Glass transition. A new approach based on cluster model of glasses

The structure of real glasses has been considered to be microheterogeneous, composed of clusters and connective tissue. Particles in the cluster are assumed to be highly correlated in positions. The tissue is considered to have a truly amorphous structure with its particles vibrating in highly anharmonic potentials. Glass transition is recognized as corresponding to the melting of clusters. A simple mathematical model has been developed which accounts for various known features associated with glass transition, such as range of glass transition temperature,T g, variation ofT g with pressure, etc. Expressions for configurational thermodynamic properties and transport properties of glass forming systems are derived from the model. The relevence and limitations of the model are also discussed.

The Influence of Bilayer Composition on the Gel to Liquid Crystalline Transition

We report molecular dynamics simulations of bilayers using a united atom model with explicit solvent molecules. The bilayer consists of the single tail cationic surfactant behenyl trimethyl ammonium chloride (BTMAC) with stearyl alcohol (SA) as the cosurfactant. We study the gel to liquid crystalline transitions in the bilayer by varying the amount of water at fixed BTMAC to SA ratio as well as by varying the BTMAC to SA ratio at fixed water content. The bilayer is found to exist in the tilted, Lβ′ phase at low temperatures, and for the compositions investigated in this study, the Lβ′ to Lα melting transition occurred in the temperature range 330−338 K. For the highest BTMAC to SA composition (2:3 molar ratio), a diffuse headgroup−water interface is observed at lower temperatures, and an increase in the d-spacing occurs prior to the melting transition. This pretransition swelling is accompanied by a sharpening in the water density variation across the headgroup region of the bilayer. Signatures of this swelling effect which can be observed in the alkane density distributions, area per headgroup, and membrane thickness are attributed to the hydrophobic effect. At a fixed bilayer composition, the transition temperature (>338 K) from the Lβ′ to Lα transition obtained for the high water content bilayer (80 wt %) is similar to that obtained with low water content (54.3 wt %), confirming that the melting transition at these water contents is dominated by chain melting.

Fishing power and standardised catch rates: Implications of missing vessel-characteristic data from the Australian eastern king prawn fishery

Standardised time series of fishery catch rates require collations of fishing power data on vessel characteristics. Linear mixed models were used to quantify fishing power trends and study the effect of missing data encountered when relying on commercial logbooks. For this, Australian eastern king prawn (Melicertus plebejus) harvests were analysed with historical (from vessel surveys) and current (from commercial logbooks) vessel data. Between 1989 and 2010, fishing power increased up to 76%. To date, both forward-filling and, alternatively, omitting records with missing vessel information from commercial logbooks produce broadly similar fishing power increases and standardised catch rates, due to the strong influence of years with complete vessel data (16 out of 23 years of data). However, if gaps in vessel information had not originated randomly and skippers from the most efficient vessels were the most diligent at filling in logbooks, considerable errors would be introduced. Also, the buffering effect of complete years would be short lived as years with missing data accumulate. Given ongoing changes in fleet profile with high-catching vessels fishing proportionately more of the fleet’s effort, compliance with logbook completion, or alternatively ongoing vessel gear surveys, is required for generating accurate estimates of fishing power and standardised catch rates.

A multi-faceted approach for quantifying the estuarine-nearshore transition in the life cycle of the bull shark, Carcharhinus leucas.

Understanding the ontogenetic habitat linkages of sharks is important for conservation and managing human interactions. We used acoustic telemetry, catch data, elemental and stable isotope signatures and dietary analyses to investigate ontogenetic habitat use in south-east Queensland, Australia, by the bull shark Carcharhinus leucas, a IUCN 'near-threatened' species that is implicated in many shark attacks on humans in urban estuaries. Sequential analyses for delta(15)N and delta(13)C of vertebrae from five adult C. leucas and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) for elemental composition from 23 C. leucas, including a pregnant female, were also used to trace ontogenetic habitat dependence. Acoustic telemetry indicated large juvenile and subadult C. leucas remained in estuarine habitats. delta(15)N values across shark vertebrae showed an ontogenetic shift in diet with total length (TL), confirmed by stomach contents. LA-ICPMS data reflected the ontogenetic movements of C. leucas from natal habitats. Differences among adults were gender related. Shifts in habitat use by subadults were correlated with a sigmoidal delta(13)C relationship with TL. C. leucas have a multipartite, stage-specific dependency in their transition between habitats along the freshwater-estuarine-marine continuum, making them particularly susceptible to the habitat alteration that is occurring globally.

Prediction of bubble growth rates and departure volumes in nucleate boiling at isolated sites

A model has been developed to predict heat transfer rates and sizes of bubbles generated during nucleate pool boiling. This model assumes conduction and a natural convective heat transfer mechanism through the liquid layer under the bubble and transient conduction from the bulk liquid. The temperature of the bulk liquid in the vicinity of the bubble is obtained by assuming a turbulent natural convection process from the hot plate to the liquid bulk. The shape of the bubble is obtained by equilibrium analysis. The bubble departure condition is predicted by a force balance equation. Good agreement has been found between the bubble radii predicted by the present theory and the ones obtained experimentally.

