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Binary or multi-component phase mixtures are of particular technical importance. Despite the wide field of application of Al 2 O 3 and ZrO 2 composites, the literature reveals contradictions about the liquidus region. Containerless processing avoids typical problems of conventional techniques like melt contamination or lack of suitable container materials. Composition ranging from 0–80 mol% ZrO 2 were melted and solidified in an aero acoustic levitator. A high-speed camera recorded the crystallization, allowing a direct correlation with the observed microstructures. Due to homogeneous nucleation, all samples exhibited significant undercooling before crystallization. The nucleation temperature of the different compositions roughly followed the slope of the liquidus line. Undercooling, solidification kinetics, and local reheating played a considerable role in microstructure formation. A lamellae eutectic microstructure was created over a large compositional range from 36–48 mol% ZrO 2. On the hypoeutectic side, the effect was attributed to solidification within the coupled zone. However, hypereutectic samples also exhibit a zirconia-rich eutectic as well. We assume impaired ZrO 2 nucleation or growth favors alumina precipitation from the melt. Aero acoustic levitation proved to be an excellent technique for studying complex high melting oxide systems, enabling a better understanding of their crystallization process. [ABSTRACT FROM AUTHOR]

Currently, wide‐color gamut perovskite light‐emitting diodes (PeLEDs) are commonly controlled through halide composition tuning. However, the formation of perovskite crystals involving different ion radii of halogens often results in structural fragility and ionic defects, leading to emission instability during operation. This study showcases a novel approach to achieving a homogeneous and low‐defect crystalline state by regulating the thermodynamic nucleation mechanism of sky‐blue perovskite, thereby enhancing emission stability. Utilizing oxygen‐plasma treatment, a highly uniform surface energy is ensured for the nickel oxide acting as a hole transport layer. This treatment not only induces homogeneous nucleation of the perovskite layer but also effectively suppresses crystal defects. Simultaneously, the uniform surface energy alleviates halide phase separation caused by Ostwald ripening. Upon optimizing the fabrication conditions for sky‐blue perovskite, the resulting PeLEDs, featuring an electroluminescent peak at 486 nm, attain a luminance of 1125.3 cd m−2 with exceptional electroluminescent stability and a T50 lifetime. Furthermore, gaining insights into the thermodynamic nucleation mechanism in mix‐halides and perovskites contributes to the advancement of research on sky‐blue PeLEDs and offers valuable perspectives for future development. [ABSTRACT FROM AUTHOR]

An approach based on the direct numerical solution of the Boltzmann kinetic equation is proposed to take into account the influence of homogeneous nucleation on the mass transfer intensity in the evaporation/condensation (recondensation) problem. On the basis of the comparison between the scales of the formation time of a critical-size droplet and the time of supersaturation propagation, it is shown that it is possible to describe the considered problem in two stages, i.e., without taking into account the influence of droplets at the first stage and with taking into account their influence at the second stage. The calculation results show that, in the case of immobile droplets, there is a strong influence of bulk condensation on the intensity of the evaporation/condensation process. [ABSTRACT FROM AUTHOR]

Nucleation of H2O vapor bubbles in magma requires surpassing a chemical supersaturation threshold via decompression. The threshold is minimized in the presence of a nucleation substrate (heterogeneous nucleation, <50 MPa), and maximized when no nucleation substrate is present (homogeneous nucleation, >100 MPa). The existence of explosively erupted aphyric rhyolite magma staged from shallow (<100 MPa) depths represents an apparent paradox that hints at the presence of a cryptic nucleation substrate. In a pair of studies focusing on Glass Mountain eruptive units from Medicine Lake, California, we characterize titanomagnetite nanolites and ultrananolites in pumice, obsidian, and vesicular obsidian (Brachfeld et al., 2024, https://doi.org/10.1029/2023GC011336), calculate titanomagnetite crystal number densities, and compare titanomagnetite abundance with the physical properties of pumice to evaluate hypotheses on the timing of titanomagnetite crystallization. Titanomagnetite crystals with grain sizes of approximately 3–33 nm are identified in pumice samples from the thermal unblocking of low‐temperature thermoremanent magnetization. The titanomagnetite number densities for pumice are 1018 to 1020 m−3, comparable to number densities in pumice and obsidian obtained from room temperature methods (Brachfeld et al., 2024, https://doi.org/10.1029/2023GC011336). This range exceeds reported bubble number densities (BND) within the pumice from the same eruptive units (average BND ∼4 × 1014 m−3). The similar abundances of nm‐scale titanomagnetite crystals in the effusive and explosive products of the same eruption, together with the lack of correlation between pumice permeability and titanomagnetite content, are consistent with titanomagnetite formation having preceded the bubble formation. Results suggest sub‐micron titanomagnetite crystals are responsible for heterogeneous bubble nucleation in this nominally aphyric rhyolite magma. Key Points: Aphyric rhyolite eruptions staged from shallow magma reservoirs lack the overpressure needed for homogeneous bubble nucleationHeterogeneous bubble nucleation may occur on sub‐µm titanomagnetite crystals, which are undetectable using standard analytical techniquesSub‐µm titanomagnetite crystals can be detected and quantified with low temperature magnetic analyses [ABSTRACT FROM AUTHOR]

It is demonstrated for 11 different combinations of organic solutes and solvents that the supersaturation dependence of homogeneous organic crystal nucleation rates from solution can be predicted from the solubility, bar a single empirical rate constant, when it is assumed that nucleation takes place in reversible aggregates of solvated solutes formed in supersaturated solutions. Reversible solute aggregation represents natural solute density fluctuations that take place in any solute/solvent system. For thermodynamically ideal solutions, the steady state size distribution, and thus the population of reversible aggregates in supersaturated solution, can be predicted quantitatively from the overall solute concentration by a simple mathematical expression. Supersaturation creates an excess of reversible aggregates with sizes exceeding that of the largest aggregate in saturated solution. It is shown that the number of these excess aggregates is proportional to experimental homogeneous nucleation rates, suggesting a rate equation for homogeneous nucleation that has only one empirical parameter, namely, a rate constant specific to the solute/solvent combination. This rate constant can be determined from standard nucleation rate data. The system-specificity of homogeneous nucleation rates thus appears to be encoded solely in a rate constant for the transformation of the large excess aggregates into crystal nuclei. The driving force for triggering nucleation events in these aggregates is likely the extremely high local supersaturation, which provides the conditions for spatiotemporally aligned bond-breaking (e.g., de-solvation) and bond-forming (e.g., solute–solute bonding) events that create stable crystal nuclei. The possible influence of heterogeneous nucleation by solid impurities is considered. [ABSTRACT FROM AUTHOR]

Polarization switching in ferroelectric hysteresis of BaTiO3 proceeds by localized nucleation and subsequent growth of domains of reverse polarization. While this process is driven by the applied electric field, thermal activation can play an important role in domain nucleation. As a consequence of the stochastic nature of thermal activation, coercive fields in small systems exhibit a significant scatter. It is demonstrated that the statistics of coercive fields observed in molecular dynamics simulations is consistent with the statistical distribution expected for field-assisted thermally activated nucleation of reverse polarization domains. The excellent quantitative agreement between the simulation data and the theory of thermally activated processes provides strong evidence that polarization switching occurs by nucleation-and-growth rather than loss of the local minimum of the Gibbs free energy function. In a pristine crystal, switching is controlled by the field at which thermal fluctuations can create a critical nucleus in the bulk (homogeneous nucleation). The analysis of crystals with various vacancy-type defects demonstrates that such defects may enable heterogeneous nucleation at reduced fields. In both cases, the statistical analysis gives access to the respective activation energies, their field dependence, and the sizes of the critical nuclei. [ABSTRACT FROM AUTHOR]

