Statistical thermodynamics of lattice models in zeolites: Implications of local versus global mean field interactions

The statistical thermodynamics of adsorption in caged zeolites is developed by treating the zeolite as an ensemble of M identical cages or subsystems. Within each cage adsorption is assumed to occur onto a lattice of n identical sites. Expressions for the average occupancy per cage are obtained by minimizing the Helmholtz free energy in the canonical ensemble subject to the constraints of constant M and constant number of adsorbates N. Adsorbate-adsorbate interactions in the Brag-Williams or mean field approximation are treated in two ways. The local mean field approximation (LMFA) is based on the local cage occupancy and the global mean field approximation (GMFA) is based on the average coverage of the ensemble. The GMFA is shown to be equivalent in formulation to treating the zeolite as a collection of interacting single site subsystems. In contrast, the treatment in the LMFA retains the description of the zeolite as an ensemble of identical cages, whose thermodynamic properties are conveniently derived in the grand canonical ensemble. For a z coordinated lattice within the zeolite cage, with epsilon(aa) as the adsorbate-adsorbate interaction parameter, the comparisons for different values of epsilon(aa)(*)=epsilon(aa)z/2kT, and number of sites per cage, n, illustrate that for -1 0. We compare the isotherms predicted with the LMFA with previous GMFA predictions [K. G. Ayappa, C. R. Kamala, and T. A. Abinandanan, J. Chem. Phys. 110, 8714 (1999)] (which incorporates both the site volume reduction and a coverage-dependent epsilon(aa)) for xenon and methane in zeolite NaA. In all cases the predicted isotherms are very similar, with the exception of a small steplike feature present in the LMFA for xenon at higher coverages. (C) 1999 American Institute of Physics. [S0021-9606(99)70333-8].

A multifold reduction in the transition Reynolds number, and ultra-fast mixing, in a micro-channel due to a dynamical instability induced by a soft wall

A dynamical instability is observed in experimental studies on micro-channels of rectangular cross-section with smallest dimension 100 and 160 mu m in which one of the walls is made of soft gel. There is a spontaneous transition from an ordered, laminar flow to a chaotic and highly mixed flow state when the Reynolds number increases beyond a critical value. The critical Reynolds number, which decreases as the elasticity modulus of the soft wall is reduced, is as low as 200 for the softest wall used here (in contrast to 1200 for a rigid-walled channel) The instability onset is observed by the breakup of a dye-stream introduced in the centre of the micro-channel, as well as the onset of wall oscillations due to laser scattering from fluorescent beads embedded in the wall of the channel. The mixing time across a channel of width 1.5 mm, measured by dye-stream and outlet conductance experiments, is smaller by a factor of 10(5) than that for a laminar flow. The increased mixing rate comes at very little cost, because the pressure drop (energy requirement to drive the flow) increases continuously and modestly at transition. The deformed shape is reconstructed numerically, and computational fluid dynamics (CFD) simulations are carried out to obtain the pressure gradient and the velocity fields for different flow rates. The pressure difference across the channel predicted by simulations is in agreement with the experiments (within experimental errors) for flow rates where the dye stream is laminar, but the experimental pressure difference is higher than the simulation prediction after dye-stream breakup. A linear stability analysis is carried out using the parallel-flow approximation, in which the wall is modelled as a neo-Hookean elastic solid, and the simulation results for the mean velocity and pressure gradient from the CFD simulations are used as inputs. The stability analysis accurately predicts the Reynolds number (based on flow rate) at which an instability is observed in the dye stream, and it also predicts that the instability first takes place at the downstream converging section of the channel, and not at the upstream diverging section. The stability analysis also indicates that the destabilization is due to the modification of the flow and the local pressure gradient due to the wall deformation; if we assume a parabolic velocity profile with the pressure gradient given by the plane Poiseuille law, the flow is always found to be stable.

