928 resultados para Mechanical Attrition Treatment
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The ability of a piezoelectric transducer in energy conversion is rapidly expanding in several applications. Some of the industrial applications for which a high power ultrasound transducer can be used are surface cleaning, water treatment, plastic welding and food sterilization. Also, a high power ultrasound transducer plays a great role in biomedical applications such as diagnostic and therapeutic applications. An ultrasound transducer is usually applied to convert electrical energy to mechanical energy and vice versa. In some high power ultrasound system, ultrasound transducers are applied as a transmitter, as a receiver or both. As a transmitter, it converts electrical energy to mechanical energy while a receiver converts mechanical energy to electrical energy as a sensor for control system. Once a piezoelectric transducer is excited by electrical signal, piezoelectric material starts to vibrate and generates ultrasound waves. A portion of the ultrasound waves which passes through the medium will be sensed by the receiver and converted to electrical energy. To drive an ultrasound transducer, an excitation signal should be properly designed otherwise undesired signal (low quality) can deteriorate the performance of the transducer (energy conversion) and increase power consumption in the system. For instance, some portion of generated power may be delivered in unwanted frequency which is not acceptable for some applications especially for biomedical applications. To achieve better performance of the transducer, along with the quality of the excitation signal, the characteristics of the high power ultrasound transducer should be taken into consideration as well. In this regard, several simulation and experimental tests are carried out in this research to model high power ultrasound transducers and systems. During these experiments, high power ultrasound transducers are excited by several excitation signals with different amplitudes and frequencies, using a network analyser, a signal generator, a high power amplifier and a multilevel converter. Also, to analyse the behaviour of the ultrasound system, the voltage ratio of the system is measured in different tests. The voltage across transmitter is measured as an input voltage then divided by the output voltage which is measured across receiver. The results of the transducer characteristics and the ultrasound system behaviour are discussed in chapter 4 and 5 of this thesis. Each piezoelectric transducer has several resonance frequencies in which its impedance has lower magnitude as compared to non-resonance frequencies. Among these resonance frequencies, just at one of those frequencies, the magnitude of the impedance is minimum. This resonance frequency is known as the main resonance frequency of the transducer. To attain higher efficiency and deliver more power to the ultrasound system, the transducer is usually excited at the main resonance frequency. Therefore, it is important to find out this frequency and other resonance frequencies. Hereof, a frequency detection method is proposed in this research which is discussed in chapter 2. An extended electrical model of the ultrasound transducer with multiple resonance frequencies consists of several RLC legs in parallel with a capacitor. Each RLC leg represents one of the resonance frequencies of the ultrasound transducer. At resonance frequency the inductor reactance and capacitor reactance cancel out each other and the resistor of this leg represents power conversion of the system at that frequency. This concept is shown in simulation and test results presented in chapter 4. To excite a high power ultrasound transducer, a high power signal is required. Multilevel converters are usually applied to generate a high power signal but the drawback of this signal is low quality in comparison with a sinusoidal signal. In some applications like ultrasound, it is extensively important to generate a high quality signal. Several control and modulation techniques are introduced in different papers to control the output voltage of the multilevel converters. One of those techniques is harmonic elimination technique. In this technique, switching angles are chosen in such way to reduce harmonic contents in the output side. It is undeniable that increasing the number of the switching angles results in more harmonic reduction. But to have more switching angles, more output voltage levels are required which increase the number of components and cost of the converter. To improve the quality of the output voltage signal with no more components, a new harmonic elimination technique is proposed in this research. Based on this new technique, more variables (DC voltage levels and switching angles) are chosen to eliminate more low order harmonics compared to conventional harmonic elimination techniques. In conventional harmonic elimination method, DC voltage levels are same and only switching angles are calculated to eliminate harmonics. Therefore, the number of eliminated harmonic is limited by the number of switching cycles. In the proposed modulation technique, the switching angles and the DC voltage levels are calculated off-line to eliminate more harmonics. Therefore, the DC voltage levels are not equal and should be regulated. To achieve this aim, a DC/DC converter is applied to adjust the DC link voltages with several capacitors. The effect of the new harmonic elimination technique on the output quality of several single phase multilevel converters is explained in chapter 3 and 6 of this thesis. According to the electrical model of high power ultrasound transducer, this device can be modelled as parallel combinations of RLC legs with a main capacitor. The impedance diagram of the transducer in frequency domain shows it has capacitive characteristics in almost all frequencies. Therefore, using a voltage source converter to drive a high power ultrasound transducer can create significant leakage current through the transducer. It happens due to significant voltage stress (dv/dt) across the transducer. To remedy this problem, LC filters are applied in some applications. For some applications such as ultrasound, using a LC filter can deteriorate the performance of the transducer by changing its characteristics and displacing the resonance frequency of the transducer. For such a case a current source converter could be a suitable choice to overcome this problem. In this regard, a current source converter is implemented and applied to excite the high power ultrasound transducer. To control the output current and voltage, a hysteresis control and unipolar modulation are used respectively. The results of this test are explained in chapter 7.
