Intrinsic kinetics of titania photocatalysis : simplified models for their investigation

Even though titanium dioxide photocatalysis has been promoted as a leading green technology for water purification, many issues have hindered its application on a large commercial scale. For the materials scientist the main issues have centred the synthesis of more efficient materials and the investigation of degradation mechanisms; whereas for the engineers the main issues have been the development of appropriate models and the evaluation of intrinsic kinetics parameters that allow the scale up or re-design of efficient large-scale photocatalytic reactors. In order to obtain intrinsic kinetics parameters the reaction must be analysed and modelled considering the influence of the radiation field, pollutant concentrations and fluid dynamics. In this way, the obtained kinetic parameters are independent of the reactor size and configuration and can be subsequently used for scale-up purposes or for the development of entirely new reactor designs. This work investigates the intrinsic kinetics of phenol degradation over titania film due to the practicality of a fixed film configuration over a slurry. A flat plate reactor was designed in order to be able to control reaction parameters that include the UV irradiance, flow rates, pollutant concentration and temperature. Particular attention was paid to the investigation of the radiation field over the reactive surface and to the issue of mass transfer limited reactions. The ability of different emission models to describe the radiation field was investigated and compared to actinometric measurements. The RAD-LSI model was found to give the best predictions over the conditions tested. Mass transfer issues often limit fixed film reactors. The influence of this phenomenon was investigated with specifically planned sets of benzoic acid experiments and with the adoption of the stagnant film model. The phenol mass transfer coefficient in the system was calculated to be km,phenol=8.5815x10-7Re0.65(ms-1). The data obtained from a wide range of experimental conditions, together with an appropriate model of the system, has enabled determination of intrinsic kinetic parameters. The experiments were performed in four different irradiation levels (70.7, 57.9, 37.1 and 20.4 W m-2) and combined with three different initial phenol concentrations (20, 40 and 80 ppm) to give a wide range of final pollutant conversions (from 22% to 85%). The simple model adopted was able to fit the wide range of conditions with only four kinetic parameters; two reaction rate constants (one for phenol and one for the family of intermediates) and their corresponding adsorption constants. The intrinsic kinetic parameters values were defined as kph = 0.5226 mmol m-1 s-1 W-1, kI = 0.120 mmol m-1 s-1 W-1, Kph = 8.5 x 10-4 m3 mmol-1 and KI = 2.2 x 10-3 m3 mmol-1. The flat plate reactor allowed the investigation of the reaction under two different light configurations; liquid and substrate side illumination. The latter of particular interest for real world applications where light absorption due to turbidity and pollutants contained in the water stream to be treated could represent a significant issue. The two light configurations allowed the investigation of the effects of film thickness and the determination of the catalyst optimal thickness. The experimental investigation confirmed the predictions of a porous medium model developed to investigate the influence of diffusion, advection and photocatalytic phenomena inside the porous titania film, with the optimal thickness value individuated at 5 ìm. The model used the intrinsic kinetic parameters obtained from the flat plate reactor to predict the influence of thickness and transport phenomena on the final observed phenol conversion without using any correction factor; the excellent match between predictions and experimental results provided further proof of the quality of the parameters obtained with the proposed method.

Frank-starling control of a left ventricular assist device

A physiological control system was developed for a rotary left ventricular assist device (LVAD) in which the target pump flow rate (LVADQ) was set as a function of left atrial pressure (LAP), mimicking the Frank-Starling mechanism. The control strategy was implemented using linear PID control and was evaluated in a pulsatile mock circulation loop using a prototyped centrifugal pump by varying pulmonary vascular resistance to alter venous return. The control strategy automatically varied pump speed (2460 to 1740 to 2700 RPM) in response to a decrease and subsequent increase in venous return. In contrast, a fixed-speed pump caused a simulated ventricular suction event during low venous return and higher ventricular volumes during high venous return. The preload sensitivity was increased from 0.011 L/min/mmHg in fixed speed mode to 0.47L/min/mmHg, a value similar to that of the native healthy heart. The sensitivity varied automatically to maintain the LAP and LVADQ within a predefined zone. This control strategy requires the implantation of a pressure sensor in the left atrium and a flow sensor around the outflow cannula of the LVAD. However, appropriate pressure sensor technology is not yet commercially available and so an alternative measure of preload such as pulsatility of pump signals should be investigated.

