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.

Evaluation. of Transverse Piezoelectric Coefficient of ZnO Thin Films Deposited on Different Flexible Substrates: A Comparative Study on the Vibration Sensing Performance

We report on the systematic comparative study of highly c-axis oriented and crystalline piezoelectric ZnO thin films deposited on four different flexible substrates for vibration sensing application. The flexible substrates employed for present experimental study were namely a metal alloy (Phynox), metal (aluminum), polyimide (Kapton), and polyester (Mylar). ZnO thin films were deposited by an RF reactive magnetron sputtering technique. ZnO thin films of similar thicknesses of 700 +/- 30 nm were deposited on four different flexible substrates to have proper comparative studies. The crystallinity, surface morphology, chemical composition, and roughness of ZnO thin films were evaluated by respective material characterization techniques. The transverse piezoelectric coefficient (d(31)) value for assessing the piezoelectric property of ZnO thin films on different flexible substrates was measured by a four-point bending method. ZnO thin films deposited on Phynox alloy substrate showed relatively better material characterization results and a higher piezoelectric d(31) coefficient value as compared to ZnO films on metal and polymer substrates. In order to experimentally verify the above observations, vibration sensing studies were performed. As expected, the ZnO thin film deposited on Phynox alloy substrate showed better vibration sensing performance. It has generated the highest peak to peak output voltage amplitude of 256 mV as compared to that of aluminum (224 mV), Kapton (144 mV), and Mylar (46 mV). Therefore, metal alloy flexible substrate proves to be a more suitable, advantageous, and versatile choice for integrating ZnO thin films as compared to metal and polymer flexible substrates for vibration sensing applications. The present experimental study is extremely important and helpful for the selection of a suitable flexible substrate for various applications in the field of sensor and actuator technology.

PROPENSITIES OF AMINO ACID RESIDUES IN PROTEINS FOR DIFFERENT REGIONS OF THE RAMACHANDRAN MAP

Using a dataset of 1164 crystal structures of largely non-homologous proteins defined at a resolution of 1.5 angstrom or better, we have investigated the (phi,psi) preferences of 20 residue types by considering the residues which occur in loops. Propensities of residue types to occur in the loops with (phi,psi) values in the aa region of the Ramachandran map has a poor correlation coefficient of 0.48 to the Chou-Fasman propensities of the residue types to occur in the a-helical segments. However the correlation coefficient between propensities of residues in loops to adopt beta conformations and those in beta-sheet is much higher (0.95). These observations suggest that a-helix formation is well influenced by the local amino acid sequence while intrinsic preference of residue types for beta-sheet plays a major role in the formation of beta-sheet. The main chain polar groups of residues in loops, that can affect the (phi,psi) values, can be involved in intra-molecular hydrogen bonding. Therefore we investigated further by considering subset of residues in loops with low (0 to 2) number of intra-molecular hydrogen bonds per residue involving main chain polar atoms. For this subset, the correlation coefficients between propensities for alpha-helix and alpha(R) region and between beta-sheet and beta-region are 0.26 and 0.64 respectively. This reiterates higher intrinsic tendency of beta-region favouring residues to adopt beta-sheet than alpha(R) region favouring residues to adopt alpha-helical structure.

A DYNAMO MODEL OF MAGNETIC ACTIVITY IN SOLAR-LIKE STARS WITH DIFFERENT ROTATIONAL VELOCITIES

We attempt to provide a quantitative theoretical explanation for the observations that Ca II H/K emission and X-ray emission from solar-like stars increase with decreasing Rossby number (i.e., with faster rotation). Assuming that these emissions are caused by magnetic cycles similar to the sunspot cycle, we construct flux transport dynamo models of 1M(circle dot) stars rotating with different rotation periods. We first compute the differential rotation and the meridional circulation inside these stars from a mean-field hydrodynamics model. Then these are substituted in our dynamo code to produce periodic solutions. We find that the dimensionless amplitude f(m) of the toroidal flux through the star increases with decreasing rotation period. The observational data can be matched if we assume the emissions to go as the power 3-4 of f(m). Assuming that the Babcock-Leighton mechanism saturates with increasing rotation, we can provide an explanation for the observed saturation of emission at low Rossby numbers. The main failure of our model is that it predicts an increase of the magnetic cycle period with increasing rotation rate, which is the opposite of what is found observationally. Much of our calculations are based on the assumption that the magnetic buoyancy makes the magnetic flux tubes rise radially from the bottom of the convection zone. Taking into account the fact that the Coriolis force diverts the magnetic flux tubes to rise parallel to the rotation axis in rapidly rotating stars, the results do not change qualitatively.

