Spin transition of 1D, 2D and 3D iron(II) complex polymers - the tug-of-war between elastic interaction and a shock-absorber effect

The structures of linear chain Fe(II) spin-crossover compounds of α,β- and α,ω-bis (tetrazol-1-yl)alkane type ligands are described in relation to their magnetic properties. The first threefold interlocked 3-D catenane Fe(II) spin-transition system, [μ-tris(1,4-bis(tetrazol-1-yl)butane-N1,N1′) iron(II)] bis(perchlorate), will be discussed. An analysis is made among the structures and the cooperativity of the spin-crossover behaviour of polynuclear Fe(II) spin-transition materials.

Flow field analysis of some mixing and conveying screw element regions, within a closely intermeshing, co-rotating twin-screw extruder.

Grafting of antioxidants and other modifiers onto polymers by reactive extrusion, has been performed successfully by the Polymer Processing and Performance Group at Aston University. Traditionally the optimum conditions for the grafting process have been established within a Brabender internal mixer. Transfer of this batch process to a continuous processor, such as an extruder, has, typically, been empirical. To have more confidence in the success of direct transfer of the process requires knowledge of, and comparison between, residence times, mixing intensities, shear rates and flow regimes in the internal mixer and in the continuous processor.The continuous processor chosen for the current work in the closely intermeshing, co-rotating twin-screw extruder (CICo-TSE). CICo-TSEs contain screw elements that convey material with a self-wiping action and are widely used for polymer compounding and blending. Of the different mixing modules contained within the CICo-TSE, the trilobal elements, which impose intensive mixing, and the mixing discs, which impose extensive mixing, are of importance when establishing the intensity of mixing. In this thesis, the flow patterns within the various regions of the single-flighted conveying screw elements and within both the trilobal element and mixing disc zones of a Betol BTS40 CICo-TSE, have been modelled using the computational fluid dynamics package Polyflow. A major obstacle encountered when solving the flow problem within all of these sets of elements, arises from both the complex geometry and the time-dependent flow boundaries as the elements rotate about their fixed axes. Simulation of the time dependent boundaries was overcome by selecting a number of sequential 2D and 3D geometries, used to represent partial mixing cycles. The flow fields were simulated using the ideal rheological properties of polypropylene and characterised in terms of velocity vectors, shear stresses generated and a parameter known as the mixing efficiency. The majority of the large 3D simulations were performed on the Cray J90 supercomputer situated at the Rutherford-Appleton laboratories, with pre- and postprocessing operations achieved via a Silicon Graphics Indy workstation. A mechanical model was constructed consisting of various CICo-TSE elements rotating within a transparent outer barrel. A technique has been developed using coloured viscous clays whereby the flow patterns and mixing characteristics within the CICo-TSE may be visualised. In order to test and verify the simulated predictions, the patterns observed within the mechanical model were compared with the flow patterns predicted by the computational model. The flow patterns within the single-flighted conveying screw elements in particular, showed good agreement between the experimental and simulated results.

Effects of relational policies in export channels

Two key causes of failure for exporters are (1) the availability of adequate resources at the point of entry, and, (2) the quality of the exporter-foreign distributor relationship. Generally, export research has found that, as foreign distributor relationship-specific investments increase and as relational bonds are established, performance improves (e.g., Bello and Gilliland 1997). However, investments and the quality of the relationship are challenged by the foreign distributor’s motivation to participate in the relationship. One way exporters deal with this issue is by developing trade policies, which we refer to as “relational policies,” that are intended to motivate relational behaviors on the part of the foreign distributor.

Developmental trajectories of part-based and configural object recognition in adolescence.

Three experiments assessed the development of children's part and configural (part-relational) processing in object recognition during adolescence. In total, 312 school children aged 7-16 years and 80 adults were tested in 3-alternative forced choice (3-AFC) tasks. They judged the correct appearance of upright and inverted presented familiar animals, artifacts, and newly learned multipart objects, which had been manipulated either in terms of individual parts or part relations. Manipulation of part relations was constrained to either metric (animals, artifacts, and multipart objects) or categorical (multipart objects only) changes. For animals and artifacts, even the youngest children were close to adult levels for the correct recognition of an individual part change. By contrast, it was not until 11-12 years of age that they achieved similar levels of performance with regard to altered metric part relations. For the newly learned multipart objects, performance was equivalent throughout the tested age range for upright presented stimuli in the case of categorical part-specific and part-relational changes. In the case of metric manipulations, the results confirmed the data pattern observed for animals and artifacts. Together, the results provide converging evidence, with studies of face recognition, for a surprisingly late consolidation of configural-metric relative to part-based object recognition.

Interactions between landcover pattern and geospatial processing methods:effects on landscape metrics and classification accuracy

Remote sensing data is routinely used in ecology to investigate the relationship between landscape pattern as characterised by land use and land cover maps, and ecological processes. Multiple factors related to the representation of geographic phenomenon have been shown to affect characterisation of landscape pattern resulting in spatial uncertainty. This study investigated the effect of the interaction between landscape spatial pattern and geospatial processing methods statistically; unlike most papers which consider the effect of each factor in isolation only. This is important since data used to calculate landscape metrics typically undergo a series of data abstraction processing tasks and are rarely performed in isolation. The geospatial processing methods tested were the aggregation method and the choice of pixel size used to aggregate data. These were compared to two components of landscape pattern, spatial heterogeneity and the proportion of landcover class area. The interactions and their effect on the final landcover map were described using landscape metrics to measure landscape pattern and classification accuracy (response variables). All landscape metrics and classification accuracy were shown to be affected by both landscape pattern and by processing methods. Large variability in the response of those variables and interactions between the explanatory variables were observed. However, even though interactions occurred, this only affected the magnitude of the difference in landscape metric values. Thus, provided that the same processing methods are used, landscapes should retain their ranking when their landscape metrics are compared. For example, highly fragmented landscapes will always have larger values for the landscape metric "number of patches" than less fragmented landscapes. But the magnitude of difference between the landscapes may change and therefore absolute values of landscape metrics may need to be interpreted with caution. The explanatory variables which had the largest effects were spatial heterogeneity and pixel size. These explanatory variables tended to result in large main effects and large interactions. The high variability in the response variables and the interaction of the explanatory variables indicate it would be difficult to make generalisations about the impact of processing on landscape pattern as only two processing methods were tested and it is likely that untested processing methods will potentially result in even greater spatial uncertainty. © 2013 Elsevier B.V.