Boundary layer transition observations on a body of revolution with surface heating and cooling in water

Boundary layer flow visualization in water with surface heat transfer was carried out on a body of revolution which had the predicted possibility of laminar separation under isothermal conditions. Flow visualization was by in-line holographic technique. Boundary layer stabilization, including elimination of laminar separation, was observed to take place on surface heating. Conversely, boundary layer destabilization was observed on surface cooling. These findings are consistent with the theoretical predictions of Wazzan et al. in The stability and transition of heated and cooled incompressible laminar boundary layers, in Proceedings of the Fourth International Heat Transfer Conference, Vol. 2, FCI 4. Elsevier, Amsterdam (1970).

Electrophilic Addition of Phenylisocyanate at gamma-CH of Thio-beta-diketonates of Some Transition Metals

The quasi-aromatic property of metal chelates of thio-beta-diketones has been studied by reacting them with phenylisocyanate, where addition takes place at the gamma-CH in a stepwise manner. Mono-thiodiketonates of Ni(II), Pd(II), cu(II) and Co(III) and the dithio-acetylacetonate of Ni(II) react with phenylisocyanate to produce mono-, di- and triphenylamido [with cobalt (III) only] substituted derivatives. In the case of tris (ethylthioacetoacetato) cobalt (III), it is found that the reaction with phenylisocyanate gives two isomers, a chocolate coloured isomer in which the phenylamido carbonyl is not coordinated while the green coloured isomer has bonding through phenylemido carbonyl oxygen. The reactions of the thiodiketonates have been compared with those of beta-diketonates and beta-ketoiminates. The reaction products have been characterised by elemental analyses, magnetic moments, and electronic, IR and 1H NMR spectral studies.

Implementation costs of Agricultural Management Practices for Water Quality Improvement in the Great Barrier Reef Catchments. CSIRO: Water for Healthy Country National Research Flagship

Executive summary. In this report we analyse implementation costs and benefits for agricultural management practices, grouped into farming systems. In order to do so, we compare plot scale gross margins for the dominant agricultural production systems (sugarcane, grazing and banana cultivation) in the NRM regions Wet Tropics, Burdekin Dry Tropics and Mackay Whitsundays. Furthermore, where available, we present investment requirements for changing to improved farming systems. It must be noted that transaction costs are not captured within this project. For sugarcane, this economic analysis shows that there are expected benefits to sugarcane growers in the different regions through transitions to C and B class farming systems. Further transition to A-class farming systems can come at a cost, depending on the capital investment required and the length of the investment period. Obviously, the costs and benefits will vary for each individual grower and will depend on their starting point and individual property scenario therefore each circumstance needs to be carefully considered before making a change in management practice. In grazing, overall, reducing stocking rates comes at a cost (reduced benefits). However, when operating at low utilisation rates in wetter country, lowering stocking rates can potentially come at a benefit. With win-win potential, extension is preferred to assist farmer in changing management practices to improve their land condition. When reducing stocking rates comes at a cost, incentives may be applicable to support change among farmers. For banana cultivation, the results indicate that the transition to C and B class management practices is a worthwhile proposition from an economic perspective. For a change from B to A class farming systems however, it is not worthwhile from a financial perspective. This is largely due to the large capital investment associated with the change in irrigation system and negative impact in whole of farm gross margin. Overall, benefits will vary for each individual grower depending on their starting point and their individual property scenario. The results presented in this report are one possible set of figures to show the changes in profitability of a grower operating in different management classes. The results in this report are not prescriptive of every landholder. Landholders will have different costs and benefits from transitioning to improved practices, even if similar operations are practiced, hence it is recommended that landholders that are willing to change management undertake their own research and analysis into the expected costs and benefits for their own soil types and property circumstances.

Round scallops and square meshes: a comparison of four codend types on the catch rates of target species and by-catch in the Queensland (Australia) saucer scallop (Amusium balloti) trawl fishery

Concern over the amount of by-catch from benthic trawl fisheries and research into the problem have increased in recent years. The present paper demonstrated that by-catch rates in the Queensland (Australia) saucer scallop (Amusium balloti) trawl fishery can be reduced by 77% (by weight) using nets fitted with a turtle excluder device (TED) and a square-mesh codend, compared with a standard diamond-mesh codend with no TED. This large reduction was achieved with no significant effect on the legal size scallop catch rate and 39% fewer undersize scallops were caught. In total, 382 taxa were recorded in the by-catch, which was dominated by sponges, portunid crabs, small demersal and benthic fish (e.g. leatherjackets, stingerfish, bearded ghouls, nemipterids, longspine emperors, lizard fish, triggerfish, flounders and rabbitfish), elasmobranchs (e.g. mainly rays) and invertebrates (e.g. sea stars, sea urchins, sea cucumbers and bivalve molluscs). Extremely high reductions in catch rate (i.e. ≥85%) were demonstrated for several by-catch species owing to the square-mesh codend. Square-mesh codends show potential as a means of greatly reducing by-catch and lowering the incidental capture and mortality of undersize scallops and Moreton Bay bugs (Thenus australiensis) in this fishery

