BET surface area of carbonaceous adsorbents: verification using geometric considerations and GCMC simulations on virtual porous carbon models

The applicability of BET model for calculation of surface area of activated carbons is checked by using molecular simulations. By calculation of geometric surface areas for the simple model carbon slit-like pore with the increasing width, and by comparison of the obtained values with those for the same systems from the VEGA ZZ package (adsorbate-accessible molecular surface), it is shown that the latter methods provide correct values. For the system where a monolayer inside a pore is created the ASA approach (GCMC, Ar, T = 87 K) underestimates the value of surface area for micropores (especially, where only one layer is observed and/or two layers of adsorbed Ar are formed). Therefore, we propose the modification of this method based on searching the relationship between the pore diameter and the number of layers in a pore. Finally BET; original andmodified ASA; and A, B and C-point surface areas are calculated for a series of virtual porous carbons using simulated Ar adsorption isotherms (GCMC and T = 87 K). The comparison of results shows that the BET method underestimates and not, as it was usually postulated, overestimates the surface areas of microporous carbons.

Testing isotherm models and recovering empirical relationships for adsorption in microporous carbons using virtual carbon models and grand canonical Monte Carlo simulations

Using the plausible model of activated carbon proposed by Harris and co-workers and grand canonical Monte Carlo simulations, we study the applicability of standard methods for describing adsorption data on microporous carbons widely used in adsorption science. Two carbon structures are studied, one with a small distribution of micropores in the range up to 1 nm, and the other with micropores covering a wide range of porosity. For both structures, adsorption isotherms of noble gases (from Ne to Xe), carbon tetrachloride and benzene are simulated. The data obtained are considered in terms of Dubinin-Radushkevich plots. Moreover, for benzene and carbon tetrachloride the temperature invariance of the characteristic curve is also studied. We show that using simulated data some empirical relationships obtained from experiment can be successfully recovered. Next we test the applicability of Dubinin's related models including the Dubinin-Izotova, Dubinin-Radushkevich-Stoeckli, and Jaroniec-Choma equations. The results obtained demonstrate the limits and applications of the models studied in the field of carbon porosity characterization.

Hyper-parallel tempering Monte Carlo simulations of Ar adsorption in new models of microporous non-graphitizing activated carbon: effect of microporosity

The adsorption of gases on microporous carbons is still poorly understood, partly because the structure of these carbons is not well known. Here, a model of microporous carbons based on fullerene- like fragments is used as the basis for a theoretical study of Ar adsorption on carbon. First, a simulation box was constructed, containing a plausible arrangement of carbon fragments. Next, using a new Monte Carlo simulation algorithm, two types of carbon fragments were gradually placed into the initial structure to increase its microporosity. Thirty six different microporous carbon structures were generated in this way. Using the method proposed recently by Bhattacharya and Gubbins ( BG), the micropore size distributions of the obtained carbon models and the average micropore diameters were calculated. For ten chosen structures, Ar adsorption isotherms ( 87 K) were simulated via the hyper- parallel tempering Monte Carlo simulation method. The isotherms obtained in this way were described by widely applied methods of microporous carbon characterisation, i. e. Nguyen and Do, Horvath - Kawazoe, high- resolution alpha(a)s plots, adsorption potential distributions and the Dubinin - Astakhov ( DA) equation. From simulated isotherms described by the DA equation, the average micropore diameters were calculated using empirical relationships proposed by different authors and they were compared with those from the BG method.

The last glacial cycle: transient simulations with an AOGCM

A number of transient climate runs simulating the last 120kyr have been carried out using FAMOUS, a fast atmosphere-ocean general circulation model (AOGCM). This is the first time such experiments have been done with a full AOGCM, providing a three-dimensional simulation of both atmosphere and ocean over this period. Our simulation thus includes internally generated temporal variability over periods from days to millennia, and physical, detailed representations of important processes such as clouds and precipitation. Although the model is fast, computational restrictions mean that the rate of change of the forcings has been increased by a factor of 10, making each experiment 12kyr long. Atmospheric greenhouse gases (GHGs), northern hemisphere ice sheets and variations in solar radiation arising from changes in the Earth's orbit are treated as forcing factors, and are applied either separately or combined in different experiments. The long-term temperature changes on Antarctica match well with reconstructions derived from ice-core data, as does variability on timescales longer than 10 kyr. Last Glacial Maximum (LGM) cooling on Greenland is reasonably well simulated, although our simulations, which lack ice-sheet meltwater forcing, do not reproduce the abrupt, millennial scale climate shifts seen in northern hemisphere climate proxies or their slower southern hemisphere counterparts. The spatial pattern of sea surface cooling at the LGM matches proxy reconstructions reasonably well. There is significant anti-correlated variability in the strengths of the Atlantic Meridional Overturning Circulation (AMOC) and the Antarctic Circumpolar Current (ACC) on timescales greater than 10kyr in our experiments. We find that GHG forcing weakens the AMOC and strengthens the ACC, whilst the presence of northern hemisphere ice-sheets strengthens the AMOC and weakens the ACC. The structure of the AMOC at the LGM is found to be sensitive to the details of the ice-sheet reconstruction used. The precessional component of the orbital forcing induces ~20kyr oscillations in the AMOC and ACC, whose amplitude is mediated by changes in the eccentricity of the Earth's orbit. These forcing influences combine, to first order, in a linear fashion to produce the mean climate and ocean variability seen in the run with all forcings.

