Phase formation and stability of alloy phases in free nanoparticles: some insights

This paper explores phase formation and phase stability in free nanoparticles of binary alloys. A procedure for estimating the size and composition dependent free energies incorporating the contributions from the interfaces has been presented. Both single phase solid solution and two phase morphology containing interphase interfaces have been considered. A free energy scenario has been evaluated for two binary alloy systems Ag-Ni and Ag-Cu to predict the microstructure of the alloy nanoparticles at different size ranges as a function of composition. Both Ag-Cu and Ag-Ni systems exhibit wide bulk immiscibility. Ag-Ni nanoparticles were synthesized using the wet chemical synthesis technique whereas Ag-Cu nanoparticles were synthesized using laser ablation of a Ag-Cu target immersed in distilled water. Microstructural and compositional characterization of Ag-Ni and Ag-Cu nanoparticles on a single nanoparticle level was conducted using transmission electron microscopy. Nanoparticle microstructures observed from the microscopic investigation have been correlated with thermodynamic calculation results. It is shown that the observed two phase microstructure consisting of Ag-Ni solid solution in partial decomposed state coexisting with pure Ag phases in the case of Ag-Ni nanoparticles can be only be rationalized by invoking the tendency for phase separation of an initial solid solution with increase in nanoparticle size. Smaller sized Ag-Ni nanoparticles prefer a single phase solid solution microstructure. Due to an increase in particle size during the synthesis process the initial solid solution decomposes into an ultrafine scale phase separated microstructure. We have shown that it is necessary to invoke critical point phenomenon and wetting transition in systems showing a critical point that leads to phase separated Ag-Ni nanoparticles providing a catalytic substrate for the nucleation of equilibrium Ag over it. In the case of the Ag-Cu system, we report the experimental observation of a core shell structure at small sizes. This can be rationalized in terms of a metastable solid solution. It is argued that the nucleation barrier can prevent the formation of biphasic morphology with an internal interface. In such a situation, demixing of the solid solution can bring the system to a lower energy configuration. This has lead to the observed core-shell morphology in the Ag-Cu system during room temperature synthesis.

Self-assembled ZnO nanoparticles on ZnO microsheet: ultrafast synthesis and tunable photoluminescence properties

We report on the tunable photoluminescence characteristics of porous ZnO microsheets fabricated within 1-5 min of microwave irradiation in the presence of a capping agent such as citric acid, and mixture of citric acid with polyvinylpyrrolidone (PVP). The UV emission intensity reduces to 60% and visible emission increases tenfold when the molar concentration of citric acid is doubled. Further diminution of the intensity of UV emission (25%) is observed when PVP is mixed with citric acid. The addition of nitrogen donor ligands to the parent precursor leads to a red shift in the visible luminescence. The deep level emission covers the entire visible spectrum and gives an impression of white light emission from these ZnO samples. The detailed luminescence mechanism of our ZnO samples is described with the help of a band diagram constructed by using the theoretical models that describe the formation energy of the defect energy levels within the energy band structure. Oxygen vacancies play the key role in the variation of the green luminescence in the ZnO microsheets. Our research findings provide an insight that it is possible to retain the microstructure and simultaneously introduce defects into ZnO. The growth of the ZnO microsheets may be due to the self assembly of the fine sheets formed during the initial stage of nucleation.

Texture evolution during hot deformation of Moly-TZM

Moly-TZM was deformed at constant strain rate of 1.0 s(-1) to investigate the high strain rate deformation behaviour by microstructural and stress response change within a temperature range of 1400-1700 degrees C. To correlate the deformation behaviour with orientational change, recrystallization and recovery of the material, the microstructural investigation was undertaken using scanning electron microscopy (SEM) of electron back scattered diffraction (EBSD). Depending on the grain size and orientation spread recrystallized grains were identified and texture was calculated. Change in grain boundary characteristics with increasing temperature was determined by the misorientation angle distribution for the deformed and recrystallized grains. Subgrain coalescence and increase in subgrain size with increasing temperature was observed, indicating recrystallization not only occurred from the nucleation of the dislocation free grains in grain boundaries but also from the subgrain rotation and merging of the subgrains by annihilation of the low angle grain boundaries. Detailed studies on the evolution of texture of recrystallized grains showed continuous increase in <001> fiber texture in recrystallised grains, in contrast to a mixed fiber <001> +<111> for the deformed grains.