UCPR rule 687 - exercise of discretion to fix costs - applicable principles

Although the Uniform Civil Procedure Rules 1999 (Qld) (UCPR) have always included a power for the court to order a party to pay an amount for costs to be fixed by the court, until recently the power was rarely used in the higher courts. In light of recent practice directions, and the changes to the procedures for assessment of costs contained in the new Chapter 17A of the UCPR, this is no longer the case. The judgment of Mullins J in ASIC v Atlantic 3 Financial (Aust) Pty Ltd [2008] QSC 9 provides some helpful guidance for practitioners about the principles which might be applied.

Non-destructive evaluation of articular cartilage defects using near-infrared (NIR) spectroscopy in osteoarthritic rat models and its direct relation to Mankin Score

Objective The aim of this study was to demonstrate the potential of near-infrared (NIR) spectroscopy for categorizing cartilage degeneration induced in animal models. Method Three models of osteoarthritic degeneration were induced in laboratory rats via one of the following methods: (i) menisectomy (MSX); (ii) anterior cruciate ligament transaction (ACLT); and (iii) intra-articular injection of mono-ido-acetete (1 mg) (MIA), in the right knee joint, with 12 rats per model group. After 8 weeks, the animals were sacrificed and tibial knee joints were collected. A custom-made nearinfrared (NIR) probe of diameter 5 mm was placed on the cartilage surface and spectral data were acquired from each specimen in the wavenumber range 4 000 – 12 500 cm−1. Following spectral data acquisition, the specimens were fixed and Safranin–O staining was performed to assess disease severity based on the Mankin scoring system. Using multivariate statistical analysis based on principal component analysis and partial least squares regression, the spectral data were then related to the Mankinscores of the samples tested. Results Mild to severe degenerative cartilage changes were observed in the subject animals. The ACLT models showed mild cartilage degeneration, MSX models moderate, and MIA severe cartilage degenerative changes both morphologically and histologically. Our result demonstrate that NIR spectroscopic information is capable of separating the cartilage samples into different groups relative to the severity of degeneration, with NIR correlating significantly with their Mankinscore (R2 = 88.85%). Conclusion We conclude that NIR is a viable tool for evaluating articularcartilage health and physical properties such as change in thickness with degeneration.

Modelling and analysis of the crush zone of a typical Australian passenger train

In this paper, a three-dimensional nonlinear rigid body model has been developed for the investigation of the crashworthiness of a passenger train using the multibody dynamics approach. This model refers to a typical design of passenger cars and train constructs commonly used in Australia. The high-energy and low-energy crush zones of the cars and the train constructs are assumed and the data are explicitly provided in the paper. The crash scenario is limited to the train colliding on to a fixed barrier symmetrically. The simulations of a single car show that this initial design is only applicable for the crash speed of 35 km/h or lower. For higher speeds (e.g. 140 km/h), the crush lengths or crush forces or both the crush zone elements will have to be enlarged. It is generally better to increase the crush length than the crush force in order to retain the low levels of the longitudinal deceleration of the passenger cars.

Methodological challenges when estimating the effects of season and seasonal exposures on birth outcomes

Background Many previous studies have found seasonal patterns in birth outcomes, but with little agreement about which season poses the highest risk. Some of the heterogeneity between studies may be explained by a previously unknown bias. The bias occurs in retrospective cohorts which include all births occurring within a fixed start and end date, which means shorter pregnancies are missed at the start of the study, and longer pregnancies are missed at the end. Our objective was to show the potential size of this bias and how to avoid it. Methods To demonstrate the bias we simulated a retrospective birth cohort with no seasonal pattern in gestation and used a range of cohort end dates. As a real example, we used a cohort of 114,063 singleton births in Brisbane between 1 July 2005 and 30 June 2009 and examined the bias when estimating changes in gestation length associated with season (using month of conception) and a seasonal exposure (temperature). We used survival analyses with temperature as a time-dependent variable. Results We found strong artificial seasonal patterns in gestation length by month of conception, which depended on the end date of the study. The bias was avoided when the day and month of the start date was just before the day and month of the end date (regardless of year), so that the longer gestations at the start of the study were balanced by the shorter gestations at the end. After removing the fixed cohort bias there was a noticeable change in the effect of temperature on gestation length. The adjusted hazard ratios were flatter at the extremes of temperature but steeper between 15 and 25°C. Conclusions Studies using retrospective birth cohorts should account for the fixed cohort bias by removing selected births to get unbiased estimates of seasonal health effects.

