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.

Application of a digital elevation model for flood modeling for the Pagsangaan River in Leyte

Flood related scientific and community-based data are rarely systematically collected and analysed in the Philippines. Over the last decades the Pagsangaan River Basin, Leyte, has experienced several flood events. However, documentation describing flood characteristics such as extent, duration or height of these floods are close to non-existing. To address this issue, computerized flood modelling was used to reproduce past events where there was data available for at least partial calibration and validation. The model was also used to provide scenario-based predictions based on A1B climate change assumptions for the area. The most important input for flood modelling is a Digital Elevation Model (DEM) of the river basin. No accurate topographic maps or Light Detection And Ranging (LIDAR)-generated data are available for the Pagsangaan River. Therefore, the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) Global Digital Elevation Map (GDEM), Version 1, was chosen as the DEM. Although the horizontal spatial resolution of 30 m is rather desirable, it contains substantial vertical errors. These were identified, different correction methods were tested and the resulting DEM was used for flood modelling. The above mentioned data were combined with cross-sections at various strategic locations of the river network, meteorological records, river water level, and current velocity to develop the 1D-2D flood model. SOBEK was used as modelling software to create different rainfall scenarios, including historic flooding events. Due to the lack of scientific data for the verification of the model quality, interviews with local stakeholders served as the gauge to judge the quality of the generated flood maps. According to interviewees, the model reflects reality more accurately than previously available flood maps. The resulting flood maps are now used by the operations centre of a local flood early warning system for warnings and evacuation alerts. Furthermore these maps can serve as a basis to identify flood hazard areas for spatial land use planning purposes.

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.

Numerical modelling and full scale testing of load bearing steel walls under real fires

Fire safety has become an important part in structural design due to the ever increasing loss of properties and lives during fires. Fire rating of load bearing wall systems made of Light gauge Steel Frames (LSF) is determined using fire tests based on the standard time-temperature curve given in ISO 834. However, modern residential buildings make use of thermoplastic materials, which mean considerably high fuel loads. Hence a detailed fire research study into the performance of load bearing LSF walls was undertaken using a series of realistic design fire curves developed based on Eurocode parametric curves and Barnett’s BFD curves. It included both full scale fire tests and numerical studies of LSF walls without any insulation, and the recently developed externally insulated composite panels. This paper presents the details of fire tests first, and then the numerical models of tested LSF wall studs. It shows that suitable finite element models can be developed to predict the fire rating of load bearing walls under real fire conditions. The paper also describes the structural and fire performances of externally insulated LSF walls in comparison to the non-insulated walls under real fires, and highlights the effects of standard and real fire curves on fire performance of LSF walls.

Thermal performance of composite panels under fire conditions using numerical studies : plasterboards, rockwool, glass fibre and cellulose insulations

In recent times, light gauge steel frame (LSF) wall systems are increasingly used in the building industry. They are usually made of cold-formed and thin-walled steel studs that are fire-protected by two layers of plasterboard on both sides. A composite LSF wall panel system was developed recently, where an insulation layer was used externally between the two plasterboards to improve the fire performance of LSF wall panels. In this research, finite element thermal models of the new composite panels were developed using a finite element program, SAFIR, to simulate their thermal performance under both standard and Eurocode design fire curves. Suitable apparent thermal properties of both the gypsum plasterboard and insulation materials were proposed and used in the numerical models. The developed models were then validated by comparing their results with available standard fire test results of composite panels. This paper presents the details of the finite element models of composite panels, the thermal analysis results in the form of time-temperature profiles under standard and Eurocode design fire curves and their comparisons with fire test results. Effects of using rockwool, glass fibre and cellulose fibre insulations with varying thickness and density were also investigated, and the results are presented in this paper. The results show that the use of composite panels in LSF wall systems will improve their fire rating, and that Eurocode design fires are likely to cause severe damage to LSF walls than standard fires.

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.