A study of the arrival over the United Kingdom in April 2010 of the Eyjafjallajökull ash cloud using ground-based lidar and numerical simulations

We make a qualitative and quantitative comparison of numericalsimulations of the ashcloud generated by the eruption of Eyjafjallajökull in April2010 with ground-basedlidar measurements at Exeter and Cardington in southern England. The numericalsimulations are performed using the Met Office’s dispersion model, NAME (Numerical Atmospheric-dispersion Modelling Environment). The results show that NAME captures many of the features of the observed ashcloud. The comparison enables us to estimate the fraction of material which survives the near-source fallout processes and enters into the distal plume. A number of simulations are performed which show that both the structure of the ashcloudover southern England and the concentration of ash within it are particularly sensitive to the height of the eruption column (and the consequent estimated mass emission rate), to the shape of the vertical source profile and the level of prescribed ‘turbulent diffusion’ (representing the mixing by the unresolved eddies) in the free troposphere with less sensitivity to the timing of the start of the eruption and the sedimentation of particulates in the distal plume.

A study on effect of built forms on urban wind environment by using CFD simulations

This paper presents a numerical study of urban air-flow for a group of five buildings that is located at the University of Reading in the United Kingdom. The airflow around these buildings has been simulated by using ANSYS CFD software package. In this study, the association between certain architectural forms: a street canyon, a semi-closure, and a courtyard-like space in a low-rise building complex, and the wind environment were investigated. The analysis of CFD results has provided detailed information on the wind patterns of these urban built forms. The numerical results have been compared with the experimental measurements within the building complex. The observed characteristics of urban wind pattern with respect to the built structures are presented as a guideline. This information is needed for the design and/or performance assessments of systems such as passive and low energy design approach, a natural or hybrid ventilation, and passive cooling. Also, the knowledge of urban wind patterns allows us to develop better design options for the application of renewable energy technologies within urban environment.

Crystallization of random aromatic copolyesters containing flexible spacer chains and side-groups

The crystallization behaviour of a series of random copolymers of varying chemical composition is reported. For polymers containing a high proportion of alternating rigid aromatic units and flexible spacers, conventional liquid crystalline and crystalline phase behaviour is observed. The introduction of a substantial fraction of a second shorter rigid unit containing side-chains leads to a broad endotherm in the d.s.c. scan covering some 150°C. Subsequent isothermal crystallization at any point within the broad endotherm leads to the generation of sharp endotherms at temperatures just above the recrystallization temperature. We attribute this behaviour to the crystallization of clusters of molecules containing similar random sequences. Such crystals are non-periodic along the chain direction.

Biaxial optical properties of thermotropic random copolyesters

The optical microstructures of thin sections of two liquid crystalline polymers are examined in the polarizing microscope. The polymers are random copolyesters based on hydroxybenzoic and hydroxynaphthoic acids (B-N), and hydroxybenzoic acid and ethylene terephthalate (B-ET). Sections cut from oriented samples, so as to include the extrusion direction, show microstructures in which there is no apparent preferred orientation of the axes describing the local optical anisotropy. The absence of preferred orientation in the microstructure, despite marked axial alignment of molecular chain segments as demonstrated by X-Ray diffraction, is interpreted in terms of the polymer having biaxial optical properties. The implication of optical biaxiality is that, although the mesophases are nematic, the orientation of the molecules is correlated about three (orthogonal) axes over distances greater than a micron. The structure is classified as a multiaxial nematic.

Implementation of a new urban energy budget scheme in the MetUM. Part I: Description and idealized simulations

This paper describes the formulation of a new urban scheme, MORUSES (Met Office–Reading Urban Surface Exchange Scheme) for use in the Met Office Unified Model. The implementation of the new scheme ensures that (1) the new scheme offers more flexibility in the parametrization of the building properties, and hence provides a more realistic representation of the fluxes; (2) the bulk outputs are in satisfactory agreement with previous observational studies; and (3) the impact of the new scheme on the energy balance fluxes is similar to the impact of the current urban scheme when set up to mimic it. As well as having a better physical basis, MORUSES also gains in flexibility in applications and adaptations to different urban materials as well as urban planning. The new scheme represents the urban area as a composition of two tiles, a canyon and a roof, using a simple 2D geometry. Sensitivity analysis to canyon geometry and thickness of the roof canopy emphasizes the gain in flexibility captured by the new scheme. Copyright © 2010 Royal Meteorological Society and Crown Copyright