Mapping the intriguing transient morphologies and the demixing behavior in PS/PVME blends in the presence of rod-like nanoparticles

The demixing behavior, transient morphologies and mechanism of phase separation in PS/PVME blends were greatly altered in the presence of a very low concentration of rod-like particles (multiwall carbon nanotubes, MWNTs). This phenomenon is due to the specific interaction of one of the phases (PVME) with the anisotropic MWNTs, which creates a heterogeneous environment in the blend. This specific interaction alters the chain dynamics in the interfacial region as against the bulk. A comprehensive analysis using isochronal temperature sweep was performed to understand the demixing temperature in the blends. The evolution of phase morphology as a function of time and temperature was assessed by polarizing optical microscopy (POM), atomic force microscopy (AFM) and scanning electron microscopy (SEM). The addition of MWNTs increased the rheological demixing temperature and the spinodal temperature in almost all the compositions. The intriguing transient morphologies were mapped, which varied from nucleation and growth to coalescence-induced viscoelastic phase separation (C-VPS) in PVME-rich blends, to spinodal decomposition in the near-critical compositions, to transient gel-induced VPS (T-VPS) in the PS-rich compositions. Mapping of the morphology development displayed two types of fracture mechanisms: ductile fracture for near-critical compositions and brittle fracture for off-critical composition. The change in the phase separation mechanism in the presence of MWNTs was due to the variation in dynamic asymmetry brought about by these anisotropic particles. All these observations were correlated by POM, SEM and AFM studies. The length of the cooperatively rearranging region (CRR), as evaluated using modulated differential scanning calorimetry (MDSC) measurements, was found to be composition-independent. The observed variation of effective glass transition of PVME (low T-g component) on blending with PS (high Tg component) and by the addition of MWNTs accounts for the dynamic heterogeneity introduced by MWNTs in the system.

Damage mechanisms in stainless steel and chromium carbide coatings under controlled environment fretting conditions

Fretting is of a serious concern in many industrial components, specifically, in nuclear industry for the safe and reliable operation of various component and/or system. Under fretting condition small amplitude oscillations induce surface degradation in the form of surface cracks and/or surface wear. Comprehensive experimental studies have been carried out simulating different fretting regimes under ambient and vacuum (10(-9) MPa) conditions and, temperature up to 400 degrees C. Studies have been carried out with stainless steel spheres on stainless steel flats, and stainless steel spheres against chromium carbide, with 25% nickel chrome binder coatings. Mechanical responses are correlated with the damage observed. It has been observed that adhesion plays a vital role in material degradation process, and its effectiveness depends on mechanical variables such as normal load, interfacial tangential displacement, characteristics of the contacting bodies and most importantly on the environment conditions. Material degradation mechanism for ductile materials involved severe plastic deformation, which results in the initiation or nucleation of cracks. Ratcheting has been observed as the governing damage mode for crack nucleation under cyclic tangential loading condition. Further, propagation of the cracks has been observed under fatigue and their orientation has been observed to be governed by the contact conditions prevailing at the contact interface. Coated surfaces show damage in the form of brittle fracture and spalling of the coatings. Existence of stick slip has been observed under high normal load and low displacement amplitude. It has also been observed that adhesion at the contact interface and instantaneous cohesive strength of the contacting bodies dictates the occurrence of material transfer. The paper discusses the mechanics and mechanisms involved in fretting damage under controlled environment conditions. (C) 2015 Elsevier B.V. All rights reserved.

