Fabrication of metal-nanoparticle-modified semiconducting copper--and silver--TCNQ materials as substrates for the reduction of chromium (VI) using thiosulfate ions at ambient temperature

The formation of readily recoverable and reusable organic semiconducting Cu- and AgTCNQ (TCNQ=7,7,8,8-tetracyanoquinodimethane) microstructures decorated with Pt and Pd metallic nanoparticles is described for the effective reduction of CrVI ions in aqueous solution at room temperature using both formic acid and an environmentally friendly thiosulfate reductant. The M-TCNQ (M=metal) materials were formed by electrocrystallisation onto a glassy carbon surface followed by galvanic replacement in the presence of H2PtCl6 or PdCl2 to form the composite material. It was found that loading of the surface with nanoparticles could easily be controlled by changing the metal salt concentration. Significantly, the M-TCNQ substrates facilitated the formation of well-isolated metal nanoparticles on their surfaces under appropriate galvanic replacement conditions. The semiconductor–metal nanoparticle combination was also found to be critical to the catalyst performance, wherein the best-performing material was CuTCNQ modified by well-isolated Pt nanoparticles with both formic acid and thiosulfate ions as the reductant.

Exploiting the facile oxidation of evaporated gold films to drive electroless silver deposition for the creation of bimetallic Au/Ag surfaces

Gold is often considered as an inert material but it has been unequivocally demonstrated that it possesses unique electronic, optical, catalytic and electrocatalytic properties when in a nanostructured form.[1] For the latter the electrochemical behaviour of gold in aqueous media has been widely studied on a plethora of gold samples, including bulk polycrystalline and single-crystal electrodes, nanoparticles, evaporated films as well as electrodeposited nanostructures, particles and thin films.[1b, 2] It is now well-established that the electrochemical behaviour of gold is not as simple as an extended double-layer charging region followed by a monolayer oxide-formation/-removal process. In fact the so-called double-layer region of gold is significantly more complicated and has been investigated with a variety of electrochemical and surface science techniques. Burke and others[3] have demonstrated that significant processes due to the oxidation of low lattice stabilised atoms or clusters of atoms occur in this region at thermally and electrochemically treated electrodes which were confirmed later by Bond[4] to be Faradaic in nature via large-amplitude Fourier transformed ac voltammetric experiments. Supporting evidence for the oxidation of gold in the double-layer region was provided by Bard,[5] who used a surface interrogation mode of scanning electrochemical microscopy to quantify the extent of this process that forms incipient oxides on the surface. These were estimated to be as high as 20% of a monolayer. This correlated with contact electrode resistance measurements,[6] capacitance measurements[7] and also electroreflection techniques...

Fatigue damage initiation life prediction for heterogeneous metals

In particle-strengthened metallic alloys, fatigue damage incubates at inclusion particles near the surface or at the change of geometries. Micromechanical simulation of inclusions such that the fatigue damage incubation mechanisms can be categorized. As micro-plasticity gradient field around different inclusions is different, a novel concept for nonlocal evaluation of micro-plasticity intensity is introduced. The effects of void aspects ration and spatial distributions are quantified for fatigue incubation life in the high-cycle fatigue regime. At last, these effects are integrated based on the statistical facts of inclusions to predict the fatigue life of structural components.

Innate and adaptive immunity at mucosal surfaces of the female reproductive tract : stratification and integration of immune protection against the transmission of sexually transmitted infections

This review examines the multiple levels of pre-existing immunity in the upper and lower female reproductive tract. In addition, we highlight the need for further research of innate and adaptive immune protection of mucosal surfaces in the female reproductive tract. Innate mechanisms include the mucus lining, a tight epithelial barrier and the secretion of antimicrobial peptides and cytokines by epithelial and innate immune cells. Stimulation of the innate immune system also serves to bridge the adaptive arm resulting in the generation of pathogen-specific humoral and cell-mediated immunity. Less understood are the multiple components that act in a coordinated way to provide a network of ongoing protection. Innate and adaptive immunity in the human female reproductive tract are influenced by the stage of menstrual cycle and are directly regulated by the sex steroid hormones, progesterone and estradiol. Furthermore, the effect of hormones on immunity is mediated both directly on immune and epithelial cells and indirectly by stimulating growth factor secretion from stromal cells. The goal of this review is to focus on the diverse aspects of the innate and adaptive immune systems that contribute to a unique network of protection throughout the female reproductive tract.

