High-pressure adsorption of supercritical gases on activated carbons: An improved approach based on the density functional theory and the bender equation of state

Adsorption of nitrogen, argon, methane, and carbon dioxide on activated carbon Norit R1 over a wide range of pressure (up to 50 MPa) at temperatures from 298 to 343 K (supercritical conditions) is analyzed by means of the density functional theory modified by incorporating the Bender equation of state, which describes the bulk phase properties with very high accuracy. It has allowed us to precisely describe the experimental data of carbon dioxide adsorption slightly above and below its critical temperatures. The pore size distribution (PSD) obtained with supercritical gases at ambient temperatures compares reasonably well with the PSD obtained with subcritical nitrogen at 77 K. Our approach does not require the skeletal density of activated carbon from helium adsorption measurements to calculate excess adsorption. Instead, this density is treated as a fitting parameter, and in all cases its values are found to fall into a very narrow range close to 2000 kg/m(3). It was shown that in the case of high-pressure adsorption of supercritical gases the PSD could be reliably obtained for the range of pore width between 0.6 and 3 run. All wider pores can be reliably characterized only in terms of surface area as their corresponding excess local isotherms are the same over a practical range of pressure.

Heat-induced and other chemical changes in commercial UHT milks

The properties of commercial directly and indirectly heated UHT milks, both after heating and during storage at room temperature for 24 weeks, were studied. Thermally induced changes were examined by changes in lactulose, furosine and acid-soluble whey proteins. The results confirmed previous reports that directly heated UHT milks suffer less heat damage than indirectly heated milk. During storage, furosine increased and bovine serum albumin in directly heat-treated milks decreased significantly. The changes in lactulose, alpha-lactalbumin and beta-lactoglobulin were not statistically significant. The data suggest that heat treatment indicators should be measured as soon as possible after processing to avoid any misinterpretations of the intensity of the heat treatment.

Submicron dispersions of hexosomes based on novel glycerate surfactants

Glycerate-based surfactants are a new class of swelling amphiphiles which swell to a finite degree with water. Among this class of surfactants, oleyl (cis-octadec-9-enyl) glycerate is very similar in structure to a well characterized mesophase-forming lipid, glyceryl monooleate (GMO). Despite the similar structural characteristics, a subtle change in connectivity of the ester bond substantially alters the binary surfactant-water phase behaviour. Whereas the phase behaviour of GMO is diverse and dominated by cubic phases, the phase behaviour of oleyl glycerate and a terpenoid analogue phytanyl (3,7,11,15-tetramethyl-hexadecane) glycerate is much simplified. Both exhibit an inverse hexagonal phase (H-II), which is stable to dilution with excess water, and an inverse micellar phase (L-II) at ambient temperatures. The inverse hexagonal phases formed by oleyl glycerate and phytanyl glycerate have been characterized using SAXS. Analogous to GMO cubosomes, the inverse hexagonal phase of phytanyl glycerate has been dispersed to form hexagonally facetted particles, termed hexosomes, whose structure has been verified using cryo-TEM.

Optical fibre sensors and their interrogation

This thesis describes novel developments in the fabrication and understanding of type IA fibre Bragg gratings, the uses of said gratings as optical sensors and the interrogation of optical sensors using tilted fibre Bragg gratings. This thesis presents the most detailed study of type IA gratings performed to date and provides the basis of a dual grating optical sensor capable of independently measuring strain and temperature. Until this work it was not known how to reliably fabricate type IA gratings or how they would react to high ambient temperatures, nor was it known what effect external parameters such as fibre type, dopant levels, inscription laser intensity, or hydrogenation levels would have on the physical properties of the grating. This comprehensive study has yielded answers to all of these unknowns and produced several unexpected uses for type IA gratings, such as the use of the previously unreported strong loss band at 1400nm to locally heat fibres by optical absorption and thereby fabricate optically tuneable gratings which do not affect directly adjacent standard gratings. Blazed fibre Bragg gratings have been studied in detail and used to produce several high quality prototype sensor interrogation systems yielding stability an accuracy values unsurpassed by similar devices reported in literature. An accurate distribution map of light radiated by blazed gratings is shown for the first time and has been studied in respect of polarisation state showing that for certain easily achievable conditions a blazed grating spectrometer may be deemed to be polarisation insensitive. In a novel implementation of the system, it is shown that the dynamic wavelength range of a blazed grating spectrometer may be at least doubled by superimposing blazed gratings.