Validation of a new hand-held electronic data capture method for continuous monitoring of subjective appetite sensations

Background When large scale trials are investigating the effects of interventions on appetite, it is paramount to efficiently monitor large amounts of human data. The original hand-held Electronic Appetite Ratings System (EARS) was designed to facilitate the administering and data management of visual analogue scales (VAS) of subjective appetite sensations. The purpose of this study was to validate a novel hand-held method (EARS II (HP® iPAQ)) against the standard Pen and Paper (P&P) method and the previously validated EARS. Methods Twelve participants (5 male, 7 female, aged 18-40) were involved in a fully repeated measures design. Participants were randomly assigned in a crossover design, to either high fat (>48% fat) or low fat (<28% fat) meal days, one week apart and completed ratings using the three data capture methods ordered according to Latin Square. The first set of appetite sensations was completed in a fasted state, immediately before a fixed breakfast. Thereafter, appetite sensations were completed every thirty minutes for 4h. An ad libitum lunch was provided immediately before completing a final set of appetite sensations. Results Repeated measures ANOVAs were conducted for ratings of hunger, fullness and desire to eat. There were no significant differences between P&P compared with either EARS or EARS II (p > 0.05). Correlation coefficients between P&P and EARS II, controlling for age and gender, were performed on Area Under the Curve ratings. R2 for Hunger (0.89), Fullness (0.96) and Desire to Eat (0.95) were statistically significant (p < 0.05). Conclusions EARS II was sensitive to the impact of a meal and recovery of appetite during the postprandial period and is therefore an effective device for monitoring appetite sensations. This study provides evidence and support for further validation of the novel EARS II method for monitoring appetite sensations during large scale studies. The added versatility means that future uses of the system provides the potential to monitor a range of other behavioural and physiological measures often important in clinical and free living trials.

Space, place and power : the spatial turn in literacy research

Place matters to literacy because the meanings of our language and actions are always materially and socially placed in the world (Scollon & Scollon, 2003). We cannot interpret signs, whether an icon, symbol, gesture, word, or action, without taking into account their associations with other meanings and objects in places. This chapter maps an emergent strand of literacy research that foregrounds place and space as constitutive, rather than a backdrop for the real action. Space and place are seen as relational and dynamic, not as fixed and unchanging. Space and place are socially produced, and hence, can be contested, re-imagined and re-made. In bringing space and place into the frame of literacy studies we see a subtle shift – a rebalancing of the semiotic with the materiality of lived, embodied, and situated experience. ...

Gender gap in household investment : a study on Bhutan

Differing parental considerations for girls and boys in households are perceived as one of the primary causes of the gender gap in school enrolment and educational attainment in developing countries, particularly in the countries in Sub-Saharan Africa and South Asia. While there are a number of studies on the gender gap focusing on education and health provision in the countries in South Asia, little is known about Bhutan. This thesis aims to explore the gender gap in the intra-household allocation of resources on schooling and health provision for children in Bhutan. This thesis investigates whether boys are shown preference by their parents in terms of educational opportunities, including enrolment and spending on schooling as well as health. To conduct examination, this study makes use of household data from the Bhutan Living Standard Survey of 2007. Using cross-sectional as well as household fixed and random effect approaches, this study attempts to analyse the gender gap in allocation of resources across households as well as within households. The analysis includes characteristics of children and households such as gender and age of children, family wealth, education and gender of household head, number of dependents and the area of residence. The findings reveal a significant gender gap in schooling of children aged six to sixteen in Bhutan. However, no robust evidence of a gender gap has been found in the allocation of health expenditure on children aged less than sixteen. Policy recommendations to alleviate the gender bias in educational opportunities of females are proposed.

Re-cementing in revision total hip replacement

Removal of well-fixed cement at revision surgery risks bone loss, cortical perforation and fracture, is time-consuming, technically demanding and carries increased risks for the patient. The cement-in-cement technique avoids these problems and when used appropriately has given favourable results at our centre when used on both the femoral and acetabular sides of the articulation. A modified technique has also been used in selected cases of infection and peri-prosthetic fracture. This chapter highlights the results to date and the operative techniques employed. It is essential to recognise that this technique relies fundamentally on the presence of a well-fixed cement mantle, and it is imperative that the criteria laid out are adhered to in order to achieve success. If there is loosening or lysis on the femoral side extending distal to the lesser trochanter or around more than just the periphery of the acetabular cement mantle, then alternative revision techniques should be employed.

On the oscillatory behavior of transient Rayleigh Benard convection of air for 2D channel flow at moderate Rayleigh numbers

Unsteady numerical simulation of Rayleigh Benard convection heat transfer from a 2D channel is performed. The oscillatory behavior is attributed to recirculation of ascending and descending flows towards the core of the channel producing organized rolled motions. Variation of the parameters such as Reynolds number, channel outlet flow area and inclination of the channel are considered. Increasing Reynolds number (for a fixed Rayleigh number), delays the generation of vortices. The reduction in the outflow area leads to the later and the less vortex generation. As the time progresses, more vortices are generated, but the reinforced mean velocity does not let the eddies to enter the core of the channel. Therefore, they attach to the wall and reduce the heat transfer area. The inclination of the channel (both positive and negative) induces the generated vortices to get closer to each other and make an enlarged vortex.