High-carbon hardline steels are primarily used for the manufacture of tire beads for both automobiles and aircraft, and vanadium (V) microalloying is an important means of adjusting the microstructure of high-carbon hardline steels. Using scanning electron microscopy (SEM), X-ray diffraction (XRD), and transmission electron microscopy (TEM), the microstructure and precipitation phases of continuous cooled high-carbon steels were characterized, and the vanadium content, carbon diffusion coefficient, and critical precipitation temperature were calculated. The results showed that as the V content increased to 0.06 wt.%, the interlamellar spacing (ILS) of the pearlite in the experimental steel decreased to 0.110 μm, and the carbon diffusion coefficient in the experimental steel decreased to 0.98 × 10−3 cm2·s−1. The pearlite content in the experimental steel with 0.02 wt.% V reached its maximum at a cooling rate of 5 °C·s−1, and a small amount of bainite was observed in the experimental steel at a cooling rate of 10 °C·s−1. The precipitated phase was VC with a diameter of ~24.73 nm, and the misfit between ferrite and VC was 5.02%, forming a semi-coherent interface between the two. Atoms gradually adjust their positions to allow the growth of VC along the ferrite direction. As the V content increased to 0.06 wt.%, the precipitation-temperature-time curve (PTT) shifted to the left, and the critical nucleation temperature for homogeneous nucleation, grain boundary nucleation, and dislocation line nucleation increased from 570.6, 676.9, and 692.4 °C to 634.6, 748.5, and 755.5 °C, respectively. [ABSTRACT FROM AUTHOR]

Perovskite thin films directly impact solar cell properties, making defect reduction crucial in perovskite solar cell research. In our study, we used perovskite quantum dots in the anti-solvent to act as nucleation centers in MAPbI3 thin films. These centers had lower nucleation barriers than homogeneous nucleation, improving perovskite crystallinity, reducing defects, and extending carrier lifetime. Fine-tuning the energy band also enhanced carrier transport. The most effective results were obtained using CsPb(Br0.5 I0.5)3 perovskite quantum dots. The resulting device, ITO/SnO2/MAPbI3 (300 nm)/spiro-OMeTAD (200 nm)/Ag (100 nm), achieved a 12.88% power conversion efficiency, a 16% increase from the standard element. The modified device maintained approximately 95% of its efficiency over 100 h in a 70% humidity environment. [ABSTRACT FROM AUTHOR]

Cavitation inception originates from nuclei in a liquid. This paper proposes a Gibbs free energy approach that provides a smooth transition from homogeneous to heterogeneous nucleation when gas is present. The impact of gas content on nucleation is explored. It is found that the gas content stabilises nuclei, a phenomenon not present in pure liquid-vapour systems. This reduces the energy barrier over that required to nucleate a vapour bubble. Different gas saturation levels are studied. Gas content can significantly reduce the energy barrier required for nucleation, and under certain circumstances eliminate it. An analytic solution for the critical radius and activation energy is obtained that accounts for gas content. The classical Blake radius is recovered as a limiting case. The hysteresis between incipience and desinence is explained using the asymmetry observed in the critical radii. The solution is used to obtain the initial bubble radius, given a critical pressure condition in cavitation susceptibility meter experiments. The relationship between initial bubble diameter and critical pressure is described by an analytic solution that accounts for gas content. Amodel for the derivative of the cumulative nuclei histogram with respect to bubble diameter is proposed. An analytic expression is obtained that shows good agreement with decades worth of experimental data compiled by Khoo et al. (Exp. Fluids, vol. 61, issue 2, 2020, pp. 1-20) from ocean to water tunnels. The expression recovers the -4 power law that is observed experimentally. [ABSTRACT FROM AUTHOR]

In this work, molecular dynamic (MD) simulations are applied to investigate the heterogeneous nucleation mechanism of KI on a graphene surface in water. As graphene is immersed in water, it mainly affects the structure of interfacial water (the topmost water layer at the interface between the substance and water). To maximize the hydrogen bonding of water, the dissolved solutes tend to accumulate to form the aggregate at the graphene surface, which undoubtedly affects the nucleation pathways of solutes in water. In comparison with homogeneous nucleation, a lower barrier may be expected during the heterogeneous nucleation of KI on a graphene surface in water. Therefore, as the graphene is immersed in water, this facilitates solute nucleation. From this work, it may be derived that heterogeneous nucleation may be closely related to the geometric characteristics of foreign surfaces, especially their geometric shape. [ABSTRACT FROM AUTHOR]

In principle, the answer to the posed titular question is undoubtedly "yes." But in practice, requisite reference data for homogeneous systems have been obtained with a treatment of intermolecular interactions that is different from that typically employed for heterogeneous systems. In this article, we assess the impact of the choice of truncation scheme when comparing water in homogeneous and inhomogeneous environments. Specifically, we use explicit free energy calculations and a simple mean field analysis to demonstrate that using the "cut-and-shift" version of the Lennard-Jones potential (common to most simple point charge models of water) results in a systematic increase in the melting temperature of ice Ih. In addition, by drawing an analogy between a change in cutoff and a change in pressure, we use existing literature data for homogeneous ice nucleation at negative pressures to suggest that enhancements due to heterogeneous nucleation may have been overestimated by several orders of magnitude. [ABSTRACT FROM AUTHOR]

The present study explores the physics behind the loading rate (dP/dt or P ˙ ≈ 1 − 1000 mN s − 1 ) dependent nanoscale plasticity (NSP) events observed during carefully controlled nanoindentation (NI) experiments on 1, 3, and 5 wt. % Titania Densified Alumina (TDA) ceramics. Characterizations of the TDA ceramics are carried out by x-ray diffraction, field emission scanning electron microscopy (FESEM), and NI techniques. A significant enhancement (∼30%) of the nanohardness of TDA ceramics occur with an enhancement in P ˙ . The results confirm that both the critical load (Pc) at which micro-pop-in or the NSP events initiate and the corresponding critical depth (hc) are sensitive functions of relative density, size of relatively finer grains, loading rate, and the amount of sintering aids. The experimentally observed empirical power law dependence of all the NSP related parameters on P ˙ is rationalized theoretically and qualitatively. It is suggested that the shear induced homogeneous dislocation nucleation underneath the nanoindenter may be the main factor contributing to the occurrence of the NSP events at relatively lower loading rates. However, especially at the relatively higher loading rates, the FESEM based evidence and the data obtained from the related NI experiments suggest that there is a more acute interconnection between the homogeneous dislocation nucleation induced profuse occurrence of the NSP events, shear band formations, and microcrack formation in the TDA ceramics. Finally, the design implications of the present results for the development of better alumina ceramics for load and strain tolerant applications are discussed. [ABSTRACT FROM AUTHOR]