Synthesis and characterisation of vinyl block copolymers

A study has been made of the anionic polymerisation of methyl methacrylate using butyllithium and polystyryl lithium as initiators and the effects of lithium chloride and aluminium alkyls on the molecular weight and molecular weight distributions. Diblock copolymers of styrene-b-methyl methacrylate were synthesised at -78oC in THF in the presence of lithium chloride, and at ambient temperatures in toluene in the presence of aluminium alkyls. Studies in the presence of lithium chloride showed that the polymerisation was difficult to control; there was no conclusive evidence of a living system and the polydispersity indices were between 1.5 and 3. However, using relatively apolar solvents, in the presence of aluminium alkyls, homopolymerisation of methyl methacrylate showed characteristics of a living polymerisation. An investigation of the effects of the structures of the lithium and aluminium alkyls on the efficiency of initiation showed that a t-butyllithium/triisobutylaluminium initiating system exhibited an efficiency of 80%, compared with lower efficiencies (typically 30%) for systems based on butyllithium/triethylaluminium.The polydispersity index was found to decrease from ∼2.2 to ∼1.5 when butyllithium was replaced by t-butyllithium. The efficiency of the initiator was found to be solely dependent on the size of the alkyl group of the aluminium component, whereas the polydispersity index was found to be solely dependent on the size of the alkyl group on the lithium component. The aluminium alkyl is thought to be co-ordinated to the ester carbonyl groups of both the monomer and polymer. There is a critical degree of polymerisation, at which point the rate of polymerisation decreases, which probably relates to a change in structure of the active chain end. Characterisation of poly(styrene )-b-poly(4-vinylpyridine) and poly(styrene)-b-poly(4-vinylpyridine methyl iodide) diblock copolymers using static light scattering techniques, showed the formation of star-shaped 'reverse' micelles when placed in toluene. Temperature effects on micellization behaviour are only exhibited for the unquaternised micelles, which showed characterisically lower aggregation numbers than their quaternised counterparts. A suitable solvent was not obtained for characterisation of the styrene-b-methyl methacrylate diblock copolymers synthesized.

Extended surface fluidized bed heat transfer

Experirnental data and theoretical calculation on the heat transfer performance of extended surface submerged: in shallow air fluidized beds ~ less than 150 mm, are presented. Energy t;ransferrence from the bed material was effected by water cooled tubes passing through the fins. The extended surface tested was either manufactured from square or radial copper fins silver soldered to a circular basic tube or commercially supplied, being of the crimped or extruded helical fin type. Performances are compared, for a wide range of geometric variables, bed configurations and fluidized materials, with plain and oval tubes operating under similar experimental conditions. A statistical analysis of all results, using a regression technique, has shown the relative importance of each significant variable. The bed to surface heat transfer coefficients are higher than those reported in earlier published work using finned tubes in much deeper beds and the heat transfer to the whole of the extended surface is at least as good as that previously reported for un-finned tubes. The improved performance is attributed partly to the absence of large bubbles in shallow beds and it is suggested that the improved circulation of the solids when constrained in the narrow passages between adjacent fins may be a contributory factor. Flow visualisation studies between a perspex extended surface and a fluidized bed using air at ambient temperatures, have demonstrated the effect of too small a fin spacing. Fin material and the bonding to the basic tube are more important in the optimisation of performance than in conventional convective applications because of the very much larger heat fluxes involved. A theoretical model of heat flow for a radial fin surface, provides data concerning the maximum heat transfer and minimum metal required to fulfil a given heat exchange duty. Results plotted in a series of charts aim at assisting the designer of shalJow fluidized beds.

