Dense carbon monoliths for supercapacitors with outstanding volumetric capacitances

A commercially available dense carbon monolith (CM) and four carbon monoliths obtained from it have been studied as electrochemical capacitor electrodes in a two-electrode cell. CM has: (i) very high density (1.17 g cm−3), (ii) high electrical conductivity (9.3 S cm−1), (iii) well-compacted and interconnected carbon spheres, (iv) homogeneous microporous structure and (v) apparent BET surface area of 957 m2g−1. It presents interesting electrochemical behaviors (e.g., excellent gravimetric capacitance and outstanding volumetric capacitance). The textural characteristics of CM (porosity and surface chemistry) have been modified by means of different treatments. The electrochemical performances of the starting and treated monoliths have been analyzed as a function of their porous textures and surface chemistry, both on gravimetric and volumetric basis. The monoliths present high specific and volumetric capacitances (292 F g−1 and 342 F cm−3), high energy densities (38 Wh kg−1 and 44 Wh L−1), and high power densities (176 W kg−1 and 183 W L−1). The specific and volumetric capacitances, especially the volumetric capacitance, are the highest ever reported for carbon monoliths. The high values are achieved due to a suitable combination of density, electrical conductivity, porosity and oxygen surface content.

Activation of a spherical carbon for toluene adsorption at low concentration

This paper complements a previous one [1] about toluene adsorption on a commercial spherical activated carbon and on samples obtained from it by CO2 or steam activation. The present paper deals with the activation of a commercial spherical carbon (SC) having low porosity and high bed density (0.85 g/cm3) using the same procedure. Our results show that SC can be well activated with CO2 or steam. The increase in the burn-off percentage leads to an increase in the gravimetric adsorption capacity (more intensively for CO2) and a decrease in bed density (more intensively for CO2). However, for similar porosity developments similar bed densities are achieved for CO2 and steam. Especial attention is paid to differences between both activating agents, comparing samples having similar or different activation rates, showing that CO2 generates more narrow porosity and penetrates more inside the spherical particles than steam. Steam activates more from the outside to the interior of the spheres and hence produces larger spheres size reductions. With both activation agents and with a suitable combination of porosity development and bed density, quite high volumetric adsorption values of toluene (up to 236 g toluene/L) can be obtained even using a low toluene concentration (200 ppmv).

Factors governing the adsorption of ethanol on spherical activated carbons

Ethanol adsorption on different activated carbons (mostly spherical ones) was investigated covering the relative pressure range from 0.001 to 1. Oxygen surface contents of the ACs were modified by oxidation (in HNO3 solution or air) and/or by thermal treatment in N2. To differentiate the concomitant effects of porosity and oxygen surface chemistry on ethanol adsorption, different sets of samples were used to analyze different relative pressure ranges (below 1000 ppmv concentration and close to unity). To see the effect of oxygen surface chemistry, selected samples having similar porosity but different oxygen contents were studied in the low relative pressure range. At low ethanol concentration (225 ppmv) adsorption is favored in oxidized samples, remarking the effect of the oxidizing treatment used (HNO3 is more effective than air) and the type of oxygen functionalities created (carboxyl and anhydride groups are more effective than phenolic, carbonyl and derivatives). To analyze the high relative pressure range, spherical and additional ACs were used. As the relative pressure of ethanol increases, the effect of oxygen-containing surface groups decreases and microporosity becomes the most important variable affecting the adsorption of ethanol.

Activated Carbon Fibre Monoliths for Hydrogen Storage

Porous adsorbents are currently investigated for hydrogen storage application. From a practical point of view, in addition to high porosity developments, high material densities are required, in order to confine as much material as possible in a tank device. In this study, we use different measured sample densities (tap, packing, compacted and monolith) for analyzing the hydrogen adsorption behavior of activated carbon fibres (ACFs) and activated carbon nanofibres (ACNFs) which were prepared by KOH and CO2 activations, respectively. Hydrogen adsorption isotherms are measured for all of the adsorbents at room temperature and under high pressures (up to 20 MPa). The obtained results confirm that (i) gravimetric H2 adsorption is directly related to the porosity of the adsorbent, (ii) volumetric H2 adsorption depends on the adsorbent porosity and importantly also on the material density, (iii) the density of the adsorbent can be improved by packing the original adsorbents under mechanical pressure or synthesizing monoliths from them, (iv) both ways (packing under pressure or preparing monoliths) considerably improve the storage capacity of the starting adsorbents, and (v) the preparation of monoliths, in addition to avoid engineering constrains of packing under mechanical pressure, has the advantage of providing high mechanical resistance and easy handling of the adsorbent.

