Influence of Spatial Variation of Hydraulic Conductivity of Municipal Solid Waste on Performance of Bioreactor Landfill

The current study analyzes the leachate distribution in the Orchard Hills Landfill, Davis Junction, Illinois, using a two-phase flow model to assess the influence of variability in hydraulic conductivity on the effectiveness of the existing leachate recirculation system and its operations through reliability analysis. Numerical modeling, using finite-difference code, is performed with due consideration to the spatial variation of hydraulic conductivity of the municipal solid waste (MSW). The inhomogeneous and anisotropic waste condition is assumed because it is a more realistic representation of the MSW. For the reliability analysis, the landfill is divided into 10 MSW layers with different mean values of vertical and horizontal hydraulic conductivities (decreasing from top to bottom), and the parametric study is performed by taking the coefficients of variation (COVs) as 50, 100, 150, and 200%. Monte Carlo simulations are performed to obtain statistical information (mean and COV) of output parameters of the (1) wetted area of the MSW, (2) maximum induced pore pressure, and (3) leachate outflow. The results of the reliability analysis are used to determine the influence of hydraulic conductivity on the effectiveness of the leachate recirculation and are discussed in the light of a deterministic approach. The study is useful in understanding the efficiency of the leachate recirculation system. (C) 2013 American Society of Civil Engineers.

Nucleation of a Stable Solid from Melt in the Presence of Multiple Metastable Intermediate Phases: Wetting, Ostwald's Step Rule, and Vanishing Polymorphs

In many systems, nucleation of a stable solid may occur in the presence of other (often more than one) metastable phases. These may be polymorphic solids or even liquid phases. Sometimes, the metastable phase might have a lower free energy minimum than the liquid but higher than the stable-solid-phase minimum and have characteristics in between the parent liquid and the globally stable solid phase. In such cases, nucleation of the solid phase from the melt may be facilitated by the metastable phase because the latter can ``wet'' the interface between the parent and the daughter phases, even though there may be no signature of the existence of metastable phase in the thermodynamic properties of the parent liquid and the stable solid phase. Straightforward application of classical nucleation theory (CNT) is flawed here as it overestimates the nucleation barrier because surface tension is overestimated (by neglecting the metastable phases of intermediate order) while the thermodynamic free energy gap between daughter and parent phases remains unchanged. In this work, we discuss a density functional theory (DFT)-based statistical mechanical approach to explore and quantify such facilitation. We construct a simple order-parameter-dependent free energy surface that we then use in DFT to calculate (i) the order parameter profile, (ii) the overall nucleation free energy barrier, and (iii) the surface tension between the parent liquid and the metastable solid and also parent liquid and stable solid phases. The theory indeed finds that the nucleation free energy barrier can decrease significantly in the presence of wetting. This approach can provide a microscopic explanation of the Ostwald step rule and the well-known phenomenon of ``disappearing polymorphs'' that depends on temperature and other thermodynamic conditions. Theory reveals a diverse scenario for phase transformation kinetics, some of which may be explored via modem nanoscopic synthetic methods.

Experimental evidence for `carbon bonding' in the solid state from charge density analysis

The validity of the newly proposed `carbon bonding', an interaction where a carbon atom acts as an electrophilic site towards a variety of nucleophiles, has been investigated in the solid state. X-ray charge density analysis provides experimental evidence for this hitherto unexplored interaction and unravels its nature and strength.

Solid-solid collapse transition in a two dimensional model molecular system

Solid-solid collapse transition in open framework structures is ubiquitous in nature. The real difficulty in understanding detailed microscopic aspects of such transitions in molecular systems arises from the interplay between different energy and length scales involved in molecular systems, often mediated through a solvent. In this work we employ Monte-Carlo simulation to study the collapse transition in a model molecular system interacting via both isotropic as well as anisotropic interactions having different length and energy scales. The model we use is known as Mercedes-Benz (MB), which, for a specific set of parameters, sustains two solid phases: honeycomb and oblique. In order to study the temperature induced collapse transition, we start with a metastable honeycomb solid and induce transition by increasing temperature. High density oblique solid so formed has two characteristic length scales corresponding to isotropic and anisotropic parts of interaction potential. Contrary to the common belief and classical nucleation theory, interestingly, we find linear strip-like nucleating clusters having significantly different order and average coordination number than the bulk stable phase. In the early stage of growth, the cluster grows as a linear strip, followed by branched and ring-like strips. The geometry of growing cluster is a consequence of the delicate balance between two types of interactions, which enables the dominance of stabilizing energy over destabilizing surface energy. The nucleus of stable oblique phase is wetted by intermediate order particles, which minimizes the surface free energy. In the case of pressure induced transition at low temperature the collapsed state is a disordered solid. The disordered solid phase has diverse local quasi-stable structures along with oblique-solid like domains. (C) 2013 AIP Publishing LLC.

