No violations of critical-point wetting in ternary three fluid-phase systems with short range interactions.

Hypothesis: In ternary three-fluid phase systems one can have either three- or just two interfaces. In a wetting transition the system switches from partial to complete wetting, i.e.

Effect of the Cooling Liquid on the Milled Interface in the Combined Process of Milling and Direct Metal Deposition.

The combination of Direct Metal Deposition (DMD) with milling offers numerous advantages for the manufacturing of complex geometry parts demanding high dimensional accuracy and surface quality. To reach this, a process strategy alternation between both processes is often required, leaving the milled surface with a layer of cooling fluid before adding material by DMD. This paper investigates the effect of cooling liquid on the milled interface in the combined process of milling and DMD.

Evidence of Sharp Transitions between Octahedral and Capped Trigonal Prism States of the Solvation Shell of the Aqueous Fe Ion.

The structure of the solvation shell of the aqueous Fe ion has been a subject of controversy due to discrepancies between experiments and different levels of theory. We address this issue by performing simulations for a wide range of ion concentrations, using various potential energy functions, supplemented by density functional theory calculations of selected configurations. The solvation shell undergoes abrupt transitions between two states: a hexacoordinated octahedral (OH) state and a capped trigonal prism (CTP) state with 7-fold coordination.

Mixing Linear Polymers with Rings and Catenanes: Bulk and Interfacial Behavior.

We derive and parameterize effective interaction potentials between a multitude of different types of ring polymers and linear chains, varying the bending rigidity and solvent quality for the former species. We further develop and apply a density functional treatment for mixtures of both disconnected (chain-ring) and connected (chain-polycatenane) mixtures of the same, drawing coexistence binodals and exploring the ensuing response functions as well as the interface and wetting behavior of the mixtures. We show that worsening of the solvent quality for the rings brings about a stronger propensity for macroscopic phase separation in the linear-polycatenane mixtures, which is predominantly of the demixing type between phases of similar overall particle density.

Holmium-Containing Metal-Organic Frameworks as Modifiers for PEBA-Based Membranes.

Recently, there has been an active search for new modifiers to create hybrid polymeric materials for various applications, in particular, membrane technology. One of the topical modifiers is metal-organic frameworks (MOFs), which can significantly alter the characteristics of obtained mixed matrix membranes (MMMs). In this work, new holmium-based MOFs (Ho-MOFs) were synthesized for polyether block amide (PEBA) modification to develop novel MMMs with improved properties.

Phase behavior and dynamics in a colloid-polymer mixture under spherical confinement.

From studies molecular dynamics simulations, we report results on structure and dynamics in mixtures of active colloids and passive polymers that are confined inside a spherical container with a repulsive boundary. All interactions in the fully passive limit are chosen in such a way that in equilibrium coexistence between colloid-rich and polymer-rich phases occurs. For most part of the studies the chosen compositions give rise to Janus-like structure: nearly one side of the sphere is occupied by the colloids and the rest by the polymers.

Unidirectional Droplet Propulsion onto Gradient Brushes without External Energy Supply.

Using extensive molecular dynamics simulation of a coarse-grained model, we demonstrate the possibility of sustained unidirectional motion (durotaxis) of droplets without external energy supply when placed on a polymer brush substrate with stiffness gradient in a certain direction. The governing key parameters for the specific substrate design studied, which determine the durotaxis efficiency, are found to be the grafting density of the brush and the droplet adhesion to the brush surface, whereas the strength of the stiffness gradient, the viscosity of the droplet, or the length of the polymer chains of the brush have only a minor effect on the process. It is shown that this durotaxial motion is driven by the steady increase of the interfacial energy between droplet and brush as the droplet moves from softer to stiffer parts of the substrate whereby the mean driving force gradually declines with decreasing roughness of the brush surface.

Depletion Interactions between Nanoparticles: The Effect of the Polymeric Depletant Stiffness.

A Density Functional Theory is employed to study depletion interactions between nanoparticles mediated by semiflexible polymers. The four key parameters are the chain contour length and the persistence length of the polymeric depletant, its radius of gyration, and the nanoparticle radius. In the Density Functional Theory calculation of the depletion interaction between the nanoparticles mediated by semiflexible polymers, the polymer gyration radius is kept constant by varying the contour length and the persistence length simultaneously.

Physical Vapor Deposition Features of Ultrathin Nanocrystals of Bi(TeSe).

