Abstract: Zeogrids and Zeotiles are hierarchical materials built from assembled MFI zeolite precursor units. Permanent secondary porosity in these materials is obtained through self assembly of nanoparticles encountered in MFI zeolite synthesis in the presence of supramolecular templates. Hereon, the aggregated species are termed nanoslabs. Zeogrids are layered materials with lateral spacings between nanoslabs creating galleries qualifying as supermicropores. Zeotiles present a diversity of tridimensional nanoslab assemblies with mesopores. Zeotile-1, -4 and -6 are hexagonal mesostructures. Zeotile-1 has triangular and hexagonal channels; Zeotile-4 has hexagonal channels interconnected via slits. Zeotile-2 has a cubic structure with gyroid type mesoporosity. The behavior of Zeogrids and Zeotiles in adsorption, membrane and chromatographic separation and catalysis has been characterized and compared with zeolites and mesoporous materials derived from unstructured silica sources. Shape selectivity was detected via adsorption of n- and iso-alkanes. The mesoporosity of Zeotiles can be exploited in chromatographic separation of biomolecules. Zeotiles present attractive separation properties relevant to CO2 sequestration. Because of its facile synthesis procedure without hydrothermal steps Zeogrid is convenient for membrane synthesis. The performance of Zeogrid membrane in gas separation, nanofiltration and pervaporation is reported. In the Beckmann rearrangement of cyclohexanone oxime Zeogrids and Zeotiles display a catalytic activity characteristic of silicalite-1 zeolites. Introduction of acidity and redox catalytic activity can be achieved via incorporation of Al and Ti atoms in the nanoslabs during synthesis. Zeogrids are active in hydrocracking, catalytic cracking, alkylation and epoxidation reactions. Zeogrids and Zeotiles often behave differently from ordered mesoporous materials as well as from zeolites and present a valuable extension of the family of hierarchical silicate based materials.

Abstract: The engineering, construction, performance and running costs of a catalytic flue gas cleaning component in the low dust area of a municipal waste incinerator is discussed. For this purpose, the case study of a Flemish incineration plant is presented, covering the history, the design procedure of the catalyst, relevant process data and the financial aspects. A reliable PCDD/F-destruction by means of oxidation by the catalyst to typical values of 0.001 ng TEQ/Nm3 has been demonstrated. At the same time, NOx− and CO-emissions are reduced by 90% and 20% to about 50 mg/Nm3 and below 10 mg/Nm3, respectively.

Abstract: Recycling of end-of-life polyvinyl chloride (PVC) calls for solutions to deal with the vast amounts of harmful phthalate plasticizers that have historically been incorporated in PVC. Here, we report on the upcycling of such waste-extracted phthalate esters into analogues of the much safer diisononyl 1,2-cyclohexanedicarboxylate plasticizer (DINCH), via a catalytic one-pot (trans)esterification-hydrogenation process. For most of the virgin phthalates, Ru/Al2O3 is a highly effective hydrogenation catalyst, yielding >99% ring-hydrogenated products under mild reaction conditions (0.1 mol% Ru, 80 degrees C, 50 bar H-2). However, applying this reaction to PVC-extracted phthalates proved problematic, (1) as benzyl phthalates are hydrogenolyzed to benzoic acids that inhibit the Ru-catalyst, and (2) because impurities in the plasticizer extract (PVC, sulfur) further retard the hydrogenation. These complications were solved by coupling the hydrogenation to an in situ (trans)esterification with a higher alcohol, and by pretreating the extract with an activated carbon adsorbent. In this way, a real phthalate extract obtained from post-consumer PVC waste was eventually completely (>99%) hydrogenated to phthalate-free, cycloaliphatic plasticizers.

Abstract: The factors mediating cation ordering in the scheelite-based molybdates and tungstates are discussed on the basis of the incommensurately modulated crystal structures of the CaEu2(BO4)(4) (B = Mo, W) red phosphors solved from high-resolution synchrotron powder X-ray diffraction data. Monoclinic CaEu2(WO4)(4) adopts a (3 + 1)-dimensionally modulated structure [superspace group I2/b(alpha beta 0)00, a = 5.238 73(1)A, b = 5.266 35(1) A, c = 11.463 19(9) A, gamma = 91.1511(2)degrees, q = 0.56153(6)a* + 0.7708(9)b*, R-F = 0.050, R-p = 0.069], whereas tetragonal CaEu2(MoO4)(4) is (3 + 2)-dimensionally modulated [superspace group I4(1)/ a(alpha beta 0)00(-beta alpha 0)00, a = 5.238 672(7) A, c = 11.548 43(2) A, q(1) = 035331(8)a* + 0.82068(9)b*, q(2) = -0.82068(9)a* + 0.55331(8)b*, R-F = 0.061, R-p = 0.082]. In both cases the modulation arises from the ordering of the Ca/Eu cations and the cation vacancies at the A-sublattice of the parent scheelite ABO(4) structure. The cation ordering is incomplete and better described with harmonic rather than with steplike occupational modulation functions. The structures respond to the variation of the effective charge and cation size at the A-position through the flexible geometry of the MoO42- and WO42- tetrahedra demonstrating an alternation of stretching the B-O bond lengths and bending the O-B-O bond angles. The tendency towards A-site cation ordering in scheelites is rationalized using the difference in ionic radii and concentration of the A-site vacancies as parameters and presented in the form of a structure map.

