The effect of mechanochemical activation upon the intercalation of a high-defect kaolinite with formamide

The effect of mechanochemical activation upon the intercalation of formamide into a high-defect kaolinite has been studied using a combination of X-ray diffraction, thermal analysis, and DRIFT spectroscopy. X-ray diffraction shows that the intensity of the d(001) spacing decreases with grinding time and that the intercalated high-defect kaolinite expands to 10.2 A. The intensity of the peak of the expanded phase of the formamide-intercalated kaolinite decreases with grinding time. Thermal analysis reveals that the evolution temperature of the adsorbed formamide and loss of the inserting molecule increases with increased grinding time. The temperature of the dehydroxylation of the formamide-intercalated high-defect kaolinite decreases from 495 to 470oC with mechanochemical activation. Changes in the surface structure of the mechanochemically activated formamide-intercalated high-defect kaolinite were followed by DRIFT spectroscopy. Fundamentally the intensity of the high-defect kaolinite hydroxyl stretching bands decreases exponentially with grinding time and simultaneously the intensity of the bands attributed to the OH stretching vibrations of water increased. It is proposed that the mechanochemical activation of the high-defect kaolinite caused the conversion of the hydroxyls to water which coordinates the kaolinite surface. Significant changes in the infrared bands assigned to the hydroxyl deformation and amide stretching and bending modes were observed. The intensity decrease of these bands was exponentially related to the grinding time. The position of the amide C&unknown;O vibrational mode was found to be sensitive to grinding time. The effect of mechanochemical activation of the high-defect kaolinite reduces the capacity of the kaolinite to be intercalated with formamide.

The modulation of outdoor running speed : the influence of gradient

This thesis aimed to investigate the way in which distance runners modulate their speed in an effort to understand the key processes and determinants of speed selection when encountering hills in natural outdoor environments. One factor which has limited the expansion of knowledge in this area has been a reliance on the motorized treadmill which constrains runners to constant speeds and gradients and only linear paths. Conversely, limits in the portability or storage capacity of available technology have restricted field research to brief durations and level courses. Therefore another aim of this thesis was to evaluate the capacity of lightweight, portable technology to measure running speed in outdoor undulating terrain. The first study of this thesis assessed the validity of a non-differential GPS to measure speed, displacement and position during human locomotion. Three healthy participants walked and ran over straight and curved courses for 59 and 34 trials respectively. A non-differential GPS receiver provided speed data by Doppler Shift and change in GPS position over time, which were compared with actual speeds determined by chronometry. Displacement data from the GPS were compared with a surveyed 100m section, while static positions were collected for 1 hour and compared with the known geodetic point. GPS speed values on the straight course were found to be closely correlated with actual speeds (Doppler shift: r = 0.9994, p < 0.001, Δ GPS position/time: r = 0.9984, p < 0.001). Actual speed errors were lowest using the Doppler shift method (90.8% of values within ± 0.1 m.sec -1). Speed was slightly underestimated on a curved path, though still highly correlated with actual speed (Doppler shift: r = 0.9985, p < 0.001, Δ GPS distance/time: r = 0.9973, p < 0.001). Distance measured by GPS was 100.46 ± 0.49m, while 86.5% of static points were within 1.5m of the actual geodetic point (mean error: 1.08 ± 0.34m, range 0.69-2.10m). Non-differential GPS demonstrated a highly accurate estimation of speed across a wide range of human locomotion velocities using only the raw signal data with a minimal decrease in accuracy around bends. This high level of resolution was matched by accurate displacement and position data. Coupled with reduced size, cost and ease of use, the use of a non-differential receiver offers a valid alternative to differential GPS in the study of overground locomotion. The second study of this dissertation examined speed regulation during overground running on a hilly course. Following an initial laboratory session to calculate physiological thresholds (VO2 max and ventilatory thresholds), eight experienced long distance runners completed a self- paced time trial over three laps of an outdoor course involving uphill, downhill and level sections. A portable gas analyser, GPS receiver and activity monitor were used to collect physiological, speed and stride frequency data. Participants ran 23% slower on uphills and 13.8% faster on downhills compared with level sections. Speeds on level sections were significantly different for 78.4 ± 7.0 seconds following an uphill and 23.6 ± 2.2 seconds following a downhill. Speed changes were primarily regulated by stride length which was 20.5% shorter uphill and 16.2% longer downhill, while stride frequency was relatively stable. Oxygen consumption averaged 100.4% of runner’s individual ventilatory thresholds on uphills, 78.9% on downhills and 89.3% on level sections. Group level speed was highly predicted using a modified gradient factor (r2 = 0.89). Individuals adopted distinct pacing strategies, both across laps and as a function of gradient. Speed was best predicted using a weighted factor to account for prior and current gradients. Oxygen consumption (VO2) limited runner’s speeds only on uphill sections, and was maintained in line with individual ventilatory thresholds. Running speed showed larger individual variation on downhill sections, while speed on the level was systematically influenced by the preceding gradient. Runners who varied their pace more as a function of gradient showed a more consistent level of oxygen consumption. These results suggest that optimising time on the level sections after hills offers the greatest potential to minimise overall time when running over undulating terrain. The third study of this thesis investigated the effect of implementing an individualised pacing strategy on running performance over an undulating course. Six trained distance runners completed three trials involving four laps (9968m) of an outdoor course involving uphill, downhill and level sections. The initial trial was self-paced in the absence of any temporal feedback. For the second and third field trials, runners were paced for the first three laps (7476m) according to two different regimes (Intervention or Control) by matching desired goal times for subsections within each gradient. The fourth lap (2492m) was completed without pacing. Goals for the Intervention trial were based on findings from study two using a modified gradient factor and elapsed distance to predict the time for each section. To maintain the same overall time across all paced conditions, times were proportionately adjusted according to split times from the self-paced trial. The alternative pacing strategy (Control) used the original split times from this initial trial. Five of the six runners increased their range of uphill to downhill speeds on the Intervention trial by more than 30%, but this was unsuccessful in achieving a more consistent level of oxygen consumption with only one runner showing a change of more than 10%. Group level adherence to the Intervention strategy was lowest on downhill sections. Three runners successfully adhered to the Intervention pacing strategy which was gauged by a low Root Mean Square error across subsections and gradients. Of these three, the two who had the largest change in uphill-downhill speeds ran their fastest overall time. This suggests that for some runners the strategy of varying speeds systematically to account for gradients and transitions may benefit race performances on courses involving hills. In summary, a non – differential receiver was found to offer highly accurate measures of speed, distance and position across the range of human locomotion speeds. Self-selected speed was found to be best predicted using a weighted factor to account for prior and current gradients. Oxygen consumption limited runner’s speeds only on uphills, speed on the level was systematically influenced by preceding gradients, while there was a much larger individual variation on downhill sections. Individuals were found to adopt distinct but unrelated pacing strategies as a function of durations and gradients, while runners who varied pace more as a function of gradient showed a more consistent level of oxygen consumption. Finally, the implementation of an individualised pacing strategy to account for gradients and transitions greatly increased runners’ range of uphill-downhill speeds and was able to improve performance in some runners. The efficiency of various gradient-speed trade- offs and the factors limiting faster downhill speeds will however require further investigation to further improve the effectiveness of the suggested strategy.

