238 resultados para theoretical Chemistry


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Due to their small collecting volume diodes are commonly used in small field dosimetry. However the relative sensitivity of a diode increases with decreasing small field size. Conversely, small air gaps have been shown to cause a significant decrease in the sensitivity of a detector as the field size is decreased. Therefore this study uses Monte Carlo simulations to look at introducing air upstream to diodes such that they measure with a constant sensitivity across all field sizes in small field dosimetry. Varying thicknesses of air were introduced onto the upstream end of two commercial diodes (PTW 60016 photon diode and PTW 60017 electron diode), as well as a theoretical unenclosed silicon chip using field sizes as small as 5 mm × 5 mm . The metric D_(w,Q)/D_(Det,Q) used in this study represents the ratio of the dose to a point of water to the dose to the diode active volume, for a particular field size and location. The optimal thickness of air required to provide a constant sensitivity across all small field sizes was found by plotting D_(w,Q)/D_(Det,Q) as a function of introduced air gap size for various field sizes, and finding the intersection point of these plots. That is, the point at which D_(w,Q)/D_(Det,Q) was constant for all field sizes was found. The optimal thickness of air was calculated to be 3.3 mm, 1.15 mm and 0.10 mm for the photon diode, electron diode and unenclosed silicon chip respectively. The variation in these results was due to the different design of each detector. When calculated with the new diode design incorporating the upstream air gap, k_(Q_clin 〖,Q〗_msr)^(f_clin 〖,f〗_msr ) was equal to unity to within statistical uncertainty (0.5 %) for all three diodes. Cross-axis profile measurements were also improved with the new detector design. The upstream air gap could be implanted on the commercial diodes via a cap consisting of the air cavity surrounded by water equivalent material. The results for the unclosed silicon chip show that an ideal small field dosimetry diode could be created by using a silicon chip with a small amount of air above it.

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Concern about the increasing atmospheric CO2 concentration and its impact on the environment has led to increasing attention directed toward finding advanced materials and technologies suited for efficient CO2 capture, storage and purification of clean-burning natural gas. In this letter, we have performed comprehensive theoretical investigation of CO2, N2, CH4 and H2 adsorption on B2CNTs. Our study shows that CO2 molecules can form strong interactions with B2CNTs with different charge states. However, N2, CH4 and H2 can only form very weak interactions with B2CNTs. Therefore, the study demonstrates B2CNTs could sever as promising materials for CO2 capture and gas separation.

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In this paper, the dissociative chemisorption of hydrogen on both pure and Ti-incorporated Mg(0001) surfaces are studied by ab initio density functional theory (DFT) calculations. The calculated dissociation barrier of hydrogen molecule on a pure Mg(0001) surface (1.05 eV) is in good agreement with comparable theoretical studies. For the Ti-incorporated Mg(0001) surface, the activated barrier decreases to 0.103 eV due to the strong interaction between the molecular orbital of hydrogen and the d metal state of Ti. This could explain the experimentally observed improvement in absorption kinetics of hydrogen when transition metals have been introduced into the magnesium materials.

