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Water freezing, initiated by ice nucleation, occurs widely in nature, ranging from cellular to global phenomena. Ice nucleation has been experimentally proven to require the formation of a critical ice nucleus, consistent with classical nucleation theory (CNT). However, the accuracy of CNT quantitative predictions of critical cluster sizes and nucleation rates has never been verified experimentally. In this study, we circumvent this difficulty by using molecular dynamics (MD) simulation. The physical properties of water/ice for CNT predictions, including density, chemical potential difference, and diffusion coefficient, are independently obtained using MD simulation, whereas the calculation of interfacial free energy is based on thermodynamic assumptions of CNT, including capillarity approximation among others. The CNT predictions are compared to the MD evaluations of brute-force simulations and forward flux sampling methods. We find that the CNT and MD predicted critical cluster sizes are consistent, and the CNT predicted nucleation rates are higher than the MD predicted values within three orders of magnitude. We also find that the ice crystallized from supercooled water is stacking-disordered ice with a stacking of cubic and hexagonal ices in four representative types of stacking. The prediction discrepancies in nucleation rate mainly arise from the stacking-disordered ice structure, the asphericity of ice cluster, the uncertainty of ice–water interfacial free energy, and the kinetic attachment rate. Our study establishes a relation between CNT and MD to predict homogeneous ice nucleation. [ABSTRACT FROM AUTHOR]

We use molecular dynamics simulations to examine the homogeneous nucleation of ice VII from metastable liquid water. An unsupervised machine learning classification identifies two distinct local structures composing Ice VII nuclei. The seeding method, combined with the classical nucleation theory (CNT), predicts the solid–liquid interfacial free energy, consistent with the value from the mold integration method. Meanwhile, the nucleation rates estimated from the CNT framework and brute force spontaneous nucleations are inconsistent, and we discuss the reasons for this discrepancy. Structural and dynamical heterogeneities suggest that the potential birthplace for an ice VII embryo is relatively ordered, although not necessarily relatively immobile. Moreover, we demonstrate that without the formation of hydrogen-bond links, ice VII embryos do not grow. [ABSTRACT FROM AUTHOR]

Molecular dynamics (MD) of the Lennard-Jones cluster in the environment of supersaturated vapor at fixed temperature and density is used for the investigation of nonisothermal nucleation. The results allow one to single out different processes occurring at different time scales, the Ornstein–Uhlenbeck fluctuations at the short time scale and a combination of slow diffusion and drift of the fluctuation packet that represents a cluster, at the long time scale. The multiscale approach is developed, in which a separate treatment of different time scales makes it possible to consider strongly correlated cluster size and temperature. This reduces the nonisothermal cluster evolution to a one-dimensional problem. The fluctuation packet drift velocity and diffusivity are calculated based on the cluster microscopic thermophysical parameters determined in this work from MD data for isothermal clusters. The proposed approach is consistent with the results of our MD simulation. [ABSTRACT FROM AUTHOR]

The crystallization of complex, concentrated alloys can result in atomic-level short-range order, composition gradients, and phase separation. These features govern the properties of the resulting alloy. While nucleation and growth in single-element metals are well understood, several open questions remain regarding the crystallization of multi-principal component alloys. We use molecular dynamics to model the crystallization of a five-element, equiatomic alloy modeled after CoCrCuFeNi upon cooling from the melt. Stochastic, homogeneous nucleation results in nuclei with a biased composition distribution, rich in Fe and Co. This deviation from the random sampling of the overall composition is driven by the internal energy and affects nuclei of a wide range of sizes, from tens of atoms all the way to super-critical sizes. This results in short-range order and compositional gradients at nanometer scales. [ABSTRACT FROM AUTHOR]

In this work, we introduce variational umbrella seeding, a novel technique for computing nucleation barriers. This new method, a refinement of the original seeding approach, is far less sensitive to the choice of order parameter for measuring the size of a nucleus. Consequently, it surpasses seeding in accuracy and umbrella sampling in computational speed. We test the method extensively and demonstrate excellent accuracy for crystal nucleation of nearly hard spheres and two distinct models of water: mW and TIP4P/ICE. This method can easily be extended to calculate nucleation barriers for homogeneous melting, condensation, and cavitation. [ABSTRACT FROM AUTHOR]

By employing brute-force molecular dynamics, umbrella sampling, and seeding simulations, we investigate homogeneous nucleation during melting and freezing of hard spheres. We provide insights into these opposing phase transitions from the standpoint of classical nucleation theory. We observe that melting has both a lower driving force and a lower interfacial tension than freezing. The lower driving force arises from the vicinity of a spinodal instability in the solid and from a strain energy. The lower interfacial tension implies that the Tolman lengths associated with melting and freezing have opposite signs, a phenomenon that we interpret with Turnbull's rule. Despite these asymmetries, the nucleation rates for freezing and melting are found to be comparable. [ABSTRACT FROM AUTHOR]

The nucleation of ice from aqueous solutions is a process essential to myriad environmental and industrial processes, but the physical factors affecting the capacity of different solutes to depress the homogeneous nucleation temperature of ice are yet poorly understood. In this work, we demonstrate that for many binary aqueous solutions of non-ionic solutes, this depression is dominated by the entropy of the liquid phase. Employing the classic Turnbull interpretation of the interfacial free energy γ ∼ T S l i q u i d − S s o l i d and estimating solution entropies with a Flory-style modification of the ideal entropy of mixing that accounts for solute size effects, we demonstrate that mixing entropy alone predicts experimental homogeneous nucleation temperatures across a wide variety of non-ionic solutions. We anticipate that this physical insight will not only enhance a fundamental understanding of homogeneous nucleation processes across fields but also open new avenues to the rational design of aqueous solutions for desired nucleation behaviors. [ABSTRACT FROM AUTHOR]

The large discrepancy among the nucleation kinetics extracted from experimental measurements and computer simulations and the prediction of the classical nucleation theory (CNT) has stimulated intense arguments about its origin in the past decades, which is crucially relevant to the validity of the CNT. In this paper, we investigate the atomistic mechanism of the nucleation in liquid Al in contact with amorphous substrates with atomic-level smooth/rough surfaces, using molecular dynamics (MD) simulations. This study reveals that the slightly distorted local fcc/hcp structures in amorphous substrates with smooth surfaces can promote heterogeneous nucleation through a structural templating mechanism, and on the other hand, homogeneous nucleation will occur at a larger undercooling through a fluctuation mechanism if the surface is rough. Thus, some impurities, previously thought to be impotent, could be activated in the homogeneous nucleation experiments. We further find that the initial growth of the nucleus on smooth surfaces of amorphous substrates is one order of magnitude faster than that in homogeneous nucleation. Both these factors could significantly contribute to the discrepancy in the nucleation kinetics. This study is also supported by a recent study of the synthesis of high-entropy alloy nanoparticles assisted with the liquid metal Ga [Cao et al., Nature 619, 73 (2023)]. In this study, we established that the boundary existed between homogeneous and heterogeneous nucleation, i.e., the structural templating is a general mechanism for heterogeneous nucleation, and in its absence, homogeneous nucleation will occur through the fluctuation mechanism. This study provides an in-depth understanding of the nucleation theory and experiments. [ABSTRACT FROM AUTHOR]

