The effect of light intensity and temperature on photocatalytic water splitting

Photocatalytic water splitting is a process which could potentially lead to commercially viable solar hydrogen production. This thesis uses an engineering perspective to investigate the technology. The effect of light intensity and temperature on photocatalytic water splitting was examined to evaluate the prospect of using solar concentration to increase the feasibility of the process. P25 TiO2 films deposited on conducting glass were used as photocatalyst electrodes and coupled with platinum electrodes which were also deposited on conducting glass. These films were used to form a photocatalysis cell and illuminated with a Xenon arc lamp to simulate solar light at intensities up to 50 suns. They were also tested at temperatures between 20°C and 100°C. The reaction demonstrated a sub-linear relationship with intensity. Photocurrent was proportional to intensity with an exponential value of 0.627. Increasing temperature resulted in an exponential relationship. This proved to follow an Arrhenius relationship with an activation energy of 10.3 kJ mol-1 and a pre-exponential factor of approximately 8.7×103. These results then formed the basis of a mathematical model which extrapolated beyond the range of the experimental tests. This model shows that the loss of efficiency from performing the reaction under high light intensity is offset by the increased reaction rate and efficiency from the associated temperature increase. This is an important finding for photocatalytic water splitting. It will direct future research in system design and materials research and may provide an avenue for the commercialisation of this technology.

Effectiveness of red light cameras on the right-angle crash involvement of motorcycles

Red light cameras (RLC) have been used to reduce right-angle collisions at signalized intersections. However, the effect of RLCs on motorcycle crashes has not been well investigated. The objective of this study is to evaluate the effectiveness of RLCs on motorcycle safety in Singapore. This is done by comparing their exposure, proneness of at-fault right-angle crashes as well as the resulting right-angle collisions at RLC with those at non-RLC sites. Estimating the crash vulnerability from not-at-fault crash involvements, the study shows that with a RLC, the relative crash vulnerability or crash-involved exposure of motorcycles at right-angle crashes is reduced. Furthermore, field investigation of motorcycle maneuvers reveal that at non-RLC arms, motorcyclists usually queue beyond the stop-line, facilitating an earlier discharge and hence become more exposed to the conflicting stream. However at arms with a RLC, motorcyclists are more restrained to avoid activating the RLC and hence become less exposed to conflicting traffic during the initial period of the green. The study also shows that in right-angle collisions, the proneness of at-fault crashes of motorcycles is lowest among all vehicle types. Hence motorcycles are more likely to be victims than the responsible parties in right-angle crashes. RLCs have also been found to be very effective in reducing at-fault crash involvements of other vehicle types which may implicate exposed motorcycles in the conflicting stream. Taking all these into account, the presence of RLCs should significantly reduce the vulnerability of motorcycles at signalized intersections.

Effects of Mobile Phone Distraction at the Onset of Amber Light: Analysis of Driving Simulator Data

Distraction whilst driving on an approach to a signalized intersection is particularly dangerous, as potential vehicular conflicts and resulting angle collisions tend to be severe. This study examines the decisions of distracted drivers during the onset of amber lights. Driving simulator data were obtained from a sample of 58 drivers under baseline and handheld mobile phone conditions at the University of IOWA - National Advanced Driving Simulator. Explanatory variables include age, gender, cell phone use, distance to stop-line, and speed. An iterative combination of decision tree and logistic regression analyses are employed to identify main effects, non-linearities, and interactions effects. Results show that novice (16-17 years) and younger (18-25 years) drivers’ had heightened amber light running risk while distracted by cell phone, and speed and distance thresholds yielded significant interaction effects. Driver experience captured by age has a multiplicative effect with distraction, making the combined effect of being inexperienced and distracted particularly risky. Solutions are needed to combat the use of mobile phones whilst driving.