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Introduction: The use of amorphous-silicon electronic portal imaging devices (a-Si EPIDs) for dosimetry is complicated by the effects of scattered radiation. In photon radiotherapy, primary signal at the detector can be accompanied by photons scattered from linear accelerator components, detector materials, intervening air, treatment room surfaces (floor, walls, etc) and from the patient/phantom being irradiated. Consequently, EPID measurements which presume to take scatter into account are highly sensitive to the identification of these contributions. One example of this susceptibility is the process of calibrating an EPID for use as a gauge of (radiological) thickness, where specific allowance must be made for the effect of phantom-scatter on the intensity of radiation measured through different thicknesses of phantom. This is usually done via a theoretical calculation which assumes that phantom scatter is linearly related to thickness and field-size. We have, however, undertaken a more detailed study of the scattering effects of fields of different dimensions when applied to phantoms of various thicknesses in order to derive scattered-primary ratios (SPRs) directly from simulation results. This allows us to make a more-accurate calibration of the EPID, and to qualify the appositeness of the theoretical SPR calculations. Methods: This study uses a full MC model of the entire linac-phantom-detector system simulated using EGSnrc/BEAMnrc codes. The Elekta linac and EPID are modelled according to specifications from the manufacturer and the intervening phantoms are modelled as rectilinear blocks of water or plastic, with their densities set to a range of physically realistic and unrealistic values. Transmissions through these various phantoms are calculated using the dose detected in the model EPID and used in an evaluation of the field-size-dependence of SPR, in different media, applying a method suggested for experimental systems by Swindell and Evans [1]. These results are compared firstly with SPRs calculated using the theoretical, linear relationship between SPR and irradiated volume, and secondly with SPRs evaluated from our own experimental data. An alternate evaluation of the SPR in each simulated system is also made by modifying the BEAMnrc user code READPHSP, to identify and count those particles in a given plane of the system that have undergone a scattering event. In addition to these simulations, which are designed to closely replicate the experimental setup, we also used MC models to examine the effects of varying the setup in experimentally challenging ways (changing the size of the air gap between the phantom and the EPID, changing the longitudinal position of the EPID itself). Experimental measurements used in this study were made using an Elekta Precise linear accelerator, operating at 6MV, with an Elekta iView GT a-Si EPID. Results and Discussion: 1. Comparison with theory: With the Elekta iView EPID fixed at 160 cm from the photon source, the phantoms, when positioned isocentrically, are located 41 to 55 cm from the surface of the panel. At this geometry, a close but imperfect agreement (differing by up to 5%) can be identified between the results of the simulations and the theoretical calculations. However, this agreement can be totally disrupted by shifting the phantom out of the isocentric position. Evidently, the allowance made for source-phantom-detector geometry by the theoretical expression for SPR is inadequate to describe the effect that phantom proximity can have on measurements made using an (infamously low-energy sensitive) a-Si EPID. 2. Comparison with experiment: For various square field sizes and across the range of phantom thicknesses, there is good agreement between simulation data and experimental measurements of the transmissions and the derived values of the primary intensities. However, the values of SPR obtained through these simulations and measurements seem to be much more sensitive to slight differences between the simulated and real systems, leading to difficulties in producing a simulated system which adequately replicates the experimental data. (For instance, small changes to simulated phantom density make large differences to resulting SPR.) 3. Comparison with direct calculation: By developing a method for directly counting the number scattered particles reaching the detector after passing through the various isocentric phantom thicknesses, we show that the experimental method discussed above is providing a good measure of the actual degree of scattering produced by the phantom. This calculation also permits the analysis of the scattering sources/sinks within the linac and EPID, as well as the phantom and intervening air. Conclusions: This work challenges the assumption that scatter to and within an EPID can be accounted for using a simple, linear model. Simulations discussed here are intended to contribute to a fuller understanding of the contribution of scattered radiation to the EPID images that are used in dosimetry calculations. Acknowledgements: This work is funded by the NHMRC, through a project grant, and supported by the Queensland University of Technology (QUT) and the Royal Brisbane and Women's Hospital, Brisbane, Australia. The authors are also grateful to Elekta for the provision of manufacturing specifications which permitted the detailed simulation of their linear accelerators and amorphous-silicon electronic portal imaging devices. Computational resources and services used in this work were provided by the HPC and Research Support Group, QUT, Brisbane, Australia.

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Students entering tertiary studies possess a diverse range of prior experiences in their academic preparation for tertiary chemistry so academics need tools to enable them to respond to issues in diversity in conceptual models possessed by entering students. Concept inventories can be used to provide formative feedback to help students identify concepts that they need to address to improve construction of subsequent understanding enabling their learning. Modular, formative learning activities that can be administered inside or outside of class in first year chemistry courses have been developed. These activities address key missing and mis-conceptions possessed by incoming student. Engagement in these learning activities by students and academics will help shift the culture of diagnostic and formative assessment within the tertiary context and address issues around the secondary/tertiary transition. This diagnostic/intervention framework is currently being trialed across five Australian tertiary institutions encompassing a large heterogeneous sample of students.

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A comprehensive study was conducted on mesoporous MCM-41. Spectroscopic examinations demonstrated that three types of silanol groups, i.e., single, (SiO)3Si-OH, hydrogen-bonded, (SiO)3Si-OH-OH-Si(SiO)3, and geminal, (SiO)2Si(OH)2, can be observed. The number of silanol groups/nm2, ?OH, as determined by NMR, varies between 2.5 and 3.0 depending on the template-removal methods. All these silanol groups were found to be the active sites for adsorption of pyridine with desorption energies of 91.4 and 52.2 kJ mol-1, respectively. However, only free silanol groups (involving single and geminal silanols) are highly accessible to the silylating agent, chlorotrimethylsilane. Silylation can modify both the physical and chemical properties of MCM-41.

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Information literacy has been a significant issue in the library community for many years. It is now being recognised as an important issue by the higher education community. This theoretical framework draws together important elements of the information literacy agenda specifically for tertiary educators and administrators. The frame-work examines three areas of primary concern: the possible outcomes of information literacy education (through outlining the characteristics of information literate people); the nature of information literacy education; and the potential role of stake-holders (including information services, faculty, staff developers and learning counsellors) in helping staff and students to be information literate. This theoretical framework forms part of the Griffith University Information Literacy Blueprint. The Blueprint was designed between June and August of 1994. The project, a quality initiative of the Division of Information Services, was led by Janice Rickards, University Librarian.

