Effect of pouring temperature on cooling slope casting of semi-solid Al-Si-Mg alloy

Present trend of semi-solid processing is directed towards rheocasting route which allows manufacturing of near-net-shape cast components directly from the prepared semi-solid slurry. Generation of globular equi-axed grains during solidification of rheocast components, compared to the columnar dendritic structure of conventional casting routes, facilitates the manufacturing of components with improved mechanical properties and structural integrity. In the present investigation, a cooling slope has been designed and indigenously fabricated to produce semi solid slurry of Al-Si-Mg (A356) alloy and successively cast in a metallic mould. The scope of the present work discusses about development of a numerical model to simulate the liquid metal flow through cooling slope using Eulerian two-phase flow approach and to investigate the effect of pouring temperature on cooling slope semi-solid slurry generation process. The two phases considered in the present model are liquid metal and air. Solid fraction evolution of the solidifying melt is tracked at different locations of the cooling slope, following Schiel's equation. The continuity equation, momentum equation and energy equation are solved considering thin wall boundary condition approach. During solidification of the liquid metal, a modified temperature recovery scheme has been employed taking care of the latent heat release and change of fraction of liquid. The results obtained from simulations are compared with experimental findings and good agreement has been found.

Fabrication of Highly Dense Nanoholes by Self-Assembled Gallium Droplet on Silicon Surface

We report the fabrication of nanoholes on silicon surface by exploiting the solubility of silicon in gallium by local droplet etching. Nanometer-sized gallium droplets yield nanoholes when annealed in ultra-high vacuum at moderate temperatures (similar to 500 degrees C) without affecting the other regions. High vacuum and moderate annealing temperatures are key parameters to obtain well-defined nanoholes with diameter comparable to that of Ga droplets. Self-assembly of Ga droplet leads to a nanohole density of 4-8 x 10(10)/cm(2).

Low dimensional fabrication of giant dielectric CaCu3Ti4O12 through soft e-beam lithography

We report low-dimensional fabrication of technologically important giant dielectric material CaCu3Ti4O12 (CCTO) using soft electron beam lithographic technique. Sol-gel precursor solution of CCTO was prepared using inorganic metal nitrates and Ti-isopropoxide. Employing the prepared precursor solution and e-beam lithographically fabricated resist mask CCTO dots with similar to 200 nm characteristic dimension were fabricated on platinized Si (111) substrate. Phase formation, chemical purity and crystalline nature of fabricated low dimensional structures were investigated with X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS) and selected area electron diffraction (SAED), respectively. Morphological investigations were carried out with the help of scanning electron microscopy (SEM) and transmission electron microscopy (TEM). This kind of solution based fabrication of patterned low-dimensional high dielectric architectures might get potential significance for cost-effective technological applications. (C) 2012 Elsevier B.V. All rights reserved.

PEO|Sncl(2)|PANI composites: as an electrolyte in solid-state battery

Solid-state polymer electrolytes possess high conductivity and have advantages compared with their liquid counterparts. The polyethylene oxide (PEO)-based polymer is a good candidate for this purpose. The PEO/SnCl2/polyaniline composite (PSP composites) at different weight percentages were prepared in anhydrous acetonitrile media. Structural studies were carried out of the prepared composites by X-ray diffraction, Fourier transmission infrared spectroscopy, and surface morphology by scanning electron microscopy. The sigma (dc) was carried out by a two-probe method, and it is found that the conductivity increases with an increase in temperature. The temperature-dependent conductivity of the composites exhibits a typical semi-conducting behavior and hence can be explained by the 1D variable range hopping model proposed by Mott. The electrochemical cell parameters for battery applications at room temperature have also been determined. The samples are fabricated for battery application in the configuration of Na: (PSP): (I-2 + C + sample), and their experimental data are measured using Wagner's polarization technique. The cell parameters result in an open-circuit voltage of 0.83 V and a short-circuit current of 912 mu A for PSP (70:30:10) composite. Hence, these composites can be used in polymer electrolyte studies.

Solid State and Solution Mediated Multistep Sequential Transformations in Metal-Organic Coordination Networks

Sequential transformation in a family of metal-organic framework compounds has been investigated employing both a solid-state as well as a solution mediated route. The compounds, cobalt oxy-bis(benzoate) and manganese oxybis(benzoate) having a two-dimensional structure, were reacted with bipyridine forming cobalt oxy-bis(benzoate)-4,4'-bipyridine and manganese oxy-bis(benzoate)-4,4'-bipyridine, respectively. The bipyridine containing compounds appear to form sequentially through stable intermediates. For the cobalt system, the transformation from a two-dimensional compound, Co(H2O)(2)(OBA)] (OBA = 4,4'-oxy-bis(benzoate)), I, to two different three-dimensional compounds, Co(bpy)(OBA)]center dot bpy, II, (bpy = 4,4'-bipyridine) and Co(bpy)(0.5)(OBA)], III, and reversibility between II and III have been investigated. In the manganese system, transformation from a two-dimensional compound, Mn(H2O)(2)(OBA)], Ia, to two different three-dimensional compounds, Mn (bpy)(OBA)]center dot bpy, Ha and Ha to Mn(bpy)(0.5)(OBA)], Ilia, has been investigated. It has also been possible to identify intermediate products during these transformation reactions. The possible pathways for the formation of the compounds were postulated.