We theoretically investigate homogeneous crystal nucleation in a solution containing a solute and a volatile solvent. The solvent evaporates from the solution, thereby continuously increasing the concentration of the solute. We view it as an idealized model for the far-out-of-equilibrium conditions present during the liquid-state manufacturing of organic electronic devices. Our model is based on classical nucleation theory, taking the solvent to be a source of the transient conditions in which the solute drops out of the solution. Other than that, the solvent is not directly involved in the nucleation process itself. We approximately solve the kinetic master equations using a combination of Laplace transforms and singular perturbation theory, providing an analytical expression for the nucleation flux. Our results predict that (i) the nucleation flux lags slightly behind a commonly used quasi-steady-state approximation. This effect is governed by two counteracting effects originating from solvent evaporation: while a faster evaporation rate results in an increasingly larger influence of the lag time on the nucleation flux, this lag time itself is found to decrease with increasing evaporation rate. Moreover, we find that (ii) the nucleation flux and the quasi-steady-state nucleation flux are never identical, except trivially in the stationary limit, and (iii) the initial induction period of the nucleation flux, which we characterize as a generalized induction time, decreases weakly with the evaporation rate. This indicates that the relevant time scale for nucleation also decreases with an increasing evaporation rate. Our analytical theory compares favorably with results from a numerical evaluation of the governing kinetic equations. [ABSTRACT FROM AUTHOR]

1-propanol/water mixtures over the whole composition range (0 < XV ≤ 1; XV is the 1-propanol volume fraction) are shown to be structurally and dynamically heterogeneous. By combining structural (x-ray diffraction), thermodynamic (differential scanning calorimetry) and dynamical probes (dielectric spectroscopy) we construct the pertinent phase diagram. It consists of liquid 1-propanol, liquid water, hexagonal ice and different hydrates, the latter sharing the same lattice. The phase diagram can be discussed in terms of four regimes, all having in common a droplet arrangement of the minority component. When water droplets are strongly confined by 1-propanol (regime I, 0.92 < XV ≤ 1; "soft" confinement), water is unable to crystallize. It has dynamics reminiscent to the ultra-viscous water phase known as high-density liquid (HDL). When water droplets are moderately confined (regime II, 0.75 < XV ≤ 0.92) water can crystallize via homogeneous nucleation. Strikingly, the homogeneous nucleation temperature is at 205 K, well within "no-man's land." The result is in line with earlier reports that soft confinement is the key to enter into the "no-man's land". When 1-propanol is the minority component (regimes III and IV), the structure and the dynamics are dominated by the 1-propanol/water interface with the formation of hydrates. The corresponding dynamical features suggest a link between hydrate formation and the two metastable phases of ultra-viscous water, HDL and low-density liquid. [ABSTRACT FROM AUTHOR]

High‐aluminum advanced high‐strength steels have received increasing interest due to their excellent combination of strength and ductility. The control of nonmetallic inclusions in steel is among the most important issue for the production of high‐aluminum steel. This study proposes a model for the evolution of size distributions of AlN inclusions during solidification of steel based on the Kampmann–Wagner numerical model and microsegregation calculation. Both homogeneous (pure AlN) and heterogeneous precipitations (AlN+oxide or MnS) are described using homogeneous nucleation and free growth models of Greer et al. respectively. The model is applied to calculate the size distributions of AlN in high‐Al (up to 5%) Fe–Cr–Al steels and high‐ and medium‐manganese steels and validated by the experimental data in the literature. The model correctly describes the influence of cooling rates on the precipitation of AlN in Fe–Cr–Al steels and high‐manganese steels, and the sizes of AlN are reduced and the number densities of AlN inclusions are increased by increasing the cooling rate. The effects of nitrogen and aluminum concentration in medium‐manganese steel on inclusion precipitation are investigated by the model calculation. The increases in nitrogen and aluminum concentration facilitate the homogeneous precipitation of AlN inclusions. [ABSTRACT FROM AUTHOR]

Among the REBa2Cu3O7‐δ (REBCO or RE123, RE = rare earth element) family, SmBCO is preferably used in top‐seeded melt‐growth (TSMG) because of its outstanding property and more controllable stoichiometry 123. Nevertheless, the refinement of Sm2BaCuO5 (Sm211) particles has been challenging for high‐performance SmBCO bulks. Conventional precursor powders (SmBa2Cu3O7‐δ plus Sm2BaCuO5) intrinsically result in enlarging Sm2BaCuO5 particles due to their coarsening and epitaxial growth during the heating process. Here, we used modified precursor powders (MPPs, Sm2O3 plus Ba2Cu3O5) in air‐processed TSMG, in which there is neither Sm211 in the beginning nor related enlargement during heating. Consequently, the nucleation catastrophe of Sm211 occurred above the peritectic temperature, which in situ formed, possessing naturally small size. Further, aiming to suppress the Sm/Ba substitution, Ba‐rich MPP, substituting Ba2Cu3O5 with Ba3Cu4O7) was employed, producing an excellent SmBCO bulk with a diameter of 24 mm: levitation force of 51.5 N and trapped field of 0.537 T. Optical micrographs and quantitative analyses confirmed the superior refinement and distribution of Sm211 particles in SmBCO bulks. Most importantly, new strategies in this work are widely applicable for developing cost‐effective and high‐performance other REBCO bulk superconductors. [ABSTRACT FROM AUTHOR]

Cirrus clouds are of great importance to the global climate, with their net radiative forcing strongly dependent on the microphysical properties that are related to the ice‐nucleating regime. However, the influence of long‐range transport of dust on primary ice formation in cirrus clouds is limitedly understood, specifically over the clean remote ocean regions. Here, two case studies show that transpacific Asian dust can impact the ice formation of cirrus clouds over the central Pacific based on Cloud‐Aerosol Lidar with Orthogonal Polarization and Cloud Profiling Radar (CPR, CloudSat) observations. One case shows a well‐developed horizontally extended cirrus embedded in a pure dust layer, with an average dust‐related ice‐nucleating particle concentration (INPC) of 7 L−1 and 96 L−1 for an ice saturation ratio Si of 1.15 and 1.25, respectively; ice crystal number concentration (ICNC) with diameters >25 and 100 μm (denoted as nice,25 μm and nice,100 μm) are 64 L−1 and 7 L−1, respectively. Another case shows that cirrus clouds with a much smaller horizontal extent appeared in the vicinity of polluted dust, with an average INPC of 42–310 L−1 for the typical higher Si of 1.25–1.35 by considering a tenfold reduction of the ice nucleation efficiency of ice crystals; nice,25 μm and nice,100 μm are 168 L−1 and 20 L−1, respectively. The estimated INPC and ICNC values suggest the dominance of ice formation by dust‐induced heterogeneous nucleation, proving that the long‐range transport of dust toward the upper troposphere and the potential influence on cirrus formation over the central Pacific should be well considered in atmospheric models. Plain Language Summary: Cirrus clouds are vital to the global radiative balance. Their net radiation effect is very uncertain, depending on the microphysical properties that are mainly determined by the ice nucleation mechanism, that is, heterogeneous and homogeneous ice nucleation. In this work, two dust‐cirrus interaction cases are studied with the combinational observations of space‐borne lidar and radar. Over the remote central Pacific, where is generally very clean, we show that the long‐range transported Asian dust can significantly influence the ice nucleation at cirrus height by acting as efficient ice‐nucleating particles (INPs). The estimated number concentrations of INPs and ice crystals reveal that dust‐induced heterogeneous nucleation is dominant in ice formation, which should thus be better considered in atmospheric and climate models. Key Points: Cloud‐Aerosol Lidar with Orthogonal Polarization (CALIOP)‐CloudSat observations corroborate that dust in the outflow regime of Asia can influence cirrus formation over the central PacificCALIOP observations indicate the strongest dust occurrence in the upper troposphere over the Pacific during the spring seasonDust transport toward the upper troposphere and the potential impact on cirrus formation should be well considered in atmospheric models [ABSTRACT FROM AUTHOR]

