A strategy for designing stable nanocrystalline alloys by thermo-kinetic synergy

Aiming to design stable nanocrystalline(NC) materials, so far, it has been proposed to construct nanostructure stability maps in terms of thermodynamic parameters, while kinetic stabilization has seldom been considered, despite the synergy of thermodynamics and kinetics. Consequently, the thermodynamically stabilized NC materials may be easily subjected to grain growth at high temperatures due to the weakly kinetic stabilization. Starting from the thermo-kinetic synergy, a stabilization criterion is proposed as a function of intrinsic solute parameters(e.g. the activation energy for bulk diffusion and the segregation enthalpy), intrinsic solvent parameters(e.g. the intrinsic activation energy for GB migration and the GB energy) and processing parameters(e.g. the grain size, the temperature and the solute concentration). Using first-principles calculations for a series of combinations between fifty-one substitutional alloying atoms as solute atoms and Fe atom as fixed solvent atom, it is shown that the thermal stability neither simply increases with increasing the segregation enthalpy as expected by thermodynamic stabilization, nor monotonically increases with increasing the activation energy for bulk diffusion as described by kinetic stabilization. By combination of thermodynamic and kinetic contributions, the current stabilization criterion evaluates quantitatively the thermal stability, thus permitting convenient comparisons among NC materials involved by various combinations of the solute atoms, the solvent atoms, or the processing conditions. Validity of this thermo-kinetic stabilization criterion has been tested by current experiment results of Fe-Y alloy and previously published data of Fe-Ni, Fe-Cr, Fe-Zr and Fe-Ag alloys,etc., which opens a new window for designing NC materials with sufficiently high thermal stability and sufficiently small grain size.     

Superhierarchical Cobalt‐Embedded Nitrogen‐Doped Porous Carbon Nanosheets as Two‐in‐One Hosts for High‐Performance Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries, based on the redox reaction between elemental sulfur and lithium metal, have attracted great interest because of their inherently high theoretical energy density. However, the severe polysulfide shuttle effect and sluggish reaction kinetics in sulfur cathodes, as well as dendrite growth in lithium‐metal anodes are great obstacles for their practical application. Herein, a two‐in‐one approach with superhierarchical cobalt‐embedded nitrogen‐doped porous carbon nanosheets (Co/N‐PCNSs) as stable hosts for both elemental sulfur and metallic lithium to improve their performance simultaneously is reported. Experimental and theoretical results reveal that stable Co nanoparticles, elaborately encapsulated by N‐doped graphitic carbon, can work synergistically with N heteroatoms to reserve the soluble polysulfides and promote the redox reaction kinetics of sulfur cathodes. Moreover, the high‐surface‐area pore structure and the Co‐enhanced lithiophilic N heteroatoms in Co/N‐PCNSs can regulate metallic lithium plating and successfully suppress lithium dendrite growth in the anodes. As a result, a full lithium–sulfur cell constructed with Co/N‐PCNSs as two‐in‐one hosts demonstrates excellent capacity retention with stable Coulombic efficiency.     

Kinetics of adsorption of dyes from aqueous solution using activated carbon prepared from waste apricot

Adsorbent (WA11Zn5) has been prepared from waste apricot by chemical activation with ZnCl(2). Pore properties of the activated carbon such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by N(2) adsorption and DFT plus software. Adsorption of three dyes, namely, Methylene Blue (MB), Malachite Green (MG), Crystal Violet (CV), onto activated carbon in aqueous solution was studied in a batch system with respect to contact time, temperature. The kinetics of adsorption of MB, MG and CV have been discussed using six kinetic models, i.e., the pseudo-first-order model, the pseudo-second-order model, the Elovich equation, the intraparticle diffusion model, the Bangham equation, the modified Freundlich equation. Kinetic parameters and correlation coefficients were determined. It was shown that the second-order kinetic equation could describe the adsorption kinetics for three dyes. The dyes uptake process was found to be controlled by external mass transfer at earlier stages (before 5 min) and by intraparticle diffusion at later stages (after 5 min). Thermodynamic parameters, such as DeltaG, DeltaH and DeltaS, have been calculated by using the thermodynamic equilibrium coefficient obtained at different temperatures and concentrations. The thermodynamics of dyes-WA11Zn5 system indicates endothermic process.     