Employee perceptions of interpersonal justice:the moderating role of attachment and cultural values

This study investigated the moderating role of national culture in the relationship between attachment orientations and employee perceptions of interpersonal justice. Three hundred and forty individuals from countries categorized (by GLOBE) as either low collectivistic ‘Anglo’ (e.g. UK, Australia, US; N = 205) or high collectivistic ‘South Asian’ (e.g. India, Malaysia, Indonesia; N = 135), responded to an online questionnaire. Attachment anxiety and avoidance were negatively related to perceptions of interpersonal justice, as expected, but against expectations the direct relationship between attachment orientations and interpersonal justice did not differ between cultures. However, supplementary analysis revealed a significant 3-way interaction. When attachment anxiety was high, avoidance was a stronger predictor of interpersonal justice perceptions but the direction of this association differed by culture. The findings suggest the importance of fit between employee attachment orientations and cultural relational values in the workplace. Practical and theoretical implications are discussed.

High-pressure XPS of crotyl alcohol selective oxidation over metallic and oxidized Pd(111)

Here, we report on the first application of high-pressure XPS (HP-XPS) to the surface catalyzed selective oxidation of a hydrocarbon over palladium, wherein the reactivity of metal and oxide surfaces in directing the oxidative dehydrogenation of crotyl alcohol (CrOH) to crotonaldehyde (CrHCO) is evaluated. Crotonaldehyde formation is disfavored over Pd(111) under all reaction conditions, with only crotyl alcohol decomposition observed. In contrast, 2D Pd5O4 and 3D PdO overlayers are able to selectively oxidize crotyl alcohol (1 mTorr) to crotonaldehyde in the presence of co-fed oxygen (140 mTorr) at temperatures as low as 40 °C. However, 2D Pd5O4 ultrathin films are unstable toward reduction by the alcohol at ambient temperature, whereas the 3D PdO oxide is able to sustain catalytic crotonaldehyde production even up to 150 °C. Co-fed oxygen is essential to stabilize palladium surface oxides toward in situ reduction by crotyl alcohol, with stability increasing with oxide film dimensionality.

Multi-frequency segmental bio-impedance device:design, development and applications

Bio-impedance analysis (BIA) provides a rapid, non-invasive technique for body composition estimation. BIA offers a convenient alternative to standard techniques such as MRI, CT scan or DEXA scan for selected types of body composition analysis. The accuracy of BIA is limited because it is an indirect method of composition analysis. It relies on linear relationships between measured impedance and morphological parameters such as height and weight to derive estimates. To overcome these underlying limitations of BIA, a multi-frequency segmental bio-impedance device was constructed through a series of iterative enhancements and improvements of existing BIA instrumentation. Key features of the design included an easy to construct current-source and compact PCB design. The final device was trialled with 22 human volunteers and measured impedance was compared against body composition estimates obtained by DEXA scan. This enabled the development of newer techniques to make BIA predictions. To add a ‘visual aspect’ to BIA, volunteers were scanned in 3D using an inexpensive scattered light gadget (Xbox Kinect controller) and 3D volumes of their limbs were compared with BIA measurements to further improve BIA predictions. A three-stage digital filtering scheme was also implemented to enable extraction of heart-rate data from recorded bio-electrical signals. Additionally modifications have been introduced to measure change in bio-impedance with motion, this could be adapted to further improve accuracy and veracity for limb composition analysis. The findings in this thesis aim to give new direction to the prediction of body composition using BIA. The design development and refinement applied to BIA in this research programme suggest new opportunities to enhance the accuracy and clinical utility of BIA for the prediction of body composition analysis. In particular, the use of bio-impedance to predict limb volumes which would provide an additional metric for body composition measurement and help distinguish between fat and muscle content.

Correspondence between muscle motion and EMG activity during whole body vibration

The aim of this study is to highlight the relation between muscle motion and electromyographyc activity during whole body vibration. This treatment is accounted for eliciting a reflex muscle activity in response to vibratory stimulation. Simultaneous recordings from quadriceps Rectus Femoris EMG and 3D muscle accelerations on fifteen subjects undergoing vibration treatments were collected. In our study vibrations were delivered via a sinusoidal oscillating platform at different frequencies (10-45 Hz), with a constant amplitude. Muscle motion was estimated by processing accelerometer data. Displacements revealed a mechanical resonant-like behaviour of the muscle; resonance frequencies and dumping factors depended on subject. Large EMG motion artifacts were removed using sharp notch filters centred at the vibration frequency and its superior harmonics. RMS values of artifact-free EMG were found correlated to the actual muscle displacement. The results were in accordance to the hypothesis of a proprioceptive response during vibration treatment. Nevertheless, motion artifacts produced an overestimation of muscle activity, therefore its removal was essential. © 2009 Springer Berlin Heidelberg.