Non-additivity of attractive potentials in modeling of N-2 and Ar adsorption isotherms on graphitized carbon black and porous carbon by means of density functional theory

We present a new approach accounting for the nonadditivity of attractive parts of solid-fluid and fluidfluid potentials to improve the quality of the description of nitrogen and argon adsorption isotherms on graphitized carbon black in the framework of non-local density functional theory. We show that the strong solid-fluid interaction in the first monolayer decreases the fluid-fluid interaction, which prevents the twodimensional phase transition to occur. This results in smoother isotherm, which agrees much better with experimental data. In the region of multi-layer coverage the conventional non-local density functional theory and grand canonical Monte Carlo simulations are known to over-predict the amount adsorbed against experimental isotherms. Accounting for the non-additivity factor decreases the solid-fluid interaction with the increase of intermolecular interactions in the dense adsorbed fluid, preventing the over-prediction of loading in the region of multi-layer adsorption. Such an improvement of the non-local density functional theory allows us to describe experimental nitrogen and argon isotherms on carbon black quite accurately with mean error of 2.5 to 5.8% instead of 17 to 26% in the conventional technique. With this approach, the local isotherms of model pores can be derived, and consequently a more reliab * le pore size distribution can be obtained. We illustrate this by applying our theory against nitrogen and argon isotherms on a number of activated carbons. The fitting between our model and the data is much better than the conventional NLDFT, suggesting the more reliable PSD obtained with our approach.

Application of density functional theory to capillary phenomena in cylindrical mesopores with radial and longitudinal density distributions

In this paper, we applied a version of the nonlocal density functional theory (NLDFT) accounting radial and longitudinal density distributions to study the adsorption and desorption of argon in finite as well as infinite cylindrical nanopores at 87.3 K. Features that have not been observed before with one-dimensional NLDFT are observed in the analysis of an inhomogeneous fluid along the axis of a finite cylindrical pore using the two-dimensional version of the NLDFT. The phase transition in pore is not strictly vapor-liquid transition as assumed and observed in the conventional version, but rather it exhibits a much elaborated feature with phase transition being complicated by the formation of solid phase. Depending on the pore size, there are more than one phase transition in the adsorption-desorption isotherm. The solid formation in finite pore has been found to be initiated by the presence of the meniscus. Details of the analysis of the extended version of NLDFT will be discussed in the paper. (C) 2004 American Institute of Physics.

Capillary phenomena in the framework of the two-dimensional density functional theory

We present results of application of the density functional theory (DFT) to adsorption and desorption in finite and infinite cylindrical pores accounting for the density distribution in radial and axial directions. Capillary condensation via formation of bridges is considered using canonical and grand canonical versions of the 2D DFT. The potential barrier of nucleation is determined as a function of the bulk pressure and the pore diameter. In the framework of the conventional assumptions on intermolecular interactions both 1D and 2D DFT versions lead to the same results and confirm the classical scenario of condensation and evaporation: the condensation occurs at the vapor-like spinodal point, and the evaporation corresponds to the equilibrium transition pressure. The analysis of experimental data on argon and nitrogen adsorption on MCM-41 samples seems to not completely corroborate this scenario, with adsorption branch being better described by the equilibrium pressure - diameter dependence. This points to the necessity of the further development of basic representations on the hysteresis phenomena.

Modeling of adsorption in finite cylindrical pores by means of density functional theory

Adsorption of argon at its boiling point infinite cylindrical pores is considered by means of the non-local density functional theory (NLDFT) with a reference to MCM-41 silica. The NLDFT was adjusted to amorphous solids, which allowed us to quantitatively describe argon adsorption isotherm on nonporous reference silica in the entire bulk pressure range. In contrast to the conventional NLDFT technique, application of the model to cylindrical pores does not show any layering before the phase transition in conformity with experimental data. The finite pore is modeled as a cylindrical cavity bounded from its mouth by an infinite flat surface perpendicular to the pore axis. The adsorption of argon in pores of 4 and 5 nm diameters is analyzed in canonical and grand canonical ensembles using a two-dimensional version of NLDFT, which accounts for the radial and longitudinal fluid density distributions. The simulation results did not show any unusual features associated with accounting for the outer surface and support the conclusions obtained from the classical analysis of capillary condensation and evaporation. That is, the spontaneous condensation occurs at the vapor-like spinodal point, which is the upper limit of mechanical stability of the liquid-like film wetting the pore wall, while the evaporation occurs via a mechanism of receding of the semispherical meniscus from the pore mouth and the complete evaporation of the core occurs at the equilibrium transition pressure. Visualization of the pore filling and empting in the form of contour lines is presented.

