Carbon-Supported Pt-TiO2 as a Methanol-Tolerant Oxygen-Reduction Catalyst for DMFCs

Carbon-supported Pt-TiO2 (Pt-TiO2/C) catalysts with varying at. wt ratios of Pt to Ti, namely, 1:1, 2:1, and 3:1, are prepared by the sol-gel method. The electrocatalytic activity of the catalysts toward oxygen reduction reaction (ORR), both in the presence and absence of methanol, is evaluated for application in direct methanol fuel cells (DMFCs). The optimum at. wt ratio of Pt to Ti in Pt-TiO2/C is established by fuel cell polarization, linear sweep voltammetry, and cyclic voltammetry studies. Pt-TiO2/C heattreated at 750 degrees C with Pt and Ti in an at. wt ratio of 2:1 shows enhanced methanol tolerance, while maintaining high catalytic activity toward ORR. The DMFC with a Pt-TiO2/C cathode catalyst exhibits an enhanced peak power density of 180 mW/cm(2) in contrast to the 80 mW/cm(2) achieved from the DMFC with carbon-supported Pt catalyst while operating under identical conditions. Complementary data on the influence of TiO2 on the crystallinity of Pt, surface morphology, and particle size, surface oxidation states of individual constituents, and bulk and surface compositions are also obtained by powder X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, energy dispersive analysis by X-ray, and inductively coupled plasm optical emission spectrometry.

CFD analysis of high frequency miniature pulse tube refrigerators for space applications with thermal non-equilibrium model

High frequency, miniature, pulse tube cryocoolers are extensively used in space applications because of their simplicity. Parametric studies of inertance type pulse tube cooler are performed with different length-to-diameter ratios of the pulse tube with the help of the FLUENT (R) package. The local thermal non-equilibrium of the gas and the matrix is taken into account for the modeling of porous zones, in addition to the wall thickness of the components. Dynamic characteristics and the actual mechanism of energy transfer in pulse are examined with the help of the pulse tube wall time constant. The heat interaction between pulse tube wall and the oscillating gas, leading to surface heat pumping, is quantified. The axial heat conduction is found to reduce the performance of the pulse tube refrigerator. The thermal non-equilibrium predicts a higher cold heat exchanger temperature compared to thermal equilibrium. The pressure drop through the porous medium has a strong non-linear effect due to the dominating influence of Forchheimer term over that of the linear Darcy term at high operating frequencies. The phase angle relationships among the pressure, temperature and the mass flow rate in the porous zones are also important in determining the performance of pulse tuberefrigerator.

Ratios of T-cell immune-effectors with tumour associated macrophages and PD-1/PD-L1 axis immune-checkpoint molecules, as prognosticators in diffuse large B cell lymphoma: A population-based study

Background Risk-stratification of diffuse large B-cell lymphoma (DLBCL) requires identification of patients with disease that is not cured despite initial R-CHOP. Although the prognostic importance of the tumour microenvironment (TME) is established, the optimal strategy to quantify it is unknown. Methods The relationship between immune-effector and inhibitory (checkpoint) genes was assessed by NanoString™ in 252 paraffin-embedded DLBCL tissues. A model to quantify net anti-tumoural immunity as an outcome predictor was tested in 158 R-CHOP treated patients, and validated in tissue/blood from two independent R-CHOP treated cohorts of 233 and 140 patients respectively. Findings T and NK-cell immune-effector molecule expression correlated with tumour associated macrophage and PD-1/PD-L1 axis markers consistent with malignant B-cells triggering a dynamic checkpoint response to adapt to and evade immune-surveillance. A tree-based survival model was performed to test if immune-effector to checkpoint ratios were prognostic. The CD4*CD8:(CD163/CD68)*PD-L1 ratio was better able to stratify overall survival than any single or combination of immune markers, distinguishing groups with disparate 4-year survivals (92% versus 47%). The immune ratio was independent of and added to the revised international prognostic index (R-IPI) and cell-of-origin (COO). Tissue findings were validated in 233 DLBCL R-CHOP treated patients. Furthermore, within the blood of 140 R-CHOP treated patients immune-effector:checkpoint ratios were associated with differential interim-PET/CT+ve/-ve expression.