Microstructure evolution in equiaxed dendritic growth

Microstructure evolution in equiaxed dendritic solidification is investigated through the study of free dendritic growth in a supercooled melt. A detailed measurement of microstructural features (such as side-branch spacings, envelope shape, projection area, and contour length) of freely growing succinonitrile dendrites is performed using images from the microgravity experiment of Glicksman and co-workers. The measurements show that the microstructure evolution of an equiaxed dendrite is divided into two regimes: an initial linear regime and a subsequent non-linear coarsening regime. It is found that unique scaling relations exist between the measured geometry parameters and the primary tip radius or speed for both regimes. The underlying mechanisms involved in dendritic structure evolution are discussed. In addition, using the phase-field method, we perform numerical experiments to investigate the effects of melt convection on equiaxed dendritic growth. The dendrite tip operating state (i.e. the tip velocity and radius) is quantitatively evaluated as a function of the flow velocity and dendrite orientations and compared with Microscopic Solvability Theory. Other structural features (such as the side-branches) of an equiaxed dendrite in the presence of flow are also examined in order to show how convection influences microstructure evolution in equiaxed dendritic growth.     

Microstructure evolution in equiaxed dendritic growth

Microstructure evolution in equiaxed dendritic solidification is investigated through the study of free dendritic growth in a supercooled melt. A detailed measurement of microstructural features (such as side-branch spacings, envelope shape, projection area, and contour length) of freely growing succinonitrile dendrites is performed using images from the microgravity experiment of Glicksman and co-workers. The measurements show that the microstructure evolution of an equiaxed dendrite is divided into two regimes: an initial linear regime and a subsequent non-linear coarsening regime. It is found that unique scaling relations exist between the measured geometry parameters and the primary tip radius or speed for both regimes. The underlying mechanisms involved in dendritic structure evolution are discussed. In addition, using the phase-field method, we perform numerical experiments to investigate the effects of melt convection on equiaxed dendritic growth. The dendrite tip operating state (i.e. the tip velocity and radius) is quantitatively evaluated as a function of the flow velocity and dendrite orientations and compared with Microscopic Solvability Theory. Other structural features (such as the side-branches) of an equiaxed dendrite in the presence of flow are also examined in order to show how convection influences microstructure evolution in equiaxed dendritic growth.     

相场法模拟Zn-Al二元合金凝固过程中的枝晶生长

建立了与温度场和溶质场相耦合的 Zn-Al 二元合金枝晶生长的相场模型,用相场法模拟了枝晶形貌及生长过程。通过分析得到的图像,研究了各向异性强度系数、界面动力学系数以及界面能对枝晶生长形貌和枝晶尖端生长速度的影响。结果表明：随着各向异性强度系数的增大,枝晶生长速率增加,且容易出现二次支臂。此外,界面动力学系数和界面能的增大也会不同程度地加速枝晶生长速率并对二次支臂的产生有着较为明显的促进作用。     

Modeling of a transition to diffusionless dendritic growth in rapid solidification of a binary alloy

Diffusionless growth of dendritic crystals results in microsegregation-free microstructures with an initial (nominal) chemical composition of solidifying systems. Normally, a transition from chemically partitioned growth to diffusionless solidification is accompanied by the morphological transition in crystal shape with the appearance of nonlinearity in the kinetic behavior of growing crystals. This phenomenon is discussed using a model of local non-equilibrium rapid solidification. Considering the transition from the solute diffusion-limited growth to purely thermally controlled growth of dendritic crystals, the model predicts the abrupt change of growth kinetics with the break points in the “dendrite tip velocity-undercooling” and “dendrite tip radius-undercooling” relationships. It is shown that the abrupt change of growth kinetics occurs with the ending of the transition to purely thermally controlled growth and the onset of diffusionless solidification. To predict the dendrite growth kinetics in a whole region of undercooling, numeric analysis shows that the model has to take into account both anisotropies of solid–liquid interfacial properties. These are anisotropy of surface energy and anisotropy of atomic kinetics of solidification.     

Elucidation of the naproxen sodium adsorption onto activated carbon prepared from waste apricot: kinetic, equilibrium and thermodynamic characterization

In this study, activated carbon (WA11Zn5) was prepared from waste apricot, which is waste in apricot plants in Malatya, by chemical activation with ZnCl(2). BET surface area of activated carbon is determined as 1060 m(2)/g. The ability of WA11Zn5, to remove naproxen sodium from effluent solutions by adsorption has been studied. Equilibrium isotherms for the adsorption of naproxen sodium on activated carbon were measured experimentally. Results were analyzed by the Langmiur, Freundlich equation using linearized correlation coefficient at 298 K. The characteristic parameters for each isotherm have been determined. Langmiur equation is found to best represent the equilibrium data for naproxen sodium-WA11Zn5 systems. The monolayer adsorption capacity of WA11Zn5 for naproxen sodium was found to be 106.38 mg/g at 298 K. The process was favorable and spontaneous. The kinetics of adsorption of naproxen sodium have been discussed using three kinetic models, i.e., the pseudo first-order model, the pseudo second-order model, the intraparticle diffusion model. Kinetic parameters and correlation coefficients were determined. It was shown that the pseudo second-order kinetic equation could describe the adsorption kinetics for naproxen sodium onto WA11Zn5. The thermodynamic parameters, such as DeltaG degrees , DeltaS degrees and DeltaH degrees, were calculated. The thermodynamics of naproxen sodium-WA11Zn5 system indicates endothermic process.     