Adsorption in slit pores and pore-size distribution: A molecular layer structure theory

A new approach is developed to analyze the thermodynamic properties of a sub-critical fluid adsorbed in a slit pore of activated carbon. The approach is based on a representation that an adsorbed fluid forms an ordered structure close to a smoothed solid surface. This ordered structure is modelled as a collection of parallel molecular layers. Such a structure allows us to express the Helmholtz free energy of a molecular layer as the sum of the intrinsic Helmholtz free energy specific to that layer and the potential energy of interaction of that layer with all other layers and the solid surface. The intrinsic Helmholtz free energy of a molecular layer is a function (at given temperature) of its two-dimensional density and it can be readily obtained from bulk-phase properties, while the interlayer potential energy interaction is determined by using the 10-4 Lennard-Jones potential. The positions of all layers close to the graphite surface or in a slit pore are considered to correspond to the minimum of the potential energy of the system. This model has led to accurate predictions of nitrogen and argon adsorption on carbon black at their normal boiling points. In the case of adsorption in slit pores, local isotherms are determined from the minimization of the grand potential. The model provides a reasonable description of the 0-1 monolayer transition, phase transition and packing effect. The adsorption of nitrogen at 77.35 K and argon at 87.29 K on activated carbons is analyzed to illustrate the potential of this theory, and the derived pore-size distribution is compared favourably with that obtained by the Density Functional Theory (DFT). The model is less time-consuming than methods such as the DFT and Monte-Carlo simulation, and most importantly it can be readily extended to the adsorption of mixtures and capillary condensation phenomena.

Critical Temperature of a Trapped Bose Gas: Comparison of Theory and Experiment

We apply the projected Gross-Pitaevskii equation (PGPE) formalism to the experimental problem of the shift in critical temperature T-c of a harmonically confined Bose gas as reported in Gerbier , Phys. Rev. Lett. 92, 030405 (2004). The PGPE method includes critical fluctuations and we find the results differ from various mean-field theories, and are in best agreement with experimental data. To unequivocally observe beyond mean-field effects, however, the experimental precision must either improve by an order of magnitude, or consider more strongly interacting systems. This is the first application of a classical field method to make quantitative comparison with experiment.

Transition in plane parallel shear flows heated internally

The stability of internally heated inclined plane parallel shear flows is examined numerically for the case of finite value of the Prandtl number, Pr. The transition in a vertical channel has already been studied for 0≤Pr≤100 with or without the application of an external pressure gradient, where the secondary flow takes the form of travelling waves (TWs) that are spanwise-independent (see works of Nagata and Generalis). In this work, in contrast to work already reported (J. Heat Trans. T. ASME 124 (2002) 635-642), we examine transition where the secondary flow takes the form of longitudinal rolls (LRs), which are independent of the steamwise direction, for Pr=7 and for a specific value of the angle of inclination of the fluid layer without the application of an external pressure gradient. We find possible bifurcation points of the secondary flow by performing a linear stability analysis that determines the neutral curve, where the basic flow, which can have two inflection points, loses stability. The linear stability of the secondary flow against three-dimensional perturbations is also examined numerically for the same value of the angle of inclination by employing Floquet theory. We identify possible bifurcation points for the tertiary flow and show that the bifurcation can be either monotone or oscillatory. © 2003 Académie des sciences. Published by Elsevier SAS. All rights reserved.

Off-farm labour supply and labour markets in rapidly changing circumstances:Bulgaria during transition

This study examines off-farm labor supply in the rapidly changing conditions of Bulgaria during the 1990s. In doing so, we make use of three different waves of the Bulgarian Integrated Household Survey, each reflecting remarkably different environmental conditions. The results suggest that standard theories of off-farm labor supply provide little guidance in situations characterized by chronic excess supply in the off-farm labor market and/or rapidly changing circumstances. In particular, the results show (1) that off-farm employment throughout the transition was predominantly determined by demand rather than by supply, and (2) that the magnitude and statistical significance of the various determinants are very sensitive to changing environmental conditions. As such, the results can be extremely relevant for both theory and policy for the many countries which may still need to go through privatization and painful restructuring as a result of financial crises and globalization.

