Accessibility of pores in coal to methane and carbon dioxide

Fluid–solid interactions in natural and engineered porous solids underlie a variety of technological processes, including geological storage of anthropogenic greenhouse gases, enhanced coal bed methane recovery, membrane separation, and heterogeneous catalysis. The size, distribution and interconnectivity of pores, the chemical and physical properties of the solid and fluid phases collectively dictate how fluid molecules migrate into and through the micro- and meso-porous media, adsorb and ultimately react with the solid surfaces. Due to the high penetration power and relatively short wavelength of neutrons, smallangle neutron scattering (SANS) as well as ultra small-angle scattering (USANS) techniques are ideally suited for assessing the phase behavior of confined fluids under pressure as well as for evaluating the total porosity in engineered and natural porous systems including coal. Here we demonstrate that SANS and USANS can be also used for determining the fraction of the pore volume that is actually accessible to fluids as a function of pore sizes and study the fraction of inaccessible pores as a function of pore size in three coals from the Illinois Basin (USA) and Bowen Basin (Australia). Experiments were performed at CO2 and methane pressures up to 780 bar, including pressures corresponding to zero average contrast condition (ZAC), which is the pressure where no scattering from the accessible pores occurs. Scattering curves at the ZAC were compared with the scattering from same coals under vacuum and analysed using a newly developed approach that shows that the volume fraction of accessible pores in these coals varies between �90% in the macropore region to �30% in the mesopore region and the variation is distinctive for each of the examined coals. The developed methodology may be also applied for assessing the volume of accessible pores in other natural underground formations of interest for CO2 sequestration, such as saline aquifers as well as for estimating closed porosity in engineered porous solids of technological importance.

Estimating local stream fish assemblage attributes: Sampling effort and efficiency at two spatial scales

As part of a wider study to develop an ecosystem-health monitoring program for wadeable streams of south-eastern Queensland, Australia, comparisons were made regarding the accuracy, precision and relative efficiency of single-pass backpack electrofishing and multiple-pass electrofishing plus supplementary seine netting to quantify fish assemblage attributes at two spatial scales (within discrete mesohabitat units and within stream reaches consisting of multiple mesohabitat units). The results demonstrate that multiple-pass electrofishing plus seine netting provide more accurate and precise estimates of fish species richness, assemblage composition and species relative abundances in comparison to single-pass electrofishing alone, and that intensive sampling of three mesohabitat units (equivalent to a riffle-run-pool sequence) is a more efficient sampling strategy to estimate reach-scale assemblage attributes than less intensive sampling over larger spatial scales. This intensive sampling protocol was sufficiently sensitive that relatively small differences in assemblage attributes (<20%) could be detected with a high statistical power (1-β > 0.95) and that relatively few stream reaches (<4) need be sampled to accurately estimate assemblage attributes close to the true population means. The merits and potential drawbacks of the intensive sampling strategy are discussed, and it is deemed to be suitable for a range of monitoring and bioassessment objectives.

Dielectric performance of polymer nanocomposites synthesized by atmospheric-pressure plasma-treated silica nanoparticles

In this study, atmospheric-pressure plasmas were applied to modify the surface of silane-coated silica nanoparticles. Subsequently nanocomposites were synthesized by incorporating plasma-treated nanoparticles into an epoxy resin matrix. Electrical testing showed that such novel dielectric materials obtained high partial discharge resistance, high dielectric breakdown strength, and enhanced endurance under highly stressed electric field. Through spectroscopic and microscopic analysis, we found surface groups of nanoparticles were activated and radicals were created after the plasma treatment. Moreover, a uniform dispersion of nanoparticles in nanocomposites was observed. It was expected that the improved dielectric performance of the nanocomposites can attribute to stronger chemical bonds formed between surface groups of plasma-treated nanoparticles and molecules in the matrix. This simple yet effective and environmentally friendly approach aims to synthesize the next generation of high-performance nanocomposite dielectric insulation materials for applications in high-voltage power systems.

Made-to-order nanocarbons through deterministic plasma nanotechnology

Through a combinatorial approach involving experimental measurement and plasma modelling, it is shown that a high degree of control over diamond-like nanocarbon film sp3/sp2 ratio (and hence film properties) may be exercised, starting at the level of electrons (through modification of the plasma electron energy distribution function). Hydrogenated amorphous carbon nanoparticle films with high percentages of diamond-like bonds are grown using a middle-frequency (2 MHz) inductively coupled Ar + CH4 plasma. The sp3 fractions measured by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy in the thin films are explained qualitatively using sp3/sp2 ratios 1) derived from calculated sp3 and sp2 hybridized precursor species densities in a global plasma discharge model and 2) measured experimentally. It is shown that at high discharge power and lower CH4 concentrations, the sp3/sp2 fraction is higher. Our results suggest that a combination of predictive modeling and experimental studies is instrumental to achieve deterministically grown made-to-order diamond-like nanocarbons suitable for a variety of applications spanning from nano-magnetic resonance imaging to spin-flip quantum information devices. This deterministic approach can be extended to graphene, carbon nanotips, nanodiamond and other nanocarbon materials for a variety of applications

