Very high methane uptake on activated carbons prepared from mesophase pitch: A compromise between microporosity and bulk density

Two petroleum residues were pyrolyzed under two different conditions to obtain pitches with low or high mesophase content. The effect of the KOH: precursor ratio and the activation temperature on the packing density and porous texture of the carbons have been studied and optimized. Activated carbons combining high micropore volume (>1 cm3/g) and high packing density (0.7 g/cm3) have been successfully prepared. Regarding excess methane adsorption capacities, the best results (160 cm3 (STP)/cm3 at 25 °C and 3.5 MPa) were obtained using the pitch with the higher content of the more organized mesophase, activated at relatively low temperature (700 °C), with a medium KOH: precursor ratio (3:1). Some of the activated carbons exhibit enhanced adsorption capacity at high pressure, giving values as high as 175 cm3 (STP)/cm3 at 25 °C and 5 MPa and 200 cm3 (STP)/cm3 at 25 °C and 10 MPa (the same amount as in an empty cylinder but at half of the pressure), indicating a contribution of large micropores and narrow mesopores to adsorption at high pressure. The density of methane in pores between 1 and 2.5 nm at pressure up to 10 MPa was estimated to understand their contribution to the total adsorption capacity.

Global assessment of soil phosphorus retention potential

Limited availability of P in soils to crops may be due to deficiency and/or severe P retention. Earlier studies that drew on large soil profile databases have indicated that it is not (yet) feasible to present meaningful values for "plant-available" soil P, obtained according to comparable analytical methods, that may be linked to soil geographical databases derived from 1:5 million scale FAO Digital Soil Map of the World, such as the 5 x 5 arc-minute version of the ISRIC-WISE database. Therefore, an alternative solution for studying possible crop responses to fertilizer-P applied to soils, at a broad scale, was sought. The approach described in this report considers the inherent capacity of soils to retain phosphorus (P retention), in various forms. Main controlling factors of P retention processes, at the broad scale under consideration, are considered to be pH, soil mineralogy, and clay content. First, derived values for these properties were used to rate the inferred capacity for P retention of the component soil units of each map unit (or grid cell) using four classes (i.e., Low, Moderate, High, and Very High). Subsequently, the overall soil phosphorus retention potential was assessed for each mapping unit, taking into account the P-ratings and relative proportion of each component soil unit. Each P retention class has been assigned to a likely fertilizer P recovery fraction, derived from the literature, thereby permitting spatially more detailed, integrated model-based studies of environmental sustainability and agricultural production at the global and continental level (< 1:5 million). Nonetheless, uncertainties remain high; the present analysis provides an approximation of world soil phosphorus retention potential.

(Table 1) Petrological description and consolidation properties of ODP Site 186-1150 and Hole 186-1151A

In order to determine the shear parameters of the forearc sedimentary strata drilled during Ocean Drilling Program Leg 186, West Pacific Seismic Network, Japan Trench, eight whole-round samples were selected from different depths in the drilled sections of Sites 1150 and 1151. Whereas Site 1150 lays above the seismically active part of the subduction zone, Site 1151 is situated in an aseismic zone. The aim of the triaxial tests was, apart from determination of the static stress strain behavior of the sediments, to test the hypothesis that the static stress strain parameter could differ for each sites. In order to simulate undrained deformation conditions according to the high clay mineral content of the strata, consolidated undrained shear tests were performed in a triaxial testing setup. Measurements of water content, grain density, organic content, and microtextural investigations under the scanning electron microscope (SEM) accompanied the compression experiments. After the saturation and consolidation stages were completed, failure occurred in the compression stage of the experiments at peak strengths of 280-7278 kPa. The stiffness moduli calculated for each sample from differential stress vs. strain curves show a linear relationship with depth and range between 181 and 5827 kPa. Under the SEM, the artificial fault planes of the tested specimen only show partial alignment of clay minerals because of the high content of microfossils.

