Infrared spectroscopic investigation of the effects of titania photocatalyst on the degradation of linear low density polyethylene film for commercial applications

There is a need in industry for a commodity polyethylene film with controllable degradation properties that will degrade in an environmentally neutral way, for applications such as shopping bags and packaging film. Additives such as starch have been shown to accelerate the degradation of plastic films, however control of degradation is required so that the film will retain its mechanical properties during storage and use, and then degrade when no longer required. By the addition of a photocatalyst it is hoped that polymer film will breakdown with exposure to sunlight. Furthermore, it is desired that the polymer film will degrade in the dark, after a short initial exposure to sunlight. Research has been undertaken into the photo- and thermo-oxidative degradation processes of 25 ìm thick LLDPE (linear low density polyethylene) film containing titania from different manufacturers. Films were aged in a suntest or in an oven at 50 °C, and the oxidation product formation was followed using IR spectroscopy. Degussa P25, Kronos 1002, and various organic-modified and doped titanias of the types Satchleben Hombitan and Hunstsman Tioxide incorporated into LLDPE films were assessed for photoactivity. Degussa P25 was found to be the most photoactive with UVA and UVC exposure. Surface modification of titania was found to reduce photoactivity. Crystal phase is thought to be among the most important factors when assessing the photoactivity of titania as a photocatalyst for degradation. Pre-irradiation with UVA or UVC for 24 hours of the film containing 3% Degussa P25 titania prior to aging in an oven resulted in embrittlement in ca. 200 days. The multivariate data analysis technique PCA (principal component analysis) was used as an exploratory tool to investigate the IR spectral data. Oxidation products formed in similar relative concentrations across all samples, confirming that titania was catalysing the oxidation of the LLDPE film without changing the oxidation pathway. PCA was also employed to compare rates of degradation in different films. PCA enabled the discovery of water vapour trapped inside cavities formed by oxidation by titania particles. Imaging ATR/FTIR spectroscopy with high lateral resolution was used in a novel experiment to examine the heterogeneous nature of oxidation of a model polymer compound caused by the presence of titania particles. A model polymer containing Degussa P25 titania was solvent cast onto the internal reflection element of the imaging ATR/FTIR and the oxidation under UVC was examined over time. Sensitisation of 5 ìm domains by titania resulted in areas of relatively high oxidation product concentration. The suitability of transmission IR with a synchrotron light source to the study of polymer film oxidation was assessed as the Australian Synchrotron in Melbourne, Australia. Challenges such as interference fringes and poor signal-to-noise ratio need to be addressed before this can become a routine technique.

Experimental investigation of a turbulent reacting plume

An experimental investigation has been made of a round, non-buoyant plume of nitric oxide, NO, in a turbulent grid flow of ozone, 03, using the Turbulent Smog Chamber at the University of Sydney. The measurements have been made at a resolution not previously reported in the literature. The reaction is conducted at non-equilibrium so there is significant interaction between turbulent mixing and chemical reaction. The plume has been characterized by a set of constant initial reactant concentration measurements consisting of radial profiles at various axial locations. Whole plume behaviour can thus be characterized and parameters are selected for a second set of fixed physical location measurements where the effects of varying the initial reactant concentrations are investigated. Careful experiment design and specially developed chemilurninescent analysers, which measure fluctuating concentrations of reactive scalars, ensure that spatial and temporal resolutions are adequate to measure the quantities of interest. Conserved scalar theory is used to define a conserved scalar from the measured reactive scalars and to define frozen, equilibrium and reaction dominated cases for the reactive scalars. Reactive scalar means and the mean reaction rate are bounded by frozen and equilibrium limits but this is not always the case for the reactant variances and covariances. The plume reactant statistics are closer to the equilibrium limit than those for the ambient reactant. The covariance term in the mean reaction rate is found to be negative and significant for all measurements made. The Toor closure was found to overestimate the mean reaction rate by 15 to 65%. Gradient model turbulent diffusivities had significant scatter and were not observed to be affected by reaction. The ratio of turbulent diffusivities for the conserved scalar mean and that for the r.m.s. was found to be approximately 1. Estimates of the ratio of the dissipation timescales of around 2 were found downstream. Estimates of the correlation coefficient between the conserved scalar and its dissipation (parallel to the mean flow) were found to be between 0.25 and the significant value of 0.5. Scalar dissipations for non-reactive and reactive scalars were found to be significantly different. Conditional statistics are found to be a useful way of investigating the reactive behaviour of the plume, effectively decoupling the interaction of chemical reaction and turbulent mixing. It is found that conditional reactive scalar means lack significant transverse dependence as has previously been found theoretically by Klimenko (1995). It is also found that conditional variance around the conditional reactive scalar means is relatively small, simplifying the closure for the conditional reaction rate. These properties are important for the Conditional Moment Closure (CMC) model for turbulent reacting flows recently proposed by Klimenko (1990) and Bilger (1993). Preliminary CMC model calculations are carried out for this flow using a simple model for the conditional scalar dissipation. Model predictions and measured conditional reactive scalar means compare favorably. The reaction dominated limit is found to indicate the maximum reactedness of a reactive scalar and is a limiting case of the CMC model. Conventional (unconditional) reactive scalar means obtained from the preliminary CMC predictions using the conserved scalar p.d.f. compare favorably with those found from experiment except where measuring position is relatively far upstream of the stoichiometric distance. Recommendations include applying a full CMC model to the flow and investigations both of the less significant terms in the conditional mean species equation and the small variation of the conditional mean with radius. Forms for the p.d.f.s, in addition to those found from experiments, could be useful for extending the CMC model to reactive flows in the atmosphere.

