Dinuclear Ru-Cu complexes : electronic characterisation and application to dye-sensitised solar cells

Dye-sensitised solar cells have emerged as an important developing technology for low-cost solar energy conversion and a crucial element of these is the dye, responsible for light harvesting and control of interfacial electron-transfer processes.[1] A number of examples of dye exist in the literature which link a ruthenium polypyridyl complex to another platinum group metal complex such as Ru (II), Os (II), Re (I) or Rh (III) via a bridging ligand.[2-6] These systems are often referred to as heterosupramolecular triads when adsorbed on the surface of TiO2 as the semiconductor becomes an active component in the system. A number of problems can arise with these types of sensitisers, for example if a flexible linker, e.g. bis-pyridylethane, is used to couple the two complexes it can be hard to control the orientation of the whole dye. This may lead to the resultant dye cation hole being closer to the surface than desired, and hence the long-lived charge-separated state is not achieved. In addition the size of these dyes may be much larger than that of a mononuclear complex and can lead to poor pore filling on the TiO2 and lower dye coverage, leading to a lower efficiency cell.[7] Despite these issues, efficient charge-separation has been achieved with polynuclear complexes and a long-lived state on the millisecond timescale has been observed for a trinuclear ruthenium complex.[8]

Formation of nanoporous materials via mild retro-Diels–Alder chemistry

Poly(styrene)-block-poly(ethylene oxide) copolymers synthesized via the combination of reversible addition fragmentation chain transfer (RAFT) polymerization and hetero Diels–Alder (HDA) cycloaddition can be cleaved in the solid state by a retro-HDA reaction occurring at 90 °C. Nanoporous films can be prepared from these polymers using a simple heating and washing procedure.

Size effects on tensile and fatigue behaviour of polycrystalline metal foils at the micrometer scale

Tensile and fatigue properties of as-rolled and annealed polycrystalline Cu foils with different thicknesses at the micrometer scale were investigated. Uniaxial tensile testing results showed that with decreasing foil thickness the uniform elongation decreases for both as-rolled and annealed foils, whereas the yield strength and ultimate tensile strength increase for as-rolled foils, but decrease for the annealed foils. For both the as-rolled or annealed foils, bending fatigue resistance decreases with decreasing the foil thickness. Deformation and fatigue damage behaviour of the free-standing foils were characterised as a function of foil thickness. In addition, the fatigue strength of various small-scale Cu foils was compared to understand they physical mechanisms of size effects on mechanical properties of the metallic material at micrometer scales.

Microwave curing of non-traditional polymer materials used in manufacture of injection moulds

Microwave heating technology is a cost-effective alternative way for heating and curing of used in polymer processing of various alternate materials. The work presented in this paper addresses the attempts made by the authors to study the glass transition temperature and curing of materials such as casting resins R2512, R2515 and laminating resin GPR 2516 in combination with two hardeners ADH 2403 and ADH 2409. The magnetron microwave generator used in this research is operating at a frequency of 2.45 GHz with a hollow rectangular waveguide. During this investigation it has been noted that microwave heated mould materials resulted with higher glass transition temperatures and better microstructure. It also noted that Microwave curing resulted in a shorter curing time to reach the maximum percentage cure. From this study it can be concluded that microwave technology can be efficiently and effectively used to cure new generation alternate polymer materials for manufacture of injection moulds in a rapid and efficient manner. Microwave curing resulted in a shorter curing time to reach the maximum percentage cure.

Exchange design patterns for electronic intermediairies

Intermediaries have introduced electronic services with varying success. One of the problems an intermediary faces is deciding what kind of exchange service it should offer to its customers and suppliers. For example, should it only provide a catalogue or should it also enable customers to order products? Developing the right exchange design is a complex undertaking because of the many design options on the one hand and the interests of multiple actors to be considered on the other. This is far more difficult than simple prescriptions like ‘creating a win-win situation’ suggest. We address this problem by developing design patterns for the exchanges between customers, intermediary, and suppliers related to role, linkage, transparency, and ovelty choices. For developing these design patterns, we studied four distinct electronic intermediaries and dentified exchange design choices that require trade-offs relating to the interests of customers, intermediary, and suppliers. The exchange design patterns contribute to the development of design theory for electronic intermediaries by filling a gap between basic business models and detailed business process designs.

