Mass and size distribution measurement of particulates from a gas turbine combustor using modern mobility analyzer and particle sizer

SMPS and DMS500 analysers were used to measure particulate size distributions in the exhaust of a fully annular aero gas turbine engine at two operating conditions to compare and analyse sources of discrepancy. A number of different dilution ratio values were utilised for the comparative analysis, and a Dekati hot diluter operating at a temperature of 623°K was also utilised to remove volatile PM prior to measurements being made. Additional work focused on observing the effect of varying the sample line temperatures to ascertain the impact. Explanations are offered for most of the trends observed, although a new, repeatable event identified in the range from 417°K to 423°K – where there was a three order of magnitude increase in the nucleation mode of the sample – requires further study.

Earthworms produce granules of intricately zoned calcite

Earthworms of the family Lumbricidae, which includes many common species, produce and secrete up to millimeter-sized calcite granules, and the intricate fine-scale zoning of their constituent crystals is unique for a biomineral. Granule calcite is produced by crystallization of amorphous calcium carbonate (ACC) that initially precipitates within the earthworm calciferous glands, then forms protogranules by accretion on quartz grain cores. Crystallization of ACC is mediated by migrating fluid films and is largely complete within 24 11 of ACC production and before granules leave the earthworm. Variations in the density of defects formed as a byproduct of trace element incorporation during calcite crystall growth have generated zoning that can be resolved by cathodoluminescence imaging at ultraviolet to blue wavelengths and using the novel technique of scanning electron microscope charge contrast imaging. Mapping of calcite crystal orientations by electron backscatter diffraction reveals an approximate radial fabric to the granules that reflects crystal growth from internal nucleation sites toward their margins. The survival within granules of ACC inclusions for months after they enter soils indicates that they crystallize only within the earthworm and in the presence of fluids containing biochemical catalysts. The earthworm probably promotes crystallization of ACC in order to prevent remobilization of the calcium carbonate by dissolution. Calcite granules vividly illustrate the role of transient precursors in biomineralization, but the underlying question of why earth-worms produce granules in volumes sufficient to have a measurable impact on soil carbon cycling remains to be answered.

Evaluation of a large-eddy model simulation of a mixed-phase altocumulus cloud using microwave radiometer, lidar and Doppler radar data

Using the Met Office large-eddy model (LEM) we simulate a mixed-phase altocumulus cloud that was observed from Chilbolton in southern England by a 94 GHz Doppler radar, a 905 nm lidar, a dual-wavelength microwave radiometer and also by four radiosondes. It is important to test and evaluate such simulations with observations, since there are significant differences between results from different cloud-resolving models for ice clouds. Simulating the Doppler radar and lidar data within the LEM allows us to compare observed and modelled quantities directly, and allows us to explore the relationships between observed and unobserved variables. For general-circulation models, which currently tend to give poor representations of mixed-phase clouds, the case shows the importance of using: (i) separate prognostic ice and liquid water, (ii) a vertical resolution that captures the thin layers of liquid water, and (iii) an accurate representation the subgrid vertical velocities that allow liquid water to form. It is shown that large-scale ascents and descents are significant for this case, and so the horizontally averaged LEM profiles are relaxed towards observed profiles to account for these. The LEM simulation then gives a reasonable. cloud, with an ice-water path approximately two thirds of that observed, with liquid water at the cloud top, as observed. However, the liquid-water cells that form in the updraughts at cloud top in the LEM have liquid-water paths (LWPs) up to half those observed, and there are too few cells, giving a mean LWP five to ten times smaller than observed. In reality, ice nucleation and fallout may deplete ice-nuclei concentrations at the cloud top, allowing more liquid water to form there, but this process is not represented in the model. Decreasing the heterogeneous nucleation rate in the LEM increased the LWP, which supports this hypothesis. The LEM captures the increase in the standard deviation in Doppler velocities (and so vertical winds) with height, but values are 1.5 to 4 times smaller than observed (although values are larger in an unforced model run, this only increases the modelled LWP by a factor of approximately two). The LEM data show that, for values larger than approximately 12 cm s(-1), the standard deviation in Doppler velocities provides an almost unbiased estimate of the standard deviation in vertical winds, but provides an overestimate for smaller values. Time-smoothing the observed Doppler velocities and modelled mass-squared-weighted fallspeeds shows that observed fallspeeds are approximately two-thirds of the modelled values. Decreasing the modelled fallspeeds to those observed increases the modelled IWC, giving an IWP 1.6 times that observed.

