stefan equations predict behaviour that is not recovered from the Nernst-Planck equations. The main difficulty in the application of the Maxwell-Stefan equations to charge transport in electrolyte solutions is knowledge of the transport parameters. In this work, we apply molecular dynamics simulations to obtain the required diffusivities, and thus we are able to incorporate microscopic behaviour into a continuum scale model. This is important due to the small size scales we are concerned with, as we are still able to retain the computational efficiency of continuum modelling. This approach provides an avenue by which the microscopic behaviour may ultimately be incorporated into a full device-scale model. The one-dimensional Maxwell-Stefan model is extended to two dimensions, representing an important first step for developing a fully-coupled interfacial charge transport model for electrochemical devices. It allows us to begin investigation into ambipolar diffusion effects, where the motion of the ions in the electrolyte is affected by the transport of electrons in the electrode. As we do not consider modelling in the solid phase in this work, this is simulated by applying a time-varying potential to one interface of our two-dimensional computational domain, thus allowing a flow field to develop in the electrolyte. Our model facilitates the observation of the transport of ions near the electrode/electrolyte interface. For the simulations considered in this work, we show that while there is some motion in the direction parallel to the interface, the interfacial coupling is not sufficient for the ions in solution to be "dragged" along the interface for long distances.

'Information in context' : co-designing workplace structures and systems for organizational learning

With the aim of advancing professional practice through better understanding how to create workplace contexts that cultivate individual and collective learning through situated 'information in context' experiences, this paper presents insights gained from three North American collaborative design (co-design) implementations. In the current project at the Auraria Library in Denver, Colorado, USA, participants use collaborative information practices to redesign face-to-face and technology-enabled communication, decision making, and planning systems. Design processes are described and results-to-date described, within an appreciative framework which values information sharing and enables knowledge creation through shared leadership.

Half metallicity in a zigzag double-walled nanotube nanodot : an Ab initio prediction

Ab initio density functional calculations were performed to study finite-length zigzag (7, 0) @ (16, 0) double-walled carbon nanotubes (DWCNTs) with H-termination at the open ends. We find that such a DWCNT nanodot displays a very large magnetic moment at the zigzag edges and the ground state displays symmetric anti-ferromagnetic coupling. When an external electric field is applied along the direction of tube axis, a gap is opened for one spin channel, whereas another spin channel remains metallic, i.e. half metallicity occurs. Our results suggest an important new avenue for the development of CNT-based spintronic materials with enhanced properties.

Computational study of methyl derivatives of ammonia borane for hydrogen storage

The structures and thermodynamic properties of methyl derivatives of ammonia–borane (BH3NH3, AB) have been studied with the frameworks of density functional theory and second-order Møller–Plesset perturbation theory. It is found that, with respect to pure AB, methyl ammonia–boranes show higher complexation energies and lower reaction enthalpies for the release of H2, together with a slight increment of the activation barrier. These results indicate that the methyl substitution can enhance the reversibility of the system and prevent the formation of BH3/NH3, but no enhancement of the release rate of H2 can be expected.

Damage identification and condition assessment of building structures using frequency response functions and neural networks

This thesis investigated the viability of using Frequency Response Functions in combination with Artificial Neural Network technique in damage assessment of building structures. The proposed approach can help overcome some of limitations associated with previously developed vibration based methods and assist in delivering more accurate and robust damage identification results. Excellent results are obtained for damage identification of the case studies proving that the proposed approach has been developed successfully.