The SEA-CALIPSO volcano imaging experiment at Montserrat : plans, campaigns at sea and on land, scientific results, and lessons learned

Since 1995 the eruption of the andesitic Soufrière Hills Volcano (SHV), Montserrat, has been studied in substantial detail. As an important contribution to this effort, the Seismic Experiment with Airgunsource-Caribbean Andesitic Lava Island Precision Seismo-geodetic Observatory (SEA-CALIPSO) experiment was devised to image the arc crust underlying Montserrat, and, if possible, the magma system at SHV using tomography and reflection seismology. Field operations were carried out in October–December 2007, with deployment of 238 seismometers on land supplementing seven volcano observatory stations, and with an array of 10 ocean-bottom seismometers deployed offshore. The RRS James Cook on NERC cruise JC19 towed a tuned airgun array plus a digital 48-channel streamer on encircling and radial tracks for 77 h about Montserrat during December 2007, firing 4414 airgun shots and yielding about 47 Gb of data. The main objecctives of the experiment were achieved. Preliminary analyses of these data published in 2010 generated images of heterogeneous high-velocity bodies representing the cores of volcanoes and subjacent intrusions, and shallow areas of low velocity on the flanks of the island that reflect volcaniclastic deposits and hydrothermal alteration. The resolution of this preliminary work did not extend beyond 5 km depth. An improved three-dimensional (3D) seismic velocity model was then obtained by inversion of 181 665 first-arrival travel times from a more-complete sampling of the dataset, yielding clear images to 7.5 km depth of a low-velocity volume that was interpreted as the magma chamber which feeds the current eruption, with an estimated volume 13 km3. Coupled thermal and seismic modelling revealed properties of the partly crystallized magma. Seismic reflection analyses aimed at imaging structures under southern Montserrat had limited success, and suggest subhorizontal layering interpreted as sills at a depth of between 6 and 19 km. Seismic reflection profiles collected offshore reveal deep fans of volcaniclastic debris and fault offsets, leading to new tectonic interpretations. This chapter presents the project goals and planning concepts, describes in detail the campaigns at sea and on land, summarizes the major results, and identifies the key lessons learned.

Modelling of a magnetocaloric system for cooling in the kilowatt range

A numerical time-dependent model of an active magnetic regenerator (AMR) was developed for cooling in the kilowatt range. Earlier numerical models have been mostly developed for cooling power in the 0.4 kW range. In contrast, this paper reports the applicability of magnetic refrigeration to the 50 kW range. A packed bed active magnetic regenerator was modelled and the influence of parameters such as geometry and operating parameters were studied for different geometries. The pressure drop for AMR bed length and particle diameter was also studied. High cooling power and coefficient of performance (COP) were achieved by optimization of the diameter of the magnetocaloric powder particles and operating frequency. The optimum operating conditions of the AMR for a cooling capacity of 50 kW was determined for a temperature span of 15 K. The predicted coefficient of performance (COP) was found to be ∼6, making it an attractive alternative to vapour compression systems.

Adaptive compliance control of a multi‐legged stair‐climbing robot based on proprioceptive data

Purpose – The purpose of this paper is to describe an innovative compliance control architecture for hybrid multi‐legged robots. The approach was verified on the hybrid legged‐wheeled robot ASGUARD, which was inspired by quadruped animals. The adaptive compliance controller allows the system to cope with a variety of stairs, very rough terrain, and is also able to move with high velocity on flat ground without changing the control parameters. Design/methodology/approach – The paper shows how this adaptivity results in a versatile controller for hybrid legged‐wheeled robots. For the locomotion control we use an adaptive model of motion pattern generators. The control approach takes into account the proprioceptive information of the torques, which are applied on the legs. The controller itself is embedded on a FPGA‐based, custom designed motor control board. An additional proprioceptive inclination feedback is used to make the same controller more robust in terms of stair‐climbing capabilities. Findings – The robot is well suited for disaster mitigation as well as for urban search and rescue missions, where it is often necessary to place sensors or cameras into dangerous or inaccessible areas to get a better situation awareness for the rescue personnel, before they enter a possibly dangerous area. A rugged, waterproof and dust‐proof corpus and the ability to swim are additional features of the robot. Originality/value – Contrary to existing approaches, a pre‐defined walking pattern for stair‐climbing was not used, but an adaptive approach based only on internal sensor information. In contrast to many other walking pattern based robots, the direct proprioceptive feedback was used in order to modify the internal control loop, thus adapting the compliance of each leg on‐line.