Shear induced crystallization in different polymorphic forms of PVDF induced by surface functionalized MWNTs in PVDF/PMMA blends

Shear induced crystallization in PVDF/PMMA blends, especially at higher fractions of PMMA, can be quite interesting in understanding the structure-property correlation and processing of these blends. In a recent submission (Phys. Chem. Chem. Phys., 2014, 16, 2693-2704), we clearly demonstrated, using dielectric spectroscopy, that the origin of segmental relaxations concerning the crystalline segments of PVDF in PVDF/PMMA blends in the presence of MWNTs (multiwalled nanotubes) was strongly contingent on the size of the crystallite. We now understand that the fraction of PMMA in the blends governs the origin of polymorphism in PVDF. This motivated us to systematically study the effect of shear on the crystallization behavior of PVDF especially in blends with different polymorphic forms of PVDF. Two model blends were selected; one with a mixture of alpha and beta crystals and the other predominantly rich in alpha crystals. Initially, physical ageing, at different oscillation frequencies (1 rad s(-1) and 0.1 rad s(-1)), was monitored by melt rheology and subsequently, the effect of steady shear was probed in situ without changing the history of the samples. Intriguingly, the rate of crystallization was observed to be significantly higher for higher oscillation frequencies, which essentially suggest that shear has induced crystallization in the blends. More interestingly, the effect of steady shear was more pronounced in the blends rich in alpha crystals (bigger crystallites as observed from SAXS) and at lower oscillation frequencies.

Cu-II-Azide Polynuclear Complexes of Three Different Building Clusters with the Same Schiff-Base Ligand: Synthesis, Structures, Magnetic Behavior, and Density Functional Theory Studies

Three copper-azido complexes Cu-4(N-3)(8)(L-1)(2)(MeOH)(2)](n) (1), Cu-4(N-3)(8)(L-1)(2)] (2), and Cu-5(N-3)(10)(L-1)(2)](n) (3) L-1 is the imine resulting from the condensation of pyridine-2-carboxaldehyde with 2-(2-pyridyl)ethylamine] have been synthesized using lower molar equivalents of the Schiff base ligand with Cu(NO3)(2)center dot 3H(2)O and an excess of NaN3. Single crystal X-ray structures show that the basic unit of the complexes 1 and 2 contains Cu-4(II) building blocks; however, they have distinct basic and overall structures due to a small change in the bridging mode of the peripheral pair of copper atoms in the linear tetranudear structures. Interestingly, these changes are the result of changing the solvent system (MeOH/H2O to EtOH/H2O) used for the synthesis, without changing the proportions of the components (metal to ligand ratio 2:1). Using even lower proportions of the ligand, another unique complex was isolated with Cu-5(II) building units, forming a two-dimensional complex (3). Magnetic susceptibility measurements over a wide range of temperature exhibit the presence of both antiferromagnetic (very weak) and ferromagnetic exchanges within the tetranuclear unit structures. Density functional theory calculations (using B3LYP functional, and two different basis sets) have been performed on the complexes 1 and 2 to provide a qualitative theoretical interpretation of their overall magnetic behavior.