Social and environmental reporting practices of organisations operating in, or sourcing products from, a developing country : evidence from Bangladesh

This research consists of a broad study in three parts of the social and environmental reporting practices of organisations operating in or sourcing products from a developing country, in this case Bangladesh. The first part of this study explores the social and environmental disclosure practices of the Bangladesh Garment Manufacturers and Exporters Association (BGMEA), the body responsible for organising the activities of 4,200 entities involved in the export of garments from Bangladesh. By way of interview, this part documents the opinions of numerous senior executives from the BGMEA with regard to any changes in the degree of social and environmental pressures since 1985. Utilising a complementary theoretical perspective that includes legitimacy theory, stakeholder theory and institutional theory this part then performs an analysis of the BGMEA's annual reports (1987-2005), t o explore the link between the perceived pressures and changes entailed therein and the social and environmental disclosure practices of the BGMEA across the period of analysis. The results show that the disclosure practices of BGMEA appear to be directly driven by the changing expectations of multinational buying companies- the group deemed to be the most powerful stakeholder group. This section is the first known study to interview managers from a large organisation in a developing country about shifting stakeholder expectations and then to link these changing expectations to annual report disclosures across an extended period of analysis. The findings then directly lead to the second major part of this thesis which investigates the social and environmental disclosure practices of two major multinational buying companies: Nike and H&M. Adopting a joint consideration of legitimacy theory and media agenda setting theory, this second part investigates the linkage between negative media attention and positive corporate social and environmental disclosures over a 19 year period. The results support the view that for those industry-related social and environmental issues that attract the greatest amount of negative media attention, these companies react by providing positive social and environmental disclosures. The results were particularly significant in relation to labour practices in developing countries-the issue that attracts the greatest amount of negative media attention for the companies in question. While the second part demonstrates that the media influences particular disclosure practices, the third part of the thesis shows what drives the media. Based on the speculation provided in the second part, the third part tests the proposition that the media is an important ally of NGOs in their quest to influence change in corporate accountabilities. Through the use of interviews, the results of this part of the study provide evidence to support previously untested perspectives about NGOs' utilisation of the m edia. The results reveal that NGOs use the media because the media is responsible for creating real changes in the operations and disclosure policies of organisations sourcing products from Bangladesh. The various pressures impacting the activities of organisations operating in or sourcing products from developing countries constitutes a fascinating area of investigation, and it is hoped that this study will motivate further research in this area.

Fabrication of Fe-doped WO3 films for NO2 sensing at lower operating temperature

Fe-doped tungsten oxide thin films with different concentrations (0 to 2.6 at%) were synthesized on glass and alumina substrates at room temperature using DC reactive sputtering and subsequently annealed at 300oC for 1 hour in air. The alumina substrate has pre-printed interdigitated Pt-electrodes for gas sensing measurements. The effects of Fe-doping on the film structure and morphology, electronic and optical properties for gas sensing were investigated. The grain size of the different films on the alumina and Pt regions of the substrate vary only slightly between 43-57 nm with median size of about 50 nm. Raman spectra showed that the integrated intensity of W=O to O–W–O bands increases with increasing Fe concentrations and this indicated an increase in the number of defects. From XPS the different concentrations of the Fe-doped films were 0.03 at%, 1.33 at% and 2.6 at%. All the films deposited on glass substrate have shown similar visible transmittance (about 70%) but the optical band gap of the pure film decreased form 3.30 eV to 3.15 eV after doping with 2.6 at% Fe. The Fe-doped WO3 film with the highest Fe concentration (2.6 at% Fe) has shown an enhanced gas sensing properties to NO2 at relatively lower operating temperature (150oC) and this can be attributed to the decrease in the optical band gap and an increase in the number of defects compared to the pure WO3 film.

Measurements of branching fraction ratios and CP asymmetries in B±→DCPK± decays in hadron collisions

We reconstruct B+/- -> D K+/- decays in a data sample collected by the CDF II detector at the Tevatron collider corresponding to 1 fb-1 of integrated luminosity. We select decay modes where the D meson decays to either K- pi+ (flavor eigenstate) or K- K+, pi- pi+ (CP-even eigenstates), and measure the direct CP asymmetry A_CP+ = 0.39 +/- 0.17(stat) +/- 0.04(syst), and the double ratio of CP-even to flavor eigenstate branching fractions R_CP+ = 1.30 +/- 0.24(stat) +/- 0.12(syst). These measurements will improve the determination of the CKM angle gamma. They are performed here for the first time using data from hadron collisions.