Can’t see the trees for the forest? Why IS-ServQual items matter

Despite longstanding concern with the dimensionality of the service quality construct as measured by ServQual and IS-ServQual instruments, variations on the IS-ServQual instrument have been enduringly prominent in both academic research and practice in the field of IS. We explain the continuing popularity of the instrument based on the salience of the item set for predicting overall customer satisfaction, suggesting that the preoccupation with the dimensions has been a distraction. The implicit mutual exclusivity of the items suggests a more appropriate conceptualization of IS-ServQual as a formative index. This conceptualization resolves the paradox in IS-ServQual research, that of how an instrument with such well-known and well-documented weaknesses continue to be very influential and widely used by academics and practitioners. A formative conceptualization acknowledges and addresses the criticisms of IS-ServQual, while simultaneously explaining its enduring salience by focusing on the items rather than the “dimensions.” By employing an opportunistic sample and adopting the most recent IS-ServQual instrument published in a leading IS journal (virtually, any valid IS- ServQual sample in combination with a previously tested instrument variant would suffice for study purposes), we demonstrate that when re-specified as both first-order and second-order formatives, IS-ServQual has good model quality metrics and high predictive power on customer satisfaction. We conclude that this formative specification has higher practical use and is more defensible theoretically.

Polymorphism in codon 17 of the CTLA-4 gene (+49 A/G) is not associated with susceptibility to rheumatoid arthritis in British Caucasians

The role of the CTLA-4 antigen in the development of autoimmune diseases is well documented, with several autoimmune disorders showing association or linkage with the CTLA-4 locus. Its role in the aetiology of rheumatoid arthritis (RA) however, remains unclear, as the functional studies of the B7-CTLA-4 pathway in mouse models of RA and genetic studies in humans have given contrasting results. We have studied the single nucleotide polymorphism at position +49 (A/G) of the CTLA-4 gene, in a cohort of 421 RA cases and 452 healthy controls from the UK. Despite the high statistical power to detect even a weak susceptibility effect, no significant association was found. We also analysed the distribution of the allele and genotype frequencies with respect to the presence of the shared epitope (a known RA susceptibility factor) and found no statistically significant differences. We conclude that, although the importance of the B7-CTLA-4 interaction in the development of RA can not be excluded, the CTLA-4 gene is unlikely to be a predisposing factor to this disease.

Defect-selective photothermal imaging: a sensitive tool for damage mapping in optical coatings

A defect-selective photothermal imaging system for the diagnostics of optical coatings is demonstrated. The instrument has been optimized for pump and probe parameters, detector performance, and signal processing algorithm. The imager is capable of mapping purely optical or thermal defects efficiently in coatings of low damage threshold and low absorbance. Detailed mapping of minor inhomogeneities at low pump power has been achieved through the simultaneous action of a low-noise fiber optic photothermal beam defection sensor and a common-mode-rejection demodulation (CMRD) technique. The linearity and sensitivity of the sensor have been examined theoretically and experimentally, and the signal to noise ratio improvement factor is found to be about 110 compared to a conventional bicell photodiode. The scanner is so designed that mapping of static or shock sensitive samples is possible. In the case of a sample with absolute absorptance of 3.8 x 10(-4), a change in absorptance of about 0.005 x 10(-4) has been detected without ambiguity, ensuring a contrast parameter of 760. This is about 1085% improvement over the conventional approach containing a bicell photodiode, at the same pump power. The merits of the system have been demonstrated by mapping two intentionally created damage sites in a MgF2 coating on fused silica at different excitation powers. Amplitude and phase maps were recorded for thermally thin and thick cases, and the results are compared to demonstrate a case which, in conventional imaging, would lead to a deceptive conclusion regarding the type and location of the damage. Also, a residual damage profile created by long term irradiation with high pump power density has been depicted.

Studies on low-intensity oxy-fuel burner

This paper presents experimental and computational results of oxy-fuel burner operating on classical flame and lameless mode for heat release rate of 26 kW/m3. The uniqueness of the burner arises from a slight asymmetric injection of oxygen at near sonic velocities. Measurements of emperature, species, total heat flux, radiative heat flux and NOx emission were carried out inside the furnace and the flow field was computationally analyzed. The flame studies were carried out for coaxial flow of oxygen and fuel jets with similar inlet velocities. This configuration results in slow mixing between fuel and oxygen and the flame is developed at distance away from the burner and the flame is bright/white in colour. In the flameless mode a slight asymmetric injection of the high velocity oxygen jet leads to a large asymmetric recirculation pattern with the recirculation ratio of 25 and the resulting flame is weak bluish in colour with little soot and acetylene formation. The classical flame in comparison is characterised by soot and acetylene formation, higher NOx and noise generation. The distribution of temperature and heat flux in the furnace is more uniform with flameless mode than with flame mode.