Finite size artifacts arise in molecular simulations of nucleation when critical nuclei are too close to their periodic images. A rigorous determination of what constitutes too close is, however, a major challenge. Recently, we devised rigorous heuristics for detecting such artifacts based on our investigation of how system size impacts the rate of heterogeneous ice nucleation [S. Hussain and A. Haji-Akbari, J. Chem. Phys. 154, 014108 (2021)]. We identified the prevalence of critical nuclei spanning across the periodic boundary, and the thermodynamic and structural properties of the liquid occupying the inter-image region as indicators of finite size artifacts. Here, we further probe the performance of such heuristics by examining the dependence of homogeneous crystal nucleation rates in the Lennard-Jones (LJ) liquid on system size. The rates depend non-monotonically on system size and vary by almost six orders of magnitude for the range of system sizes considered here. We confirm that the prevalence of spanning critical nuclei is the primary indicator of finite size artifacts and almost fully explains the observed variations in rate. Proximity, or structuring of the inter-image liquid, however, is not as strong of an indicator due to the fragmented nature of crystalline nuclei. As a result, the dependence of rate on system size is subtle for the systems with a minuscule fraction of spanning critical nuclei. These observations indicate that our heuristics are universally applicable to different modes of nucleation (homogeneous and heterogeneous) in different systems even if they might be overly stringent for homogeneous nucleation, e.g., in the LJ system. [ABSTRACT FROM AUTHOR]

Semicrystalline polymers are ubiquitous, yet despite their fundamental and industrial importance, the theory of homogeneous nucleation from a melt remains a subject of debate. A key component of the controversy is that polymer crystallization is a non-equilibrium process, making it difficult to distinguish between effects that are purely kinetic and those that arise from the underlying thermodynamics. Due to computational cost constraints, simulations of polymer crystallization typically employ non-equilibrium molecular dynamics techniques with large degrees of undercooling that further exacerbate the coupling between thermodynamics and kinetics. In a departure from this approach, in this study, we isolate the near-equilibrium nucleation behavior of a simple model of a melt of short, semiflexible oligomers. We employ several Monte Carlo methods and compute a phase diagram in the temperature–density plane along with two-dimensional free energy landscapes (FELs) that characterize the nucleation behavior. The phase diagram shows the existence of ordered nematic and crystalline phases in addition to the disordered melt phase. The minimum free energy path in the FEL for the melt–crystal transition shows a cooperative transition, where nematic order and monomer positional order move in tandem as the system crystallizes. This near-equilibrium phase transition mechanism broadly agrees with recent evidence that polymer stiffness plays an important role in crystallization but differs in the specifics of the mechanism from several recent theories. We conclude that the computation of multidimensional FELs for models that are larger and more fine-grained will be important for evaluating and refining theories of homogeneous nucleation for polymer crystallization. [ABSTRACT FROM AUTHOR]

The Reiss theory for binary homogeneous nucleation in binary vapor mixtures is critically analyzed and further developed. Based on the analysis of phase space trajectories in the supercritical zone of the phase transition, carried out within the framework of the theory of two-dimensional dynamical systems and supplemented by the flux matching condition at the boundary of the critical zone, it is shown how the theory should be modified. The proposed modification is equivalent to the earlier modifications by Langer and Stauffer, based on additional trial assumptions (ansatz) for solving the steady state equation for the non-equilibrium size distribution function, but reveals and substantiates the approximation underlying their approach. The extension of the Reiss theory to binary vapors in inert carrier (atmospheric) gases is justified. Copyright © 2023 American Association for Aerosol Research [ABSTRACT FROM AUTHOR]

In Li metal batteries, the rational construction of artificial solid electrolyte interphase (ASEI) can homogenize the Li‐ion flowing and Li‐mass plating/stripping, and reinforce the mechanical and electrochemical stabilities of electrode–electrolyte interface. Here, an ordered‐mesoporous powder zirconium oxophosphate (ZrOP) is proposed to construct a Li‐ion conductive ASEI by brushing ZrOP on metallic Li. The P‐induced amorphization in ZrOP is expected to accelerate the spontaneous lithiation reaction and promote the generation of P‐contained Li‐ion conductors and LiF domains in ASEI during Li anode cycling. The electrochemical activation of ASEI with promoted ionic conductivity and interconnected porous network is favorable for the homogeneous nucleation and growth of Li metal grains (with ≈10 µm in size), and the suppression of Li dendrites and volume expansion during long‐term Li plating and stripping. The ZrOP‐modified Li symmetric cell enables a long lifespan of over 1600 h at 1 mA cm−2, and the corresponding LiNi0.8Co0.1Mn0.1O2 (NCM811) based full cell displays a stable cycling for at least 300 cycles with a capacity retention of 80% at 1 C. The modified thin Li foil (40 µm in thickness) anode also enables a multilayered pouch cell based on a high‐loading NCM811 cathode with stable cycling and reversible capacity over 1 Ah. [ABSTRACT FROM AUTHOR]

Representing detailed atmospheric aerosol processes in global Earth system models (ESMs) has proven challenging both from a computational and a parameterization perspective. The representation of secondary organic aerosol (SOA) formation and new particle formation (NPF) in large ESMs are generally constructed with low detail to save computational costs. The simplification could result in losing the representation of some processes. In this study, we test and evaluate a new approach for improving the description of NPF processes in the ESM EC-Earth3 (ECE3) without loss of significant computational time. The current NPF scheme in EC-Earth3 is derived from the nucleation of low-volatility organic vapors and sulfuric acid (H2SO4) together with a homogeneous water-H2SO4 nucleation scheme. We expand the existing schemes and introduce a new look-up table approach that incorporates detailed formation rate predictions by molecular modeling of sulfuric acid-ammonia nucleation (H2SO4-NH3). We apply tables of particle formation rates for H2SO4-NH3 nucleation, including dependence on temperature, atmospheric ion production rate, and molecular cluster scavenging sink. The resulting differences between using the H2SO4-NH3 nucleation in ECE3 and the original default ECE3 scheme are evaluated and compared with a focus on changes in aerosol composition, cloud properties, and radiation balance. From this new nucleation scheme, EC-Earth3's global average aerosol concentrations in the sub-100 nm sizes increased by 12–28 %. Aerosol concentrations above 100 nm and the direct radiative effect (in Wm−2) from the changed nucleation only resulted in minor changes. However, the radiative effect from clouds affected by aerosols from the new nucleation scheme resulted in a global decrease (cooling effect) by 0.28–1 Wm−2. Additionally, several stations with observed aerosol size number distribution measurements are compared with the model results to examine the performance of the NPF schemes. [ABSTRACT FROM AUTHOR]

With the Paris Agreement, the installed capacity of green power, such as photovoltaic (PV) and wind power, is growing rapidly at a rate of more than 10 % per year. The practical application of these green electrical energies is limited by the relative lag in the scale of energy storage systems. In response to the pressure on energy storage systems, we explored the feasibility of supplying DC power directly from a PV plant to an industrial electrolyzer by comparing the electrodeposition behavior of Fe2+ in a sulfuric acid system from stabilized DC and fluctuating PV power sources. We found that the factor that damages the stable operation of an iron electrodeposition system the most is the presence of hydrogen evolution reactions, where the generation of hydrogen bubbles reduces the current efficiency of the electrodeposition system and, in severe cases, destroys the surface morphology of the deposited products, causing devastating damage to the system. On this basis, we designed a simple scheme that uses heterogeneous bubble nucleation instead of homogeneous bubble nucleation for rapid bubble expulsion from the cathode surface. Benefiting from the rapid transfer of bubbles, the current efficiency of the electrodeposited iron system increases by 1.25%–10 % at different current densities, and the maximum roughness decreases by 129–2,396 nm, which considerably improves the stability of the electrodeposited iron system for PV power. This work provides useful experimental support for the transformation of the traditional steel smelting industry, which is characterized by high carbon emission and energy consumption, into an environmentally friendly industry. • Explored the feasibility of directly using photovoltaic energy for electrodeposition. • A Het/Hom cathode has been proposed for rapid removal of adsorbed bubbles. • Benefiting from rapid removal of bubbles, the CE has been improved by 1.25%–10 %. • The energy consumption of electrodeposited iron has been reduced by 690 kWh/t-Fe. • The decrease in R max by 129-2,396 nm ensures the stability of the equipment. [ABSTRACT FROM AUTHOR]