Halogen Bonds in Crystal Engineering: Like Hydrogen Bonds yet Different

CONSPECTUS: The halogen bond is an attractive interaction in which an electrophilic halogen atom approaches a negatively polarized species. Short halogen atom contacts in crystals have been known for around 50 years. Such contacts are found in two varieties: type I, which is symmetrical, and type II, which is bent. Both are influenced by geometric and chemical considerations. Our research group has been using halogen atom interactions as design elements in crystal engineering, for nearly 30 years. These interactions include halogen center dot center dot center dot halogen interactions (X center dot center dot center dot X) and halogen center dot center dot center dot heteroatom interactions (X center dot center dot center dot B). Many X center dot center dot center dot X and almost all X center dot center dot center dot B contacts can be classified as halogen bonds. In this Account, we illustrate examples of crystal engineering where one can build up from previous knowledge with a focus that is provided by the modern definition of the halogen bond. We also comment on the similarities and differences between halogen bonds and hydrogen bonds. These interactions are similar because the protagonist atoms halogen and hydrogen are both electrophilic in nature. The interactions are distinctive because the size of a halogen atom is of consequence when compared with the atomic sizes of, for example, C, N, and O, unlike that of a hydrogen atom. Conclusions may be drawn pertaining to the nature of X center dot center dot center dot X interactions from the Cambridge Structural Database (CSD). There is a clear geometric and chemical distinction between type I and type II, with only type II being halogen bonds. Cl/Br isostructurality is explained based on a geometric model. In parallel, experimental studies on 3,4-dichlorophenol and its congeners shed light on the nature of halogen center dot center dot center dot halogen interactions and reveal the chemical difference between Cl and Br. Variable temperature studies also show differences between type I and type II contacts. In terms of crystal design, halogen bonds offer a unique opportunity in the strength, atom size and interaction gradation; this may be used in the design of ternary cocrystals. Structural modularity in which an entire crystal structure is defined as a combination of modules is rationalized on the basis of the intermediate strength of a halogen bond. The specific directionality of the halogen bond makes it a good tool to achieve orthogonality in molecular crystals. Mechanical properties can be tuned systematically by varying these orthogonally oriented halogen center dot center dot center dot halogen interactions. In a further development, halogen bonds are shown to play a systematic role in organization of LSAMs (long range synthon aufbau module), which are bigger structural units containing multiple synthons. With a formal definition in place, this may be the right time to look at differences between halogen bonds and hydrogen bonds and exploit them in more subtle ways in crystal engineering.

Finite size scaling in crossover among different random matrix ensembles in microscopic lattice models

Using numerical diagonalization we study the crossover among different random matrix ensembles (Poissonian, Gaussian orthogonal ensemble (GOE), Gaussian unitary ensemble (GUE) and Gaussian symplectic ensemble (GSE)) realized in two different microscopic models. The specific diagnostic tool used to study the crossovers is the level spacing distribution. The first model is a one-dimensional lattice model of interacting hard-core bosons (or equivalently spin 1/2 objects) and the other a higher dimensional model of non-interacting particles with disorder and spin-orbit coupling. We find that the perturbation causing the crossover among the different ensembles scales to zero with system size as a power law with an exponent that depends on the ensembles between which the crossover takes place. This exponent is independent of microscopic details of the perturbation. We also find that the crossover from the Poissonian ensemble to the other three is dominated by the Poissonian to GOE crossover which introduces level repulsion while the crossover from GOE to GUE or GOE to GSE associated with symmetry breaking introduces a subdominant contribution. We also conjecture that the exponent is dependent on whether the system contains interactions among the elementary degrees of freedom or not and is independent of the dimensionality of the system.

Comparative study of different nonconserving time integrators for wave propagation in hyperelastic waveguides

This paper addresses the formulation and numerical efficiency of various numerical models of different nonconserving time integrators for studying wave propagation in nonlinear hyperelastic waveguides. The study includes different nonlinear finite element formulations based on standard Galerkin finite element model, time domain spectral finite element model, Taylor-Galerkin finite element model, generalized Galerkin finite element model and frequency domain spectral finite element model. A comparative study on the computational efficiency of these different models is made using a hyperelastic rod model, and the optimal computational scheme is identified. The identified scheme is then used to study the propagation of transverse and longitudinal waves in a Timoshenko beam with Murnaghan material nonlinearity.

Diffusion of components via different modes during growth of the A15-V(3)Gaphase

Based on an interdiffusion study using an incremental diffusion couple in the V-Ga binary system, we have shown that V diffuses via the lattice, whereas Ga does so via grain boundaries, for the growth of the V3Ga phase. We estimate the contributions from the two different mechanisms, which are usually difficult to delineate in an interdiffusion study. Available tracer diffusion studies and the atomic arrangement in the crystal structure have been considered for a discussion on the diffusion mechanisms.

