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.

Dynamic compression behavior of reactive spark plasma sintered ultrafine grained (Hf, Zr)B-2-SiC composites

This paper reports the dynamic compression behavior of ultrafine grained (Hf, Zr)B-2-SiC composites, sintered using reactive spark plasma sintering at 1600 degrees C for 10 min. Dynamic strength of similar to 2.3 GPa has been measured using Split Hopkinson Pressure Bar (SHPB) tests in a reproducible manner at strain rates of 800-1300 s(-1). A comparison with competing boride based armor ceramics, in reference to the spectrum of properties evaluated, establishes the potential of (Hf, Zr)B-2-SiC composites for armor applications. (C) 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Detection of a quantum particle on a lattice under repeated projective measurements

We consider a quantum particle, moving on a lattice with a tight-binding Hamiltonian, which is subjected to measurements to detect its arrival at a particular chosen set of sites. The projective measurements are made at regular time intervals tau, and we consider the evolution of the wave function until the time a detection occurs. We study the probabilities of its first detection at some time and, conversely, the probability of it not being detected (i.e., surviving) up to that time. We propose a general perturbative approach for understanding the dynamics which maps the evolution operator, which consists of unitary transformations followed by projections, to one described by a non-Hermitian Hamiltonian. For some examples of a particle moving on one-and two-dimensional lattices with one or more detection sites, we use this approach to find exact expressions for the survival probability and find excellent agreement with direct numerical results. A mean-field model with hopping between all pairs of sites and detection at one site is solved exactly. For the one-and two-dimensional systems, the survival probability is shown to have a power-law decay with time, where the power depends on the initial position of the particle. Finally, we show an interesting and nontrivial connection between the dynamics of the particle in our model and the evolution of a particle under a non-Hermitian Hamiltonian with a large absorbing potential at some sites.

Volume conservation issues in incompressible smoothed particle hydrodynamics

A divergence-free velocity field is usually sought in numerical simulations of incompressible fluids. We show that the particle methods that compute a divergence-free velocity field to achieve incompressibility suffer from a volume conservation issue when a finite time-step position update scheme is used. Further, we propose a deformation gradient based approach to arrive at a velocity field that reduces the volume conservation issues in free surface flows and maintains density uniformity in internal flows while retaining the simplicity of first order time updates. (C) 2015 Elsevier Inc. All rights reserved.

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.

Multiobjective fuzzy optimization for sustainable groundwater management using particle swarm optimization and analytic element method

Groundwater management involves conflicting objectives as maximization of discharge contradicts the criteria of minimum pumping cost and minimum piping cost. In addition, available data contains uncertainties such as market fluctuations, variations in water levels of wells and variations of ground water policies. A fuzzy model is to be evolved to tackle the uncertainties, and a multiobjective optimization is to be conducted to simultaneously satisfy the contradicting objectives. Towards this end, a multiobjective fuzzy optimization model is evolved. To get at the upper and lower bounds of the individual objectives, particle Swarm optimization (PSO) is adopted. The analytic element method (AEM) is employed to obtain the operating potentio metric head. In this study, a multiobjective fuzzy optimization model considering three conflicting objectives is developed using PSO and AEM methods for obtaining a sustainable groundwater management policy. The developed model is applied to a case study, and it is demonstrated that the compromise solution satisfies all the objectives with adequate levels of satisfaction. Sensitivity analysis is carried out by varying the parameters, and it is shown that the effect of any such variation is quite significant. Copyright (c) 2015 John Wiley & Sons, Ltd.

A Few Case Studies on the Correlation of Particle Network and Its Stability on the Ionic Conductivity of Solid-Liquid Composite Electrolytes

