Studies of the radiation chemistry and grafting of a fluoropolymer

The radiation chemistry and the grafting of a fluoropolymer, poly(tetrafluoroethylene-coperfluoropropyl vinyl ether) (PFA), was investigated with the aim of developing a highly stable grafted support for use in solid phase organic chemistry (SPOC). A radiation-induced grafting method was used whereby the PFA was exposed to ionizing radiation to form free radicals capable of initiating graft copolymerization of styrene. To fully investigate this process, both the radiation chemistry of PFA and the grafting of styrene to PFA were examined. Radiation alone was found to have a detrimental effect on PFA when irradiated at 303 K. This was evident from the loss in the mechanical properties due to chain scission reactions. This meant that when radiation was used for the grafting reactions, the total radiation dose needed to be kept as low as possible. The radicals produced when PFA was exposed to radiation were examined using electron spin resonance spectroscopy. Both main-chain (–CF2–C.F–CF2-) and end-chain (–CF2–C.F2) radicals were identified. The stability of the majority of the main-chain radicals when the polymer was heated above the glass transition temperature suggested that they were present mainly in the crystalline regions of the polymer, while the end-chain radicals were predominately located in the amorphous regions. The radical yield at 77 K was lower than the radical yield at 303 K suggesting that cage recombination at low temperatures inhibited free radicals from stabilizing. High-speed MAS 19F NMR was used to identify the non-volatile products after irradiation of PFA over a wide temperature range. The major products observed over the irradiation temperature 303 to 633 K included new saturated chain ends, short fluoromethyl side chains in both the amorphous and crystalline regions, and long branch points. The proportion of the radiolytic products shifted from mainly chain scission products at low irradiation temperatures to extensive branching at higher irradiation temperatures. Calculations of G values revealed that net crosslinking only occurred when PFA was irradiated in the melt. Minor products after irradiation at elevated temperatures included internal and terminal double bonds and CF3 groups adjacent to double bonds. The volatile products after irradiation at 303 K included tetrafluoromethane (CF4) and oxygen-containing species from loss of the perfluoropropyl ether side chains of PFA as identified by mass spectrometry and FTIR spectroscopy. The chemical changes induced by radiation exposure were accompanied by changes in the thermal properties of the polymer. Changes in the crystallinity and thermal stability of PFA after irradiation were examined using DSC and TGA techniques. The equilibrium melting temperature of untreated PFA was 599 K as determined using a method of extrapolation of the melting temperatures of imperfectly formed crystals. After low temperature irradiation, radiation- induced crystallization was prevalent due to scission of strained tie molecules, loss of perfluoropropyl ether side chains, and lowering of the molecular weight which promoted chain alignment and hence higher crystallinity. After irradiation at high temperatures, the presence of short and long branches hindered crystallization, lowering the overall crystallinity. The thermal stability of the PFA decreased with increasing radiation dose and temperature due to the introduction of defect groups. Styrene was graft copolymerized to PFA using -radiation as the initiation source with the aim of preparing a graft copolymer suitable as a support for SPOC. Various grafting conditions were studied, such as the total dose, dose rate, solvent effects and addition of nitroxides to create “living” graft chains. The effect of dose rate was examined when grafting styrene vapour to PFA using the simultaneous grafting method. The initial rate of grafting was found to be independent of the dose rate which implied that the reaction was diffusion controlled. When the styrene was dissolved in various solvents for the grafting reaction, the graft yield was strongly dependent of the type and concentration of the solvent used. The greatest graft yield was observed when the solvent swelled the grafted layers and the substrate. Microprobe Raman spectroscopy was used to map the penetration of the graft into the substrate. The grafted layer was found to contain both poly(styrene) (PS) and PFA and became thicker with increasing radiation dose and graft yield which showed that grafting began at the surface and progressively penetrated the substrate as the grafted layer was swollen. The molecular weight of the grafted PS was estimated by measuring the molecular weight of the non-covalently bonded homopolymer formed in the grafted layers using SEC. The molecular weight of the occluded homopolymer was an order of magnitude greater than the free homopolymer formed in the surrounding solution suggesting that the high viscosity in the grafted regions led to long PS grafts. When a nitroxide mediated free radical polymerization was used, grafting occurred within the substrate and not on the surface due to diffusion of styrene into the substrate at the high temperatures needed for the reaction to proceed. Loading tests were used to measure the capacity of the PS graft to be functionialized with aminomethyl groups then further derivatized. These loading tests showed that samples grafted in a solution of styrene and methanol had superior loading capacity over samples graft using other solvents due to the shallow penetration and hence better accessibility of the graft when methanol was used as a solvent.

