Role of the Molar Volume on Estimated Diffusion Coefficients

The role of the molar volume on the estimated diffusion parameters has been speculated for decades. The Matano-Boltzmann method was the first to be developed for the estimation of the variation of the interdiffusion coefficients with composition. However, this could be used only when the molar volume varies ideally or remains constant. Although there are no such systems, this method is still being used to consider the ideal variation. More efficient methods were developed by Sauer-Freise, Den Broeder, and Wagner to tackle this problem. However, there is a lack of research indicating the most efficient method. We have shown that Wagner's method is the most suitable one when the molar volume deviates from the ideal value. Similarly, there are two methods for the estimation of the ratio of intrinsic diffusion coefficients at the Kirkendall marker plane proposed by Heumann and van Loo. The Heumann method, like the Matano-Boltzmann method, is suitable to use only when the molar volume varies more or less ideally or remains constant. In most of the real systems, where molar volume deviates from the ideality, it is safe to use the van Loo method. We have shown that the Heumann method introduces large errors even for a very small deviation of the molar volume from the ideal value. On the other hand, the van Loo method is relatively less sensitive to it. Overall, the estimation of the intrinsic diffusion coefficient is more sensitive than the interdiffusion coefficient.

Strain-Induced Hierarchy of Energy Levels in CdS/ZnS Nanocrystals

Aside of size and shape, the strain induced by the mismatch of lattice parameters between core and shell in the nanocrystalline regime is an additional degree of freedom to engineer the electron energy levels. Herein, CdS/ZnS core/shell nanocrystals (NCs) with shell thickness up to four monolayers are studied. As a manifestation of strain, the low temperature radiative lifetime measurements indicate a reduction in Stokes shift from 36 meV for CdS to 5 meV for CdS/ZnS with four monolayers of overcoating. Concomitant crossover of S- and P-symmetric hole levels is observed which can be understood in the framework of theoretical calculations predicting flipping the hierarchy of ground hole state by the strain in CdS NCs. Furthermore, a nonmonotonic variation of higher energy levels in strained CdS NCs is discussed.

Deployment strategy for controlled morphologies in sessile, mixed colloidal droplets

Colloidal systems offer an effective medium to micro-engineer complex structures without involving sophisticated fabrication procedures. This article presents a deployment strategy of multiple droplets of different colloidal composition and utilizes the inherent capillary flow driven self assembly of nanoparticles to construct stacks of multiple materials on a given glass substrate. Here we used aqueous nano-crystalline titania and nano-amorphous silica solutions as the two materials. Initially, a pure nanotitania (nanosilica) droplet is deployed and allowed to dry partially. Subsequently, a second droplet of pure nanosilica (nanotitania) is deployed co-axially on the partially dried precipitate. The proposed deployment strategy allowed significant morphological differences when the deployment order of nanosilica and nanotitania were interchanged. Compositional analysis performed using EDX (Energy Dispersive X-ray spectroscopy) showed preferential deposition of nanosilica and nanotitania along the radial as well as the axial plane of the final deposit pattern. The underlying mechanism for such a phenomenon could be attributed to the contact line dynamics of a sessile double droplet. We also observe heteroaggregation of the nanosilica-nanotitania interaction along a narrow interface which resulted in nanotitania particles clustering into isolated islands embedded into a matrix of nanosilica particles. Overall, this work elucidates the evaporation driven dynamics of a mixed colloidal system which displays both macroscopic as well as microscopic phenomena. Such a system could be used to generate ordered arrays of functional materials with engineered micro to nano-scale properties.

Plasmon-mediated emergence of collective emission and enhanced quantum efficiency in quantum dot films

We present experimental and theoretical results on monolayer colloidal cadmium selenide quantum dot films embedded with tiny gold nanoparticles. By varying the density of the embedded gold nanoparticles, we were able to engineer a plasmon-mediated crossover from emission quenching to enhancement regime at interparticle distances for which only quenching of emission is expected. This crossover and a nonmonotonic variation of photoluminescence intensity and decay rate, in experiments, is explained in terms of a model for plasmon-mediated collective emission of quantum emitters which points to the emergence of a new regime in plasmon-exciton interactions. The presented methodology to achieve enhancement in optical quantum efficiency for optimal doping of gold nanoparticles in such ultrathin high-density quantum dot films can be beneficial for new-generation displays and photodetectors.