Hydrolysis of N2O5 on submicron sulfuric acid aerosols

The kinetics of reactive uptake of gaseous N2O5 on submicron sulfuric acid aerosol particles has been investigated using a laminar flow reactor coupled with a differential mobility analyzer (DMA) to characterize the aerosol. The particles were generated by homogeneous nucleation of SO3/H2O mixtures. In the H2SO4 concentration range 26.3−64.5 wt % the uptake coefficient was γ = 0.033 ± 0.004, independent of acid strength. For an acid strength of 45 wt % γ was found to decrease with increasing temperature over the range 263−298 K. From this, temperature dependence values of −115 ± 30 kJ/mol and −25.5 ± 8.4 J/K mol were determined for the changes in enthalpy and entropy of the uptake process, respectively. The results are consistent with a previous model of N2O5 hydrolysis involving both a direct and an acid catalyzed mechanism, with uptake under the experimental conditions limited by mass accommodation.

Results from the CERN pilot CLOUD experiment

During a 4-week run in October–November 2006, a pilot experiment was performed at the CERN Proton Synchrotron in preparation for the Cosmics Leaving OUtdoor Droplets (CLOUD) experiment, whose aim is to study the possible influence of cosmic rays on clouds. The purpose of the pilot experiment was firstly to carry out exploratory measurements of the effect of ionising particle radiation on aerosol formation from trace H2SO4 vapour and secondly to provide technical input for the CLOUD design. A total of 44 nucleation bursts were produced and recorded, with formation rates of particles above the 3 nm detection threshold of between 0.1 and 100 cm−3 s−1, and growth rates between 2 and 37 nm h−1. The corresponding H2SO4 concentrations were typically around 106 cm−3 or less. The experimentally-measured formation rates and H2SO4 concentrations are comparable to those found in the atmosphere, supporting the idea that sulphuric acid is involved in the nucleation of atmospheric aerosols. However, sulphuric acid alone is not able to explain the observed rapid growth rates, which suggests the presence of additional trace vapours in the aerosol chamber, whose identity is unknown. By analysing the charged fraction, a few of the aerosol bursts appear to have a contribution from ion-induced nucleation and ion-ion recombination to form neutral clusters. Some indications were also found for the accelerator beam timing and intensity to influence the aerosol particle formation rate at the highest experimental SO2 concentrations of 6 ppb, although none was found at lower concentrations. Overall, the exploratory measurements provide suggestive evidence for ion-induced nucleation or ion-ion recombination as sources of aerosol particles. However in order to quantify the conditions under which ion processes become significant, improvements are needed in controlling the experimental variables and in the reproducibility of the experiments. Finally, concerning technical aspects, the most important lessons for the CLOUD design include the stringent requirement of internal cleanliness of the aerosol chamber, as well as maintenance of extremely stable temperatures (variations below 0.1 _C).

The role of Ti3+ interstitials in TiO2(110) reduction and oxidation

Here we describe results which teach us much about the mechanism of the reduction and oxidation of TiO2(110) by the application of scanning tunnelling microscopy imaging at high temperatures. Titania reduces at high temperature by thermal oxygen loss to leave localized (i.e. Ti3+) and delocalized electrons on the lattice Ti, and a reduced titania interstitial that diffuses into the bulk of the crystal. The interstitial titania can be recalled to the surface by treatment in very low pressures of oxygen, occurring at a significant rate even at 573 K. This re-oxidation occurs by re-growth of titania layers in a Volmer-Weber manner, by a repeating sequence in which in-growth of extra titania within the cross-linked (1 x 2) structure completes the (1 x 1) bulk termination. The next layer then initiates with the nucleation of points and strings which extend to form islands of cross-linked (1 x 2), which once again grow and fill in to reform the (1 x 1). This process continues in a cyclical manner to form many new layers of well-ordered titania. The details of the mechanism and kinetics of the process are considered.