Prandtl number scaling of the unsteady natural convection boundary layer adjacent to a vertical flat plate for Pr > 1 subject to ramp surface heat flux

It is found in the literature that the existing scaling results for the boundary layer thickness, velocity and steady state time for the natural convection flow over an evenly heated plate provide a very poor prediction of the Prandtl number dependency of the flow. However, those scalings provide a good prediction of two other governing parameters’ dependency, the Rayleigh number and the aspect ratio. Therefore, an improved scaling analysis using a triple-layer integral approach and direct numerical simulations have been performed for the natural convection boundary layer along a semi-infinite flat plate with uniform surface heat flux. This heat flux is a ramp function of time, where the temperature gradient on the surface increases with time up to some specific time and then remains constant. The growth of the boundary layer strongly depends on the ramp time. If the ramp time is sufficiently long, the boundary layer reaches a quasi steady mode before the growth of the temperature gradient is completed. In this mode, the thermal boundary layer at first grows in thickness and then contracts with increasing time. However, if the ramp time is sufficiently short, the boundary layer develops differently, but after the wall temperature gradient growth is completed, the boundary layer develops as though the startup had been instantaneous.

Prandtl number scaling of natural convection of the flow on an inclined at plate due to uniform surface heat flux

A new scaling analysis has been performed for the unsteady natural convection boundary layer under a downward facing inclined plate with uniform heat flux. The development of the thermal or viscous boundary layers may be classified into three distinct stages including an early stage, a transitional stage and a steady stage, which can be clearly identified in the analytical as well as numerical results. Earlier scaling shows that the existing scaling laws of the boundary layer thickness, velocity and steady state time scales for the natural convection flow on a heated plate of uniform heat flux provide a very poor prediction of the Prandtl number dependency. However, those scalings performed very well with Rayleigh number and aspect ratio dependency. In this study, a modifed Prandtl number scaling has been developed using a triple-layer integral approach for Pr > 1. It is seen that in comparison to the direct numerical simulations, the new scaling performs considerably better than the previous scaling.

Dynamics of rod and cone photoreceptor interactions under mesopic light levels

Visual adaptation regulates contrast sensitivity during dynamically changing light conditions (Crawford, 1947; Hecht, Haig & Chase, 1937). These adaptation dynamics are unknown under dim (mesopic) light levels when the rod (R) and long (L), medium (M) and short (S) wavelength cone photoreceptor classes contribute to vision via interactions in shared non-opponent Magnocellular (MC), chromatically opponent Parvocellular (PC) and Koniocellular (KC) visual pathways (Dacey, 2000). This study investigated the time-course of adaptation and post-receptoral pathways mediating receptor specific rod and cone interactions under mesopic illumination. A four-primary photostimulator (Pokorny, Smithson & Quinlan, 2004) was used to independently control the activity of the four photoreceptor classes and their post-receptoral visual athways in human observers. In the first experiment, the contrast sensitivity and time-course of visual adaptation under mesopic illumination were measured for receptoral (L, S, R) and post-receptoral (LMS, LMSR, L-M) stimuli. An incremental (Rapid-ON) sawtooth conditioning pulse biased detection to ON-cells within the visual pathways and sensitivity was assayed relative to pulse onset using a briefly presented incremental probe that did not alter adaptation. Cone.Cone interactions with luminance stimuli (L cone, LMS, LMSR) reduced sensitivity by 15% and the time course of recovery was 25± 5ms-1 (μ ± SEM). PC mediated (+L-M) chromatic stimuli sensitivity loss was less (8%) than for luminance and recovery was slower (μ = 2.95 ± 0.05 ms-1), with KC mediated (S cone) chromatic stimuli showing a high sensitivity loss (38%) and the slowest recovery time (1.6 ± 0.2 ms-1). Rod-Rod interactions increased sensitivity by 20% and the time course of recovery was 0.7 ± 0.2 ms-1 (μ ± SD). Compared to these interaction types, Rod-Cone interactions reduced sensitivity to a lesser degree (5%) and showed the fastest recovery (μ = 43 ± 7 ms-1). In the second experiment, rod contribution to the magnocellular, parvocellular and koniocellular post-receptoral pathways under mesopic illumination was determined as a function of incremental stimulus duration and waveform (rectangular; sawtooth) using a rod colour match procedure (Cao, Pokorny & Smith, 2005; Cao, Pokorny, Smith & Zele, 2008a). For a 30% rod increment, a cone match required a decrease in [L/(L+M)] and an increase in [L+M] and [S/(L+M)], giving a greenish-blue and brighter appearance for probe durations of 75 ms or longer. Probe durations less than 75 ms showed an increase in [L+M] and no change in chromaticity [L/(L+M) or S/(L+M)], uggesting mediation by the MC pathway only for short duration rod stimuli. s We advance previous studies by determining the time-course and nature of photoreceptor specific retinal interactions in the three post-receptoral pathways under mesopic illumination. In the first experiment, the time-course of adaptation for ON cell processing was determined, revealing opponent cell facilitation in chromatic PC and KC pathways. The Rod-Rod and Rod-Cone data identify previously unknown interaction types that act to maintain contrast sensitivity during dynamically changing light conditions and improve the speed of light adaptation under mesopic light levels. The second experiment determined the degree of rod contribution to the inferred post-eceptoral pathways as a function of the temporal properties of the rod signal. r The understanding of the mechanisms underlying interactions between photoreceptors under mesopic illumination has implications for the study of retinal disease. Visual function has been shown to be reduced in persons with age-related maculopathy (ARM) risk genotypes prior to clinical signs of the disease (Feigl, Cao, Morris & Zele, 2011) and disturbances in rod-mediated adaptation have been shown in early phases of ARM (Dimitrov, Guymer, Zele, Anderson & Vingrys, 2008; Feigl, Brown, Lovie-Kitchin & Swann, 2005). Also, the understanding of retinal networks controlling vision enables the development of international lighting standards to optimise visual performance nder dim light levels (e.g. work-place environments, transportation).

