Effects of local nonequilibrium in rapid eutectic solidification: Part 2: analysis of effects and comparison to experiment

The developed model of diffusion‐limited and diffusionless solidification of a eutectic alloy describes the relation “undercooling (Δ T )‐velocity ( V )‐interlamellar spacing (λ)” for two cases. Namely, when the solidification front velocity V is smaller than the solute diffusion speed in bulk liquid V D , V V D , the solidification is mainly controlled by kinetic and thermal undercoolings. New expressions for the solute distribution coefficient and slope of the liquidus lines are supplied. The influence of the model parameters on the growth kinetics during eutectic solidification is discussed. Model predictions are compared with experimental data for the solidification of an Fe–B alloy with eutectic composition. Computational results show that the model agrees well with experimental data especially for low and high undercoolings, extending the undercooling range that can be covered by sharp interface modeling

Kinetic transition in the order–disorder transformation at a solid/liquid interface

Phase-field analysis for the kinetic transition in an ordered crystal structure growing from an undercooled liquid is carried out. The results are interpreted on the basis of analytical and numerical solutions of equations describing the dynamics of the phase field, the long-range order parameter as well as the atomic diffusion within the crystal/liquid interface and in the bulk crystal. As an example, the growth of a binary A50B50 crystal is described, and critical undercoolings at characteristic changes of growth velocity and the long-range order parameter are defined. For rapidly growing crystals, analogies and qualitative differences are found in comparison with known non-equilibrium effects, particularly solute trapping and disorder trapping. The results and model predictions are compared qualitatively with results of the theory of kinetic phase transitions (Chernov 1968 Sov. Phys. JETP 26, 1182–1190) and with experimental data obtained for rapid dendritic solidification of congruently melting alloy with order–disorder transition (Hartmann et al. 2009 Europhys. Lett. 87, 40007 (doi:10.1209/0295-5075/87/40007)). This article is part of the theme issue ‘From atomistic interfaces to dendritic patterns’. © 2018 The Author(s) Published by the Royal Society. All rights reserved.Russian Science Foundation, RSF: 16-11-1009550WM1541Deutsche Forschungsgemeinschaft, DFGData accessibility. This article has no additional data. Authors’ contributions. All the authors contributed equally to the present research paper. Competing interests. The authors declare that they have no competing interests. Funding. This work was supported by the Russian Science Foundation (grant no. 16-11-10095), the German Space Center Space Management (under contract number 50WM1541) and the Deutsche Forschungsgemeinschaft (DFG) (under grant no. Re1261/8-2)

Rheology, dispersion, and cure kinetics of epoxy filled with amine‐ and non‐functionalized reduced graphene oxide for composite manufacturing

This study evaluates the effect of plasma surface functionalization of reduced graphene oxide particles on the processing characteristics and homogeneity of dispersion of a bisphenol A‐(epichlorhydrin) epoxy matrix and amine‐based hardener with varying weight fractions from 0.00 to 1.50 wt%. It was observed that amine‐functionalized reduced graphene oxide leads to a more drastic viscosity increase of up to 18‐fold of the uncured suspensions and that its presence influences the conversion rates of the curing reaction. Optical microscopy of thin sections and transmission electron microscopy analysis showed that a more homogeneous dispersion of the particles could be achieved especially at higher weight fractions by using an appropriate surface functionalization. This knowledge can be used to define suitable processing conditions for epoxies with amine‐based hardeners depending on the loading and functionalization of graphene‐related particles

Effects of Local Nonequilibrium in Rapid Eutectic Solidification—Part 2: Analysis of Effects and Comparison to Experiment

