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.

The cost of carbon : capital market effects of the proposed emission trading scheme (ETS)

In March 2008, the Australian Government announced its intention to introduce a national Emissions Trading Scheme (ETS), now expected to start in 2015. This impending development provides an ideal setting to investigate the impact an ETS in Australia will have on the market valuation of Australian Securities Exchange (ASX) firms. This is the first empirical study into the pricing effects of the ETS in Australia. Primarily, we hypothesize that firm value will be negatively related to a firm's carbon intensity profile. That is, there will be a greater impact on firm value for high carbon emitters in the period prior (2007) to the introduction of the ETS, whether for reasons relating to the existence of unbooked liabilities associated with future compliance and/or abatement costs, or for reasons relating to reduced future earnings. Using a sample of 58 Australian listed firms (constrained by the current availability of emissions data) which comprise larger, more profitable and less risky listed Australian firms, we first undertake an event study focusing on five distinct information events argued to impact the probability of the proposed ETS being enacted. Here, we find direct evidence that the capital market is indeed pricing the proposed ETS. Second, using a modified version of the Ohlson (1995) valuation model, we undertake a valuation analysis designed not only to complement the event study results, but more importantly to provide insights into the capital market's assessment of the magnitude of the economic impact of the proposed ETS as reflected in market capitalization. Here, our results show that the market assesses the most carbon intensive sample firms a market value decrement relative to other sample firms of between 7% and 10% of market capitalization. Further, based on the carbon emission profile of the sample firms we imply a ‘future carbon permit price’ of between AUD$17 per tonne and AUD$26 per tonne of carbon dioxide emitted. This study is more precise than industry reports, which set a carbon price of between AUD$15 to AUD$74 per tonne.

The correlation between electric field emission phenomenon and Schottky contact reverse bias characteristics in nanostructured systems

Two different morphologies of nanotextured molybdenum oxide were deposited by thermal evaporation. By measuring their field emission (FE) properties, an enhancement factor was extracted. Subsequently, these films were coated with a thin layer of Pt to form Schottky contacts. The current-voltage (I-V) characteristics showed low magnitude reverse breakdown voltages, which we attributed to the localized electric field enhancement. An enhancement factor was obtained from the I-V curves. We will show that the enhancement factor extracted from the I-V curves is in good agreement with the enhancement factor extracted from the FE measurements.

Offsetting methane emissions : an alternative to emission equivalence metrics

It is widely recognised that defining trade-offs between greenhouse gas emissions using ‘emission equivalence’ based on global warming potentials (GWPs) referenced to carbon dioxide produces anomalous results when applied to methane. The short atmospheric lifetime of methane, compared to the timescales of CO2 uptake, leads to the greenhouse warming depending strongly on the temporal pattern of emission substitution. We argue that a more appropriate way to consider the relationship between the warming effects of methane and carbon dioxide is to define a ‘mixed metric’ that compares ongoing methane emissions (or reductions) to one-off emissions (or reductions) of carbon dioxide. Quantifying this approach, we propose that a one-off sequestration of 1 t of carbon would offset an ongoing methane emission in the range 0.90–1.05 kg CH4 per year. We present an example of how our approach would apply to rangeland cattle production, and consider the broader context of mitigation of climate change, noting the reverse trade-off would raise significant challenges in managing the risk of non-compliance. Our analysis is consistent with other approaches to addressing the criticisms of GWP-based emission equivalence, but provides a simpler and more robust approach while still achieving close equivalence of climate mitigation outcomes ranging over decadal to multi-century timescales.

Ammonia emissions from a representative in-use fleet of vehicles in Guangzhou

Emission rates of ammonia (NH3) are reported for a fleet of 130 light-, medium-, and heavy-duty vehicles recruited in Guangzhou, China. NH3 measurements were performed using Nessler's Reagents spectrophotometry and nationwide standard chassis dynamometer test cycles required by Chinese EPA. Emissions of CO and NOx were also measured during these test cycles. Emission factors of NH3 were calculated for each type of vehicle and used to estimate the total emissions of NH3 from motor vehicles in Guangzhou (GZ) in 2009. Emission factors of NH3 show large variations among different categories of vehicles, with a range from 4 to 138 mg km-1. The average emissions of NH3 in Guangzhou in 2009 were estimated to be 983 t, with a range from 373 to 2136 t. In addition, it was found that vehicles with the highest NH3 emission rates possess the following characteristics: mediumand heavy-duty vehicles, certified with out-of-date emission standards, mid-range odometer readings, and higher CO and NOx emission rates. The results of this study will be useful for developing NH3 emissions inventories in Guangzhou and other urban areas in China.

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.