Controlling air solubility to maintain `'Cassie'' state for sustained drag reduction

`'Cassie'' state of wetting can be established by trapping air pockets on the crevices of textured hydrophobic surfaces, leading to significant drag reduction. However, this drag reduction cannot be sustained due to gradual dissolution of trapped air into water. In this paper, we explore the possibility of sustaining the underwater Cassie state of wetting in a microchannel by controlling the solubility of air in water; the solubility being changed by controlling the local absolute pressure near the surface. We show that using this method, we can in fact make the water locally supersaturated with air thus encouraging the growth of trapped air pockets on the surface. In this case, the water acts as a pumping medium, delivering air to the crevices of the hydrophobic surface in the microchannel, where the presence of air pockets is most beneficial from the drag reduction perspective. In our experiments, the air trapped on a textured surface is visualized using total internal reflection based technique, at different local absolute pressures with the pressure drop (or drag) also being simultaneously measured. We find that, by controlling the pressure and hence the solubility close to the surface, we can either shrink or grow the trapped air bubbles, uniformly over a large surface area. The experiments show that, by precisely controlling the pressure and hence the solubility we can sustain the `'Cassie state'' over extended periods of time. This method thus provides a means of getting sustained drag reduction from a textured hydrophobic surface in channel flows. (C) 2014 Elsevier B.V. All rights reserved.

STM verification of the reduction of the Young's modulus of CdS nanoparticles at smaller sizes

We demonstrate the first STM evaluation of the Young's modulus (E) of nanoparticles (NPs) of different sizes. The sample deformation induced by tip-sample interaction has been determined using current-distance (I-Z) spectroscopy. As a result of tip-sample interaction, and the induced surface deformations, the I-z curves deviates from pure exponential dependence. Normally, in order to analyze the deformation quantitatively, the tip radius must be known. We show, that this necessity is eliminated by measuring the deformation on a substrate with a known Young's modulus (Au(111)) and estimating the tip radius, and afterwards, using the same tip (with a known radius) to measure the (unknown) Young's modulus of another sample (nanoparticles of CdS). The Young's modulus values found for 3 NP's samples of average diameters of 3.7, 6 and 7.5 nm, were E similar to 73%, 78% and 88% of the bulk value, respectively. These results are in a good agreement with the theoretically predicted reduction of the Young's modulus due to the changes in hydrostatic stresses which resulted from surface tension in nanoparticles with different sizes. Our calculation using third order elastic constants gives a reduction of E which scales linearly with 1/r (r is the NP's radius). This demonstrates the applicability of scanning tunneling spectroscopy for local mechanical characterization of nanoobjects. The method does not include a direct measurement of the tip-sample force but is rather based on the study of the relative elastic response. (C) 2014 Elsevier B.V. All rights reserved.

Sustainable IT and IT for sustainability

Energy and sustainability have become one of the most critical issues of our generation. While the abundant potential of renewable energy such as solar and wind provides a real opportunity for sustainability, their intermittency and uncertainty present a daunting operating challenge. This thesis aims to develop analytical models, deployable algorithms, and real systems to enable efficient integration of renewable energy into complex distributed systems with limited information.

The first thrust of the thesis is to make IT systems more sustainable by facilitating the integration of renewable energy into these systems. IT represents the fastest growing sectors in energy usage and greenhouse gas pollution. Over the last decade there are dramatic improvements in the energy efficiency of IT systems, but the efficiency improvements do not necessarily lead to reduction in energy consumption because more servers are demanded. Further, little effort has been put in making IT more sustainable, and most of the improvements are from improved "engineering" rather than improved "algorithms". In contrast, my work focuses on developing algorithms with rigorous theoretical analysis that improve the sustainability of IT. In particular, this thesis seeks to exploit the flexibilities of cloud workloads both (i) in time by scheduling delay-tolerant workloads and (ii) in space by routing requests to geographically diverse data centers. These opportunities allow data centers to adaptively respond to renewable availability, varying cooling efficiency, and fluctuating energy prices, while still meeting performance requirements. The design of the enabling algorithms is however very challenging because of limited information, non-smooth objective functions and the need for distributed control. Novel distributed algorithms are developed with theoretically provable guarantees to enable the "follow the renewables" routing. Moving from theory to practice, I helped HP design and implement industry's first Net-zero Energy Data Center.