The developed model of diffusion-limited and diffusionless solidification of a eutectic alloy describes the relation “undercooling (ΔT)-velocity (V)-interlamellar spacing (λ)” for two cases. Namely, when the solidification front velocity V is smaller than the solute diffusion speed in bulk liquid VD, V < VD, the model predicts a regime of eutectic solidification similarly to known classical models. If the solidification front velocity V is higher than the diffusion speed, V > VD, the solidification is mainly controlled by kinetic and thermal undercoolings. New expressions for the solute distribution coefficient and slope of the liquidus lines are supplied. The influence of the model parameters on the growth kinetics during eutectic solidification is discussed. Model predictions are compared with experimental data for the solidification of an Fe–B alloy with eutectic composition. Computational results show that the model agrees well with experimental data especially for low and high undercoolings, extending the undercooling range that can be covered by sharp interface modeling. © 2021 The Authors. Mathematical Methods in the Applied Sciences published by John Wiley & Sons Ltd.This work was also financially supported by the German Science Foundation (DFG) GA1142/11-1, the Science and Technology Program of Shaanxi Province (No. 2016KJXX-87), and the Foundation of Shaanxi Provincial Department of Education (No. 18JS050). Open access funding enabled and organized by Projekt DEAL

A classical description of subnanometer resolution by atomic features in metallic structures

Recent experiments have evidenced sub-nanometer resolution in plasmonic-enhanced probe spectroscopy. Such a high resolution cannot be simply explained using the commonly considered radii of metallic nanoparticles on plasmonic probes. In this contribution the effects of defects as small as a single atom found on spherical plasmonic particles acting as probing tips are investigated in connection with the spatial resolution provided. The presence of abundant edge and corner sites with atomic scale dimensions in crystalline metallic nanoparticles is evident from transmission electron microscopy (TEM) images. Electrodynamic calculations based on the Finite Element Method (FEM) are implemented to reveal the impact of the presence of such atomic features in probing tips on the lateral spatial resolution and field localization. Our analysis is developed for three different configurations, and under resonant and non-resonant illumination conditions, respectively. Based on this analysis, the limits of field enhancement, lateral resolution and field confinement in plasmon-enhanced spectroscopy and microscopy are inferred, reaching values below 1 nanometer for reasonable atomic sizes

Microstructure and morphology of Si crystals grown in pure Si and Al-Si melts

Microstructure of Al-40 wt%Si samples solidified in electromagnetic levitation furnace is studied at high melt undercooling. Primary Si with feathery and dendritic structures is observed. As this takes place, single Si crystals either contain secondary dendrite arms or represent faceted structures. Our experiments show that at a certain undercooling, there exists the microstructural transition zone of faceted to non-faceted growth. Also, we analyze the shape of dendritic crystals solidifying from liquid Si as well as from hypereutectic Al-Si melts at high growth undercoolings. The shapes of dendrite tips grown at undercoolings >100 K along the surface of levitated Al-40 wt%Si droplets are compared with pure Si dendrite tips from the literature. The dendrite tips are digitized and superimposed with theoretical shape function recently derived by stitching the Ivantsov and Brener solutions. We show that experimental and theoretical dendrite tips are in good agreement for Si and Al-Si samples. © 2022 IOP Publishing Ltd.Deutsche Forschungsgemeinschaft, DFG, (Re1261/23)Russian Science Foundation, RSF, (21-79-10012)LVT gratefully acknowledges fruitful discussions about the theoretical results with Prof. Peter Galenko, and financial support from the Russian Science Foundation (Project No. 21-79-10012). MR and DML are grateful for financial support by Deutsche Forschungsgemeinschaft, Grant Re1261/23

Nanostructured Cu2_2O Synthesized via Bipolar Electrochemistry

Cuprous oxide (Cu$_2$O) was synthesized for the first time via an open bipolar electrochemistry (BPE) approach and characterized in parallel with the commercially available material. As compared to the reference, Cu$_2$O formed through a BPE reaction demonstrated a decrease in particle size; an increase in photocurrent; more efficient light scavenging; and structure-correlated changes in the flat band potential and charge carrier concentration. More importantly, as-synthesized oxides were all phase-pure, defect-free, and had an average crystallite size of 20 nm. Ultimately, this study demonstrates the impact of reaction conditions (e.g., applied potential, reaction time) on structure, morphology, surface chemistry, and photo-electrochemical activity of semiconducting oxides, and at the same time, the ability to maintain a green synthetic protocol and potentially create a scalable product. In the proposed BPE synthesis, we introduced a common food supplement (potassium gluconate) as a reducing and complexing agent, and as an electrolyte, allowing us to replace the more harmful reactants that are conventionally used in Cu$_2$O production. In addition, in the BPE process very corrosive reactants, such as hydroxides and metal precursors (required for synthesis of oxides), are generated in situ in stoichiometric quantity, providing an alternative methodology to generate various nanostructured materials in high yields under mild conditions