Abstract: ''1201'' Tl-based substituted cuprates of the type (Tl1-xMx) Sr2CuO5 have been synthesized for M = Nb, Ta, or W. These materials do not superconduct due to a statistical distribution of some of the M for Cu. The remarkable feature of these materials is the ordering observed between Tl and M in the (Tl1-xMx-epsilon)O plane. The type of ordering depends on the composition and shows remarkable similarities with the ordering in Ni-Mo or other so-called 1 1/2 0 type fcc-based alloys or with the ordering in rocksalt oxides TiOx. The short-range order, for M = W, can be readily interpreted in terms of a mixing of nano-clusters with two different compositions. These observations of two-dimensional ordering confirm recent ideas about ordering in three-dimensional fcc-based alloys.

Abstract: Molecular dynamics simulations are used to study the effects of different cations on the permeation of charged polymers through flat capillaries with heights below 2 nm. Interestingly, we found that, despite being monovalent, Li+ , Na+ , and K+ cations have different effects on polymer permeation, which consequently affects their transmission speed throughout those capillaries. We attribute this phenomenon to the interplay of the cations' hydration free energies and the hydrodynamic drag in front of the polymer when it enters the capillary. Different alkali cations exhibit different surface versus bulk preferences in small clusters of water under the influence of an external electric field. This paper presents a tool to control the speed of charged polymers in confined spaces using cations.

Abstract: Understanding the behaviour of vortices under nanoscale confinement in superconducting circuits is important for the development of superconducting electronics and quantum technologies. Using numerical simulations based on the Ginzburg-Landau theory for non-homogeneous superconductivity in the presence of magnetic fields, we detail how lateral confinement organises vortices in a long superconducting nanostripe, presenting a phase diagram of vortex configurations as a function of the stripe width and magnetic field. We discuss why the average vortex density is reduced and reveal that confinement influences vortex dynamics in the dissipative regime under sourced electrical current, mapping out transitions between asynchronous and synchronous vortex rows crossing the nanostripe as the current is varied. Synchronous crossings are of particular interest, since they cause single-mode modulations in the voltage drop along the stripe in a high (typically GHz to THz) frequency range.

Abstract: Sanitation systems are built to be robust, that is, they are dimensioned to cope with population growth and other variability that occurs throughout their lifetime. It was recently shown that building sanitation systems in phases is more cost effective than one robust design. This phasing can take place by building small autonomous decentralised units that operate closer to the actual demand. Research has shown that variability and uncertainty in urban development does affect the cost effectiveness of this approach. Previous studies do not, however, consider the entire sanitation system from collection to treatment. The aim of this study is to assess the economic performance of three sanitation systems with different scales and systems characteristics under a variety of urban development pathways. Three systems are studied: (I) a centralised conventional activated sludge treatment, (II) a community on site source separation grey water and black water treatment and (III) a hybrid with grey water treatment at neighbourhood scale and black water treatment off site. A modelling approach is taken that combines a simulation of greenfield urban growth, a model of the wastewater collection and treatment infrastructure design properties and a model that translates design parameters into discounted asset lifetime costs. Monte Carlo simulations are used to evaluate the economic performance under uncertain development trends. Results show that the conventional system outperforms both of the other systems when total discounted lifetime costs are assessed, because it benefits from economies of scale. However, when population growth is lower than expected, the source-separated system is more cost effective, because of reduced idle capacity. The hybrid system is not competitive under any circumstance due to the costly double piping and treatment. (C) 2016 Elsevier Ltd. All rights reserved.

Abstract: We present a theoretical study of the electrical generation of acoustic-phonon emission from graphene at room temperature. The drift velocity (v(x)) and temperature of electrons driven by dc electric field (F-x) are determined by solving self-consistently the momentum-and energy-balance equations derived from the Boltzmann equation. We find that in the presence of impurity, acoustic-and optic-phonon scattering, v(x) can be much larger than the longitudinal (v(l)) and transverse (v(t)) sound velocities in graphene even within the linear response regime. As a result, although the acoustic Cerenkov effect cannot be obviously seen in the analytical formulas, the enhanced acoustic-phonon emission can be observed with increasing F-x when v(x) > v(l) and v > v(t). The frequency of acoustic-phonon emission from graphene can be above 10 THz, which is much higher than that generated from conventional semiconductor systems. This study is pertinent to the application of graphene as hypersonic devices such as terahertz sound sources. (C) 2013 AIP Publishing LLC.