The development of ground impact models for the analysis of the risks associated with Unmanned Aircraft Operations over inhabited areas

With the emergence of Unmanned Aircraft Systems (UAS) there is a growing need for safety standards and regulatory frameworks to manage the risks associated with their operations. The primary driver for airworthiness regulations (i.e., those governing the design, manufacture, maintenance and operation of UAS) are the risks presented to people in the regions overflown by the aircraft. Models characterising the nature of these risks are needed to inform the development of airworthiness regulations. The output from these models should include measures of the collective, individual and societal risk. A brief review of these measures is provided. Based on the review, it was determined that the model of the operation of an UAS over inhabited areas must be capable of describing the distribution of possible impact locations, given a failure at a particular point in the flight plan. Existing models either do not take the impact distribution into consideration, or propose complex and computationally expensive methods for its calculation. A computationally efficient approach for estimating the boundary (and in turn area) of the impact distribution for fixed wing unmanned aircraft is proposed. A series of geometric templates that approximate the impact distributions are derived using an empirical analysis of the results obtained from a 6-Degree of Freedom (6DoF) simulation. The impact distributions can be aggregated to provide impact footprint distributions for a range of generic phases of flight and missions. The maximum impact footprint areas obtained from the geometric template are shown to have a relative error of typically less than 1% compared to the areas calculated using the computationally more expensive 6DoF simulation. Computation times for the geometric models are on the order of one second or less, using a standard desktop computer. Future work includes characterising the distribution of impact locations within the footprint boundaries.

Embedding human expert cognition and real-time trajectory planning in autonomous UAS

This thesis presents a new approach to compute and optimize feasible three dimensional (3D) flight trajectories using aspects of Human Decision Making (HDM) strategies, for fixed wing Unmanned Aircraft (UA) operating in low altitude environments in the presence of real time planning deadlines. The underlying trajectory generation strategy involves the application of Manoeuvre Automaton (MA) theory to create sets of candidate flight manoeuvres which implicitly incorporate platform dynamic constraints. Feasible trajectories are formed through the concatenation of predefined flight manoeuvres in an optimized manner. During typical UAS operations, multiple objectives may exist, therefore the use of multi-objective optimization can potentially allow for convergence to a solution which better reflects overall mission requirements and HDM preferences. A GUI interface was developed to allow for knowledge capture from a human expert during simulated mission scenarios. The expert decision data captured is converted into value functions and corresponding criteria weightings using UTilite Additive (UTA) theory. The inclusion of preferences elicited from HDM decision data within an Automated Decision System (ADS) allows for the generation of trajectories which more closely represent the candidate HDM’s decision strategies. A novel Computationally Adaptive Trajectory Decision optimization System (CATDS) has been developed and implemented in simulation to dynamically manage, calculate and schedule system execution parameters to ensure that the trajectory solution search can generate a feasible solution, if one exists, within a given length of time. The inclusion of the CATDS potentially increases overall mission efficiency and may allow for the implementation of the system on different UAS platforms with varying onboard computational capabilities. These approaches have been demonstrated in simulation using a fixed wing UAS operating in low altitude environments with obstacles present.

The utilization of waste date seed as bio-oil and activated carbon by pyrolysis process

The renovation of biomass waste in the form of date seed waste into activated carbon and biofuel by fixed bed pyrolysis reactor has been focused in this study to obtain gaseous, liquid, and solid products. The date seed in particle form is pyrolysed in an externally heated fixed bed reactor with nitrogen as the carrier gas. The reactor is heated from 400◦C to 600◦C. A maximum liquid yield of 50wt.% and char of 30wt.% are obtained at a reactor bed temperature of 500◦C with a running time of 120 minutes. The oil is found to possess favorable flash point and reasonable density and viscosity. The higher calorific value is found to be 28.636 MJ/kg which is significantly higher than other biomass derived. Decolonization of 85–97% is recorded for the textile effluent and 75–90% for the tannery effluent, in all cases decreasing with temperature increase. Good adsorption capacity of the prepared activated carbon in case of diluted textile and tannery effluent was found.

Whe' yu' from?