Abundance of calcareous nannofossils across the K/T boundary at ODP Hole 113-690C (Table 1)

A biostratigraphically continuous, but intensely bioturbated, Cretaceous/Tertiary boundary sequence was cored during Ocean Drilling Program (ODP) Leg 113 on Maud Rise (65°S) in the Weddell Sea off East Antarctica. This interval is the first recovered by ODP/DSDP in the South Atlantic sector of the Southern Ocean and offers a unique opportunity to study the nannofossil sequences leading up to and beyond the terminal Cretaceous event at a high southern latitude. The K/T boundary lies just within Chron 29R and is placed at ODP Sample 113-690C-15X-4, 41.5 cm. An iridium anomaly was independently noted at about this level as well. Upper Maestrichtian-lower Paleocene sediments consist mostly of light-colored nannofossil chalks. Dark brown sediments at the base of the Danian (Zone CPla) are characterized by an increased clay content attributed to a drop in calcareous microplankton productivity following the terminal Cretaceous event. Although delineation of the boundary is hampered by intense bioturbation, the sharp color contrast between overlying clay-rich, dark brown chalks of the Tertiary and light cream colored chalks of the Cretaceous aids in the selection of the K/T horizon. Several dark colored burrows sampled at intervals as far as 1.3 m below the boundary and within the light colored Cretaceous chalk were found to contain up to 17% Tertiary nannofossils. Calcareous nannofossils from the boundary interval were divided into three groups for quantitative study. The three groups, "Cretaceous," "Tertiary," and "Survivor," exhibit a sequential change across the boundary with the Cretaceous forms giving way to a Survivor-dominated assemblage beginning at the boundary followed shortly thereafter by the appearance of the Tertiary taxa, Cruciplacolithus and Hornibrookina. The species, H. edwardsii, comprises nearly 50% of the assemblage just above the Zone CPla/CPlb boundary, an abundance not reported elsewhere at this level. Calculation of individual species abundances reveals several additional differences between this K/T boundary interval and those studied from middle and low latitude sections. The percentage of Thoracosphaera is much lower at the boundary in this section and a small form, Prediscosphaera stoveri, is extremely abundant in Cretaceous sediments just below the boundary.

Description of recent sediments of Nile Delta, Red Sea and Gulf of Aden (Table 1-3)

The study of textural, structural, chemical, and physical properties of fine-grained recent marine sediments leads to the conclusion that only a few compositional factors are responsible for significant changes in mass physical characteristics in the upper meters below sea bottom. Fossil-induced porosity increases water content and liquid limit. It also seems to have partially influenced the plastic limit and plasticity index of calcareous sandy silts from the Red Sea and the western Gulf of Aden so that they become similar to the montmorillonite rich prodelta clays from the Nile Delta. Diagrams based on liquid limit and plasticity loose their original meaning in these cases. Activity of sediments rich in microorganisms can be higher than that of montmorillonitic clay. The shear strength-depth relationship of normally consolidated sediments is surprisingly little influenced by changes in sand or clay content and clay mineralogy. Only high lime content, submarine erosion and beginning cementation increase the strength considerably. Erosional disconformities near the present surface can be deduced from the strength-depth curve when as little as 1 or 2 m sediment have been removed. Flat or irregular strength-depth curves indicate beginning cementation and probably discontinuous sedimentation, provided the composition of the material remains in some degree constant. In our samples diagenetic pyrite, but no recristallisation of carbonates could be detected under the microscope. Underconsolidation and excess pore-water pressure, factors which tend to foster submarine slides, mud lumps, and diapiric folding, seem to be restricted Varito areas with mainly rapidly deposited, homogeneous or layered sediments. But where an abundance of burrowing organisms increases the vertical permeability of the sediment, normal consolidation and stable deposits are to be expected, at least in the upper meters below the present surface. According to 14C-determinations on calcareous microorganisms the rate of deposition of the investigated sediments seems to range from 26 to 167 cm per 1000 years.

