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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]

The task of a first principles theoretical calculation of the rate of gas–liquid nucleation has remained largely incomplete despite the existence of reliable results from unbiased simulation studies at large supersaturation. Although the classical nucleation theory formulated by Becker–Doring–Zeldovich about a century ago provides an elegant, widely used picture of nucleation in a first-order phase transition, the theory finds difficulties in predicting the rate accurately, especially in the case of gas-to-liquid nucleation. Here, we use a multiple-order parameter description to construct the nucleation free energy surface needed to calculate the nucleation rate. A multidimensional non-Markovian (MDNM) rate theory formulation that generalizes Langer's well-known nucleation theory by using the Grote–Hynes MDNM treatment is used to obtain the rate of barrier crossing. We find good agreement of the theory with the rate obtained by direct unbiased molecular dynamics simulations—the latter is feasible at large supersaturation, S. The theory gives an experimentally strong dependence of the rate of nucleation on supersaturation, S. Interestingly, we find a strong influence of the frequency-dependent friction coefficient at the barrier top. This arises from multiple recrossings of the barrier surface. We find that a Markovian theory, such as Langer's formulation, fails to capture the rate quantitatively. In addition, the multidimensional transition state theory expression performs poorly, revealing the underlying role of the friction coefficient. [ABSTRACT FROM AUTHOR]

Flow-enhanced nucleation (FEN) of n-pentacontahectane (C150) under biaxial extensional flows of varying strain rate ratios is studied using nonequilibrium molecular dynamics simulation. The nucleation rates thus calculated are used to test previously published FEN models based on invariants of the conformation tensor of Kuhn segments and the extra stress tensor. Models based on the conformation tensor provide a more accurate description of FEN observed in biaxial flow simulations than those based on the extra stress tensor. In addition, the formation of nematic domains previously reported to be stabilized by shear or extensional flow is absent in equibiaxial flows. However, such domains do form in non-equibiaxial flows, and nucleation occurs in these domains preferentially. The shape and orientation of nuclei formed under biaxial flows of various strengths and strain rate ratios are also reported. [ABSTRACT FROM AUTHOR]

Molecular-level nucleation has not been clearly understood due to the complexity of multi-body potentials and the stochastic, rare nature of the process. This work utilizes molecular dynamics (MD) simulations, incorporating a first-principles-based deep neural network (DNN) potential model, to investigate homogeneous water vapor condensation. The nucleation rates and critical nucleus sizes predicted by the DNN model are compared against commonly used semi-empirical models, namely extended simple point charge (SPC/E), TIP4P, and OPC, in addition to classical nucleation theory (CNT). The nucleation rates from the DNN model are comparable with those from the OPC model yet surpass the rates from the SPC/E and TIP4P models, a discrepancy that could mainly arise from the overestimated bulk free energy by SPC/E and TIP4P. The surface free energy predicted by CNT is lower than that in MD simulations, while its bulk free energy is higher than that in MD simulations, irrespective of the potential model used. Further analysis of cluster properties with the DNN model unveils pronounced variations of O–H bond length and H–O–H bond angle, along with averaged bond lengths and angles that are enlarged during embryonic cluster formation. Properties such as cluster surface free energy and liquid-to-vapor density transition profiles exhibit significant deviations from CNT assumptions. [ABSTRACT FROM AUTHOR]

According to the classic theory of nucleation around a charged particle, dipoles induced in the particle's neighbors by the charged nucleation center decrease the electric field around it. This reduces the system's Gibbs energy and thus increases the nucleation rate. Unlike the situation of a neutral gas and an already existing charged particle, in plasma, charging the center of nucleation is the result of the separation of charges (a negatively charged center and a positively charged surrounding). This process being similar to charging of a capacitor, it demands extra energy, and thus increases the Gibbs energy. As a result, the nucleation rate decreases in comparison with the nucleation rate in a neutral medium. In this work, the process of nucleation in a plasma is considered and the nucleation rate is calculated. It is shown that for the conditions typical for arcs used for the production of nanoparticles, the reduction in the nucleation rate is an order of magnitude or higher. [ABSTRACT FROM AUTHOR]