Disorder trapping by rapidly moving phase interface in an undercooled liquid

Non-equilibrium phenomena such as the disappearance of solute drag, the origin of solute trapping and evolution of disorder trapping occur during fast transformations with originating metastable phases [D.M. Herlach, P.K. Galenko, D. Holland-Moritz, Metastable solids from undrercooled melts (Elsevier, Amsterdam, 2007)]. In the present work, a theoretical investigation of disorder trapping by a rapidly moving phase interface is presented. Using a model of fast phase transformations, a system of governing equations for the diffusion of atoms, and the evolution of both long-range order parameter and phase field variable is formulated. First numerical solutions are carried out for a congruently melting binary alloy system

Mathematical modeling of dendrite growth in an Al–Ge alloy with convective flow

A theory of stable dendrite growth in an undercooled binary melt is developed for the case of intense convection. Conductive heat and mass transfer boundary conditions are replaced by convective conditions, where the flux of heat (or solute) is proportional to the temperature or concentration difference between the surface of the dendrite and far from it. The marginal mode of perturbation wavelengths is calculated using the linear morphological stability analysis. Combining this analysis with the solvability theory, we have derived a selection criterion that represents the first condition to define a combination of dendrite tip velocity and tip diameter. The second condition—the undercooling balance—is derived for intense convection. The theory under consideration determines the dendrite tip velocity and tip diameter for low undercooling. This convective theory is combined with the classical theory of dendritic growth (conductive boundary conditions), which is valid for moderate and high undercooling. Thus, the entire range of melt undercooling is covered. Our results are in good agreement with experiments on Al–Ge crystallization. © 2021 The Authors. Mathematical Methods in the Applied Sciences published by John Wiley & Sons Ltd.Ministry of Education and Science of the Russian Federation, Minobrnauka: 075-02-2021-1387; Russian Science Foundation, RSF: 21-19-00279; Foundation for the Advancement of Theoretical Physics and Mathematics: 21-1-3-11-1L.V.T. acknowledges financial support from the Ministry of Science and Higher Education of the Russian Federation (project 075-02-2021-1387 for the development of the regional scientific and educational mathematical center “Ural Mathematical Center”) for the linear stability analysis. Moreover, she is grateful to the Foundation for the Advancement of Theoretical Physics and Mathematics “BASIS” (project No. 21-1-3-11-1) for the development of solvability theory. P.K.G. and D.V.A. acknowledge the Russian Science Foundation (Project No. 21-19-00279) for the stitching of selection criteria, computer simulations, and comparison with experimental data. Open Access funding enabled and organized by Projekt DEAL

Copper Thiophosphate (Cu3PS4) as Electrode for Sodium-Ion Batteries with Ether Electrolyte

Sections PDFPDF Tools Share Abstract Lithium and sodium thiophosphates (and related compounds) have recently attracted attention because of their potential use as solid electrolytes in solid‐state batteries. These compounds, however, exhibit only limited stability in practice as they react with the electrodes. The decomposition products partially remain redox active hence leading to excess capacity. The redox activity of thiophosphates is explicitly used to act as electrode for sodium‐ion batteries. Copper thiophosphate (Cu3PS4) is used as a model system. The storage behavior between 0.01 and 2.5 V versus Na+/Na is studied in half cells using different electrolytes with 1 m NaPF6 in diglyme showing the best result. Cu3PS4 shows highly reversible charge storage with capacities of about 580 mAh g−1 for more than 200 cycles @120 mA g−1 and about 450 mAh g−1 for 1400 cycles @1 A g−1. The redox behavior is studied by operando X‐ray diffraction and X‐ray photoelectron spectroscopy. During initial sodiation, Cu3PS4 undergoes a conversion reaction including the formation of Cu and Na2S. During cycling, the redox activity seems dominated by sulfur. Interestingly, the capacity of Cu3PS4 for lithium storage is smaller, leading to about 170 mAh g−1 after 200 cycles. The results demonstrate that thiophosphates can lead to reversible charge storage over several hundred cycles without any notable capacity decay.Peer Reviewe