High energy states of gold and their importance in electrocatalytic processes at surfaces and interfaces

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.

Characterisation of two distinctly different processes associated with the electrocrystallization of microcrystals of phase I CuTCNQ (TCNQ= 7, 7, 8, 8-tetracyanoquinodimethane)

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.

Probing second harmonic components of pH-sensitive Redox processes in a mesoporous TiO2-Nafion film electrode with Fourier-transformed large-amplitude sinusoidally modulated voltammetry

Electrochemical processes in mesoporous TiO2-Nafion thin films deposited on indium tin oxide (ITO) electrodes are inherently complex and affected by capacitance, Ohmic iR-drop, RC-time constant phenomena, and by potential and pH-dependent conductivity. In this study, large-amplitude sinusoidally modulated voltammetry (LASMV) is employed to provide access to almost purely Faradaic-based current data from second harmonic components, as well as capacitance and potential domain information from the fundamental harmonic for mesoporous TiO2-Nafion film electrodes. The LASMV response has been investigated with and without an immobilized one-electron redox system, ferrocenylmethyltrimethylammonium+. Results clearly demonstrate that the electron transfer associated with the immobilized ferrocene derivative follows two independent pathways i) electron hopping within the Nafion network and ii) conduction through the TiO2 backbone. The pH effect on the voltammetric response for the TiO2 reduction pathway (ii) can be clearly identified in the 2nd harmonic LASMV response with the diffusion controlled ferrocene response (i) acting as a pH independent reference. Application of second harmonic data derived from LASMV measurement, because of the minimal contribution from capacitance currents, may lead to reference-free pH sensing with systems like that found for ferrocene derivatives.

Electrochemically-induced TCNQ/Mn TCNQ 2 (H2O) 2 (TCNQ= 7, 7, 8, 8-Tetracyanoquinodimethane) solid-solid interconversion : two voltammetrically distinct processes that allow selective generation of nanofiber or nanorod network morphologies

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.

Decoration of active sites to create bimetallic surfaces and its implication for electrochemical processes

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.

Efficiency and productivity of Singapore's manufacturing sector 2001-2010 : an analysis using bootstrapped truncated approach

This paper seeks to explain the lagging productivity in Singapore’s manufacturing noted in the statements of the Economic Strategies Committee Report 2010. Two methods are employed: the Malmquist productivity to measure total factor productivity (TFP) change and Simar and Wilson’s (2007) bootstrapped truncated regression approach which first derives bias-corrected efficiency estimates before being regressed against explanatory variables to help quantify sources of inefficiencies. The findings reveal that growth in total factor productivity was attributed to efficiency change with no technical progress. Sources of efficiency were attributed to quality of worker and flexible work arrangements while the use of foreign workers lowered efficiency.

How international entrepreneurship characteristics influence Internet capabilities for the international business processes of the firm

This research explores the relationship between international entrepreneurship characteristics and the use of Internet capabilities for the international business processes of the firm. It has been suggested, that the accumulation of a firms Internet capability can assist international operations, especially when operating in fast changing dynamic Internet environments. However, international entrepreneurship characteristics which are seen as a precursor to leveraging Internet capabilities are still vague. Given this finding, eight case studies of small and medium sized travel and tourism firms were selected to investigate the influence of international entrepreneurship characteristics, and Internet capabilities for international business processes. Based on the eight in-depth case studies, the results signify that successful international entrepreneurial firms which encompass high levels of international innovativeness and proactiveness behaviour integrate Internet capabilities to a greater degree. Our findings also indicate that the prior international business experience, international risk-taking propensity and international networking characteristics are not necessarily precursors to successful integration of Internet capabilities for international business processes. On the contrary, international business experience and international networks actually lead to a reliance on traditional mechanisms of internationalisation and can dilute the development of Internet capabilities for international business processes.