Ownership structure and investment finance in transition economies:a survey of evidence from large firms in Hungary and Poland

Using survey data on 157 large private Hungarian and Polish companies this paper investigates links between ownership structures and CEOs’ expectations with regard to sources of finance for investment. The Bayesian estimation is used to deal with the small sample restrictions, while classical methods provide robustness checks. We found a hump-shaped relationship between ownership concentration and expectations of relying on public equity. The latter is most likely for firms where the largest investor owns between 25 percent and 49 percent of shares, just below the legal control threshold. More profitable firms rely on retained earnings for their investment finance, consistent with the ‘pecking order’ theory of financing. Finally, firms for which the largest shareholder is a domestic institutional investor are more likely to borrow from domestic banks.

Putting supply chain learning theory into practice:lessons from an Irish case

The logistics service market is currently going through a fundamental transition. The development of closer relationships with customers and the continuous adaptation of products and services, represent potentially successful approaches to the development of improved competitive capability. To this end knowledge resources and learning processes increasingly represent key elements within the evolving framework of the 3PL business. This paper describes the case of NITL’s Foundation Certificate Programme (FCP) learning programme with specific reference to its use in addressing some of current shortcomings related to supply chain knowledge and skills in the Irish third party logistics (3PL) industry. The FCP rationale is based on the need to move from traditional approaches of supply chain organisation where the various links in the chain were measured and managed in isolation from each other and thus tended to operate at cross purposes, towards more integrated approaches.

Tackling transition! Peer mentoring in engineering education:a UK perspective

This paper builds on previous work (Clark, 2009; Clark & Andrews 2011, 2014) to continue the debate around a seemingly universal question…“How can educational theory be applied to engineering education in such a way so as to make the subject more accessible and attractive to students? It argues that there are three key elements to student success; Relationships, Variety & Synergy (RVS). By further examining the purposefully developed bespoke learning and teaching approach constructed around these three elements (RVS) the discourse in this paper links educational theory to engineering education and in doing so further develops arguments for the introduction of a purposefully designed pedagogic approach for use in engineering education.

Transition and foreign aid policies in the Visegrád countries:a path dependant approach

The paper argues that the current emerging international development policies of the Visegrád (V4) countries are heavily influenced by the certain aspects of the Communist past and the transition process. Due to these influences, the V4 countries have difficulties in adapting the foreign aid practices of Western donors and this leads to the emergence of a unique Central and Eastern European development cooperation model. As an analytical background, the paper builds on the path dependency theory of transition. A certain degree of path dependence is clearly visible in V4 foreign aid policies, and the paper analyses some aspects of this phenomenon: how these new emerging foreign aid donors select their partner countries, how much they spend on aid, how they formulate their aid delivery policies and institutions and what role the non-state actors play. The main conclusions of the paper are that the legacies of the Communist past have a clear influence and the V4 countries still have a long way to go in adapting their aid policies to international requirements.

The new institutionalism in the context of Kosovo's transition:regulatory institutions in contested states

This article explores the new institutionalist literature in political economy in the context of Kosovo's contested statehood, focusing on institutional arbitrage and legitimacy. This article considers both the consequences of institutions for actors' behaviour and the norms that shape this, as well as the factors determining the legitimacy of institutions. In doing so, it combines the new institutionalist theory with documentary and interview material collected during research on energy regulation in one contested state, Kosovo. Rather than singling out one particular variety of "new institutionalism", the article attempts to blend insights from historical (or "political"), rational choice, and sociological institutionalism. © 2014 © 2014 Taylor & Francis.

Transition and Foreign Aid Policies in the Visegrád Countries: A Path Dependant Approach

The paper argues that the current emerging international development policies of the Visegrád (V4) countries are heavily influenced by the certain aspects of the communist past and the transition process. Due to these influences, the V4 countries have difficulties in adapting the foreign aid practices of Western donors and this leads to the emergence of a unique Central and Eastern European development cooperation model. As an analytical background, the paper builds on the path dependency theory of transition. A certain degree of path dependence is clearly visible in V4 foreign aid policies, and the paper analyzes some aspects of this phenomenon: how these new emerging foreign aid donors select their partner countries, how much they spend on aid, how they formulate their aid delivery policies and institutions and what role the non state actors play. The main conclusions of the paper are that the legacies of the communist past have a clear influence and the V4 countries still have a long way to go in adapting their aid policies to international requirements.