The economics of credence goods: An experimental investigation of the role of verifiability, liability, competition and reputation in credence goods markets

Credence goods markets are characterized by asymmetric information between sellers and consumers that may give rise to inefficiencies, such as under- and overtreatment or market break-down. We study in a large experiment with 936 participants the determinants for efficiency in credence goods markets. While theory predicts that either liability or verifiability yields efficiency, we find that liability has a crucial, but verifiability only a minor effect. Allowing sellers to build up reputation has little influence, as predicted. Seller competition drives down prices and yields maximal trade, but does not lead to higher efficiency as long as liability is violated.

Who needs it? An exploratory investigation into the reaction of small and medium enterprises to mobile data technologies

The technological environment in which contemporary small and medium-sized enterprises (SMEs) operate can only be described as dynamic. The seemingly exponential nature of technological change, characterised by perceived increases in the benefits associated with various technologies, shortening product life cycles and changing standards, provides for the small and medium-sized enterprise a complex and challenging operational context. The development of infrastructures capable of supporting the Wireless Application Protocol (WAP)and associated 'wireless' applications represents the latest generation of technological innovation with potential appeal to SMEs and end-users alike. The primary aim of this research was to understand the mobile data technology needs of SMEs in a regional setting. The research was especially concerned with perceived needs across three market segments; non-adopters of new technology, partial-adopters of new technology and full-adopters of new technology. Working with an industry partner, focus groups were conducted with each of these segments with the discussions focused on the use of the latest WP products and services. Some of the results are presented in this paper.

Modeling the effects of strategic flexibility, organisational learning on e-business adoption and competitive advantage : an empirical investigation

The role of intangible firm capabilities as a source of competitive advantage has come into prominence in marketing strategy literature, due to the Resource Based View. This paper applies the Resource Based View and hypothesizes that strategic flexibility and organisation learning, conceptualised as capabilities, positively effect e-business adoption and competitive advantage. Partial Lease Squares analysis suggest that theoretical constructs function as hypothesised and explain a significant variation on e-business adoption and competitive advantage. Firms adopting e-business should develop capabilities such as strategic flexibility and organisation learning and that vendor firms may segment their potential clients based on these capabilities.

A preliminary investigation of the role of the Phenylalynine: Tyrosine Ratio in children with early and continuously treated phenylketonuria : toward identification of “safe” levels

Children with early and continuously treated phenylketonuria (ECT-PKU) remain at risk of developing executive function (EF) deficits. There is some evidence that a high phenylalanine to tyrosine ratio (phe:tyr) is more strongly associated with impaired EF development than high phenylalanine alone. This study examined EF in a sample of 11 adolescents against concurrent and historical levels of phenylalanine, phe:tyr, and tyrosine. Lifetime measures of phe:tyr were more strongly associated with EF than phenylalanine-only measures. Children with a lifetime phe:tyr less than 6 demonstrated normal EF, whereas children who had a lifetime phe:tyr above 6, on average, demonstrated clinically impaired EF.