Understanding the ice nucleation mechanism in the catalyst layers (CLs) of proton exchange membrane (PEM) fuel cells and inhibiting icing by designing the CLs can optimize the cold start strategies, which can enhance the performance of PEM fuel cells. Herein, mitigating the structural matching and templating effects by adjusting the surface morphology and wettability can inhibit icing on the platinum (Pt) catalyst surface effectively. The Pt(211) surface can inhibit icing because the atomic spacing of (211) crystalline surface is much larger than the characteristic distance of ice crystal, thereby mitigating the structural matching effects. A water overlayer on the Pt surface induced by the strong attraction of Pt can act as a template for ice layers and plays an important role in the icing process. Buckling of water overlayer due to the larger atomic spacing of (211) crystalline surface mitigates the templating effect and inhibits icing. Moreover, the water overlayer on the hydrophobic Pt(211) surface with fewer water molecules also mitigates the templating effect, which makes ice nucleation more difficult than homogeneous nucleation. These findings reveal the ice nucleation mechanisms on the Pt catalyst surface from the molecular level and are valuable for catalyst designs to inhibit icing in CL. [ABSTRACT FROM AUTHOR]

[Display omitted] • SiO 2 @G-M layer on Cu collector is achieved at one-step. • SiO 2 @G-M offers a stable Li deposition stable at a high capacity of 2 mAh cm−2. • LiFePO 4 -based AFLMBs offer a specific capacity of 129.82 mAh g−1 at 0.5C after 100 cycles. Anode-free lithium metal batteries (AFLBs) have attracted considerable attention due to their high theoretical specific capacity and absence of Li. However, the heterogeneous Li deposition and stripping on the lithiophobic Cu collector hamper AFLBs in practice. To achieve a uniform and reversible Li deposition, a carbon-based layer on the Cu collector has attracted intense interest due to its high conductivity. However, the 2D single-component carbon-based interface is inadequate lithiophilic for obtaining the homogeneous Li deposition and preventing the lithium dendrite from piercing the separator. Herein, we present a 3D embedded lithiophilic SiO 2 nanoparticles-graphene nanosheet matrix (SiO 2 @G-M) on the Cu collector by organic nano carbon source. In this structure, the lithiophilic SiO 2 nanoparticles as active points promote the homogeneous lithium nucleation and the 3D graphene nanosheet matrix offers homogenous electron distribution and voids to prevent the piercing. Finally, SiO 2 @G-M/Li cell shows a high coulombic efficiency of 98.62 % after 100 cycles at a high current density of 2 mA cm−2 with an areal capacity of 1 mAh cm−2. [ABSTRACT FROM AUTHOR]

This study involved a numerical investigation of the homogeneous nucleation of CO2 from a CO2–Ar gas mixture in a supersonic nozzle with a throat size of 2.11 mm, a total pressure of 61.15 kPa, and a total temperature of 293.15 K. The flow conditions covered the cryogenic temperature range (∼75 K). Therefore, the surface tension of the clusters was calculated using the Tolman–Tanaka correction, and nucleation growth was evaluated considering both free molecular and continuum regimes. Numerical simulations were conducted for a wide range of CO2 mole fractions (3%–39%). In particular, the effect of the CO2 mole fraction on the condensation-shock position—approximately the Wilson point—was investigated. For 3%, 12%, 24%, and 39%, the condensation shock occurred at 0.048, 0.043, 0.046, and 0.054 m from the throat, respectively. When the mole fraction was low (≤10%), the condensation-shock position moved downstream as the mole fraction decreased. This trend was attributed to a lower nucleation rate. In contrast, when the mole fraction was high (≥10%), the condensation-shock position moved downstream as the mole fraction increased. This was because the CO2 equilibrium pressure rose more rapidly than the CO2 vapor pressure as the mole fraction increases. [ABSTRACT FROM AUTHOR]

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Developing high‐rate lithium‐metal battery (LMB) with superior energy density and operation durability is of significance, which shows enormous potential to be extensively applied. However, the commercialized polyolefin separators exhibit inferior ability to resist the elevated internal temperature and inhibit the lithium (Li) dendrite growth, especially for LMBs under high‐rate operations. With undesired Li+‐anion solvated structures in the electrolyte, previous separator modification strategies usually meet a dilemma to simultaneously increase the Li+ transference number and decrease the anion transference number. Here, a facile and scalable strategy are reported to prepare high‐performance sandwiched separators with polyolefin separators coated by single‐atom zirconium coordination polyimide aerogel (Zr‐PIA) layers, which can achieve a stable LMB operation at 20 C for 2700 cycles with a capacity retention of 94.6%, substantially outperforming its counterpart separator without Zr. Both the experimental and theoretical studies suggest that the Zr‐PIA layer with nanoporous architecture and anion‐trapping Zr sites can effectively increase the Li+ transference number without sacrificing the overall ion conductivity, enabling a rapid, selective and uniform Li+ flux through the separator. Such features can facilitate homogeneous the Li nucleation/deposition and mitigate Li dendrite growth, leading to enhanced battery durability and safety. [ABSTRACT FROM AUTHOR]

Ferroelectric perovskites are pivotal in diverse technological applications; however, a gap persists in our comprehension of their mechanical properties, emphasizing the need for additional exploration. In the present study, we report on the nanomechanical behavior of BiFeO 3 ceramics in the force range between 200 μN and 2 mN, including the evolution of the hardness and the reduced Young's modulus from (9.9 ± 0.4) GPa and (113.7 ± 6.9) GPa, respectively, with increasing force. A sequence of plastic-deformation mechanisms under the cube-corner probe was revealed through a first pop-in analysis in combination with a variety of electron microscopy techniques, starting with a homogeneous dislocation nucleation, multiplication and rearrangement leading to sub-grain formation, a phenomenon observed in metals but not in ceramics. [ABSTRACT FROM AUTHOR]