Temporal summation of intrinsically photosensitive retinal ganglion cell (ipRGC) contributions to the human pupil.

Purpose: IpRGCs mediate non-image forming functions including photoentrainment and the pupil light reflex (PLR). Temporal summation increases visual sensitivity and decreases temporal resolution for image forming vision, but the summation properties of nonimage forming vision are unknown. We investigated the temporal summation of inner (ipRGC) and outer (rod/cone) retinal inputs to the PLR. Method: The consensual PLR of the left eye was measured in six participants with normal vision using a Maxwellian view infrared pupillometer. Temporal summation was investigated using a double-pulse protocol (100 ms stimulus pairs; 0–1024 ms inter-stimulus interval, ISI) presented to the dilated fellow right eye (Tropicamide 1%). Stimulus lights (blue λmax = 460 nm; red λmax = 638 nm) biased activity to inneror outer retinal inputs to non-image forming vision. Temporal summation was measured suprathreshold (15.2 log photons.cm−2.s−1 at the cornea) and subthreshold (11.4 log photons.cm−2.s−1 at the cornea). Results: RM-ANOVAs showed the suprathreshold and subthreshold 6 second post illumination pupil response (PIPR: expressed as percentage baseline diameter) did not significantly vary for red or blue stimuli (p > .05). The PIPR for a subthreshold red 16 ms double-pulse control condition did not significantly differ with ISI (p > .05). The maximum constriction amplitude for red and blue 100 ms double- pulse stimuli did not significantly vary with ISI (p > .05). Conclusion: The non-significant changes in suprathreshold PIPR and subthreshold maximum pupil constriction indicate that inner retinal ipRGC inputs and outer retinal photoreceptor inputs to the PLR do not show temporal summation. The results suggest a fundamental difference between the temporal summation characteristics of image forming and non-image forming vision.

Hybrid graphene and graphitic carbon nitride nanocomposite : gap opening, electron–hole puddle, interfacial charge transfer, and enhanced visible light response

Opening up a band gap and finding a suitable substrate material are two big challenges for building graphene-based nanodevices. Using state-of-the-art hybrid density functional theory incorporating long range dispersion corrections, we investigate the interface between optically active graphitic carbon nitride (g-C3N4) and electronically active graphene. We find an inhomogeneous planar substrate (g-C3N4) promotes electronrich and hole-rich regions, i.e., forming a well-defined electron−hole puddle, on the supported graphene layer. The composite displays significant charge transfer from graphene to the g-C3N4 substrate, which alters the electronic properties of both components. In particular, the strong electronic coupling at the graphene/g-C3N4 interface opens a 70 meV gap in g-C3N4-supported graphene, a feature that can potentially allow overcoming the graphene’s band gap hurdle in constructing field effect transistors. Additionally, the 2-D planar structure of g-C3N4 is free of dangling bonds, providing an ideal substrate for graphene to sit on. Furthermore, when compared to a pure g-C3N4 monolayer, the hybrid graphene/g-C3N4 complex displays an enhanced optical absorption in the visible region, a promising feature for novel photovoltaic and photocatalytic applications.

Hybrid graphene/titania nanocomposite : interface charge transfer, hole doping, and sensitization for visible light response

We demonstrated for the first time by large-scale ab initio calculations that a graphene/titania interface in the ground electronic state forms a charge-transfer complex due to the large difference of work functions between graphene and titania, leading to substantial hole doping in graphene. Interestingly, electrons in the upper valence band can be directly excited from graphene to the conduction band, that is, the 3d orbitals of titania, under visible light irradiation. This should yield well-separated electron−hole pairs, with potentially high photocatalytic or photovoltaic performance in hybrid graphene and titania nanocomposites. Experimental wavelength-dependent photocurrent generation of the graphene/titania photoanode demonstrated noticeable visible light response and evidently verified our ab initio prediction.