An investigation of dose calculation accuracy in intensity-modulated radiotherapy of sites in the head & neck

Knowledge of the accuracy of dose calculations in intensity-modulated radiotherapy of the head and neck is essential for clinical confidence in these highly conformal treatments. High dose gradients are frequently placed very close to critical structures, such as the spinal cord, and good coverage of complex shaped nodal target volumes is important for long term-local control. A phantom study is presented comparing the performance of standard clinical pencil-beam and collapsed-cone dose algorithms to Monte Carlo calculation and three-dimensional gel dosimetry measurement. All calculations and measurements are normalized to the median dose in the primary planning target volume, making this a purely relative study. The phantom simulates tissue, air and bone for a typical neck section and is treated using an inverse-planned 5-field IMRT treatment, similar in character to clinically used class solutions. Results indicate that the pencil-beam algorithm fails to correctly model the relative dose distribution surrounding the air cavity, leading to an overestimate of the target coverage. The collapsed-cone and Monte Carlo results are very similar, indicating that the clinical collapsed-cone algorithm is perfectly sufficient for routine clinical use. The gel measurement shows generally good agreement with the collapsed-cone and Monte Carlo calculated dose, particularly in the spinal cord dose and nodal target coverage, thus giving greater confidence in the use of this class solution.

Negative Mood Regulation (NMR) expectancies, mood, and affect intensity among clients in substance disorder treatment facilities

Negative mood regulation (NMR) expectancies, stress, anxiety, depression and affect intensity were examined by means of self-report questionnaires in 158 volunteers, including 99 clients enrolled in addiction treatment programs. As expected, addicts reported significantly higher levels of stress, anxiety, depression and affect intensity and lower levels of NMR compared to non-addict controls. NMR was negatively correlated with stress, anxiety, depression and affect intensity. The findings indicate that mood self-regulation is impaired in addicts. Low NMR and high affect intensity may predispose to substance abuse and addiction, or alternatively may reflect chronic drug-induced affective dysregulation.