Educating for digital futures : what the learning strategies of digital content professionals can teach higher education

Beginning in the second half of the 20th century, ICTs transformed many societies from industrial societies in which manufacturing was the central focus, into knowledge societies in which dealing effectively with data and information has become a central element of work (Anderson, 2008). To meet the needs of the knowledge society, universities must reinvent their structures and processes, their curricula and pedagogic practices. In addition to this, of course higher education is itself subject to the sweeping influence of ICTs. But what might effective higher education look like in the 21st century? In designing higher education systems and learning experiences which are responsive to the learning needs of the future and exploit the possibilities offered by ICTs, we can learn much from the existing professional development strategies of people who are already successful in 21st century fields, such as digital media. In this study, I ask: (1) what are the learning challenges faced by digital media professionals in the 21st century? (2) what are the various roles of formal and informal education in their professional learning strategies at present? (3) how do they prefer to acquire needed capabilities? In-depth interviews were undertaken with successful Australian digital media professionals working in micro businesses and SMEs to answer these questions. The strongest thematic grouping that emerged from the interviews related to the need for continual learning and relearning because of the sheer rate of change in the digital media industries. Four dialectical relationships became apparent from the interviewees’ commentaries around the learning imperatives arising out of the immense and continual changes occurring in the digital content industries: (1) currency vs best practice (2) diversification vs specialisation of products and services (3) creative outputs vs commercial outcomes (4) more learning opportunities vs less opportunity to learn. These findings point to the importance of ‘learning how to learn’ as a 21st century capability. The interviewees were ambivalent about university courses as preparation for professional life in their fields. Higher education was described by several interviewees as having relatively little value-add beyond what one described as “really expensive credentialling services.” For all interviewees in this study, informal learning strategies were the preferred methods of acquiring the majority of knowledge and skills, both for ongoing and initial professional development. Informal learning has no ‘curriculum’ per se, and tends to be opportunistic, unstructured, pedagogically agile and far more self-directed than formal learning (Eraut, 2004). In an industry impacted by constant change, informal learning is clearly both essential and ubiquitous. Inspired by the professional development strategies of the digital media professionals in this study, I propose a 21st century model of the university as a broad, open learning ecology, which also includes industry, professionals, users, and university researchers. If created and managed appropriately, the university learning network becomes the conduit and knowledge integrator for the latest research and industry trends, which students and professionals alike can access as needed.

A time-based quantitative approach for selecting lean strategies for manufacturing organisations

Lean strategies have been developed to eliminate or reduce waste and thus improve operational efficiency in a manufacturing environment. However, in practice, manufacturers encounter difficulties to select appropriate lean strategies within their resource constraints and to quantitatively evaluate the perceived value of manufacturing waste reduction. This paper presents a methodology developed to quantitatively evaluate the contribution of lean strategies selected to reduce manufacturing wastes within the manufacturers’ resource (time) constraints. A mathematical model has been developed for evaluating the perceived value of lean strategies to manufacturing waste reduction and a step-by-step methodology is provided for selecting appropriate lean strategies to improve the manufacturing performance within their resource constraints. A computer program is developed in MATLAB for finding the optimum solution. With the help of a case study, the proposed methodology and developed model has been validated. A ‘lean strategy-wastes’ correlation matrix has been proposed to establish the relationship between the manufacturing wastes and lean strategies. Using the correlation matrix and applying the proposed methodology and developed mathematical model, authors came out with optimised perceived value of reduction of a manufacturer's wastes by implementing appropriate lean strategies within a manufacturer's resources constraints. Results also demonstrate that the perceived value of reduction of manufacturing wastes can significantly be changed based on policies and product strategy taken by a manufacturer. The proposed methodology can also be used in dynamic situations by changing the input in the programme developed in MATLAB. By identifying appropriate lean strategies for specific manufacturing wastes, a manufacturer can better prioritise implementation efforts and resources to maximise the success of implementing lean strategies in their organisation.