Simulation of constrained dendrite growth of multicomponent alloys using a Calphad method

Abstract

The conventional theory of constrained dendrite growth for binary alloys has been extended to multicomponent alloys based on the Calphad method by consideration of solute interactions in each phase. The variable solute partition coefficients and liquidus slopes under different tip undercooling were calculated in detail for a series of Al-Si-Mg alloys. Their influence on the kinetics of dendrite growth was demonstrated quantitatively. The most important microstructure scale, the primary dendrite spacing, was predicted in several Al-Si-Mg alloys. By comparing with the experimental results of former researchers, it is found that the present method coupled with Calphad is a satisfactory way for the prediction of primary dendrite arm spacing.     

Controlling Nucleation in Lithium Metal Anodes

Rechargeable batteries are regarded as the most promising candidates for practical applications in portable electronic devices and electric vehicles. In recent decades, lithium metal batteries (LMBs) have been extensively studied due to their ultrahigh energy densities. However, short lifespan and poor safety caused by uncontrollable dendrite growth hinder their commercial applications. Besides, a clear understanding of Li nucleation and growth has not yet been obtained. In this Review, the failure mechanisms of Li metal anodes are ascribed to high reactivity of lithium, virtually infinite volume changes, and notorious dendrite growth. The principles of Li deposition nucleation and early dendrite growth are discussed and summarized. Correspondingly, four rational strategies of controlling nucleation are proposed to guide Li nucleation and growth. Finally, perspectives for understanding the Li metal deposition process and realizing safe and high‐energy rechargeable LMBs are given.     

Defect chemistry of the high-Tc superconductors

In the high temperature superconductors the critical temperature is intimately connected to the electronic charge-carrier concentration. The absolute values of this quantity and its dependencies on the controlling parameters temperature, oxygen partial pressure and doping content, is phenomenologically determined by the thermodynamics and kinetics of reactions involving point defects. Due to the low mobility of the ionic constituents the behavior at elevated temperatures is particularly important. Here, the kinetics are controlled by the mass transport parameters, essentially by the ionic conductivity. The scientific discipline whose objective is precisely described in the above terms is called defect chemistry. It quantitatively deals with the nature of excess and lacking native ionic or electronic particles as well as with foreign species. It describes the thermodynamics and kinetics of their formation, annihilation, interaction and motion in the phase under consideration and thus determines the chemistry within this phase.     

热致相分离法聚合物膜形成机理与形貌控制

介绍了近年来热致相分离(TIPS)法聚合物多孔膜研究的新进展.从热力学角度总结了TIPS的成膜机理,相图是理解TIPS机理的重要工具;液滴生长和晶粒生长是研究制膜体系TIPS动力学的两个方面.膜形貌由热力学、动力学共同控制,聚合物分子量、稀释剂种类、溶液固含量、冷却速率、成核剂是控制膜结构的五个重要方面.     

Examining Concentration-Reliant Zn Deposition/Stripping Behavior in Organic Alcohol/Sulfones-Modified Aqueous Electrolytes

The practical application of Zn metal anodes in electronic devices is hindered by dendrite growth and parasitic reactions. Electrolyte optimization, particularly the introduction of organic co-solvents, is widely used to circumvent these challenges. Various organic solvents in a wide range of concentrations have been reported; however, their influences and corresponding working mechanisms at different concentrations are largely unexplored in the same organic species. Herein, economical, low-flammable ethylene glycol (EG) is used as a model co-solvent in aqueous electrolytes to examine the relationship between its concentration, anode-stabilizing effect, and mechanism. Two maximal values are observed for the lifetime of Zn/Zn symmetric batteries under EG concentrations from 0.05 vol% to 48 vol%. Zn metal anodes can stably run for over 1700 h at a low EG content (0.25 vol%) and high EG content (40 vol%). Based on the complementary experimental and theoretical calculations, the enhancements in low- and high-content EG are ascribed to the specific surface adsorption for suppressed dendrite growth and the regulated solvation structure for inhibited side reactions, respectively. Intriguingly, a similar concentration-reliant bimodal phenomenon is observed in other low-flammable organic solvents (e.g., glycerol and dimethyl sulfoxide), thereby suggesting universality of this study and providing insight into electrolyte optimization.     