Community response to disasters in Indonesia : Gotong Royong; a double edged-sword

Indonesia is a country spread across wide-ranging archipelago, located in South East Asia between two oceans, the Indian and the Pacific. Indonesia is well known as an active tectonic region because it lies on top of three major active tectonic plates: the Eurasian in the North, the Indian Ocean-Australian in the South, and the Pacific plate in the East. The southern and eastern part of the country features a range of volcanic arcs, volcanic mountains, and lowlands with 500 young volcanoes, of which 128 are active and thus representing 15% of the world’s active volcanoes. In the period 2002-2007, approximately 1782 disasters occurred, with hundreds of thousands of lives lost and billions of rupiah in losses incurred: (Floods - 1183 instances, cyclones - 272 instances, and landslides - 252 instances). Of these, the 2004 Aceh tsunami and the 2006 central Java earthquake (impacting predominantly city and suburbs of Yogyakarta) were the most significant. Even so, disaster management experts believe lessons learnt from the two major natural disasters needs to be formalised into laws and institutions before another disaster occurs, regardless of the type of natural disaster – i.e. Volcano eruption or landslide; as opposed to tsunami or earthquake. Following in the wake of disasters occurring in Yogyakarta, many of its community members responded by banding together as one, with the determination of rebuilding its villages and cities through the spirit of ‘gotong royong’. The idea of social interaction; in particular as a collective, consensual, and cooperative nation; has predominantly formed the ideological basis of Indonesia’s societal nature. Many Indonesian terms cohere to this ideology, such as: ‘koperasi” (cooperatives as the basis of economic interactions), ‘musyawarah’ (consensual nature in decision making), and ‘gotong royong’ (mutual assistance). ‘Gotong royong’ has become a key cultural operator in Indonesia, in particular In Jogjakarta. Appropriately so as ‘gotong royong’ is depicted from the traditional Javanese village, where labour is accomplished through reciprocal exchange and the villagers are motivated by a general ethos of selfishness and concern for the common good. The culture of ‘gotong royong’ promotes positive values such as social harmony and mutual reciprocation in disaster-affected areas provides the necessary spirit needed to endure the hardships and for all involved. While gotong royong emphasises the positive notions of mutual family support and deep community level activity there is a potential for contrast against government lead disaster response and recovery management activities especially in settings where sporadic governance mechanisms exist and transparency and accountability in the recovery process of public infrastructure assets have been questioned. This paper thus questions whether Gotong Royong is a double-edged sword, and explores the potential marriage of community values and governance mechanisms for future disaster management planning and practice.

Refined plastic hinge analysis of steel frame structures comprising non-compact sections : II : verification

Application of "advanced analysis" methods suitable for non-linear analysis and design of steel frame structures permits direct and accurate determination of ultimate system strengths, without resort to simplified elastic methods of analysis and semi-empirical specification equations. However, the application of advanced analysis methods has previously been restricted to steel frames comprising only compact sections that are not influenced by the effects of local buckling. A refined plastic hinge method suitable for practical advanced analysis of steel frame structures comprising non-compact sections is presented in a companion paper. The method implicitly accounts for the effects of gradual cross-sectional yielding, longitudinal spread of plasticity, initial geometric imperfections, residual stresses, and local buckling. The accuracy and precision of the method for the analysis of steel frames comprising non-compact sections is established in this paper by comparison with a comprehensive range of analytical benchmark frame solutions. The refined plastic hinge method is shown to be more accurate and precise than the conventional individual member design methods based on elastic analysis and specification equations.

Analytical benchmark solutions for steel frame structures subject to local buckling effects

Application of "advanced analysis" methods suitable for non-linear analysis and design of steel frame structures permits direct and accurate determination of ultimate system strengths, without resort to simplified elastic methods of analysis and semi-empirical specification equations. However, the application of advanced analysis methods has previously been restricted to steel frames comprising only compact sections that are not influenced by the effects of local buckling. A research project has been conducted with the aim of developing concentrated plasticity methods suitable for practical advanced analysis of steel frame structures comprising non-compact sections. This paper contains a comprehensive set of analytical benchmark solutions for steel frames comprising non-compact sections, which can be used to verify the accuracy of simplified concentrated plasticity methods of advanced analysis. The analytical benchmark solutions were obtained using a distributed plasticity shell finite element model that explicitly accounts for the effects of gradual cross-sectional yielding, longitudinal spread of plasticity, initial geometric imperfections, residual stresses, and local buckling. A brief description and verification of the shell finite element model is provided in this paper.