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Purpose: Electronic Portal Imaging Devices (EPIDs) are available with most linear accelerators (Amonuk, 2002), the current technology being amorphous silicon flat panel imagers. EPIDs are currently used routinely in patient positioning before radiotherapy treatments. There has been an increasing interest in using EPID technology tor dosimetric verification of radiotherapy treatments (van Elmpt, 2008). A straightforward technique involves the EPID panel being used to measure the fluence exiting the patient during a treatment which is then compared to a prediction of the fluence based on the treatment plan. However, there are a number of significant limitations which exist in this Method: Resulting in a limited proliferation ot this technique in a clinical environment. In this paper, we aim to present a technique of simulating IMRT fields using Monte Carlo to predict the dose in an EPID which can then be compared to the measured dose in the EPID. Materials: Measurements were made using an iView GT flat panel a-SI EPfD mounted on an Elekta Synergy linear accelerator. The images from the EPID were acquired using the XIS software (Heimann Imaging Systems). Monte Carlo simulations were performed using the BEAMnrc and DOSXVZnrc user codes. The IMRT fieids to be delivered were taken from the treatment planning system in DICOMRT format and converted into BEAMnrc and DOSXYZnrc input files using an in-house application (Crowe, 2009). Additionally. all image processing and analysis was performed using another in-house application written using the Interactive Data Language (IDL) (In Visual Information Systems). Comparison between the measured and Monte Carlo EPID images was performed using a gamma analysis (Low, 1998) incorporating dose and distance to agreement criteria. Results: The fluence maps recorded by the EPID were found to provide good agreement between measured and simulated data. Figure 1 shows an example of measured and simulated IMRT dose images and profiles in the x and y directions. "A technique for the quantitative evaluation of dose distributions", Med Phys, 25(5) May 1998 S. Crowe, 1. Kairn, A. Fielding, "The Development of a Monte Carlo system to verify Radiotherapy treatment dose calculations", Radiotherapy & Oncology, Volume 92, Supplement 1, August 2009, Pages S71-S71.
