Influence of oxidation and reduction conditions upon the morphology of silica-supported polycrystalline silver catalysts

The effect of oxidation and reduction conditions upon the morphology of polycrystalline silver catalysts has been investigated by means of in situ Fourier-transform infrared (FTIR) spectroscopy. Characterization of the sample was achieved by inspection of the νas(COO) band profile of adsorbed formate, recorded after dosing with formic acid at ambient temperature. Evidence was obtained for the existence of a silver surface reconstructed by the presence of subsurface oxygen in addition to the conventional family of Ag(111) and Ag(110) crystal faces. Oxidation at 773 K facilitated the reconstruction of silver planes due to the formation of subsurface oxygen species. Prolonged oxygen treatment at 773 K also caused particle fragmentation as a consequence of excessive oxygen penetration of the silver catalyst at defect sites. It was also deduced that the presence of oxygen in the gas phase stabilized the growth of silver planes which could form stronger bonds with oxygen. In contrast, high-temperature thermal treatment in vacuum induced significant sintering of the silver catalyst. Reduction at 773 K resulted in substantial quantities of dissolved hydrogen (and probably hydroxy species) in the bulk silver structure. Furthermore, enhanced defect formation in the catalyst was also noted, as evidenced by the increased concentration of formate species associated with oxygen-reconstructed silver faces.

Distributed low-power image processing in wireless sensor networks for intelligent video surveillance applications

Distributed Wireless Smart Camera (DWSC) network is a special type of Wireless Sensor Network (WSN) that processes captured images in a distributed manner. While image processing on DWSCs sees a great potential for growth, with its applications possessing a vast practical application domain such as security surveillance and health care, it suffers from tremendous constraints. In addition to the limitations of conventional WSNs, image processing on DWSCs requires more computational power, bandwidth and energy that presents significant challenges for large scale deployments. This dissertation has developed a number of algorithms that are highly scalable, portable, energy efficient and performance efficient, with considerations of practical constraints imposed by the hardware and the nature of WSN. More specifically, these algorithms tackle the problems of multi-object tracking and localisation in distributed wireless smart camera net- works and optimal camera configuration determination. Addressing the first problem of multi-object tracking and localisation requires solving a large array of sub-problems. The sub-problems that are discussed in this dissertation are calibration of internal parameters, multi-camera calibration for localisation and object handover for tracking. These topics have been covered extensively in computer vision literatures, however new algorithms must be invented to accommodate the various constraints introduced and required by the DWSC platform. A technique has been developed for the automatic calibration of low-cost cameras which are assumed to be restricted in their freedom of movement to either pan or tilt movements. Camera internal parameters, including focal length, principal point, lens distortion parameter and the angle and axis of rotation, can be recovered from a minimum set of two images of the camera, provided that the axis of rotation between the two images goes through the camera's optical centre and is parallel to either the vertical (panning) or horizontal (tilting) axis of the image. For object localisation, a novel approach has been developed for the calibration of a network of non-overlapping DWSCs in terms of their ground plane homographies, which can then be used for localising objects. In the proposed approach, a robot travels through the camera network while updating its position in a global coordinate frame, which it broadcasts to the cameras. The cameras use this, along with the image plane location of the robot, to compute a mapping from their image planes to the global coordinate frame. This is combined with an occupancy map generated by the robot during the mapping process to localised objects moving within the network. In addition, to deal with the problem of object handover between DWSCs of non-overlapping fields of view, a highly-scalable, distributed protocol has been designed. Cameras that follow the proposed protocol transmit object descriptions to a selected set of neighbours that are determined using a predictive forwarding strategy. The received descriptions are then matched at the subsequent camera on the object's path using a probability maximisation process with locally generated descriptions. The second problem of camera placement emerges naturally when these pervasive devices are put into real use. The locations, orientations, lens types etc. of the cameras must be chosen in a way that the utility of the network is maximised (e.g. maximum coverage) while user requirements are met. To deal with this, a statistical formulation of the problem of determining optimal camera configurations has been introduced and a Trans-Dimensional Simulated Annealing (TDSA) algorithm has been proposed to effectively solve the problem.

