Adsorption of Lennard-Jones fluids in carbon slit pores of a finite length. A computer simulation study

The adsorption of simple Lennard-Jones fluids in a carbon slit pore of finite length was studied with Canonical Ensemble (NVT) and Gibbs Ensemble Monte Carlo Simulations (GEMC). The Canonical Ensemble was a collection of cubic simulation boxes in which a finite pore resides, while the Gibbs Ensemble was that of the pore space of the finite pore. Argon was used as a model for Lennard-Jones fluids, while the adsorbent was modelled as a finite carbon slit pore whose two walls were composed of three graphene layers with carbon atoms arranged in a hexagonal pattern. The Lennard-Jones (LJ) 12-6 potential model was used to compute the interaction energy between two fluid particles, and also between a fluid particle and a carbon atom. Argon adsorption isotherms were obtained at 87.3 K for pore widths of 1.0, 1.5 and 2.0 nm using both Canonical and Gibbs Ensembles. These results were compared with isotherms obtained with corresponding infinite pores using Grand Canonical Ensembles. The effects of the number of cycles necessary to reach equilibrium, the initial allocation of particles, the displacement step and the simulation box size were particularly investigated in the Monte Carlo simulation with Canonical Ensembles. Of these parameters, the displacement step had the most significant effect on the performance of the Monte Carlo simulation. The simulation box size was also important, especially at low pressures at which the size must be sufficiently large to have a statistically acceptable number of particles in the bulk phase. Finally, it was found that the Canonical Ensemble and the Gibbs Ensemble both yielded the same isotherm (within statistical error); however, the computation time for GEMC was shorter than that for canonical ensemble simulation. However, the latter method described the proper interface between the reservoir and the adsorbed phase (and hence the meniscus).

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.

The adsorption of water in finite carbon pores

Grand canonical Monte Carlo simulations were applied to the adsorption of SPCE model water in finite graphitic pores with different configurations of carbonyl functional groups on only one surface and several pore sizes. It was found that almost all finite pores studied exhibit capillary condensation behaviour preceded by adsorption around the functional groups. Desorption showed the reverse transitions from a filled to a near empty pore resulting in a clear hysteresis loop in all pores except for some of the configurations of the 1.0nm pore. Carbonyl configurations had a strong effect on the filling pressure of all pores except, in some cases, in 1.0nm pores. A decrease in carbonyl neighbour density would result in a higher filling pressure. The emptying pressure was negligibly affected by the configuration of functional groups. Both the filling and emptying pressures increased with increasing pore size but the effect on the emptying pressure was much less. At pressures lower than the pore filling pressure, the adsorption of water was shown to have an extremely strong dependence on the neighbour density with adsorption changing from Type IV to Type III to linear as the neighbour density decreased. The isosteric heat was also calculated for these configurations to reveal its strong dependence on the neighbour density. These results were compared with literature experimental results for water and carbon black and found to qualitatively agree.

Pore size distribution analysis of activated carbons: Application of density functional theory using nongraphitized carbon black as a reference system

The application of nonlocal density functional theory (NLDFT) to determine pore size distribution (PSD) of activated carbons using a nongraphitized carbon black, instead of graphitized thermal carbon black, as a reference system is explored. We show that in this case nitrogen and argon adsorption isotherms in activated carbons are precisely correlated by the theory, and such an excellent correlation would never be possible if the pore wall surface was assumed to be identical to that of graphitized carbon black. It suggests that pore wall surfaces of activated carbon are closer to that of amorphous solids because of defects of crystalline lattice, finite pore length, and the presence of active centers.. etc. Application of the NLDFT adapted to amorphous solids resulted in quantitative description of N-2 and Ar adsorption isotherms on nongraphitized carbon black BP280 at their respective boiling points. In the present paper we determined solid-fluid potentials from experimental adsorption isotherms on nongraphitized carbon black and subsequently used those potentials to model adsorption in slit pores and generate a corresponding set of local isotherms, which we used to determine the PSD functions of different activated carbons. (c) 2005 Elsevier Ltd. All rights reserved.