Age model of ODP Site 184-1146 (Table 1)

Clay mineral assemblages at ODP Site 1146 in the northern South China Sea are used to investigate sediment source and transport processes and to evaluate the evolution of the East Asian monsoon over the past 2 Myr. Clay minerals consist mainly of illite (22-43%) and smectite (12-48%), with associated chlorite (10-30%), kaolinite (2-18%), and random mixed-layer clays (5-22%). Hydrodynamic and mineralogical studies indicate that illite and chlorite sources include Taiwan and the Yangtze River, that smectite and mixed-layer clays originate predominantly from Luzon and Indonesia, and that kaolinite is primarily derived from the Pearl River. Mineral assemblages indicate strong glacial-interglacial cyclicity, with high illite, chlorite, and kaolinite content during glacials and high smectite and mixed-layer clay content during interglacials. During interglacials, summer enhanced monsoon (southwesterly) currents transport more smectite and mixed-layer clays to Site 1146 whereas during glacials, enhanced winter monsoon (northerly) currents transport more illite and chlorite from Taiwan and the Yangtze River. The ratio (smectite+mixed layers)/(illite+chlorite) was adopted as a proxy for East Asian monsoon variability. Higher ratios indicate strengthened summer-monsoon winds and weakened winter-monsoon winds during interglacials. In contrast, lower ratios indicate a strongly intensified winter monsoon and weakened summer monsoon during glacials. Spectral analysis indicates the mineral ratio was dominantly forced by monsoon variability prior to the development of large-scale glaciation at 1.2 Myr and by both monsoon variability and the effects of changing sea level in the interval 1.2 Myr to present.

Correlation between wet bulk density and carbonate content from IODP Hole 321-U1338A, 321-U1338B and 321-U1338C

Sediment cores collected from the Eastern Equatorial Pacific Ocean display a clear positive second-order relationship between wet bulk density (WBD) and carbonate content. This has long interested the paleoceanography community because detailed Gamma Ray Attenuation Porosity Evaluator (GRAPE) measurements, which approximate WBD, might be used to determine records of carbonate content at very high temporal resolution. Although general causes for the relationship are known, they have not been presented and discussed systematically on the basis of first principles. In this study, we measure the mass and carbonate content of 50 sediment samples with known WBD from Site U1338, before and after rinsing with de-ionized water; we also determine the mass related proportion of coarse (> 63 µm) material. Samples exhibit clear relationships between WBD, carbonate content, mass loss upon rinsing, and grain size. We develop a series of mathematical expressions to describe these relationships, and solve them numerically. As noted by previous workers, the second-order relationship between WBD and carbonate content results from the mixing of biogenic carbonate and biogenic silica, which have different grain densities and different porosities. However, at high carbonate content, a wide range in WBD occurs because samples with greater amounts of coarse carbonate have higher porosity. Moreover compaction impacts carbonate particles more than biogenic silica particles. As such, a single two-component equation cannot be used to determine carbonate content accurately across depth intervals where both the porosity and type of carbonate vary. Instead, the WBD-carbonate relationship is described by an infinite series of curves, each which represents mixing of multiple sediment components with different densities and porosities. Dissolved ions also precipitate from pore space during sample drying, which adds mass to the sediment. Without rinsing samples, simple empirical relationships between WBD and carbonate content are further skewed by salt dilution.