Microstructure and properties of artificial grain boundaries in epitaxial YBA2Cu3O7-δ thin films grown on [001] tilt YZrO2 bicrystals

The microstructure of artificial grain boundaries in YBa2Cu3O7-δ (YBCO) thin films grown on [001] tilt YZrO2 (YSZ) bicrystal substrates has been characterized using transmission electron microscopy and atomic force microscopy. Despite a relatively straight morphology of the substrate boundaries, the film boundaries were wavy. The waviness was a result of the combined effects of grooving at the substrate boundaries prior to the film deposition and an island-growth mechanism for YBCO on YSZ substrates. The dihedral angle of the groove walls varied with the misorientation angle and depended on the symmetry of the substrate boundary. The amplitudes of the film boundary waviness compared well with the widths of the grooves. In addition, the grooves induced local bending of the YBCO lattice planes and additional tilt components perpendicular to the c-axis close to the film boundaries. © 1995.

Observation of exsolution textures within Ba-Cu-O-rich solidified melts of Y-Ba-Cu-O materials and their relationship to Y123 nucleation and texturing

Layers (about 60-100 μm thick) of almost pure BaCuO2 (BC1), as determined using X-ray diffractometry (XRD) and scanning electron microscopy (SEM), coat the surfaces of YBa2Cu3O7-x (Y123) samples partial melt processed using a single-zone vertical furnace. The actual Cu/Ba ratio of the BC1 phase is 1.2-1.3 as determined using energy dispersive X-ray spectrometry (EDS). The nominally BC1 phase displays an exsolution of BC1.5 or BC2 in the form of thin plates (about 50-100 nm thick) along {100}-type cleavage planes or facets. The exsolved phase also fills cracks within the BC1 layer that require it to be in a molten state at some stage of processing. The samples were influenced by Pt contamination from the supporting wire, which may have stabilised the BC1.5 phase. Many of the Y123 grains have the same morphology as the exsolution domains, and run nearly parallel to the thin plates of the exsolved phases, strongly indicating that Y123 nucleation took place at the interface between the BC1 and the BC1.5 or BC2 exsolved phases. The network of nearly parallel exsolved 'channels' provides a matrix and a mechanism through which a high degree of local texture can be initiated in the material.

A nanometre-scale non-periodic structural variation in high temperature superconducting ceramics and the implications for properties

Non-periodic structural variation has been found in the high Tc cuprates, YBa2Cu3O7-x and Hg0.67Pb0.33Ba2Ca2Cu 3O8+δ, by image analysis of high resolution transmission electron microscope (HRTEM) images. We use two methods for analysis of the HRTEM images. The first method is a means for measuring the bending of lattice fringes at twin planes. The second method is a low-pass filter technique which enhances information contained by diffuse-scattered electrons and reveals what appears to be an interference effect between domains of differing lattice parameter in the top and bottom of the thin foil. We believe that these methods of image analysis could be usefully applied to the many thousands of HRTEM images that have been collected by other workers in the high temperature superconductor field. This work provides direct structural evidence for phase separation in high Tc cuprates, and gives support to recent stripes models that have been proposed to explain various angle resolved photoelectron spectroscopy and nuclear magnetic resonance data. We believe that the structural variation is a response to an opening of an electronic solubility gap where holes are not uniformly distributed in the material but are confined to metallic stripes. Optimum doping may occur as a consequence of the diffuse boundaries between stripes which arise from spinodal decomposition. Theoretical ideas about the high Tc cuprates which treat the cuprates as homogeneous may need to be modified in order to take account of this type of structural variation.