The second thrust of this thesis is to use IT systems to improve the sustainability and efficiency of our energy infrastructure through data center demand response. The main challenges as we integrate more renewable sources to the existing power grid come from the fluctuation and unpredictability of renewable generation. Although energy storage and reserves can potentially solve the issues, they are very costly. One promising alternative is to make the cloud data centers demand responsive. The potential of such an approach is huge.

To realize this potential, we need adaptive and distributed control of cloud data centers and new electricity market designs for distributed electricity resources. My work is progressing in both directions. In particular, I have designed online algorithms with theoretically guaranteed performance for data center operators to deal with uncertainties under popular demand response programs. Based on local control rules of customers, I have further designed new pricing schemes for demand response to align the interests of customers, utility companies, and the society to improve social welfare.

Charter and Party Boat Operators in the U.S. Gulf of Mexico: A Social Structure Perspective

To better address the charter and party boat fishery needs in the U.S. Gulf of Mexico, fishery managers must understand the linkages between the industry and other groups and organizations that affect its success. Gulf state charter and party boat operators were interviewed to ascertain the extent of their social network linkages, membership in community organizations, business community relationships, and linkages to information sources. Approximately one-third to one-half of the charter and party boat operators did not belong to local community organizations that could assist their business through tourism promotion or natural resource protection. Despite their limited integration in the community, the vast majority of operators gave and received referrals from other businesses. Of four major information sources, the National Weather Service and the County Marine Extension agents were rated highest and lowest, respectively, in mean importance to charter and party boat operators. Results suggest that business success can be enhanced by strengthening network ties between operators and local businesses, chambers of commerce, and tourism organizations. For this to occur, individual operators and charter/party boat organizations need to become more effective in representing industry interests. Informational linkages between industry and govemment agencies also need improvement.

Optimal H2 order-one reduction by solving eigenproblems for polynomial equations

A method is given for solving an optimal H2 approximation problem for SISO linear time-invariant stable systems. The method, based on constructive algebra, guarantees that the global optimum is found; it does not involve any gradient-based search, and hence avoids the usual problems of local minima. We examine mostly the case when the model order is reduced by one, and when the original system has distinct poles. This case exhibits special structure which allows us to provide a complete solution. The problem is converted into linear algebra by exhibiting a finite-dimensional basis for a certain space, and can then be solved by eigenvalue calculations, following the methods developed by Stetter and Moeller. The use of Buchberger's algorithm is avoided by writing the first-order optimality conditions in a special form, from which a Groebner basis is immediately available. Compared with our previous work the method presented here has much smaller time and memory requirements, and can therefore be applied to systems of significantly higher McMillan degree. In addition, some hypotheses which were required in the previous work have been removed. Some examples are included.

A criterion for local interconvertibility between all-tripartite Gaussian states

We arrive at a necessary and sufficient criterion that can be readily used for interconvertibility between general, all-tripartite Gaussian states under local quantum operation. The derivation involves a systematic reduction that converts the original complex conditions in high-dimensional, 6n x 6n matrix space eventually into 2 x 2 matrix problems.

Detecting a set of entanglement measures in an unknown tripartite quantum state by local operations and classical communication

We propose a more general method for detecting a set of entanglement measures, i.e., negativities, in an arbitrary tripartite quantum state by local operations and classical communication. To accomplish the detection task using this method, three observers do not need to perform partial transposition maps by the structural physical approximation; instead, they only need to collectively measure some functions via three local networks supplemented by a classical communication. With these functions, they are able to determine the set of negativities related to the tripartite quantum state.

Reduction-Based Model Updating of a Scaled Offshore Platform Structure

This paper attempts to develop a reduction-based model updating technique for jacket offshore platform structure. A reduced model is used instead of the direct finite-element model of the real structure in order to circumvent such difficulties as huge degrees of freedom and incomplete experimental data that are usually civil engineers' trouble during the model updating. The whole process consists of three steps: reduction of FE model, the first model updating to minimize the reduction error, and the second model updating to minimize the modeling error of the reduced model and the real structure. According to the performance of jacket platforms, a local-rigidity assumption is employed to obtain the reduced model. The technique is applied in a downscale model of a four-legged offshore platform where its effectiveness is well proven. Furthermore, a comparison between the real structure and its numerical models in the following model validation shows that the updated models have good approximation to the real structure. Besides, some difficulties in the field of model updating are also discussed.

