Anomalous piezoelectric response due to stabilization of two ferroelectric phases in Zr-modified BaTiO3

The lead-free Ba (Ti1-xZrx)O-3 ceramic has shown enhanced piezo-response (d(33)) in a narrow composition interval (0.01 <= x <= 0.03) exhibiting the coexistence of two ferroelectric phases. The system presents two electric-field-dependent-property regimes: (i) a low field regime (E < 1.7 kV mm(-1)) where d(33) is nearly independent of the poling field, and (ii) (E > 1.7 kV mm(-1)) for which d(33) drops sharply. X-ray diffraction studies revealed that the later phenomenon is related to field driven irreversible structural transformation, which tends to drive the system away from an equilibrium two phase state to a nearly single phase metastable state.

On the Mechanism of Phase Transfer Catalysis in Brust-Schiffrin Synthesis of Metal Nanoparticles

The two-phase Brust-Schiffrin method (BSM) is used to synthesize highly stable nanoparticles of noble metals. A phase transfer catalyst (PTC) is used to bring in aqueous phase soluble precursors into the organic phase to enable particle synthesis there. Two different mechanisms for phase transfer are advanced in the literature. The first mechanism considers PTC to bring in an aqueous phase soluble precursor by complexing with it. The second mechanism considers the ionic species to be contained in inverse micelles of PTC, with a water core inside. A comprehensive experimental study involving measurement of interfacial tension, viscosity, water content by Karl-Fischer titration, static light scattering, H-1 NMR, and small-angle X-ray scattering is reported in this work to establish that the phase transfer catalyst tetraoctylammonium bromide transfers ions by complexing with them, instead of encapsulating them in inverse micelles. The findings have implications for particle synthesis in two-phase methods such as BSM and their modification to produce more monodispersed particles.

Anomalous polarization in the antiferroelectric-ferroelectric phase coexistence state in PbZrO3-Bi(Mg1/2Ti1/2)O-3

The ferroelectric system (1-x)PbZrO3-(x)Bi(Mg1/2Ti1/2)O-3 has been investigated as a function of composition, temperature, and electric field by x-ray powder diffraction, dielectric, and ferroelectric measurements. Within the solubility limit (x similar to 0.25), the system evolves from an orthorhombic-antiferroelectric to rhombohedral-ferroelectric state through a phase coexistence region. The highest polarization was found not for the composition exhibiting a pure ferroelectric state, but for a composition x = 0.15 exhibiting ferroelectric + antiferroelectric phase coexistence close to the rhombohedral phase boundary. Electric poling of the equilibrium two-phase state led to irreversible enhancement in the rhombohedral phase fraction suggesting that the enhanced polarization is related to the enhanced polarizability of the lattice due to first order criticality as in ferroelectric-ferroelectric morphotropic phase boundary systems. (C) 2013 AIP Publishing LLC.

Phase relations in the system Ca-Ta-O and thermodynamics of calcium tantalates in relation to calciothermic reduction of Ta2O5

Phase equilibria of the system Ca-Ta-O is established by equilibrating eleven samples at 1200 K for prolonged periods and phase identification in quenched samples by optical and scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction. Four ternary oxides are identified: CaTa4O11, CaTa2O6, Ca2Ta2O7 and Ca4Ta2O9. Isothermal section of the phase diagram is composed using the results. Thermodynamic properties of the ternary oxides are measured in the temperature range from 975 to 1275 K employing solid-state galvanic cells incorporating single crystal CaF2 as the solid electrolyte. The cells essentially measure the chemical potentials of CaO in two-phase fields (Ta2O5 + CaTa4O11), (CaTa4O11 + CaTa2O6), (CaTa2O6 + Ca2Ta2O7), and (Ca2Ta2O7 + Ca4Ta2O9) of the pseudo-binary system CaO-Ta2O5. The standard Gibbs energies of formation of the four ternary oxides from their component binary oxides Ta2O5 and CaO are given by: Delta G(f)((ox))(o) (CaTa4O11) (+/- 482)/J mol(-1) = -58644+21.497 (T/K) Delta G(f)((ox))(o) (CaTa2O6) (+/- 618)/J mol(-1) = -55122+21.893 (T/K) Delta G(f)((ox))(o) (Ca2Ta2O7) (+/- 729)/J mol(-1) = -82562+31.843 (T/K) Delta G(f)((ox))(o) (Ca4Ta2O9) (+/- 955)/J mol(-1) = -126598+48.859 (T/K) The Gibbs energy of formation of the four ternary compounds obtained in this study differs significantly from that reported in the literature. The thermodynamic data and phase diagram are used for understanding the mechanism and kinetics of calciothermic and electrochemical reduction of Ta2O5 to metal. (C) 2014 Elsevier B.V. All rights reserved.