A Predictive Thermal Habitat Model for Harbor Seals in the Northwest Atlantic

We analyzed projections of current and future ambient temperatures along the eastern United States in relationship to the thermal tolerance of harbor seals in air. Using the earth systems model (HadGEM2-ES) and representative concentration pathways (RCPs) 4.5 and 8.5, which are indicative of two different atmospheric CO2 concentrations, we were able to examine possible shifts in distribution based on three metrics: current preferences, the thermal limit of juveniles, and the thermal limits of adults. Our analysis focused on average ambient temperatures because harbor seals are least effective at regulating their body temperature in air, making them most susceptible to rising air temperatures in the coming years. Our study focused on the months of May, June, and August from 2041-2060 (2050) and 2061-2080 (2070) as these are the historic months in which harbor seals are known to annually come ashore to pup, breed, and molt. May, June, and August are also some of the warmest months of the year. We found that breeding colonies along the eastern United States will be limited by the thermal tolerance of juvenile harbor seals in air, while their foraging range will extend as far south as the thermal tolerance of adult harbor seals in air. Our analysis revealed that in 2070, harbor seal pups should be absent from the United States coastline nearing the end of the summer due to exceptionally high air temperatures.

Benthos activity, abundance and biomass in surface sediments off Morocco, Northwest Africa

Macro- and meiobenthic abundance and biomass as well as metabolic activity (respiration, ETS activity) have been studied along a transect ranging from 130 to 3000 m water depth off northern Morocco (35° N) during "Meteor" cruise No. 53 (1980). The distribution of chloroplastic pigment concentration (chlorophyll a, pheophytins) in the sediment has been investigated as a measure of sedimented primary organic matter. High chloroplastic pigment concentrations were found on the shelf and around the shelf break, but values declined rapidly between 200 and 600 m depth. Below 1200 m pigment concentrations remained at a relatively uniform low level. Macrobenthic abundance and biomass (wet weight) decreased with increasing water depth and with distance from the shore. Significant changes occurred between the shelf and upper slope and below 2000 m depth. Meiobenthic abundance and biomass (ash free dry weight) followed the same general pattern, but changes were found below 400 and 800 m depth. In the depth range of 1200 to 3000 m values differ only slightly. Meiofauna abundance and biomass show a good correlation with the sedimentary chloroplastic pigment concentrations. Respiratory activity of sediment cores, measured by a shipboard technique at ambient temperatures, decreased with water depth and shows a good correlation with the pigment concentrations. ETS activity was highest on the shelf and decreased with water depth, with significant changes between 200 and 400 m, and below 1200 m depth, respectively. Activity was generally highest in the top 5 cm of the sediment and was measurable, at all stations, down to 15 cm sediment depth. Shelf and upper slope stations exhibited a vertical distribution pattern of ETS activity in the sediment column, different from that of deeper stations. The importance of biological activity measurements as an estimate of productivity is discussed. To prove the thesis that differences in benthic abundance, biomass and activity reflect differences in pelagic surface primary production, in the case of the NW-African coast caused by different upwelling intensities, the values from 35° N were compared with data from 21° N (permanent upwelling activity) and 17° N (ca. 9 months upwelling per year). On the shelf and upper slope (< 500 m) hydrographical conditions (currents, internal waves) influence the deposition of organic matter and cause a biomass minimum between 200 and 400 m depth in some regions. But, in general, macrobenthic abundance and biomass increases with enhanced upwelling activity and reaches a maximum in the area off Cape Blanc (21° N). On the shelf and in the shelf break region meiofauna densities are higher at 35° N in comparison to 21° N; but in contrast to the decreasing meiofauna abundance with increasing water depth at 35° N, an abundance maximum between 400 and 1200 m depth is formed in the Cape Blanc region; this maximum coincides with the maximum of sedimentary chloroplastic pigment equivalents. The comparison of ETS activities between 35° N and 21° N shows on the shelf activity at 21° N is up to 14 times higher and on the slope 4-9 times higher, which demonstrates that benthic activity responds to the surface productivity regime.