Wear of high aluminium zinc-based alloys in plain bearing applications

Two zinc-based alloys of high aluminium content, Super Cosmal alloy containing 60% Al, 6% Si, 1% Cu, 0.3% Mn and HAZCA alloy containing 60% Al, 8% Si, 2% Cu, 0.06% Mg were produced by sand casting. Foundry characteristics in particular, fluidity, mode of solidification and feeding ability were examined. Metallographic analysis of structures was carried out using optical and scanning electron microscopy and their mechanical properties were determined using standard techniques. Dry wear characteristics were determined using a pin-on-disc test, and boundary-lubricated wear was studied using full bearing tests. Results from casting experiments were evaluated and compared with the behaviour of a standard ZA-27 alloy and those from tribological tests with both ZA-27 alloy and a leaded tin-bronze (SAE660) under the same testing conditions. The presence of silicon was beneficial, reducing the temperature range of solidification, improving feeding efficiency and reducing gravity segregation of phases. Use of chills and melt degassing was found necessary to achieve soundness and enhanced mechanical properties. Dry wear tests were performed against a steel counterface for sliding speeds of 0.25, 0.5, 1.0 and 2 m/s and for a range of loads up to 15 kgf. The high aluminium alloys showed wear rates as low as those of ZA-27 at speeds of 0.25 and 0.5 m/s for the whole range of applied loads. ZA-27 performed better at higher speeds. The build up of a surface film on the wearing surface of the test pins was found to be responsible for the mild type of wear of the zinc based alloys. The constitution of the surface film was determined as a complex mixture of aluminium, zinc and iron oxides and metallic elements derived from both sliding materials. For full bearing tests, bushes were machined from sand cast bars and were tested against a steel shaft in the presence of a light spindle oil as the lubricant. Results showed that all zinc based alloys run-in more rapidly than bronze, and that wear in Super Cosmal and HAZCA alloys after prolonged running were similar to those in ZA-27 bearings and significantly smaller than those of the bronze.

Comparing dissimilarity measures for content-based image retrieval

Dissimilarity measurement plays a crucial role in content-based image retrieval, where data objects and queries are represented as vectors in high-dimensional content feature spaces. Given the large number of dissimilarity measures that exist in many fields, a crucial research question arises: Is there a dependency, if yes, what is the dependency, of a dissimilarity measure’s retrieval performance, on different feature spaces? In this paper, we summarize fourteen core dissimilarity measures and classify them into three categories. A systematic performance comparison is carried out to test the effectiveness of these dissimilarity measures with six different feature spaces and some of their combinations on the Corel image collection. From our experimental results, we have drawn a number of observations and insights on dissimilarity measurement in content-based image retrieval, which will lay a foundation for developing more effective image search technologies.

Facilitating intuitive-guided learning in a serious game through integration with a learning content management system

Increased global uptake of entertainment gaming has the potential to lead to high expectations of engagement and interactivity from users of technology-enhanced learning environments. Blended approaches to implementing game-based learning as part of distance or technology-enhanced education have led to demonstrations of the benefits they might bring, allowing learners to interact with immersive technologies as part of a broader, structured learning experience. In this article, we explore how the integration of a serious game can be extended to a learning content management system (LCMS) to support a blended and holistic approach, described as an 'intuitive-guided' method. Through a case study within the EU-Funded Adaptive Learning via Intuitive/Interactive, Collaborative and Emotional Systems (ALICE) project, a technical integration of a gaming engine with a proprietary LCMS is demonstrated, building upon earlier work and demonstrating how this approach might be realized. In particular, how this method can support an intuitive-guided approach to learning is considered, whereby the learner is given the potential to explore a non-linear environment whilst scaffolding and blending provide guidance ensuring targeted learning objectives are met. Through an evaluation of the developed prototype with 32 students aged 14-16 across two Italian schools, a varied response from learners is observed, coupled with a positive reception from tutors. The study demonstrates that challenges remain in providing high-fidelity content in a classroom environment, particularly as an increasing gap in technology availability between leisure and school times emerges.