Contrasting Effects of Graphene Oxide and Poly(ethylenimine) on the Polymorphism in Poly(vinylidene fluoride)

The nature of interaction between a heteronucleating agent (graphene oxide, GO) and a strongly polar macromolecule (poly(ethylenimine), PEI) with poly(vinylidene fluoride) (PVDF) influencing the crystalline structure and morphology has been systematically investigated in this work. PEI interacts with PVDF via ion-dipole interaction, which helps in lowering the free energy barrier for nucleation thereby promoting faster crystallization. In contrast, besides interacting with PVDF, GO also promotes heteronucleation in PVDF. We observed that both GO and PEI have very different effects on the overall crystalline morphology of PVDF. For instance, the neat PVDF showed a mixture of both alpha and beta phases when cooled from the melt. However, incorporation of 0.1 wt % GO resulted in phase transformation from the stable alpha-phase to polar beta-polymorph in PVDF. In contrast, PEI, which also resulted in faster crystallization in PVDF predominantly, resulted in the stable alpha- phase. Various techniques like Fourier transform infrared spectroscopy, X-ray diffraction, and differential scanning calorimetry were employed to confirm the phase transformations in PVDF. PEI was further grafted onto GO nanosheets to understand the combined effects of both GO and PEI on the polymorphism in PVDF. The PVDF/PEI-GO composite showed a mixture of phases, predominantly rich in a. These phenomenal effects were further analyzed and corroborated with the specific interaction between GO and PEI with PVDF using X-ray photon scattering (XPS) and NMR. In addition, the dielectric permittivity increased significantly in the presence of GO and PEI in the composites. For instance, PVDF/PEI-GO showed the highest permittivity of 39 at 100 Hz.

Effect of Particle Concentration on Shape Deformation and Secondary Atomization Characteristics of a Burning Nanotitania Dispersion Droplet

Secondary atomization characteristics of burning bicomponent (ethanol-water) droplets containing titania nanoparticles (NPs) in dilute (0.5% and 1 wt.%) and dense concentrations (5% and 7.5 wt.%) are studied experimentally at atmospheric pressure under normal gravity. It is observed that both types of nanofuel droplets undergo distinct modes of secondary breakup, which are primarily responsible for transporting particles from the droplet domain to the flame zone. For dilute nanosuspensions, disruptive response is characterized by low intensity atomization modes that cause small-scale localized flame distortion. In contrast, the disruption behavior at dense concentrations is governed by high intensity bubble ejections, which result in severe disruption of the flame envelope.

Dissecting Ubiquitin Folding Using the Self-Organized Polymer Model

Folding of Ubiquitin (Ub), a functionally important protein found in eukaryotic organisms, is investigated at low and neutral pH at different temperatures using simulations of the coarse-grained self-organized-polymer model with side chains (SOP-SC). The melting temperatures (T-m's), identified with the peaks in the heat capacity curves, decrease as pH decreases, in qualitative agreement with experiments. The calculated radius of gyration, showing dramatic variations with pH, is in excellent agreement with scattering experiments. At T-m Ub folds in a two-state manner at low and neutral pH. Clustering analysis of the conformations sampled in equilibrium folding trajectories at T-m with multiple transitions between the folded and unfolded states, shows a network of metastable states connecting the native and unfolded states. At low and neutral pH, Ub folds with high probability through a preferred set of conformations resulting in a pH-dependent dominant folding pathway. Folding kinetics reveal that Ub assembly at low pH occurs by multiple pathways involving a combination of nucleation-collapse and diffusion collision mechanism. The mechanism by which Ub folds is dictated by the stability of the key secondary structural elements responsible for establishing long-range contacts and collapse of Ub. Nucleation collapse mechanism holds if the stability of these elements are marginal, as would be the case at elevated temperatures. If the lifetimes associated with these structured microdomains are on the order of hundreds of microseconds, then Ub folding follows the diffusion collision mechanism with intermediates, many of which coincide with those found in equilibrium. Folding at neutral pH is a sequential process with a populated intermediate resembling that sampled at equilibrium. The transition state structures, obtained using a P-fold analysis, are homogeneous and globular with most of the secondary and tertiary structures being native-like. Many of our findings for both the thermodynamics and kinetics of folding are not only in agreement with experiments but also provide missing details not resolvable in standard experiments. The key prediction that folding mechanism varies dramatically with pH is amenable to experimental tests.