Hydrological cycle in the Danube basin in present-day and XXII century simulations by IPCCAR4 global climate models

We present an intercomparison and verification analysis of 20 GCMs (Global Circulation Models) included in the 4th IPCC assessment report regarding their representation of the hydrological cycle on the Danube river basin for 1961–2000 and for the 2161–2200 SRESA1B scenario runs. The basin-scale properties of the hydrological cycle are computed by spatially integrating the precipitation, evaporation, and runoff fields using the Voronoi-Thiessen tessellation formalism. The span of the model- simulated mean annual water balances is of the same order of magnitude of the observed Danube discharge of the Delta; the true value is within the range simulated by the models. Some land components seem to have deficiencies since there are cases of violation of water conservation when annual means are considered. The overall performance and the degree of agreement of the GCMs are comparable to those of the RCMs (Regional Climate Models) analyzed in a previous work, in spite of the much higher resolution and common nesting of the RCMs. The reanalyses are shown to feature several inconsistencies and cannot be used as a verification benchmark for the hydrological cycle in the Danubian region. In the scenario runs, for basically all models the water balance decreases, whereas its interannual variability increases. Changes in the strength of the hydrological cycle are not consistent among models: it is confirmed that capturing the impact of climate change on the hydrological cycle is not an easy task over land areas. Moreover, in several cases we find that qualitatively different behaviors emerge among the models: the ensemble mean does not represent any sort of average model, and often it falls between the models’ clusters.

From symmetry breaking to Poisson Point Process in 2D Voronoi Tessellations: the generic nature of hexagons

We bridge the properties of the regular triangular, square, and hexagonal honeycomb Voronoi tessellations of the plane to the Poisson-Voronoi case, thus analyzing in a common framework symmetry breaking processes and the approach to uniform random distributions of tessellation-generating points. We resort to ensemble simulations of tessellations generated by points whose regular positions are perturbed through a Gaussian noise, whose variance is given by the parameter α2 times the square of the inverse of the average density of points. We analyze the number of sides, the area, and the perimeter of the Voronoi cells. For all valuesα >0, hexagons constitute the most common class of cells, and 2-parameter gamma distributions provide an efficient description of the statistical properties of the analyzed geometrical characteristics. The introduction of noise destroys the triangular and square tessellations, which are structurally unstable, as their topological properties are discontinuous in α = 0. On the contrary, the honeycomb hexagonal tessellation is topologically stable and, experimentally, all Voronoi cells are hexagonal for small but finite noise withα <0.12. For all tessellations and for small values of α, we observe a linear dependence on α of the ensemble mean of the standard deviation of the area and perimeter of the cells. Already for a moderate amount of Gaussian noise (α >0.5), memory of the specific initial unperturbed state is lost, because the statistical properties of the three perturbed regular tessellations are indistinguishable. When α >2, results converge to those of Poisson-Voronoi tessellations. The geometrical properties of n-sided cells change with α until the Poisson- Voronoi limit is reached for α > 2; in this limit the Desch law for perimeters is shown to be not valid and a square root dependence on n is established. This law allows for an easy link to the Lewis law for areas and agrees with exact asymptotic results. Finally, for α >1, the ensemble mean of the cells area and perimeter restricted to the hexagonal cells agree remarkably well with the full ensemble mean; this reinforces the idea that hexagons, beyond their ubiquitous numerical prominence, can be interpreted as typical polygons in 2D Voronoi tessellations.

Three-dimensional random Voronoi tessellations: From cubic crystal lattices to Poisson point processes

We perturb the SC, BCC, and FCC crystal structures with a spatial Gaussian noise whose adimensional strength is controlled by the parameter a, and analyze the topological and metrical properties of the resulting Voronoi Tessellations (VT). The topological properties of the VT of the SC and FCC crystals are unstable with respect to the introduction of noise, because the corresponding polyhedra are geometrically degenerate, whereas the tessellation of the BCC crystal is topologically stable even against noise of small but finite intensity. For weak noise, the mean area of the perturbed BCC and FCC crystals VT increases quadratically with a. In the case of perturbed SCC crystals, there is an optimal amount of noise that minimizes the mean area of the cells. Already for a moderate noise (a>0.5), the properties of the three perturbed VT are indistinguishable, and for intense noise (a>2), results converge to the Poisson-VT limit. Notably, 2-parameter gamma distributions are an excellent model for the empirical of of all considered properties. The VT of the perturbed BCC and FCC structures are local maxima for the isoperimetric quotient, which measures the degre of sphericity of the cells, among space filling VT. In the BCC case, this suggests a weaker form of the recentluy disproved Kelvin conjecture. Due to the fluctuations of the shape of the cells, anomalous scalings with exponents >3/2 is observed between the area and the volumes of the cells, and, except for the FCC case, also for a->0. In the Poisson-VT limit, the exponent is about 1.67. As the number of faces is positively correlated with the sphericity of the cells, the anomalous scaling is heavily reduced when we perform powerlaw fits separately on cells with a specific number of faces.