Laser-radar data fusion with Gaussian Process Implicit Surfaces

This work considers the problem of building high-fidelity 3D representations of the environment from sensor data acquired by mobile robots. Multi-sensor data fusion allows for more complete and accurate representations, and for more reliable perception, especially when different sensing modalities are used. In this paper, we propose a thorough experimental analysis of the performance of 3D surface reconstruction from laser and mm-wave radar data using Gaussian Process Implicit Surfaces (GPIS), in a realistic field robotics scenario. We first analyse the performance of GPIS using raw laser data alone and raw radar data alone, respectively, with different choices of covariance matrices and different resolutions of the input data. We then evaluate and compare the performance of two different GPIS fusion approaches. The first, state-of-the-art approach directly fuses raw data from laser and radar. The alternative approach proposed in this paper first computes an initial estimate of the surface from each single source of data, and then fuses these two estimates. We show that this method outperforms the state of the art, especially in situations where the sensors react differently to the targets they perceive.

Controlling whole blood activation and resultant clot properties by carboxyl and alkyl functional groups on material surfaces : a possible therapeutic approach for enhancing bone healing

Most research virtually ignores the important role of a blood clot in supporting bone healing. In this study, we investigated the effects of surface functional groups carboxyl and alkyl on whole blood coagulation, complement activation and blood clot formation. We synthesised and tested a series of materials with different ratios of carboxyl (–COOH) and alkyl (–CH3, –CH2CH3 and –(CH2)3CH3) groups. We found that surfaces with –COOH/–(CH2)3CH3 induced a faster coagulation activation than those with –COOH/– CH3 and –CH2CH3, regardless of the –COOH ratios. An increase in –COOH ratios on –COOH/–CH3 and –CH2CH3 surfaces decreased the rate of coagulation activation. The pattern of complement activation was entirely similar to that of surface-induced coagulation. All material coated surfaces resulted in clots with thicker fibrin in a denser network at the clot/material interface and a significantly slower initial fibrinolysis when compared to uncoated glass surfaces. The amounts of platelet-derived growth factor-AB (PDGF-AB) and transforming growth factor-b (TGF-b1) released from an intact clot were higher than a lysed clot. The release of PDGF-AB was found to be correlated with the fibrin density. This study demonstrated that surface chemistry can significantly influence the activation of blood coagulation and complement system, resultant clot structure, susceptibility to fibrinolysis as well as release of growth factors, which are important factors determining the bone healing process.

From single crystal surfaces to single atoms : investigating active sites in electrocatalysis

Electrocatalytic processes will undoubtedly be at the heart of energising future transportation and technology with the added importance of being able to create the necessary fuels required to do so in an environmentally friendly and cost effective manner. For this to be successful two almost mutually exclusive surface properties need to be reconciled, namely producing highly active/reactive surface sites that exhibit long term stability. This article reviews the various approaches which have been undertaken to study the elusive nature of these active sites on metal surfaces which are considered as adatoms or clusters of adatoms with low coordination number. This includes the pioneering studies at extended well defined stepped single crystal surfaces using cyclic voltammetry up to the highly sophisticated in situ electrochemical imaging techniques used to study chemically synthesised nanomaterials. By combining the information attained from single crystal surfaces, individual nanoparticles of defined size and shape, density functional theory calculations and new concepts such as mesoporous multimetallic thin films and single atom electrocatalysts new insights into the design and fabrication of materials with highly active but stable active sites can be achieved. The area of electrocatalysis is therefore not only a fascinating and exciting field in terms of realistic technological and economical benefits but also from the fundamental understanding that can be acquired by studying such an array of interesting materials.