Numerical study of laminar, standing hydraulic jumps in a planar geometry

We solve the two-dimensional, planar Navier-Stokes equations to simulate a laminar, standing hydraulic jump using a Volume-of-Fluid method. The geometry downstream of the jump has been designed to be similar to experimental conditions by including a pit at the edge of the platform over which liquid film flows. We obtain jumps with and without separation. Increasing the inlet Froude number pushes the jump downstream and makes the slope of the jump weaker, consistent with experimental observations of circular jumps, and decreasing the Reynolds number brings the jump upstream while making it steeper. We study the effect of the length of the domain and that of a downstream obstacle on the structure and location of the jump. The transient flow which leads to a final steady jump is described for the first time to our knowledge. In the moderate Reynolds number regime, we obtain steady undular jumps with a separated bubble underneath the first few undulations. Interestingly, surface tension leads to shortening of wavelength of these undulations. We show that the undulations can be explained using the inviscid theory of Benjamin and Lighthill (Proc. R. Soc. London, Ser. A, 1954). We hope this new finding will motivate experimental verification.

Coupled Mechanisms of Precipitation and Atomization in Burning Nanofluid Fuel Droplets

Understanding the combustion characteristics of fuel droplets laden with energetic nanoparticles (NP) is pivotal for lowering ignition delay, reducing pollutant emissions and increasing the combustion efficiency in next generation combustors. In this study, first we elucidate the feedback coupling between two key interacting mechanisms, namely, secondary atomization and particle agglomeration; that govern the effective mass fraction of NPs within the droplet. Second, we show how the initial NP concentration modulates their relative dominance leading to a masterslave configuration. Secondary atomization of novel nanofuels is a crucial process since it enables an effective transport of dispersed NPs to the flame (a pre-requisite condition for NPs to burn). Contrarily, NP agglomeration at the droplet surface leads to shell formation thereby retaining NPs inside the droplet. In particular, we show that at dense concentrations shell formation (master process) dominates over secondary atomization (slave) while at dilute particle loading it is the high frequency bubble ejections (master) that disrupt shell formation (slave) through its rupture and continuous outflux of NPs. This results in distinct combustion residues at dilute and dense concentrations, thereby providing a method of manufacturing flame synthesized microstructures with distinct morphologies.

PREDICTION OF TRANSITIONAL AND SEPARATED BOUNDARY LAYERS IN A COMPRESSOR CASCADE

Numerical simulations were performed of experiments from a cascade of stator blades at three low Reynolds numbers representative of flight conditions. Solutions were assessed by comparing blade surface pressures, velocity and turbulence intensity along blade normals at several stations along the suction surface and in the wake. At Re = 210,000 and 380,000 the laminar boundary layer over the suction surface separates and reattaches with significant turbulence fluctuations. A new 3-equation transition model, the k-k(L)-omega model, was used to simulate this flow. Predicted locations of the separation bubble, and profiles of velocity and turbulence fluctuations on blade-normal lines at various stations along the blade were found to be quite close to measurements. Suction surface pressure distributions were not as close at the lower Re. The solution with the standard k-omega SST model showed significant differences in all quantities. At Re = 640,000 transition occurs earlier and it is a turbulent boundary layer that separates near the trailing edge. The solution with the Reynolds stress model was found to be quite close to the experiment in the separated region also, unlike the k-omega SST solution. Three-dimensional computations were performed at Re = 380,000 and 640,000. In both cases there were no significant differences between the midspan solution from 3D computations and the 2D solutions. However, the 3D solutions exhibited flow features observed in the experiments the nearly 2D structure of the flow over most of the span at 380,000 and the spanwise growth of corner vortices from the endwall at 640,000.