Applicability of partition ratios, mercuric chloride complexes, and chromatographic behavior for the identification of carotenoids

Partition ratios and M50 values of different carotenoids in hexaneaqueous methanol were determined. Mercuric chloride complexes of 14 epoxy carotenoids were prepared and their absorption maxima in acetone were estimated. The difference in chromatographic behavior of carotenoid epoxides on alumina and magnesium oxide-Celite columns is discussed. It is shown that the magnesium oxide-Celite column behaves as a reverse-phase chromatographic column to alumina column.

Environmental and climatic dependences of stable isotope ratios in tree rings on different temporal scales

This work examines stable isotope ratios of carbon, oxygen and hydrogen in annual growth rings of trees. Isotopic composition in wood cellulose is used as a tool to study past climate. The method benefits from the accurate and precise dating provided by dendrochronology. In this study the origin, nature and the strength of climatic correlations are studied on different temporal scales and at different sites in Finland. The origin of carbon isotopic signal is in photosynthetic fractionation. The basic physical and chemical fractionations involved are reasonably well understood. This was confirmed by measuring instantaneous photosynthetic discrimination on Scots pine (Pinus sylvestris L.). The internal conductance of CO2 was recognized to have a significant impact on the observed fractionation, and further investigations are suggested to quantify its role in controlling the isotopic signal of photosynthates. Isotopic composition of the produced biomass can potentially be affected by variety of external factors that induce physiological changes in trees. Response of carbon isotopic signal in tree ring cellulose to changes in resource availability was assessed in a manipulation experiment. It showed that the signal was relatively stable despite of changes in water and nitrogen availability to the tree. Palaeoclimatic reconstructions are typically based on functions describing empirical relationship between isotopic and climatic parameters. These empirical relationships may change depending on the site conditions, species and timeframe studied. Annual variation in Scots pine tree ring carbon and oxygen isotopic composition was studied in northern and in central eastern Finland and annual variation in tree ring latewood carbon, oxygen and hydrogen isotopic ratio in Oak (Quercus robur L.) was studied in southern Finland. In all of the studied sites at least one of the studied isotope ratios was shown to record climate strongly enough to be used in climatic reconstructions. Using the observed relationships, four-century-long climate reconstructions from living Scots pine were created for northern and central eastern Finland. Also temporal stability of the relationships between three proxy indicators, tree ring growth and carbon and oxygen isotopic composition was studied during the four-hundred-year period. Isotope ratios measured from tree rings in Finland were shown to be sensitive indicators of climate. Increasing understanding of environmental controls and physiological mechanisms affecting tree ring isotopic composition will make possible more accurate interpretation of isotope data. This study also demonstrated that by measuring multiple isotopes and physical proxies from the same tree rings, additional information on tree physiology can be obtained. Thus isotopic ratios measured from tree ring cellulose provide means to improve the reliability of climate reconstructions.

Performance study of high operating temperature HgCdTe mid wave infrared detector through numerical modeling

The design of present generation uncooled Hg1-xCdxTe infrared photon detectors relies on complex heterostructures with a basic unit cell of type (n) under bar (+)/pi/(p) under bar (+). We present an analysis of double barrier (n) under bar (+)/pi/(p) under bar (+) mid wave infrared (x = 0.3) HgCdTe detector for near room temperature operation using numerical computations. The present work proposes an accurate and generalized methodology in terms of the device design, material properties, and operation temperature to study the effects of position dependence of carrier concentration, electrostatic potential, and generation-recombination (g-r) rates on detector performance. Position dependent profiles of electrostatic potential, carrier concentration, and g-r rates were simulated numerically. Performance of detector was studied as function of doping concentration of absorber and contact layers, width of both layers and minority carrier lifetime. Responsivity similar to 0.38 A W-1, noise current similar to 6 x 10(-14) A/Hz(1/2) and D* similar to 3.1 x 10(10)cm Hz(1/2) W-1 at 0.1 V reverse bias have been calculated using optimized values of doping concentration, absorber width and carrier lifetime. The suitability of the method has been illustrated by demonstrating the feasibility of achieving the optimum device performance by carefully selecting the device design and other parameters. (C) 2010 American Institute of Physics. doi:10.1063/1.3463379]