More light at the end of the tunnel – apixaban in atrial fibrillation

Introduction: Subjects with atrial fibrillation are at risk of thromboembolic events. The vitamin K antagonists (e.g., warfarin) are useful at preventing coagulation in atrial fibrillation, but are difficult to use. One of the FXa inhibitors, oral apixaban, has been tested as an anticoagulant in atrial fibrillation. Areas covered: In ARISTOTLE (Apixaban for reduction in stroke and other thromboembolic events in atrial fibrillation) apixaban was compared to warfarin in subjects with atrial fibrillation, and shown to cause a lower rate of stroke or systemic embolism and of major bleeding, than warfarin. In the AVERROES (Apixaban versus acetylsalicylic acid [ASA] to prevent stroke in atrial fibrillations patients who have failed or are unsuitable for vitamin K antagonist treatment) trial, stroke or systemic embolism occurred less often with apixaban than aspirin, whereas the occurrence of major bleeding was similar in the groups. Expert opinion: Apixaban is much easier for subjects with atrial fibrillation to use than warfarin, as it does not require regular monitoring by a health professional, with dosage adjustment. In addition to replacing warfarin in subjects with atrial fibrillation who are unable or not prepared to use warfarin, apixaban has the potential to replace warfarin more widely in the prevention of thromboembolism in subjects with atrial fibrillation.

Assessment of daily light and ultraviolet exposure in young adults

Purpose: There are some limited reports, based on questionnaire data, which suggest that outdoor activity decreases the risk of myopia in children and may offset the myopia risk associated with prolonged near work. The aim of this study was to explore the relationship between near work, indoor illumination, daily sunlight and ultraviolet (UV) exposure in emmetropic and myopic University students, given that University students perform significant amounts of near work and as a group have a high prevalence of myopia. Methods: Participants were 35 students, aged 17 to 25 years who were classified as being emmetropic (n=13), or having stable (n=12) or progressing myopia (n=10). During waking hours on three separate days participants wore a light sensor data logger (HOBO) and a polysulphone UV dosimeter; these devices measured daily illuminance and accumulative UV exposure respectively; participants also completed a daily activity log. Results: No significant between group differences were observed for average daily illuminance (p=0.732), number of hours per day spent in sunlight (p=0.266), outdoor shade (p=0.726), bright indoor/dim outdoor light (p=0.574) or dim room illumination (p=0.484). Daily UV exposure was significantly different across the groups (p=0.003); with stable myopes experiencing the greatest UV exposure (versus emmetropes p=0.002; versus progressing myopes p=0.004). Conclusions: The current literature suggests there is a link between myopia protection and spending time outdoors in children. Our data provides some evidence of this relationship in young adults and highlights the need for larger studies to further investigate this relationship longitudinally.

