Phase separation in the presence of fractal aggregates.

Liquid-liquid phase separation in diverse manufacturing and biological contexts often occurs in the presence of aggregated particles or complex-shaped structures that do not actively participate in the phase separation process, but these "background" structures can serve to direct the macroscale phase separation morphology by their local symmetry-breaking presence. We perform Cahn-Hilliard phase-field simulations in two dimensions to investigate the morphological evolution, wetting, and domain growth phenomena during the phase separation of a binary mixture in contact with model fractal aggregates. Our simulations reveal that phase separation initially accelerates around the fractal due to the driving force of wetting, leading to the formation of the target composition patterns about the fractals, as previously observed for circular particles. After the formation of a wetting layer on the fractal, however, we observe a dramatic slowing-down in the kinetics of phase separation, and the characteristic domain size eventually "pins" to a finite value or approaches an asymptotic scaling regime as an ordinary phase if the phase separation loses memory of the aggregates when the scale of phase separation becomes much larger than the aggregate. Furthermore, we perform simulations to examine the effects of compositional interference between fractals with a view to elucidating interesting novel morphological features in the phase-separating mixture. Our findings should be helpful in understanding the qualitative aspects of the phase separation processes in mixtures containing particle aggregates relevant for coating, catalyst, adhesive, and electronic applications as well as in diverse biological contexts, where phase separation occurs in the presence of irregular heterogeneities.

Quantum integrability and chaos in a periodic Toda lattice with balanced loss-gain.

We consider an equal-mass quantum Toda lattice with balanced loss-gain for two and three particles. The two-particle Toda lattice is integrable, and two integrals of motion that are in involution have been found. The bound-state energy and the corresponding eigenfunctions have been obtained numerically for a few low-lying states. The three-particle quantum Toda lattice with balanced loss-gain and velocity-mediated coupling admits mixed phases of integrability and chaos depending on the value of the loss-gain parameter. We have obtained analytic expressions for two integrals of motion that are in involution. Although an analytic expression for the third integral has not been found, the numerical investigation suggests integrability below a critical value of the loss-gain strength and chaos above this critical value. The level spacing distribution changes from the Wigner-Dyson to the Poisson distribution as the loss-gain parameter passes through this critical value and approaches zero. An identical behavior is seen in terms of the gap-ratio distribution of the energy levels. The existence of mixed phases of quantum integrability and chaos in the specified ranges of the loss-gain parameter has also been confirmed independently via the study of level repulsion and complexity in higher order excited states.

Nanometal surface energy transfer (NSET) from biologically active heterocyclic ligands to silver nanoparticles induces enhanced antimicrobial activity against gram-positive bacteria.

Herein we report the formation of a nanometal surface energy transfer (NSET) pair between a donor biologically active heterocyclic luminescent ligand such as 3-(1,3-Dioxoisoindolin-2-yl)-N, N-dimethylpropan-1-ammonium perchlorate (S4PNL; λem-408 nm) and an acceptor silver nanoparticle (Ag NP; λabs-406 nm). When the S4PNL ligand interacts with Ag NPs, the quenching in their luminescence intensity at 408 nm is noticed, with a Stern-Volmer constant of 0.8 × 104 M-1. The present donor-acceptor pair displays a binding constant of 2.8 × 104 M-1 and binding sites of 1.12. The current work shows the energy transfer from a molecular dipole (S4PNL) to a nanometal surface (Ag NP) and thus follows the nanometal surface energy transfer (NSET) ruler with an energy transfer efficiency of 80.0%, 50% energy transfer efficiency distance (d0) of 4.9 nm, donor-acceptor distance of 3.4 nm. The alteration in the zeta potential value of S4PNL upon interaction with AgNP clearly demonstrates the strong electrostatic interaction between donor and acceptor. Importantly, the current NSET pair shows enhanced antimicrobial activity against gram-positive bacteria such as Bacillus cereus (B. cereus) in comparison to their parent components i.e. S4PNL ligand and Ag NP. The NSET pair shows maximum inhibition against B. cereus (9202.21 ± 463.26 CFU/ml.) at 10% while minimum inhibition is observed at 0.01% of it (39,887.19 ± 242.67 CFU/ml.).

Impact of particle arrays on phase separation composition patterns.

We examine the symmetry-breaking effect of fixed constellations of particles on the surface-directed spinodal decomposition of binary blends in the presence of particles whose surfaces have a preferential affinity for one of the components. Our phase-field simulations indicate that the phase separation morphology in the presence of particle arrays can be tuned to have a continuous, droplet, lamellar, or hybrid morphology depending on the interparticle spacing, blend composition, and time. In particular, when the interparticle spacing is large compared to the spinodal wavelength, a transient target pattern composed of alternate rings of preferred and non-preferred phases emerges at early times, tending to adopt the symmetry of the particle configuration. We reveal that such target patterns stabilize for certain characteristic length, time, and composition scales characteristic of the pure phase-separating mixture. To illustrate the general range of phenomena exhibited by mixture-particle systems, we simulate the effects of single-particle, multi-particle, and cluster-particle systems having multiple geometrical configurations of the particle characteristic of pattern substrates on phase separation. Our simulations show that tailoring the particle configuration, or substrate pattern configuration, a relative fluid-particle composition should allow the desirable control of the phase separation morphology as in block copolymer materials, but where the scales accessible to this approach of organizing phase-separated fluids usually are significantly larger. Limited experiments confirm the trends observed in our simulations, which should provide some guidance in engineering patterned blend and other mixtures of technological interest.