Homogeneous nucleation is the prominent mechanism of glaciation in cirrus and other high-altitude clouds. Ice nucleation rates can be studied in laboratory assays that gradually lower the temperature of pure water droplets. These experiments can be performed with different cooling rates, with different droplet sizes, and often with a distribution of droplet sizes. We combine nucleation theory, survival probability analysis, and published data on the fraction of frozen droplets as a function of temperature to understand how the cooling rate, droplet size, and size dispersity influence the nucleation rates. The framework, implemented in the Python code AINTBAD (Analysis of Ice nucleation Temperature for B and A Determination), provides a temperature-dependent nucleation rate on a per volume basis, in terms of approximately temperature-independent prefactor (A) and barrier (B) parameters. We find that dispersion in droplet diameters of less than an order of magnitude, if not properly included in the analysis, can cause apparent nucleation barriers to be underestimated by 50 %. This result highlights the importance of droplet size dispersion in efforts to model glaciation in the polydisperse droplets of clouds. We also developed a theoretical framework, implemented in the Python code IPA (Inhomogeneous Poisson Analysis), to predict the fraction of frozen droplets at each temperature for arbitrary droplet size dispersions and cooling rates. Finally, we present a sensitivity analysis for the effect of temperature uncertainty on the nucleation spectrum. Our framework can improve models for ice nucleation in clouds by explicitly accounting for droplet polydispersity and cooling rates. [ABSTRACT FROM AUTHOR]

Rationally designing a current collector that can maintain low lithium (Li) porosity and smooth morphology while enduring high‐loading Li deposition is crucial for realizing the high energy density of Li metal batteries, but it is still challengeable. Herein, a Li2ZnCu3 alloy‐modified Cu foil is reported as a stable current collector to fulfill the stable high‐loading Li deposition. Benefiting from the in situ alloying, the generated numerous Li2ZnCu3@Cu heterojunctions induce a homogeneous Li nucleation and dense growth even at an ultrahigh capacity of 12 mAh cm−2. Such a spatial structure endows the overall Li2ZnCu3@Cu electrode with the manipulated steric hindrance and outmost surface electric potential to suppress the side reactions during Li stripping and plating. The resultant Li||Li2ZnCu3@Cu asymmetric cell preserves an ultrahigh average Coulombic efficiency of 99.2 % at 3 mA cm−2/6 mAh cm−2 over 200 cycles. Moreover, the Li‐Li2ZnCu3@Cu||LiFePO4 cell maintains a cycling stability of 87.5 % after 300 cycles. After coupling with the LiCoO2 cathode (4 mAh cm−2), the cell exhibits a high energy density of 407.4 Wh kg−1 with remarkable cycling reversibility at an N/P ratio of 3. All these findings present a doable way to realize the high‐capacity, dendrite‐free, and dense Li deposition for high‐performance Li metal batteries. [ABSTRACT FROM AUTHOR]

In practical applications, intermetallic compounds like Laves phase and metal carbides adversely affect the performance of nickel‐based superalloys. Using a high‐temperature confocal laser scanning microscope, the solidification process of as‐cast GH3625 alloy containing Mg at different cooling rates (−20, −35, and −50 °C min−1) is studied. Fitting curves of the volume fraction of the solid phase with solidification temperature before and after Mg treatment are obtained. Trends of solid phase transformation rates with solidification temperature are determined. Differential scanning calorimetry is employed to analyze and statistically evaluate the melting temperature range and enthalpy of each phase during the melting process. Experimental results demonstrate that Mg treatment significantly accelerates the alloy solidification at the cooling rates of −20 and −35 °C min−1, while reducing the area of residual liquid phase at the same solidification temperature, disrupting the Laves/NbC eutectic relationship, and regularizing NbC morphology, transitioning its distribution from aggregation to dispersion. After Mg treatment, the precipitation of the Laves phase is significantly reduced. As a result, the influence mechanism of Mg treatment on the phase transformation and microstructure of GH3625 is clarified based on homogeneous nucleation theory. [ABSTRACT FROM AUTHOR]

Understanding the nucleation behavior of water in dilute polymeric solutions is quintessential for the development of suitable artificial ice recrystallization inhibition (IRI) agents. Although poly(vinyl alcohol) (PVA) is found to be one of the most potent biomimetic IRI agents, the molecular understanding of the nucleation behavior of water in the presence of PVA is still lacking. Here, we use molecular dynamics to elucidate the role of concentration, degree of supercooling, degree of polymerization, and amphiphilicity of PVA and PVA-like polymers on the homogeneous nucleation of water in dilute polymeric solutions using the seeding method. Using classical nucleation theory (CNT), our simulations indicate an increase in the chemical potential difference between ice and melt that favors ice nucleation. However, it also predicts a significant increase in the ice–melt interfacial energy that impedes nucleation. The relative increase in the interfacial energy dominates the increase in the chemical potential difference, which results in a decrease in the nucleation rate of water with an increase in the solute concentration. This study contradicts the previous simulation study that suggested the promotion of homogeneous ice nucleation by PVA and supports the experimental observations of the heterogeneous origins of ice nucleation. Our results also suggest the non-classical origins of ice nucleation in polymeric solutions and the limitation of the CNT in predicting heterogeneous ice nucleation in polymeric solutions. [ABSTRACT FROM AUTHOR]

[Display omitted] Liquid-liquid phase separation is a key phenomenon in the formation of membrane-less structures within the cell, appearing as liquid biomolecular condensates. Protein condensates are the most studied for their biological relevance, and their tendency to evolve, resulting in the formation of aggregates with a high level of order called amyloid. In this study, it is demonstrated that Human Insulin forms micrometric, round amyloid-like structures at room temperature within sub-microliter scale aqueous compartments. These distinctive particles feature a solid core enveloped by a fluid-like corona and form at the interface between the aqueous compartment and the glass coverslip upon which they are cast. Quantitative fluorescence microscopy is used to study in real-time the formation of amyloid-like superstructures. Their formation results driven by liquid–liquid phase separation process that arises from spatially heterogeneous distribution of nuclei at the glass-water interface. The proposed experimental setup allows modifying the surface-to-volume ratio of the aqueous compartments, which affects the aggregation rate and particle size, while also inducing fine alterations in the molecular structures of the final assemblies. These findings enhance the understanding of the factors governing amyloid structure formation, shedding light on the catalytic role of surfaces in this process. [ABSTRACT FROM AUTHOR]

[Display omitted] Graphene Oxide (GO)-templated deposition of inorganic materials through synthesis on dispersed single sheets of GO is often complicated by the loss of the desired 2D morphology owing to the coagulation of GO sheets at high salt concentrations and non-templated homogenous nucleation. Modifying GO with anionic polymer is expected to solve both problems by i) enhancing electrostatic(steric) stabilization upon exposure to high concentrations of the ionic precursors, and ii) offering additional nucleation sites at the grafted anionic moieties to avoid homogeneous secondary nucleation. GO was grafted with branched copolymers of poly(ethylene glycol) methacrylate (PEGMA 500) and diethylene glycol dimethacrylate (DEGDMA) and ω -vinyl terminated methacrylic acid macromonomer (P(MAA)), the latter serving as an addition-fragmentation chain transfer agent. The colloidal stability of GO dispersions in water toward salt was evaluated before and after modification. Precipitation of calcium phosphate (CaP) was performed by incubating modified GO in the precursor solutions. The conditions were optimized to maximize the nucleation selectively onto GO without homogeneous CaP nucleation and coagulation of the GO-sheets. The copolymer grafted GO-sheets shows superior colloidal stability when dispersed in water. No aggregation occurs in the incubating ionic CaP precursor solutions. The optimum templated deposition of CaP onto the GO sheets by precipitation is to add a second shot of precursors after the nucleation stage to obtain GO sheets fully decorated with calcium phosphate nanorods without self-nucleation. Via the careful design on the GO modification and incubation process, the growth of calcium phosphate nanorods were confined in the desired 2D order exclusively, hereby achieving the goal of an efficient GO-templated synthesis. [ABSTRACT FROM AUTHOR]