(Table T1) Physical properties of minicores from ODP Leg 193 sites, PACMANUS field

Permeability of the ocean crust is one of the most crucial parameters for constraining submarine fluid flow systems. Active hydrothermal fields are dynamic areas where fluid flow strongly affects the geochemistry and biology of the surrounding environment. There have been few permeability measurements in these regions, especially in felsic-hosted hydrothermal systems. We present a data set of 38 permeability and porosity measurements from the PACMANUS hydrothermal field, an actively venting, felsic hydrothermal field in the eastern Manus Basin. Permeability was measured using a complex transient method on 2.54-cm minicores. Permeability varies greatly between the samples, spanning over five orders of magnitude. Permeability decreases with both depth and decreasing porosity. When the alteration intensity of individual samples is considered, relationships between depth and porosity and permeability become more clearly defined. For incompletely altered samples (defined as >5% fresh rock), permeability and porosity are constant with depth. For completely altered samples (defined as <5% fresh rock), permeability and porosity decrease with depth. On average, the permeability values from the PACMANUS hydrothermal field are greater than those in other submarine environments using similar core-scale laboratory measurements; the average permeability, 4.5 x 10-16 m**2, is two to four orders of magnitude greater than in other areas. Although the core-scale permeability is higher than in other seafloor environments, it is still too low to obtain the fluid velocities observed in the PACMANUS hydrothermal field based on simplified analytical calculations. It is likely that core-scale permeability measurements are not representative of bulk rock permeability of the hydrothermal system overall, and that the latter is predominantly fracture controlled.

Bulk sediment parameter of surface sediment samples (Table 3)

Comparison of rates of accumulation of organic carbon in surface marine sediments from the central North Pacific, the continental margins off northwest Africa, northwest and southwest America, the Argentine Basin, and the western Baltic Sea with primary production rates suggests that the fraction of primary produced organic carbon preserved in the sediments is universally related to the bulk sedimentation rate. Accordingly, less than 0.01% of the primary production becomes fossilized in slowly accumulating pelagic sediments [(2 to 6 mm (1000 y)**-1] of the Central Pacific, 0.1 to 2% in moderately rapidly accumulating [2 to 13 cm (1000 y)**-1] hemipelagic sediments off northwest Africa, northwest America (Oregon) and southeast America (Argentina), and 11 to 18% in rapidly accumulating [66 to 140 cm (1000 y)**-1] hemipelagic sediments off southwest America (Peru) and in the Baltic Sea. The emiprical expression: %Org-C = (0.0030*R*S**0.30)/(ps(1-Theta)) implies that the sedimentary organic carbon content (% Org-C) doubles with each 10-fold increase in sedimentation rate (S), assuming that other factors remain constant; i.e., primary production (R), porosity and sediment density (ps). This expression also predicts the sedimentary organic carbon content from the primary production rate, sedimentation rate, dry density of solids, and their porosity; it may be used to estimate paleoproductivity as well. Applying this relationship to a sediment core from the continental rise off northwest Africa (Spanish Sahara) suggests that productivity there during interglacial oxygen isotope stages 1 and 5 was about the same as today but was higher by a factor of 2 to 3 during glacial stages 2, 3, and 6.

Geochemistry of ODP Hole 111-504B basalts (Table 2)

Fifty samples of basalt recovered during ODP Leg 111 from the dikes (Layer 2C) of Hole 504B (1350.0-1562.3 m below seafloor) were analyzed by X-ray-fluorescence techniques. All of the samples are highly depleted in magmaphile elements relative to other mid-ocean ridge basalts, with TiO2 = 0.75-1.24 wt%, Na2O = 1.59-2.22 wt%, Zr = 38-64 ppm, Nb = 0.3-1.5 ppm, and Y = 20-30 ppm (for samples containing 0%-2% phenocrysts), but have ratios of highly incompatible elements similar to normal Type I mid-ocean ridge basalts (e.g., Zr/Nb > 30). Abundances of compatible elements are similar to those of typical mid-ocean ridge basalts, with MgO = 7.2-9.2 wt%, Fe2O3* = 9.3-12.5 wt%, Ni = 55-164 ppm, and Cr = 26-388 ppm. Approximately 2% of the samples recovered from the top part of Hole 504B are similar to normal Type I or Type II ocean floor basalts. However, all of the analyzed Leg 111 samples from Hole 504B are depleted basalts. Aphyric dike rocks from Leg 111 are virtually identical to the depleted aphyric samples recovered from the pillow lavas and dikes in the upper 1075 m of Hole 504B during DSDP Legs 69, 70, and 83, with the exception of elements readily altered by seawater (Sr, Rb, and K). These elements reach a maximum in both abundance and variability in the pillow lavas of the upper 571.5 m of Hole 504B and decline to more constant values in the dike system sampled on Legs 83 and 111, apparently as a result of a decrease in porosity and increase in alteration temperatures relative to the pillow lavas. Based on compositional similarities to the vast majority of the pillows and flows, the dikes sampled on Leg 111 appear to be the feeder system for the pillow lavas in the upper part of Hole 504B. The incompatible-element-depleted compositions of the Costa Rica Rift Zone basalts are consistent with multistage melting of a normal mid-ocean ridge source.