Crystallization in poly(L-lactide)-b-poly(epsilon-caprolactone) double crystalline diblock copolymers: a study using X-ray scattering, differential scanning calorimetry, and polarized optical microscopy

The crystallization of well-defined poly(L-lactide)-b-poly(epsilon-caprolactone) diblock copolymers, PLLA-b-PCL, was investigated by time-resolved X-ray techniques, polarized optical microscopy (POM), and differential scanning calorimetry (DSC). Two compositions were studied that contained 44 and 60 wt % poly(L-lactide), PLLA (they are referred to as (L44C5614)-C-11 and (L60C409)-C-12, respectively, with the molecular weight of each block in kg/mol as superscript). The copolymers were found to be initially miscible in the melt according to small-angle X-ray scattering measurements (SAXS). Their thermal behavior was also indicative of samples whose crystallization proceeds from a mixed melt. Sequential isothermal crystallization from the melt at 100 degreesC (for 30 min) and then at 30 degreesC (for 15 min) was measured. At 100 degreesC only the PLLA block is capable of crystallization, and its crystallization kinetics was followed by both WAXS and DSC; comparable results were obtained that indicated an instantaneous nucleation with three-dimensional superstructures (Avrami index of approximately 3). The spherulitic nature of the superstructure was confirmed by POM. When the temperature was decreased to 30 degreesC, the PCL block was able to crystallize within the PLLA negative spherulites (with an Avrami index of 2, as opposed to 3 in homo-PCL), and its crystallization rate was much slower than an equivalent homo-PCL. Time-resolved SAXS experiments in (L60C409)-C-12 revealed an initial melt mixed morphology at 165 degreesC that upon cooling transformed into a transient microphase-separated lamellar structure prior to crystallization at 100 degreesC.

Thermal Fractionation and isothermal crystallization of polyethylene nanocomposites prepared by in situ polymerization

Nanocomposites of high-density polyethylene (HDPE) and carbon nanotubes (CNT) of different geometries (single wall, double wall, and multiwall; SWNT, DWNT, and MWNT) were prepared by in situ polymerization of ethylene on CNT whose surface had been previously treated with a metallocene catalytic system. In this work, we have studied the effects of applying the successive self-nucleation and annealing thermal fractionation technique (SSA) to the nanocomposites and have also determined the influence of composition and type of CNT on the isothermal crystallization behavior of the HDPE. SSA results indicate that all types of CNT induce the formation of a population of thicker lamellar crystals that melt at higher temperatures as compared to the crystals formed in neat HDPE prepared under the same catalytic and polymerization conditions and subjected to the same SSA treatment. Furthermore, the peculiar morphology induced by the CNT on the HDPE matrix allows the resolution of thermal fractionation to be much better. The isothermal crystallization results indicated that the strong nucleation effect caused by CNT reduced the supercooling needed for crystallization. The interaction between the HDPE chains and the surface of the CNT is probably very strong as judged by the results obtained, even though it is only physical in nature. When the total crystallinity achieved during isothermal crystallization is considered as a function of CNT content, it was found that a competition between nucleation and topological confinement could account for the results. At low CNT content the crystallinity increases (because of the nucleating effect of CNT on HDPE), however, at higher CNT content there is a dramatic reduction in crystallinity reflecting the increased confinement experienced by the HDPE chains at the interfaces which are extremely large in these nanocomposites. Another consequence of these strong interactions is the remarkable decrease in Avrami index as CNT content increases. When the Avrami index reduces to I or lower, nucleation dominates the overall kinetics as a consequence of confinement effects. Wide-angle X-ray experiments were performed at a high-energy synchrotron source and demonstrated that no change in the orthorhombic unit cell of HDPE occurred during crystallization with or without CNT.

Rate-dependent fracture toughness of polycrystalline ice

A series of three-point bend tests using single edge notched testpieces of pure polycrystalline ice have been performed at three different temperatures (–20°C, –30°C and –40°C). The displacement rate was varied from 1 mm/min to 100 mm/min, producing the crack tip strain rates from about 10–3 to 10–1 s–1. The results show that (a) the fracture toughness of pure polycrystalline ice given by the critical stress intensity factor (K IC) is much lower than that measured from the J—integral under identical conditions; (b) from the determination of K IC, the fracture toughness of pure polycrystalline ice decreases with increasing strain rate and there is good power law relationship between them; (c) from the measurement of the J—integral, a different tendency was appeared: when the crack tip strain rate exceeds a critical value of 6 × 10–3 s–1, the fracture toughness is almost constant but when the crack tip strain rate is less than this value, the fracture toughness increases with decreasing crack tip strain rate. Re-examination of the mechanisms of rate-dependent fracture toughness of pure polycrystalline ice shows that the effect of strain rate is related not only to the blunting of crack tips due to plasticity, creep and stress relaxation but also to the nucleation and growth of microcracks in the specimen.