Production of syngas from steam reforming and CO removal with water gas shift reaction over nanosized Zr0.95Ru0.05O2-delta solid solution

This study presents the synthesis, characterization, and kinetics of steam reforming of methane and water gas shift (WGS) reactions over highly active and coke resistant Zr0.93Ru0.05O2-delta. The catalyst showed high activity at low temperatures for both the reactions. For WGS reaction, 99% conversion of CO with 100% H-2 selectivity was observed below 290 degrees C. The detailed kinetic studies including influence of gas phase product species, effect of temperature and catalyst loading on the reaction rates have been investigated. For the reforming reaction, the rate of reaction is first order in CH4 concentration and independent of CO and H2O concentration. This indicates that the adsorptive dissociation of CH4 is the rate determining step. The catalyst also showed excellent coke resistance even under a stoichiometric steam/carbon ratio. A lack of CO methanation activity is an important finding of present study and this is attributed to the ionic nature of Ru species. The associative mechanism involving the surface formate as an intermediate was used to correlate experimental data. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Selective and Efficient Detection of Nitro-Aromatic Explosives in Multiple Media including Water, Micelles, Organogel, and Solid Support

Selective detection of nitro-aromatic compounds (NACs) at nanomolar concentration is achieved for the first time in multiple media including water, micelles or in organogels as well as using test strips. Mechanism of interaction of NACs with highly fluorescent p-phenylenevinylene-based molecules has been described as the electron transfer phenomenon from the electron-rich chromophoric probe to the electron deficient NACs. The selectivity in sensing is guided by the pK(a) of the probes as well as the NACs under consideration. TNP-induced selective gel-to-sol transition in THF medium is also observed through the reorganization of molecular self-assembly and the portable test trips are made successfully for rapid on-site detection purpose.

Rheological characterization of semi-solid A356 aluminium alloy

Rheological behavior of semi-solid slurries forms the backbone of semi-solid processing of metallic alloys. In particular, the effects of several process and metallurgical parameters such as shear rate, shear time, temperature, rest time and size, distribution and morphology of the primary phase on the viscosity of the slurry needs in-depth characterization. In the present work, rheological behaviour of the semisolid aluminium alloy (A356) slurry is investigated by using a high temperature Searle type Rheometer using concentric cylinders. Three different types of experiment are carried out: isothermal test, continuous cooling test and steady state test. Continuous decrease in viscosity is observed with increasing shear rate at a fixed temperature (isothermal test). It is also found that the viscosity increases with decreasing temperature for a particular shear rate due to increasing solid fraction (continuous cooling test). Thixotropic nature of the slurry is confirmed from the hysteresis loops obtained during experimentation. Time dependence of slurry viscosity has been evaluated from the steady state tests. After a longer shearing time under isothermal conditions the starting dendritic structure of the said alloy is transformed into globular grains due to abrasion, agglomeration, welding and ripening.

Role of different factors affecting interdiffusion in Cu(Ga) and Cu(Si) solid solutions

A detailed diffusion study was carried out on Cu(Ga) and Cu(Si) solid solutions in order to assess the role of different factors in the behaviour of the diffusing components. The faster diffusing species in the two systems, interdiffusion, intrinsic and impurity diffusion coefficients, are determined to facilitate the discussion. It was found that Cu was more mobile in the Cu-Si system, whereas Ga was the faster diffusing species in the Cu-Ga system. In both systems, the interdiffusion coefficients increased with increasing amount of solute (e.g. Si or Ga) in the matrix (Cu). Impurity diffusion coefficients for Si and Ga in Cu, found out by extrapolating interdiffusion coefficient data to zero composition of the solute, were both higher than the Cu tracer diffusion coefficient. These observed trends in diffusion behaviour could be rationalized by considering: (i) formation energies and concentration of vacancies, (ii) elastic moduli (indicating bond strengths) of the elements and (iii) the interaction parameters and the related thermodynamic factors. In summary, we have shown here that all the factors introduced in this paper should be considered simultaneously to understand interdiffusion in solid solutions. Otherwise, some of the aspects may look unusual or even impossible to explain.

Photophysical, electrochemical and solid state properties of diketopyrrolopyrrole based molecular materials: importance of the donor group