This paper explores the kinetics of the crystallization of potassium sulfate in a stirred bed crystallizer through experimental investigation. Employing classical nucleation theory, the homogeneous and heterogeneous nucleation mechanisms of potassium sulfate were investigated. The induction time and critical nucleation parameters, including the surface tension (γ), critical nucleation radius (r*), critical nucleation free energy (ΔG*), and critical nucleation molecule number (i*), were meticulously determined under varying temperatures and supersaturation ratios. The experimental findings revealed that as the temperature and supersaturation ratio increased, the induction time, critical nucleation free energy, critical nucleation radius, and critical molecule number decreased whereas the nucleation rate increased. The crystalline shape remains relatively unaltered with respect to temperature and supersaturation ratio, yet the particle size (D10, D50, D90) increases as the supersaturation and temperature increase. The variations in the measured nucleation parameters align well with the predictions of classical nucleation theory. Furthermore, the kinetic equations of crystal nucleation and the growth rate in a stirred crystallization system were fitted using population balance equations. The results demonstrate that the growth rate increases with increasing supersaturation and stirring rates. Additionally, the effects of the parameters in the nucleation rate equation suggested that the suspension density exerted the greatest influence, followed by the supersaturation ratio and stirring rate. This extensive research provides invaluable theoretical guidance for optimizing the crystallization process and designing industrial crystallizers. [ABSTRACT FROM AUTHOR]

Nucleation behaviors in glasses/supercooled liquids (SCLs) such as lithium disilicate Li2O–2SiO2, cordierite Mg2Al4Si5O18, fresnoite Ba2TiSi2O8, and K2O–Nb2O5–GeO2/TeO2 glasses were analyzed and discussed from the interfacial energy γ at SCL–nucleus interfaces and nanoscale composition fluctuations. Based on the fragility concept for SCLs and the intrinsic origin of γ, the magnitude order of γ(fragile SCL) < γ(strong SCL) was proposed to be a crucial guide for an understanding of high homogeneous nucleation rates and prominent nanocrystallization. The role of nucleating agent TiO2/ZrO2 in accelerating the nucleation rate in cordierite‐based and β‐spodumene‐type Li2O–Al2O3–SiO2‐based glasses was discussed from the new perspective of γ(homoepitaxial‐like nucleation) < γ(heteroepitaxial‐like nucleation). Ferroelectric nanocrystals such as SrxBa1–xNb2O6 in borate glasses and fluoride nanocrystals such as CaF2 are also well understood from the proposed guidelines. The present article provides a new perspective for nucleation in glasses/SCLs, contributing to the comprehensive composition design of new innovative glass‐ceramics. [ABSTRACT FROM AUTHOR]

Deposition and accumulation of amyloid fibrils is a hallmark of a group of diseases called amyloidosis and neurodegenerative disorders. Although polypeptides potentially have a fibril-forming propensity, native proteins have evolved into proper functional conformations to avoid aggregation and fibril formation. Understanding the mechanism for regulation of fibril formation of native proteins provides clues for the rational design of molecules for inhibiting fibril formation. Although fibril formation is a complex multistep reaction, experimentally obtained fibril formation curves can be fitted with the Finke-Watzky (F-W) two-step model for homogeneous nucleation followed by autocatalytic fibril growth. The resultant F-W rate constants for nucleation and fibril formation provide information on the chemical kinetics of fibril formation. Using the F-W two-step model analysis, we investigated the physicochemical mechanisms of fibril formation of a Parkinson's disease protein a-synuclein (aS) and a systemic amyloidosis protein apolipoprotein A-I (apoA-I). The results indicate that the C-terminal region of aS enthalpically and entropically suppresses nucleation through the intramolecular interaction with the N-terminal region and the intermolecular interaction with existing fibrils. In contrast, the nucleation of the N-terminal fragment of apoA-I is entropically driven likely due to dehydration of large hydrophobic segments in the molecule. Based on our recent findings, we discuss the similarity and difference of the fibril formation mechanisms of aS and the N-terminal fragment of apoA-I from the physicochemical viewpoints. [ABSTRACT FROM AUTHOR]

Herein, we demonstrate the synthesis of bifunctional nickel cobalt selenide@nickel telluride (NixCo12‐xSe@NiTe) core–shell heterostructures via an electrodeposition approach for overall urea electrolysis and supercapacitors. The 3D vertically orientated NiTe dendritic frameworks induce the homogeneous nucleation of 2D NixCo12‐xSe nanosheet arrays along similar crystal directions and bring a strong interfacial binding between the integrated active components. In particular, the optimized Ni6Co6Se@NiTe with an interface coupling effect works in concert to tune the intrinsic activity. It only needs a low overpotential of 1.33 V to yield a current density of 10 mA cm−2 for alkaline urea electrolysis. Meanwhile, the full urea catalysis driven only by Ni6Co6Se@NiTe achieves 10 mA cm−2 at a potential of 1.38 V and can approach a constant level of the current response for 40 h. Besides, the integrated Ni6Co6Se@NiTe electrode delivers an enhanced specific capacity (223 mA h g−1 at 1 A g−1) with a high cycling stability. Consequently, a hybrid asymmetric supercapacitor (HASC) device based on Ni6Co6Se@NiTe exhibits a favorable rate capability and reaches a high energy density of 67.7 Wh kg−1 and a power density of 724.8 W kg−1 with an exceptional capacity retention of 92.4% after sequential 12 000 cycles at 5 A g−1. [ABSTRACT FROM AUTHOR]

Highlights: The tailored KCoMnNiMgZnF3-HEC cathode delivers extremely high discharge capacity (22,104 mAh g−1), outstanding long-term cyclability (over 500 h), preceding majority of traditional catalysts reported. Entropy effect of multiple sites in KCoMnNiMgZnF3-HEC engenders appropriate regulation of 3d orbital structure, leading to a moderate hybridization with the p orbital of key intermediate. The homogeneous nucleation of Li2O2 is achieved on multiple cation site, contributing to effective mass transfer at the three-phase interface, and thus, the reversibility of O2/Li2O2 conversion. High-entropy catalysts featuring exceptional properties are, in no doubt, playing an increasingly significant role in aprotic lithium-oxygen batteries. Despite extensive effort devoted to tracing the origin of their unparalleled performance, the relationships between multiple active sites and reaction intermediates are still obscure. Here, enlightened by theoretical screening, we tailor a high-entropy perovskite fluoride (KCoMnNiMgZnF3-HEC) with various active sites to overcome the limitations of conventional catalysts in redox process. The entropy effect modulates the d-band center and d orbital occupancy of active centers, which optimizes the d–p hybridization between catalytic sites and key intermediates, enabling a moderate adsorption of LiO2 and thus reinforcing the reaction kinetics. As a result, the Li–O2 battery with KCoMnNiMgZnF3-HEC catalyst delivers a minimal discharge/charge polarization and long-term cycle stability, preceding majority of traditional catalysts reported. These encouraging results provide inspiring insights into the electron manipulation and d orbital structure optimization for advanced electrocatalyst. [ABSTRACT FROM AUTHOR]