Mathematical relationships for metal build-up on urban road surfaces based on traffic and land use characteristics

The study investigated the influence of traffic and land use parameters on metal build-up on urban road surfaces. Mathematical relationships were developed to predict metals originating from fuel combustion and vehicle wear. The analysis undertaken found that nickel and chromium originate from exhaust emissions, lead, copper and zinc from vehicle wear, cadmium from both exhaust and wear and manganese from geogenic sources. Land use does not demonstrate a clear pattern in relation to the metal build-up process, though its inherent characteristics such as traffic activities exert influence. The equation derived for fuel related metal load has high cross-validated coefficient of determination (Q2) and low Standard Error of Cross-Validation (SECV) values indicates that the model is reliable, while the equation derived for wear-related metal load has low Q2 and high SECV values suggesting its use only in preliminary investigations. Relative Prediction Error values for both equations are considered to be well within the error limits for a complex system such as an urban road surface. These equations will be beneficial for developing reliable stormwater treatment strategies in urban areas which specifically focus on mitigation of metal pollution.

Beyond actuality : locating an authentic hybridity between heterogeneous media in an installation art practice

Addressing possibilities for authentic combinations of diverse media within an installation setting, this research tested hybrid blends of the physical, digital and temporal to explore liminal space and image. The practice led research reflected on creation of artworks from three perspectives – material, immaterial and hybrid – and in doing so, developed a new methodological structure that extends conventional forms of triangulation. This study explored how physical and digital elements each sought hierarchical presence, yet simultaneously coexisted, thereby extending the visual and conceptual potential of the work. Outcomes demonstrated how utilising and recording transitional processes of hybrid imagery achieved a convergence of diverse, experiential forms. "Hybrid authority" – an authentic convergence of disparate elements – was articulated in the creation and public sharing of processual works and the creation of an innovative framework for hybrid art practice.

Paint spray mass spectrometry for the detection of additives from polymers on conducting surfaces

Paint Spray is developed as a direct sampling ionisation method for mass spectrometric analysis of additives in polymer-based surface coatings. The technique simply involves applying an external high voltage (5 kV) to the wetted sample placed in front of the mass spectrometer inlet and represents a much simpler ionisation technique compared to those currently available. The capabilities of Paint Spray are demonstrated herein with the detection of four commercially available hindered amine light stabilisers; TINUVIN® 770, TINUVIN® 292, TINUVIN® 123 and TINUVIN® 152 directly from thermoset polyester-based coil coatings. Paint Spray requires no sample preparation or pre-treatment and combined with its simplicity - requiring no specialised equipment - makes it ideal for use by non-specialists. The application of Paint Spray for industrial use has significant potential as sample collection from a coil coating production line and Paint Spray ionisation could enable fast quality control screening at high sensitivity.

Measuring the mechanical properties of ground ophthalmic polymer surfaces using nanoindentation

This work is motivated by the need to efficiently machine the edges of ophthalmic polymer lenses for mounting in spectacle or instrument frames. The polymer materials used are required to have suitable optical characteristics such high refractive index and Abbe number, combined with low density and high scratch and impact resistance. Edge surface finish is an important aesthetic consideration; its quality is governed by the material removal operation and the physical properties of the material being processed. The wear behaviour of polymer materials is not as straightforward as for other materials due to their molecular and structural complexity, not to mention their time-dependent properties. Four commercial ophthalmic polymers have been studied in this work using nanoindentation techniques which are evaluated as tools for probing surface mechanical properties in order to better understand the grinding response of polymer materials.

A neutron diffraction investigation of residual stresses in rail ends after severe deformation of rail surfaces

Insulated rail joints (IRJs) are a primary component of the rail track safety and signalling systems. Rails are supported by two fishplates which are fastened by bolts and nuts and, with the support of sleepers and track ballast, form an integrated assembly. IRJ failure can result from progressive defects, the propagation of which is influenced by residual stresses in the rail. Residual stresses change significantly during service due to the complex deformation and damage effects associated with wheel rolling, sliding and impact. IRJ failures can occur when metal flows over the insulated rail gap (typically 6-8 mm width), breaks the electrically isolated section of track and results in malfunction of the track signalling system. In this investigation, residual stress measurements were obtained from rail-ends which had undergone controlled amounts of surface plastic deformation using a full scale wheel-on-track simulation test rig. Results were compared with those obtained from similar investigations performed on rail ends associated with ex-service IRJs. Residual stresses were measured by neutron diffraction at the Australian Nuclear Science and Technology Organisation (ANSTO). Measurements with constant gauge volume 3x3x3 mm3 were carried in the central vertical plane on 5mm thick sliced rail samples cut by an electric discharge machine (EDM). Stress evolution at the rail ends was found to exhibit characteristics similar to those of the ex-service rails, with a compressive zone of 5mm deep that is counterbalanced by a tension zone beneath, extending to a depth of around 15mm. However, in contrast to the ex-service rails, the type of stress distribution in the test-rig deformed samples was apparently different due to the localization of load under the particular test conditions. In the latter, in contrast with clear stress evolution, there was no obvious evolution of d0. Since d0 reflects rather long-term accumulation of crystal lattice damage and microstructural changes due to service load, the loading history of the test rig samples has not reached the same level as the ex-service rails. It is concluded that the wheel-on-rail simulation rig provides the potential capability for testing the wheel-rail rolling contact conditions in rails, rail ends and insulated rail joints.