General framework for acoustic emission during plastic deformation

Despite the long history, so far there is no general theoretical framework for calculating the acoustic emission spectrum accompanying any plastic deformation. We set up a discrete wave equation with plastic strain rate as a source term and include the Rayleigh-dissipation function to represent dissipation accompanying acoustic emission. We devise a method of bridging the widely separated time scales of plastic deformation and elastic degrees of freedom. While this equation is applicable to any type of plastic deformation, it should be supplemented by evolution equations for the dislocation microstructure for calculating the plastic strain rate. The efficacy of the framework is illustrated by considering three distinct cases of plastic deformation. The first one is the acoustic emission during a typical continuous yield exhibiting a smooth stress-strain curve. We first construct an appropriate set of evolution equations for two types of dislocation densities and then show that the shape of the model stress-strain curve and accompanying acoustic emission spectrum match very well with experimental results. The second and the third are the more complex cases of the Portevin-Le Chatelier bands and the Luders band. These two cases are dealt with in the context of the Ananthakrishna model since the model predicts the three types of the Portevin-Le Chatelier bands and also Luders-like bands. Our results show that for the type-C bands where the serration amplitude is large, the acoustic emission spectrum consists of well-separated bursts of acoustic emission. At higher strain rates of hopping type-B bands, the burst-type acoustic emission spectrum tends to overlap, forming a nearly continuous background with some sharp acoustic emission bursts. The latter can be identified with the nucleation of new bands. The acoustic emission spectrum associated with the continuously propagating type-A band is continuous. These predictions are consistent with experimental results. More importantly, our study shows that the low-amplitude continuous acoustic emission spectrum seen in both the type-B and type-A band regimes is directly correlated to small-amplitude serrations induced by propagating bands. The acoustic emission spectrum of the Luders-like band matches with recent experiments as well. In all of these cases, acoustic emission signals are burstlike, reflecting the intermittent character of dislocation-mediated plastic flow.

Effect of absolute pressure on flow through a textured hydrophobic microchannel

The potential of textured hydrophobic surfaces to provide substantial drag reduction has been attributed to the presence of air bubbles trapped on the surface cavities. In this paper, we present results on water flow past a textured hydrophobic surface, while systematically varying the absolute pressure close to the surface. Trapped air bubbles on the surface are directly visualized, along with simultaneous pressure drop measurements across the surface in a microchannel configuration. We find that varying the absolute pressure within the channel greatly influences the trapped air bubble behavior, causing a consequent effect on the pressure drop (drag). When the absolute pressure within the channel is maintained below atmospheric pressure, we find that the air bubbles grow in size, merge and eventually detach from the surface. This growth and subsequent merging of the air bubbles leads to a substantial increase in the pressure drop. On the other hand, a pressure above the atmospheric pressure within the channel leads to gradual shrinkage and eventual disappearance of trapped air bubbles. We find that in this case, air bubbles do cause reduction in the pressure drop with the minimum pressure drop (or maximum drag reduction) occurring when the bubbles are flush with the surface. These results show that the trapped air bubble dynamics and the pressure drop across a textured hydrophobic microchannel are very significantly dependent on the absolute pressure within the channel. The results obtained hold important implications toward achieving sustained drag reduction in microfluidic applications.

Single-step, size-controlled synthesis of colloidal silver nanoparticles stabilized by octadecylamine

A single step process for the synthesis of size-controlled silver nanoparticles has been developed using a bifunctional molecule, octadecylamine (ODA). Octadecylamine complexes to Ag+ ions electrostatically, reduce them, and subsequently stabilizes the nanoparticles thus formed. Hence, octadecylamine simultaneously functions as both a reducing and a stabilizing agent. The amine-capped nanoparticles can be obtained in the form of dry powder, which is readily redispersible in aqueous and organic solvents. The particle size, and the nucleation and growth kinetics of silver nanoparticles could be tuned by varying the molar ratio of ODA to AgNO3. The UV-vis spectra of nanoparticles prepared with different concentrations of ODA displayed the well-defined plasmon band with maximum absorption around 425 nm. The formation of silver metallic nanoparticles was confirmed by their XRD pattern. The binding of ODA molecule on the surface of silver has been studied by FT-IR and NMR spectroscopy. The formation of well-dispersed spherical Ag nanoparticles has been confirmed by TEM analysis. The particle size and distribution are found to be dependent on the molar concentration of the amine molecule. Open aperture z-scans have been performed to measure the nonlinearity of Ag nanoparticles. (C) 2015 Published by Elsevier B.V.

Effect of Nb orientation and deformation on the growth of Nb3Sn intermetallic superconductor by bronze technique

The growth of Nb3Sn by bronze technique on single crystals and deformed Nb is studied. The grain boundary diffusion-controlled growth rate is found to be higher for Nb-(0 1 3) than Nb-(0 1 1) because of smaller grain size of Nb3Sn. The difference in grain size is explained with the help of surface energies leading to different nucleation barrier. Significantly finer grains and higher growth rate of the product phase is found for rolled Nb because of available defects acting as potential nucleation sites.