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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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Introduction: Recent advances in the planning and delivery of radiotherapy treatments have resulted in improvements in the accuracy and precision with which therapeutic radiation can be administered. As the complexity of the treatments increases it becomes more difficult to predict the dose distribution in the patient accurately. Monte Carlo (MC) methods have the potential to improve the accuracy of the dose calculations and are increasingly being recognised as the ‘gold standard’ for predicting dose deposition in the patient [1]. This project has three main aims: 1. To develop tools that enable the transfer of treatment plan information from the treatment planning system (TPS) to a MC dose calculation engine. 2. To develop tools for comparing the 3D dose distributions calculated by the TPS and the MC dose engine. 3. To investigate the radiobiological significance of any errors between the TPS patient dose distribution and the MC dose distribution in terms of Tumour Control Probability (TCP) and Normal Tissue Complication Probabilities (NTCP). The work presented here addresses the first two aims. Methods: (1a) Plan Importing: A database of commissioned accelerator models (Elekta Precise and Varian 2100CD) has been developed for treatment simulations in the MC system (EGSnrc/BEAMnrc). Beam descriptions can be exported from the TPS using the widespread DICOM framework, and the resultant files are parsed with the assistance of a software library (PixelMed Java DICOM Toolkit). The information in these files (such as the monitor units, the jaw positions and gantry orientation) is used to construct a plan-specific accelerator model which allows an accurate simulation of the patient treatment field. (1b) Dose Simulation: The calculation of a dose distribution requires patient CT images which are prepared for the MC simulation using a tool (CTCREATE) packaged with the system. Beam simulation results are converted to absolute dose per- MU using calibration factors recorded during the commissioning process and treatment simulation. These distributions are combined according to the MU meter settings stored in the exported plan to produce an accurate description of the prescribed dose to the patient. (2) Dose Comparison: TPS dose calculations can be obtained using either a DICOM export or by direct retrieval of binary dose files from the file system. Dose difference, gamma evaluation and normalised dose difference algorithms [2] were employed for the comparison of the TPS dose distribution and the MC dose distribution. These implementations are spatial resolution independent and able to interpolate for comparisons. Results and Discussion: The tools successfully produced Monte Carlo input files for a variety of plans exported from the Eclipse (Varian Medical Systems) and Pinnacle (Philips Medical Systems) planning systems: ranging in complexity from a single uniform square field to a five-field step and shoot IMRT treatment. The simulation of collimated beams has been verified geometrically, and validation of dose distributions in a simple body phantom (QUASAR) will follow. The developed dose comparison algorithms have also been tested with controlled dose distribution changes. Conclusion: The capability of the developed code to independently process treatment plans has been demonstrated. A number of limitations exist: only static fields are currently supported (dynamic wedges and dynamic IMRT will require further development), and the process has not been tested for planning systems other than Eclipse and Pinnacle. The tools will be used to independently assess the accuracy of the current treatment planning system dose calculation algorithms for complex treatment deliveries such as IMRT in treatment sites where patient inhomogeneities are expected to be significant. Acknowledgements: Computational resources and services used in this work were provided by the HPC and Research Support Group, Queensland University of Technology, Brisbane, Australia. Pinnacle dose parsing made possible with the help of Paul Reich, North Coast Cancer Institute, North Coast, New South Wales.
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Introduction: The motivation for developing megavoltage (and kilovoltage) cone beam CT (MV CBCT) capabilities in the radiotherapy treatment room was primarily based on the need to improve patient set-up accuracy. There has recently been an interest in using the cone beam CT data for treatment planning. Accurate treatment planning, however, requires knowledge of the electron density of the tissues receiving radiation in order to calculate dose distributions. This is obtained from CT, utilising a conversion between CT number and electron density of various tissues. The use of MV CBCT has particular advantages compared to treatment planning with kilovoltage CT in the presence of high atomic number materials and requires the conversion of pixel values from the image sets to electron density. Therefore, a study was undertaken to characterise the pixel value to electron density relationship for the Siemens MV CBCT system, MVision, and determine the effect, if any, of differing the number of monitor units used for acquisition. If a significant difference with number of monitor units was seen then pixel value to ED conversions may be required for each of the clinical settings. The calibration of the MV CT images for electron density offers the possibility for a daily recalculation of the dose distribution and the introduction of new adaptive radiotherapy treatment strategies. Methods: A Gammex Electron Density CT Phantom was imaged with the MVCB CT system. The pixel value for each of the sixteen inserts, which ranged from 0.292 to 1.707 relative electron density to the background solid water, was determined by taking the mean value from within a region of interest centred on the insert, over 5 slices within the centre of the phantom. These results were averaged and plotted against the relative electron densities of each insert with a linear least squares fit was preformed. This procedure was performed for images acquired with 5, 8, 15 and 60 monitor units. Results: The linear relationship between MVCT pixel value and ED was demonstrated for all monitor unit settings and over a range of electron densities. The number of monitor units utilised was found to have no significant impact on this relationship. Discussion: It was found that the number of MU utilised does not significantly alter the pixel value obtained for different ED materials. However, to ensure the most accurate and reproducible MV to ED calibration, one MU setting should be chosen and used routinely. To ensure accuracy for the clinical situation this MU setting should correspond to that which is used clinically. If more than one MU setting is used clinically then an average of the CT values acquired with different numbers of MU could be utilized without loss in accuracy. Conclusions: No significant differences have been shown between the pixel value to ED conversion for the Siemens MV CT cone beam unit with change in monitor units. Thus as single conversion curve could be utilised for MV CT treatment planning. To fully utilise MV CT imaging for radiotherapy treatment planning further work will be undertaken to ensure all corrections have been made and dose calculations verified. These dose calculations may be either for treatment planning purposes or for reconstructing the delivered dose distribution from transit dosimetry measurements made using electronic portal imaging devices. This will potentially allow the cumulative dose distribution to be determined through the patient’s multi-fraction treatment and adaptive treatment strategies developed to optimize the tumour response.