"Whe' yu' from?" The question was put to me as I wandered, camera in hand, in the old square of Spanish Town, Jamaica's former capital. The local man, lounging in the shade of one of the colonial Georgian buildings that enclose the square, was mildly curious about what he took to be a typical white tourish photgraphing the sights of the decayed historic town. At that time, my home was in Kingston where i lived with my wife and baby son. I was then working in the Jamaican Government Town Planning Department in a job that took me all over the island. Turning to my questioner, I replied, "Kingston". There was a brief pause, and then the man spoke again: "No Man! Whe' yu' really from?" I still have difficulties when asked this question. Where am I from? What does this question mean? Does it refer to where I was born, where I spent my previous life or where I live now? Does it have a broader meaning, an enquiry about my origins in terms of background and previous experience? The following chapters are my attempt to answer these questions for my own satisfaction and, I hope, for the amusement of others who may be interested in the life of an ordinary English boy whose dream to travel and see the world was realized in ways he could not possibly have imagined. Finding an appropriate title for this book was difficult. Thursday's Child, North and South and War and Peace all came to mind but, unfortunately for me, those titles had been appropriated by other writers. Thursdays's Child is quite a popular book title, presumably because people who were born on that day and, in the words of the nursery rhyme, had 'far to go', are especially likely to have travellers' tales to tell or life stories of the rags-to-riches variety. Born on a Thursday, I have travelled a lot and I suppose that I have gone far in life. Coming from a working class family, I 'got on' by 'getting a good education' and a 'good job'. I decided against adding to the list of Thursday's Children. North and South would have reflected my life in Britain, spent in both the North and South of England, and my later years, divided between the Northern and Southern Hemispheres of the globe, as well as in countries commonly referred to as the 'advanced' North and the 'underdeveloped' South. North and South has already been appropriated by Mrs Gaskell, something that did not deter one popular American writer from using the title for a book of his. My memories of World War Two and the years afterwards made War and Peace a possible candidate, but readers expectnig an epic tale of Tolstoyan proportions may have been disappointed. To my knowledge, no other book has the title "Whe' Yu' From?". I am grateful to the Jamaican man whose question lingered in my memory and provided the title of this memoir, written decades later. This book is a word picture. It is, in a sense, a self-portrait, and like all portraits, it captures something of the character, it attempts to tell the truth, but it is not the whole truth. This is because it is not my intention to write my entire life story; rather I wish to tell about some of the things in my experience of life that have seemed important or interesting to me. Unlike a painted portrait, the picture I have created is intended to suggest the passage of time. While, for most of us in Western society, time is linear and unidirectional, like the flight of an arrov or the trajectory of a bullet, memory rearranges things, calling up images of the past in no particular order, making connections that may link events in various patterns, circular, web-like, superimposed. The stream of consciousness is very unlike that of streams we encounter in the physical world. Connections are made in all directions; thoughts hop back and forth in time and space, from topic to topic. My book is a composition drawn from periods, events and thoughts as I remember them. Like life itself, it is made up of patches, some good, some bad, but in my experience, always fascinating. In recording my memories, I have been as accurate as possible. Little of what I have written is about spectacular sights and strange customs. Much of it focuses on my more modest explorations includng observations of everyday things that have attracted my attention. Reading through the chapters, I am struck by my childhood freedom to roam and engage in 'dangerous' activities like climbing trees and playing beside streams, things that many children today are no longer allowed to enjoy. Also noticeable is the survival of traditions and superstitions from the distant past. Obvious too, is my preoccupation with place names, both official ones that appear on maps and sign boards and those used by locals and children, names rarely seen in print. If there is any uniting theme to be found in what I have written, it must be my education in the fields, woods and streets of my English homeland, in the various other countries in which I have lived and travelled, as well as more formally from books and in classrooms. Much of my book is concerned with people and places. Many of the people I mention are among those who have been, and often have remained, important and close to me. Others I remember from only the briefest of encounters, but they remain in my memory because of some specific incident or circumstance that fixed a lasting image in my mind. Some of my closest friends and relatives, however, appear nowhere in these pages or they receive only the slightest mention. This is not because they played an unimportant roles in my life. It is because this book is not the whole story. Among those whe receive little or no mention are some who are especially close to me, with whom I have shared happy and sad times and who have shown me and my family much kindness, giving support when this was needed. Some I have known since childhood and have popped up at various times in my life, often in different parts of the world. Although years may pass without me seeing them, in an important sense they are always with me. These people know who they are. I hope that they know how much I love and appreciate them. When writing my memoir, I consulted a few of the people mentioned in this book, but in the main, I have relied on my own memory, asided by daiary and notebook entries and old correspondence. In the preparation of this manuscript, I benefited greatly from the expert advice and encouragement of Neil Marr of BeWrite Books. My wife Anne, inspiration for this book, also contributed in the valuable role of critic. She has my undying gratitude.