We discuss here the crucial role of the particle network and its stability on the long-range ion transport in solid liquid composite electrolytes. The solid liquid composite electrolytes chosen for the study here comprise nanometer sized silica (SiO2) particles having various surface chemical functionalities dispersed in nonaqueous lithium salt solutions, viz, lithium perchlorate (LiClO4) in two different polyethylene glycol based solvents. These systems constitute representative examples of an independent class of soft matter electrolytes known as ``soggy sand'' electrolytes, which have tremendous potential in diverse electrochemical devices. The oxide additive acts as a heterogeneous dopant creating free charge carriers and enhancing the local ion transport. For long-range transport, however, a stable spanning particle network is needed. Systematic experimental investigations here reveal that the spatial and time dependent characteristics of the particle network in the liquid solution are nontrivial. The network characteristics are predominantly determined by the chemical makeup of the electrolyte components and the chemical interactions between them. It is noteworthy that in this study the steady state macroscopic ionic conductivity and viscosity of the solid liquid composite electrolyte are observed to be greatly determined by the additive oxide surface chemical functionality, solvent chemical composition, and solvent dielectric constant.

Review: Overcoming the paradox of strength and ductility in ultrafine-grained materials at low temperatures

Ultrafine-grained (UFG) materials with grain sizes in the submicrometer or nanometer range may be prepared through the application of severe plastic deformation (SPD) to bulk coarse-grained solids. These materials generally exhibit high strength but only very limited ductility in low-temperature testing, thereby giving rise to the so-called paradox of strength and ductility. This paradox is examined and a new quantitative diagram is presented which permits the easy insertion of experimental data. It is shown that relatively simple procedures are available for achieving both high strength and high ductility in UFG materials including processing the material to a very high strain and/or applying a very short-term anneal immediately after the SPD processing. Significant evidence is now available demonstrating the occurrence of grain boundary sliding in these materials at low temperatures, where this is attributed to the presence of non-equilibrium grain boundaries and the occurrence of enhanced diffusion along these boundaries.

Many-Body Localization in the Presence of a Single-Particle Mobility Edge

In one dimension, noninteracting particles can undergo a localization-delocalization transition in a quasiperiodic potential. Recent studies have suggested that this transition transforms into a many-body localization (MBL) transition upon the introduction of interactions. It has also been shown that mobility edges can appear in the single particle spectrum for certain types of quasiperiodic potentials. Here, we investigate the effect of interactions in two models with such mobility edges. Employing the technique of exact diagonalization for finite-sized systems, we calculate the level spacing distribution, time evolution of entanglement entropy, optical conductivity, and return probability to detect MBL. We find that MBL does indeed occur in one of the two models we study, but the entanglement appears to grow faster than logarithmically with time unlike in other MBL systems.

Twinning induced enhancement of fracture toughness in ultrafine grained Hydroxyapatite-Calcium Titanate composites

Despite being highly bioactive and biocompatible, the limitations of monolithic hydroxyapatite (HA) include extremely low fracture toughness, poor electrical conductivity. While addressing these issues, the present study demonstrates how CaTiO3 (CT) addition to HA can be utilized to obtain a combination of long crack fracture toughness (1.7 MPa m(1/2) SEVNB technique) and flexural strength of 98-155 MPa (3-point bending) and a moderate tensile strength (diametral compression) of 17-36 MPa. The enhancement in fracture resistance in spark plasma sintered HA-CT composites has been explained in reference to the observed twin morphology. TEM reveals the presence of twins in CT grains due to 1800 rotation about 101]. The measured properties along with our earlier reports on biocompatibility and electrical properties make HA-CT suitable for bone tissue engineering applications. When compared with other competing HA-based biocomposites, HA-CT composites are found to have a better combination of properties useful for medium load bearing implant applications. (C) 2015 Elsevier Ltd. All rights reserved.

A flame particle tracking analysis of turbulence-chemistry interaction in hydrogen-air premixed flames