In this study, according to the Dinger model, aqueous Si 3 N 4 slurries with a solid loading of 63 vol% and a viscosity lower than 1.0 Pa s were successfully prepared using two-grade Si 3 N 4 powders with D 50 = 7.2 μm and 9.4 μm as starting materials. These resulting slurries exhibited good rheological properties and suspension stability. Notably, the presence of β-Si 3 N 4 seeds existed in the starting materials effectively reduced the nucleation barrier by transforming homogeneous nucleation into heterogeneous nucleation. Consequently, it facilitated the reconstructive phase transformation of α-Si 3 N 4 to β-Si 3 N 4 , promoted the anisotropic growth of β-Si 3 N 4 nucleation, and resulted in the final formation of the bimodal microstructure. This unique microstructure significantly enhanced the mechanical properties of Si 3 N 4 ceramics, resulting in a high flexural strength of 1011.4 MPa and a fracture toughness of 14.8 MPa m1/2. These excellent properties were achieved through the combination of gelcasting and gas pressure sintering. Simultaneously, the Si 3 N 4 ceramics exhibited a low thermal conductivity of 47.7 W m−1 K−1, mainly owing to the low density of 95.3 %, the presence of low-thermal-conductivity silicate-based noncrystalline substances, and the possible existence of lattice oxygen in Si 3 N 4 crystals. [ABSTRACT FROM AUTHOR]

Warm Air Intrusions (WAI) are responsible for the transportation of warm and moist airmasses 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. RHi is affected by and can 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 are both geometrically and optically thicker compared to AC cirrus. WAI cirrus and the layer directly surrounding them, are more frequently supersaturated, also at high supersaturations over the threshold for homogeneous ice nucleation (HOM). AC cirrus have a supersaturation dominated cloud top and a subsaturated cloud base. WAI cirrus also have high supersaturations at cloud top, but also at cloud base. [ABSTRACT FROM AUTHOR]

The reactive crystallisation of ammonium di-uranate (NH4U2O7) from uranyl nitrate (UO2 (NO3)2) and ammonia (NH3) is a key process in the nuclear fuel cycle towards uranium-bearing fuel preparation. However, the process kinetics and mechanism remain poorly understood and the modelling of the reactive crystallisation of NH4U2O7(ADU) is not available. Hence, this work aims to determine the kinetics and mechanisms of the nucleation and growth of ADU through induction time measurements by comparing sonochemical and conventional precipitation methods. Induction was measured as functions of initial supersaturation starting from S = 1.07 to S = 1.875 and in a temperature range of 30 °C to 80 °C. The solubility data of ADU were also found experimentally. The trends in the experimental data suggest that two nucleation mechanisms co-exist: heterogeneous and homogeneous nucleation at low and high supersaturations respectively. Due to acoustic cavitation of the ultrasound prompting micromixing, the induction time is markedly reduced in the sonochemical route owing to the reduction of the energy barrier for nucleation. The induction time data were also analysed to calculate the interfacial energy (γ) and other parameters including the radius of the critical nucleus (r*), critical free energy of the nucleus (ΔG*) and nucleation rate (J). Determination of nucleation kinetics gives us insights into the fundamentals of the ADU crystallisation process for control and optimisation. [ABSTRACT FROM AUTHOR]

The flotation agent is an important collector in the production of potassium chloride and is brought into the crystallization stage with the reflux of the mother liquor. Octadecylamine Hydrochloride (ODA), 1-Dodecylamine Hydrochloride (DAH) and Sodium 1-dodecanesulfonate (SDS) were selected to study their effect on the nucleation of potassium chloride. Focused Beam Reflectance Measurement was used to collect the nucleation-induced periods of KCl in the presence of flotation agents at different supersaturations. Then, empirical equations, classical nucleation theory and growth mechanism equations were employed for data analysis. It was found that the presence of flotation agents increased the nucleation sequence m, and m(ODA) > m(SDS) > m(DAH) > m(H2O). In addition, the interfacial energy data obtained using classical nucleation theory suggest that the flotation agents used in our paper promoted the homogeneous nucleation of KCl (reduced from 5.3934 mJ·m−2 to 5.1434 mJ·m−2) and inhibited the heterogeneous nucleation of KCl (increased from 2.8054 mJ·m−2 to 3.6004 mJ·m−2). This investigation also revealed that the growth of potassium chloride was consistent with the 2D nucleation-mediated growth mechanism, and the addition of flotation agent did not change the growth mechanism of potassium chloride. Finally, the particle size distribution results were exactly consistent with the order of nucleation order m. The study of nucleation kinetics and growth mechanisms of different flotation agents on potassium chloride can provide guidance for optimizing the production process of potassium chloride and developing new flotation agents. [ABSTRACT FROM AUTHOR]

We present an asymptotic approach for the systematic investigation of the effect of gravity waves (GWs) on ice clouds formed through homogeneous nucleation. In particular, we consider high- and midfrequency GWs in the tropopause region driving the formation of ice clouds, modeled with a double-moment bulk ice microphysics scheme. The asymptotic approach allows for identifying reduced equations for self-consistent description of the ice dynamics forced by GWs including the effects of diffusional growth and nucleation of ice crystals. Further, corresponding analytical solutions for a monochromatic GW are derived under a single-parcel approximation. The results provide a simple expression for the nucleated number of ice crystals in a nucleation event. It is demonstrated that the asymptotic solutions capture the dynamics of the full ice model and accurately predict the nucleated ice crystal number. The present approach is extended to allow for superposition of GWs, as well as for variable ice crystal mean mass in the deposition. Implications of the results for an improved representation of GW variability in cirrus parameterizations are discussed. [ABSTRACT FROM AUTHOR]

In this work, the surface of single-wall carbon nanotubes (SWCNTs) was functionalized with amide group to improve the interfacial adhesion and dispersion of the SWCNT within an ultrahigh molecular weight polyethylene (UHMWPE) polymer matrix. The UHMWPE/SWCNTs nanocomposites were prepared by ultra-sonication mixing and hot press molding methods. Fourier transform infrared spectroscopy results confirm the amide functionalization. The prepared nanocomposites were characterized based on morphology, structure, and mechanical properties by scanning electron microscopy, X-ray diffraction, and a Universal Testing Machine, respectively. The crystallinity, crystal size, space between atomic lattice and lattice constant were calculated from XRD spectra. The results show an increase in the UHMWPE crystallinity when adding pristine SWCNTs and Amide-SWCNTs (1–5 wt %) due to changing the nucleation type of the UHMWPE from homogeneous to heterogeneous nucleation, which led to accelerating the nucleation process and the formation of more crystalline grains. The tensile test results show an increase in toughness of ~ 95% when adding 4 wt % Amide-SWCNTs. This indicates that the amide group achieved good interfacial adhesion and dispersion compared to pristine SWCNTs. [ABSTRACT FROM AUTHOR]

