Chemical potential of germanium in its solid solutions with Cu, Ag and Au

Thin foils of copper, silver and gold were equilibrated with tetragonal GeO2 under controlled View the MathML source gas streams at 1000 K. The equilibrium concentration of germanium in the foils was determined by the X-ray fluorescence technique. The standard free energy of formation of tetragonal GeO2 was measured by a solid oxide galvanic cell. The chemical potential of germanium calculated from the experimental data and the free energies of formation of carbon monoxide and carbon dioxide was found to decrease in the sequence Ag + Ge > Au + Ge > Cu + Ge. The more negative value for the chemical potential of germanium in solid copper, compared to that in solid gold, cannot be explained in terms of the strain energy factor, electro-negativity differences or the vaporization energies of the solvent, and suggests that the d band and its hybridization with s electrons are an important factor in determining the absolute values for the chemical potential in dilute solutions. However, the variation of the chemical potential with solute concentration can be correlated to the concentration of s and p electrons in the outer shell.

Relation between Local Structure and Glass Forming Ability of Liquid Alloys

An attempt has been made to describe the glass forming ability (GFA) of liquid alloys, using the concepts of the short range order (SRO) and middle range order (MRO) characterizing the liquid structure.A new approach to obtain good GFA of liquid alloys is based on the following four main factors: (1) formation of new SRO and competitive correlation with two or more kinds of SROs for crystallization, (2) stabilization of dense random packing by interaction between different types of SRO, (3) formation of stable cluster (SC) or middle range order (MRO) by harmonious coupling of SROs, and (4) difference between SRO characterizing the liquid structure and the near-neighbor environment in the corresponding equilibrium crystalline phases. The atomic volume mismatch estimated from the cube of the atomic radius was found to be a close relation with the minimum solute concentration for glass formation. This empirical guideline enables us to provide the optimum solute concentration for good GFA in some ternary alloys. Model structures, denoted by Bernal type and the Chemical Order type, were again tested in the novel description for the glass structure as a function of solute concentration. We illustrated the related energetics of the completion between crystal embryo and different types of SRO. Recent systematic measurements also provide that thermal diffusivity of alloys in the liquid state may be a good indicator of their GFA.

A resistometric study of solute–solute interaction in dilute aluminium–silver alloys

The experimentally determined apparent vacancy formation energy values in dilute aluminium—silver alloys showed a divergence from calculated values at higher solute fractions. This is explained in terms of a solute—solute interaction energy of the order of 0.10 ev which exists when the binding energy between a vacancy and a solute atom pair is reduced to zero.

An operator-splitting finite element method for the efficient parallel solution of multidimensional population balance systems

A finite element method for solving multidimensional population balance systems is proposed where the balance of fluid velocity, temperature and solute partial density is considered as a two-dimensional system and the balance of particle size distribution as a three-dimensional one. The method is based on a dimensional splitting into physical space and internal property variables. In addition, the operator splitting allows to decouple the equations for temperature, solute partial density and particle size distribution. Further, a nodal point based parallel finite element algorithm for multi-dimensional population balance systems is presented. The method is applied to study a crystallization process assuming, for simplicity, a size independent growth rate and neglecting agglomeration and breakage of particles. Simulations for different wall temperatures are performed to show the effect of cooling on the crystal growth. Although the method is described in detail only for the case of d=2 space and s=1 internal property variables it has the potential to be extendable to d+s variables, d=2, 3 and s >= 1. (C) 2011 Elsevier Ltd. All rights reserved.

Decoupling of diffusion from viscosity: Difference scenario for translational and rotational motions

Recent experiments have indicated a dramatically different viscosity dependence of the translational and the rotational diffusion coefficients in a supercooled liquid as the glass transition temperature is approached from above. While the translational motion seems to be decoupled from the rising viscosity (eta), the rotational motion seems to remain firmly coupled to eta. In order to understand the microscopic origin of this behavior, we have carried nut detailed theoretical calculations of both the quantities by using a self-consistent mode-coupling theory (MCT). it is found that when the size of the solute is same as that of the solvent molecules, the conventional MCT fails to predict the observed decoupling. The solvent inhomogeneity is found to play a decisive role in determining the decoupling. The difference in the viscosity dependence between rotation and translational diffusion coefficient is discussed.