Energy conversion assessment of vacuum, slow and fast pyrolysis processes for low and high ash paper waste sludge

The performance of vacuum, slow and fast pyrolysis processes to transfer energy from the paper waste sludge (PWS) to liquid and solid products was compared. Paper waste sludges with low and high ash content (8.5 and 46.7 wt.%) were converted under optimised conditions for temperature and pellet size to maximise both product yields and energy content. Comparison of the gross energy conversions, as a combination of the bio-oil/tarry phase and char (ECsum), revealed that the fast pyrolysis performance was between 18.5% and 20.1% higher for the low ash PWS, and 18.4% and 36.5% higher for high ash PWS, when compared to the slow and vacuum pyrolysis processes respectively. For both PWSs, this finding was mainly attributed to higher production of condensable organic compounds and lower water yields during FP. The low ash PWS chars, fast pyrolysis bio-oils and vacuum pyrolysis tarry phase products had high calorific values (∼18-23 MJ kg-1) making them promising for energy applications. Considering the low calorific values of the chars from alternative pyrolysis processes (∼4-7 MJ kg-1), the high ash PWS should rather be converted to fast pyrolysis bio-oil to maximise the recovery of usable energy products.

A compartmental CFD-PBM model of high shear wet granulation

The conventional, geometrically lumped description of the physical processes inside a high shear granulator is not reliable for process design and scale-up. In this study, a compartmental Population Balance Model (PBM) with spatial dependence is developed and validated in two lab-scale high shear granulation processes using a 1.9L MiPro granulator and 4L DIOSNA granulator. The compartmental structure is built using a heuristic approach based on computational fluid dynamics (CFD) analysis, which includes the overall flow pattern, velocity and solids concentration. The constant volume Monte Carlo approach is implemented to solve the multi-compartment population balance equations. Different spatial dependent mechanisms are included in the compartmental PBM to describe granule growth. It is concluded that for both cases (low and high liquid content), the adjustment of parameters (e.g. layering, coalescence and breakage rate) can provide a quantitative prediction of the granulation process.

Negative relationships between the nutrient and carbohydrate content of the seagrass Thalassia testudinum

This study documents relationships between plant nutrient content and rhizome carbohydrate content of a widely distributed seagrass species, Thalassia testudinum, in Florida. Five distinct seagrass beds were sampled for leaf nitrogen, leaf phosphorus, and rhizome carbohydrate content from 1997 to 1999. All variables displayed marked intra- and inter- regional variation. Elemental ratios (mean N:P ± S.E.) were lowest for Charlotte Harbor (9.9 ± 0.2) and highest for Florida Bay (53.5 ± 0.9), indicating regional shifts in the nutrient content of plant material. Rhizome carbohydrate content (mean ± S.E.) was lowest for Anclote Keys (21.8 ± 1.6 mg g−1 FM), and highest for Homosassa Bay (40.7 ± 1.7 mg g−1 FM). Within each region, significant negative correlations between plant nutrient and rhizome carbohydrate content were detected; thus, nutrient-replete plants displayed low carbohydrate content, while nutrient-deplete plants displayed high carbohydrate content. Spearman's rank correlations between nutrient and carbohydrate content varied from a minimum in Tampa Bay (ρ = −0.2) to a maximum in Charlotte Harbor (ρ = −0.73). Linear regressions on log-transformed data revealed similar trends. This consistent trend across five distinct regions suggests that nutrient supply may play an important role in the regulation of carbon storage within seagrasses. Here we present a new hypothesis for studies which aim to explain the carbohydrate dynamics of benthic plants.

High pressure and low temperature study of ammonia borane and lithium amidoborane