Poly(vinyl alcohol) (PVA) has ice binding and ice nucleating properties. Here, we explore the dependence of the molecular size of PVA on its ice nucleation activity. For this purpose, we studied ice nucleation in aqueous solutions of PVA samples with molar masses ranging from 370 to 145 000 g mol−1, with a particular focus on oligomer samples with low molar mass. The experiments employed a novel microfluidic setup that is a follow-up on the previous WeIzmann Supercooled Droplets Observation on a Microarray (WISDOM) design by Reicher et al. The modified setup introduced and characterized here, termed nanoliter Bielefeld Ice Nucleation ARraY (nanoBINARY), uses droplet microfluidics with droplets (96 ± 4) µm in diameter and a fluorinated continuous oil phase and surfactant. A comparison of homogeneous and heterogeneous ice nucleation data obtained with nanoBINARY to those obtained with WISDOM shows very good agreement, underpinning its ability to study low-temperature ice nucleators as well as homogeneous ice nucleation due to the low background of impurities. The experiments on aqueous PVA solutions revealed that the ice nucleation activity of shorter PVA chains strongly decreases with a decrease in molar mass. While the cumulative number of ice nucleating sites per mass nm of polymers with different molar masses is the same, it becomes smaller for oligomers and completely vanishes for dimer and monomer representatives such as 1,3-butanediol, propan-2-ol, and ethanol, most likely because these molecules become too small to effectively stabilize the critical ice embryo. Overall, our results are consistent with PVA polymers and oligomers acting as heterogeneous ice nucleators. [ABSTRACT FROM AUTHOR]

We study low-salt, binary aqueous suspensions of charged colloidal spheres of size ratio Γ = 0.57, number densities below the eutectic number density nE, and number fractions of p = 1.00–0.40. The typical phase obtained by solidification from a homogeneous shear-melt is a substitutional alloy with a body centered cubic structure. In strictly gas-tight vials, the polycrystalline solid is stable against melting and further phase transformation for extended times. For comparison, we also prepare the same samples by slow, mechanically undisturbed deionization in commercial slit cells. These cells feature a complex but well reproducible sequence of global and local gradients in salt concentration, number density, and composition as induced by successive deionization, phoretic transport, and differential settling of the components, respectively. Moreover, they provide an extended bottom surface suitable for heterogeneous nucleation of the β-phase. We give a detailed qualitative characterization of the crystallization processes using imaging and optical microscopy. By contrast to the bulk samples, the initial alloy formation is not volume-filling, and we now observe also α- and β-phases with low solubility of the odd component. In addition to the initial homogeneous nucleation route, the interplay of gradients opens various further crystallization and transformation pathways leading to a great diversity of microstructures. Upon a subsequent increase in salt concentration, the crystals melt again. Wall-based, pebble-shaped β-phase crystals and facetted α-crystals melt last. Our observations suggest that the substitutional alloys formed in bulk experiments by homogeneous nucleation and subsequent growth are mechanically stable in the absence of solid–fluid interfaces but thermodynamically metastable. [ABSTRACT FROM AUTHOR]

In this work, we shall estimate via computer simulations the homogeneous nucleation rate for the methane hydrate at 400 bars for a supercooling of about 35 K. The TIP4P/ICE model and a Lennard-Jones center were used for water and methane, respectively. To estimate the nucleation rate, the seeding technique was employed. Clusters of the methane hydrate of different sizes were inserted into the aqueous phase of a two-phase gas–liquid equilibrium system at 260 K and 400 bars. Using these systems, we determined the size at which the cluster of the hydrate is critical (i.e., it has 50% probability of either growing or melting). Since nucleation rates estimated from the seeding technique are sensitive to the choice of the order parameter used to determine the size of the cluster of the solid, we considered several possibilities. We performed brute force simulations of an aqueous solution of methane in water in which the concentration of methane was several times higher than the equilibrium concentration (i.e., the solution was supersaturated). From brute force runs, we infer the value of the nucleation rate for this system rigorously. Subsequently, seeding runs were carried out for this system, and it was found that only two of the considered order parameters were able to reproduce the value of the nucleation rate obtained from brute force simulations. By using these two order parameters, we estimated the nucleation rate under experimental conditions (400 bars and 260 K) to be of the order of log10 (J/(m3 s)) = −7(5). [ABSTRACT FROM AUTHOR]

Designing an efficient modification molecule to mitigate non‐radiative recombination at the NiOx/perovskite interface and improve perovskite quality represents a challenging yet crucial endeavor for achieving high‐performance inverted perovskite solar cells (PSCs). Herein, we synthesized a novel fullerene‐based hole transport molecule, designated as FHTM, by integrating C60 with 12 carbazole‐based moieties, and applied it as a modification molecule at the NiOx/perovskite interface. The in situ self‐doping effect, triggered by electron transfer between carbazole‐based moiety and C60 within the FHTM molecule, along with the extended π conjugated moiety of carbazole groups, significantly enhances FHTM's hole mobility. Coupled with optimized energy level alignment and enhanced interface interactions, the FHTM significantly enhances hole extraction and transport in corresponding devices. Additionally, the introduced FHTM efficiently promotes homogeneous nucleation of perovskite, resulting in high‐quality perovskite films. These combined improvements led to the FHTM‐based PSCs yielding a champion efficiency of 25.58 % (Certified: 25.04 %), notably surpassing that of the control device (20.91 %). Furthermore, the unencapsulated device maintained 93 % of its initial efficiency after 1000 hours of maximum power point tracking under continuous one‐sun illumination. This study highlights the potential of functionalized fullerenes as hole transport materials, opening up new avenues for their application in the field of PSCs. [ABSTRACT FROM AUTHOR]

The desublimation crystallization of trace impurity gas at the temperature of liquid hydrogen and liquid oxygen is a common problem in cryogenic engineering, which usually leads to the failure of cryogenic liquid transportation. Liquid hydrogen and liquid oxygen are important aerospace propellants. In the pressurization process of cryogenic liquid propellant, a small amount of water vapor and other gases in the pressurized gas would appear desublimation and crystallization at low temperature. Inevitably, as the tail gas of hydrogen combustion, water vapor sometimes diffused into cryogenic liquid. This kind of desublimation crystallization was accompanied by heat and mass transfer, accompanied by gas-solid phase transition, moving boundary, random and extremely complicated crystallization growth process. It was of great engineering practical significance to study the heat and mass transfer mechanism and law of this complex desublimation phase change phenomenon for the progress and development of engineering technologies such as refrigeration, cryogenics and aerospace. In this paper, based on the homogeneous desublimation theory, the pressurization system of liquid oxygen tank with oxygen containing trace water vapor was taken as the research object, and the basic data of ice crystal formation and growth during pressurization, such as crystallization quantity, crystallization speed and size distribution, were calculated theoretically. It provided a theoretical basis for the experimental study of the real dynamic characteristics and laws of desublimation crystallization in the propulsion system. The research methods and conclusions in this paper also had some guiding significance for the use of liquid hydrogen in the storage, transportation and use of the hydrogen energy. • Provided a challenging crystallography study on the space application of liquid hydrogen and liquid oxygen. • Described the complicated desublimation crystallization with accompanied by heat and mass transfer. • Provided dynamic characteristics of crystallization quantity, crystallization speed and size distribution. • Simulated the nucleation and ice growth accurately for many generations crystals evolved. • Suitable for crystallization of trace impurities during liquid hydrogen storage and transportation. [ABSTRACT FROM AUTHOR]