Gaussian regression and optimal finite dimensional linear models

The problem of regression under Gaussian assumptions is treated generally. The relationship between Bayesian prediction, regularization and smoothing is elucidated. The ideal regression is the posterior mean and its computation scales as O(n³), where n is the sample size. We show that the optimal m-dimensional linear model under a given prior is spanned by the first m eigenfunctions of a covariance operator, which is a trace-class operator. This is an infinite dimensional analogue of principal component analysis. The importance of Hilbert space methods to practical statistics is also discussed.

A CFD approach on the effect of particle size on char entrainment in bubbling fluidised bed reactors

The fluid – particle interaction inside a 41.7 mg s-1 fluidised bed reactor is modelled. Three char particles of sizes 500 µm, 250 µm, and 100 µm are injected into the fluidised bed and the momentum transport from the fluidising gas and fluidised sand is modelled. Due to the fluidising conditions and reactor design the char particles will either be entrained from the reactor or remain inside the bubbling bed. The particle size is the factor that differentiates the particle motion inside the reactor and their efficient entrainment out of it. A 3-Dimensional simulation has been performed with a completele revised momentum transport model for bubble three-phase flow according to the literature as an extension to the commercial finite volume code FLUENT 6.2.

A critical assessment of the finite element method for calculating electric and magnetic fields

The present dissertation is concerned with the determination of the magnetic field distribution in ma[.rnetic electron lenses by means of the finite element method. In the differential form of this method a Poisson type equation is solved by numerical methods over a finite boundary. Previous methods of adapting this procedure to the requirements of digital computers have restricted its use to computers of extremely large core size. It is shown that by reformulating the boundary conditions, a considerable reduction in core store can be achieved for a given accuracy of field distribution. The magnetic field distribution of a lens may also be calculated by the integral form of the finite element rnethod. This eliminates boundary problems mentioned but introduces other difficulties. After a careful analysis of both methods it has proved possible to combine the advantages of both in a .new approach to the problem which may be called the 'differential-integral' finite element method. The application of this method to the determination of the magnetic field distribution of some new types of magnetic lenses is described. In the course of the work considerable re-programming of standard programs was necessary in order to reduce the core store requirements to a minimum.

Development of surface flaw thresholds for pre-cured fiber reinforced polymer and groove size tolerance for near surface mounted fiber reinforced polymer retrofit systems

Since the introduction of fiber reinforced polymers (FRP) for the repair and retrofit of concrete structures in the 1980’s, considerable research has been devoted to the feasibility of their application and predictive modeling of their performance. However, the effects of flaws present in the constitutive components and the practices in substrate preparation and treatment have not yet been thoroughly studied. This research aims at investigating the effect of surface preparation and treatment for the pre-cured FRP systems and the groove size tolerance for near surface mounted (NSM) FRP systems; and to set thresholds for guaranteed system performance. This study was conducted as part of the National Cooperative Highway Research Program (NCHRP) Project 10-59B to develop construction specifications and process control manual for repair and retrofit of concrete structures using bonded FRP systems. The research included both analytical and experimental components. The experimental program for the pre-cured FRP systems consisted of a total of twenty-four (24) reinforced concrete (RC) T-beams with various surface preparation parameters and surface flaws, including roughness, flatness, voids and cracks (cuts). For the NSM FRP systems, a total of twelve (12) additional RC T-beams were tested with different grooves sizes for FRP bars and strips. The analytical program included developing an elaborate nonlinear finite element model using the general purpose software ANSYS. The bond interface between FRP and concrete was modeled by a series of nonlinear springs. The model was validated against test data from the present study as well as those available from the literature. The model was subsequently used to extend the experimental range of parameters for surface flatness in pre-cured FRP systems and for groove size study in the NSM FRP systems. Test results, confirmed by further analyses, indicated that contrary to the general belief in the industry, the impact of surface roughness on the global performance of pre-cured FRP systems was negligible. The study also verified that threshold limits set for wet lay-up FRP systems can be extended to pre-cured systems. The study showed that larger surface voids and cracks (cuts) can adversely impact both the strength and ductility of pre-cured FRP systems. On the other hand, frequency (or spacing) of surface cracks (cuts) may only affect system ductility rather than its strength. Finally, within the range studied, groove size tolerance of ±1/8 in. does not appear to have an adverse effect on the performance of NSM FRP systems.