Isolation and characterization of a bioflocculant from Bacillus megaterium for turbidity and arsenic removal

A biodegradable flocculant was produced during growth of Bacillus megaterium. The major component of the bioflocculant was found to be a polysaccharide composed of some proteins. Fourier transform infrared (FTIR) spectra analysis revealed the presence of carboxyl and hydroxyl groups in the bioflocculant, and thermal characterization by differential scanning calorimetly (DSC) showed the transition and crystalline melting point at 90-105 degrees C. The effects of bioflocculant dosage and pH on the flocculation of mineral suspensions were evaluated. The bioflocculant exhibited good flocculating capability on mineral suspensions and achieved flocculating efficiencies of 90 percent for k-aolinite and 85 percent for hematite suspensions at a dosage of only 5 mL/L. The maximum arsenite removal was found to be 90 percent at a bioflocculant dosage of 2 g/L, which is better than traditional chemicalflocculants. This study demonstrates that microbial bioflocculants have potential for application in environmental cleanup, such as in the flocculation of mineral fines and in the remediation of solutions that contain toxic heavy metals.

Size Effects on Strength in the Transition from Single-to-Polycrystalline Behavior

During the transition from single crystalline to polycrystalline behavior, the available data show the strength increasing or decreasing as the number of grains in a cross section is reduced. Tensile experiments were conducted on polycrystalline Ni with grain sizes (d) between 16 and 140 mu m and varying specimen thickness (t), covering a range of lambda (-t/d) between similar to 0.5 and 20. With a decrease in lambda, the data revealed a consistent trend of strength being independent of lambda at large lambda, an increase in strength, and then a decrease in strength. Microstructural studies revealed that lower constraints enabled easier rotation of the surface grains and texture evolution, independent of the specimen thickness. In specimen interiors, there was a greater ease of rotation in thinner samples. Measurements of misorientation deviations within grains revealed important differences in the specimen interiors. A simple model is developed taking into account the additional geometrically necessary dislocations due to variations in the behavior of surface and interior grains, leading to additional strengthening. A suitable combination of this strengthening and surface weakening can give rise to wide range of possibilities with a decrease in lambda, including weakening, strengthening, and strengthening and weakening.

On the Structural Stability of Melt Spun Ribbons of Fe95-x Zr (x) B4Cu1 (x=7 and 9) Alloys and Correlation with Their Magnetic Properties

Melt spun ribbons of Fe95-x Zr (x) B4Cu1 with x = 7 (Z7B4) and 9 (Z9B4) alloys have been prepared, and their structure and magnetic properties have been evaluated using XRD, DSC, TEM, VSM, and Mossbauer spectroscopy. The glass forming ability (GFA) of both alloys has been calculated theoretically using thermodynamical parameters, and Z9B4 alloy is found to possess higher GFA than that of Z7B4 alloy which is validated by XRD results. On annealing, the amorphous Z7B4 ribbon crystallizes into nanocrystalline alpha-Fe, whereas amorphous Z9B4 ribbon shows two-stage crystallization process, first partially to bcc solid solution which is then transformed to nanocrystalline alpha-Fe and Fe2Zr phases exhibiting bimodal distribution. A detailed phase analysis using Mossbauer spectroscopy through hyperfine field distribution of phases has been carried out to understand the crystallization behavior of Z7B4 and Z9B4 alloy ribbons. In order to understand the phase transformation behavior of Z7B4 and Z9B4 ribbons, molar Gibbs free energies of amorphous, alpha-Fe, and Fe2Zr phases have been evaluated. It is found that in case of Z7B4, alpha-Fe is always a stable phase, whereas Fe2Zr is stable at higher temperature for Z9B4. (C) The Minerals, Metals & Materials Society and ASM International 2015