Exact relaxation dynamics and quantum information scrambling in multiply quenched harmonic chains.

The quantum dynamics of isolated systems under quench condition exhibits a variety of interesting features depending on the integrable/chaotic nature of system. We study the exact dynamics of trivially integrable system of harmonic chains under a multiple quench protocol. Out of time ordered correlator of two Hermitian operators at large time displays scrambling in the thermodynamic limit. In this limit, the entanglement entropy and the central component of momentum distribution both saturate to a steady-state value. We also show that reduced density matrix assumes the diagonal form long after multiple quenches for large system size. These exact results involving infinite-dimensional Hilbert space are indicative of dynamical equilibration for a trivially integrable harmonic chain.

High-throughput assessment of vacancy formation and surface energies of materials using classical force-fields.

In this work, we present an open access database for surface and vacancy-formation energies using classical force-fields (FFs). These quantities are essential in understanding diffusion behavior, nanoparticle formation and catalytic activities. FFs are often designed for a specific application, hence, this database allows the user to understand whether a FF is suitable for investigating particular defect and surface-related material properties. The FF results are compared to density functional theory and experimental data whenever applicable for validation. At present, we have 17 506 surface energies and 1000 vacancy formation energies calculation in our database and the database is still growing. All the data generated, and the computational tools used, are shared publicly at the following websites: www.ctcms.nist.gov/~knc6/periodic.html, https://jarvis.nist.gov and https://github.com/usnistgov/jarvis. Approximations used during the high-throughput calculations are clearly mentioned. Using some of the example cases, we show how our data can be used to directly compare different FFs for a material and to interpret experimental findings such as using Wulff construction for predicting equilibrium shape of nanoparticles. Similarly, the vacancy formation energies data can be useful in understanding diffusion related properties.

Simulation of temperature, stress and microstructure fields during laser deposition of Ti-6Al-4V.

We study the evolution of prior columnar ß phase, interface L phase, and α phase during directional solidification of a Ti-6Al-4V melt pool. Finite element simulations estimate the solidification temperature and velocity fields in the melt pool and analyze the stress field and thermal distortions in the solidified part during the laser powder bed fusion process. A phase-field model uses the temperature and velocity fields to predict the formation of columnar prior-ß(Ti) phase. During the solidification of ß phase from an undercooled liquid, the residual liquid below the solidus temperature within the ß columns results in α phase. The finite element simulated stress and strain fields are correlated with the length scales and volume fractions of the microstructure fields. Finally, the coalescence behavior of the ß(Ti) cells during solidification is illustrated. The above analyses are important as they can be used for proactive control of the subsequent modeling of the heat treatment processes.

Simulation and analysis of γ-Ni cellular growth during laser powder deposition of Ni-based superalloys.

Cellular or dendritic microstructures that result as a function of additive manufacturing solidification conditions in a Ni-based melt pool are simulated in the present work using three-dimensional phase-field simulations. A macroscopic thermal model is used to obtain the temperature gradient G and the solidification velocity V which are provided as inputs to the phase-field model. We extract the cell spacings, cell core compositions, and cell tip as well as mushy zone temperatures from the simulated microstructures as a function of V. Cell spacings are compared with different scaling laws that correlate to the solidification conditions and approximated by G-mV-n. Cell core compositions are compared with the analytical solutions of a dendrite growth theory and found to be in good agreement. Through analysis of the mushy zone, we extract a characteristic bridging plane, where the primary γ phase coalesces across the intercellular liquid channels at a γ fraction between 0.6 and 0.7. The temperature and the γ fraction in this plane are found to decrease with increasing V. The simulated microstructural features are significant as they can be used as inputs for the simulation of subsequent heat treatment processes.

Application of Finite Element, Phase-field, and CALPHAD-based Methods to Additive Manufacturing of Ni-based Superalloys.

Numerical simulations are used in this work to investigate aspects of microstructure and microseg-regation during rapid solidification of a Ni-based superalloy in a laser powder bed fusion additive manufacturing process. Thermal modeling by finite element analysis simulates the laser melt pool, with surface temperatures in agreement with in situ thermographic measurements on Inconel 625. Geometric and thermal features of the simulated melt pools are extracted and used in subsequent mesoscale simulations. Solidification in the melt pool is simulated on two length scales. For the multicomponent alloy Inconel 625, microsegregation between dendrite arms is calculated using the Scheil-Gulliver solidification model and DICTRA software. Phase-field simulations, using Ni-Nb as a binary analogue to Inconel 625, produced microstructures with primary cellular/dendritic arm spacings in agreement with measured spacings in experimentally observed microstructures and a lesser extent of microsegregation than predicted by DICTRA simulations. The composition profiles are used to compare thermodynamic driving forces for nucleation against experimentally observed precipitates identified by electron and X-ray diffraction analyses. Our analysis lists the precipitates that may form from FCC phase of enriched interdendritic compositions and compares these against experimentally observed phases from 1 h heat treatments at two temperatures: stress relief at 1143 K (870 °C) or homogenization at 1423 K (1150 °C).