Application of lean production to reducing operational waste in a tile manufacturing process

Roofing tile manufacturing is a mass production process with high operational and inventory wastes and costs. Due to huge operational costs, excessive inventory and wastes, and quality problems, roofing tile manufacturers are trying to implement lean manufacturing practice in their operations in order to remain competitive in an ncreasingly competitive global market. The aim of this research is to evaluate the possibility of reducing the operational and inventory costs of the tile manufacturing process through waste minimization. This paper analyses the current waste situation in a tile manufacturing process and develops current and future value stream mapping for such a process with a view to implementing lean principles in manufacturing. The focus of the approach is on cost reduction by eliminating non-value-added activities.

Secure stream cipher initialisation processes

Stream ciphers are symmetric key cryptosystems that are used commonly to provide confidentiality for a wide range of applications; such as mobile phone, pay TV and Internet data transmissions. This research examines the features and properties of the initialisation processes of existing stream ciphers to identify flaws and weaknesses, then presents recommendations to improve the security of future cipher designs. This research investigates well-known stream ciphers: A5/1, Sfinks and the Common Scrambling Algorithm Stream Cipher (CSA-SC). This research focused on the security of the initialisation process. The recommendations given are based on both the results in the literature and the work in this thesis.

Process mining for clinical processes: A comparative analysis of four Australian hospitals

Business process analysis and process mining, particularly within the health care domain, remain under-utilised. Applied research that employs such techniques to routinely collected, health care data enables stakeholders to empirically investigate care as it is delivered by different health providers. However, cross-organisational mining and the comparative analysis of processes present a set of unique challenges in terms of ensuring population and activity comparability, visualising the mined models and interpreting the results. Without addressing these issues, health providers will find it difficult to use process mining insights, and the potential benefits of evidence-based process improvement within health will remain unrealised. In this paper, we present a brief introduction on the nature of health care processes; a review of the process mining in health literature; and a case study conducted to explore and learn how health care data, and cross-organisational comparisons with process mining techniques may be approached. The case study applies process mining techniques to administrative and clinical data for patients who present with chest pain symptoms at one of four public hospitals in South Australia. We demonstrate an approach that provides detailed insights into clinical (quality of patient health) and fiscal (hospital budget) pressures in health care practice. We conclude by discussing the key lessons learned from our experience in conducting business process analysis and process mining based on the data from four different hospitals.

How to guarantee compliance between workflows and product lifecycles?

Product Lifecycle Management (PLM) systems are widely used in the manufacturing industry. A core feature of such systems is to provide support for versioning of product data. As workflow functionality is increasingly used in PLM systems, the possibility emerges that the versioning transitions for product objects as encapsulated in process models do not comply with the valid version control policies mandated in the objects’ actual lifecycles. In this paper we propose a solution to tackle the (non-)compliance issues between processes and object version control policies. We formally define the notion of compliance between these two artifacts in product lifecycle management and then develop a compliance checking method which employs a well-established workflow analysis technique. This forms the basis of a tool which offers automated support to the proposed approach. By applying the approach to a collection of real-life specifications in a main PLM system, we demonstrate the practical applicability of our solution to the field.

Self-organization processes in field-invasion team sports

In nature, the interactions between agents in a complex system (fish schools; colonies of ants) are governed by information that is locally created. Each agent self-organizes (adjusts) its behaviour, not through a central command centre, but based on variables that emerge from the interactions with other system agents in the neighbourhood. Self-organization has been proposed as a mechanism to explain the tendencies for individual performers to interact with each other in field-invasion sports teams, displaying functional co-adaptive behaviours, without the need for central control. The relevance of self-organization as a mechanism that explains pattern-forming dynamics within attacker-defender interactions in field-invasion sports has been sustained in the literature. Nonetheless, other levels of interpersonal coordination, such as intra-team interactions, still raise important questions, particularly with reference to the role of leadership or match strategies that have been prescribed in advance by a coach. The existence of key properties of complex systems, such as system degeneracy, nonlinearity or contextual dependency, suggests that self-organization is a functional mechanism to explain the emergence of interpersonal coordination tendencies within intra-team interactions. In this opinion article we propose how leadership may act as a key constraint on the emergent, self-organizational tendencies of performers in field-invasion sports.