(Table 1) Physical properties of ODP Site 129-801

Compressional wave velocities and densities were measured for 6 basalt samples from ODP Hole 801B and 16 samples from ODP Hole 801C, a site that represents the first drilling of Jurassic-age crustal rocks in the Pacific basin. Incremental measurements, taken to a total pressure of 200 MPa, show a systematic decrease in velocity with increasing porosity and a related increase with increasing wet-bulk density. A comparison of the plot of porosity vs. compressional wave velocity with the theoretical equation from Wyllie et al. (1958) suggests this equation is inappropriate for oceanic basalts because of mineral alteration in high porosity samples. Also of interest is the dramatic change in velocity across a hydrothermal boundary. Basalts below this hydrothermal layer have a mean velocity of 6.05 km/s at 60 MPa while those above show a mean velocity of 4.55 km/s at 60 MPa. The low velocity values of the basalts above the hydrothermal deposit may be attributed to the higher porosity and composition observed in these rocks; the higher porosity is possibly the result of increased exposure to circulating seawater.

Physical properties of sediment core CRP-1

The relationship between whole-core compressional wave velocities and gamma-ray attenuation porosities of sediments cored at CRP-1 is examined and compared with results from core-plug samples and global models. Both core-plug and whole-core velocities show a strong dependence on porosity: this relationship appears to be independent of lithology. In the range from 0.1 to 0.4 of fractional porosity (Miocene strata), plug velocities are generally 0.2 - 0.5 km s-1 higher than whole-core velocities. Possible reasons include decreased rigidity in the whole core and diagenetic changes in the plugs. Possibly both velocity measurements are correct but neither is fully representative for in situ conditions. It appears that the core-plug results are more compatible with data from other regions than the whole-core data. After removing first-order compaction control from the whole-core porosity record, a second-order control by clay content can be quantified as a simple positive linear regression (R=0.6). In contrast, after correction for first-order control, porosity and velocity are not significantly influenced by lonestone abundance except for rare, very large lonestones.

Segregation band formation in Al-Si die castings

Banded defects are often found in high-pressure die castings. These bands can contain segregation, porosity, and/or tears, and changing casting conditions and alloy are known to change the position and make-up of the bands. Due to the complex, dynamic nature of the high-pressure die-casting (HPDC) process, it is very difficult to study the effect of individual parameters on band formation. In the work presented here, bands of segregation similar to those found in cold-chamber HPDC aluminum alloys were found in laboratory gravity die castings. Samples were cast with a range of fraction solids from 0 to 0.3 and the effect of die temperature and external solid fraction on segregation bands was investigated. The results are considered with reference to the theological properties of the filling semisolid metal and a formation mechanism for bands is proposed by considering flow past a solidifying immobile wall layer.

Effects of rock properties on specific cutting energy in linear cutting of sandstones by picks

Specific cutting energy (SE) has been widely used to assess the rock cuttability for mechanical excavation purposes. Some prediction models were developed for SE through correlating rock properties with SE values. However, some of the textural and compositional rock parameters i.e. texture coefficient and feldspar, mafic, and felsic mineral contents were not considered. The present study is to investigate the effects of previously ignored rock parameters along with engineering rock properties on SE. Mineralogical and petrographic analyses, rock mechanics, and linear rock cutting tests were performed on sandstone samples taken from sites around Ankara, Turkey. Relationships between SE and rock properties were evaluated using bivariate correlation and linear regression analyses. The tests and subsequent analyses revealed that the texture coefficient and feldspar content of sandstones affected rock cuttability, evidenced by significant correlations between these parameters and SE at a 90% confidence level. Felsic and mafic mineral contents of sandstones did not exhibit any statistically significant correlation against SE. Cementation coefficient, effective porosity, and pore volume had good correlations against SE. Poisson's ratio, Brazilian tensile strength, Shore scleroscope hardness, Schmidt hammer hardness, dry density, and point load strength index showed very strong linear correlations against SE at confidence levels of 95% and above, all of which were also found suitable to be used in predicting SE individually, depending on the results of regression analysis, ANOVA, Student's t-tests, and R2 values. Poisson's ratio exhibited the highest correlation with SE and seemed to be the most reliable SE prediction tool in sandstones.