Numerical studies of load bearing LSF walls under realistic design fire conditions

Fire safety of light gauge steel frame (LSF) stud walls is important in the design of buildings. Currently LSF walls are increasingly used in the building industry, and are usually made of cold-formed and thin-walled steel studs that are fire-protected by two layers of plasterboard on both sides. Many experimental and numerical studies have been undertaken to investigate the fire performance of load bearing LSF walls under standard fire conditions. However, the standard time-temperature curve does not represent the fire load present in typical residential and commercial buildings that include considerable amount of thermoplastic materials. Real building fires are unlikely to follow a standard time-temperature curve. However, only limited research has been undertaken to investigate the fire performance of load bearing LSF walls under realistic design fire conditions. Therefore in this research, finite element thermal models of the traditional LSF wall panels without cavity insulation and the new LSF composite wall panels were developed to simulate their fire performance under recently developed realistic design fire curves. Suitable thermal properties were proposed for plasterboards and insulations based on laboratory tests and literature review. The developed models were then validated by comparing their thermal performance results with available results from realistic design fire tests, and were later used in parametric studies. This paper presents the details of the developed finite element thermal models of load bearing LSF wall panels under realistic design fire time-temperature curves and the re-sults. It shows that finite element thermal models can be used to predict the fire performance of load bearing LSF walls with varying configurations of insulations and plasterboards under realistic design fires. Failure times of load bearing LSF walls were also predicted based on the results from finite element thermal analyses.

Shear design of cold-formed steel beams using direct strength method

This paper presents the direct strength method (DSM) equations for cold-formed steel beams subject to shear. Light gauge cold-formed steel sections have been developed as more economical building solutions to the alternative heavier hot-rolled sections in the commercial and residential markets. Cold-formed lipped channel beams (LCB), LiteSteel beams (LSB) and hollow flange beams (HFB) are commonly used as flexural members such as floor joists and bearers. However, their shear capacities are determined based on conservative design rules. For the shear design of cold-formed web panels, their elastic shear buckling strength must be determined accurately including the potential post-buckling strength. Currently the elastic shear buckling coefficients of web panels are determined by assuming conservatively that the web panels are simply supported at the junction between the flange and web elements and ignore the post-buckling strength. Hence experimental and numerical studies were conducted to investigate the shear behaviour and strength of LSBs, LCBs and HFBs. New direct strength method (DSM) based design equations were proposed to determine the ultimate shear capacities of cold-formed steel beams. An improved equation for the higher elastic shear buckling coefficient of cold-formed steel beams was proposed based on finite element analysis results and included in the DSM design equations. A new post-buckling coefficient was also introduced in the DSM equation to include the available post-buckling strength of cold-formed steel beams.

Rod and cone pathway signaling and interaction under mesopic illumination

This study investigates the time-course and post-receptoral pathway signaling of photoreceptor interactions when the rod (R) and three cone (L, M, S) photoreceptor classes contribute to mesopic vision. A four-primary photostimulator independently controls photoreceptor activity in human observers. The first experiment defines the temporal adaptation response of receptoral (L-, S-cone, rod) and post-receptoral (LMS, LMSR,+L-M) signaling and interactions. Here we show that nonopponent cone-cone interactions (L-cone, LMS, LMSR) have monophasic temporal response patterns whereas opponent signals (+L-M, S-cone) show biphasic response patterns with slower recovery. By comparison, rod-cone interactions with nonopponent signals have faster adaptation responses and reduced sensitivity loss whereas opponent rod-cone interactions are small or absent. Additionally, the rod-rod interaction differs from these interaction types and acts to increase rod sensitivity due to temporal summation but with a slower time course. The second experiment shows that the temporal profile of the rod signal alters the relative rod contributions to the three primary post-receptoral pathways. We demonstrate that rod signals generate luminance (þLþM) signals mediated via the MC pathway with all rod temporal profiles and chromatic signals (L/LþM, S/LþM) in both the PC and KC pathways with durations .75 ms. Thus, we propose that the change in relative weighting of rod signals within the post-receptoral pathways contributes to the sensitivity and temporal response of rod and cone pathway signaling and interactions.