Suspended sediment properties and suspended sediment flux estimates in an inundated urban environment during a major flood event

During a major flood event, the inundation of urban environments leads to some complicated flow motion most often associated with significant sediment fluxes. In the present study, a series of field measurements were conducted in an inundated section of the City of Brisbane (Australia) about the peak of a major flood in January 2011. Some experiments were performed to use ADV backscatter amplitude as a surrogate estimate of the suspended sediment concentration (SSC) during the flood event. The flood water deposit samples were predominantly silty material with a median particle size about 25 μm and they exhibited a non-Newtonian behavior under rheological testing. In the inundated urban environment during the flood, estimates of suspended sediment concentration presented a general trend with increasing SSC for decreasing water depth. The suspended sediment flux data showed some substantial sediment flux amplitudes consistent with the murky appearance of floodwaters. Altogether the results highlighted the large suspended sediment loads and fluctuations in the inundated urban setting associated possibly with a non-Newtonian behavior. During the receding flood, some unusual long-period oscillations were observed (periods about 18 min), although the cause of these oscillations remains unknown. The field deployment was conducted in challenging conditions highlighting a number of practical issues during a natural disaster.

Accuracy of FEM and BEM for electromagnetic flux calculations in high power applications

The development and design of electric high power devices with electromagnetic computer-aided engineering (EM-CAE) software such as the Finite Element Method (FEM) and Boundary Element Method (BEM) has been widely adopted. This paper presents the analysis of a Fault Current Limiter (FCL), which acts as a high-voltage surge protector for power grids. A prototype FCL was built. The magnetic flux in the core and the resulting electromagnetic forces in the winding of the FCL were analyzed using both FEM and BEM. An experiment on the prototype was conducted in a laboratory. The data obtained from the experiment is compared to the numerical solutions to determine the suitability and accuracy of the two methods.

Selective reductions using visible light photocatalysts of supported gold nanoparticles

Photocatalytic synthesis using visible light is a desirable chemical process because of its potential to utilize sunlight. Supported gold nanoparticles (Au-NPs) were found to be efficient photocatalysts and the effects of the supports were identified including CeO2, TiO2, ZrO2, Al2O3, and zeolite Y. In particular Au/CeO2 exhibited the high catalytic activity to reduce nitroaromatics to azo compounds, hydrogenate azobenzene to hydroazobenzene, reduce ketones to alcohols, and deoxygenate epoxides to alkenes at ambient temperatures, under irradiation of visible light (or simulated sunlight). The reac-tive efficiency depends on two primary factors: one is the light adsorption of catalysts and another is the driving ability of catalysts corresponding to the reactants. The light absorption by Au-NPs is due to surface plasmon resonance effect or inter-band electron transition; this is related to the reduction ability of the photocatalysts. Irradiation with shorter wavelengths can excite the conduction electrons in Au-NPs to higher energy levels and as a result, induce reduction with more negative reduction potentials. It is known when irradiated with light the Au-NPs can abstract hydrogen from isopropanol forming Au-H species on the Au-NP surface. Hence, we proposed that the active Au-H species will react with the N=O, N=N, C=O double bonds or epoxide bonds, which are weakened by the interaction with the excited electrons in the Au-NPs, and yield the final reductive products. The reacting power of the Au-H species depends on the energy of the excited electrons in Au-NPs: the higher the electronic energy, the stronger the reduction ability of the Au-H species. This finding demonstrates that we can tune the reduction ability of the photocatalysts by manipulating the irradiation wavelength.