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This presentation discusses the limited research of urban rehabilitation service evaluations and assesses the progress of Goori House Rehabilitation Service, identifying issues preventing a sustainable organisational future.
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Nonthermal plasma (NTP) treatment of exhaust gas is a promising technology for both nitrogen oxides (NOX) and particulate matter (PM) reduction by introducing plasma into the exhaust gases. This paper considers the effect of NTP on PM mass reduction, PM size distribution, and PM removal efficiency. The experiments are performed on real exhaust gases from a diesel engine. The NTP is generated by applying high-voltage pulses using a pulsed power supply across a dielectric barrier discharge (DBD) reactor. The effects of the applied high-voltage pulses up to 19.44 kVpp with repetition rate of 10 kHz are investigated. In this paper, it is shown that the PM removal and PM size distribution need to be considered both together, as it is possible to achieve high PM removal efficiency with undesirable increase in the number of small particles. Regarding these two important factors, in this paper, 17 kVpp voltage level is determined to be an optimum point for the given configuration. Moreover, particles deposition on the surface of the DBD reactor is found to be a significant phenomenon, which should be considered in all plasma PM removal tests.
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Accuracy of dose delivery in external beam radiotherapy is usually verified with electronic portal imaging (EPI) in which the treatment beam is used to check the positioning of the patient. However the resulting megavoltage x-ray images suffer from poor quality. The image quality can be improved by developing a special operating mode in the linear accelerator. The existing treatment beam is modified such that it produces enough low-energy photons for imaging. In this work the problem of optimizing the beam/detector combination to achieve optimal electronic portal image quality is addressed. The linac used for this study was modified to produce two experimental photon beams. These beams, named Al6 and Al10, were non-flat and were produced by 4MeV electrons hitting aluminum targets, 6 and 10mm thick respectively. The images produced by a conventional EPI system (6MV treatment beam and camera-based EPID with a Cu plate & Gd2O2S screen ) were compared with the images produced by the experimental beams and various screens with the same camera). The contrast of 0.8cm bone equivalent material in 5 cm water increased from 1.5% for the conventional system to 11% for the combination of Al6 beam with a 200mg/cm2 Gd2O2S screen. The signal-to-noise ratio calculated for 1cGy flood field images increased by about a factor of two for the same EPI systems. The spatial resolution of the two imaging systems was comparable. This work demonstrates that significant improvements in portal image contrast can be obtained by simultaneous optimization of the linac spectrum and EPI detector.