Detection of excessive diesel engine piston slap using acoustic emission signals

This paper presents a study whereby a series of tests was undertaken using a naturally aspirated 4 cylinder, 2.216 litre, Perkins Diesel engine fitted with a piston having an undersized skirt. This experimental simulation resulted in engine running conditions that included abnormally high levels of piston slap occurring in one of the cylinders. The detectability of the resultant Diesel engine piston slap was investigated using acoustic emission signals. Data corresponding to both normal and piston slap engine running conditions was captured using acoustic emission transducers along with both; in-cylinder pressure and top-dead centre reference signals. Using these signals it was possible to demonstrate that the increased piston slap running conditions were distinguishable by monitoring the piston slap events occurring near the piston mid-stroke positions. However, when monitoring the piston slap events occurring near the TDC/BDC piston stroke positions, the normal and excessive piston slap engine running condition were not clearly distinguishable.

Development and validation of a new self-report instrument for measuring sedentary behaviors and light-intensity physical activity in adults

Background Low levels of physical activity and high levels of sedentary behavior (SB) are major public health concerns. This study was designed to develop and validate the 7-day Sedentary (S) and Light Intensity Physical Activity (LIPA) Log (7-day SLIPA Log), a self-report measure of specific daily behaviors. Method To develop the log, 62 specific SB and LIPA behaviors were chosen from the Compendium of Physical Activities. Face-to-face interviews were conducted with 32 sedentary volunteers to identify domains and behaviors of SB and LIPA. To validate the log, a further 22 sedentary adults were recruited to wear the GT3X for 7 consecutive days and nights. Results Pearson correlations (r) between the 7-day SLIPA Log and GT3X were significant for sedentary (r =.86, p < 0.001), for LIPA (r =.80, p < 0.001). Lying and sitting postures were positively correlated with GT3X output (r =.60 and r =.64, p < 0.001, respectively). No significant correlation was found for standing posture (r =.14, p = 0.53).The kappa values between the 7-day SLIPA Log and GT3X variables ranged from 0.09–0.61, indicating poor to good agreement. Conclusion The 7-day SLIPA Log is a valid self-report measure of SB and LIPA in specific behavioral domains.

Synthetic reevesite-like material as a visible light photocatalyst for the decontamination of water

A synthetic reevesite-like material has been shown to decolorize selected dyes and degrade phenolic contaminants photocatalytically in water when irradiated with visible light. This material can photoactively decolorize dyes such as bromophenol blue, bromocresol green, bromothymol blue, thymol blue and methyl orange in less than 15 min under visible light radiation in the absence of additional oxidizing agents. Conversely, phenolic compounds suc has phenol, p-chlorophenol and p-nitrophenol are photocat- alytically degraded in approximately 3hwith additional H2O2 when irradiated with visible light. These reactions offer potentially energy effective pathways for the removal of recalcitrant organic waste contaminants.

Variation in leaf structure of the invasive Madeira vine (Anredera cordifolia, Basellaceae) at different light levels

Madeira vine (Anredera cordifolia (Ten.) Steenis) is a climber in the angiosperm family Basellaceae. It is native to South America and has naturalised in Australia. It is regarded as a serious environmental weed because of the structural damage it causes to native vegetation. The present study, for the first time, documents anatomical and morphological traits of the leaves of A. cordifolia and considers their implications for its ecology and physiology. Plants were grown under three different light levels, and anatomical and morphological leaf characters were compared among light levels, among cohorts, and with documented traits of the related species, Basella alba L. Stomata were present on both the adaxial and abaxial sides of the leaf, with significantly more stomata on the abaxial side and under high light. This may account for the ability of this species to fix large amounts of carbon and rapidly respond to light gaps. The leaves had very narrow veins and no sclerenchyma, suggesting a low construction cost that is associated with invasive plants. There was no significant difference in any of the traits among different cohorts, which agrees with the claim that A. cordifolia primarily propagates vegetatively. The anatomy and morphology of A. cordifolia was similar to that of B. alba.

Characterisation of combustion related acoustic emission sources for diesel engine condition monitoring

This thesis represents a major step forward in understanding the link between the development of combustion related faults in diesel engines and the generation of acoustic emissions. The findings presented throughout the thesis provide a foundation so that future diesel engine monitoring systems are able to more effectively detect and monitor developing faults. In undertaking this research knowledge concerning engine function and relevant failure mechanisms was combined with different modelling methods to generate a framework that was used to effectively identify fault related activity within acoustic emissions recorded from different engines.

