Liquid ordering induced heterogeneities in homogeneous nucleation during solidification of pure metals

Homogeneous crystal nucleation is prone to formation of defects and often experiences heterogeneities,the inferences of which are crucial in processing crystalline materials and controlling their physical properties. It has been debated in literature whether the associated heterogeneities are an integral part of the homogenous nucleation. In this study by integrating a probabilistic approach with large-scale molecular dynamics simulations based on the most advanced high-temperature interatomic potentials, we attempt to address the ambiguity over the sources and mechanisms of heterogeneities in homogenous nucleation during solidification of pure melts. Different classes of structured metals are investigated for this purpose,including face-centered cubic aluminum, body-centered cubic iron, and hexagonal close-packed magnesium. The results reveal, regardless of the element type or the solidified crystal structure, that the densification process of liquid metals is accompanied by short-range orderings of atoms prior to the formation of crystals, controlling the heterogeneities during homogenous nucleation.

Coating of SiC Powder with Nano YAG Phase

SiC-YAG(Y3Al5O12) ceramic composite powders were prepared by co-precipitation coating method. Mechanism of co-precipitation coating of SiC powders with Y3+ and Al3+ precursors was investigated. If the concentration of [OH-] ion in the solution is controlled within the range between critical values for heterogeneous nucleation and homogeneous nucleation, Y3+ and Al3+ precipitation precursors can be coated on the surface of SiC particles. Y3+ and Al3+ precipitation precursors transform into YAG phase after calcining at 1000 ℃ without the formation of YAM and YAP phases. The formation temperature of YAG phase is about 600 ℃ lower than that of conventional powder mixing method. The effect of pH value of the solution and precipitant titration rate on coating quality of SiC-YAG composite powders was also studied. The results show that co-precipitation coating can be realized at a final pH of 9 and a precipitant titration rate of 5 ml·min-1.

Integration of homogeneous and heterogeneous nucleation growth via 3D alloy framework for stable Na/K metal anode

Sodium/Potassium(Na/K)metal anodes have been considered as the promising anodes for next-generation Na/K secondary batteries owing to their ultrahigh specific capacity,low redox potential and low cost.However,their practical application is still hampered due to unstable solid electrolyte interphase,infinite volume change,and dendrite growth.Herein,we design a 3D-Na_(3)Bi/3D-K_(3)Bi alloy host which enables the homogeneous and heterogeneous nucleation growth of Na/K metal.The unique structure with periodic alternating of electron and ion conductivity improves the mass transfer kinetics and prevents the volume expansion during cycling.Meanwhile,the sodiophilicity of Na_(3)Bi/potassiophilicity of K_(3)Bi framework can avoid dendritic growth.Cycling lifespans over 700 h with 1 mAh cm^(−2)for 3D-Na_(3)Bi@Na electrode and about 450 h with 1 mAh cm^(−2)for 3D-K_(3)Bi@K electrode are achieved,respectively.3D-Na_(3)Bi@Na||Na_(3)V_(2)(PO_(4))3 full battery shows sustainable cycle performance over 400 cycles.This design provides a simple but effective approach for achieving safety of sodium/potassium metal anodes.

Resolving Mixed Intermediate Phases in Methylammonium-Free Sn-Pb Alloyed Perovskites for High-Performance Solar Cells

The complete elimination of methylammonium(MA)cations in Sn-Pb composites can extend their light and thermal stabilities.Unfortunately,MA-free Sn-Pb alloyed perovskite thin films suffer from wrinkled surfaces and poor crystallization,due to the coexistence of mixed intermediate phases.Here,we report an additive strategy for finely regulating the impurities in the intermediate phase of Cs_(0.25)FA_(0.75)Pb_(0.6)Sn_(0.4)I_(3)and,thereby,obtaining high-performance solar cells.We introduced d-homoserine lactone hydrochloride(D-HLH)to form hydrogen bonds and strong Pb-O/Sn-O bonds with perovskite precursors,thereby weakening the incomplete complexation effect between polar aprotic solvents(e.g.,DMSO)and organic(FAI)or inorganic(CsI,PbI_(2),and SnI_(2))components,and balancing their nucleation processes.This treatment completely transformed mixed intermediate phases into pure preformed perovskite nuclei prior to thermal anneal-ing.Besides,this D-HLH substantially inhibited the oxidation of Sn^(2+) species.This strategy generated a record efficiency of 21.61%,with a Voc of 0.88 V for an MA-free Sn-Pb device,and an efficiency of 23.82%for its tandem device.The unencapsulated devices displayed impressive thermal stability at 85℃ for 300 h and much improved continuous operation stability at MPP for 120 h.