Hydrogen has been considered as a potentially efficient and environmentally friendly alternative energy solution. However, one of the most important scientific and technical challenges that the "hydrogen economy" faces is the development of safe and economically viable on-board hydrogen storage for fuel cell applications, especially to the transportation sector. Ammonia borane (BH3NH 3), a solid state hydrogen storage material, possesses exceptionally high hydrogen content (19.6 wt%).However, a fairly high temperature is required to release all the hydrogen atoms, along with the emission of toxic borazine. Recently research interests are focusing on the improvement of H2 discharge from ammonia borane (AB) including lowering the dehydrogenation temperature and enhancing hydrogen release rate using different techniques. Till now the detailed information about the bonding characteristics of AB is not sufficient to understand details about its phases and structures. ^ Elemental substitution of ammonia borane produces metal amidoboranes. Introduction of metal atoms to the ammonia borane structure may alter the bonding characteristics. Lithium amidoborane is synthesized by ball milling of ammonia borane and lithium hydride. High pressure study of molecular crystal provides unique insight into the intermolecular bonding forces and phase stability. During this dissertation, Raman spectroscopic study of lithium amidoborane has been carried out at high pressure in a diamond anvil cell. It has been identified that there is no dihydrogen bond in the lithium amidoborane structure, whereas dihydrogen bond is the characteristic bond of the parent compound ammonia borane. It has also been identified that the B-H bond becomes weaker, whereas B-N and N-H bonds become stronger than those in the parent compound ammonia borane. At high pressure up to 15 GPa, Raman spectroscopic study indicates two phase transformations of lithium amidoborane, whereas synchrotron X-ray diffraction data indicates only one phase transformation of this material. ^ Pressure and temperature has a significant effect on the structural stability of ammonia borane. This dissertation explored the phase transformation behavior of ammonia borane at high pressure and low temperature using in situ Raman spectroscopy. The P-T phase boundary between the tetragonal (I4mm) and orthorhombic (Pmn21) phases of ammonia borane has been determined. The transition has a positive Clapeyron slope which indicates the transition is of exothermic in nature. Influence of nanoconfinemment on the I4mm to Pmn2 1 phase transition of ammonia borane was also investigated. Mesoporus silica scaffolds SBA-15 with pore size of ~8 nm and MCM-41 with pore size of 2.1-2.7 nm, were used to nanoconfine ammonia borane. During cooling down, the I4mm to Pmn21 phase transition was not observed in MCM-41 nanoconfined ammonia borane, whereas the SBA-15 nanocondfined ammonia borane shows the phase transition at ~195 K. Four new phases of ammonia borane were also identified at high pressure up to 15 GPa and low temperature down to 90 K.^

Novos adsorventes para aplicação na remoção de enxofre de combustíveis

Currently the market requires increasingly pure oil derivatives and, with that, comes the need for new methods for obtaining those products that are more efficient and economically viable. Considering the removal of sulfur from diesel, most refineries uses catalytic hydrogenation process, the hydrodesulfurization. These processes needs high energy content and high cost of production and has low efficiency in removing sulfur at low concentrations (below 500 ppm). The adsorption presents itself as an efficient and economically viable alternative in relation to the techniques currently used. With that, the main purpose of this work is to develop and optimize the obtaining of new adsorbents based on diatomite, modified with two non ionic surfactants microemulsions, adding efficiency to the material, to its application on removal of sulfur present in commercial diesel. Analyses were undertaken of scanning electron microscopy (SEM), x-ray diffraction (XRD), x-ray fluorescence (XRF), thermogravimetry (TG) and N2 adsorption (BET) for characterization of new materials obtained. The variables used for diatomite modification were: microemulsion points for each surfactant (RNX 95 and UNTL 90), microemulsion aqueous phase through the use or non-use of salts (CaCl2 and BaCl2), the contact time during the modification and the contact form. The study of adsorption capacity of materials obtained was performed using a statistical modeling to evaluate the influence of salt concentration in the aqueous phase (20 ppm to 1500 ppm), finite bath temperature (25 to 60° C) and the concentration of sulphur in diesel. It was observed that the temperature and the concentration of sulphur (300 to 1100 ppm) were the most significant parameters, in which increasing their values increase the ability of modified clay to adsorb the sulphur in diesel fuel. Adsorption capacity increased from 0.43 to mg/g 1.34 mg/g with microemulsion point optimization and with the addition of salts.