Basis Reduction Algorithms and Subset Sum Problems

This thesis investigates a new approach to lattice basis reduction suggested by M. Seysen. Seysen's algorithm attempts to globally reduce a lattice basis, whereas the Lenstra, Lenstra, Lovasz (LLL) family of reduction algorithms concentrates on local reductions. We show that Seysen's algorithm is well suited for reducing certain classes of lattice bases, and often requires much less time in practice than the LLL algorithm. We also demonstrate how Seysen's algorithm for basis reduction may be applied to subset sum problems. Seysen's technique, used in combination with the LLL algorithm, and other heuristics, enables us to solve a much larger class of subset sum problems than was previously possible.

Trash: a local solution to a global problem

Gemstone Team GREEN JUSTICE

Prediction of reinforcement corrosion in concrete and its effects on concrete cracking and strength reduction

Based on extensive research on reinforcing steel corrosion in concrete in the past decades, it is now possible to estimate the effect of the progression of reinforcement corrosion in concrete infrastructure on its structural performance. There are still areas of considerable uncertainty in the models and in the data available, however This paper uses a recently developed model for reinforcement corrosion in concrete to improve the estimation process and to indicate the practical implications. In particular stochastic models are used to estimate the time likely to elapse for each phase of the whole corrosion process: initiation, corrosion-induced concrete cracking, and structural strength reduction. It was found that, for practical flexural structures subject to chloride attacks, corrosion initiation may start quite early in their service life. It was also found that, once the structure is considered to be unserviceable due to corrosion-induced cracking, there is considerable remaining service life before the structure can be considered to have become unsafe. The procedure proposed in the paper has the potential to serve as a rational tool for practitioners, operators, and asset managers to make decisions about the optimal timing of repairs, strengthening, and/or rehabilitation of corrosion-affected concrete infrastructure. Timely intervention has the potential to prolong the service life of infrastructure.

Entanglement between collective operators in a linear harmonic chain

We investigate entanglement between collective operators of two blocks of oscillators in an infinite linear harmonic chain. These operators are defined as averages over local operators (individual oscillators) in the blocks. On the one hand, this approach of "physical blocks" meets realistic experimental conditions, where measurement apparatuses do not interact with single oscillators but rather with a whole bunch of them, i.e., where in contrast to usually studied "mathematical blocks" not every possible measurement is allowed. On the other, this formalism naturally allows the generalization to blocks which may consist of several noncontiguous regions. We quantify entanglement between the collective operators by a measure based on the Peres-Horodecki criterion and show how it can be extracted and transferred to two qubits. Entanglement between two blocks is found even in the case where none of the oscillators from one block is entangled with an oscillator from the other, showing genuine bipartite entanglement between collective operators. Allowing the blocks to consist of a periodic sequence of subblocks, we verify that entanglement scales at most with the total boundary region. We also apply the approach of collective operators to scalar quantum field theory.

Ecoturismo en comunidades rurales: análisis de los impactos negativos para la población local. Un estudio de caso

En los últimos años han aparecido nuevas formas de turismo más sostenibles, donde existen elementos relacionados con el descanso, el disfrute y la protección del medio ambiente o el conocimiento de la cultura local, a través de políticas que favorecen la sostenibilidad del destino. En este sentido, el ecoturismo se configura como una tipología turística que se desarrolla en contacto con la naturaleza. Este turismo ayuda a mejorar el desarrollo socioeconómico de las comunidades locales, a la vez, que fomenta la conservación de los recursos naturales y el respeto hacia el medio ambiente. Aunque, esta tipología de turismo también genera importantes impactos negativos. El objetivo principal de esta investigación es analizar los impactos socioeconómicos, culturales y medioambientales percibidos por el ecoturismo por parte de los residentes de comunidades rurales de República Dominicana. La técnica de recolección de datos utilizada ha consistido en un cuestionario. Entre las principales conclusiones, cabe destacar que actualmente no se perciben impactos negativos, pero si hay una serie de elementos que hay que ir considerando, con la finalidad de que no se conviertan en un impacto a corto plazo para la comunidad rural.