Effects of variation in the palm stearin: palm olein ratio on the crystallisation of a low-trans shortening

Changes in the theological properties during crystallisation and in the crystal size and morphology of blends containing rapeseed oil with varying percentages of palm stearin (POs) and palm olein (POf) have been studied. The crystals formed from all three blends were studied by confocal laser scanning microscopy, light microscopy and environmental scanning electron microscopy, which revealed the development of clusters of 3-5 individual elementary "spherulites" in the early stages of crystallisation. The saturated triacylglycerol content of the solid crystals separated at the onset of crystallisation was much greater than that in the total fat. Fat blends with a higher content of palm stearin had a more rapid nucleation rate when observed by light microscopy, and this caused an earlier change in the rheological properties of the fat during crystallisation. Using a low torque amplitude (0.005 Pa, which was within the linear viscoelastic region of all samples studied) and a frequency of 1 Hz, the viscoelastic properties of melted fat during cooling were studied. All samples, prior to crystallisation, showed weak viscoelastic liquid behaviour (G '', loss modulus >G', storage modulus). After crystallisation a more "solid like" behaviour was observed (G' similar to or greater than G ''). The blend having the highest concentration of POs was found to have the earliest onset of crystallisation (27% w/w POs; 12 mins, 22% w/w POs; 13.5 mins, 17% w/w POs, 15 mins, respectively). However, there were no significant differences in the time to the point when G' became greater than G' among the three blends. (c) 2006 Elsevier Ltd. All rights reserved.

Comparison of predictions of baking volume using large deformation rheological properties

Three large deformation rheological tests, the Kieffer dough extensibility system, the D/R dough inflation system and the 2 g mixograph test, were carried out on doughs made from a large number of winter wheat lines and cultivars grown in Poland. These lines and cultivars represented a broad spread in baking performance in order to assess their suitability as predictors of baking volume. The parameters most closely associated with baking volume were strain hardening index, bubble failure strain, and mixograph bandwidth at 10min. Simple correlations with baking volume indicate that bubble failure strain and strain hardening index give the highest correlations, whilst the use of best subsets regression, which selects the best combination of parameters, gave increased correlations with R-2 = 0.865 for dough inflation parameters, R-2 = 0. 842 for Kieffer parameters and R-2 = 0.760 for mixograph parameters. (c) 2007 Elsevier Ltd. All rights reserved.

Rheology and the breadmaking process

The applications of rheology to the main processes encountered during breadmaking (mixing, sheeting, fermentation and baking) are reviewed. The most commonly used rheological test methods and their relationships to product functionality are reviewed. It is shown that the most commonly used method for rheological testing of doughs, shear oscillation dynamic rheology, is generally used under deformation conditions inappropriate for breadmaking and shows little relationship with end-use performance. The frequency range used in conventional shear oscillation tests is limited to the plateau region, which is insensitive to changes in the HMW glutenin polymers thought to be responsible for variations in baking quality. The appropriate deformation conditions can be accessed either by long-time creep or relaxation measurements, or by large deformation extensional measurements at low strain rates and elevated temperatures. Molecular size and structure of the gluten polymers that make up the major structural components of wheat are related to their rheological properties via modern polymer rheology concepts. Interactions between polymer chain entanglements and branching are seen to be the key mechanisms determining the rheology of HMW polymers. Recent work confirms the observation that the dynamic shear plateau modulus is essentially independent of variations in MW of glutens amongst wheat varieties of varying baking performance and also that it is not the size of the soluble glutenin polymers, but the secondary structural and rheological properties of the insoluble polymer fraction that are mainly responsible for variations in baking performance. Extensional strain hardening has been shown to be a sensitive indicator of entanglements and long-chain branching in HMW polymers, and is well related to baking performance of bread doughs. The Considere failure criterion for instability in extension of polymers defines a region below which bubble walls become unstable, and predicts that when strain hardening falls below a value of around 1, bubble walls are no longer stable and coalesce rapidly, resulting in loss of gas retention and lower volume and texture. Strain hardening in doughs has been shown to reach this value at increasingly higher temperatures for better breadmaking varieties and is directly related to bubble stability and baking performance. (C) 2003 Elsevier Ltd. All rights reserved.