Structural and electronic properties of ultrathin nanocrystals of chalcogenide Bi(Te Se) were studied. The nanocrystals were formed from the parent compound BiTeSe on as-grown and thermally oxidized Si(100) substrates using Ar-assisted physical vapor deposition, resulting in well-faceted single crystals several quintuple layers thick and a few hundreds nanometers large. The chemical composition and structure of the nanocrystals were analyzed by energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, electron backscattering, and X-ray diffraction.

Implementation of rapid microwave sintering using a 24 GHz gyrotron system.

Rapid microwave sintering of different oxide ceramics with heating rates up to 300 °C/min and zero hold time has been implemented using a 24 GHz gyrotron-based system for high-temperature processing of materials. The design of the system, principle of operation, and process control are described. Particular attention is given to the design of thermal insulation assemblies and the implementation of temperature measurement in an environment with intense electromagnetic fields.

Spin splitting in monoperiodic systems described by magnetic line groups.

In this paper we report the classification of all the 81 magnetic line group families into seven spin splitting prototypes, in analogy to the similar classification previously reported for the 1651 magnetic space groups, 528 magnetic layer groups, and 394 magnetic rod groups. According to this classification, electrically induced (Pekar-Rashba) spin splitting is possible in the antiferromagnetic structures described by magnetic line groups of type I (no anti-unitary operations) and III, both in the presence and in the absence of the space inversion operation. As a specific example, a group theoretical analysis of spin splitting in CoO (8, 8) nanotube is carried out and its predictions are confirmed bydensity functional theory calculations.

Wetting transitions of polymer solutions: Effects of chain length and chain stiffness.

Wetting and drying phenomena are studied for flexible and semiflexible polymer solutions via coarse-grained molecular dynamics simulations and density functional theory calculations. This study is based on the use of Young's equation for the contact angle, determining all relevant surface tensions from the anisotropy of the pressure tensor. The solvent quality (or effective temperature, equivalently) is varied systematically, while all other interactions remain unaltered.

Bulk phase behavior and interfacial properties of binary mixtures of Lennard-Jones chains and solvent: a density functional theory study.

A Density Functional Theory study is performed to analyze both bulk and interfacial properties of solvent-polymer binary mixtures. The effects of increasing polymer chain length on the bulk phase diagram morphology and interfacial tension are presented and compared to the prior simulation results. Good agreement between simulation and Density Functional Theory is found, including its ability to reproduce the density inversion phenomenon for highly asymmetric solvent-polymer binary mixtures.

Laser Remelting Process Simulation and Optimization for Additive Manufacturing of Nickel-Based Super Alloys.

Nickel-based super alloys are popular for applications in the energy and aerospace industries due to their excellent corrosion and high-temperature resistance. Direct metal deposition (DMD) of nickel alloys has reached technology readiness for several applications, especially for the repair of turbomachinery components. However, issues related to part quality and defect formation during the DMD process still persist.

Nanoparticle diffusion in polymer melts in the presence of weak nanoparticle-monomer attractive interactions: A mode-coupling theory study.

Mode-coupling theory is developed and employed to compute the nanoparticle diffusion coefficient in polymer solutions. Theoretical results are compared with molecular dynamics simulation data for a similar model. The theory properly reproduces the simulated effects of the nanoparticle size, mass, and concentration on the nanoparticle diffusion coefficient.

Interactions between Sterically Stabilized Nanoparticles: The Effects of Brush Bidispersity and Chain Stiffness.

Density Functional Theory is employed to study structural properties and interactions between solvent-free polymer-grafted nanoparticles. Both monodisperse and bidisperse polymer brushes with variable chain stiffness are considered. The three major control parameters are the grafting density, the grafted chain length, and its stiffness.

Blends of Semiflexible Polymers: Interplay of Nematic Order and Phase Separation.

Mixtures of semiflexible polymers with a mismatch in either their persistence lengths or their contour lengths are studied by Density Functional Theory and Molecular Dynamics simulation. Considering lyotropic solutions under good solvent conditions, the mole fraction and pressure is systematically varied for several cases of bending stiffness κ (the normalized persistence length) and chain length . For binary mixtures with different chain length (i.

Phase behavior of colloid-polymer mixtures in planar, spherical, and cylindrical confinement: A density functional theory study.