Microstructure Formation in Dissimilar Metal Welds: Electron Beam Welding of Ti/Ni

We present results for electron beam welding of a binary Ti/Ni dissimilar metal couple. The difference in physical properties of the base metals and metallurgical features (thermodynamics and kinetics) of the system influence both macroscopic transport and microstructure development in the weld. Microstructures near the fusion interfaces are markedly different from those inside the weld region. At the Ti side, Ti2Ni dendrites are observed to grow toward the fusion interface, while in the Ni side, layered growth of gamma-Ni, Ni3Ti, and Ni3Ti + NiTi eutectic is observed. Different morphologies of the latter eutectic constitute the predominant microstructure inside the weld metal region. These results are compared and contrasted with those from laser welding of the same binary couple, and a scheme of solidification is proposed to explain the observations. This highlights notable departures from welding of similar and other dissimilar metals such as a significant asymmetry in heat transport that governs progress of solidification from each side of the couple, and a lack of unique liquidus isotherm characterizing the liquid-solid front.

Evolution of Texture and Microstructure in Deformed and Annealed Copper-Iron Multilayer

The effect of multiple phases on the evolution of texture during cold rolling and annealing of a copper-iron multilayer, fabricated by accumulative roll bonding, has been studied. The presence of an iron layer affects the deformation texture of the copper layer only at very large strains. On the other hand, a strong effect of copper on iron is observed at both small and large strains. At smaller strains, the larger deformation carried by the copper suppresses the texture development in the iron, whereas, at higher strains, selection of specific orientation relationship at the interface influences the texture of the iron layer. Shear banding and continuous dynamic recrystallization were found to influence the evolution of texture in the copper layer. The influence of large plastic deformation on the recrystallization behavior of copper is demonstrated with the suppression of typical fcc annealing texture components, described as constrained recrystallization. Evolution of typical annealing texture component is suppressed because of the multilayer microstructure. The plane of the interface formed during deformation is determined by a combination of the rolling texture of individual phases, constrained annealing, and the tendency to form a low-energy interface between the two phases during annealing.

Combined Effect of Cryogel Matrix and Temperature-Reversible Soluble-Insoluble Polymer for the Development of in Vitro Human Liver Tissue

Hepatic cell culture on a three-dimensional (3D) matrix or as a hepatosphere appears to be a promising in vitro biomimetic system for liver tissue engineering applications. In this study, we have combined the concept of a 3D scaffold and a spheroid culture to develop an in vitro model to engineer liver tissue for drug screening. We have evaluated the potential of poly(ethylene glycol)-alginate-gelatin (PAG) cryogel matrix for in vitro culture of human liver cell lines. The synthesized cryogel matrix has a flow rate of 7 mL/min and water uptake capacity of 94% that enables easy nutrient transportation in the in vitro cell culture. Youngs modulus of 2.4 kPa and viscoelastic property determine the soft and elastic nature of synthesized cryogel. Biocompatibility of PAG cryogel was evaluated through MTT assay of HepG2 and Huh-7 cells on matrices. The proliferation and functionality of the liver cells were enhanced by culturing hepatic cells as spheroids (hepatospheres) on the PAG cryogel using temperature-reversible soluble-insoluble polymer, poly(N-isopropylacrylamide) (PNIPAAm). Pore size of the cryogel above 100 mu m modulated spheroid size that can prevent hypoxia condition within the spheroid culture. Both the hepatic cells have shown a significant difference (P < 0.05) in terms of cell number and functionality when cultured with PNIPAAm. After 10 days of culture using 0.05% PNIPAAm, the cell number increased by 11- and 7-fold in case of HepG2 and Huh-7 cells, respectively. Similarly, after 10 days of hepatic spheroids culture on PAG cryogel, the albumin production, urea secretion, and CYP450 activity were significantly higher in case of culture with PNIPAAm. The developed tissue mass on the PAG cryogel in the presence of PNIPAAm possess polarity, which was confirmed using F-actin staining and by presence of intercellular bile canalicular lumen. The developed cryogel matrix supports liver cells proliferation and functionality and therefore can be used for in vitro and in vivo drug testing.