Sub-tropical high-density, low rise residential buildings: case study 3

The case study 3 team viewed the mitigation of noise and air pollution generated in the transport corridor that borders the study site to be a paramount driver of the urban design solution. These key urban planning strategies were adopted: * Spatial separation from transport corridor pollution source. A linear green zone and environmental buffer was proposed adjacent to the transport corridor to mitigate the environmental noise and air quality impacts of the corridor, and to offer residents opportunities for recreation * Open space forming the key structural principle for neighbourhood design. A significant open space system underpins the planning and manages surface water flows. * Urban blocks running on east-west axis. The open space rationale emphasises an east-west pattern for local streets. Street alignment allows for predominantly north-south facing terrace type buildings which both face the street and overlook the green courtyard formed by the perimeter buildings. The results of the ESD assessment of the typologies conclude that the design will achieve good outcomes through: * Lower than average construction costs compared with other similar projects * Thermal comfort; A good balance between daylight access and solar gains is achieved * The energy rating achieved for the units is 8.5 stars.

Intensity dependent residual amplitude modulation in electro-optic phase modulators

Residual amplitude modulation (RAM) mechanisms in electro-optic phase modulators are detrimental in applications that require high purity phase modulation of the incident laser beam. While the origins of RAMare not fully understood, measurements have revealed that it depends on the beam properties of the laser as well as the properties of the medium. Here we present experimental and theoretical results that demonstrate, for the first time, the dependence of RAM production in electro-optic phase modulators on beam intensity. The results show an order of magnitude increase in the level of RAM, around 10 dB, with a fifteenfold enhancement in the input intensity from 12 to 190 mW/mm 2. We show that this intensity dependent RAM is photorefractive in origin. © 2012 Optical Society of America.

The effect of light intensity and temperature on photocatalytic water splitting

Photocatalytic water splitting is a process which could potentially lead to commercially viable solar hydrogen production. This thesis uses an engineering perspective to investigate the technology. The effect of light intensity and temperature on photocatalytic water splitting was examined to evaluate the prospect of using solar concentration to increase the feasibility of the process. P25 TiO2 films deposited on conducting glass were used as photocatalyst electrodes and coupled with platinum electrodes which were also deposited on conducting glass. These films were used to form a photocatalysis cell and illuminated with a Xenon arc lamp to simulate solar light at intensities up to 50 suns. They were also tested at temperatures between 20°C and 100°C. The reaction demonstrated a sub-linear relationship with intensity. Photocurrent was proportional to intensity with an exponential value of 0.627. Increasing temperature resulted in an exponential relationship. This proved to follow an Arrhenius relationship with an activation energy of 10.3 kJ mol-1 and a pre-exponential factor of approximately 8.7×103. These results then formed the basis of a mathematical model which extrapolated beyond the range of the experimental tests. This model shows that the loss of efficiency from performing the reaction under high light intensity is offset by the increased reaction rate and efficiency from the associated temperature increase. This is an important finding for photocatalytic water splitting. It will direct future research in system design and materials research and may provide an avenue for the commercialisation of this technology.

Simple rules to contain an invasive species with a complex life cycle and high dispersal capacity

Designing practical rules for controlling invasive species is a challenging task for managers, particularly when species are long-lived, have complex life cycles and high dispersal capacities. Previous findings derived from plant matrix population analyses suggest that effective control of long-lived invaders may be achieved by focusing on killing adult plants. However, the cost-effectiveness of managing different life stages has not been evaluated. We illustrate the benefits of integrating matrix population models with decision theory to undertake this evaluation, using empirical data from the largest infestation of mesquite (Leguminosae: Prosopis spp) within Australia. We include in our model the mesquite life cycle, different dispersal rates and control actions that target individuals at different life stages with varying costs, depending on the intensity of control effort. We then use stochastic dynamic programming to derive cost-effective control strategies that minimize the cost of controlling the core infestation locally below a density threshold and the future cost of control arising from infestation of adjacent areas via seed dispersal. Through sensitivity analysis, we show that four robust management rules guide the allocation of resources between mesquite life stages for this infestation: (i) When there is no seed dispersal, no action is required until density of adults exceeds the control threshold and then only control of adults is needed; (ii) when there is seed dispersal, control strategy is dependent on knowledge of the density of adults and large juveniles (LJ) and broad categories of dispersal rates only; (iii) if density of adults is higher than density of LJ, controlling adults is most cost-effective; (iv) alternatively, if density of LJ is equal or higher than density of adults, management efforts should be spread between adults, large and to a lesser extent small juveniles, but never saplings. Synthesis and applications.In this study, we show that simple rules can be found for managing invasive plants with complex life cycles and high dispersal rates when population models are combined with decision theory. In the case of our mesquite population, focussing effort on controlling adults is not always the most cost-effective way to meet our management objective.