We investigate the nucleation dynamics of the three-dimensional random field Ising model under an external field. We use umbrella sampling to compute the free-energy cost of a critical nucleus and use forward flux sampling for the direct estimation of nucleation rates. For moderate to strong disorder, our results indicate that the size of the nucleating cluster is not a good reaction coordinate, contrary to the pure Ising model. We rectify this problem by introducing a coordinate that also accounts for the location of the nucleus. Using the free energy barrier to predict the nucleation rate, we find reasonable agreement, although deviations become stronger as disorder increases. We attribute this effect to cluster shape fluctuations. We also discuss finite-size effects on the nucleation rate. [ABSTRACT FROM AUTHOR]

Molecular dynamics simulations have been widely used in exploring the nucleation behavior of many systems, including gas hydrates. Gas hydrates are ice-like solids in which gas molecules are trapped in water cages. During hydrate formation, a considerable amount of heat is released, and previous work has reported that the choice of temperature control scheme may affect the behavior of hydrate formation. The origins of this effect have remained an open question. To address this question, extensive NVE simulations and thermostatted (NPT and NVT) simulations with different temperature coupling strengths have been performed and compared for systems where a water nanodroplet is immersed in a H2S liquid. Detailed analysis of the hydrate structures and their mechanisms of formation has been carried out. Slower nucleation rates in NVE simulations in comparison to NPT simulations have been observed in agreement with previous studies. Probability distributions for various temperature measures along with their spatial distributions have been examined. Interestingly, a comparison of these temperature distributions reveals a small yet noticeable difference in the widths of the distributions for water. The somewhat reduced fluctuations in the temperature for the water species in the NVE simulations appear to be responsible for reducing the hydrate nucleation rate. We further conjecture that the NVE-impeded nucleation rate may be the result of the finite size of the surroundings (here the liquid H2S portion of the system). Additionally, a local spatial temperature gradient arising from the heat released during hydrate formation could not be detected. [ABSTRACT FROM AUTHOR]

The work W to form a nucleus (also known as the critical nucleus) is a key quantity in the description of nucleation phenomena because of its exponentially strong effect on the nucleation rate. The present study provides a general approximate expression for W, which comprises a hierarchy of approximations to the dependence of W on the experimentally controlled overpressure Δp of a nucleating multicomponent phase. This general expression is used to derive explicit formulas for the lowest-order members of the W(Δp) hierarchy as well as for the respective lowest-order approximations to the Δp dependences of the nucleus surface tension, the nucleus radius, the Gibbs–Tolman length, and the stationary nucleation rate. The second-order and the third-order approximations to the W(Δp) dependence are confronted with available W(Δp) data, and the latter is found to agree very well with the data. The results obtained are applicable to homogeneous single-component or multicomponent nucleation from the binodal to the spinodal of the old phase, i.e., in the entire range of the old-phase metastability. [ABSTRACT FROM AUTHOR]

The propensity of water to remain in a metastable liquid state at temperatures below its equilibrium melting point holds significant potential for cryopreserving biological material such as tissues and organs. The benefits conferred are a direct result of progressively reducing metabolic expenditure due to colder temperatures while simultaneously avoiding the irreversible damage caused by the crystallization of ice. Unfortunately, the freezing of water in bulk systems of clinical relevance is dominated by random heterogeneous nucleation initiated by uncharacterized trace impurities, and the marked unpredictability of this behavior has prevented the implementation of supercooling outside of controlled laboratory settings and in volumes larger than a few milliliters. Here, we develop a statistical model that jointly captures both the inherent stochastic nature of nucleation using conventional Poisson statistics as well as the random variability of heterogeneous nucleation catalysis through bivariate extreme value statistics. Individually, these two classes of models cannot account for both the time-dependent nature of nucleation and the sample-to-sample variability associated with heterogeneous catalysis, and traditional extreme value models have only considered variations of the characteristic nucleation temperature. We conduct a series of constant cooling rate and isothermal nucleation experiments with physiological saline solutions and leverage the statistical model to evaluate the natural variability of kinetic and thermodynamic nucleation parameters. By quantifying freezing probability as a function of temperature, supercooled duration, and system volume while accounting for nucleation site variability, this study also provides a basis for the rational design of stable supercooled biopreservation protocols. [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]