The global atmospheric electrical circuit and climate

Evidence is emerging for physical links among clouds, global temperatures, the global atmospheric electrical circuit and cosmic ray ionisation. The global circuit extends throughout the atmosphere from the planetary surface to the lower layers of the ionosphere. Cosmic rays are the principal source of atmospheric ions away from the continental boundary layer: the ions formed permit a vertical conduction current to flow in the fair weather part of the global circuit. Through the (inverse) solar modulation of cosmic rays, the resulting columnar ionisation changes may allow the global circuit to convey a solar influence to meteorological phenomena of the lower atmosphere. Electrical effects on non-thunderstorm clouds have been proposed to occur via the ion-assisted formation of ultra-fine aerosol, which can grow to sizes able to act as cloud condensation nuclei, or through the increased ice nucleation capability of charged aerosols. Even small atmospheric electrical modulations on the aerosol size distribution can affect cloud properties and modify the radiative balance of the atmosphere, through changes communicated globally by the atmospheric electrical circuit. Despite a long history of work in related areas of geophysics, the direct and inverse relationships between the global circuit and global climate remain largely quantitatively unexplored. From reviewing atmospheric electrical measurements made over two centuries and possible paleoclimate proxies, global atmospheric electrical circuit variability should be expected on many timescales

Theoretical studies of the interface between water and Langmuir films of aliphatic alcohols

The interface between water and Langmuir films of long chain aliphatic molecules is investigated using accurate intermolecular potentials. The stabilities of various ice structures which could form at the interface are examined. Antiferroelectric ice is found to be the most stable, but this stability depends crucially on the first layer of water. Ferroelectric structures are found to collapse upon relaxation. Our model was not able to differentiate between the different nucleation properties of C31H63OH and C30H61OH. A better description of the alcohol–water interaction is probably required to account for this difference.

Chemical and aerosol characterisation of the troposphere over West Africa during the monsoon period as part of AMMA

During June, July and August 2006 five aircraft took part in a campaign over West Africa to observe the aerosol content and chemical composition of the troposphere and lower stratosphere as part of the African Monsoon Multidisciplinary Analysis (AMMA) project. These are the first such measurements in this region during the monsoon period. In addition to providing an overview of the tropospheric composition, this paper provides a description of the measurement strategy (flights performed, instrumental payloads, wing-tip to wing-tip comparisons) and points to some of the important findings discussed in more detail in other papers in this special issue. The ozone data exhibits an "S" shaped vertical profile which appears to result from significant losses in the lower troposphere due to rapid deposition to forested areas and photochemical destruction in the moist monsoon air, and convective uplift of ozone-poor air to the upper troposphere. This profile is disturbed, particularly in the south of the region, by the intrusions in the lower and middle troposphere of air from the southern hemisphere impacted by biomass burning. Comparisons with longer term data sets suggest the impact of these intrusions on West Africa in 2006 was greater than in other recent wet seasons. There is evidence for net photochemical production of ozone in these biomass burning plumes as well as in urban plumes, in particular that from Lagos, convective outflow in the upper troposphere and in boundary layer air affected by nitrogen oxide emissions from recently wetted soils. This latter effect, along with enhanced deposition to the forested areas, contributes to a latitudinal gradient of ozone in the lower troposphere. Biogenic volatile organic compounds are also important in defining the composition both for the boundary layer and upper tropospheric convective outflow. Mineral dust was found to be the most abundant and ubiquitous aerosol type in the atmosphere over Western Africa. Data collected within AMMA indicate that injection of dust to altitudes favourable for long-range transport (i.e. in the upper Sahelian planetary boundary layer) can occur behind the leading edge of mesoscale convective system (MCS) cold-pools. Research within AMMA also provides the first estimates of secondary organic aerosols across the West African Sahel and have shown that organic mass loadings vary between 0 and 2 μg m−3 with a median concentration of 1.07 μg m−3. The vertical distribution of nucleation mode particle concentrations reveals that significant and fairly strong particle formation events did occur for a considerable fraction of measurement time above 8 km (and only there). Very low concentrations were observed in general in the fresh outflow of active MCSs, likely as the result of efficient wet removal of aerosol particles due to heavy precipitation inside the convective cells of the MCSs. This wet removal initially affects all particle size ranges as clearly shown by all measurements in the vicinity of MCSs.