Recent observations of crystallization by thermal chemical vapor deposition systems indicate that the classical mechanism of nucleation and growth is followed. Information on aragonite nanocrystal growth and formation on substrate have been lacking due to the lack of reports on diffusional growth that can observe calcium carbonate nucleation processes in thin film formation. This report is important due to the additive‐free method able to grow stable single‐phase nanocrystals without the presence of other phases, amorphous or impurities. This work demonstrates homogeneous nucleation occurred in gas phase reaction in a constant flow of carbon dioxide gas (100 sccm) with optimally 0.5 M calcium chloride precursor in atmospheric pressure at 400 °C resulting in a calculated crystallite size of 27.8 nm. X‐ray diffraction and energy dispersive spectrometer confirm the presence of calcium carbonate nanocrystal, whereas its structural changes are observed by its micrograph from field emission scanning electron microscope. The aim is to convey its importance in gaining control of aragonite nanocrystal morphology and structural properties, and thus generate nanocrystals with controlled phase. This work may contribute to development of more sensitive and crucial applications of calcium carbonate nanocrystal thin film such as in biosensors and biomedical. [ABSTRACT FROM AUTHOR]

Nucleation is a fundamental and general process at the initial stage of first-order phase transition. Although various models based on the classical nucleation theory (CNT) have been proposed to explain the energetics and kinetics of nucleation, detailed understanding at nanoscale is still required. Here, in view of the homogeneous bubble nucleation, we focus on cavity formation, in which evaluation of the size dependence of free energy change is the key issue. We propose the application of a formula in stochastic thermodynamics, the Jarzynski equality, for data analysis of molecular dynamics (MD) simulation to evaluate the free energy of cavity formation. As a test case, we performed a series of MD simulations with a Lennard-Jones (LJ) fluid system. By applying an external spherical force field to equilibrated LJ liquid, we evaluated the free energy change during cavity growth as the Jarzynski's ensemble average of required works. A fairly smooth free energy curve was obtained as a function of bubble radius in metastable liquid of mildly negative pressure conditions. [ABSTRACT FROM AUTHOR]

The transition from heterogeneous nucleation of nanoscale hardening S-phase precipitates on dislocation lines in cold-rolled aluminium alloy 2024 (Al–Cu–Mg) to a spatially homogeneous distribution during artificial ageing is studied by means of in situ and ex situ transmission electron microscopy (TEM). Three stages of precipitate evolution following nucleation on dislocation lines are established: (i) Growth and coalescence on dislocation lines, (ii) Ostwald ripening controlled by pipe diffusion, and (iii) Ostwald ripening controlled by volume diffusion. Whilst Ostwald ripening controlled by pipe diffusion is active (stage (ii) and transition from stage (ii) to stage (iii)) dislocation annihilation and/or re-arrangement can occur. [ABSTRACT FROM AUTHOR]

Crystallization kinetics were used to develop a spherulite growth model, which can determine local crystalline distributions through an optimization algorithm. Kinetics were used to simulate spherulite homogeneous nucleation, growth, and heterogeneous nucleation in a domain discretized into voxels. From this, an overall crystallinity was found, and an algorithm was used to find crystallinities of individual spherulites based on volume. Then, local crystallinities within the spherulites were found based on distance relative to the nucleus. Results show validation of this model to differential scanning calorimetry data for polyether ether ketone at different cooldown rates, and to experimental microscopic images of spherulite morphologies. Application of this model to various cooldown rates and the effect on crystalline distributions are also shown. This model serves as a tool for predicting the resulting semi-crystalline microstructures of polymers for different manufacturing methods. These can then be directly converted into a multiscale thermomechanical model. [ABSTRACT FROM AUTHOR]

The study reports the significance of carbon presence in affecting void nucleation in Fe. Without carbon, void nucleation rates decrease gradually at high temperatures but remain significantly high and almost saturated at low temperatures. With carbon present, even at 1 atomic parts per million, void nucleation rates show a low-temperature cutoff. With higher carbon levels, the nucleation temperature window becomes narrower, the maximum nucleation rate becomes lower, and the temperature of maximum void nucleation shifts to a higher temperature. Fundamentally, this is caused by the change in effective vacancy diffusivity due to the formation of carbon-vacancy complexes. The high sensitivity of void nucleation to carbon comes from the high sensitivity of void nucleation to the vacancy arrival rate in a void. The void nucleation is calculated by first obtaining the effective vacancy diffusivity considering the carbon effect, then calculating the defect concentration and defect flux change considering both carbon effects and pre-existing dislocations, and finally calculating the void nucleation rate based on the recently corrected homogeneous void nucleation theory. The study is important not only in the fundamental understanding of impurity effects in ion/neutron irradiation but also in alloy engineering for judiciously introducing impurities to increase swelling resistance, as well as in the development of simulation and modeling methodologies applicable to other metals. [ABSTRACT FROM AUTHOR]

In the framework of the Polyakov quark-meson model with two flavors, the bubble dynamics of a first-order phase transition in the region of high density and low temperature are investigated by using the homogeneous thermal nucleation theory. In mean-field approximation, after obtaining the effective potential with the inclusion of the fermionic vacuum term, we build a geometric method to search two existing minima, which can be actually connected by a bounce interpolated between a local minimum to an adjacent global one. For both weak and strong first-order hadron quark phase transitions, as fixing the chemical potentials at  μ = 306 MeV  and  μ = 310 MeV , the bubble profiles, the surface tension, the typical radius of the bounce, and the saddle-point action as a function of temperature are numerically calculated in the presence of a nucleation bubble. It is found that the surface tension remains at a very small value even when the density is high. It is also noticed that the deconfinement phase transition does not change the chiral phase transition dramatically for light quarks and phase boundaries for hadron and quark matter should be resized properly according to the saddle-point action evaluated on the bounce solution. [ABSTRACT FROM AUTHOR]

The modified Reiss theory of binary homogeneous nucleation is applied to liquid aerosols of highly diluted composition in the approximation of a weak solution. In the framework of the weak solution model, the size, composition and formation free energy of the critical nucleus is calculated analytically, explicitly demonstrating the decrease in critical humidity in the presence of the second component, revealed in the numerical calculations from the literature. On this base, the nucleation rate is calculated using the Reiss kinetic theory in two different cases of humidity below and above 100%. Various modifications of the Reiss theory in the limit of a low content of the second component proposed in the literature are critically analyzed and contradicted. Copyright © 2024 American Association for Aerosol Research [ABSTRACT FROM AUTHOR]