Application of high voltage, high frequency pulsed electromagnetic field on cortical bone tissue

Over the last few decades, electric and electromagnetic fields have achieved important role as stimulator and therapeutic facility in biology and medicine. In particular, low magnitude, low frequency, pulsed electromagnetic field has shown significant positive effect on bone fracture healing and some bone diseases treatment. Nevertheless, to date, little attention has been paid to investigate the possible effect of high frequency, high magnitude pulsed electromagnetic field (pulse power) on functional behaviour and biomechanical properties of bone tissue. Bone is a dynamic, complex organ, which is made of bone materials (consisting of organic components, inorganic mineral and water) known as extracellular matrix, and bone cells (live part). The cells give the bone the capability of self-repairing by adapting itself to its mechanical environment. The specific bone material composite comprising of collagen matrix reinforced with mineral apatite provides the bone with particular biomechanical properties in an anisotropic, inhomogeneous structure. This project hypothesized to investigate the possible effect of pulse power signals on cortical bone characteristics through evaluating the fundamental mechanical properties of bone material. A positive buck-boost converter was applied to generate adjustable high voltage, high frequency pulses up to 500 V and 10 kHz. Bone shows distinctive characteristics in different loading mode. Thus, functional behaviour of bone in response to pulse power excitation were elucidated by using three different conventional mechanical tests applying three-point bending load in elastic region, tensile and compressive loading until failure. Flexural stiffness, tensile and compressive strength, hysteresis and total fracture energy were determined as measure of main bone characteristics. To assess bone structure variation due to pulse power excitation in deeper aspect, a supplementary fractographic study was also conducted using scanning electron micrograph from tensile fracture surfaces. Furthermore, a non-destructive ultrasonic technique was applied for determination and comparison of bone elasticity before and after pulse power stimulation. This method provided the ability to evaluate the stiffness of millimetre-sized bone samples in three orthogonal directions. According to the results of non-destructive bending test, the flexural elasticity of cortical bone samples appeared to remain unchanged due to pulse power excitation. Similar results were observed in the bone stiffness for all three orthogonal directions obtained from ultrasonic technique and in the bone stiffness from the compression test. From tensile tests, no significant changes were found in tensile strength and total strain energy absorption of the bone samples exposed to pulse power compared with those of the control samples. Also, the apparent microstructure of the fracture surfaces of PP-exposed samples (including porosity and microcracks diffusion) showed no significant variation due to pulse power stimulation. Nevertheless, the compressive strength and toughness of millimetre-sized samples appeared to increase when the samples were exposed to 66 hours high power pulsed electromagnetic field through screws with small contact cross-section (increasing the pulsed electric field intensity) compare to the control samples. This can show the different load-bearing characteristics of cortical bone tissue in response to pulse power excitation and effectiveness of this type of stimulation on smaller-sized samples. These overall results may address that although, the pulse power stimulation can influence the arrangement or the quality of the collagen network causing the bone strength and toughness augmentation, it apparently did not affect the mineral phase of the cortical bone material. The results also confirmed that the indirect application of high power pulsed electromagnetic field at 500 V and 10 kHz through capacitive coupling method, was athermal and did not damage the bone tissue construction.

The effect of warm-up intensity on range of motion and anaerobic performance

Although there is a paucity of scientific support for the benefits of warm-up, athletes commonly warm up prior to activity with the intention of improving performance and reducing the incidence of injuries. The purpose of this study was to examine the role of warm-up intensity on both range of motion (ROM) and anaerobic performance. Nine males (age = 21.7 +/- 1.6 years, height = 1.77 +/- 0.04 m, weight = 80.2 +/- 6.8 kg, and VO2max = 60.4 +/- 5.4 ml/kg/min) completed four trials. Each trial consisted of hip, knee, and ankle ROM evaluation using an electronic inclinometer and an anaerobic capacity test on the treadmill (time to fatigue at 13 km/hr and 20% grade). Subjects underwent no warm-up or a warm-up of 15 minutes running at 60, 70 or 80% VO2max followed by a series of lower limb stretches. Intensity of warm-up had little effect on ROM, since ankle dorsiflexion and hip extension significantly increased in all warm-up conditions, hip flexion significantly increased only after the 80% VO2max warm-up, and knee flexion did not change after any warm-up. Heart rate and body temperature were significantly increased (p < 0.05) prior to anaerobic performance for each of the warm-up conditions, but anaerobic performance improved significantly only after warm-up at 60% VO2max (10%) and 70% VO2max (13%). A 15-minute warm-up at an intensity of 60-70% VO2max is therefore recommended to improve ROM and enhance subsequent anaerobic performance.