Aeration for plant root respiration in a tidal marsh

This paper investigates the tidal effects on aeration conditions for plant root respiration in a tidal marsh. We extend the work of Ursino et al. ( 2004) by using a two-phase model for air and water flows in the marsh. Simulations have been conducted to examine directly the link between the airflow dynamics and the aeration condition in the marsh soil. The results show that the effects of entrapped air on water movement in the vadose zone are significant in certain circumstances. Single-phase models based on Richards' equation, which neglect such effects, may not be adequate for quantifying the aeration condition in tidal marsh. The optimal aeration condition, represented by the maximum of the integral magnitude of tidally advected air mass ( TAAM) flux, is found to occur near the tidal creek for the four soil textures simulated. This may explain the observation that some salt marsh plant species grow better near tidal creeks than in the inner marsh areas. Our analyses, based on the two-phase model and predicted TAAM flux magnitude, provide further insight into the positive feedback'' mechanism proposed by Ursino et al. ( 2004). That is, pioneer plants may grow successfully near the creek where the root aeration condition is optimal. The roots of the pioneer plants can soften and loosen the rhizosphere soil, which increases the evapotranspiration rate, the soil porosity, and absolute permeability and weakens the capillary effects. These, in turn, improve further the root aeration conditions and may lead to colonization by plants less resistant to anaerobic conditions.

Prediction of slurry transport in SAG mills using SPH fluid flow in a dynamic DEM based porous media

DEM modelling of the motion of coarse fractions of the charge inside SAG mills has now been well established for more than a decade. In these models the effect of slurry has broadly been ignored due to its complexity. Smoothed particle hydrodynamics (SPH) provides a particle based method for modelling complex free surface fluid flows and is well suited to modelling fluid flow in mills. Previous modelling has demonstrated the powerful ability of SPH to capture dynamic fluid flow effects such as lifters crashing into slurry pools, fluid draining from lifters, flow through grates and pulp lifter discharge. However, all these examples were limited by the ability to model only the slurry in the mill without the charge. In this paper, we represent the charge as a dynamic porous media through which the SPH fluid is then able to flow. The porous media properties (specifically the spatial distribution of porosity and velocity) are predicted by time averaging the mill charge predicted using a large scale DEM model. This allows prediction of transient and steady state slurry distributions in the mill and allows its variation with operating parameters, slurry viscosity and slurry volume, to be explored. (C) 2006 Published by Elsevier Ltd.

Effects of rock properties on specific cutting energy in linear cutting of sandstones by picks

Specific cutting energy (SE) has been widely used to assess the rock cuttability for mechanical excavation purposes. Some prediction models were developed for SE through correlating rock properties with SE values. However, some of the textural and compositional rock parameters i.e. texture coefficient and feldspar, mafic, and felsic mineral contents were not considered. The present study is to investigate the effects of previously ignored rock parameters along with engineering rock properties on SE. Mineralogical and petrographic analyses, rock mechanics, and linear rock cutting tests were performed on sandstone samples taken from sites around Ankara, Turkey. Relationships between SE and rock properties were evaluated using bivariate correlation and linear regression analyses. The tests and subsequent analyses revealed that the texture coefficient and feldspar content of sandstones affected rock cuttability, evidenced by significant correlations between these parameters and SE at a 90% confidence level. Felsic and mafic mineral contents of sandstones did not exhibit any statistically significant correlation against SE. Cementation coefficient, effective porosity, and pore volume had good correlations against SE. Poisson's ratio, Brazilian tensile strength, Shore scleroscope hardness, Schmidt hammer hardness, dry density, and point load strength index showed very strong linear correlations against SE at confidence levels of 95% and above, all of which were also found suitable to be used in predicting SE individually, depending on the results of regression analysis, ANOVA, Student's t-tests, and R-2 values. Poisson's ratio exhibited the highest correlation with SE and seemed to be the most reliable SE prediction tool in sandstones.

A late Pleistocene predator-accumulated avifauna from Kids Cave, West Coast, South Island, New Zealand

A fossil deposit excavated from the floor of Kids Cave, West Coast, South Island, New Zealand, is interpreted as having been primarily accumulated by New Zealand falcon Falco novaeseelandiae, with some contribution by Haast's eagle Harpagornis moorei. The fauna is rich: 3699 bones represented 41 bird species, two frog species, unspecified geckoes and skinks, and one bat species. Fossil deposition was mainly within the Last Glacial Maximum from about 22,000 cal yr bp to about 15,000 cal yr bp, with a marked change in sediment characteristics at the onset of the LGM's coldest period. Chronological control is given by three Uranium-series dates for a speleothem and radiocarbon AMS dating of four avian eggshell samples and one bone. The fauna is the first extensive predator accumulation of LGM age described from the West Coast of the South Island, and it indicates a palaeoenvironment of a mosaic of shrublands with forest patches. The onset of the coldest part of the LGM (Aurora 3 glacial advance, 19,500 - 19,000 cal yrs bp) saw marked climate cooling/drying affecting the site, but the avifauna indicates that although open-country taxa became more common in this period, some forest persisted nearby throughout the remainder of the LGM.