The structure of Pavlovian fear conditioning in the amygdala

Do different brains forming a specific memory allocate the same groups of neurons to encode it? One way to test this question is to map neurons encoding the same memory and quantitatively compare their locations across individual brains. In a previous study, we used this strategy to uncover a common topography of neurons in the dorsolateral amygdala (LAd) that expressed a learning-induced and plasticity-related kinase (p42/44 mitogen-activated protein kinase; pMAPK), following auditory Pavlovian fear conditioning. In this series of experiments, we extend our initial findings to ask to what extent this functional topography depends upon intrinsic neuronal structure. We first showed that the majority (87 %) of pMAPK expression in the lateral amygdala was restricted to principal-type neurons. Next, we verified a neuroanatomical reference point for amygdala alignment using in vivo magnetic resonance imaging and in vitro morphometrics. We then determined that the topography of neurons encoding auditory fear conditioning was not exclusively governed by principal neuron cytoarchitecture. These data suggest that functional patterning of neurons undergoing plasticity in the amygdala following Pavlovian fear conditioning is specific to memory formation itself. Further, the spatial allocation of activated neurons in the LAd was specific to cued (auditory), but not contextual, fear conditioning. Spatial analyses conducted at another coronal plane revealed another spatial map unique to fear conditioning, providing additional evidence that the functional topography of fear memory storing cells in the LAd is non-random and stable. Overall, these data provide evidence for a spatial organizing principle governing the functional allocation of fear memory in the amygdala.

The effect of organ motion of radiotherapy plans

Organ motion as a result of respiration is an important field of research for medical physics. Knowledge of magnitude and direction of this motion is necessary to allow for more accurate radiotherapy treatment planning. This will result in higher doses to the tumour whilst sparing healthy tissue. This project involved human trials, where the radiation therapy patient's kidneys were CT scanned under three different conditions; whilst free breathing (FB), breath-hold at normal tidal inspiration (BHIN), and breath-hold at normal tidal expiration (BHEX). The magnitude of motion was measured by recording the outline of the kidney from a Beam's Eye View (BEV). The centre of mass of this 2D shape was calculated for each set using "ImageJ" software and the magnitude of movement determined from the change in the centroid's coordinates between the BHIN and BHEX scans. The movement ranged from, for the left and right kidneys, 4-46mm and 2-44mm in the superior/inferior (axial) plane, 1-21mm and 2- 16mm in the anterior/posterior (coronal) plane, and 0-6mm and 0-8mm in the lateral/medial (sagittal) plane. From exhale to inhale, the kidneys tended to move inferiorly, anteriorly and laterally. A standard radiotherapy plan, designed to treat the para-aortics with opposed lateral fields was performed on the free breathing (planning) CT set. The field size and arrangement was set up using the same parameters for each subject. The prescription was to deliver 45 Gray in 25 fractions. This field arrangement and prescription was then copied over to the breath hold CT sets, and the dosimetric differences were compared using Dose Volume Histograms (DVH). The point of comparison for the three sets was recorded as the percentage volume of kidney receiving less than or equal to 10 Gray. The QUASAR respiratory motion phantom was used with the range of motion determined from the human study. The phantom was imaged, planned and treated with a linear accelerator with dose determined by film. The effect of the motion was measured by the change in the penumbra of the film and compared to the penumbra from the treatment planning system.

Predator Crown-of-Thorns Starfish (Acanthaster planci) Outbreak, Mass Mortality of Corals, and Cascading Effects on Reef Fish and Benthic Communities