The Asakura-Oosawa (AO) model of colloid-polymer mixtures has been extensively studied over the past several decades both via computer simulations and Density Functional Theory (DFT). At this point, its structural and thermodynamic properties both in the bulk and in contact with flat structureless walls are well understood. At the same time, the phase behavior of AO mixtures in spherical cavities and cylindrical pores, while thoroughly investigated by simulations, has not received a comparably detailed DFT treatment.

Multiscale Approaches for Confined Ring Polymer Solutions.

We apply a hierarchy of multiscale modeling approaches to investigate the structure of ring polymer solutions under planar confinement. In particular, we employ both monomer-resolved (MR-DFT) and a coarse-grained (CG-DFT) density functional theories for fully flexible ring polymers, with the former based on a flexible tangent hard-sphere model and the latter based on an effective soft-colloid representation, to elucidate the ring polymer organization within slits of variable width in different concentration regimes. The predicted monomer and polymer center-of-mass densities in confinement, as well as the surface tension at the solution-wall interface, are compared to explicit molecular dynamics (MD) simulations.

When does Wenzel's extension of Young's equation for the contact angle of droplets apply? A density functional study.

The contact angle of a liquid droplet on a surface under partial wetting conditions differs for a nanoscopically rough or periodically corrugated surface from its value for a perfectly flat surface. Wenzel's relation attributes this difference simply to the geometric magnification of the surface area (by a factor r), but the validity of this idea is controversial. We elucidate this problem by model calculations for a sinusoidal corrugation of the form z(y) = Δ cos(2πy/λ), for a potential of short range σ acting from the wall on the fluid particles.

Colossal Spin Splitting in the Monolayer of the Collinear Antiferromagnet MnF.

In this Letter we report on the colossal spin splitting (on the order of several electronvolts) in the collinear antiferromagnetic (AFM) MnF (110) monolayer, which we obtained from first-principles calculations and explain in terms of group-theoretical analysis. This Pekar-Rashba AFM-induced spin splitting with a magnetic mechanism does not require the presence of spin-orbit coupling such as with a traditional Rashba-Dresselhaus electric mechanism. Furthermore, it was observed for all wave vectors, including high-symmetry points of the two-dimensional (2D) Brillouin zone.

Phase Behavior of Lyotropic Liquid-Crystalline Polymers under Varying Solvent Conditions: Effect of External Fields on the Phase Diagram.

In this work, we report a Density Functional Theory based study of phase behavior of lyotropic liquid-crystalline polymers under both good and varying solvent conditions in the presence of external electric or magnetic field. Our microscopic model for the good solvent case is based on the tangent hard-sphere chain with bond-bending potential to account for the chain stiffness; the variable solvent quality is modeled by adding attractive monomer-monomer interactions. The phase diagrams are constructed in three intensive variables (temperature, pressure, and field strength), and are characterized by the presence of critical and triple lines, which originate from the critical and triple points of the corresponding zero-field case.

Phase Separation and Nematic Order in Lyotropic Solutions: Two Types of Polymers with Different Stiffnesses in a Common Solvent.

The interplay of the isotropic-nematic transition and phase separation in lyotropic solutions of two types of semiflexible macromolecules with pronounced difference in chain stiffness is studied by Density Functional Theory and Molecular Dynamics simulations. While the width of the isotropic-nematic two-phase coexistence region is narrow for solutions with a single type of semiflexible chain, the two-phase coexistence region widens for solutions containing two types of chains with rather disparate stiffness. In the nematic phase, both types of chains contribute to the nematic order, with intermediate values of the order parameter compared to the corresponding single component solutions.

Entropic Unmixing in Nematic Blends of Semiflexible Polymers.

Binary mixtures of semiflexible polymers with the same chain length, but different persistence lengths, separate into two coexisting different nematic phases when the osmotic pressure of the lyotropic solution is varied. Molecular Dynamics simulations and Density Functional Theory predict phase diagrams either with a triple point, where the isotropic phase coexists with two nematic phases or a critical point of unmixing within the nematic mixture. The difference in locally preferred bond angles between the constituents drives this unmixing without any attractive interactions between monomers.

The effect of build orientation on both flexural quasi-static and fatigue behaviours of filament deposited PA6 polymer.

The present paper aims to study the effect of manufacturing build orientation on both flexural quasi-static and fatigue behaviours of semi-crystalline polyamide 6 obtained by Fused Filament Fabrication (FFF), by considering the porosity and surface roughness. The glass transition temperature, melting temperature, and crystallinity degree were measured complementary to understand better the process. Fatigue analysis is here fully described in visco-elastic domain of material.