Digital design communication : measuring learner technological prowess and self-efficacy in problem resolution

Currently the Bachelor of Design is the generic degree offered to the four disciplines of Architecture, Landscape Architecture, Industrial Design, and Interior Design within the School of Design at the Queensland University of Technology. Regardless of discipline, Digital Communication is a core unit taken by the 600 first year students entering the Bachelor of Design degree. Within the design disciplines the communication of the designer's intentions is achieved primarily through the use of graphic images, with written information being considered as supportive or secondary. As such, Digital Communication attempts to educate learners in the fundamentals of this graphic design communication, using a generic digital or software tool. Past iterations of the unit have not acknowledged the subtle difference in design communication of the different design disciplines involved, and has used a single generic software tool. Following a review of the unit in 2008, it was decided that a single generic software tool was no longer entirely sufficient. This decision was based on the recognition that there was an increasing emergence of discipline specific digital tools, and an expressed student desire and apparent aptitude to learn these discipline specific tools. As a result the unit was reconstructed in 2009 to offer both discipline specific and generic software instruction, if elected by the student. This paper, apart from offering the general context and pedagogy of the existing and restructured units, will more importantly offer research data that validates the changes made to the unit. Most significant of this new data is the results of surveys that authenticate actual student aptitude versus desire in learning discipline specific tools. This is done through an exposure of student self efficacy in problem resolution and technological prowess - generally and specifically within the unit. More traditional means of validation is also presented that includes the results of the generic university-wide Learning Experience Survey of the unit, as well as a comparison between the assessment results of the restructured unit versus the previous year.

Bengali handwritten character recognition using modified syntactic method

Several approaches have been proposed to recognize handwritten Bengali characters using different curve fitting algorithms and curvature analysis. In this paper, a new algorithm (Curve-fitting Algorithm) to identify various strokes of a handwritten character is developed. The curve-fitting algorithm helps recognizing various strokes of different patterns (line, quadratic curve) precisely. This reduces the error elimination burden heavily. Implementation of this Modified Syntactic Method demonstrates significant improvement in the recognition of Bengali handwritten characters.

Improved correlation-based modal strain energy method for global damage detection of truss bridge structures

The previous investigations have shown that the modal strain energy correlation method, MSEC, could successfully identify the damage of truss bridge structures. However, it has to incorporate the sensitivity matrix to estimate damage and is not reliable in certain damage detection cases. This paper presents an improved MSEC method where the prediction of modal strain energy change vector is differently obtained by running the eigensolutions on-line in optimisation iterations. The particular trail damage treatment group maximising the fitness function close to unity is identified as the detected damage location. This improvement is then compared with the original MSEC method along with other typical correlation-based methods on the finite element model of a simple truss bridge. The contributions to damage detection accuracy of each considered mode is also weighed and discussed. The iterative searching process is operated by using genetic algorithm. The results demonstrate that the improved MSEC method suffices the demand in detecting the damage of truss bridge structures, even when noised measurement is considered.

AFM study of forces between silicon oil and hydrophobic - hydrophylic surfaces in aqueous solutions

An investigation has been made of the interactions between silicone oil and various solid substrates immersed in aqueous solutions. Measurements were made using an atomic force microscope (AFM) using the colloid-probe method. The silicone oil drop is simulated by coating a small silica sphere with the oil, and measuring the force as this coated sphere is brought close to contact with a flat solid surface. It is found that the silicone oil surface is negatively charged, which causes a double-layer repulsion between the oil drop and another negatively charged surface such as mica. With hydrophilic solids, this repulsion is strong enough to prevent attachment of the drop to the solid. However, with hydrophobic surfaces there is an additional attractive force which overcomes the double-layer repulsion, and the silicone oil drop attaches to the solid. A "ramp" force appears in some, but not all, of the data sets. There is circumstantial evidence that this force results from compression of the silicone oil film coated on the glass sphere.

Establishing indigeneity in African pluralities using PRO169 parameters and a case study for measuring their inclusivity

The concept of the indigenous person or group in Africa is a contentious one. The current argument is that there exist no indigenous people in Africa because all Africans are indigenous. The obverse considers those Africans who have not been touched by colonialism and lost their traditional cultures commensurate with attachments to the lands or a distinguishable traditional lifestyle to be indigenous. This paper argues in favor of the latter. People who live in the global telos and do not participate in a distinct traditional culture that has been attached to the land for centuries are not indigenous. It is argued that this cultural divergence between modern and traditional is the major identifying point to settle the indigenous-non indigenous African debate. Finally, the paper looks at inclusive development and provides a new political analysis model for quantifying inclusivity so as to measure the inclusivity of indigenous peoples.