Molecular Cage Impregnated Palladium Nanoparticles: Efficient, Additive-Free Heterogeneous Catalysts for Cyanation of Aryl Halides

Two shape-persistent covalent cages (CC1(r) and CC2(r)) have been devised from triphenyl amine-based trialdehydes and cyclohexane diamine building blocks utilizing the dynamic imine chemistry followed by imine bond reduction. The cage compounds have been characterized by several spectroscopic techniques which suggest that CC1(r) and CC2(r) are 2+3] and 8+12] self-assembled architectures, respectively. These state-of-the-art molecules have a porous interior and stable aromatic backbone with multiple palladium binding sites to engineer the controlled synthesis and stabilization of ultrafine palladium nanoparticles (PdNPs). As-synthesized cage-embedded PdNPs have been characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and powder X-ray diffraction (PXRD). Inductively coupled plasma optical emission spectrometry reveals that Pd@CC1(r) and Pd@CC2(r) have 40 and 25 wt% palladium loading, respectively. On the basis of TEM analysis, it has been estimated that as small as similar to 1.8 nm PdNPs could be stabilized inside the CC1(r), while larger CC2(r) could stabilize similar to 3.7 nm NPs. In contrast, reduction of palladium salts in the absence of the cages form structure less agglomerates. The well-dispersed cage-embedded NPs exhibit efficient catalytic performance in the cyanation of aryl halides under heterogeneous, additive-free condition. Moreover, these materials have excellent stability and recyclability without any agglomeration of PdNPs after several cycles.

Orientation Selection and Microstructural Evolution in Directionally Solidified Tb0.3Dy0.7Fe1.95

Tb0.3Dy0.7Fe1.95 alloy was directionally solidified by using a modified Bridgman technique at a wide range of growth rates of 5 to 100 cm/h. The directionally grown samples exhibited plane front solidification morphology up to a growth rate of 90 cm/h. Typical island banding feature was observed closer to the chilled end, which eventually gave rise to irregular peritectic coupled growth (PCG). The PCG gained prominence with an increase in the growth rate. The texture study revealed formation of strong aOE (c) 311 > texture in a lower growth rate regime, aOE (c) 110 > and ``rotated aOE (c) 110 > aEuroe in an intermediate growth regime, and aOE (c) 112 > in a higher growth rate regime. In-depth analysis of the atomic configuration of a solid-liquid interface revealed that the growth texture is influenced by the kinetics of atomic attachment to the solid-liquid interface, which is intimately related to a planar packing fraction and an atomic stacking sequence of the interfacial plane. The mechanism proposed in this article is novel and will be useful in addressing the orientation selection mechanism of topologically closed packed intermetallic systems. The samples grown at a higher growth rate exhibit larger magnetostriction (lambda) and d lambda/dH owing to the absence of pro-peritectic (Tb,Dy)Fe-3 and formation of aOE (c) 112 > texture, which lies closer to the easy magnetization direction (EMD).

Resputtering Effect on Nanocrystalline Ni-Ti Alloy Films

We report on the effect of resputtering on the properties of nanocrystalline Ni-Ti alloy thin films deposited using co-sputtering of Ni and Ti targets. In order to facilitate the formation of nanocrystalline phases, films were deposited at room temperature and 573 K (300 A degrees C) with substrate bias voltage of -100 V. The influence of substrate material on the composition, surface topography microstructure, and phase formations of nanocrystalline Ni-Ti thin films was also systematically investigated. The preferential resputtering of Ti adatoms was lesser for Ni-Ti films deposited on quartz substrate owing to high surface roughness of 4.87 nm compared to roughness value of 1.27 nm for Si(100) substrate.