Controlling Long-Range Ordered Self-assembly of Solid-Binding Peptide Monolayers on Atomically Flat Layered Materials

Thesis (Master's)--University of Washington, 2016-06

A Method of Preparing Future Hourly Weather Data for the Study of Global Warming Impact on the Built Environment

The dynamic interaction between building systems and external climate is extremely complex, involving a large number of difficult-to-predict variables. In order to study the impact of global warming on the built environment, the use of building simulation techniques together with forecast weather data are often necessary. Since all building simulation programs require hourly meteorological input data for their thermal comfort and energy evaluation, the provision of suitable weather data becomes critical. Based on a review of the existing weather data generation models, this paper presents an effective method to generate approximate future hourly weather data suitable for the study of the impact of global warming. Depending on the level of information available for the prediction of future weather condition, it is shown that either the method of retaining to current level, constant offset method or diurnal modelling method may be used to generate the future hourly variation of an individual weather parameter. An example of the application of this method to the different global warming scenarios in Australia is presented. Since there is no reliable projection of possible change in air humidity, solar radiation or wind characters, as a first approximation, these parameters have been assumed to remain at the current level. A sensitivity test of their impact on the building energy performance shows that there is generally a good linear relationship between building cooling load and the changes of weather variables of solar radiation, relative humidity or wind speed.

Micro-structure differences in kaolinite suspensions

SEM observations of the aqueous suspensions of kaolinite from Birdwood (South Australia) and Georgia (USA) show noticeable differences in number of physical behaviour which has been explained by different microstructure constitution.. Birdwood kaolinite dispersion gels are observed at very low solid loadings in comparison with Georgia KGa-1 kaolinite dispersions which remain fluid at higher solids loading. To explain this behaviour, the specific particle interactions of Birdwood kaolinite, different from interaction in Georgia kaolinite have been proposed. These interactions may be brought about by the presence of nano-bubbles on clay crystal edges and may force clay particles to aggregate by bubble coalescence. This explains the predominance of stair step edge-edge like (EE) contacts in suspension of Birdwood kaolinite. Such EE linked particles build long strings that form a spacious cell structure. Hydrocarbon contamination of colloidal kaolinite particles and low aspect ratio are discussed as possible explanations of this unusual behaviour of Birdwood kaolinite. In Georgia KGa-1 kaolinite dispersions instead of EE contact between platelets displayed in Birdwood kaolinite, most particles have edge to face (EF) contacts building a cardhouse structure. Such an arrangement is much less voluminous in comparison with the Birdwood kaolinite cellular honeycomb structure observed previously in smectite aqueous suspensions. Such structural characteristics of KGa-1 kaolinite particles enable higher solid volume fractions pulps to form before significantly networked gel consistency is attained.

Teacher educators embrace philosophy: reflections on a new way of looking at preparing pre-service teachers

Over the last decade in Australia, the role of the teacher has changed. Teachers are now expected to model and foster in their students a wide range of skills such as critical thinking, self-regulated learning, knowledge of self and others and lifelong learning. These changes are having a significant impact on the design of pre-service teacher education programmes, with university educators re-evaluating the teacher training curriculum and embedded pedagogical processes in order to consider how they might develop these skills in pre-service teachers. One approach is to consider the processes and practices inherent in philosophical inquiry. This paper reports on three participants’ reflections of a 12-week philosophy programme that was conducted for teacher educators at Queensland’s University of Technology (QUT) in 2008. The programme was facilitated by teachers from Buranda State School who have been teaching philosophy in their P-7 school for more than ten years. This paper provides insight into teacher educators’ reflections on the philosophy programme and the associated changes and challenges of implementing such a programme in pre-service teacher education degrees.

Doped poly(vinylidene fluoride) as solid polymer electrolyte in nanocrystalline dye-sensitized solar cell

A new solid composite polymer electrolyte was reported by incorporating Azino-bis-(3-ethyl benzo thiazoline-6-sulphonate) ion [ABTS] as dopant in poly(vinylidene flouride) along with redox couple (1-/13-). Under certain conditions, the electrolyte composition forms brush like nano-rods while it is doped with Azino-bis-(3-ethly) benzo thiazoline-6-sulphonate) ion [ABTS], a pi-electron donor. The polymer electrolyte forms nanoscale interpenetrating network with the crystalline order of the polymer electrolyte that seems to be a desirable architecture for the active layer of the photoelectrochemical cell. With this new polymer electrolyte, dye-sensitized solar cell was fabricated using N3 dye absorbed over Ti02- nonoparticles (photoanode) and conducting carbon cement coated on the conducting press (FTO, photocathode). This polymer composite has been successfully used as a promising candidate as solid polymer electrolyte in nanocrystalline dye-sensitized solar cell.

Solid-state nanocrystalline dye-sensitized solar cell using 2-mercapto benzimidazole doped poly(ethylene oxide) as a new polymer electrolyte

New composite doped poly (ethylene oxide) polymer electrolyte was developed using 2-mercapto benzimidazole as plasticizer and iodide/triiodide as redox couple. The fabrication of the cell involves Poly(ethylene oxide)/ 2-mercapto benzimidazole / iodide/triiodide as polymer electrolyte in dye-sensitized solar cell fabricated with N3 dye and TiO2 nanoparticles as the photoanode and Platinum coated FTO (fluorine doped SnO2) as counter electrode. The current-volatage characteristics under simulated sunlight AM1.5 shows a short circuit current Isc of 8.7mA and open circuit photovoltage 508 mV. The conductivity measurements for the new polymer electrolyte and the photoelectrochemical measurments were carried out systematically. In 2-mercapto benzimidazole the electron rich sulphur and nitrogen atoms, act as pi-electron donors that form good interaction with iodine which plays a vital role in the performance of the fabricated dye-sensitized solar cells. The resonance effect increases the stability of the cell to a considerable extent. These results suggest that the new composite polymer electrolyte performs as a promising new doped polymer-electrolyte.

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.

Grafted fluoropolymers as supports for solid-phase organic chemistry : preparation and characterization

Solid-phase organic chemistry has rapidly expanded in the last decade, and, as a consequence, so has the need for the development of supports that can withstand the extreme conditions required to facilitate some reactions. The authors here prepare a thermally stable, grafted fluoropolymer support (see Figure for an example) in three solvents, and found that the penetration of the graft was greatest in dichloromethane.

Low moisture mud from solid bowl decanters

The high moisture content of mill mud (typically 75–80% for Australian factories) results in high transportation costs for the redistribution of mud onto cane farms. The high transportation cost relative to the nutrient value of the mill mud results in many milling companies subsidising the cost of this recycle to ensure a wide distribution across the cane supply area. An average mill would generate about 100 000 t of mud (at 75% moisture) in a crushing season. The development of mud processing facilities that will produce a low moisture mud that can be effectively incorporated into cane land with existing or modified spreading equipment will improve the cost efficiency of mud redistribution to farms; provide an economical fertiliser alternative to more farms in the supply area; and reduce the potential for adverse environmental impacts from farms. A research investigation assessing solid bowl decanter centrifuges to produce low moisture mud with low residual pol was undertaken and the results compared to the performance of existing rotary vacuum filters in factory trials. The decanters were operated on filter mud feed in parallel with the rotary vacuum filters to allow comparisons of performance. Samples of feed, mud product and filtrate were analysed to provide performance indicators. The decanter centrifuge could produce mud cakes with very low moistures and residual pol levels. Spreading trials in cane fields indicated that the dry cake could be spread easily by standard mud trucks and by trucks designed specifically to spread fertiliser.