In-situ measurements of concentration and temperature during transient solidification of aqueous solution of ammonium chloride using laser interferometry

The variation in temperature and concentration plays a crucial role in predicting the final microstructure during solidification of a binary alloy. Most of the experimental techniques used to measure concentration and temperature are intrusive in nature and affect the flow field. In this paper, the main focus is laid on in-situ, non-intrusive, transient measurement of concentration and temperature during the solidification of a binary mixture of aqueous ammonium chloride solution (a metal-analog system) in a top cooled cavity using laser based Mach-Zehnder Interferometric technique. It was found from the interferogram, that the angular deviation of fringe pattern and the total number of fringes exhibit significant sensitivity to refractive index and hence are functions of the local temperature and concentration of the NH4Cl solution inside the cavity. Using the fringe characteristics, calibration curves were established for the range of temperature and concentration levels expected during the solidification process. In the actual solidification experiment, two hypoeutectic solutions (5% and 15% NH4Cl) were chosen. The calibration curves were used to determine the temperature and concentration of the solution inside the cavity during solidification of 5% and 15% NH4Cl solution at different instants of time. The measurement was carried out at a fixed point in the cavity, and the concentration variation with time was recorded as the solid-liquid interface approached the measurement point. The measurement exhibited distinct zones of concentration distribution caused by solute rejection and Rayleigh Benard convection. Further studies involving flow visualization with laser scattering confirmed the Rayleigh Benard convection. Computational modeling was also performed, which corroborated the experimental findings. (C) 2011 Elsevier Ltd. All rights reserved.

Modeling of ternary solubilities of solids in supercritical carbon dioxide in the presence of cosolvents or cosolutes

The investigation of ternary solubilities of solids is essential for the efficient design of extraction processes. The ternary solubilities of solids for cosolvent and cosolute systems are complex functions of temperature, pressure and cosolvent/cosolute composition. The intermolecular interactions between the molecules have a significant role in the solubilities of mixed solids in SCCO2 and cosolvent ternary systems. Two model equations were developed for ternary SCCO2 + cosolvent/cosolute systems by using association and activity coefficient models. Both the model equations consist of five adjustable parameters and correlate the ternary solubilities of solids in terms of temperature, pressure, density and cosolvent/cosolute composition. The model equation for cosolvent systems correlated 43 solid pollutants-cosolvent-SCCO2, while the model equation for cosolute systems correlated 19 solute-cosolute-SCCO2 systems available in literature. The average AARD of the model equations are 4.73% and 4.87% for cosolvent ternary systems and mixed solids in SCCO2, respectively. (C) 2011 Elsevier B.V. All rights reserved.

Polymorphs, Salts, and Cocrystals: What's in a Name?

The December 2011 release of a draft United States Food and Drug Administration (FDA) guidance concerning regulatory classification of pharmaceutical cocrystals of active pharmaceutical ingredients (APIs) addressed two matters of topical interest to the crystal engineering and pharmaceutical science communities: (1) a proposed definition of cocrystals; (2) a proposed classification of pharmaceutical cocrystals as dissociable ``API-excipient'' molecular complexes. The Indo U.S. Bilateral Meeting sponsored by the Indo-U.S. Science and Technology Forum titled The Evolving Role of Solid State Chemistry in Pharmaceutical Science was held in Manesar near Delhi, India, from February 2-4, 2012. A session of the meeting was devoted to discussion of the FDA guidance draft. The debate generated strong consensus on the need to define cocrystals more broadly and to classify them like salts. It was also concluded that the diversity of API crystal forms makes it difficult to classify solid forms into three categories that are mutually exclusive. This perspective summarizes the discussion in the Indo-U.S. Bilateral Meeting and includes contributions from researchers who were not participants in the meeting.