Diketopyrrolopyrrole (DPP) based molecular semiconductors have emerged as promising materials for high performance active layers in organic solar cells. It is imperative to comprehend the origin of such a property by investigating the fundamental structure property correlation. In this report we have investigated the role of the donor group in DPP based donor-acceptor- donor (D-A-D) structure to govern the solid state, photophysical and electrochemical properties. We have prepared three derivatives of DPP with varying strengths of the donor groups, such as phenyl (PDPP-Hex), thiophene (TDPP-Hex) and selenophene (SeDPP-Hex). The influence of the donor units on the solid state packing was studied by single crystal X-ray diffraction. The photophysical, electrochemical and density functional theory ( DFT) results were combined to elucidate the structural and electronic properties of three DPP derivatives. We found that these DPP derivatives crystallized in the monoclinic space group P21/c and show herringbone packing in the crystal lattice. The derivatives exhibit weak p-p stacking interactions as two neighboring molecules slip away from each other with varied torsional angles at the donor units. The high torsional angle of 32 degrees ( PDPP-Hex) between the phenyl and lactam ring results in weak intramolecular interactions between the donor and acceptor, while TDPP-Hex and SeDPP-Hex show lower torsional angles of 9 degrees and 12 degrees with a strong overlap between the donor and acceptor units. The photophysical properties reveal that PDPP-Hex exhibits a high Stokes shift of 0.32 eV and SeDPP- Hex shows a high molar absorption co-efficient of 33 600 L mol -1 1 cm -1 1 with a low band gap of similar to 2.2 eV. The electrochemical studies of SeDPP- Hex indicate the pronounced effect of selenium in stabilizing the LUMO energy levels and this further emphasizes the importance of chalcogens in developing new n-type organic semiconductors for optoelectronic devices.

Transition from Cassie to impaled state during drop impact on groove-textured solid surfaces

Liquid drops impacted on textured surfaces undergo a transition from the Cassie state characterized by the presence of air pockets inside the roughness valleys below the drop to an impaled state with at least one of the roughness valleys filled with drop liquid. This occurs when the drop impact velocity exceeds a particular value referred to as the critical impact velocity. The present study investigates such a transition process during water drop impact on surfaces textured with unidirectional parallel grooves referred to as groove-textured surfaces. The process of liquid impalement into a groove in the vicinity of drop impact through de-pinning of the three-phase contact line (TPCL) beneath the drop as well as the critical impact velocity were identified experimentally from high speed video recordings of water drop impact on six different groove-textured surfaces made from intrinsically hydrophilic (stainless steel) as well as intrinsically hydrophobic (PDMS and rough aluminum) materials. The surface energy of various 2-D configurations of liquid-vapor interface beneath the drop near the drop impact point was theoretically investigated to identify the locally stable configurations and establish a pathway for the liquid impalement process. A force balance analysis performed on the liquid-vapor interface configuration just prior to TPCL de-pinning provided an expression for the critical drop impact velocity, U-o,U-cr, beyond which the drop state transitions from the Cassie to an impaled state. The theoretical model predicts that Uo, cr increases with the increase in pillar side angle, a, and intrinsic hydrophobicity whereas it decreases with the increase in groove top width, w, of the groove-textured surface. The quantitative predictions of the theoretical model were found to show good agreement with the experimental measurements of U-o,U-cr plotted against the surface texture geometry factor in our model, {tan(alpha/2)/w}(0.5).

Symbiosis in Solid State Interconversion and Synthon Modularity in Hydroxybenzoic Acid-Hexamine Adducts

Systematic cocrystallization of hydroxybenzoic acids with hexamine using liquid-assisted grinding shows facile solid state interconversion among different stoichiometric variants. The reversible interconversion caused by varying both the acid and base components in tandem is shown to be a consequence of hydrogen-bonded synthon modularity present in all representative crystal structures. Among a total of 11 complexes, three are salts and eight are cocrystals. The insulated synthons appear as conserved tetrameric motifs in the structures, and the mechanism of interconversion is closely monitored by the synthon modularity. The interconversion is consistent with the theoretically computed stabilization energies of all the tetramers found in this series of cocrystals based on atoms in molecule calculations.

Biomimetic molecular organization of naphthalene diimide in the solid state: tunable (chiro-) optical, viscoelastic and nanoscale properties

The interfacing of aromatic molecules with biomolecules to design functional molecular materials is a promising area of research. Intermolecular interactions determine the performance of these materials and therefore, precise control over the molecular organization is necessary to improve functional properties. Herein we describe the tunable biomimetic molecular engineering of a promising n-type organic semiconductor, naphthalene diimide (NDI), in the solid state by introducing minute structural mutations in the form of amino acids with variable Ca-functionality. For the first time we could achieve all four possible crystal packing modes, namely cofacial, brickwork, herringbone and slipped stacks of the NDI system. Furthermore, amino acid conjugated NDIs exhibit ultrasonication induced organogels with tunable visco-elastic and temperature responsive emission properties. The amino acid-NDI conjugates self-assemble into 0D nanospheres and 1D nanofibers in their gel state while the ethylamine-NDI conjugate forms 2D sheets from its solution. Photophysical studies indicated the remarkable influence of molecular ordering on the absorption and fluorescence properties of NDIs. Interestingly, the circular dichroism (CD) and X-ray diffraction (XRD) studies revealed the existence of helical ordering of NDIs in both solution and solid state. The chiral amino acids and their conformations with respect to the central NDI core are found to influence the nature of the helical organization of NDIs. Consequently, the origin of the preferential handedness in the helical organization is attributed to transcription of chiral information from the amino acid to the NDI core. On account of these unique properties, the materials derived from NDI-conjugates might find a wide range of future interdisciplinary applications from materials to biomedicine.