Exploration of supersonic confined mixing layer: Effect of dissimilar gases at different temperatures

The growth rate of high-speed mixing layer between two dissimilar gases is explored through the model free simulation results. To analyse the cause for the higher mixing layer growth rate in comparison to the existing values reported in literature, the results were compared with the model free simulations of mixing of two high-speed streams of nitrogen (similar gas) at matched temperature and density. The analysis indicates that pressure and density fluctuations no longer remain correlated completely for the mixing layer formed between two dissimilar gases at different temperatures in contrast to the complete pressure density correlation for similar gases. It has been observed that the correlation between temperature and density fluctuations is near -1.0 for dissimilar gases in the mixing layer region and is much higher than for similar gases. It is concluded that mixing layer of similar gases shows a decrease in growth rate due to compressibility effect, while that of dissimilar gases shows a decrease due to dominant temperature effect on density.

Simultaneous co-ordination of three cytosine ligands displaying different binding sites around the copper centres

We report the synthesis and structural characterization of a polymeric ternary copper-cytosine-phenanthroline complex, Cu-4(phen)(3)-(mu(3)-cyt)(2)(mu-OH)(cyt)(OH)Cl-3](n)center dot 16H(2)O, where three cytosine ligands with different binding sites have simultaneously complexed to the four copper metal centres. Interestingly, the complex exhibits two different coordination geometries around the metal centres.

Mammalian Frugivores With Different Foraging Behavior Can Show Similar Seed Dispersal Effectiveness

Frugivores with disparate foraging behavior are considered to vary in their seed dispersal effectiveness (SDE). Measured SDEs for gibbons and macaques for a primate-fruit' were comparable despite the different foraging and movement behavior of the primates. This could help facilitate fruit trait convergence in diverse fruit-frugivore networks.

Rotational spectra of propargyl alcohol dimer: A dimer bound with three different types of hydrogen bonds

Pure rotational spectra of the propargyl alcohol dimer and its three deuterium isotopologues have been observed in the 4 to 13 GHz range using a pulsed-nozzle Fourier transform microwave spectrometer. For the parent dimer, a total of 51 transitions could be observed and fitted within experimental uncertainty. For two mono-substituted and one bi-substituted deuterium isotopologues, a total of 14, 17, and 19 transitions were observed, respectively. The observed rotational constants for the parent dimer A = 2321.8335(4) MHz, B = 1150.4774(2) MHz, and C = 1124.8898(2) MHz] are close to those of the most stable structure predicted by ab initio calculations. Spectra of the three deuterated isotopologues and Kraitchman analysis positively confirm this structure. Geometrical parameters and ``Atoms in Molecules'' analysis on the observed structure reveal that the two propargyl alcohol units in the dimer are bound by three different types of hydrogen bonds: O-H center dot center dot center dot O, O-H center dot center dot center dot pi, and C-H center dot center dot center dot pi. To the best of our knowledge, propargyl alcohol seems to be the smallest molecule forming a homodimer with three different points of contact. (C) 2014 AIP Publishing LLC.

Enhancing the photocatalytic efficiency of sprayed ZnO thin films through double doping (Sn plus F) and annealing under different ambiences

Doubly (Sn + F) doped zinc oxide (ZnO:Sn:F) thin films were deposited onto glass substrates using a simplified spray pyrolysis technique. The deposited films were annealed at 400 degrees C under two different ambiences (air and vacuum) for 2 h. The photocatalytic activity of these films was assessed through photocatalytic decolorization kinetics of Methylene Blue (MB) dye and the decolorization efficiency of the annealed films was compared with that of their as-deposited counterpart. The photocatalytic studies reveal that the ZnO:Sn:F films annealed under vacuum environment exhibits better photocatalytic efficiency when compared with both air annealed and as-deposited films. The SEM and TEM images depict that the surface of each of the films has an overlayer comprising of nanobars formed on a bottom layer, having spherical grains. The studies show that the diameter of the nanobars plays crucial role in enhancing the photocatalytic activity of the ZnO:Sn:F films. The structural, optical and electrical studies substantiate the discussions on the photocatalytic ability of the deposited films. (C) 2014 Elsevier B.V. All rights reserved.