Sluggish redox kinetics and severe polysulfide shuttling are major hurdles for the commercialization of lithium–sulfur (Li–S) batteries. Transition‐metal compound catalysts offer a promising solution by providing excellent polysulfide adsorption capabilities, outstanding catalytic activities, and homogeneous nucleation control of Li2S2/Li2S. The electronic structure of transition‐metal sites in catalysts can also be fine‐tuned through bi‐metallic coupling, which can further improve the catalytic activities. In this study, bi‐metallic nickel molybdenum phosphide is co‐synthesized with Li2S and carbon through a carbothermal reduction process, forming a cathode composite (Li2S @ NixMoyPz @ C). This process is not only advantageous for large‐scale manufacturing due to its simplicity, but also ensures homogeneous integration and distribution of the catalyst within the cathode composite. Furthermore, applying Li2S as an active material allows the creation of an anode‐free cell configuration, enhancing the overall cell energy density. The anode‐free cell with the Li2S @ NixMoyPz @ C composite cathode demonstrates an outstanding capacity retention of 50% over 300 cycles at a negative‐to‐positive capacity (N/P) ratio of 1. Additionally, the bi‐metallic phosphide integrated Li2S cathode composite delivers a remarkable anode‐free pouch cell performance of 703 mA h g−1 (on Li2S basis) under the challenging conditions of an E/Li2S ratio of 4.5. [ABSTRACT FROM AUTHOR]

The symmetry-breaking first-order phase transition between superfluid phases 3 He-A and 3 He-B can be triggered extrinsically by ionising radiation or heterogeneous nucleation arising from the details of the sample cell construction. However, the role of potential homogeneous intrinsic nucleation mechanisms remains elusive. Discovering and resolving the intrinsic processes may have cosmological consequences, since an analogous first-order phase transition, and the production of gravitational waves, has been predicted for the very early stages of the expanding Universe in many extensions of the Standard Model of particle physics. Here we introduce a new approach for probing the phase transition in superfluid 3 He. The setup consists of a novel stepped-height nanofluidic sample container with close to atomically smooth walls. The 3 He is confined in five tiny nanofabricated volumes and assayed non-invasively by NMR. Tuning of the state of 3 He by confinement is used to isolate each of these five volumes so that the phase transitions in them can occur independently and free from any obvious sources of heterogeneous nucleation. The small volumes also ensure that the transitions triggered by ionising radiation are strongly suppressed. Here we present the preliminary measurements using this setup, showing both strong supercooling of 3 He-A and superheating of 3 He-B, with stochastic processes dominating the phase transitions between the two. The objective is to study the nucleation as a function of temperature and pressure over the full phase diagram, to both better test the proposed extrinsic mechanisms and seek potential parallel intrinsic mechanisms. [ABSTRACT FROM AUTHOR]

Simultaneous deoxidation of Al/Ti in steel was performed to analyze the TiS-containing inclusions, TiS single inclusions and Al2O3(or TixOy)-TiS two-layered inclusions were observed in the steel smaple. Density functional theory calculations were performed to study the structures and properties of the intermediate products of TiS before critical nucleation, and the nucleation mechanism of TiS in Al/Ti simultaneously deoxidized steel was discussed based on homogeneous and heterogeneous nucleation modes. The results show that the TiS nucleation is controlled by the formation of (TiS)n clusters; the homogeneous nucleation of TiS inclusions in the steel can only occur using (TiS)n clusters with n ≥ 4, whereas the heterogeneous nucleation of (TiS)n clusters on the surfaces of Al2O3 and Ti2O3 can occur using all the (TiS)n clusters. As a result, the inclusions of Al2O3 and Ti2O3 can act as effective sites to induce the heterogeneous nucleation of TiS inclusions in steel. The Gibbs free energy change values for the (TiS)n clusters formed on the Ti2O3 surface were lower than those on the Al2O3 surface, and the mismatch values of Ti2O3(001)-TiS(001) interface were smaller than those of Al2O3(001)-TiS(001) interface. Thus, TiS inclusions formed more easily on the surface of Ti2O3 than on Al2O3. [ABSTRACT FROM AUTHOR]

In order to gain insight into the influence of grain size on precipitation thermodynamics, bulk materials of coarse-grained (CG), ultrafine-grained (UFG) (with or without dislocations), and nanocrystalline (NC) 7075 Al alloy have been fabricated by solid solution treatment, equal-channel angular pressing (ECAP), or high-pressure torsion (HPT) processes. The precipitation behavior and the corresponding thermal phenomenon were studied by transmission electron microscopy (TEM) and differential scanning calorimetry (DSC) heating. The results indicated that there are significant differences in precipitation thermodynamics among the four bulk materials. In the CG and UFG materials without dislocations, homogeneous nucleation is the primary precipitation mechanism. However, the nucleation of the GP zones is suppressed at lower temperatures due to a reduction in the number of residual vacancies and the supersaturation in the UFG interiors. This is attributed to the absorption of vacancies and solute atoms by a greater volume of grain boundaries. It can be observed that the greater the excess of vacancies remaining in grain interiors, the lower the temperature at which nucleation of GP zones occurs. Defect-assisted heterogeneous nucleation was identified as the predominant precipitation mechanism in the UFG materials with dislocations and the NC materials. These defects encompass dislocations, lattice distortions, and grain boundaries. The decomposition processes of solid solutions were found to be almost complete at a lower temperature. The presence of dislocations, lattice distortions, and grain boundaries enables solute atoms to diffuse at a much faster rate, significantly enhancing the precipitation rate and reducing the nucleation and formation energies of various precipitate phases. [ABSTRACT FROM AUTHOR]

Methane hydrates are important from a scientific and industrial perspective, and form by nucleation and growth from a supersaturated aqueous solution of methane. Molecular simulation is able to shed light on the process of homogeneous nucleation of hydrates, using straightforward molecular dynamics or rare event enhanced sampling techniques with atomistic and coarse grained force fields. In our previous work [Arjun, T. A. Berendsen, and P. G. Bolhuis, Proc. Natl. Acad. Sci. U. S. A. 116, 19305 (2019)], we performed transition path sampling (TPS) simulations using all atom force fields under moderate driving forces at high pressure, which enabled unbiased atomistic insight into the formation of methane hydrates. The supersaturation in these simulations was influenced by the Laplace pressure induced by the spherical gas reservoir. Here, we investigate the effect of removing this influence. Focusing on the supercooled, supersaturated regime to keep the system size tractable, our TPS simulations indicate that nuclei form amorphous structures below roughly 260 K and crystalline sI structures above 260 K. For these temperatures, the average transition path lengths are significantly longer than in our previous study, pushing the boundaries of what can be achieved with TPS. The temperature to observe a critical nucleus of certain size was roughly 20 K lower compared to a spherical reservoir due to the lower concentration of methane in the solution, yielding a reduced driving force. We analyze the TPS results using a model based on classical nucleation theory. The corresponding free energy barriers are estimated and found to be consistent with previous predictions, thus adding to the overall picture of the hydrate formation process. [ABSTRACT FROM AUTHOR]