We provide experimental observations of the nucleation and growth of water capillary bridges in nanometer gaps between a laterally moving atomic force microscope probe and a smooth silicon wafer. We find rising nucleation rates with increasing lateral velocity and a smaller separation gap. The interplay between nucleation rate and lateral velocity is attributed to the entrainment of water molecules into the gap by the combination of lateral motion and collisions of the water molecules with the surfaces of the interface. The capillary volume of the full-grown water bridge increases with the distance between the two surfaces and can be limited by lateral shearing at high velocities. Our experimental results demonstrate a novel method to study in situ how water diffusion and transport impact dynamic interfaces at the nanoscale, ultimately leading to friction and adhesion forces at the macroscale. [ABSTRACT FROM AUTHOR]

One of the most accepted hypothesis to explain the anomalous behavior of water is the presence of a critical point between two liquids, the liquid–liquid critical point (LLCP), buried within the deep supercooled regime. Unfortunately, such hypothesis is hard to be experimentally confirmed due to fast freezing. Here, we show that the TIP4P/Ice water potential shifted by 400 bar can reproduce with unprecedented accuracy the experimental isothermal compressibility of water and its liquid equation of state for a wide pressure and temperature range. We find, both by extrapolation of response function maxima and by a Maxwell construction, that the location of the model LLCP is consistent with previous calculations. According to the pressure shift needed to recover the experimental behavior of supercooled water, we estimate the experimental LLCP to be located around 1250 bar and 195 K. We use the model to estimate the ice nucleation rate (J) in the vicinity of the hypothesized LLCP experimental location and obtain J = 1024 m−3 s−1. Thereby, experiments where the ratio between the cooling rate and the sample volume is equal or larger than the estimated nucleation rate could probe liquid–liquid equilibrium before freezing. Such conditions are not accessible in common experiments with microdroplets cooled at a few kelvin per second, but they could be, for instance, using nanodroplets of around 50 nm radius observed in a millisecond timescale. [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]

In this study, the hydration kinetics of ultrahigh-performance concrete (UHPC) with carbon nanofibers (CNFs) are investigated. According to classic nucleation theory, nanomaterials, such as CNFs applied in cementitious materials, can act as nucleating sites for hydration products, accelerating the hydration process. While the increased surface area governs the hydration reaction rate in classic nucleation theory, test results for CNFs in UHPC have provided the opposite trend. Namely, the addition of CNFs caused retardation of the hydration reaction. This observation could be due to the pretreatment of CNFs: the application of chemical surfactant and the ultrasonic dispersion process (UDP). Due to van der Waal's forces and the hydrophobic property of the fibers, CNFs tend to bundle together during the mixing stage with cementitious material. The chemical surfactants and UDP are applied to CNFs to avoid this agglomeration and enable dispersion. The selected chemical surfactant, a polycarboxylate-ether-based high-range water reducer (HRWR), has been proven to retard the hydration process. In this study, we find that the UDP further enhances the functionality of the effects of the HRWR, such that the retardation action of the HRWR dominates the hydration kinetics. Different amounts of HRWR and CNFs were used in this study, and their effect on hydration kinetics was studied using an isothermal conduction calorimeter (ICC). The behavior of the modified samples was compared with UHPC controls without any modifications. A new hydration model was developed based on the data collected from the ICC results. This model enables the prediction of the heat production rate as a function of the fineness modulus and the HRWR:CNF ratio (R). [ABSTRACT FROM AUTHOR]

• Limitations of applying theory to predict heterogeneous ice nucleation are discussed. • Models for describing ice nucleation on a surface are reviewed. • Experimental methods for nucleation measurements are analyzed. • Statistical analysis techniques for freezing delay data is discussed. • Machine learning models for heterogeneous ice nucleation are reviewed. The freezing of water on surfaces is an important phase change process with an outsized influence in both natural and engineered systems. Liquid water below the melting temperature can persist for a finite time in a metastable, supercooled state until freezing initiates through nucleation, a process enhanced by the presence of a surface. Despite the importance of this phenomenon, current methods remain inadequate to predict ice nucleation rates across surface types, and experimental data is difficult to compare due to the differing methodologies used, limiting further understanding. This review synthesizes established frameworks modeling ice nucleation and analyzes limitations in applying classical nucleation theory toward quantitative prediction. Simplified, theory-inspired models used to describe the nucleation rate as a function of temperature are discussed. Additionally, models describing how the ice nucleation rate may vary across a surface are compared. Current experimental methods for measuring ice nucleation rates on surfaces are assessed for their ability to produce accurate data that can lead to greater consistency between studies. Variability in results based on factors such as humidity and triple interface effects are discussed. Statistical analysis approaches for experimental freezing data are reviewed. Experimental observations of nonstationary ice nucleation in an unexpectedly large time scale are discussed in the context of experimental methods. Finally, the potential of emerging machine learning techniques to aid in predicting heterogeneous ice nucleation is discussed. [Display omitted] [ABSTRACT FROM AUTHOR]