Particles with selective wetting affect spinodal decomposition microstructures.

We have used mesoscale simulations to study the effect of immobile particles on microstructure formation during spinodal decomposition in ternary mixtures such as polymer blends. Specifically, we have explored a regime of interparticle spacings (which are a few times the characteristic spinodal length scale) in which we might expect interesting new effects arising from interactions among wetting, spinodal decomposition and coarsening. In this paper, we report three new effects for systems in which the particle phase has a strong preference for being wetted by one of the components (say, A). In the presence of particles, microstructures are not bicontinuous in a symmetric mixture. An asymmetric mixture, on the other hand, first forms a non-bicontinuous microstructure which then evolves into a bicontinuous one at intermediate times. Moreover, while wetting of the particle phase by the preferred component (A) creates alternating A-rich and B-rich layers around the particles, curvature-driven coarsening leads to shrinking and disappearance of the first A-rich layer, leaving a layer of the non-preferred component in contact with the particle. At late simulation times, domains of the matrix components coarsen following the Lifshitz-Slyozov-Wagner law, R1(t) ∼ t1/3.

Interphase anisotropy effects on lamellar eutectics: a numerical study.

In directional solidification of binary eutectics, it is often observed that two-phase lamellar growth patterns grow tilted with respect to the direction z of the imposed temperature gradient. This crystallographic effect depends on the orientation of the two crystal phases α and ß with respect to z. Recently, an approximate theory was formulated that predicts the lamellar tilt angle as a function of the anisotropy of the free energy of the solid(α)-solid(ß) interphase boundary. We use two different numerical methods-phase field (PF) and dynamic boundary integral (BI)-to simulate the growth of steady periodic patterns in two dimensions as a function of the angle θ(R) between z and a reference crystallographic axis for a fixed relative orientation of α and ß crystals, that is, for a given anisotropy function (Wulff plot) of the interphase boundary. For Wulff plots without unstable interphase-boundary orientations, the two simulation methods are in excellent agreement with each other and confirm the general validity of the previously proposed theory. In addition, a crystallographic "locking" of the lamellae onto a facet plane is well reproduced in the simulations. When unstable orientations are present in the Wulff plot, it is expected that two distinct values of the tilt angle can appear for the same crystal orientation over a finite θ(R) range. This bistable behavior, which has been observed experimentally, is well reproduced by BI simulations but not by the PF model. Possible reasons for this discrepancy are discussed.

Crystallization behavior of anhydrous milk fat-sunflower oil wax blends.

This research evaluates the effect of sunflower oil wax (SFOw) addition on the crystallization behavior and functional properties of anhydrous milk fat (AMF). Induction times of nucleation, melting behavior, microstructure of crystals, and hardness were evaluated for samples of pure AMF and AMF with 0.1 and 0.25% SFOw. Results from this research show that the addition of waxes induced the onset of crystallization of AMF by inducing its nucleation, as evidenced by decreased induction times of nucleation and the formation of smaller crystals. Crystal growth after tempering was also promoted by waxes, and significantly harder lipid networks were obtained. Results presented in this paper suggest that SFOw can be used as an additive to alter the physiochemical properties of low trans-fatty acid lipids.

A simulation based method to assess inversion algorithms for transverse relaxation data.

NMR relaxometry is a very useful tool for understanding various chemical and physical phenomena in complex multiphase systems. A Carr-Purcell-Meiboom-Gill (CPMG) [P.T. Callaghan, Principles of Nuclear Magnetic Resonance Microscopy, Clarendon Press, Oxford, 1991] experiment is an easy and quick way to obtain transverse relaxation constant (T2) in low field. Most of the samples usually have a distribution of T2 values. Extraction of this distribution of T2s from the noisy decay data is essentially an ill-posed inverse problem. Various inversion approaches have been used to solve this problem, to date. A major issue in using an inversion algorithm is determining how accurate the computed distribution is. A systematic analysis of an inversion algorithm, UPEN [G.C. Borgia, R.J.S. Brown, P. Fantazzini, Uniform-penalty inversion of multiexponential decay data, Journal of Magnetic Resonance 132 (1998) 65-77; G.C. Borgia, R.J.S. Brown, P. Fantazzini, Uniform-penalty inversion of multiexponential decay data II. Data spacing, T2 data, systematic data errors, and diagnostics, Journal of Magnetic Resonance 147 (2000) 273-285] was performed by means of simulated CPMG data generation. Through our simulation technique and statistical analyses, the effects of various experimental parameters on the computed distribution were evaluated. We converged to the true distribution by matching up the inversion results from a series of true decay data and a noisy simulated data. In addition to simulation studies, the same approach was also applied on real experimental data to support the simulation results.