Double tax agreements and the international allocation of business income in Australia

Increasingly, the effectiveness of the present system of taxation of international businesses is being questioned. The problem associated with the taxation of such businesses is twofold. A system of international taxation must be a fair and equitable system, distributing profits between the relevant jurisdictions and, in doing so, avoiding double taxation. At the same time, the prevention of fiscal evasion must be secured. In an attempt to achieve a fair and equitable system Australia adopts unilateral, bilateral and multilateral measures to avoid double taxation and restrict the avoidance of tax. The first step in ascertaining the international allocation of business income is to consider the taxation of business income according to domestic law, that is, the unilateral measures. The treatment of international business income under the Australian domestic law, that is, the Income Tax Assessment Act 1936 (Cth) and Income Tax Assessment Act 1997 (Cth), will depend on two concepts, first, whether the taxpayer is a resident of Australia and secondly, whether the income is sourced in Australia. After the taxation of business profits has been determined according to domestic law it is necessary to consider the applicability of the bilateral measures, that is, the Double Tax Agreements (DTAs) to which Australia is a party, as the DTAs will override the domestic law where there is any conflict. Australia is a party to 40 DTAs with another seven presently being negotiated. The preamble to Australia's DTAs provides that the purpose of such agreements is 'to conclude an Agreement for the avoidance of double taxation and the prevention of fiscal evasion with respect to taxes on income'. Both purposes, for different reasons, are equally important. It has been said that: The taxpayer hopes the treaty will prevent the double taxation of his income; the tax gatherer hopes the treaty will prevent fiscal evasion; and the politician just hopes. The first purpose, the avoidance of double taxation, is achieved through the provision of rules whereby the Contracting States agree to the classification of income and the allocation of that income to a particular State. In this sense DTAs do not allocate jurisdiction to tax but rather provide an arrangement whereby the States agree to restrict their substantive law. The restriction is either through the non-taxing of the income or via the provision of a tax credit.

Experimental impact and finite element analysis of a composite, portable road safety barrier

This thesis provides an experimental and computational platform for investigating the performance and behaviour of water filled, plastic portable road safety barriers in an isolated impact scenario. A schedule of experimental impact tests were conducted assessing the impact response of an existing design of road safety barrier utilising a novel horizontal impact testing system. A coupled finite element and smooth particle hydrodynamic model of the barrier system was developed and validated against the results of the experimental tests. The validated model was subsequently used to assess the effect of certain composite materials on the impact performance of the water filled, portable road safety barrier system.

Double standards in special medical research : questioning the discrepancy between requirements for medical research involving incompetent adults and medical research involving children

Medical research represents a substantial departure from conventional medical care. Medical care is patient-orientated, with decisions based on the best interests and/or wishes of the person receiving the care. In contrast, medical research is future-directed. Primarily it aims to contribute new knowledge about illness or disease, or new knowledge about interventions, such as drugs, that impact upon some human condition. Current State and Territory laws and research ethics guidelines in Australia relating to the review of medical research appropriately acknowledge that the functions of medical care and medical research differ. Prior to a medical research project commencing, the study must be reviewed and approved by a Human Research Ethics Committee (HREC). For medical research involving incompetent adults, some jurisdictions require an additional, independent safeguard by way of tribunal or court approval of medical research protocols. This extra review process reflects the uncertainty of medical research involvement, and the difficulties surrogate decision-makers of incompetent adults face in making decisions about others, and deliberating about the risks and benefits of research involvement. Parents of children also face the same difficulties when making decisions about their child’s research involvement. However, unlike the position concerning incompetent adults, there are no similar safeguards under Australian law in relation to the approval of medical research involving children. This column questions why this discrepancy exists with a view to generating further dialogue on the topic.