Temperature dependent structural and dielectric investigations of PbZr0.5Ti0.5O3 solid solution at the morphotropic phase boundary

PbZr1-xTixO3 ceramics synthesised by low temperature calcination followed by sintering at 1280 degrees C show a Morphotropic Phase Boundary (MPB) for compositions of x=0.44-0.51. The morphotropic phase boundary is wider for samples with smaller grain sizes due to the synthesis route. A Rietveld analysis is performed on a composition of x=0.5 composition to quantify the phase fractions of the tetragonal and monoclinic phases present in the PZT system. Temperature dependent X-ray diffraction and dielectric studies of PbZr0.5Ti0.5O3 composition demonstrated a phase transformation from monoclinic to tetragonal at 270 degrees C followed by a ferroelectric tetragonal to a paraelectric cubic transition at 370 degrees C. Thus, the poling of these ceramics should be performed below 270 degrees C to benefit from the presence of a monoclinic phase. (C) 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

COMPARATIVE EVALUATION OF THERMAL CONDUCTIVITY OF ZIRCONIA SOLID AND HONEYCOMB STRUCTURES

Porous zirconia ceramic monoliths have been extensively used in thermo-structural applications due to their inherent low thermal conductivity in combination with their adaptability to form complicated shapes through advanced ceramic processing techniques. However, extruded cellular honeycomb structures made from these materials have been less explored for thermal management applications. There exist large potential applications due to their unique configurations, resulting in better heat-management mechanisms. Some of the studies carried out on zirconia honeycombs are safeguarded through patents due to its technical importance, or the information is not in the public domain. In the present study, for the sake of comparison, honeycomb specimens with varying wall thicknesses and unit cell lengths maintaining almost same bulk density of around 90% theoretical and relative density of 0.34-0.37 were prepared and subjected to thermal conductivity evaluation along with the solid samples with relative density of 1.0 using monotonic heating regime methodology. In addition, the effect of channel shape was also evaluated using square and triangular channeled honeycombs with the same relative densities. The results obtained from these specimens were correlated with their configurations to bring out the advantages accrued by using the honeycomb with these configurations. It was observed that a significant decrease in thermal conductivity was achieved in honeycombs, which can be attributed to the behavior of various heat transfer mechanisms that are operative at high temperatures in combination with the considerable reduction in thermal mass and the consequent conduction through the solids.

Fabrication and characterization of micro-arc oxidized fluoride containing titania films on Cp Ti

The present study is focussed at establishing an appropriate electrolyte system for developing electrochemically stable and fluorine (F) containing titania (F-TiO2) films on Cp Ti by micro-arc oxidation (MAO) technique. To fabricate the F-TiO2 films on Cp Ti, different electrolyte solutions of chosen concentrations of tri-sodium orthophosphate (TSOP, Na3PO4 center dot I2H2O), potassium hydroxide (KOH) and various F-containing compounds such as ammonium fluoride (NH4F), potassium fluoride (KF), sodium fluoride (NaF) and potassium fluorotitanate (K2TiF6) are employed. The structural and morphological characteristics, thickness and elemental composition of the developed films have been assessed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) techniques. The in-vitro electrochemical corrosion behavior of the films was studied under Kokubo simulated body fluid (SBF) environment by potentiodynamic polarization, long term potential measurement and electrochemical impedance spectroscopy (EIS) methods. The XRD and SEM-EDS results show that the rutile content in the films vary in the range of 15-37 wt% and the F and P contents in the films is found to be in the range of 2-3 at% and 2.9-4.7 at% respectively, suggesting that the anatase to rutile phase transformation and the incorporation of F and P into the films are significantly controlled by the respective electrolyte solution. The SEM elemental mapping results show that the electrolyte borne F and P elements are incorporated and distributed uniformly in all the films. Among all the films under study, the film developed with 5 g TSOP+2 g KOH+3 g K2TiF6 electrolyte system exhibits considerably improved in-vitro corrosion resistance and therefore best suited for biomedical applications. (C) 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

The Relationship of Solid-State Plasticity to Mechanochromic Luminescence in Difluoroboron Avobenzone Polymorphs

In solid-state mechanochromic luminescence (ML) materials, it remains a challenge to establish the origin of fluorescence color changes upon mechanical action and to determine why only some fluorophores exhibit ML behavior. The study of mechanical properties by nanoindentation, followed by ML experiments on green- and cyan-emitting polymorphs of difluoroboron avobenzone reveals that upon smearing, the plastically deformable cyan form shows a prominent color change to yellow, while in the harder green form the redshifted emission is barely detectable. Crystal structure analysis reveals the presence of slip planes in the softer cyan form that can facilitate the formation of recoverable and low energy defects in the structure. Hence, the cyan form exhibits prominent and reversible ML behavior. This suggests a potential design strategy for efficient ML materials.