Surface Snow, Firn and Ice Core Composition in Polar Areas in Relation to Atmospheric Aerosol and Gas Concentrations: Critical Aspects

The paper addresses some of the problems surrounding the relation between ice core chemical signals and atmospheric chemical composition in polar areas. The topic is important as the reconstruction of past climate and past atmospheric chemical composition is based on the assumption that chemical concentrations in the air, snow, firn and ice core are correlated. Ice core interpretation of aerosol is more straightforward than that of reactive gases. The transfer functions of gaseous species strongly interacting with ice are complex and additional field and laboratory experiments are required. Ice core chemical signals depend on the chemical composition of precipitations, which are related to the physics of precipitation formation, the chemical composition of the atmosphere, and post-depositional processes. Published papers reporting data on the chemical composition of snow seldom consider the fact that crystal formation and growth in cloud (rimed or unrimed) or near the ground (clear-sky precipitations), hoar-frost formation and surface riming determine different chemical concentrations, even assuming constant background concentration in the atmosphere. This paper discusses the physical and chemical processes affecting the formation of precipitations in polar areas, and the process of scavenging gases from non-growing and growing crystals. Attention is mainly focused on the processes involving nitrate anion in snow, hoar frost and firn. Knowledge of the chemical relationship between surface snow and atmospheric chemical concentration could be enhanced by considering specific events, such as snow falling from cloud, clear sky precipitation, and surface hoar or riming surface, with simultaneous air sampling. In conclusion, field and laboratory experiments are still required to study the scavenging processes during crystal formation.

Nucleation and Growth Kinetics of MgO in Molten Steel

The size, number, morphology and type of inclusion particles are the key factors to estimate the quality of steel product. Although considerable efforts have been made in the mathematical modeling of inclusion growth, few papers were involved in inclusionts nucleation and collision-growth, and all the existing researches about the behaviors of magnesia inclusion were based on the experiments. Thus, a mathematical model was developed to investigate the nucleation, Ostwald ripening and collision-growth of magnesia inclusion in the molten steel. Numerical results showed that the predicted particle size distributions are consistent with the previous experimental data. For the magnesia inclusions smaller than 100 nm, Brownian collision is the main collision modes. For the inclusions ranging from 0.1 to 10μm, Brownian collision and turbulent collision are the main collision modes. For the inclusions ranging from 10 to 100μm, turbulent collision and Stokes collision are the main collision modes. Thus, the strong turbulent flow can decrease the peak-value diameter of the magnesia inclusion effectively.

A REAL-TIME AFM STUDY ON CRYSTAL NUCLEATION AND GROWTH IN NANODROPLETS OF ISOTACTIC POLYPROPYLENE

Isotactic polypropylene （iPP） nanodroplets were prepared by using the classical droplet method in this study. The formation of nanodroplets allowed the controlled observation of polymer nucleation as well as access to crystal growth at exceptionally high supercooling in /PP. Three cases including the heterogeneous nucleation and fast crystallization in iPP droplets, the formation of multiple independent homogeneous nuclei within a single droplet and a single nucleus within a single droplet were detected by using atomic force microscopy （AFM） during gradually cooling after remelting the nanodroplets. Moreover, it is found that when the volume of droplet is larger than the value of ca. 130000 nm3, the first case was observed. Otherwise, the latter two cases appeared. The temperature at which the onset of nucleation was observed in individual droplets was found to be mainly dependent on height of the droplets when the size scale of the droplet is comparable to the size of the critical nucleus in at least one dimension, which indicates the nucleation behavior under confinement.

The Effect of Self-nucleation on Isothermal Crystallization Kinetics of Poly(butylene succinate)(PBS) Investigated by Differential Fast Scanning Calorimetry

Differential fast scanning calorimetry（DFSC） was employed on the study of self-nucleation behavior of poly（butylene succinate）（PBS）.The ultra-fast cooling ability of DFSC allows investigating the effect of self-nucleation on the isothermal crystallization kinetics over a wide temperature range.Crystallization half-time,instead of crystallization peak temperature,was used to describe the self-nucleation behavior,and the self-nucleation domain for the samples crystallized at different temperatures was determined.Due to the competition between homogenous nucleation and self-nuclei,the effect of self-nucleation was less pronounced at high supercooling than that for the sample isothermally crystallized at higher temperature.An efficiency scale to judge the efficiency of nucleating agents from the crystallization half-time was also introduced in this work.

Effect of Hydrogen on Dislocation Nucleation and Motion:Nanoindentation Experiment and Discrete Dislocation Dynamics Simulation

The hydrogen effect on the nucleation and motion of dislocations in single-crystal bcc Fe with(110)surface was investigated by both nanoindentation experiments and discrete dislocation dynamics(DDD)simulation.The results of nanoindentation experiments showed that the pop-in load decreased evidently for the electrochemical hydrogen charging specimen,indicating that the dislocation nucleation strength might be reduced by hydrogen.In addition,the decrease of hardness due to hydrogen charging was also captured,implying that the dislocation motion might be promoted by hydrogen.By incorporating the effect of hydrogen on dislocation core energy,a DDD model was specifically proposed to investigate the influence of hydrogen on dislocation nucleation and motion.The results of DDD simulation revealed that under the effect of hydrogen,the dislocation nucleation strength is decreased and the motion of dislocation is promoted.