Artful surfaces : an ethnographic study exploring the use of space in design studios

A largely overlooked aspect of creative design practices is how physical space in design studios plays a role in supporting designers' everyday work. In particular, studio surfaces such as designers' desks, office walls, notice boards, clipboards and drawing boards are full of informative, inspirational and creative artefacts such as, sketches, drawings, posters, story-boards and Post-it notes. Studio surfaces are not just the carriers of information but importantly they are sites of methodic design practices, i.e. they indicate, to an extent, how design is being carried out. This article describes the results of an ethnographic study on the use of workplace surfaces in design studios, from two academic design departments. Using the field study results, the article introduces an idea of ‘artful surfaces’. Artful surfaces emphasise how artfully designers integrate these surfaces into their everyday work and how the organisation of these surfaces comes about helping designers in accomplishing their creative and innovative design practices. Using examples from the field study, the article shows that artful surfaces have both functional and inspirational characteristics. From the field study, three types of artful surfaces are identified: personal; shared; and project-specific. The article suggests that a greater insight into how these artful surfaces are created and used could lead to better design of novel display technologies to support designers' everyday work.

Artful surfaces in design practices

A largely overlooked aspect of innovative design practices is how workplace surfaces play a role in supporting designers' everyday work. In this paper we introduce the idea of artful surfaces. Artful surfaces (Figure 1) are full of informative, inspirational and creative artefacts that help designers accomplish their everyday design practices. The way these surfaces are created and used could provide information about how designers work. We identify four types of artful surfaces: personal, shared, project-specific and live surfaces; and describe them using examples.

Spatially-explicit modelling of grassland classes - an improved method of integrating a climate-based classification model with interpolated climate surfaces

Spatially-explicit modelling of grassland classes is important to site-specific planning for improving grassland and environmental management over large areas. In this study, a climate-based grassland classification model, the Comprehensive and Sequential Classification System (CSCS) was integrated with spatially interpolated climate data to classify grassland in Gansu province, China. The study area is characterized by complex topographic features imposed by plateaus, high mountains, basins and deserts. To improve the quality of the interpolated climate data and the quality of the spatial classification over this complex topography, three linear regression methods, namely an analytic method based on multiple regression and residues (AMMRR), a modification of the AMMRR method through adding the effect of slope and aspect to the interpolation analysis (M-AMMRR) and a method which replaces the IDW approach for residue interpolation in M-AMMRR with an ordinary kriging approach (I-AMMRR), for interpolating climate variables were evaluated. The interpolation outcomes from the best interpolation method were then used in the CSCS model to classify the grassland in the study area. Climate variables interpolated included the annual cumulative temperature and annual total precipitation. The results indicated that the AMMRR and M-AMMRR methods generated acceptable climate surfaces but the best model fit and cross validation result were achieved by the I-AMMRR method. Twenty-six grassland classes were classified for the study area. The four grassland vegetation classes that covered more than half of the total study area were "cool temperate-arid temperate zonal semi-desert", "cool temperate-humid forest steppe and deciduous broad-leaved forest", "temperate-extra-arid temperate zonal desert", and "frigid per-humid rain tundra and alpine meadow". The vegetation classification map generated in this study provides spatial information on the locations and extents of the different grassland classes. This information can be used to facilitate government agencies' decision-making in land-use planning and environmental management, and for vegetation and biodiversity conservation. The information can also be used to assist land managers in the estimation of safe carrying capacities which will help to prevent overgrazing and land degradation.