This study explores the hot deformation behavior of Al–Zn–Mg–Cu alloy through uniaxial hot compression (200 °C–450°C) using the Gleeble-1500. True stress–strain curves were corrected, and three models were established: the Arrhenius model, strain compensated (SC) Arrhenius model, and strain compensated recrystallization temperature (RT) segmentation-based (TS-SC) Arrhenius model. Comparative analysis revealed the limited predictive accuracy of the SC Arrhenius model, with a 25.12% average absolute relative error (AARE), while the TS-SC Arrhenius model exhibited a significantly improved to 9.901% AARE. Material parameter calculations displayed variations across the temperature range. The SC Arrhenius model, utilizing an average slope method for parameter computation, failed to consider temperature-induced disparities, limiting its predictive capability. Hot processing map, utilizing the Murty improved Dynamic Materials Model (DMM), indicated optimal conditions for stable forming of the Al–Zn–Mg–Cu alloy. Microstructural analysis revealed MgZn2 precipitation induced by hot deformation, with crystallographic defects enhancing nucleation rates and precipitate refinement. [ABSTRACT FROM AUTHOR]

The microstructure and mechanical properties of marine 10Ni5CrMoV steel are systematically investigated at tempering temperatures ranging from 630 to 670 °C. With increasing tempering temperature, several key parameters exhibit notable changes: the volume fraction of reversed austenite decreases from 17.36% to 13.39%. The equivalent grain size increases from 0.91 to 1.09 μm. The equivalent diameter of precipitates increases from 59 to 79 nm. The dislocation density decreases from 0.82 × 10−15 to 0.51 × 10−15 m−2. As the tempering temperature increases, the pinning effect of precipitates on dislocations and martensite laths decreases. This leads to reductions in both dislocation strengthening and precipitation strengthening mechanisms. Consequently, the yield strength of the specimen decreases from 876 to 683 MPa. The increase in the ductile‐brittle transition temperature of the specimens from −116 to −95 °C can be attributed to several factors. First, the increase in precipitate size reduces the critical nucleation stress of cleavage cracks and promotes the nucleation of such cracks. Additionally, the decrease in dislocation density mobility leads to a reduction in the dimple nucleation rate, thereby diminishing the role of dimples in hindering crack propagation. [ABSTRACT FROM AUTHOR]

Metal–organic framework (MOF) membranes with rich functionality and tunable pore system are promising for precise molecular separation; however, it remains a challenge to develop defect‐free high‐connectivity MOF membrane with high water stability owing to uncontrollable nucleation and growth rate during fabrication process. Herein, we report on a confined‐coordination induced intergrowth strategy to fabricate lattice‐defect‐free Zr‐MOF membrane towards precise molecular separation. The confined‐coordination space properties (size and shape) and environment (water or DMF) were regulated to slow down the coordination reaction rate via controlling the counter‐diffusion of MOF precursors (metal cluster and ligand), thereby inter‐growing MOF crystals into integrated membrane. The resulting Zr‐MOF membrane with angstrom‐sized lattice apertures exhibits excellent separation performance both for gas separation and water desalination process. It was achieved H2 permeance of ~1200 GPU and H2/CO2 selectivity of ~67; water permeance of ~8 L ⋅ m−2 ⋅ h−1 ⋅ bar−1 and MgCl2 rejection of ~95 %, which are one to two orders of magnitude higher than those of state‐of‐the‐art membranes. The molecular transport mechanism related to size‐sieving effect and transition energy barrier differential of molecules and ions was revealed by density functional theory calculations. Our work provides a facile approach and fundamental insights towards developing precise molecular sieving membranes. [ABSTRACT FROM AUTHOR]