The HarmonyGrid : music, space and performance in grid music systems

This research explores music in space, as experienced through performing and music-making with interactive systems. It explores how musical parameters may be presented spatially and displayed visually with a view to their exploration by a musician during performance. Spatial arrangements of musical components, especially pitches and harmonies, have been widely studied in the literature, but the current capabilities of interactive systems allow the improvisational exploration of these musical spaces as part of a performance practice. This research focuses on quantised spatial organisation of musical parameters that can be categorised as grid music systems (GMSs), and interactive music systems based on them. The research explores and surveys existing and historical uses of GMSs, and develops and demonstrates the use of a novel grid music system designed for whole body interaction. Grid music systems provide plotting of spatialised input to construct patterned music on a two-dimensional grid layout. GMSs are navigated to construct a sequence of parametric steps, for example a series of pitches, rhythmic values, a chord sequence, or terraced dynamic steps. While they are conceptually simple when only controlling one musical dimension, grid systems may be layered to enable complex and satisfying musical results. These systems have proved a viable, effective, accessible and engaging means of music-making for the general user as well as the musician. GMSs have been widely used in electronic and digital music technologies, where they have generally been applied to small portable devices and software systems such as step sequencers and drum machines. This research shows that by scaling up a grid music system, music-making and musical improvisation are enhanced, gaining several advantages: (1) Full body location becomes the spatial input to the grid. The system becomes a partially immersive one in four related ways: spatially, graphically, sonically and musically. (2) Detection of body location by tracking enables hands-free operation, thereby allowing the playing of a musical instrument in addition to “playing” the grid system. (3) Visual information regarding musical parameters may be enhanced so that the performer may fully engage with existing spatial knowledge of musical materials. The result is that existing spatial knowledge is overlaid on, and combined with, music-space. Music-space is a new concept produced by the research, and is similar to notions of other musical spaces including soundscape, acoustic space, Smalley's “circumspace” and “immersive space” (2007, 48-52), and Lotis's “ambiophony” (2003), but is rather more textural and “alive”—and therefore very conducive to interaction. Music-space is that space occupied by music, set within normal space, which may be perceived by a person located within, or moving around in that space. Music-space has a perceivable “texture” made of tensions and relaxations, and contains spatial patterns of these formed by musical elements such as notes, harmonies, and sounds, changing over time. The music may be performed by live musicians, created electronically, or be prerecorded. Large-scale GMSs have the capability not only to interactively display musical information as music representative space, but to allow music-space to co-exist with it. Moving around the grid, the performer may interact in real time with musical materials in music-space, as they form over squares or move in paths. Additionally he/she may sense the textural matrix of the music-space while being immersed in surround sound covering the grid. The HarmonyGrid is a new computer-based interactive performance system developed during this research that provides a generative music-making system intended to accompany, or play along with, an improvising musician. This large-scale GMS employs full-body motion tracking over a projected grid. Playing with the system creates an enhanced performance employing live interactive music, along with graphical and spatial activity. Although one other experimental system provides certain aspects of immersive music-making, currently only the HarmonyGrid provides an environment to explore and experience music-space in a GMS.