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The Chemistry Discipline Network has recently completed two distinct mapping exercises. The first is a snapshot of chemistry taught at 12 institutions around Australia in 2011. There were many similarities but also important differences in the content taught and assessed at different institutions. There were also significant differences in delivery, particularly laboratory contact hours, as well as forms and weightings of assessment. The second mapping exercise mapped the chemistry degrees at three institutions to the Threshold Learning Outcomes for chemistry. Importantly, some of the TLOs were addressed by multiple units at all institutions, while others were not met, or were met at an introductory level only. The exercise also exposed some challenges in using the TLOs as currently written.

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In this report, a detailed FTIR fitting analysis was used to recognize Mg, Zn and Al homogeneous distribution in MgxZnyAl(x+y)/2-Layered double hydroxide (LDH) hydroxyl layer. In detail, OH-Mg2Al:OH-Mg3 ratios decreased from 95.2:4.8 (MIR) and 94.2:5.8 (NIR) to 58.9:41.1 (MIR) and 61.8:38.2 (NIR), when Mg:Al increased from 2.2:1.0 to 4.1:1.0 in MgAl-LDHs. These fitting results were similar with theoretical calculations of 94.3:5.7 and 59.0:41.0. In a further analysis of MgxZnyAl(x+y)/2-LDHs, OH bonded Zn2Mg, Zn2Al, MgZnAl, Mg2Al and Mg2Zn peaks were identified at 3420, 3430, 3445–3450, 3454 and 3545 cm-1, respectively. With the decrease of Mg:Zn from 3:1 to 1:3, metal-hydroxyl bands changed from OH-Mg2Al and MgZnAl (with a ratio of 49.4:50.6) to OH-MgZnAl and Zn2Al (with a ratio of 55.0:45.0). They were also similar with theoretical calculations of 47.6:52.4 and 54.6:45.4. As a result, these results show that there is an ordered cation distribution in MgxZnyAl(x+y)/2-LDH, and FTIR is feasible in recognizing this structure.

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Water reuse through greywater irrigation has been adopted worldwide and has been proposed as a potential sustainable solution to increased water demands. Despite widespread adoption there is limited domestic knowledge of greywater reuse, there is no pressure to produce lowlevel phosphorus products and current guidelines and legislation, such as those in Australia, may be inadequate due to the lack of long-term data to provide a sound scientific basis. Research has clearly identified phosphorus as a potential environmental risk to waterways from many forms of irrigation. To assess the sustainability of greywater irrigation, this study compared four residential lots that had been irrigated with greywater for four years and adjacent non-irrigated lots that acted as controls. Each lot was monitored for the volume of greywater applied and selected physic-chemical water quality parameters and soil chemistry profiles were analysed. The non-irrigated soil profiles showed low levels of phosphorus and were used as controls. The Mechlich3 Phosphorus ratio (M3PSR) and Phosphate Environmental Risk Index (PERI) were used to determine the environmental risk of phosphorus leaching from the irrigated soils. Soil phosphorus concentrations were compared to theoretical greywater irrigation loadings. The measured phosphorus soil concentrations and the estimated greywater loadings were of similar magnitude. Sustainable greywater reuse is possible; however incorrect use and/or a lack of understanding of how household products affect greywater can result in phosphorus posing a significant risk to the environment.

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This chapter briefly introduces the concepts and modeling of gas/isotope separation by two dimensional carbon frameworks, i.e. porous graphene and carbon nanomeshes, on the basis of reviewing recent literatures. The small size of evenly distributed pores on these carbon frameworks make them ideal not only for the separation of small gas molecules but also for isotope separation by utilizing the different zero point energies induced by confinement of the pores. The related simulations were treated by transition state theory, an affordable yet precise method that could be adopted in combination with different levels of theory. Such method could be employed to evaluate the performance, as well as to aid the design, of other 2D carbon frameworks toward the goal of gas/isotope separation in the future.