Antiproton induced DNA damage : proton like in flight, carbon-ion light near rest

Biological validation of new radiotherapy modalities is essential to understand their therapeutic potential. Antiprotons have been proposed for cancer therapy due to enhanced dose deposition provided by antiproton-nucleon annihilation. We assessed cellular DNA damage and relative biological effectiveness (RBE) of a clinically relevant antiproton beam. Despite a modest LET (~19 keV/μm), antiproton spread out Bragg peak (SOBP) irradiation caused significant residual γ-H2AX foci compared to X-ray, proton and antiproton plateau irradiation. RBE of ~1.48 in the SOBP and ~1 in the plateau were measured and used for a qualitative effective dose curve comparison with proton and carbon-ions. Foci in the antiproton SOBP were larger and more structured compared to X-rays, protons and carbon-ions. This is likely due to overlapping particle tracks near the annihilation vertex, creating spatially correlated DNA lesions. No biological effects were observed at 28–42 mm away from the primary beam suggesting minimal risk from long-range secondary particles.

Fire performance of LSF walls made of hollow flange section studs

Load bearing Light Gauge Steel Frame (LSF) walls made of cold-formed steel studs and tracks are commonly used in residential and commercial buildings. Fire safety of these walls is essential to minimize the damage caused by fire related accidents. Past investigations on the fire performance of load bearing LSF wall systems have been limited to LSF walls made of conventional lipped channel section studs. Although structurally efficient hollow flange steel sections are available in the building industry, they are not used as LSF wall studs due to the lack of fire performance data for such walls. The hollow flange sections have torsionally rigid hollow flanges that eliminate the occurrence of local and distortional buckling to an extent, thereby increasing their structural efficiency. The weaknesses of hollow flange sections such as lower lateral distortional buckling capacity are also eliminated when they are used as studs of LSF walls as the plasterboard restraints will prevent any lateral movement. Therefore hollow flange sections can be considered as structurally more efficient studs for use in LSF wall systems. This paper reports the full scale fire tests of LSF walls made of hollow flange section studs under standard fire conditions. The frames were made of 1.6 mm thick and 150 mm deep hollow flange section studs with two closed rectangular flanges of 45 mm width x 15 mm depth. Dual plasterboards were attached on both sides of the test wall panels. The load ratio was varied and the failure times, the lateral deflections and the axial displacements of the test walls were obtained. The failure behaviour of LSF walls made of hollow flange section studs was found to be different to that of LSF walls made of conventional lipped channel section studs. The results of these fire tests show that hollow flange section studs have a higher potential in being used in load bearing LSF Walls.

Cold-formed steel columns subject to local buckling at elevated temperatures

Fire safety design of building structures has received greater attention in recent times due to continuing losses of properties and lives in fires. However, the structural behaviour of thin-walled cold-formed steel columns under fire conditions is not well understood despite the increasing use of light gauge steels in building construction. Cold-formed steel columns are often subject to local buckling effects. Therefore a series of laboratory tests of lipped and unlipped channel columns made of varying steel thicknesses and grades was undertaken at uniform elevated temperatures up to 700°C under steady state conditions. Finite element models of the tested columns were also developed, and their elastic buckling and nonlinear analysis results were compared with test results at elevated temperatures. Effects of the degradation of mechanical properties of steel with temperature were included in the finite element analyses. The use of accurately measured yield stress, elasticity modulus and stress-strain curves at elevated temperatures provided a good comparison of the ultimate loads and load-deflection curves from tests and finite element analyses. The commonly used effective width design rules and the direct strength method at ambient temperature were then used to predict the ultimate loads at elevated temperatures by using the reduced mechanical properties. By comparing these predicted ultimate loads with those from tests and finite element analyses, the accuracy of using this design approach was evaluated.