Investigation of inclusions trapped inside Libyan Desert glass by Raman microscopy

Several specimens of Libyan Desert Glass (LDG), an enigmatic natural glass from Egypt, were subjected to investigation by micro-Raman spectroscopy. The spectra of inclusions inside the LDG samples were successfully measured through the layers of glass and the mineral species were identified on this basis. The presence of cristobalite as typical for high-temperature melt products was confirmed, together with co-existing quartz. TiO2 was determined in two polymorphic species, rutile and anatase. Micro-Raman spectroscopy proved also the presence of minerals unusual for high-temperature glasses such as anhydrite and aragonite.

Development of a multi-scale finite element model of the osteoporotic lumbar vertebral body for the investigation of apparent level vertebra mechanics and micro-level trabecular mechanics.

Osteoporotic spinal fractures are a major concern in ageing Western societies. This study develops a multi-scale finite element (FE) model of the osteoporotic lumbar vertebral body to study the mechanics of vertebral compression fracture at both the apparent (whole vertebral body) and micro-structural (internal trabecular bone core)levels. Model predictions were verified against experimental data, and found to provide a reasonably good representation of the mechanics of the osteoporotic vertebral body. This novel modelling methodology will allow detailed investigation of how trabecular bone loss in osteoporosis affects vertebral stiffness and strength in the lumbar spine.

Investigation of 'off-line‘ relaxation phenomena in oil filled transformers

Power transformers are one of the most important and costly equipment in power generation, transmission and distribution systems. Current average age of transformers in Australia is around 25 years and there is a strong economical tendency to use them up to 50 years or more. As the transformers operate, they get degraded due to different loading and environmental operating stressed conditions. In today‘s competitive energy market with the penetration of distributed energy sources, the transformers are stressed more with minimum required maintenance. The modern asset management program tries to increase the usage life time of power transformers with prognostic techniques using condition indicators. In the case of oil filled transformers, condition monitoring methods based on dissolved gas analysis, polarization studies, partial discharge studies, frequency response analysis studies to check the mechanical integrity, IR heat monitoring and other vibration monitoring techniques are in use. In the current research program, studies have been initiated to identify the degradation of insulating materials by the electrical relaxation technique known as dielectrometry. Aging leads to main degradation products like moisture and other oxidized products due to fluctuating thermal and electrical loading. By applying repetitive low frequency high voltage sine wave perturbations in the range of 100 to 200 V peak across available terminals of power transformer, the conductive and polarization parameters of insulation aging are identified. An in-house novel digital instrument is developed to record the low leakage response of repetitive polarization currents in three terminals configuration. The technique is tested with known three transformers of rating 5 kVA or more. The effects of stressing polarization voltage level, polarizing wave shapes and various terminal configurations provide characteristic aging relaxation information. By using different analyses, sensitive parameters of aging are identified and it is presented in this thesis.

Tracking rail safety : incident and accident investigation in Australia

Scoping Project: Currently no national or structured learning framework available in Aus or NZ Current Project: Develop a national training program & capability framework for rail incident investigators - Establish the potential market demand - Define the curricula for a multi-level national training program - Explore training providers & delivery options

Physiological investigation of periosteum structure and its application in periosteum tissue engineering