Abstract: This paper focuses on the investigation of CF4 decomposition in a low-pressure inductively coupled plasma by means of a global model. The influence of O2 on the CF4 decomposition process is studied for conditions used in semiconductor manufacturing processes. The model is applied for different powers and O2 contents ranging between 2% and 98% in the CF4/O2 gas mixture. The model includes the reaction mechanisms in the gas phase coupled with the surface reactions and sticking probabilities of the species at the walls. The calculation results are first compared with experimental results from the literature (for the electron density, temperature and F atom density) at a specific power, in the entire range of CF4/O2 gas mixture ratios, and the obtained agreements indicate the validity of the model. The main products of the gas mixture, obtained from this model, include CO, CO2 and COF2 together with a low fraction of F2. The most effective reactions for the formation and loss of the various species in this process are also determined in detail. Decomposition of CF4 produces mostly CF3 and F radicals. These radicals also contribute to the backward reactions, forming again CF4. This study reveals that the maximum decomposition efficiency of CF4 is achieved at a CF4/O2 ratio equal to 1, at the applied power of 300 W.

Abstract: The structural transitions of the ground state of a system of repulsively interacting particles confined in a quasi-one-dimensional channel, and the effect of the interparticle interaction as well as the functional form of the confinement potential on those transitions are investigated. Although the nonsequential ordering of transitions (non-SOT), i.e., the 1 – 2 – 4 – 3 – 4 – 5 – 6 – ... sequence of chain configurations with increasing density, is widely robust as predicted in a number of theoretical studies, the sequential ordering of transitions (SOT), i.e., the 1 – 2 – 3 – 4 – 5 – 6 – ... chain, is found as the ground state for long-ranged interparticle interaction and hard-wall-like confinement potentials. We found an energy barrier between every two different phases around its transition point, which plays an important role in the preference of the system to follow either a SOT or a non-SOT. However, that preferential transition requires also the stability of the phases during the transition. Additionally, we analyze the effect of a small structural disorder on the transition between the two phases around its transition point. Our results show that a small deformation of the triangular structure changes dramatically the picture of the transition between two phases, removing in a considerable region the non-SOT in the system. This feature could explain the fact that the non-SOT is, up to now, not observed in experimental systems, and suggests a more advanced experimental setup to detect the non-SOT.

Abstract: Thin films of C/Mo/W deposited using combined UBM/HIPIMS sputtering show 2-8 nm clusters of material richer in Mo and W than the matrix (found by EDS microanalysis), with structures that resemble graphitic onions with the metal atoms arranged regularly within them. EELS microanalysis showed the clusters to be rich in W and Mo. As the time averaged power used in the pulsed HIPIMS magnetron was increased, the clusters became more defined, larger, and arranged into layers with amorphous matrix between them. Films deposited with average HIPIMS powers of 4 kW and 6 kW also showed a periodic modulation of the cluster density within the finer layers giving secondary, wider stripes in TEM. By analysing the ratio between the finer and coarser layers, it was found that this meta-layering is related to the substrate rotation in the deposition chamber but in a non-straightforward way. Reasons for this are proposed. The detailed structure of the clusters remains unknown and is the subject of further work. Fluctuation electron microscopy results indicated the presence of crystal planes with the graphite interlayer spacing, crystal planes in hexagonal WC perpendicular to the basal plane, and some plane spacings found in Mo2C. Other peaks in the FEM results suggested symmetry-related starting points for future determination of the structure of the clusters.

Abstract: We studied the morphology of ramps in REBa2CU3O7 (REBCO) epitaxial films on SrTiO3 substrates, fabricated by RF magnetron sputter deposition and pulsed laser deposition (PLD), by scanning probe microscopy (SPM) and high resolution electron microscopy (HREM). The ramps were fabricated by Ar ion beam etching using masks of standard photoresist and TIN. AFM-studies on ramps in sputter deposited films show a strong dependence, i.e. formation of facets and ridges, on the angle of incidence of the ion beam with respect to the substrate surface as well as the rotation angle with respect to the crystal axes of the substrate. Ramps in pulsed laser deposited films did not show this dependence, Furthermore, we studied the effect of an anneal step prior to the deposition of barrier layers (i.e. PrBa2CU3O7, SrTiO3, CeO2) on the ramp. First results show a recrystallization of the ramp surface, resulting in terraces and a non-homogeneous growth of the barrier material on top of it. The thickness variations, for thin layers of barrier material, con even become much larger than expected from the amount of deposited material and are dependent on the deposition and anneal conditions. HREM studies show a well defined interface between barrier layer and electrodes. The angle of the ramp depends on the etch rate of the mask and REBCO, and on the angle of incidence of the ion beam. TiN has a much lower etch rate compared to photoresist, resulting in an angle of the ramp comparable to the angle of incidence, resulting in a low etching rate on the ramp. These results will lead to improved electrical characteristics of ramp-type junctions.