Customization of the design of antenna using genetic algorithm and finite-difference time-domain technique

Antenna design is an iterative process in which structures are analyzed and changed to comply with certain performance parameters required. The classic approach starts with analyzing a "known" structure, obtaining the value of its performance parameter and changing this structure until the "target" value is achieved. This process relies on having an initial structure, which follows some known or "intuitive" patterns already familiar to the designer. The purpose of this research was to develop a method of designing UWB antennas. What is new in this proposal is that the design process is reversed: the designer will start with the target performance parameter and obtain a structure as the result of the design process. This method provided a new way to replicate and optimize existing performance parameters. The base of the method was the use of a Genetic Algorithm (GA) adapted to the format of the chromosome that will be evaluated by the Electromagnetic (EM) solver. For the electromagnetic study we used XFDTD™ program, based in the Finite-Difference Time-Domain technique. The programming portion of the method was created under the MatLab environment, which serves as the interface for converting chromosomes, file formats and transferring of data between the XFDTD™ and GA. A high level of customization had to be written into the code to work with the specific files generated by the XFDTD™ program. Two types of cost functions were evaluated; the first one seeking broadband performance within the UWB band, and the second one searching for curve replication of a reference geometry. The performance of the method was evaluated considering the speed provided by the computer resources used. Balance between accuracy, data file size and speed of execution was achieved by defining parameters in the GA code as well as changing the internal parameters of the XFDTD™ projects. The results showed that the GA produced geometries that were analyzed by the XFDTD™ program and changed following the search criteria until reaching the target value of the cost function. Results also showed how the parameters can change the search criteria and influence the running of the code to provide a variety of geometries.

Development of Surface Flaw Thresholds for Pre-Cured Fiber Reinforced Polymer and Groove Size Tolerance for Near Surface Mounted Fiber Reinforced Polymer Retrofit Systems

Since the introduction of fiber reinforced polymers (FRP) for the repair and retrofit of concrete structures in the 1980’s, considerable research has been devoted to the feasibility of their application and predictive modeling of their performance. However, the effects of flaws present in the constitutive components and the practices in substrate preparation and treatment have not yet been thoroughly studied. This research aims at investigating the effect of surface preparation and treatment for the pre-cured FRP systems and the groove size tolerance for near surface mounted (NSM) FRP systems; and to set thresholds for guaranteed system performance. The research included both analytical and experimental components. The experimental program for the pre-cured FRP systems consisted of a total of twenty-four (24) reinforced concrete (RC) T-beams with various surface preparation parameters and surface flaws, including roughness, flatness, voids and cracks (cuts). For the NSM FRP systems, a total of twelve (12) additional RC T-beams were tested with different grooves sizes for FRP bars and strips. The analytical program included developing an elaborate nonlinear finite element model using the general purpose software ANSYS. The model was subsequently used to extend the experimental range of parameters for surface flatness in pre-cured FRP systems, and for groove size study in the NSM FRP systems. Test results, confirmed by further analyses, indicated that contrary to the general belief in the industry, the impact of surface roughness on the global performance of pre-cured FRP systems was negligible. The study also verified that threshold limits set for wet lay-up FRP systems can be extended to pre-cured systems. The study showed that larger surface voids and cracks (cuts) can adversely impact both the strength and ductility of pre-cured FRP systems. On the other hand, frequency (or spacing) of surface cracks (cuts) may only affect system ductility rather than its strength. Finally, within the range studied, groove size tolerance of +1/8 in. does not appear to have an adverse effect on the performance of NSM FRP systems.

A Posteriori Error Analysis of hp-Version Discontinuous Galerkin Finite Element Methods for Second-Order Quasilinear Elliptic Problems

We develop the a-posteriori error analysis of hp-version interior-penalty discontinuous Galerkin finite element methods for a class of second-order quasilinear elliptic partial differential equations. Computable upper and lower bounds on the error are derived in terms of a natural (mesh-dependent) energy norm. The bounds are explicit in the local mesh size and the local degree of the approximating polynomial. The performance of the proposed estimators within an automatic hp-adaptive refinement procedure is studied through numerical experiments.