Molecular cocrystals of 5-(4-bromophenyl)-1,3,4-thiadiazol-2-amine: hydrogen bonding in the structures of the 1:1 adduct with 2-(naphthalen-2-yloxy)acetic acid and the salt with 3,5-dinitrobenzoic acid

The structures of the anhydrous products from the interaction of 2-amino-5-(4-bromophenyl)-1,3,4-thiadiazole with (2-naphthoxy)acetic acid, the 1:1 adduct C8H6BrN3S . C12H10O3 (I) and 3,5-dinitrobenzoic acid, the salt C8H7BrN3S+ C7H3N2O6- (II) have been determined. In the adduct (I), a heterodimer is formed through a cyclic hydrogen-bonding motif [graph set R2/2(8)], involving carboxylic acid O-H...N(hetero)and amine N-H...O(carboxyl) interactions. The heterodimers are essentially planar with a thiadiazole to naphthyl ring dihedral angle of 15.9(2)deg. and the intramolecular thiadiazole to phenyl ring angle of 4.7(2)deg. An amine N-H...N(hetero) hydrogen bond between the heterodimers generates a one-dimensional chain structure extending down [001]. Also present are weak benzene-benzene and naphthalene-naphthalene pi-pi stacking interactions down the b axis [minimum ring centroid separation, 3.936(3) Ang.]. With the salt (II), the cation-anion association is also through a cyclic R2/2(8) motif but involving duplex N-H...O(carboxyl) hydrogen bonds, giving a heterodimer which is close to planar [dihedral angles between the thiadiazole ring and the two benzene rings, 5.00(16)deg. (intra) and 7.23(15)deg. (inter)]. A secondary centrosymmetric cyclic N-H...O(carboxyl) hydrogen-bonding association involving the second amino H-atom generates a heterotetramer. Also present in the crystal are weak pi-pi i-\p interactions between thiadiazolium rings [minimum ring centroid separation, 3.936(3)Ang.], as well as a short Br...O(nitro) interaction [3.314(4)Ang.]. The two structures reported here now provide a total of three crystallographically characterized examples of co-crystalline products from the interaction of 2-amino-5-(4-bromophenyl)-1,3,4-thiadiazole with carboxylic acids, of which only one involves proton-transfer.

Randomised, double blind, placebo-controlled trial of Echinacea supplementation in air travellers

Objective. To identify whether a standardised Echinacea formulation is effective in the prevention of respiratory and other symptoms associated with long-haul flights. Methods. 175 adults participated in a randomised, double-blind placebo-controlled trial travelling back from Australia to America, Europe, or Africa for a period of 1–5 weeks on commercial flights via economy class. Participants took Echinacea (root extract, standardised to 4.4 mg alkylamides) or placebo tablets. Participants were surveyed before, immediately after travel, and at 4 weeks after travel regarding upper respiratory symptoms and travel-related quality of life. Results. Respiratory symptoms for both groups increased significantly during travel (

Elastic buckling analysis of ideal thin-walled structures under combined loading using a finite strip method

The details of an application of the finite strip method to the elastic buckling analysis of thin-walled structures with various boundary conditions and subjected to single or combined loadings of longitudinal compression, transverse compression, bending and shear are presented. The presence of shear loading is accounted for by modifying the displacement functions which are commonly used in cases when shear is absent. A program based on the finite strip method was used to obtain the elastic buckling stress, buckling plot and buckling mode of thin-walled structures and some of these results are presented.

Vibrational spectroscopic study of the natural layered double hydroxide manasseite now defined as hydrotalcite-2H – Mg6Al2(OH)16[CO3]⋅4H2O

Raman and thermo-Raman spectroscopy have been applied to study the mineral formerly known as manasseite now simply renamed as hydrotalcite-2H Mg6Al2(OH)16[CO3]⋅4H2O. The mineral is a member of the homonymous hydrotalcite supergroup. Hydrogen bond distances calculated using a Libowitzky-type empirical function varied between 2.61 and 3.00 Å. Stronger hydrogen bonds were formed by water units as compared to the hydroxyl units. Raman spectroscopy enabled the identification of bands attributed to the hydroxyl units. Two Raman bands at 1059 and 1064 cm-1 are assigned to symmetric stretching modes of the carbonate anion. Thermal treatment shifts these bands to higher wavenumbers indicating a change in the strength of the carbonate bonding.