Metal–organic framework (MOF) membranes with rich functionality and tunable pore system are promising for precise molecular separation; however, it remains a challenge to develop defect‐free high‐connectivity MOF membrane with high water stability owing to uncontrollable nucleation and growth rate during fabrication process. Herein, we report on a confined‐coordination induced intergrowth strategy to fabricate lattice‐defect‐free Zr‐MOF membrane towards precise molecular separation. The confined‐coordination space properties (size and shape) and environment (water or DMF) were regulated to slow down the coordination reaction rate via controlling the counter‐diffusion of MOF precursors (metal cluster and ligand), thereby inter‐growing MOF crystals into integrated membrane. The resulting Zr‐MOF membrane with angstrom‐sized lattice apertures exhibits excellent separation performance both for gas separation and water desalination process. It was achieved H2 permeance of ~1200 GPU and H2/CO2 selectivity of ~67; water permeance of ~8 L ⋅ m−2 ⋅ h−1 ⋅ bar−1 and MgCl2 rejection of ~95 %, which are one to two orders of magnitude higher than those of state‐of‐the‐art membranes. The molecular transport mechanism related to size‐sieving effect and transition energy barrier differential of molecules and ions was revealed by density functional theory calculations. Our work provides a facile approach and fundamental insights towards developing precise molecular sieving membranes. [ABSTRACT FROM AUTHOR]

High-strength low-alloy steels are widely used, but their traditional heat-treatment process is complex, energy-intensive, and makes it difficult to fully exploit the material's potential. In this paper, the electropulsing processing technology was applied to the quenching and tempering process of ZG25SiMn2CrB steel. Through microstructural characterization and mechanical property testing, the influence of electropulsing on the solid-state phase transition process of annealing steel was systematically studied. The heating process of the specimen with the annealing state (initial state) is the diffusion-type transition. As the discharge time increased, the microstructure gradually transformed from ferrite/pearlitic to slate martensite. Optimal mechanical properties and fine microstructure were achieved after quenching at 500 ms. The steel subjected to rapid tempering with 160 ms electropulsing exhibited good, comprehensive mechanical properties (tensile strength 1609 MPa, yield strength 1401.27 MPa, elongation 11.63%, and hardness 48.68 HRC). These favorable mechanical properties are attributed to the coupled impact of thermal and non-thermal effects induced by high-density pulse current. Specifically, the thermal effect provides the thermodynamic conditions for phase transformation, while the non-thermal effect reduces the nucleation barrier of austenite, which increases the nucleation rate during instantaneous heating, and the following rapid cooling suppresses the growth of austenite grains. Additionally, the fine microstructure prevents the occurrence of temper brittleness. [ABSTRACT FROM AUTHOR]

Crystal nucleating agents offer an effective strategy for controlling the morphology, dimensional stability and rate of solidification of polymers during processing. Molecular dynamics (MD) simulation can shed light on nucleation behavior at the nanoscopic length and time scales over which nucleation occurs. In this work, crystal nucleation of a polyethylene oligomer, n-pentacontane, on three graphene-like substrates, hexagonal boron nitride (hBN), molybdenum disulfide (MoS2), and tungsten disulfide (WS2), was simulated, and the thermodynamic efficiencies of these substrates as nucleating agents were determined. Experimental measurements of heterogeneous nucleation of a high-density polyethylene on nanoparticles of these three graphene-like materials were performed using the method of dispersed microdroplets in an immiscible polystyrene matrix. Qualitative agreement between simulations and experiments was observed for trends in nucleation rate, J, and interfacial free energy difference, Δσ, with J hBN > J MoS 2 > J WS 2 . The simulations are then used to gain additional insight into the mechanisms of nucleation. Epitaxy is confirmed in all systems, with small mismatches in lattice spacing being accommodated by strain in the oligomer crystal. However, epitaxy alone is insufficient to explain the observed trends. The strength of interaction between the nucleating agent and the polyethylene oligomer is found to be the strongest predictor of nucleating agent efficiency. The strength of interaction is in turn related to the density of interaction sites at the interface: hBN has the highest density, and thus the fastest nucleation rate. [ABSTRACT FROM AUTHOR]