A Multi-phase Approach for Improving Information Diffusion in Social Networks

For maximizing influence spread in a social network, given a certain budget on the number of seed nodes, we investigate the effects of selecting and activating the seed nodes in multiple phases. In particular, we formulate an appropriate objective function for two-phase influence maximization under the independent cascade model, investigate its properties, and propose algorithms for determining the seed nodes in the two phases. We also study the problem of determining an optimal budget-split and delay between the two phases.

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.

Structural crossover from nonmodulated to long-period modulated tetragonal phase and anomalous change in ferroelectric properties in the lead-free piezoelectric Na1/2Bi1/2TiO3-BaTiO3

The highly complex structure-property interrelationship in the lead-free piezoelectric (x) Na1/2Bi1/2TiO3 - (1 - x) BaTiO3 is a subject of considerable contemporary debate. Using comprehensive x-ray, neutron diffraction, dielectric, and ferroelectric studies, we have shown the existence of a new criticality in this system at x = 0.80, i.e., well within the conventional tetragonal phase field. This criticality manifests as a nonmonotonic variation of the tetragonality and coercivity and is shown to be associated with a crossover from a nonmodulated tetragonal phase (for x < 0.8) to a long-period modulated tetragonal phase (for x > 0.80). It is shown that the stabilization of long-period modulation introduces a characteristic depolarization temperature in the system. While differing qualitatively from the two-phase model often suggested for the critical compositions of this system, our results support the view with regard to the tendency in perovskites to stabilize long-period modulated structures as a result of complex interplay of antiferrodistortive modes Bellaiche and Iniguez, Phys. Rev. B 88, 014104 ( 2013); Prosandeev, Wang, Ren, Iniguez, ands Bellaiche, Adv. Funct. Mater. 23, 234 (2013)].

A method for coupling the phase-field model based on a grand-potential formalism to thermodynamic databases

In this paper we derive an approach for the effective utilization of thermodynamic data in phase-field simulations. While the most widely used methodology for multi-component alloys is following the work by Eiken et al. (2006), wherein, an extrapolative scheme is utilized in conjunction with the TQ interface for deriving the driving force for phase transformation, a corresponding simplistic method based on the formulation of a parabolic free-energy model incorporating all the thermodynamics has been laid out for binary alloys in the work by Folch and Plapp (2005). In the following, we extend this latter approach for multi-component alloys in the framework of the grand-potential formalism. The coupling is applied for the case of the binary eutectic solidification in the Cr-Ni alloy and two-phase solidification in the ternary eutectic alloy (Al-Cr-Ni). A thermodynamic justification entails the basis of the formulation and places it in context of the bigger picture of Integrated Computational Materials Engineering. (C) 2015 Elsevier Ltd. All rights reserved.

Interrelationship between Interphase Boundaries and Phase Contents near the Critical Compositions of Lead-Free Ferroelectric (Na0.5Bi0.5)TiO3-BaTiO3

Heterophase structures in lead-free perovskite-type ferroelectric solid solutions of (1 - z)(Na0.5Bi0.5)TiO3 - zBaTiO(3) are analysed for a few critical compositions near the morphotropic phase boundary (z = 0.05-0.07). Examples of the phase coexistence and elastic matching of the phases from different symmetry groups are considered to find optimum volume fractions of specific domain types and coexisting phases at the complete stress relief in two-phase samples. Some interrelations between these volume fractions are described using variants of the domain arrangement at changes in the composition and unit-cell parameters. The evaluated room-temperature volume fractions of the ferroelectric monoclinic (Cm symmetry) and tetragonal (P4mm symmetry) phases near the morphotropic phase boundary are in agreement with experimental data.

Simulation of Coal Combustion by AUSM Turbulence-Chemistry Char Combustion Model and a Full Two-Fluid Model

An algebraic unified second-order moment (AUSM) turbulence-chemistry model of char combustion is introduced in this paper, to calculate the effect of particle temperature fluctuation on char combustion. The AUSM model is used to simulate gas-particle flows, in coal combustion in a pulverized coal combustor, together with a full two-fluid model for reacting gas-particle flows and coal combustion, including the sub-models as the k-epsilon-k(p) two-phase turbulence niodel, the EBU-Arrhenius volatile and CO combustion model, and the six-flux radiation model. A new method for calculating particle mass flow rate is also used in this model to correct particle outflow rate and mass flow rate for inside sections, which can obey the principle of mass conservation for the particle phase and can also speed up the iterating convergence of the computation procedure effectively. The simulation results indicate that, the AUSM char combustion model is more preferable to the old char combustion model, since the later totally eliminate the influence of particle temperature fluctuation on char combustion rate.