A modified quality control method for manufacturing process in mask industry

Masks are widely used in different industries, for example, traditional metal industry, hospitals or semiconductor industry. Quality is a critical issue in mask industry as it is related to public health and safety. Traditional quality practices for manufacturing process have some limitations in implementing them in mask industries. This paper aims to investigate the suitability of Six Sigma quality control method for the manufacturing process in the mask industry to provide high quality products, enhancing the process capacity, reducing the defects and the returned goods arising in a selected mask manufacturing company. This paper suggests that modifications necessary in Six Sigma method for effective implementation in mask industry.

A point interpolation method with locally smoothed strain field (PIM-LS2) for mechanics problems using triangular mesh

A point interpolation method with locally smoothed strain field (PIM-LS2) is developed for mechanics problems using a triangular background mesh. In the PIM-LS2, the strain within each sub-cell of a nodal domain is assumed to be the average strain over the adjacent sub-cells of the neighboring element sharing the same field node. We prove theoretically that the energy norm of the smoothed strain field in PIM-LS2 is equivalent to that of the compatible strain field, and then prove that the solution of the PIM- LS2 converges to the exact solution of the original strong form. Furthermore, the softening effects of PIM-LS2 to system and the effects of the number of sub-cells that participated in the smoothing operation on the convergence of PIM-LS2 are investigated. Intensive numerical studies verify the convergence, softening effects and bound properties of the PIM-LS2, and show that the very ‘‘tight’’ lower and upper bound solutions can be obtained using PIM-LS2.

A numerical method to quantify differential axial shortening in concrete buildings

Differential distortion comprising axial shortening and consequent rotation in concrete buildings is caused by the time dependent effects of “shrinkage”, “creep” and “elastic” deformation. Reinforcement content, variable concrete modulus, volume to surface area ratio of elements and environmental conditions influence these distortions and their detrimental effects escalate with increasing height and geometric complexity of structure and non vertical load paths. Differential distortion has a significant impact on building envelopes, building services, secondary systems and the life time serviceability and performance of a building. Existing methods for quantifying these effects are unable to capture the complexity of such time dependent effects. This paper develops a numerical procedure that can accurately quantify the differential axial shortening that contributes significantly to total distortion in concrete buildings by taking into consideration (i) construction sequence and (ii) time varying values of Young’s Modulus of reinforced concrete and creep and shrinkage. Finite element techniques are used with time history analysis to simulate the response to staged construction. This procedure is discussed herein and illustrated through an example.

A new method for improving reliability and line loss in distribution networks

In this paper, both Distributed Generators (DG) and capacitors are allocated and sized optimally for improving line loss and reliability. The objective function is composed of the investment cost of DGs and capacitors along with loss and reliability which are converted to the genuine dollar. The bus voltage and line current are considered as constraints which should be satisfied during the optimization procedure. Hybrid Particle Swarm Optimization as a heuristic based technique is used as the optimization method. The IEEE 69-bus test system is modified and employed to evaluate the proposed algorithm. The results illustrate that the lowest cost planning is found by optimizing both DGs and capacitors in distribution networks.