Infrared spectrum of formamide in the solid phase

Infrared spectra of solid formamide are reported as a function of temperature. Solid formamide samples were prepared at 30 K and then annealed to higher temperatures (300 K) with infrared transmission spectra being recorded over the entire temperature range. The NH2 vibrations of the formamide molecule were found to be particularly very sensitive to temperature change. The IR spectra revealed a phase change occurring in solid formamide between 155 and 165 K. Spectral changes observed above and below the phase transition may be attributed to a rearrangement between formamide dimers and the formation of polymers is proposed at higher temperatures.

Diaminotriazine substituted diphenyl ether: reversible structural transformation and solvent dependent solid state fluorescence

The effect of molecular shape and position of hydrogen bonding functionality in the solid state structural self-assembly was investigated using diaminotriazine substituted diphenyl ether based positional isomers (1-5). The molecular shape was modulated by changing diaminotriazine position that produced channel supramolecular structures in 1, 3 and 5. There exists a direct correlation between the molecular shape and three dimensional structures; more linear molecules resulted in close-packing whereas molecules with a labyrinthine topology formed a channel structure. Supramolecular aspects pertaining to the influence of solvent of crystallization in structure formation and reversible structural transformation in solid state were also explored. 1-5 exhibited tunable solid state fluorescence (lambda(max) = 437-496 nm) depending on the diaminotriazine substitutional position and 3 showed solvent-dependent solid state fluorescence. The present study describes the generation of a supramolecular channel structure with functional properties such as tunable fluorescence by varying the position of hydrogen bond functionality and solvent of crystallization.

Synthesis of nanosized Ce0.85M0.1Ru0.05O2-delta (M = Si, Fe) solid solution exhibiting high CO oxidation and water gas shift activity

Nanosized Ce0.85M0.1Ru0.05O2-delta (M = Si, Fe) has been synthesized using a low temperature sonication method and characterized using XRD, TEM, XPS and H-2-TPR. The potential application of both the solid solutions has been explored as exhaust catalysts by performing CO oxidation. The addition of Si- and Fe-in Ce0.95Ru0.05O2-delta greatly enhanced the reducibility of Ce0.85M0.1Ru0.05O2-delta (M = Si, Fe), as indicated by the H-2-TPR study. The oxygen storage capacity has been used to correlate surface oxygen reactivity to the CO oxidation activity. Both the compounds reversibly release lattice oxygen and exhibit excellent CO oxidation activity with 99% conversion below 200 degrees C. A bifunctional reaction mechanism involving CO oxidation by the extraction of lattice oxygen and rejuvenation of oxide vacancy with gas feed O-2 has been used to correlate experimental data. The performance of both the solid solutions has also been investigated for energy application by performing the water gas shift reaction. The present catalysts are highly active and selective towards the hydrogen production and a lack of methanation activity is an important finding of present study.

Determination of favorable inter-particle interactions for formation of substitutionally ordered solid phases from a binary mixture of oppositely charged colloidal suspensions

The solid phase formed by a binary mixture of oppositely charged colloidal particles can be either substitutionally ordered or substitutionally disordered depending on the nature and strength of interactions among the particles. In this work, we use Monte Carlo molecular simulations along with the Gibbs-Duhem integration technique to map out the favorable inter-particle interactions for the formation of substitutionally ordered crystalline phases from a fluid phase. The inter-particle interactions are modeled using the hard core Yukawa potential but the method can be easily extended to other systems of interest. The study obtains a map of interactions depicting regions indicating the type of the crystalline aggregate that forms upon phase transition.

Revisiting borylanilines: unique solid-state structures and insight into photophysical properties

The structure and photophysical properties of two known borylanilines, 4-(dimesitylboryl)aniline (1) and 4-(dimesitylboryl)-3,5-dimethylaniline (2), have been investigated. 1 and 2 have similar donor and acceptor centers but differ in their molecular conformations. Compounds 1 and 2 have been structurally characterized, and they exhibit a rare form of intermolecular N-H - - -pi electrostatic interactions. The structure and photophysical properties of 1 and 2 are discussed in the context of computational results.

Interdiffusion and solid solution strengthening in Ni-Co-Pt and Ni-Co-Fe ternary systems

Diffusion couple experiments are conducted in Co-Ni-Pt system at 1200 degrees C and in Co-Ni-Fe system at 1150 degrees C, by coupling binary alloys with the third element. Uphill diffusion is observed for both Co and Ni in Pt rich corner of the Co-Ni-Pt system, whereas in the Co-Ni-Fe system, it is observed for Co. Main and cross interdiffusion coefficients are calculated at the composition of intersection of two independent diffusion profiles. In both the systems, the main interdiffusion coefficients are positive over the whole composition range and the cross interdiffusion coefficients show both positive and negative values at different regions. Hardness measured by performing the nanoindentations on diffusion couples of both the systems shows the higher values at intermediate compositions.