Temporal Moments for Reactive Transport through Fractured Impermeable/Permeable Formations

The transport of reactive solutes through fractured porous formations has been analyzed. The transport through the porous block is represented by a general multiprocess nonequilibrium equation (MPNE), which, for the fracture, is represented by an advection-dispersion equation with linear equilibrium sorption and first-order transformation. An implicit finite-difference technique has been used to solve the two coupled equations. The transport characteristics have been analyzed in terms of zeroth, first, and second temporal moments of the solute in the fracture. The solute behavior for fractured impermeable and fractured permeable formations are first compared and the effects of various fracture and matrix transport parameters are analyzed. Subsequently, the transport through a fractured permeable formation is analyzed to ascertain the effect of equilibrium sorption, rate-limited sorption, and the multiprocess nonequilibrium transport process. It was found that the temporal moments were nearly identical for the fractured impermeable and permeable formations when both the diffusion coefficient and the first-order transformation coefficient were relatively large. The multiprocess nonequilibrium model resulted in a smaller mass recovery in the fracture and higher dispersion than the equilibrium and rate-limited sorption models. DOI: 10.1061/(ASCE)HE.19435584.0000586. (C) 2012 American Society of Civil Engineers.

Cyclodextrin and its complexation for resolution of isomers using diffusion ordered spectroscopy

Diffusion ordered spectroscopy (DOSY) generally fails to separate the peaks pertaining to isomeric species possessing identical molecular weights and similar hydrodynamic radii. The present study demonstrates the resolution of isomers using alpha/beta-cyclodextrin as a co-solute by Matrix Assisted Diffusion Ordered Spectroscopy. The resolution of isomers has been achieved by measuring the significant differences in the diffusion rates between the positional isomers of aminobenzoic acids, benzenedicarboxylic acids and between the cis, trans isomers, fumaric acid and maleic acid. (C) 2012 Elsevier B.V. All rights reserved.

Effects of different modes of hot cross-rolling in 7010 aluminum alloy: part II. mechanical properties anisotropy

The influence of microstructure and texture developed by different modes of hot cross-rolling on in-plane anisotropy (A (IP)) of yield strength, work hardening behavior, and anisotropy of Knoop hardness (KHN) yield locus has been investigated. The A (IP) and work hardening behavior are evaluated by tensile testing at 0 deg, 45 deg, and 90 deg to the rolling direction, while yield loci have been generated by directional KHN measurements. It has been observed that specimens especially in the peak-aged temper, in spite of having a strong, rotated Brass texture, show low A (IP). The results are discussed on the basis of Schmid factor analyses in conjunction with microstructural features, namely grain morphology and precipitation effects. For the specimen having a single-component texture, the yield strength variation as a function of orientation can be rationalized by the Schmid factor analysis of a perfectly textured material behaving as a quasi-single crystal. The work hardening behavior is significantly affected by the presence of solute in the matrix and the state of precipitation rather than texture, while yield loci derived from KHN measurements reiterate the low anisotropy of the materials. Theoretic yield loci calculated from the texture data using the visco-plastic self-consistent model and Hill's anisotropic equation are compared with that obtained experimentally.

Mutation analysis of the SLC4A11 gene in Indian families with congenital hereditary endothelial dystrophy 2 and a review of the literature

Purpose: Congenital hereditary endothelial dystrophy 2 (CHED2) is an autosomal recessive disorder caused by mutations in the solute carrier family 4, sodium borate transporter, member 11 (SLC4A11) gene. The purpose of this study was to identify the genetic cause of CHED2 in six Indian families and catalog all known mutations in the SLC4A11 gene. Methods: Peripheral blood samples were collected from individuals of the families with CHED2 and used in genomic DNA isolation. PCR primers were used to amplify the entire coding region including intron-exon junctions of SLC4A11. Amplicons were subsequently sequenced to identify the mutations. Results: DNA sequence analysis of the six families identified four novel (viz., p.Thr262Ile, p.Gly417Arg, p.Cys611Arg, and p.His724Asp) mutations and one known p.Arg869His homozygous mutation in the SLC4A11 gene. The mutation p.Gly417Arg was identified in two families. Conclusions: This study increases the mutation spectrum of the SLC4A11 gene. A review of the literature showed that the total number of mutations in the SLC4A11 gene described to date is 78. Most of the mutations are missense, followed by insertions-deletions. The present study will be helpful in genetic diagnosis of the families reported here.