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This research project frames an emerging field – fashion curation – through a theoretical, historical, and practical enquiry. Recent decades have seen fashion curation grow rapidly as a form of praxis and an area of academic attention, predominantly in museums and universities. Within this context, two major models for conceptualising the role of the fashion curator have emerged: the institutional and the independent curator. This project proposes and applies a third model: the adjunct fashion curator. In developing this model my project seeks to move the growing dialogue around fashion curation away from exclusively focusing on the museum. By proposing a third curatorial model for fashion, this research draws on the past of fashion display and exhibition for its context, while simultaneously exploring the adjunct model through my curatorial practice. The impact of sites of display, the role of gender, and the relationship between art and fashion are explored as pivotal themes in the development of fashion curation and thus provide contextual grounding for the proposal of the adjunct curatorial model. Alongside a theoretical and historical account of fashion curation, I conduct a practice-led inquiry that explores these themes through five exhibition projects and one photographic series. I argue that the introduction and application of the adjunct model enables curatorial practitioners to sensitively work around the dominant museum model, and circumvent the divide between institutional and independent curation. Introducing the adjunct model allows the curator to develop personalised narratives relating to the experience of fashion and clothing as an exhibited phenomenon in a variety of institutional and non-institutional sites. Hence this research project contributes to a developing field by proposing a valuable and nuanced model for fashion curation.

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Electrostatic discharges have been identified as the most likely cause in a number of incidents of fire and explosion with unexplained ignitions. The lack of data and suitable models for this ignition mechanism creates a void in the analysis to quantify the importance of static electricity as a credible ignition mechanism. Quantifiable hazard analysis of the risk of ignition by static discharge cannot, therefore, be entirely carried out with our current understanding of this phenomenon. The study of electrostatics has been ongoing for a long time. However, it was not until the wide spread use of electronics that research was developed for the protection of electronics from electrostatic discharges. Current experimental models for electrostatic discharge developed for intrinsic safety with electronics are inadequate for ignition analysis and typically are not supported by theoretical analysis. A preliminary simulation and experiment with low voltage was designed to investigate the characteristics of energy dissipation and provided a basis for a high voltage investigation. It was seen that for a low voltage the discharge energy represents about 10% of the initial capacitive energy available and that the energy dissipation was within 10 ns of the initial discharge. The potential difference is greatest at the initial break down when the largest amount of the energy is dissipated. The discharge pathway is then established and minimal energy is dissipated as energy dissipation becomes greatly influenced by other components and stray resistance in the discharge circuit. From the initial low voltage simulation work, the importance of the energy dissipation and the characteristic of the discharge were determined. After the preliminary low voltage work was completed, a high voltage discharge experiment was designed and fabricated. Voltage and current measurement were recorded on the discharge circuit allowing the discharge characteristic to be recorded and energy dissipation in the discharge circuit calculated. Discharge energy calculations show consistency with the low voltage work relating to discharge energy with about 30-40% of the total initial capacitive energy being discharged in the resulting high voltage arc. After the system was characterised and operation validated, high voltage ignition energy measurements were conducted on a solution of n-Pentane evaporating in a 250 cm3 chamber. A series of ignition experiments were conducted to determine the minimum ignition energy of n-Pentane. The data from the ignition work was analysed with standard statistical regression methods for tests that return binary (yes/no) data and found to be in agreement with recent publications. The research demonstrates that energy dissipation is heavily dependent on the circuit configuration and most especially by the discharge circuit's capacitance and resistance. The analysis established a discharge profile for the discharges studied and validates the application of this methodology for further research into different materials and atmospheres; by systematically looking at discharge profiles of test materials with various parameters (e.g., capacitance, inductance, and resistance). Systematic experiments looking at the discharge characteristics of the spark will also help understand the way energy is dissipated in an electrostatic discharge enabling a better understanding of the ignition characteristics of materials in terms of energy and the dissipation of that energy in an electrostatic discharge.

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Residential balcony design influences speech interference levels caused by road traffic noise and a simplified design methodology is needed for optimising balcony acoustic treatments. This research comprehensively assesses speech interference levels and benefits of nine different balcony designs situated in urban street canyons through the use of a combined direct, specular reflection and diffuse reflection path theoretical model. This thesis outlines the theory, analysis and results that lead up to the presentation of a practical design guide which can be used to predict the acoustic effects of balcony geometry and acoustic treatments in streets with variable geometry and acoustic characteristics.

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This paper conceptualizes knowledge governance (KG) in project-based organizations (PBOs) and its methodological approaches for empirical investigation. Three key contributions towards a multi-faceted view of KG and an understanding of KG in PBOs are advanced. These contributions include a definition of KG in PBOs, a conceptual framework to investigate KG and a methodological framework for empirical inquiry into KG in PBO settings. Our definition highlights the contingent nature of KG processes in relation to their organizational context. The conceptual framework addresses macro- and micro-level elements of KG and their interaction. The methodological framework proposes five different research approaches, structured by differentiation and integration of various ontological and epistemological stances. Together these contributions provide a novel platform for understanding KG in PBOs and developing new insights into the design and execution of research on KG within PBOs.