Hybrid light-emitting diodes based on ZnO nanowires

ZnO is a wide band-gap semiconductor that has several desirable properties for optoelectronic devices. With its large exciton binding energy of ~60 meV, ZnO is a promising candidate for high stability, room-temperature luminescent and lasing devices [1]. Ultraviolet light-emitting diodes (LEDs) based on ZnO homojunctions had been reported [2,3], while preparing stable p-type ZnO is still a challenge. An alternative way is to use other p-type semiconductors, ether inorganic or organic, to form heterojunctions with the naturally n-type ZnO. The crystal structure of wurtzite ZnO can be described as Zn and O atomic layers alternately stacked along the [0001] direction. Because of the fastest growth rate over the polar (0001) facet, ZnO crystals tend to grow into one-dimensional structures, such as nanowires and nanobelts. Since the first report of ZnO nanobelts in 2001 [4], ZnO nanostructures have been particularly studied for their potential applications in nano-sized devices. Various growth methods have been developed for growing ZnO nanostructures, such as chemical vapor deposition (CVD), Metal-organic CVD (MOCVD), aqueous growth and electrodeposition [5]. Based on the successful synthesis of ZnO nanowires/nanorods, various types of hybrid light-emitting diodes (LEDs) were made. Inorganic p-type semiconductors, such as GaN, Si and SiC, have been used as substrates to grown ZnO nanorods/nanowires for making LEDs. GaN is an ideal material that matches ZnO not only in the crystal structure but also in the energy band levels. However, to prepare Mg-doped p-GaN films via epitaxial growth is still costly. In comparison, the organic semiconductors are inexpensive and have many options to select, for a large variety of p-type polymer or small-molecule semiconductors are now commercially available. The organic semiconductor has the limitation of durability and environmental stability. Many polymer semiconductors are susceptible to damage by humidity or mere exposure to oxygen in the air. Also the carrier mobilities of polymer semiconductors are generally lower than the inorganic semiconductors. However, the combination of polymer semiconductors and ZnO nanostructures opens the way for making flexible LEDs. There are few reports on the hybrid LEDs based on ZnO/polymer heterojunctions, some of them showed the characteristic UV electroluminescence (EL) of ZnO. This chapter reports recent progress of the hybrid LEDs based on ZnO nanowires and other inorganic/organic semiconductors. We provide an overview of the ZnO-nanowire-based hybrid LEDs from the perspectives of the device configuration, growth methods of ZnO nanowires and the selection of p-type semiconductors. Also the device performances and remaining issues are presented.

Magnetic flux analysis in superconducting Fault Current Limiters under short-circuit conditions

In order to obtain a more compact Superconducting Fault Current limiter (SFCL), a special geometry of core and AC coil is required. This results in a unique magnetic flux pattern which differs from those associated with conventional round core arrangements. In this paper the magnetic flux density within a Fault Current Limiter (FCL) is described. Both experimental and analytical approaches are considered. A small scale prototype of an FCL was constructed in order to conduct the experiments. This prototype comprises a single phase. The analysis covers both the steady state and the short-circuit condition. Simulation results were obtained using commercial software based on the Finite Element Method (FEM). The magnetic flux saturating the cores, leakage magnetic flux giving rise to electromagnetic forces and leakage magnetic flux flowing in the enclosing tank are computed.

Examination of distracted driving and yellow light running : analysis of simulator data

Driving on an approach to a signalized intersection while distracted is particularly dangerous, as potential vehicular conflicts and resulting angle collisions tend to be severe. Given the prevalence and importance of this particular scenario, the decisions and actions of distracted drivers during the onset of yellow lights are the focus of this study. Driving simulator data were obtained from a sample of 58 drivers under baseline and handheld mobile phone conditions at the University of Iowa - National Advanced Driving Simulator. Explanatory variables included age, gender, cell phone use, distance to stop-line, and speed. Although there is extensive research on drivers’ responses to yellow traffic signals, the examination has been conducted from a traditional regression-based approach, which does not necessary provide the underlying relations and patterns among the sampled data. In this paper, we exploit the benefits of both classical statistical inference and data mining techniques to identify the a priori relationships among main effects, non-linearities, and interaction effects. Results suggest that novice (16-17 years) and young drivers’ (18-25 years) have heightened yellow light running risk while distracted by a cell phone conversation. Driver experience captured by age has a multiplicative effect with distraction, making the combined effect of being inexperienced and distracted particularly risky. Overall, distracted drivers across most tested groups tend to reduce the propensity of yellow light running as the distance to stop line increases, exhibiting risk compensation on a critical driving situation.