The flammability of metallic materials in normal and reduced gravity

Metallic materials exposed to oxygen-enriched atmospheres – as commonly used in the medical, aerospace, aviation and numerous chemical processing industries – represent a significant fire hazard which must be addressed during design, maintenance and operation. Hence, accurate knowledge of metallic materials flammability is required. Reduced gravity (i.e. space-based) operations present additional unique concerns, where the absence of gravity must also be taken into account. The flammability of metallic materials has historically been quantified using three standardised test methods developed by NASA, ASTM and ISO. These tests typically involve the forceful (promoted) ignition of a test sample (typically a 3.2 mm diameter cylindrical rod) in pressurised oxygen. A test sample is defined as flammable when it undergoes burning that is independent of the ignition process utilised. In the standardised tests, this is indicated by the propagation of burning further than a defined amount, or „burn criterion.. The burn criterion in use at the onset of this project was arbitrarily selected, and did not accurately reflect the length a sample must burn in order to be burning independent of the ignition event and, in some cases, required complete consumption of the test sample for a metallic material to be considered flammable. It has been demonstrated that a) a metallic material.s propensity to support burning is altered by any increase in test sample temperature greater than ~250-300 oC and b) promoted ignition causes an increase in temperature of the test sample in the region closest to the igniter, a region referred to as the Heat Affected Zone (HAZ). If a test sample continues to burn past the HAZ (where the HAZ is defined as the region of the test sample above the igniter that undergoes an increase in temperature of greater than or equal to 250 oC by the end of the ignition event), it is burning independent of the igniter, and should be considered flammable. The extent of the HAZ, therefore, can be used to justify the selection of the burn criterion. A two dimensional mathematical model was developed in order to predict the extent of the HAZ created in a standard test sample by a typical igniter. The model was validated against previous theoretical and experimental work performed in collaboration with NASA, and then used to predict the extent of the HAZ for different metallic materials in several configurations. The extent of HAZ predicted varied significantly, ranging from ~2-27 mm depending on the test sample thermal properties and test conditions (i.e. pressure). The magnitude of the HAZ was found to increase with increasing thermal diffusivity, and decreasing pressure (due to slower ignition times). Based upon the findings of this work, a new burn criterion requiring 30 mm of the test sample to be consumed (from the top of the ignition promoter) was recommended and validated. This new burn criterion was subsequently included in the latest revision of the ASTM G124 and NASA 6001B international test standards that are used to evaluate metallic material flammability in oxygen. These revisions also have the added benefit of enabling the conduct of reduced gravity metallic material flammability testing in strict accordance with the ASTM G124 standard, allowing measurement and comparison of the relative flammability (i.e. Lowest Burn Pressure (LBP), Highest No-Burn Pressure (HNBP) and average Regression Rate of the Melting Interface(RRMI)) of metallic materials in normal and reduced gravity, as well as determination of the applicability of normal gravity test results to reduced gravity use environments. This is important, as currently most space-based applications will typically use normal gravity information in order to qualify systems and/or components for reduced gravity use. This is shown here to be non-conservative for metallic materials which are more flammable in reduced gravity. The flammability of two metallic materials, Inconel® 718 and 316 stainless steel (both commonly used to manufacture components for oxygen service in both terrestrial and space-based systems) was evaluated in normal and reduced gravity using the new ASTM G124-10 test standard. This allowed direct comparison of the flammability of the two metallic materials in normal gravity and reduced gravity respectively. The results of this work clearly show, for the first time, that metallic materials are more flammable in reduced gravity than in normal gravity when testing is conducted as described in the ASTM G124-10 test standard. This was shown to be the case in terms of both higher regression rates (i.e. faster consumption of the test sample – fuel), and burning at lower pressures in reduced gravity. Specifically, it was found that the LBP for 3.2 mm diameter Inconel® 718 and 316 stainless steel test samples decreased by 50% from 3.45 MPa (500 psia) in normal gravity to 1.72 MPa (250 psia) in reduced gravity for the Inconel® 718, and 25% from 3.45 MPa (500 psia) in normal gravity to 2.76 MPa (400 psia) in reduced gravity for the 316 stainless steel. The average RRMI increased by factors of 2.2 (27.2 mm/s in 2.24 MPa (325 psia) oxygen in reduced gravity compared to 12.8 mm/s in 4.48 MPa (650 psia) oxygen in normal gravity) for the Inconel® 718 and 1.6 (15.0 mm/s in 2.76 MPa (400 psia) oxygen in reduced gravity compared to 9.5 mm/s in 5.17 MPa (750 psia) oxygen in normal gravity) for the 316 stainless steel. Reasons for the increased flammability of metallic materials in reduced gravity compared to normal gravity are discussed, based upon the observations made during reduced gravity testing and previous work. Finally, the implications (for fire safety and engineering applications) of these results are presented and discussed, in particular, examining methods for mitigating the risk of a fire in reduced gravity.

A rights management approach to protection of privacy in a cloud of electronic health records

A patient-centric DRM approach is proposed for protecting privacy of health records stored in a cloud storage based on the patient's preferences and without the need to trust the service provider. Contrary to the current server-side access control solutions, this approach protects the privacy of records from the service provider, and also controls the usage of data after it is released to an authorized user.