The association between time spent outdoors and myopia using a novel biomarker of outdoor light exposure

PURPOSE: We sought to determine whether conjunctival ultraviolet autofluorescence (UVAF), a biomarker of outdoor light exposure, is associated with myopia. METHODS: We performed a cross-sectional study on Norfolk Island and recruited individuals aged ≥ 15 years. Participants completed a sun-exposure questionnaire and underwent non-cycloplegic autorefraction. Conjunctival UVAF used a specially adapted electronic flash system fitted with UV-transmission filters (transmittance range 300-400 nm, peak 365 nm) as the excitation source. Temporal and nasal conjunctival UVAF was measured in both eyes using computerized photographic analysis with the sum referred to as "total UVAF." RESULTS: In 636 participants, prevalence of myopia decreased with an increasing quartile of total UVAF (P(trend) = 0.002). Median total UVAF was lower in subjects with myopia (spherical equivalent [SE] ≤ -1.0 diopter [D]) than participants without myopia: 16.6 mm(2) versus 28.6 mm(2), P = 0.001. In the multivariable model that adjusted for age, sex, smoking, cataract, height and weight, UVAF was independently associated with myopia (SE ≤ -1.0 D): odds ratio (OR) for total UVAF (per 10 mm(2)) was 0.81, 95% confidence interval (CI) 0.69 to 0.94, P = 0.007. UVAF was also significantly associated with myopia when analysis was restricted to subjects <50 years, and in moderate-severe myopia (SE ≤ -3.0 D). Prevalence of myopia decreased with increasing time outdoors (P(trend) = 0.03), but time outdoors was not associated with myopia on multivariable analysis. CONCLUSIONS: Study authors identified a protective association between increasing UVAF and myopia. The protective association of higher UVAF against myopia was stronger than that of increased levels of time spent outdoors as measured by this study's questionnaire. Future studies should investigate the association between UVAF and incident myopia, and its relationship to myopic progression.

Excursion guidance criteria to guide control of peak emission and exposure to airborne engineered particles

The overall aim of our research was to characterize airborne particles from selected nanotechnology processes and to utilize the data to develop and test quantitative particle concentration-based criteria that can be used to trigger an assessment of particle emission controls. We investigated particle number concentration (PNC), particle mass (PM) concentration, count median diameter (CMD), alveolar deposited surface area, elemental composition, and morphology from sampling of aerosols arising from six nanotechnology processes. These included fibrous and non-fibrous particles, including carbon nanotubes (CNTs). We adopted standard occupational hygiene principles in relation to controlling peak emission and exposures, as outlined by both Safe Work Australia, (1) and the American Conference of Governmental Industrial Hygienists (ACGIH®). (2) The results from the study were used to analyses peak and 30-minute averaged particle number and mass concentration values measured during the operation of the nanotechnology processes. Analysis of peak (highest value recorded) and 30-minute averaged particle number and mass concentration values revealed: Peak PNC20–1000 nm emitted from the nanotechnology processes were up to three orders of magnitude greater than the local background particle concentration (LBPC). Peak PNC300–3000 nm was up to an order of magnitude greater, and PM2.5 concentrations up to four orders of magnitude greater. For three of these nanotechnology processes, the 30-minute average particle number and mass concentrations were also significantly different from the LBPC (p-value < 0.001). We propose emission or exposure controls may need to be implemented or modified, or further assessment of the controls be undertaken, if concentrations exceed three times the LBPC, which is also used as the local particle reference value, for more than a total of 30 minutes during a workday, and/or if a single short-term measurement exceeds five times the local particle reference value. The use of these quantitative criteria, which we are terming the universal excursion guidance criteria, will account for the typical variation in LBPC and inaccuracy of instruments, while precautionary enough to highlight peaks in particle concentration likely to be associated with particle emission from the nanotechnology process. Recommendations on when to utilize local excursion guidance criteria are also provided.

Remote measurement of diesel locomotive emission factors and particle size distributions

A technique for analysing exhaust emission plumes from unmodified locomotives under real world conditions is described and applied to the task of characterizing plumes from railway trains servicing an Australian shipping port. The method utilizes the simultaneous measurement, downwind of the railway line, of the following pollutants; particle number, PM2.5 mass fraction, SO2, NOx and CO2, with the last of these being used as an indicator of fuel combustion. Emission factors are then derived, in terms of number of particles and mass of pollutant emitted per unit mass of fuel consumed. Particle number size distributions are also presented. The practical advantages of the method are discussed including the capacity to routinely collect emission factor data for passing trains and to thereby build up a comprehensive real world database for a wide range of pollutants. Samples from 56 train movements were collected, analyzed and presented. The quantitative results for emission factors are: EF(N)=(1.7±1)×1016 kg-1, EF(PM2.5)= (1.1±0.5) g·kg-1, EF(NOx)= (28±14) g·kg-1, and EF(SO2 )= (1.4±0.4) g·kg-1. The findings are compared with comparable previously published work. Statistically significant (p<α, α=0.05) correlations within the group of locomotives sampled were found between the emission factors for particle number and both SO2 and NOx.