By theoretically considering the critical size during homogeneous nucleation and the atomic mass of different metals, the equation to determine the sizes of nanoparticles prepared by pulsed wire discharge (PWD) is revisited. The new equation is successful at predicting the sizes of Mg particles, for which submicrometer particles were previously reported to be prepared by PWD, even though their sizes were substantially larger than those of nanoparticles such as Cu, Ni, Ag, or Pd prepared by PWD. The temperature of the cross section of the plasma/vapor cloud at the midpoint of the wire when the plasma/vapor expansion attained its maximum volume was estimated to be approximately 0.7 times the boiling temperature of Mg and 0.56 times the boiling temperature of Cu, Ni, Ag, and Pd. These estimated temperatures are assumed to be nucleation temperature and can be predicted by the latent heat of vaporization. The critical sizes of the nanoparticles at these temperatures were calculated, which complemented the previously proposed equation for the determination of particle size by Tokoi et al. [Jpn. J. Appl. Phys. 52(5R), 055001 (2013)]. The estimated temperature T during this time was verified by investigating the temporal evolution of the temperature along the radial axis using conventional hydrodynamic equations. Mg and Cu wires were also experimentally discharged for comparison of the plasma/vapor cloud conditions during the time of interest using a high-speed camera. The consistency of the high-speed photographs with the simulation results, along with the validity for different nanoparticles prepared by PWD, confirmed the feasibility of the revisited equation. [ABSTRACT FROM AUTHOR]

The most intriguing hypothesis explaining many water anomalies is a metastable liquid–liquid phase transition (LLPT) at high pressure and low temperatures, experimentally hidden by homogeneous nucleation. Recent infrared spectroscopic experiments showed that upon addition of hydrazinium trifluoroacetate to water, the supercooled ionic solution undergoes a sharp, reversible LLPT at ambient pressure, possible offspring of that in pure water. Here, we calculate the temperature-dependent signature of the OH-stretching band, reporting on the low/high density phase of water, in neat water and in the same experimentally investigated ionic solution. The comparison between the infrared signature of the pure liquid and that of the ionic solution can be achieved only computationally, providing insight into the nature of the experimentally observed phase transition and allowing us to investigate the effects of ionic compounds on the high to low density supercooled liquid water transition. We show that the experimentally observed crossover behavior in the ionic solution can be reproduced only if the phase transition between the low- and high-density liquid states of water is coupled to a mixing–unmixing transition between the water component and the ions: at low temperatures, water and ions are separated and the water component is a low density liquid. At high temperatures, water and ions get mixed and the water component is a high-density liquid. The separation at low temperatures into ion-rich and ion-poor regions allows unveiling the polyamorphic nature of liquid water, leading to a crossover behavior resembling that observed in supercooled neat water under high pressure. [ABSTRACT FROM AUTHOR]

The buried interface has important effect on carrier extraction and nonradiative recombination of perovksite solar cells (PSCs). Herein, to inactivate the buried interfacial defects of perovskite and boost the crystallization quality of perovskite film, 3‐amino‐1‐adamantanol (AAD) serves as a pre‐buried interface modifier on nickel oxide (NiOx) surface to regulate the nucleation and crystallization process of perovskite precursor. The amino and hydroxyl groups in AAD molecule can synchronously coordinate with nickel ion (Ni3+) in NiOx and lead ion in perovskite, respectively. The dual action favors the ordered arrangement of AAD molecules between NiOx and perovskite, which not only enhances hole extraction in hole transport layer, but also provides active sites for homogeneous nucleation. Furthermore, AAD modifier blocks the unfavorable reaction between Ni3+ and perovskite, and effectively passivates the buried interfacial defects. The optimal inverted PSCs achieve a champion power conversion efficiency of 22.21% with negligible hysteresis, favorable thermal, optical, and long‐term stability. Thus, this strategy of modulating perovskite nucleation and crystallization by pre‐buried modifier is feasible for achieving efficient and stable inverted perovskite solar cells. [ABSTRACT FROM AUTHOR]

A physical understanding of the progression from flow‐driven (quasi‐static) poromechanical deformation to dynamic fault rupture is critical to the resilient operations of several engineering systems. These processes are bridged by a progression from fault reactivation to the spontaneous nucleation of unstable sliding. Toward addressing this challenge, novel automatic time step size control methods are developed to enable accurate and efficient simulation of these dynamics and transitions from the first principles. The controllers combine local models for discretization error and Coulomb failure conditions to automatically adjust the time step size across several orders of magnitude. The methods do not require additional empirical or theoretical input and can resolve the pre‐rupture, interseismic, and seismic periods to the allowed accuracy. The computational results reveal that the proposed methods automatically capture the onset of reactivation and nucleation for homogeneous and heterogeneous fields. Hydrodynamic and structural heterogeneity lead to disparate critical nucleation sizes compared to those predicted by theory. The results highlight its potential in predicting induced seismicity in realistic subsurface engineering systems and at practical scales. Key Points: Automatic time step controller to resolve flow, fault reactivation, and coseismic rupture under geologic complexity from first principlesSimultaneous local error control and monitoring of rupture progression to adapt the simulation time scale across seven orders of magnitudeSimulations (multiphase flow and inertial mechanics) of complex scenarios show alternative approaches can be significantly inaccurate [ABSTRACT FROM AUTHOR]

Separators swelling in aqueous electrolytes can cause inhomogeneous ion flux and unregulated dendrite propagation, yet the corresponding phenomenon and mitigation strategy are rarely studied. This article deals with the issue of pore structure variation caused by separator swelling in aqueous zinc‐ion batteries (AZBs) by employing nanocellulose separator as a representative example. A multifunctional separator composed of Zr4+‐hydrolysate‐coated nanocellulose (Zr‐CNF) is developed by in situ hydrolysis of Zr4+, which demonstrates excellent swelling resistance, pore‐structure stability, and percolating porosity due to cross‐linking and hydrogen bond shielding effect. Consequently, the homogeneous Zn‐ion flux, high ionic conductivity, and Zn2+ transfer number are maintained upon cycling. Moreover, the amorphous ZrO containing coating induces a homogeneous directional electric field around the interface, accelerating the Zn2+ influx, reducing the nucleation overpotential, and promoting homogeneous nucleation for Zn deposition. The Zr‐CNF separator enable dendrite‐free Zn anode with high Coulombic efficiency (99.7%) and exceptional cyclability for 680 h under 5 mA cm−2/5 mAh cm−2. The feasibility of the Zr‐CNF separator is verified in PANI/V2O5‐based AZBs and activated carbon‐based Zn‐ion capacitors. This study provides a facile approach to address separator swelling issue, enlightening novel insights into the efficient and sustainable aqueous battery technologies in the future. [ABSTRACT FROM AUTHOR]

We conduct nanoindentation to investigate dislocation nucleation in SrTiO3 (STO) single crystals with surface orientations of (0 0 1), (0 1 1), and (1 1 1) with loading/unloading rates of 25, 250, and 2500 μN/s. Results reveal that the critical loads (Pc) at which "pop‐in" event occurs depend strongly on surface orientations, but slightly related to loading rate. Based on Pc, the critical shear stress that triggers dislocation nucleation was determined by extracting the maximum resolved shear stress (τmax) along the slip systems of STO using the Hertzian solution. The dislocation activation shear stress (τa) was determined by averaging τmax. The determined τa is 9.0–12.0 GPa, close to the shear strength (∼G/2π) of STO, indicating that homogeneous dislocation nucleation dominates the pop‐in events. The consistency of the determined τa demonstrates that the frameworks for nanoindentation pop‐in analysis established for metals can be extended to ceramics, whereas the influence of the limited slip systems should be taken into consideration. Additionally, we estimated the activation volume and the activation energy via the statistical model proposed by Schuh et al. The small values of the determined activation volume (0.6–9.8 Å3) and the activation energy (0.13–0.70 eV) indicate that the dislocation nucleation possibly begins from a single‐atom migration and local point defects may participate in the dislocation nucleation process. That is, heterogeneous nucleation may exist initially but the homogeneous dislocation nucleation dominates the pop‐in events. [ABSTRACT FROM AUTHOR]