Seawater carbonate chemistry and biological processes during experiments with spider crab Hyas araneus, 2009

Future scenarios for the oceans project combined developments of CO2 accumulation and global warming and their impact on marine ecosystems. The synergistic impact of both factors was addressed by studying the effect of elevated CO2 concentrations on thermal tolerance of the cold-eurythermal spider crab Hyas araneus from the population around Helgoland. Here ambient temperatures characterize the southernmost distribution limit of this species. Animals were exposed to present day normocapnia (380 ppm CO2), CO2 levels expected towards 2100 (710 ppm) and beyond (3000 ppm). Heart rate and haemolymph PO2 (PeO2) were measured during progressive short term cooling from 10 to 0°C and during warming from 10 to 25°C. An increase of PeO2 occurred during cooling, the highest values being reached at 0°C under all three CO2 levels. Heart rate increased during warming until a critical temperature (Tc) was reached. The putative Tc under normocapnia was presumably >25°C, from where it fell to 23.5°C under 710 ppm and then 21.1°C under 3000 ppm. At the same time, thermal sensitivity, as seen in the Q10 values of heart rate, rose with increasing CO2concentration in the warmth. Our results suggest a narrowing of the thermal window of Hyas araneus under moderate increases in CO2 levels by exacerbation of the heat or cold induced oxygen and capacity limitation of thermal tolerance.

Genetic variation of temperature-regulated curd induction in cauliflower: elucidation of floral transition by genome-wide association mapping and gene expression analysis

Cauliflower (Brassica oleracea var. botrytis) is a vernalization-responsive crop. High ambient temperatures delay harvest time. The elucidation of the genetic regulation of floral transition is highly interesting for a precise harvest scheduling and to ensure stable market supply. This study aims at genetic dissection of temperature-dependent curd induction in cauliflower by genome-wide association studies and gene expression analysis. To assess temperature dependent curd induction, two greenhouse trials under distinct temperature regimes were conducted on a diversity panel consisting of 111 cauliflower commercial parent lines, genotyped with 14,385 SNPs. Broad phenotypic variation and high heritability (0.93) were observed for temperature-related curd induction within the cauliflower population. GWA mapping identified a total of 18 QTL localized on chromosomes O1, O2, O3, O4, O6, O8, and O9 for curding time under two distinct temperature regimes. Among those, several QTL are localized within regions of promising candidate flowering genes. Inferring population structure and genetic relatedness among the diversity set assigned three main genetic clusters. Linkage disequilibrium (LD) patterns estimated global LD extent of r(2) = 0.06 and a maximum physical distance of 400 kb for genetic linkage. Transcriptional profiling of flowering genes FLOWERING LOCUS C (BoFLC) and VERNALIZATION 2 (BoVRN2) was performed, showing increased expression levels of BoVRN2 in genotypes with faster curding. However, functional relevance of BoVRN2 and BoFLC2 could not consistently be supported, which probably suggests to act facultative and/or might evidence for BoVRN2/BoFLC-independent mechanisms in temperature regulated floral transition in cauliflower. Genetic insights in temperature-regulated curd induction can underpin genetically informed phenology models and benefit molecular breeding strategies toward the development of thermo-tolerant cultivars.

Adição de superplastificante e anti-segregante à base de CMC em pastas de cimento para Poços de Petróleo