Outbreaks of the coral-killing seastar Acanthaster planci are intense disturbances that can decimate coral reefs. These events consist of the emergence of large swarms of the predatory seastar that feed on reef-building corals, often leading to widespread devastation of coral populations. While cyclic occurrences of such outbreaks are reported from many tropical reefs throughout the Indo-Pacific, their causes are hotly debated, and the spatio-temporal dynamics of the outbreaks and impacts to reef communities remain unclear. Based on observations of a recent event around the island of Moorea, French Polynesia, we show that Acanthaster outbreaks are methodic, slow-paced, and diffusive biological disturbances. Acanthaster outbreaks on insular reef systems like Moorea's appear to originate from restricted areas confined to the ocean-exposed base of reefs. Elevated Acanthaster densities then progressively spread to adjacent and shallower locations by migrations of seastars in aggregative waves that eventually affect the entire reef system. The directional migration across reefs appears to be a search for prey as reef portions affected by dense seastar aggregations are rapidly depleted of living corals and subsequently left behind. Coral decline on impacted reefs occurs by the sequential consumption of species in the order of Acanthaster feeding preferences. Acanthaster outbreaks thus result in predictable alteration of the coral community structure. The outbreak we report here is among the most intense and devastating ever reported. Using a hierarchical, multi-scale approach, we also show how sessile benthic communities and resident coral-feeding fish assemblages were subsequently affected by the decline of corals. By elucidating the processes involved in an Acanthaster outbreak, our study contributes to comprehending this widespread disturbance and should thus benefit targeted management actions for coral reef ecosystems.

Pitfalls in the use of kappa when interpreting agreement between multiple raters in reliability studies

OBJECTIVE To compare different reliability coefficients (exact agreement, and variations of the kappa (generalised, Cohen's and Prevalence Adjusted and Biased Adjusted (PABAK))) for four physiotherapists conducting visual assessments of scapulae. DESIGN Inter-therapist reliability study. SETTING Research laboratory. PARTICIPANTS 30 individuals with no history of neck or shoulder pain were recruited with no obvious significant postural abnormalities. MAIN OUTCOME MEASURES Ratings of scapular posture were recorded in multiple biomechanical planes under four test conditions (at rest, and while under three isometric conditions) by four physiotherapists. RESULTS The magnitude of discrepancy between the two therapist pairs was 0.04 to 0.76 for Cohen's kappa, and 0.00 to 0.86 for PABAK. In comparison, the generalised kappa provided a score between the two paired kappa coefficients. The difference between mean generalised kappa coefficients and mean Cohen's kappa (0.02) and between mean generalised kappa and PABAK (0.02) were negligible, but the magnitude of difference between the generalised kappa and paired kappa within each plane and condition was substantial; 0.02 to 0.57 for Cohen's kappa and 0.02 to 0.63 for PABAK, respectively. CONCLUSIONS Calculating coefficients for therapist pairs alone may result in inconsistent findings. In contrast, the generalised kappa provided a coefficient close to the mean of the paired kappa coefficients. These findings support an assertion that generalised kappa may lead to a better representation of reliability between three or more raters and that reliability studies only calculating agreement between two raters should be interpreted with caution. However, generalised kappa may mask more extreme cases of agreement (or disagreement) that paired comparisons may reveal.

Knitted images : specimens

Knitting, as a conduit for multiple literacies takes on embodied practice and becomes research, investigation, theorization, and brings about physical and metaphysical theorizing on Deleuzian and Guattarian (1980/1987) concepts of the rhizome: the looping and constructing of the knitted planes prompt thoughts about the project that seem just ‘beyond the level of consciousness’ (Semetsky 2007, p. 200)...

H2-O2 porous fuel injection in a radical farming scramjet

This paper reports on the experimental testing of oxygen compatible ceramic matrix composite porous injectors in a nominally two-dimensional hydrogen fuelled and oxygen enriched radical farming scramjet in the T4 shock tunnel facility. All experiments were performed at a dynamic pressure of 146 kPa, an equivalent flight Mach number of 9.7, a stagnation pressure and enthalpy of 40MPa and 4.3 MJ/kg respectively and at a fuelling condition that resulted in an average equivalence ratio of 0.472. Oxygen was pre-mixed with the fuel prior to injection to achieve enrichment percentages of approximately 13%, 15% and 17%. These levels ensured that the hydrogen-oxidiser mix injected into the engine always remained too fuel rich to sustain a flame without any additional mixing with the captured air. Addition of pre-mixed oxygen with the fuel was found to significantly alter the performance of the engine; enhancing both combustion and ignition and converting a previously observed limited combustion condition into one with sustained and noticeable combustion induced pressure rise. Increases in the enrichment percentage lead to further increases in combustion levels and acted to reduce ignition lengths within the engine. Suppressed combustion runs, where a nitrogen test gas was used, confirmed that the pressure rise observed in these experiments as attributed to the oxygen enrichment and not associated with the increased mass injected.