Interactions of turbulence, molecular transport, and energy transport, coupled with chemistry play a crucial role in the evolution of flame surface geometry, propagation, annihilation, and local extinction/re-ignition characteristics of intensely turbulent premixed flames. This study seeks to understand how these interactions affect flame surface annihilation of lean hydrogen-air premixed turbulent flames. Direct numerical simulations (DNSs) are conducted at different parametric conditions with a detailed reaction mechanism and transport properties for hydrogen-air flames. Flame particle tracking (FPT) technique is used to follow specific flame surface segments. An analytical expression for the local displacement flame speed (S-d) of a temperature isosurface is considered, and the contributions of transport, chemistry, and kinematics on the displacement flame speed at different turbulence-flame interaction conditions are identified. In general, the displacement flame speed for the flame particles is found to increase with time for all conditions considered. This is because, eventually all flame surfaces and their resident flame particles approach annihilation by reactant island formation at the end of stretching and folding processes induced by turbulence. Statistics of principal curvature evolving in time, obtained using FPT, suggest that these islands are ellipsoidal on average enclosing fresh reactants. Further examinations show that the increase in S-d is caused by the increased negative curvature of the flame surface and eventual homogenization of temperature gradients as these reactant islands shrink due to flame propagation and turbulent mixing. Finally, the evolution of the normalized, averaged, displacement flame speed vs. stretch Karlovitz number are found to collapse on a narrow band, suggesting that a unified description of flame speed dependence on stretch rate may be possible in the Lagrangian description. (C) 2015 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Ultrafine graphene oxide-CoFe2O4 nanoparticle composite as T-1 and T-2 contrast agent for magnetic resonance imaging

Graphene oxide-CoFe2O4 nanoparticle composites were synthesized using a two step synthesis method in which graphene oxide was initially synthesized followed by precipitation of CoFe2O4 nanoparticles in a reaction mixture containing graphene oxide. Samples were extracted from the reaction mixture at different times at 80 degrees C. All the extracted samples contained CoFe2O4 nanoparticles formed over the graphene oxide. It was observed that the increase in the reflux time significantly increased the saturation magnetization value for the superparamagnetic nanoparticles in the composite. It was also noticed that the size of the nanoparticles increased with increase in the reflux time. Transverse relaxivity of the water protons increased monotonically with increase in the reflux time. Whereas, the longitudinal relaxivity value initially increased and then decreased with the reflux time. Graphene oxide-CoFe2O4 nanoparticle composites also exhibit biocompatibility towards the MCF-7 cell line.

Effect of particle size of sand and surface asperities of reinforcement on their interface shear behaviour

This paper investigates the effect of particle size of sand and the surface asperities of reinforcing material on their interlocking mechanism and its influence on the interfacial shear strength under direct sliding condition. Three sands of different sizes with similar morphological characteristics and four different types of reinforcing materials with different surface features were used in this study. Interface direct shear tests on these materials were performed in a specially developed symmetric loading interface direct shear test setup. Morphological characteristics of sand particles were determined from digital image analysis and the surface roughness of the reinforcing materials was measured using an analytical expression developed for this purpose. Interface direct shear tests at three different normal stresses were carried out by shearing the sand on the reinforcing material fixed to a smooth surface. Test results revealed that the peak interfacial friction and dilation angles are hugely dependent upon the interlocking between the sand particles and the asperities of reinforcing material, which in turn depends on the relative size of sand particles and asperities. Asperity ratio (AS/D-50) of interlocking materials, which is defined as the ratio of asperity spacing of the reinforcing material and the mean particle size of sand was found to govern the interfacial shear strength with highest interfacial strength measured when the asperity ratio was equal to one, which represents the closest fitting of sand particles into the asperities. It was also understood that the surface roughness of the reinforcing material influences the shear strength to an extent, the influence being more pronounced in coarser particles. Shear bands in the interface shear tests were analysed through image segmentation technique and it was observed that the ratio of shear band thickness (t) to the median particle size (D-50) was maximum when the AS/D-50 was equal to one. (C) 2015 Elsevier Ltd. All rights reserved.

Visualisation of charge-transfer excitations in donor-acceptor molecules using the particle-hole map: a case study

Charge-transfer (CT) excitations are essential for photovoltaic phenomena in organic solar cells. Owing to the complexity of molecular geometries and orbital coupling, a detailed analysis and spatial visualisation of CT processes can be challenging. In this paper, a new detail-oriented visualisation scheme, the particle-hole map (PHM), is applied and explained for the purpose of spatial analysis of excitations in organic molecules. The PHM can be obtained from the output of a time-dependent density-functional theory calculation with negligible additional computational cost, and provides a useful physical picture for understanding the origins and destinations of electrons and holes during an excitation process. As an example, we consider intramolecular CT excitations in Diketopyrrolopyrrole-based molecules, and relate our findings to experimental results.