Relation Between the Diffusivity, Viscosity, and Ionic Radius of LiCl in Water, Methanol, and Ethylene Glycol: A Molecular Dynamics Simulation

A molecular dynamics (MD) investigation of LiCl in water, methanol, and ethylene glycol (EG) at 298 K is reported. Several; structural and dynamical properties of the ions as well as the solvent such as self-diffusivity, radial distribution functions, void and neck distributions, velocity autocorrelation functions, and mean residence times of solvent in the first solvation shell have been computed. The results show that the reciprocal relationship between the self-diffusivity of the ions and the viscosity is valid in almost all solvents with the exception of water. From an analysis of radial distribution functions and coordination numbers the nature of hydrogen bonding within the solvent and its influence on the void and neck distribution becomes evident. It is seen that the solvent solvent interaction is important in EG while solute solvent interactions dominate in water and methanol. From Voronoi tessellation, it is seen that the voids and necks within methanol are larger as compared to those within water or EG. On the basis of the void and neck distributions obtained from MD simulations and literature experimental data of limiting ion conductivity for various ions of different sizes we show that there is a relation between the void and neck radius on e one hand and dependence of conductivity on the ionic radius on the other. It is shown that the presence of large diameter voids and necks in methanol is responsible for maximum in limiting ion conductivity (lambda(0)) of TMA(+), while in water in EG, the maximum is seen for Rb+. In the case of monovalent anions, maximum in lambda(0) as a function ionic radius is seen for Br- in water EG but for the larger ClO4- ion in methanol. The relation between the void and neck distribution and the variation in lambda(0) with ionic radius arises via the Levitation effect which is discussed. These studies show the importance of the solvent structure and the associated void structure.

An enthalpy-based model of dendritic growth in a convecting binary alloy melt

Purpose-In the present work, a numerical method, based on the well established enthalpy technique, is developed to simulate the growth of binary alloy equiaxed dendrites in presence of melt convection. The paper aims to discuss these issues. Design/methodology/approach-The principle of volume-averaging is used to formulate the governing equations (mass, momentum, energy and species conservation) which are solved using a coupled explicit-implicit method. The velocity and pressure fields are obtained using a fully implicit finite volume approach whereas the energy and species conservation equations are solved explicitly to obtain the enthalpy and solute concentration fields. As a model problem, simulation of the growth of a single crystal in a two-dimensional cavity filled with an undercooled melt is performed. Findings-Comparison of the simulation results with available solutions obtained using level set method and the phase field method shows good agreement. The effects of melt flow on dendrite growth rate and solute distribution along the solid-liquid interface are studied. A faster growth rate of the upstream dendrite arm in case of binary alloys is observed, which can be attributed to the enhanced heat transfer due to convection as well as lower solute pile-up at the solid-liquid interface. Subsequently, the influence of thermal and solutal Peclet number and undercooling on the dendrite tip velocity is investigated. Originality/value-As the present enthalpy based microscopic solidification model with melt convection is based on a framework similar to popularly used enthalpy models at the macroscopic scale, it lays the foundation to develop effective multiscale solidification.

Stability of fluctuating and transient aggregates of amphiphilic solutes in aqueous binary mixtures: Studies of dimethylsulfoxide, ethanol, and tert-butyl alcohol

In aqueous binary mixtures, amphiphilic solutes such as dimethylsulfoxide (DMSO), ethanol, tertbutyl alcohol (TBA), etc., are known to form aggregates (or large clusters) at small to intermediate solute concentrations. These aggregates are transient in nature. Although the system remains homogeneous on macroscopic length and time scales, the microheterogeneous aggregation may profoundly affect the properties of the mixture in several distinct ways, particularly if the survival times of the aggregates are longer than density relaxation times of the binary liquid. Here we propose a theoretical scheme to quantify the lifetime and thus the stability of these microheterogeneous clusters, and apply the scheme to calculate the same for water-ethanol, water-DMSO, and water-TBA mixtures. We show that the lifetime of these clusters can range from less than a picosecond (ps) for ethanol clusters to few tens of ps for DMSO and TBA clusters. This helps explaining the absence of a strong composition dependent anomaly in water-ethanol mixtures but the presence of the same in water-DMSO and water-TBA mixtures. (C) 2013 AIP Publishing LLC.