Although many different materials, techniques and methods, including artificial or engineered bone substitutes, have been used to repair various bone defects, the restoration of critical-sized bone defects caused by trauma, surgery or congenital malformation is still a great challenge to orthopedic surgeons. One important fact that has been neglected in the pursuit of resolutions for large bone defect healing is that most physiological bone defect healing needs the periosteum and stripping off the periosteum may result in non-union or non-healed bone defects. Periosteum plays very important roles not only in bone development but also in bone defect healing. The purpose of this project was to construct a functional periosteum in vitro using a single stem cell source and then test its ability to aid the repair of critical-sized bone defect in animal models. This project was designed with three separate but closely-linked parts which in the end led to four independent papers. The first part of this study investigated the structural and cellular features in periostea from diaphyseal and metaphyseal bone surfaces in rats of different ages or with osteoporosis. Histological and immunohistological methods were used in this part of the study. Results revealed that the structure and cell populations in periosteum are both age-related and site-specific. The diaphyseal periosteum showed age-related degeneration, whereas the metaphyseal periosteum is more destructive in older aged rats. The periosteum from osteoporotic bones differs from normal bones both in terms of structure and cell populations. This is especially evident in the cambial layer of the metaphyseal area. Bone resorption appears to be more active in the periosteum from osteoporotic bones, whereas bone formation activity is comparable between the osteoporotic and normal bone. The dysregulation of bone resorption and formation in the periosteum may also be the effect of the interaction between various neural pathways and the cell populations residing within it. One of the most important aspects in periosteum engineering is how to introduce new blood vessels into the engineered periosteum to help form vascularized bone tissues in bone defect areas. The second part of this study was designed to investigate the possibility of differentiating bone marrow stromal cells (BMSCs) into the endothelial cells and using them to construct vascularized periosteum. The endothelial cell differentiation of BMSCs was induced in pro-angiogenic media under both normoxia and CoCl2 (hypoxia-mimicking agent)-induced hypoxia conditions. The VEGF/PEDF expression pattern, endothelial cell specific marker expression, in vitro and in vivo vascularization ability of BMSCs cultured in different situations were assessed. Results revealed that BMSCs most likely cannot be differentiated into endothelial cells through the application of pro-angiogenic growth factors or by culturing under CoCl2-induced hypoxic conditions. However, they may be involved in angiogenesis as regulators under both normoxia and hypoxia conditions. Two major angiogenesis-related growth factors, VEGF (pro-angiogenic) and PEDF (anti-angiogenic) were found to have altered their expressions in accordance with the extracellular environment. BMSCs treated with the hypoxia-mimicking agent CoCl2 expressed more VEGF and less PEDF and enhanced the vascularization of subcutaneous implants in vivo. Based on the findings of the second part, the CoCl2 pre-treated BMSCs were used to construct periosteum, and the in vivo vascularization and osteogenesis of the constructed periosteum were assessed in the third part of this project. The findings of the third part revealed that BMSCs pre-treated with CoCl2 could enhance both ectopic and orthotopic osteogenesis of BMSCs-derived osteoblasts and vascularization at the early osteogenic stage, and the endothelial cells (HUVECs), which were used as positive control, were only capable of promoting osteogenesis after four-weeks. The subcutaneous area of the mouse is most likely inappropriate for assessing new bone formation on collagen scaffolds. This study demonstrated the potential application of CoCl2 pre-treated BMSCs in the tissue engineering not only for periosteum but also bone or other vascularized tissues. In summary, the structure and cell populations in periosteum are age-related, site-specific and closely linked with bone health status. BMSCs as a stem cell source for periosteum engineering are not endothelial cell progenitors but regulators, and CoCl2-treated BMSCs expressed more VEGF and less PEDF. These CoCl2-treated BMSCs enhanced both vascularization and osteogenesis in constructed periosteum transplanted in vivo.

An investigation of a process for environmental banking appropriate to Queensland

This thesis examines the advanced North American environmental mitigation schemes for their applicability to Queensland. Compensatory wetland mitigation banking, in particular, is concerned with in-perpetuity management and protection - the basic concerns of the Queensland public about its unique environment. The process has actively engaged the North American market and become a thriving industry that (for the most part) effectively designs, creates and builds (or enhances) environmental habitat. A methodology was designed to undertake a comprehensive review of the history, evolution and concepts of the North American wetland mitigation banking system - before and after the implementation of a significant new compensatory wetland mitigation banking regulation in 2008. The Delphi technique was then used to determine the principles and working components of wetland mitigation banking. Results were then applied to formulate a questionnaire to review Australian marketbased instruments (including offsetting policies) against these North American principles. Following this, two case studies established guiding principles for implementation based on two components of the North American wetland mitigation banking program. The subsequent outcomes confirmed that environmental banking is a workable concept in North America and that it is worth applying in Queensland. The majority of offsetting policies in Australia have adopted some principles of the North American mitigation programs. Examination reveals that however, they fail to provide adequate incentives for private landowners to participate because the essential trading mechanisms are not employed. Much can thus be learnt from the North American situation - where private enterprise has devised appropriate free market concepts. The consequent environmental banking process (as adapted from the North American programs) should be implemented in Queensland. It can then focus here on engaging the private sector, where the majority of naturally productive lands are managed.