Suomen maankuoren kivilajikoostumuksen tulkinta seismisistä aineistoista

Aim of this study is to investigate composition of the crust in Finland using seismic wide-angle velocity models and laboratory measurements on P- and S-wave velocities of different rock types. The velocities adopted from wide-angle velocity models were compared with laboratory velocities of different rock types corrected for the crustal PT conditions in the study area. The wide-angle velocity models indicate that the P-wave velocity does not only increase step-wise at boundaries of major crustal layers, but there is also gradual increase of velocity within the layers. On the other hand, the laboratory measurements of velocities indicate that no single rock type is able to provide the gradual downward increasing trends. Thus, there must be gradual vertical changes in rock composition. The downward increase of velocities indicates that the composition of the crust becomes gradually more mafic with increasing depth. Even though single rock types cannot simulate the wide-angle model velocities, it can be done with a mixture of rock types. There are a large number of rock type mixtures giving the correct P-wave velocities. Therefore, the inverse solution of rock types and their proportions from velocities is a non-unique problem if only P-wave velocities is available. Amount of the possible rock type mixtures can be limitted using S-wave velocities, reflection seismic results and other geological and geophysical results of the study area. Crustal model FINMIX-2 is presented in this study and it suggest that the crustal velocity profiles can be simulated with rock type mixtures, where the upper crust consists of felsic gneisses and granitic-granodioritic rocks with a minor contribution of quartzite, amphibolite and diabase. In the middle crust the amphibolite proportion increases. The lower crust consists of tonalitic gneiss, mafic garnet granulite, hornblendite, pyroxenite and minor mafic eclogite. This composition model is in agreement with deep crustal kimberlite-hosted xenolith data in eastern Finland and reflectivity of the FIRE (Finnish Reflection Experiment). According to FINMIX-2 model the Moho is deeper and the crustal composition is a more mafic than an average global continental model would suggest. Composition models of southern Finland are quite similar than FINMIX-2 model. However, there are minor differencies between the models, which indicates areal differences of composition. Models of northern Finland shows that the crustal thickness is smaller than southern Finland and composition of the upper crust is different. Density profiles calculated from the lithological models suggest that there is practically no density contrast at Moho in areas of the high-velocity lower crust. This implies that crustal thickness in the central Fennoscandian Shield may have been controlled by the densities of the lower crustal and upper mantle rocks.

Accelerator Mass Spectrometry and Bayesian Data Analysis

Accelerator mass spectrometry (AMS) is an ultrasensitive technique for measuring the concentration of a single isotope. The electric and magnetic fields of an electrostatic accelerator system are used to filter out other isotopes from the ion beam. The high velocity means that molecules can be destroyed and removed from the measurement background. As a result, concentrations down to one atom in 10^16 atoms are measurable. This thesis describes the construction of the new AMS system in the Accelerator Laboratory of the University of Helsinki. The system is described in detail along with the relevant ion optics. System performance and some of the 14C measurements done with the system are described. In a second part of the thesis, a novel statistical model for the analysis of AMS data is presented. Bayesian methods are used in order to make the best use of the available information. In the new model, instrumental drift is modelled with a continuous first-order autoregressive process. This enables rigorous normalization to standards measured at different times. The Poisson statistical nature of a 14C measurement is also taken into account properly, so that uncertainty estimates are much more stable. It is shown that, overall, the new model improves both the accuracy and the precision of AMS measurements. In particular, the results can be improved for samples with very low 14C concentrations or measured only a few times.

A dynamical approach to the spatio-temporal features of the Portevin-Le Chatelier effect

We show that the extended Ananthakrishna's model exhibits all the features of the Portevin - Le Chatelier effect including the three types of bands. The model reproduces the recently observed crossover from a low dimensional chaotic state at low and medium strain rates to a high dimensional power law state of stress drops at high strain rates. The dynamics of crossover is elucidated through a study of the Lyapunov spectrum.

Study of gas cavity size hysteresis in a packed bed using DEM

When a high velocity gas jet is introduced into a packed bed a cavity is formed. The size of the cavity shows hysteresis on increasing and decreasing gas flow rates. This hysteresis leads to different cavity sizes at same gas flow rate depending on the bed history. The size of cavity affects the gas flow profiles in the packed bed. In this study the cavity size hysteresis phenomenon has been modeled using discrete element method along with turbulent gas flow. A reasonable agreement has been found between computed and experimental results on cavity size ysteresis. The effect of various parameters, such as nozzle height from the bed bottom and packing height, on the cavity size hysteresis has been studied. It is found that inter-particle interaction forces along with gas drag and bed porosity play an important role in describing the cavity size hysteresis. The injection of gas flow allows the particles to go to an unconstrained state than they were previously in, and their ability to remain in that state, even under decreased gas drag force, leads to the phenomenon of cavity size hysteresis. (c) 2007 Elsevier Ltd. All rights reserved.