Modelling the pH dependence of the kinetics of aerobic p-nitrophenol biodegradation

There are a number of publications in the literature that might indicate a connection between pH and the kinetics of the aerobic p-nitrophenol (PNP) biodegradation. In this study two hypotheses were postulated to elucidate the kinetics dependence on pH: (i) the substrate inhibition does not depend on the pH value, therefore the half-saturation coefficient and the substrate inhibition constant will be the same at any pH and (ii) the substrate inhibition depends on the pH value, therefore the half-saturation coefficient and the substrate inhibition constant will have a different value depending on the pH. A PNP-degrading activated sludge was used to carry out three batch respirometric experiments at different pH values: 6.5±0.1, 7.0±0.1, 8.0±0.1. The ability to describe the experimental results with the kinetic models derived from both postulated hypotheses was quantitatively evaluated through the norm of the prediction error array. The time course of specific oxygen uptake rate and PNP concentration was satisfactorily described by a Haldane kinetics that includes the pH effect, based on the PNP acid-base equilibrium, on the kinetic parameters. The results suggest that the nonionised form of PNP is the real substrate and also the inhibitor of the aerobic PNP biodegradation.     

A Modified Cellular Automaton Model for the Quantitative Prediction of Equiaxed and Columnar Dendritic Growth

Since the characteristic of dendrite is an important factor determining the performance of castings, a twodimensional cellular automaton model with decentered square algorithm is developed for quantitatively predicting the dendritic growth during solidification process. The growth kinetics of solid/liquid interface are determined by the local equilibrium composition and local actual liquid composition, and the calculation of the solid fraction increment is based on these two compositions to avoid the solution of growth velocity. In order to validate the developed model, quantitative simulations of steady-state dendritic features over a range of undercooling was performed and the results exhibited good agreement with the predictions of LGK（Liptone Glicksman-Kurz） model. Meanwhile, it is demonstrated that the proposed model can be applied to simulate multiple equiaxed dendritic growth, as well as columnar dendritic growth with or without equiaxed grain formation in directional solidification of AleC u alloys. It has been shown that the model is able to simulate the growth process of multi-dendrites with various preferential orientations and can reproduce a wide range of complex dendritic growth phenomena such as nucleation, coarsening of dendrite arms, side branching in dendritic morphologies, competitive growth as well as the interaction among surrounding dendrites.     

工业企业总平面系统布置方案的分形描述与优化选择

从分析组成总平面系统的作业单位之间的空间关联关系入手,应用分形方法描述总平面系统,即以关联维数分别表征总平面系统的理想图式与现实可行布置方案的空间关联程度.进而通过定义两关联维数的比值为趋近度水平,衡量各个现实总平面系统布置方案对于理想图式的趋近程度,并根据趋近度水平的大小实现总平面系统布置方案的优化选择.结合对某钢铁企业的实例分析,验证了对总平面系统进行分形描述的可行性以及优化选择的有效性.     

A novel integrated model combining Cellular Automata and Phase Field methods for microstructure evolution during solidification of multi-component and multi-phase alloys

A novel numerical model is developed by integrating Cellular Automata (CA) and Phase Field (PF) methods to predict the dendrite growth of multi-component and multi-phase alloys during the solidification process. The micro-scale CA model is built to track dendrite growth and associated mass redistribution, while the 1D PF model reformulated in a polar coordinate system is used to calculate the growth kinetics for the CA interface cells. The integrated CAPF model can take advantage of the high computational efficiency of the CA model and the comprehensive physical background of the PF model. The model has been validated against an analytical model and then applied to the cases of casting and laser welding processes. Good quantitative agreement is obtained between the simulated results and the experiments.     

Phase-field modelling on effect of pressure on growth kinetics of Mg–Al–Sn alloy

The effects of pressure on dendritic growth kinetics of Mg–Al–Sn alloy were investigated using a ternary phase-field model coupled with thermodynamics with pressure effects and experiments. The results showed that the improved growth velocity and nucleation rate caused by pressure had the opposite effects on grain size. For one-grain growth, the dendrite was larger and more developed under pressure of 85?MPa than that under ambient pressure owing to larger thermodynamic driving force, and thus higher growth velocity. However, when nucleation was considered in multigrain growth case, the average grain size under pressure was smaller owing to less growth space. Growth velocity decreased with the increase in Sn content, on which pressure had no great influence.