An investigation of foot and ankle problems experienced by nurses

Relatively little information has been reported about foot and ankle problems experienced by nurses, despite anecdotal evidence which suggests they are common ailments. The purpose of this study was to improve knowledge about the prevalence of foot and ankle musculoskeletal disorders (MSDs) and to explore relationships between these MSDs and proposed risk factors. A review of the literature relating to work-related MSDs, MSDs in nursing, foot and lower-limb MSDs, screening for work-related MSDs, foot discomfort, footwear and the prevalence of foot problems in the community was undertaken. Based on the review, theoretical risk factors were proposed that pertained to the individual characteristics of the nurses, their work activity or their work environment. Three studies were then undertaken. A cross-sectional survey of 304 nurses, working in a large tertiary paediatric hospital, established the prevalence of foot and ankle MSDs. The survey collected information about self-reported risk factors of interest. The second study involved the clinical examination of a subgroup of 40 nurses, to examine changes in body discomfort, foot discomfort and postural sway over the course of a single work shift. Objective measurements of additional risk factors, such as individual foot posture (arch index) and the hardness of shoe midsoles, were performed. A final study was used to confirm the test-retest reliability of important aspects of the survey and key clinical measurements. Foot and ankle problems were the most common MSDs experienced by nurses in the preceding seven days (42.7% of nurses). They were the second most common MSDs to cause disability in the last 12 months (17.4% of nurses), and the third most common MSDs experienced by nurses in the last 12 months (54% of nurses). Substantial foot discomfort (Visual Analogue Scale (VAS) score of 50mm or more) was experienced by 48.5% of nurses at sometime in the last 12 months. Individual risk factors, such as obesity and the number of self-reported foot conditions (e.g., callouses, curled toes, flat feet) were strongly associated with the likelihood of experiencing foot problems in the last seven days or during the last 12 months. These risk factors showed consistent associations with disabling foot conditions and substantial foot discomfort. Some of these associations were dependent upon work-related risk factors, such as the location within the hospital and the average hours worked per week. Working in the intensive care unit was associated with higher odds of experiencing foot problems within the last seven days, foot problems in the last 12 months and foot problems that impaired activity in the last 12 months. Changes in foot discomfort experienced within a day, showed large individual variability. Fifteen of the forty nurses experienced moderate/substantial foot discomfort at the end of their shift (VAS 25+mm). Analysis of the association between risk factors and moderate/substantial foot discomfort revealed that foot discomfort was less likely for nurses who were older, had greater BMI or had lower foot arches, as indicated by higher arch index scores. The nurses’ postural sway decreased over the course of the work shift, suggesting improved body balance by the end of the day. These findings were unexpected. Further clinical studies examining individual nurses on several work shifts are needed to confirm these results, particularly due to the small sample size and the single measurement occasion. There are more than 280,000 nurses registered to practice in Australia. The nursing workforce is ageing and the prevalence of foot problems will increase. If the prevalence estimates from this study are extrapolated to the profession generally, more than 70,000 hospital nurses have experienced substantial foot discomfort and 25-30,000 hospital nurses have been limited in their activity due to foot problems during the last 12 months. Nurses with underlying foot conditions were more likely to report having foot problems at work. Strategies to prevent or manage foot conditions exist and they should be disseminated to nurses. Obesity is a significant risk factor for foot and ankle MSDs and these nurses may need particular assistance to manage foot problems. The risk of foot problems for particular groups of nurses, e.g. obese nurses, may vary depending upon the location within the hospital. Further research is needed to confirm the findings of this study. Similar studies should be conducted in other occupational groups that require workers to stand for prolonged periods.