Armchair or Zigzag? A tool for characterizing graphene edge

Electronic, magnetic, and structural properties of graphene flakes depend sensitively upon the type of edge atoms. We present a simple software tool for determining the type of edge atoms in a honeycomb lattice. The algorithm is based on nearest neighbor counting. Whether an edge atom is of armchair or zigzag type is decided by the unique pattern of its nearest neighbors. Particular attention is paid to the practical aspects of using the tool, as additional features such as extracting out the edges from the lattice could help in analyzing images from transmission microscopy or other experimental probes. Ultimately, the tool in combination with density-functional theory or tight-binding method can also be helpful in correlating the properties of graphene flakes with the different armchair-to-zigzag ratios. Program summary Program title: edgecount Catalogue identifier: AEIA_v1_0 Program summary URL: http://cpc.cs.qub.ac.uk/summaries/AEIA_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 66685 No. of bytes in distributed program, including test data, etc.: 485 381 Distribution format: tar.gz Programming language: FORTRAN 90/95 Computer: Most UNIX-based platforms Operating system: Linux, Mac OS Classification: 16.1, 7.8 Nature of problem: Detection and classification of edge atoms in a finite patch of honeycomb lattice. Solution method: Build nearest neighbor (NN) list; assign types to edge atoms on the basis of their NN pattern. Running time: Typically similar to second(s) for all examples. (C) 2010 Elsevier B.V. All rights reserved.

Stable carbon isotope ratios in Asian elephant collagen: implications for dietary studies

Stable carbon isotope ratios in bone collagen have been used in a variety of dietary studies in modern and fossil animals, including humans. Inherent in the stable isotope technique is the assumption that the isotopic signature is a reflection of the diet and is persistent in collagen because this is a relatively inert protein. Carbon isotope analyses of bones from a southern Indian population of Asian elephant (Elephas maximus), a long-lived mammal that alternates seasonally between a predominantly C3 (browse) and C4 (grass) plant diet, showed two patterns that have important implications for dietary interpretation based on isotopic studies. Relative to the quantity of the two plant types consumed on average, the ?13C signal in collagen indicated that more carbon was incorporated from C3 plants, possibly due to their higher protein contribution. There was a much greater variance in ?13C values of collagen in sub-adult (range -10.5� to-22.7�, variance=14.51) compared to adult animals (range -16.0� to -20.3�, variance=1.85) pointing to high collagen turnover rates and non-persistent isotopic signatures in younger, growing animals. It thus seems important to correct for any significant relative differences in nutritive value of food types and also consider the age of an animal before drawing definite conclusions about its diet from isotope ratios.

Male-biased adult sex ratios and their significance for cooperative breeding in dhole, Cuon alpinus, packs

Two free-ranging packs of dholes (Asiatic wild dog, Cuon alpinus) were monitored for a period of 6 yr (Sep. 1990-Sep. 1996) in the Mudumalai sanctuary, southern India. Demographic data on age structure, litter-size, sex ratio and age and sex specific dispersal were collected. Behavioural data on social interactions and reproductive behaviour among pack members were obtained to determine the frequencies of dominant and subordinate behaviours shown by malt: and female pack members and a measure of each male's reproductive access to females. Behaviours displayed by pack members at dens were recorded to determine whether any age- or sex-specific role specialization existed during pup care. Tenures for dominant males and females within the pack were calculated to ascertain the rate of breeding vacancies occurring within packs. Approximate levels of genetic relatedness within packs were determined by studying pedigrees. In most years one study pack had a male-biased adult sex ratio. This was caused by almost twofold higher dispersal of adult females over adult males. A considerable variance existed in the percentage of sub-adults dispersing from the two packs. Differences existed in the frequencies of dominant and subordinate behaviours shown by males. For males, dominance ranks and ranks based on submissive behaviours were not correlated with frequencies of reproductive behaviours. Subordinate males also displayed reproductive behaviours. In packs, dominant males had lower tenures than dominant females indicating that among males breeding vacancies arose more quickly. The litter size was found to be negatively correlated with the age of the breeding female. There were no significant differences across individuals of varying age or sex classes in the display of pup care behaviours. Significant differences did exist among individual adults. Genetic relatedness among packs tended to vary temporally as a consequence of possible mating by subordinate animals and immigration of new males into the pack. In conclusion, it appears that males delay dispersal and cooperate within their natal packs because of the variety of reproductive strategies they could pursue within. A combination of ecological constraints and the difficulties of achieving breeding status within non-natal packs may make early dispersal and independent breeding less beneficial.