A detailed investigation of nominally 2-D radical-farming scramjet combustion

This paper reports on an investigation of the flow/chemistry coupling inside a nominally two-dimensional inlet-fuelled scramjet configuration. The experiments were conducted at a freestream Mach number of 7.3 and a total flow enthalpy of 4.3MJ/kg corresponding to a Mach 9.7 flight condition. The phenomenon of radical-farming has been studied in detail using two-dimensional OH* chemiluminescence imaging and emission spectroscopy. High signal levels of excited OH (OH*) were detected behind the first shock reflections inside the combustion chamber upstream of any measurable pressure rise from combustion, which occurred towards the rear of the combustor. The production of OH in the first hot pocket initiates the ignition process and then accelerates the combustion process in the next downstream hot pocket. This was confirmed by numerical simulations of premixed hydrogen/air flow through the scramjet. Chemical kinetics analyses reveal that the ignition process is governed by the interaction between various reaction groups leading to a chainbranching explosion for low mean temperature and pressure combustion flowfields.

The SCRAMSPACE I scramjet flight design and construction

The design activities of the development of the SCRAMSPACE I scramjet-powered free-flight experiment are described in this paper. The objectives of this flight are first described together with the definition of the primary, secondary and tertiary experiments. The Scramjet configuration studied is first discussed together with the rocket motor system selected for this flight. The different flight sequences are then explained, highlighting the SCRAMSPACE I free-flyer separation and re-orientation procedures. A design trade-off study is then described considering vehicle stability, packaging, thermo-structural analysis and trajectory, discussing the alignment of the predicted performance with the mission scientific requirements. The global system architecture and instrumentation of the vehicle are then explained. The conclusions of this design phase are that a vehicle design has been produced which is able to meet the mission scientific goals and the procurement & construction of the vehicle are ongoing.

Chemiluminescence imaging in supersonic combustors operating in radical-farming mode

Emission spectroscopy was used to investigate ignition and combustion characteristics of supersonic combustion ramjet engines. Two-dimensional scramjet models with inlet injection, fuelled with hydrogen gas, were used in the study. The scramjet engines were configured to operate in radical farming mode, where combustion radicals are formed behind shock waves reflected at the walls. The chemiluminescence emission signals were recorded in a two-dimensional, time-integrated fashion to give information on the location and distribution of the radical farms in the combustors. High signal levels were detected in localised regions immediately downstream of shock reflections, an indication of localised hydroxyl formation supporting the concept of radical farming. Results are presented for a symmetric as well as an asymmetric scramjet geometry. These data represent the first successful visualisation of radical farms in the hot pockets of a supersonic combustor. Spectrally resolved measurements have been obtained in the ultraviolet wavelength range between 300 and 400 nm. This data shows that the OH! chemiluminescence signal around 306nm is not the most dominant source of radiation observed in the radical farms.

Radiative and total heat transfer measurements to a Titan Explorer model

Radiative and total heat transfer at the flow stagnation point of a 1:40.8 binary scaled model of the Titan Explorer vehicle were measured in the X3 expansion tube. Results from the current study illustrated that with the addition of CH4 into a N2 test gas radiative heat transfer could be detected. For a test gas of 5% CH4 and 95% N2, simulating an atmospheric model for Titanic aerocapture, approximately 4% of the experimentally measured total stagnation point heat transfer was found to be due to radiation. This was in comparison to < 1% measured for a test gas of pure nitrogen. When scaled to the flight vehicle, experimental results indicate a 64% contribution of radiation (test gas 5% CH4/95% N2). Previous numerical results however have predicted this contribution to be between 80-92%. Thus, experimental results from the current study suggest that numerical analyses are over-predicting the radiative heat transfer on the flight vehicle.