Heavy vehicle suspensions : testing and analysis

Transport regulators consider that, with respect to pavement damage, heavy vehicles (HVs) are the riskiest vehicles on the road network. That HV suspension design contributes to road and bridge damage has been recognised for some decades. This thesis deals with some aspects of HV suspension characteristics, particularly (but not exclusively) air suspensions. This is in the areas of developing low-cost in-service heavy vehicle (HV) suspension testing, the effects of larger-than-industry-standard longitudinal air lines and the characteristics of on-board mass (OBM) systems for HVs. All these areas, whilst seemingly disparate, seek to inform the management of HVs, reduce of their impact on the network asset and/or provide a measurement mechanism for worn HV suspensions. A number of project management groups at the State and National level in Australia have been, and will be, presented with the results of the project that resulted in this thesis. This should serve to inform their activities applicable to this research. A number of HVs were tested for various characteristics. These tests were used to form a number of conclusions about HV suspension behaviours. Wheel forces from road test data were analysed. A “novel roughness” measure was developed and applied to the road test data to determine dynamic load sharing, amongst other research outcomes. Further, it was proposed that this approach could inform future development of pavement models incorporating roughness and peak wheel forces. Left/right variations in wheel forces and wheel force variations for different speeds were also presented. This led on to some conclusions regarding suspension and wheel force frequencies, their transmission to the pavement and repetitive wheel loads in the spatial domain. An improved method of determining dynamic load sharing was developed and presented. It used the correlation coefficient between two elements of a HV to determine dynamic load sharing. This was validated against a mature dynamic loadsharing metric, the dynamic load sharing coefficient (de Pont, 1997). This was the first time that the technique of measuring correlation between elements on a HV has been used for a test case vs. a control case for two different sized air lines. That dynamic load sharing was improved at the air springs was shown for the test case of the large longitudinal air lines. The statistically significant improvement in dynamic load sharing at the air springs from larger longitudinal air lines varied from approximately 30 percent to 80 percent. Dynamic load sharing at the wheels was improved only for low air line flow events for the test case of larger longitudinal air lines. Statistically significant improvements to some suspension metrics across the range of test speeds and “novel roughness” values were evident from the use of larger longitudinal air lines, but these were not uniform. Of note were improvements to suspension metrics involving peak dynamic forces ranging from below the error margin to approximately 24 percent. Abstract models of HV suspensions were developed from the results of some of the tests. Those models were used to propose further development of, and future directions of research into, further gains in HV dynamic load sharing. This was from alterations to currently available damping characteristics combined with implementation of large longitudinal air lines. In-service testing of HV suspensions was found to be possible within a documented range from below the error margin to an error of approximately 16 percent. These results were in comparison with either the manufacturer’s certified data or test results replicating the Australian standard for “road-friendly” HV suspensions, Vehicle Standards Bulletin 11. OBM accuracy testing and development of tamper evidence from OBM data were detailed for over 2000 individual data points across twelve test and control OBM systems from eight suppliers installed on eleven HVs. The results indicated that 95 percent of contemporary OBM systems available in Australia are accurate to +/- 500 kg. The total variation in OBM linearity, after three outliers in the data were removed, was 0.5 percent. A tamper indicator and other OBM metrics that could be used by jurisdictions to determine tamper events were developed and documented. That OBM systems could be used as one vector for in-service testing of HV suspensions was one of a number of synergies between the seemingly disparate streams of this project.

Developing a theatre of the integrated actor : the application of the Suzuki actor training method within three theatrical contexts

This research project examines the application of the Suzuki Actor Training Method (the Suzuki Method) within the work ofTadashi Suzuki's company in Japan, the Shizuoka Performing Arts Complex (SPAC), within the work of Brisbane theatre company Frank:Austral Asian Performance Ensemble (Frank:AAPE), and as related to the development of the theatre performance Surfacing. These three theatrical contexts have been studied from the viewpoint of a "participant- observer". The researcher has trained in the Suzuki Method with Frank:AAPE and SP AC, performed with Frank:AAPE, and was the solo performer and collaborative developer in the performance Surfacing (directed by Leah Mercer). Observations of these three groups are based on a phenomenological definition of the "integrated actor", an actor who is able to achieve a totality or unity between the body and the mind, and between the body and the voice, through a powerful sense of intention. The term "integrated actor" has been informed by the philosophy of Merleau-Ponty and his concept of the "lived body". Three main hypotheses are presented in this study: that the Suzuki Method focuses on actors learning through their body; that the Suzuki Method presents an holistic approach to the body and the voice; and that the Suzuki Method develops actors with a strong sense of intention. These three aspects of the Suzuki Method are explored in relation to the stylistic features of the work of SPAC, Frank:AAPE and the performance Surfacing.

Measuring the success of ABC training in South Africa: A case study in the production of Western Liberal broadcast news values

In 1993 the Australian Broadcasting Corporation was contracted by the Australian Government to assist in the reshaping of the South African Broadcasting Corporation from a state-run broadcaster to a respected and trusted national broadcaster for all people in the newly democratic South Africa. Broadcast journalism training was identified by ABC consultant Bob Wurth as possibly the greatest need for SABC Radio. This thesis examines the ABC's role in South Africa and the effectiveness of its radio journalism training project considering the organisational, structural, cultural and political constraints of the SABC. This thesis will show through interviews and participant observation the difficulties in achieving the production of Western Liberal journalism values at the SABC within the time constraints set by the project funded by the Australian Government and the particular South African morays.