Two-way coupling model for shock-induced laminar boundary-layer flows of a dusty gas

The present paper describes a numerical two-way coupling model for shock-induced laminar boundary-layer flows of a dust-laden gas and studies the transverse migration of fine particles under the action of Saffman lift force. The governing equations are formulated in the dilute two-phase continuum framework with consideration of the finiteness of the particle Reynolds and Knudsen numbers. The full Lagrangian method is explored for calculating the dispersed-phase flow fields (including the number density of particles) in the regions of intersecting particle trajectories. The computation results show a significant reaction of the particles on the two-phase boundary-layer structure when the mass loading ratio of particles takes finite values.

The kinetic-theory for dilute solid liquid 2-phase flow

On the basis of a brief review of the continuum theory for macroscopic descriptions and the kinetic theory for microscopic descriptions in solid/liquid two-phase flows, some suggestions are presented, i.e. the solid phase may be described by the Boltzmann equation and the liquid phase still be described by conservation laws in the continuum theory. Among them the action force on the particles by the liquid fluid is a coupling factor which connects the phases. For dilute steady solid/liquid two-phase flows, the particle velocity distribution function can be derived by analogy with the procedures in the kinetic theory of gas molecules for the equilibrium state instead of being assumed, as previous investigators did. This done, more detailed information, such as the velocity probability density distribution, mean velocity distribution and fluctuating intensity etc. can be obtained directly from the particle velocity distribution function or from its integration. Experiments have been performed for dilute solid/liquid two-phase flow in a 4 x 6 cm2 sized circulating square pipe system by means of laser Doppler anemometry so that the theories can be examined. The comparisons show that the theories agree very well with all the measured data.

Novel method to construct a quality map for phase unwrapping based on modulation and the phase gradient

A novel method to construct a quality map, called modulation-phase-gradient variance (MPGV), is proposed, based on modulation and the phase gradient. The MPGV map is successfully applied to two phase-unwrapping algorithms - the improved weighted least square and the quality-guided unwrapping algorithm. Both simulated and experimental data testify to the validity of our proposed quality map. Moreover, the unwrapped-phase results show that the new quality map can have higher reliability than the conventional phase-derivative variance quality map in helping to unwrap noisy, low-modulation, and/or discontinuous phase maps. (c) 2006 Society of Photo-Optical Instrumentation Engineers.

Novel method to construct a quality map for phase unwrapping based on modulation and the phase gradient

A novel method to construct a quality map, called modulation-phase-gradient variance (MPGV), is proposed, based on modulation and the phase gradient. The MPGV map is successfully applied to two phase-unwrapping algorithms - the improved weighted least square and the quality-guided unwrapping algorithm. Both simulated and experimental data testify to the validity of our proposed quality map. Moreover, the unwrapped-phase results show that the new quality map can have higher reliability than the conventional phase-derivative variance quality map in helping to unwrap noisy, low-modulation, and/or discontinuous phase maps. (c) 2006 Society of Photo-Optical Instrumentation Engineers.

A uniform phase representation for the harmonic model in speech synthesis applications

Feature-based vocoders, e.g., STRAIGHT, offer a way to manipulate the perceived characteristics of the speech signal in speech transformation and synthesis. For the harmonic model, which provide excellent perceived quality, features for the amplitude parameters already exist (e.g., Line Spectral Frequencies (LSF), Mel-Frequency Cepstral Coefficients (MFCC)). However, because of the wrapping of the phase parameters, phase features are more difficult to design. To randomize the phase of the harmonic model during synthesis, a voicing feature is commonly used, which distinguishes voiced and unvoiced segments. However, voice production allows smooth transitions between voiced/unvoiced states which makes voicing segmentation sometimes tricky to estimate. In this article, two-phase features are suggested to represent the phase of the harmonic model in a uniform way, without voicing decision. The synthesis quality of the resulting vocoder has been evaluated, using subjective listening tests, in the context of resynthesis, pitch scaling, and Hidden Markov Model (HMM)-based synthesis. The experiments show that the suggested signal model is comparable to STRAIGHT or even better in some scenarios. They also reveal some limitations of the harmonic framework itself in the case of high fundamental frequencies.