Oil well cementing materials consist of slurries of Special class Portland cement dispersed in water. Admixtures can be used to provide the necessary fluidity, so the material can be efficiently pumped down as well as penetrate porous rocks with controlled filter loss. Construction admixtures can be used to modify the properties of oil well cements provided they can withstand and hold their properties at the higher than ambient temperatures usually encountered in oil fields. In civil construction, superplasticizer play the role of dispersants that reduce the facto r of water cement improve mechanical properties and fluidity of the cement, whereas anti-segregation agents improve the workability of the slurry. In the present study, oil well cement slurries were produced adding both a dispersant and an anti-segregation agent conventionally used in Portland CPII-Z-32 RS cement aiming at materials for primary cementing and squeeze operations. Three basic aspects were evaluated: fluidity, filter loss and the synergetic effect of the admixtures at two temperatures, i.e., 27°C and 56°C, following API RP 10B practical recommendations. The slurries were prepared using admixture concentrations varying from 2.60 Kgf/m3 (0.02 gallft3) to 5.82 Kgf/m3 (0.045 galJft3) BWOC. The density of the slurries was set to 1.89 g/cm3 (15.8 Ib/gal). 0.30 to 0.60% BWOC of a CMC-based anti-segregation agent was added to the cement to control the filter loss. The results showed that the addition of anti-segregation at concentrations above 0.55% by weight of cement resulted in the increased viscosity of the folders in temperatures evaluated. The increasing the temperature of the tests led to a reduction in the performance of anti-segregation. At concentrations of 5.20 kgf/m3 (0,040 gallft3) and 5.82 Kgf/m3 (0,045 gal/ft 3) observed a better performance of the properties evaluated in the proposed system. At low temperature was observed instability in the readings of rheology for all concentrations of anti-segregation. Contents that increasing the concentration of anti¬-segregation is limited concentrations greater than 0.55 % BWOC of the CMC in temperature analyzed. The use of the system with CMC promoted a good performance against the properties evaluated. The principal function of anti¬-segregation was optimized with increasing concentration of superplasticizer, at temperatures above the 2rC. The study of the behaviour of systemic additives, resulting in slurries of cement, which can be optimized face studies of other intrinsic properties in oil fields

Trapping phenomena in AlGaN and InAlN barrier HEMTs with different geometries

PAPER Trapping phenomena in AlGaN and InAlN barrier HEMTs with different geometries S Martin-Horcajo1, A Wang1, A Bosca1, M F Romero1, M J Tadjer1,2, A D Koehler2, T J Anderson2 and F Calle1 Published 11 February 2015 • © 2015 IOP Publishing Ltd Semiconductor Science and Technology, Volume 30, Number 3 Article PDF Figures References Citations Metrics 350 Total downloads Cited by 1 articles Export citation and abstract BibTeX RIS Turn on MathJax Share this article Article information Abstract Trapping effects were evaluated by means of pulsed measurements under different quiescent biases for GaN/AlGaN/GaN and GaN/InAlN/GaN. It was found that devices with an AlGaN barrier underwent an increase in the on-resistance, and a drain current and transconductance reduction without measurable threshold voltage change, suggesting the location of the traps in the gate-drain access region. In contrast, devices with an InAlN barrier showed a transconductance and a decrease in drain associated with a significant positive shift of threshold voltage, indicating that the traps were likely located under the gate region; as well as an on-resistance degradation probably associated with the presence of surface traps in the gate-drain access region. Furthermore, measurements of drain current transients at different ambient temperatures revealed that the activation energy of electron traps was 0.43 eV and 0.38 eV for AlGaN and InAlN barrier devices, respectively. Experimental and simulation results demonstrated the influence of device geometry on the observed trapping effects, since devices with larger gate lengths and gate-to-drain distance values exhibited less noticeable charge trapping effects.

Ambient stored garlic is higher yielding than garlic stored at cooler temperatures

This experiment evaluated the effect of storage temperature on garlic emergence and yield. Six treatments, '5°C + heat', '5°C - heat', '15°C + heat', '15°C - heat', 'ambient + heat' and 'ambient - heat' were imposed. The heat treatment included a stepped heat treatment of between 30 and 38°C over a 42 day period. Highest emergence rate and yield was obtained for treatments stored under ambient conditions. Garlic stored at cool temperatures of either 5 or 15°C had poorer emergence and lower yields that were commercially unviable. Heat treatment had no observable effect on emergence or yield in ambient or 15°C treatments but in 5°C treatments, yield was significantly greater when the heat treatment was applied but nonetheless was still commercially unviable. The recommendations from this experiment are that in subtropical climates garlic seed-bulbs should be stored under ambient conditions. © ISHS.