Infrared and Mössbauer spectroscopic study of the metal-insulator transition in some oxides of perovskite structure

The IR spectra of some LaNi1−xBxO3 (B = Cr, Fe, and Co) compounds having perovskite structure have been studied in the range 1000−300 cm−1. An investigation of the changes in the metal-oxygen stretching frequency as x → xc from the insulating side has been carried out. An important feature is that as x → xc the vibrational features in the infrared spectra disappear when the resistivity is not, vert, similar10−1 Ω cm which is of two orders of magnitude more than the value of varrho0 at which the temperature coefficient of resistance changes sign. Mössbauer studies on Fe-containing samples with various conductivities show that the isomer shift decreases as conductivity increases which is indicative of larger Fe---O overlap.

A Novel Approach to the Study of Surface Oxidation States and Oxidation of Transition Metals by Auger Electron Spectroscopy

L$_{23}$ M$_{45}$ M$_{45}$/L$_{23}$ M$_{23}$ M$_{45}$, L$_{23}$ M$_{45}$ M$_{45}$/L$_{23}$ M$_{23}$ M$_{23}$ and L$_{23}$ M$_{23}$ M$_{45}$/L$_{23}$ M$_{23}$ M$_{23}$ Auger intensity ratios in transition metal oxides and sulphides are shown to be directly related to the number of valence electrons in the metal as well as to its oxidation state. The metal Auger intensity ratios provide a unique probe, independent of O (KLL) intensity, to study surface oxidation states of metals. These intensity ratios have been effectively employed to investigate surface oxidation of nickel, iron and copper. The oxidation studies have unravelled some interesting aspects of surface oxidation.

Photo-Electron Spectroscopic Studies Of The Adsorption Of Organic-Molecules With Lone Pair Orbitals On Transition-Metal Surfaces

Ultraviolet and x-ray photoelectron spectroscopy have been employed to investigate the adsorption of methanol, ethanol, diethylether, acetaldehyde, acetone, methyl acetate and methylamine on surfaces of Fe, Ni and Cu. All these molecules adsorb molecularly at low temperatures (≤100 K). Lone pair orbitals of these molecules are stabilized on these metal surfaces (by 0·4–1·0eV) due to molecular chemisorption. The molecules generally undergo transformations as the temperature is raised to 120 K or above. The new species produced seems to depend on the metal surface. Some of the product species identified are methoxy species, formaldehyde and carbon monoxide in the case of methanol and methyl acetate, ethoxy species in the case of ethanol and 2-propanol in the case of acetone.

Feasibility of a stepped wedge cluster RCT and concurrent observational sub-study to evaluate the effects of modified ward night lighting on inpatient fall rates and sleep quality: A protocol for a pilot trial

Background: Falls among hospitalised patients impose a considerable burden on health systems globally and prevention is a priority. Some patient-level interventions have been effective in reducing falls, but others have not. An alternative and promising approach to reducing inpatient falls is through the modification of the hospital physical environment and the night lighting of hospital wards is a leading candidate for investigation. In this pilot trial, we will determine the feasibility of conducting a main trial to evaluate the effects of modified night lighting on inpatient ward level fall rates. We will test also the feasibility of collecting novel forms of patient level data through a concurrent observational sub-study. Methods/design: A stepped wedge, cluster randomised controlled trial will be conducted in six inpatient wards over 14 months in a metropolitan teaching hospital in Brisbane (Australia). The intervention will consist of supplementary night lighting installed across all patient rooms within study wards. The planned placement of luminaires, configurations and spectral characteristics are based on prior published research and pre-trial testing and modification. We will collect data on rates of falls on study wards (falls per 1000 patient days), the proportion of patients who fall once or more, and average length of stay. We will recruit two patients per ward per month to a concurrent observational sub-study aimed at understanding potential impacts on a range of patient sleep and mobility behaviour. The effect on the environment will be monitored with sensors to detect variation in light levels and night-time room activity. We will also collect data on possible patient-level confounders including demographics, pre-admission sleep quality, reported vision, hearing impairment and functional status. Discussion: This pragmatic pilot trial will assess the feasibility of conducting a main trial to investigate the effects of modified night lighting on inpatient fall rates using several new methods previously untested in the context of environmental modifications and patient safety. Pilot data collected through both parts of the trial will be utilised to inform sample size calculations, trial design and final data collection methods for a subsequent main trial.