On the size of the fibers of spectral maps induced by semialgebraic embeddings

Let S(M) be the ring of (continuous) semialgebraic functions on a semialgebraic set M and S*(M) its subring of bounded semialgebraic functions. In this work we compute the size of the fibers of the spectral maps Spec(j)1:Spec(S(N))→Spec(S(M)) and Spec(j)2:Spec(S*(N))→Spec(S*(M)) induced by the inclusion j:N M of a semialgebraic subset N of M. The ring S(M) can be understood as the localization of S*(M) at the multiplicative subset WM of those bounded semialgebraic functions on M with empty zero set. This provides a natural inclusion iM:Spec(S(M)) Spec(S*(M)) that reduces both problems above to an analysis of the fibers of the spectral map Spec(j)2:Spec(S*(N))→Spec(S*(M)). If we denote Z:=ClSpec(S*(M))(M N), it holds that the restriction map Spec(j)2|:Spec(S*(N)) Spec(j)2-1(Z)→Spec(S*(M)) Z is a homeomorphism. Our problem concentrates on the computation of the size of the fibers of Spec(j)2 at the points of Z. The size of the fibers of prime ideals "close" to the complement Y:=M N provides valuable information concerning how N is immersed inside M. If N is dense in M, the map Spec(j)2 is surjective and the generic fiber of a prime ideal p∈Z contains infinitely many elements. However, finite fibers may also appear and we provide a criterium to decide when the fiber Spec(j)2-1(p) is a finite set for p∈Z. If such is the case, our procedure allows us to compute the size s of Spec(j)2-1(p). If in addition N is locally compact and M is pure dimensional, s coincides with the number of minimal prime ideals contained in p. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Finite difference calculations of permeability in large domains in a wide porosity range.

Determining effective hydraulic, thermal, mechanical and electrical properties of porous materials by means of classical physical experiments is often time-consuming and expensive. Thus, accurate numerical calculations of material properties are of increasing interest in geophysical, manufacturing, bio-mechanical and environmental applications, among other fields. Characteristic material properties (e.g. intrinsic permeability, thermal conductivity and elastic moduli) depend on morphological details on the porescale such as shape and size of pores and pore throats or cracks. To obtain reliable predictions of these properties it is necessary to perform numerical analyses of sufficiently large unit cells. Such representative volume elements require optimized numerical simulation techniques. Current state-of-the-art simulation tools to calculate effective permeabilities of porous materials are based on various methods, e.g. lattice Boltzmann, finite volumes or explicit jump Stokes methods. All approaches still have limitations in the maximum size of the simulation domain. In response to these deficits of the well-established methods we propose an efficient and reliable numerical method which allows to calculate intrinsic permeabilities directly from voxel-based data obtained from 3D imaging techniques like X-ray microtomography. We present a modelling framework based on a parallel finite differences solver, allowing the calculation of large domains with relative low computing requirements (i.e. desktop computers). The presented method is validated in a diverse selection of materials, obtaining accurate results for a large range of porosities, wider than the ranges previously reported. Ongoing work includes the estimation of other effective properties of porous media.

Finite-strain laminates: Bending-enhanced hexahedron and delamination

With a new finite strain anisotropic framework, we introduce a unified approach for constitutive model- ing and delamination of composites. We describe a finite-strain semi-implicit integration algorithm and the application to assumed-strain hexahedra. In a laminate composite, the laminae are modeled by an anisotropic Kirchhoff/Saint-Venant material and the interfaces are modeled by the exponential cohesive law with intrinsic characteristic length and the criterion by Benzeggagh and Kenane for the equivalent fracture toughness. For the element formulation, a weighted least-squares algorithm is used to calculate the mixed strain. Löwdin frames are used to model orthotropic materials without the added task of per- forming a polar decomposition or empirical frames. To assess the validity of our proposals and inspect step and mesh size dependence, a least-squares based hexahedral element is implemented and tested in depth in both deformation and delamination examples.