Analysing DBD plasma lamp intensity versus power consumption using a push-pull pulsed power supply

In this paper characteristic of a DBD (Dielectric Barrier Discharge) plasma lamp is investigated based on the lamp intensity and power consumption. A pulsed power supply with controllable parameters based on a push-pull converter is developed for lamp excitation at different voltage levels and repetition rate. The experimentations were conducted for 28 different operating points with the frequency range of 2 kHz to 15 Khz at output voltage levels of between 7.4 kV up to 13 kV. The obtained results show the feasibility of finding an optimum operation point due to nonlinear behaviour of the DBD lamp.

Measurement error of rearfoot kinematics during running between a 100Hz and 30Hz camera

Background: Measurement accuracy is critical for biomechanical gait assessment. Very few studies have determined the accuracy of common clinical rearfoot variables between cameras with different collection frequencies. Research question: What is the measurement error for common rearfoot gait parameters when using a standard 30Hz digital camera compared to 100Hz camera? Type of study: Descriptive. Methods: 100 footfalls were recorded from 10 subjects ( 10 footfalls per subject) running on a treadmill at 2.68m/s. A high-speed digital timer, accurate within 1ms served as an external reference. Markers were placed along the vertical axis of the heel counter and the long axis of the shank. 2D coordinates for the four markers were determined from heel strike to heel lift. Variables of interest included time of heel strike (THS), time of heel lift (THL), time to maximum eversion (TMax), and maximum rearfoot eversion angle (EvMax). Results: THS difference was 29.77ms (+/- 8.77), THL difference was 35.64ms (+/- 6.85), and TMax difference was 16.50ms (+/- 2.54). These temporal values represent a difference equal to 11.9%, 14.3%, and 6.6% of the stance phase of running gait, respectively. EvMax difference was 1.02 degrees (+/- 0.46). Conclusions: A 30Hz camera is accurate, compared to a high-frequency camera, in determining TMax and EvMax during a clinical gait analysis. However, relatively large differences, in excess of 12% of the stance phase of gait, for THS and THL variables were measured.

Development and validation of a new self-report instrument for measuring sedentary behaviors and light-intensity physical activity in adults

Background Low levels of physical activity and high levels of sedentary behavior (SB) are major public health concerns. This study was designed to develop and validate the 7-day Sedentary (S) and Light Intensity Physical Activity (LIPA) Log (7-day SLIPA Log), a self-report measure of specific daily behaviors. Method To develop the log, 62 specific SB and LIPA behaviors were chosen from the Compendium of Physical Activities. Face-to-face interviews were conducted with 32 sedentary volunteers to identify domains and behaviors of SB and LIPA. To validate the log, a further 22 sedentary adults were recruited to wear the GT3X for 7 consecutive days and nights. Results Pearson correlations (r) between the 7-day SLIPA Log and GT3X were significant for sedentary (r =.86, p < 0.001), for LIPA (r =.80, p < 0.001). Lying and sitting postures were positively correlated with GT3X output (r =.60 and r =.64, p < 0.001, respectively). No significant correlation was found for standing posture (r =.14, p = 0.53).The kappa values between the 7-day SLIPA Log and GT3X variables ranged from 0.09–0.61, indicating poor to good agreement. Conclusion The 7-day SLIPA Log is a valid self-report measure of SB and LIPA in specific behavioral domains.

Investigation of the intensity dependence of amplitude noise in electro-optic phase modulators

This thesis studied the source of instability in optical phase modulators used in high accuracy laser measurement systems. The nonlinear origin of the amplitude noise helped further reducing this instability in applications that rely on phase modulators to function. This outcome will have positive impacts on the development of new methods in the amplitude noise suppression.

Neuromuscular hamstring function in response to intermittent running and previous injury

This thesis examined the impact of previous hamstring injury and fatigue on the function of the hamstring muscles and their neural control. The work established the role of neuromuscular inhibition after hamstring injury and involved the development of a new field testing device for eccentric hamstring strength, which is now in high demand in elite sport worldwide. David has four peer-reviewed publications from this doctoral work.