Aqueous Zn batteries are attracting extensive attentions, but their application is still hindered by H2O‐induced Zn‐corrosion and hydrogen evolution reactions. Addition of organic solvents into aqueous electrolytes to limit the H2O activity is a promising solution, but at the cost of greatly reduced Zn anode kinetics. Here we propose a simple strategy for this challenge by adding 50 mM iodine ions into an organic‐water (1,2‐dimethoxyethane (DME)+water) hybrid electrolyte, which enables the electrolyte simultaneously owns the advantages of low H2O activity and accelerated Zn kinetics. We demonstrate that the DME breaks the H2O hydrogen‐bond network and exclude H2O from Zn2+ solvation shell. And the I− is firmly adsorbed on the Zn anode, reducing the Zn2+ de‐solvation barrier from 74.33 kJ mol−1 to 32.26 kJ mol−1 and inducing homogeneous nucleation behavior. With such electrolyte, the Zn//Zn symmetric cell exhibits a record high cycling lifetime (14.5 months) and achieves high Zn anode utilization (75.5 %). In particular, the Zn//VS2@SS full cell with the optimized electrolyte stably cycles for 170 cycles at a low N : P ratio (3.64). Even with the cathode mass‐loading of 16.7 mg cm−2, the full cell maintains the areal capacity of 0.96 mAh cm−2 after 1600 cycles. [ABSTRACT FROM AUTHOR]

The perovskite solar cells (PSCs) are promising for commercialization and practical application. However, high‐quality perovskite films are normally fabricated in inert gas‐filled glovebox, followed by thermal annealing, which is energy‐consuming and thus not cost‐effective. In this study, a simple manufacturing strategy is demonstrated to fabricate the highly‐crystalline perovskite films in ambient air (a relative humidity of over ≈50%) at room temperature via blade‐coating without the subsequent thermal–annealing. The perovskite precursor chemistry is tailored by solvent engineering via employing 2‐methoxyethanol, which can strongly coordinate with ammonium halide species, thus forming highly uniform small‐sized colloids and facilitating the homogeneous nucleation and rapid crystallization of perovskite films even at room temperature. The resultant PSCs fabricated with ambient‐processed, annealing‐free MAPbI3 perovskite films exhibit a champion efficiency up to 19.16% with negligible hysteresis and improved reproducibility, which is on par with the high‐temperature annealed counterparts fabricated in N2, and represented one of the highest reported efficiencies for the room‐temperature processed PSCs in ambient air. The unencapsulated devices show extended lifespan over 1000 h with nearly no efficiency loss. [ABSTRACT FROM AUTHOR]

Cirrus clouds play an essential role in regulating the global radiative balance and climate by both reflecting the incoming shortwave solar radiation and reserving the outgoing longwave radiation in the atmosphere. The cirrus-induced net radiative forcing is mainly determined by their microphysical properties, which are strongly associated with the competition between two ice-nucleating mechanisms, i.e., heterogeneous and homogeneous nucleation. However, it is still not well understood whether the long-range transoceanic dust can potentially urge heterogeneous nucleation to the initial ice formation in cirrus clouds even farther over vast remote ocean regions and the response of dominant ice-nucleating mechanism to the concentrations of available ice nucleating particles (INPs). Here we report on the influence of transpacific dust plumes on the ice formation in cirrus clouds via heterogeneous nucleation based on the combined observations of space-borne instruments, i.e., the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) and Cloud Profiling Radar (CPR). Two cases near Midway Island (28.21° N, 177.38° W), located in the central Pacific, are studied, in which the long-range transported dust plumes originate from intense Asian dust events. For both cases, partial cloud parcels show the typical in-cloud ice crystal number concentrations (ICNC) of <100 L-1 for heterogeneous nucleation with a good agreement (within an order of magnitude) of in-cloud ICNC and nearby dust-related INP concentration (INPC) values, indicating that dust-related heterogeneous nucleation is dominated in ice formation. In addition, for the other parts of clouds without sufficient INP supply, homogeneous nucleation can still be dominated with ICNC values exceeding 300 L-1. Therefore, dust events with sufficient intensity are capable of conducting long-range transport and influencing cirrus formation over remote ocean regions. This study shows that the natural supply of effective INPs to the upper troposphere, such as long-range transported dust aerosols can increase the cloud cover to reflect more solar radiation over oceanic regions and modulate the microphysical properties of cirrus clouds through different ice-nucleating regimes, both of which may further result in a cooling effect on global climate and should be well considered in climate evaluation. [ABSTRACT FROM AUTHOR]

This study investigates the solid‐state structure of a copolymer composed of polyethylene glycol (PEG) and azacalixarene, which has two s‐triazine rings and two phenyl rings alternately crosslinked by amino groups. Azacalixarene derivatives containing a low‐molecular‐weight linker moiety and exhibiting an amorphous structure have been synthesized in previous studies; however, in this study, they are crystallized by the substitution of the linker moiety with PEG. The spherulites formed by the corresponding copolymer possess the ability to form higher‐order structures, growing up to a diameter of 1.7 mm depending on the crystallization conditions. The azacalixarene‐PEG copolymer forms negative spherulites via homogeneous nucleation and exhibits a lamellar period at 13.8 nm. The lamellar crystalline part itself is 5.8 nm in thickness; bulky amorphous regions are also observed in the copolymer structure. Reciprocal lattice analysis results reveal that the crystal parts form a packing structure similar to the crystal lattice of PEG. The promotion of spherulite growth is predicted to reflect the characteristics of the corresponding copolymer, which crystallizes while universally containing many amorphous regions. [ABSTRACT FROM AUTHOR]

Plagioclase microlites in a magma nucleate and grow in response to melt supersaturation (Δϕplag). The resultant frozen plagioclase crystal size distribution (CSD) preserves the history of decompression pathways (dP/dt). SNGPlag is a numerical model that calculates the equilibrium composition of a decompressing magma and nucleates and grows plagioclase in response to an imposed Δϕplag. Here, we test a new version of SNGPlag calibrated for use with basaltic andesite magmas and model dP/dt for the ca. 12.6 ka Curacautín eruption of Llaima volcano, Chile. Instantaneous nucleation (Nplag) and growth (Gplag) rates of plagioclase were computed using the experimental results of Shea and Hammer (J Volcanol Geotherm Res 260:127–145, 10.1016/j.jvolgeores.2013.04.018, 2013) and used for SNGPlag modeling of basaltic andesite composition. Maximum Nplag of 6.1 × 105 cm h−1 is achieved at a Δϕplag of 44% and the maximum Gplag of 27.4 μm h−1 is achieved at a Δϕplag of 29%. Our modeled log dP/dtavg range from 2.69 ± 0.09 to 6.89 ± 0.96 MPa h−1 (1σ) with an average duration of decompression from 0.87 ± 0.25 to 16.13 ± 0.29 h assuming a starting pressure Pi of 110–150 MPa. These rates are similar to those derived from mafic decompression experiments for other explosive eruptions. Using assumptions for lithostatic pressure gradients (dP/dz), we calculate ascent rates of < 1–6 m s−1. We conducted a second set of Monte Carlo simulations using Pi of 15–30 MPa to investigate the influence of shallower decompression, resulting in log dP/dtavg from 2.86 ± 0.49 to 6.00 ± 0.86 MPa h−1. The dP/dt modeled here is two orders of magnitude lower than those calculated by Valdivia et al. (Bull Volcanol, 10.1007/s00445-021-01514-8, 2022) for the same eruption using a bubble number density meter, and suggests homogeneous nucleation raises dP/dt by orders of magnitude in the shallow conduit. Our modeling further supports the rapid-ascent hypothesis for driving highly explosive mafic eruptions. [ABSTRACT FROM AUTHOR]