Phase transitions of proteins are strongly influenced by surface chemical modifications or mutations. Human γD-crystallin (HGD) single-mutants have been extensively studied because they are associated with the onset of juvenile cataract. However, they have also provided a rich library of molecules to examine how specific inter-protein interactions direct protein assembly, providing new insights and valuable experimental data for coarse-grained patchy-particle models. Here, we demonstrate that the addition of new inter-protein interactions by mutagenesis is additive and increases the number and variety of condensed phases formed by proteins. When double mutations incorporating two specific single point mutations are made, the properties of both single mutations are retained in addition to the formation of a new condensed phase. We find that the HGD double-mutant P23VC110M self-assembles into spherical particles with retrograde solubility, orthorhombic crystals, and needle/plate shape crystals, while retaining the ability to undergo liquid–liquid phase separation. This rich polymorphism is only partially predicted by the experimental data on the constituent single mutants. We also report a previously un-characterized amorphous protein particle, with unique properties that differ from those of protein spherulites, protein particulates previously described. The particles we observe are amorphous, reversible with temperature, tens of microns in size, and perfectly spherical. When they are grown on pristine surfaces, they appear to form by homogeneous nucleation, making them unique, and we believe a new form of protein condensate. This work highlights the challenges in predicting protein behavior, which has frustrated rational assembly and crystallization but also provides rich data to develop new coarse-grained models to explain the observed polymorphism. [ABSTRACT FROM AUTHOR]

The crystallization temperature of deeply undercooled Cu–Ge alloy melts is repeatedly measured. A statistical analysis is applied on the undercooling distributions obtained from nine different compositions, ranging from the pure semimetal (Ge) to the pure metal (Cu). By considering each undercooling distribution as an inhomogeneous Poisson process, the nucleation rates for every composition are calculated. The Thompson–Spaepen model for homogeneous nucleation in binary alloys is applied, enabling the estimation of nucleation parameters, such as kinetic pre-factors and interfacial energies, as a function of composition. Furthermore, the Turnbull coefficient α, a dimensionless solid–liquid interfacial energy constant, is also calculated as a function of alloy constitution, suggesting a dependence on the liquid composition. The composition-dependent changes of α are of considerable importance, since the α is originally defined for pure systems as a quantity dependent on crystal structure, and is nevertheless used for describing nucleation kinetics of binary and glass forming multi-component alloy systems. [ABSTRACT FROM AUTHOR]

Freezing of water is the most common liquid-to-crystal phase transition on Earth; however, despite its critical implications on climate change and cryopreservation among other disciplines, its characterization through experimental and computational techniques remains elusive. In this work, we make use of computer simulations to measure the nucleation rate (J) of water at normal pressure under different supercooling conditions, ranging from 215 to 240 K. We employ two different water models: mW, a coarse-grained potential for water, and TIP4P/ICE, an atomistic nonpolarizable water model that provides one of the most accurate representations of the different ice phases. To evaluate J, we apply the Lattice Mold technique, a computational method based on the use of molds to induce the nucleus formation from the metastable liquid under conditions at which observing spontaneous nucleation would be unfeasible. With this method, we obtain estimates of the nucleation rate for ice Ih and Ic and a stacking mixture of ice Ih/Ic, reaching consensus with most of the previously reported rates, although differing with some others. Furthermore, we confirm that the predicted nucleation rates obtained by the TIP4P/ICE model are in better agreement with experimental data than those obtained through the mW potential. Taken together, our study provides a reliable methodology to measure nucleation rates in a simple and computationally efficient manner that contributes to benchmarking the freezing behavior of two popular water models. [ABSTRACT FROM AUTHOR]

Aqueous Zn‐based batteries (AZBs) have appealed numerous attentions in the energy storage field due to their low cost, environmental friendliness and high safety. However, the Zn metal anode faces severe challenges of short cycle life because of the dendrite growth and side reactions, which hinders the practical application of AZBs. Herein, an artificial coating layer of cyclized polyacrylonitrile (cPAN) is designed on the Zn anode through spin‐coating and thermal treatment. The cPAN layer possesses abundant N‐containing groups and delocalized π‐conjugation structure, which endows the Zn anode with low nucleation barrier and homogeneous electric field. Benefiting from these synergetic advantages, the nucleation overpotential of Zn is remarkably decreased. Furthermore, no obvious byproduct is observed on the cPANZ‐Zn after cycling. As a result, the resultant cPANZ‐Zn anode delivers a long lifespan of 600 h and high reversibility. cPANZ‐Zn||MnO2 full cells are further assembled and exhibited stable cycling and high rate capability. [ABSTRACT FROM AUTHOR]

Warm-air intrusions (WAIs) are responsible for the transportation of warm and moist air masses from the mid-latitudes into the high Arctic (> 70° N). In this work, we study cirrus clouds that form during WAI events (WAI cirrus) and during undisturbed Arctic conditions (AC cirrus) and investigate possible differences between the two cloud types based on their macrophysical and optical properties with a focus on relative humidity over ice (RHi). We use airborne measurements from the combined high-spectral-resolution and differential-absorption lidar, WALES, performed during the HALO-(AC) 3 campaign. We classify each research flight and the measured clouds as either AC or WAI, based on the ambient conditions, and study the macrophysical, geometrical and optical characteristics for each cirrus group. As our main parameter we choose the relative humidity over ice (RHi), which we calculate RHi by combining the lidar water vapor measurements with model temperatures. Ice formation occurs at certain RHi values depending on the dominant nucleation process taking place. RHi can thus be used as an indication of the nucleation process and the structure of cirrus clouds. We find that during WAI events the Arctic is warmer and moister and WAI cirrus clouds are both geometrically and optically thicker compared to AC cirrus. WAI cirrus clouds and the layer directly surrounding them are more frequently supersaturated, also at high supersaturations over the threshold for homogeneous ice nucleation (HOM). AC cirrus clouds have a supersaturation-dominated cloud top and a subsaturated cloud base. WAI cirrus clouds also have high supersaturations at cloud top but also at cloud base. [ABSTRACT FROM AUTHOR]

Molecular dynamics simulation was applied to investigate the interaction between precipitate and 10 1 ¯ 2 twin in Mg-Al alloy in this work. Three sets of simulation including twin nucleation, propagation and growth affected by precipitate were performed. The results show the introduction of precipitate has little effect on neither the homogeneous twin nucleation at random site inside the grain nor the heterogeneous nucleation at grain boundary. During twin propagation, the blocking effect of precipitate to the twin tip depends on its size. The twin tip can bypass the precipitate when the precipitate is not long enough. When the length of precipitate is much larger than the thickness of twin, the twin tip will be completely blocked by the precipitate with elastic bending occurring at the junction. During the twin growth, it is found that the precipitate plays not only an obstacle but a source for the twinning dislocations gliding along the twin boundary. The blocking effect of precipitate on twin growth shows a size effect. The influences of width and thickness on precipitation hardening are significantly greater than that of length. [ABSTRACT FROM AUTHOR]