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We have taken a new method of calibrating portal images of IMRT beams and used this to measure patient set-up accuracy and delivery errors, such as leaf errors and segment intensity errors during treatment. A calibration technique was used to remove the intensity modulations from the images leaving equivalent open field images that show patient anatomy that can be used for verification of the patient position. The images of the treatment beam can also be used to verify the delivery of the beam in terms of multileaf collimator leaf position and dosimetric errors. A series of controlled experiments delivering an IMRT anterior beam to the head and neck of a humanoid phantom were undertaken. A 2mm translation in the position of the phantom could be detected. With intentional introduction of delivery errors into the beam this method allowed us to detect leaf positioning errors of 2mm and variation in monitor units of 1%. The method was then applied to the case of a patient who received IMRT treatment to the larynx and cervical nodes. The anterior IMRT beam was imaged during four fractions and the images calibrated and investigated for the characteristic signs of patient position error and delivery error that were shown in the control experiments. No significant errors were seen. The method of imaging the IMRT beam and calibrating the images to remove the intensity modulations can be a useful tool in verifying both the patient position and the delivery of the beam.
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This investigation has demonstrated the need for thermal treatment of seawater neutralised red mud (SWRM) in order to obtain reasonable adsorption of Reactive Blue dye 19 (RB 19). Thermal treatment results in a greater surface area, which results in an increased adsorption capacity due to more available adsorption sites. Adsorption of RB 19 has been found to be best achieved in acidic conditions using SWNRM400 (heated to 400 �C) with an adsorption capacity of 416.7 mg/g compared to 250.0 mg/g for untreated SWNRM. Kinetic studies indicate a pseudosecond-order reaction mechanism is responsible for the adsorption of RB 19 using SWNRM, which indicates adsorption occurs by electrostatic interactions.
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Mortality and cost outcomes of elderly intensive care unit (ICU) trauma patients were characterised in a retrospective cohort study from an Australian tertiary ICU. Trauma patients admitted between January 2000 and December 2005 were grouped into three major age categories: aged ≥65 years admitted into ICU (n=272); aged ≥65 years admitted into general ward (n=610) and aged <65 years admitted into ICU (n=1617). Hospital mortality predictors were characterised as odds ratios (OR) using logistic regression. The impact of predictor variables on (log) total hospital-stay costs was determined using least squares regression. An alternate treatment-effects regression model estimated the mortality cost-effect as an endogenous variable. Mortality predictors (P ≤0.0001, comparator: ICU ≥65 years, ventilated) were: ICU <65 not-ventilated (OR 0.014); ICU <65 ventilated (OR 0.090); ICU age ≥65 not-ventilated (OR 0.061) and ward ≥65 (OR 0.086); increasing injury severity score and increased Charlson comorbidity index of 1 and 2, compared with zero (OR 2.21 [1.40 to 3.48] and OR 2.57 [1.45 to 4.55]). The raw mean daily ICU and hospital costs in A$ 2005 (US$) for age <65 and ≥65 to ICU, and ≥65 to the ward were; for year 2000: ICU, $2717 (1462) and $2777 (1494); hospital, $1837 (988) and $1590 (855); ward $933 (502); for year 2005: ICU, $3202 (2393) and $3086 (2307); hospital, $1938 (1449) and $1914 (1431); ward $1180 (882). Cost increments were predicted by age ≥65 and ICU admission, increasing injury severity score, mechanical ventilation, Charlson comorbidity index increments and hospital survival. Mortalitycost-effect was estimated at -63% by least squares regression and -82% by treatment-effects regression model. Patient demographic factors, injury severity and its consequences predict both cost and survival in trauma. The cost mortality effect was biased upwards by conventional least squares regression estimation.
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BACKGROUND: The treatment for deep surgical site infection (SSI) following primary total hip arthroplasty (THA) varies internationally and it is at present unclear which treatment approaches are used in Australia. The aim of this study is to identify current treatment approaches in Queensland, Australia, show success rates and quantify the costs of different treatments. METHODS: Data for patients undergoing primary THA and treatment for infection between January 2006 and December 2009 in Queensland hospitals were extracted from routinely used hospital databases. Records were linked with pathology information to confirm positive organisms. Diagnosis and treatment of infection was determined using ICD-10-AM and ACHI codes, respectively. Treatment costs were estimated based on AR-DRG cost accounting codes assigned to each patient hospital episode. RESULTS: A total of n=114 patients with deep surgical site infection were identified. The majority of patients (74%) were first treated with debridement, antibiotics and implant retention (DAIR), which was successful in eradicating the infection in 60.3% of patients with an average cost of $13,187. The remaining first treatments were 1-stage revision, successful in 89.7% with average costs of $27,006, and 2-stage revisions, successful in 92.9% of cases with average costs of $42,772. Multiple treatments following 'failed DAIR' cost on average $29,560, for failed 1-stage revision were $24,357, for failed 2-stage revision were $70,381 and were $23,805 for excision arthroplasty. CONCLUSIONS: As treatment costs in Australia are high primary prevention is important and the economics of competing treatment choices should be carefully considered. These currently vary greatly across international settings.