In this study, the effect of the initial phases of the Si-bearing near-α titanium alloy Ti–6Al–2.75Sn–4Zr–0.4Mo–0.45Si (Ti-1100) on Vickers microhardness during aging at 600°C from 5 min to 42 days was investigated by transmission electron microscopy. The initial phases included α′ martensite and α phases. The variation in the hardness of the specimen with the initial α′ martensite phase occurred in the following order: the decrease caused by dislocation recovery, the increase caused by silicide precipitation, the decrease caused by silicide coarsening, and the increase caused by α² precipitation. As for the initial α phase, hardness initially decreased and then increased because of dislocation recovery and silicide/α² precipitation, respectively. The difference in age-hardening behavior resulted from the difference between the dislocation amounts in the two initial phases. Silicide precipitation was promoted by dislocations, whereas α² precipitation occurred via homogeneous nucleation irrespective of the dislocations. [ABSTRACT FROM AUTHOR]

The critical cooling rates, required for suppressing the crystallization of Fe40Ni40P14B6 melt, were estimated in the frames of the classical crystallization theory (homogeneous nucleation, linear isotropic growth, and kinetics according to the Johnson–Mehl–Avrami–Kolmogorov model). Estimations were made using the calculated time–temperature–transformation isothermal diagrams as well as the Kolmogorov integral equation, written for the case of continuous cooling. Temperature dependences of crystal nucleation and growth rates were calculated using both thermodynamic and kinetic parameters, governing the formation of crystals in the amorphous phase, as well as by the three-parameter temperature-dependent diffusion coefficient, proposed in this work. The critical cooling rates for various equation combinations, describing crystal nucleation and growth, critical cooling rates have been determined, and the conditions for correct prediction of the Fe40Ni40P14B6 melt tendency to amorphization have been established. [ABSTRACT FROM AUTHOR]

New homogeneous nucleation experiments are presented at 240 K for water in carrier gas mixtures of nitrogen with carbon dioxide molar fractions of 5%, 15%, and 25%. The pulse expansion wave tube is used to test three different pressure conditions, namely, 0.1, 1, and 2 MPa. In addition, a restricted series of nucleation experiments is presented for 25% carbon dioxide mixtures at temperatures of 234 and 236 K at 0.1 MPa. As pressure and carbon dioxide content are increased, the nucleation rate increases accordingly. This behavior is attributed to the reduction in the water surface tension by the adsorption of carrier gas molecules. The new data are compared with theoretical predictions based on the classical nucleation theory and on extrapolations of empirical surface tension data to the supercooled conditions at 240 K. The extrapolation is carried out on the basis of a theoretical adsorption/surface tension model, extended to multi-component mixtures. The theoretical model appears to strongly overestimate the pressure and composition dependence. At relatively low pressures of 0.1 MPa, a reduction in the nucleation rates is found due to an incomplete thermalization of colliding clusters and carrier gas molecules. The observed decrease in the nucleation rate is supported by the theoretical model of Barrett, generalized here for water in multi-component carrier gas mixtures. The temperature dependence of the nucleation rate at 0.1 MPa follows the scaling model proposed by Hale [J. Chem. Phys. 122, 204509 (2005)]. [ABSTRACT FROM AUTHOR]

High energy ball milling of metallic powders leads to high reactivity in the milled mixture. The reaction is often faster and starts at a lower temperature. However, the mechanisms responsible for this high reactivity are not yet completely understood. The aim of this study is to evaluate one of the possible activating factors of this heightened reactivity: nano-scale mixing of the reagents. Molecular dynamics was used to analyze the role of an amorphous Ni–Al mixing layer, mimicking the powder microstructure after milling, between two Ni layers. The impact of temperature and stoichiometry was investigated in relation to the formation of the B 2 -NiAl intermetallic compound. At low temperatures, pre-mixing does not seem to slow down the diffusion of Ni atoms in an amorphous Al region. Homogeneous nucleation was observed in this peculiar milled microstructure. These two phenomena explain why the nano-scale mixing observed experimentally after high energy milling is indeed an activating factor in the reactivity of metallic systems such as Ni–Al. [ABSTRACT FROM AUTHOR]

It is demonstrated for 11 different combinations of organic solutes and solvents that the supersaturation dependence of homogeneous organic crystal nucleation rates from solution can be predicted from the solubility, bar a single empirical rate constant, when it is assumed that nucleation takes place in reversible aggregates of solvated solutes formed in supersaturated solutions. Reversible solute aggregation represents natural solute density fluctuations that take place in any solute/solvent system. For thermodynamically ideal solutions, the steady state size distribution, and thus the population of reversible aggregates in supersaturated solution, can be predicted quantitatively from the overall solute concentration by a simple mathematical expression. Supersaturation creates an excess of reversible aggregates with sizes exceeding that of the largest aggregate in saturated solution. It is shown that the number of these excess aggregates is proportional to experimental homogeneous nucleation rates, suggesting a rate equation for homogeneous nucleation that has only one empirical parameter, namely, a rate constant specific to the solute/solvent combination. This rate constant can be determined from standard nucleation rate data. The system-specificity of homogeneous nucleation rates thus appears to be encoded solely in a rate constant for the transformation of the large excess aggregates into crystal nuclei. The driving force for triggering nucleation events in these aggregates is likely the extremely high local supersaturation, which provides the conditions for spatiotemporally aligned bond-breaking (e.g., de-solvation) and bond-forming (e.g., solute–solute bonding) events that create stable crystal nuclei. The possible influence of heterogeneous nucleation by solid impurities is considered.

Homogeneous nucleation of water is investigated in argon and in nitrogen at about 240 K and 0.1 MPa, 1 MPa, and 2 MPa by means of a pulse expansion wave tube. The surface tension reduction at high pressure qualitatively explains the observed enhancement of the nucleation rate of water in argon as well as in nitrogen. The differences in nucleation rates for the two mixtures at high pressure are consistent with the differences in adsorption behavior of the different carrier gas molecules. At low pressure, there is not enough carrier gas available to ensure the growing clusters are adequately thermalized by collisions with carrier gas molecules so that the nucleation rate is lower than under isothermal conditions. This reduction depends on the carrier gas, pressure, and temperature. A qualitative agreement between experiments and theory is found for argon and nitrogen as carrier gases. As expected, the reduction in the nucleation rates is more pronounced at higher temperatures. For helium as the carrier gas, non-isothermal effects appear to be substantially stronger than predicted by theory. The critical cluster sizes are determined experimentally and theoretically according to the Gibbs–Thomson equation, showing a reasonable agreement as documented in the literature. Finally, we propose an empirical correction of the classical nucleation theory for the nucleation rate calculation. The empirical expression is in agreement with the experimental data for the analyzed mixtures (water–helium, water–argon, and water–nitrogen) and thermodynamic conditions (0.06 MPa–2 MPa and 220 K–260 K). [ABSTRACT FROM AUTHOR]