Calcium ions promote osteogenic differentiation and mineralization of human dental pulp cells : implication for pulp capping materials

Calcium (Ca) is the main element of most pulp capping materials and plays an essential role in mineralization. Different pulp capping materials can release various concentrations of Ca ions leading to different clinical outcomes. The purpose of this study was to investigate the effects of various concentrations of Ca ions on the growth and osteogenic differentiation of human dental pulp cells (hDPCs). Different concentrations of Ca ions were added to growth culture medium and osteogenic inductive culture medium. A Cell Counting Kit-8 (CCK-8) was used to determine the proliferation of hDPCs in growth culture medium. Osteogenic differentiation and mineralization were measured by alkaline phosphatase (ALP) assay, Alizarin red S/von kossa staining, calcium content quantitative assay. The selected osteogenic differentiation markers were investigated by quantitative real-time polymerase chain reaction (qRT-PCR). Within the range of 1.8–16.2 mM, increased concentrations of Ca ions had no effect on cell proliferation, but led to changes in osteogenic differentiation. It was noted that enhanced mineralized matrix nodule formation was found in higher Ca ions concentrations; however, ALP activity and gene expression were reduced. qRT-PCR results showed a trend towards down-regulated mRNA expression of type I collagen (COL1A2) and Runx2 at elevated concentrations of Ca ions, whereas osteopontin (OPN) and osteocalcin (OCN) mRNA expression was significantly up-regulated. Ca ions content in the culture media can significantly influence the osteogenic properties of hDPCs, indicating the importance of optimizing Ca ions release from dental pulp capping materials in order to achieve desirable clinical outcomes.

Biomaterials in orthopedic bone plates : a review

This paper aims to review biomaterials used in manufacturing bone plates including advances in recent years and prospect in the future. It has found among all biomaterials, currently titanium and stainless steel alloys are the most common in production of bone plates. Other biomaterials such as Mg alloys, Ta alloys, SMAs, carbon fiber composites and bioceramics are potentially suitable for bone plates because of their advantages in biocompatibility, bioactivity and biodegradability. However, today either they are not used in bone plates or have limited applications in only some flexible small-size implants. This problem is mainly related to their poor mechanical properties. Additionally, production processes play an effective role. Therefore, in the future, further studies should be conducted to solve these problems and make them feasible for heavy-duty bone plates.

Editorial : Decolonising action research (Electronic Version)

This edition of the ALAR Action learning action research journal aims to capture some of the current dilemmas, solutions and actions researchers experience in the decolonising space. This collection of papers demonstrates that researchers are not only undertaking action research with and within Indigenous and non-Indigenous contexts, but that they are doing so in exciting and dynamic ways across a diversity of situations. First we will address some of the literature on decolonisation. Then we will explain how this specific edition of the Journal came to fruition and aspects of action research.

Polymer self assembly on carbon nanotubes

This chapter analyses the poly(3-hexylthiophene) self-assembly on carbon nanotubes and the interaction between the two materials forming a new hybrid nanostructure. The chapter starts with a review of the several studies investigating polymers and biomolecules self-assembled on nanotubes. Then conducting polymers and polythiophenes are briefly introduced. Accordingly, carbon nanotube structure and properties are reported in Sect. 3. The experimental section starts with the bulk characterisation of polymer thin films with the inclusion of uniformly distributed carbon nanotubes. By using volume film analysis techniques (AFM, TEM, UV–Vis and Raman), we show how the polymer’s higher degree of order is a direct consequence of interaction with carbon nanotubes. Nevertheless, it is through the use of nanoscale analysis and molecular dynamic simulations that the self-assembly of the polymer on the nanotube surface can be clearly evidenced and characterised. In Sect. 6, the effect of the carbon templating structure on the P3HT organisation on the surface is investigated, showing the chirality-driven polymer assembly on the carbon nanotube surface. The interaction between P3HT and CNTs brings also to charge transfer, with the modification of physical properties for both species. In particular, the alteration of the polymer electronic properties and the modification of the nanotube mechanical structure are a direct consequence of the P3HT p-p stacking on the nanotube surface. Finally, some considerations based on molecular dynamics studies are reported in order to confirm and support the experimental results discussed.