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This work is motivated by the need to efficiently machine the edges of ophthalmic polymer lenses for mounting in spectacle or instrument frames. The polymer materials used are required to have suitable optical characteristics such high refractive index and Abbe number, combined with low density and high scratch and impact resistance. Edge surface finish is an important aesthetic consideration; its quality is governed by the material removal operation and the physical properties of the material being processed. The wear behaviour of polymer materials is not as straightforward as for other materials due to their molecular and structural complexity, not to mention their time-dependent properties. Four commercial ophthalmic polymers have been studied in this work using nanoindentation techniques which are evaluated as tools for probing surface mechanical properties in order to better understand the grinding response of polymer materials.
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The effect of oxidation and reduction conditions upon the morphology of polycrystalline silver catalysts has been investigated by means of in situ Fourier-transform infrared (FTIR) spectroscopy. Characterization of the sample was achieved by inspection of the νas(COO) band profile of adsorbed formate, recorded after dosing with formic acid at ambient temperature. Evidence was obtained for the existence of a silver surface reconstructed by the presence of subsurface oxygen in addition to the conventional family of Ag(111) and Ag(110) crystal faces. Oxidation at 773 K facilitated the reconstruction of silver planes due to the formation of subsurface oxygen species. Prolonged oxygen treatment at 773 K also caused particle fragmentation as a consequence of excessive oxygen penetration of the silver catalyst at defect sites. It was also deduced that the presence of oxygen in the gas phase stabilized the growth of silver planes which could form stronger bonds with oxygen. In contrast, high-temperature thermal treatment in vacuum induced significant sintering of the silver catalyst. Reduction at 773 K resulted in substantial quantities of dissolved hydrogen (and probably hydroxy species) in the bulk silver structure. Furthermore, enhanced defect formation in the catalyst was also noted, as evidenced by the increased concentration of formate species associated with oxygen-reconstructed silver faces.
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Raman and Fourier transform infrared (FT-IR) spectroscopy have been applied to a systematic investigation of the adsorption and decomposition of dichlorodifluoromethane (CCl2F2, CFC-12), fluorotrichloromethane (CCl3F, CFC-11), chlorodifluoromethane (CHClF2, HCFC-22) and molecular chlorine on oxide surfaces. Additionally, the effects of heating and ultraviolet photolysis of the CFC and HCFCs adsorbed on the oxide surfaces have been investigated. Spectral features for these species indicated a small wavenumber shift (1-6 cm-1) associated with the adsorbed phase. Some evidence, specifically the appearance of the Raman band at 507 cm-1, is presented to show that chlorine decomposition species are associated with these oxide surfaces. It was concluded that the new spectral feature (at ca. 507 cm-1) related with the decomposition of the CFC and HCFC molecules was an important indicator of the extent to which the reaction between the adsorbed CFC and HCFC and oxide surface has taken place. The extent of CFC-surface interaction has been quantified in terms of a maximum (Raman) frequency shift parameter (AM). Wavenumber shifts suggest both cation-adsorbate and non-specific adsorption interactions are occurring in the internal channels of the zeolites. Slow decomposition of the adsorbed CFCs under ultraviolet-visible photolysis (at ? > 300 nm) and/or thermal treatment was observed spectroscopically. Using FT-IR spectroscopy, the formation of gas-phase products (CO, CO2, HCl) both onyn photolysis and heating was evident. Results of these measurements are compared with the observed atmospheric reactivity of these compounds.