The formation of new mineral phases in confined environments, especially in porous media, is crucial for various geological processes like mineralization and diagenesis. The nucleation and precipitation of minerals are initiated at the microscale through fluid‐rock interaction, where dissolution of primary phases leads to supersaturated conditions and nucleation and growth of secondary ones. Previous research has focused primarily on either precipitation or nucleation, without fully exploring their combined impact. Our study introduces a computational framework that integrates classical nucleation theory with the micro‐continuum method. We validated our model by comparing with experiments, and discovered that different surface nucleation rate changes the mode of precipitation from a preferential to uniform precipitate textures. Furthermore, our study uncovered that the conventional deterministic precipitation method tends to underestimate the permeability of the porous matrix. In contrast, the new framework significantly improves model accuracy by incorporating preferential precipitation and heterogeneous nucleation. Plain Language Summary: The formation of minerals in confined environments, especially in porous media, is important for both natural processes and industrial applications. The resulting solid phases can greatly affect the porosity and permeability of the porous structure. Many previous studies have focused on either nucleation or precipitation, we still have a limited understanding of how both processes interact at different scales. In this study, we integrated the Darcy‐Brinkman‐Stokes method and classical nucleation theory to investigate the interplay between nucleation, precipitation, species transport, and their impact on permeability. Our findings show that adjusting the surface nucleation rates can change the mode of mineral precipitation from preferential to uniform. We also found that the traditional deterministic precipitation method underestimates permeability in certain scenario. Therefore, considering probabilistic nucleation is crucial when there is preferential precipitation and heterogeneous nucleation on the interfaces between the minerals and surrounding liquid under reactive flow conditions. Key Points: The proposed computational framework focuses on investigating the heterogeneity of nucleation and its effects on mineral precipitationThe new model is validated by comparing with experimental data, demonstrating an agreement in both nucleation morphology and rateThe new model integrates probabilistic nucleation, resulting in a notable enhancement in the accuracy of permeability predictions [ABSTRACT FROM AUTHOR]

2‐Methoxyethanol (2ME), as a more environmentally friendly solvent with a lower boiling point compared to dimethylformamide, is ideal for the fabrication of perovskite solar cells (PSCs). However, when 2ME is used for antisolvent‐free deposition of perovskite films, an uncontrolled nucleation process and an easy phase transition to the δ‐phase often occur. Herein, an ultrafast nucleation process is developed using methylamine chloride (MACl) and n‐butylammonium chloride (BACl) as dual additives in 2ME without further solvent addition. While MACl can rapidly induce MACl‐based nuclei to initiate the nucleation process for formamidinium lead iodide (FAPbI3), the addition of BACl to the precursor with MACl can further increase the nucleation rate and density of nuclei, and bypass the transition from δ‐ to α‐phase during crystal growth to obtain a highly crystalline and pinhole‐free perovskite film. As a result, the FAPbI3 PSCs achieve a power conversion efficiency (PCE) of 23.6%. This work provides a new inspiration for controlling the crystal quality of perovskite thin films via nucleation rate suitable for upscaling. [ABSTRACT FROM AUTHOR]

The slow formation rate and low nucleation rate of carbon dioxide hydrate were common problems in current research. Many scholars focused on the promotion of gas hydrates by carbon nanotubes, whereas they ignored carbon microtubes, which were similar in structure and properties to carbon nanotubes and had more structural advantages. In this article, the effects of system temperature (1, 2, and 3 °C), pressure (3, 3.5, and 4 MPa), gas–liquid ratio (3:2, 4:1, and 5:1) and different types of carbon microtube concentration (0.01, 0.05, and 0.1 mg/mL) on the growth kinetics of carbon dioxide hydrate were investigated using orthogonal experiment method in a high-pressure reactor. The results revealed that compared to the pure carbon microtube system, amination, carboxylation, and hydroxylation carbon microtube systems improved the probability of carbon dioxide hydrate generation by 11–22%, with the shortest induction time of 0.23 hour. The highest gas storage capacity was 31.71 V/V under the carboxylated carbon microtube system. In the pure carbon, aminocarbon, carboxylated carbon and hydroxylated carbon microtube systems, the primary factors affecting the induction time were temperature, gas–liquid ratio, pressure and concentration. The gas–liquid ratio was the primary factor influencing the gas storage capacity of the carboxylated carbon microtubes; however, temperature was the primary factor affecting the gas storage capacity of the remaining three systems. Finally, we compared the effects of modified hydrophilic groups on the formation of carbon dioxide hydrate and made a conjecture. [ABSTRACT FROM AUTHOR]

It is a valid path to realize the zero discharge of coal chemical wastewater by using the fractional crystallization method to recycle the miscellaneous salt in high-salinity wastewater. In this study, the thermodynamics and nucleation kinetics of sodium chloride (NaCl) and sodium sulfate (Na2SO4) crystallization in coal chemical wastewater were systematically studied. Through analyses of solubility, metastable zone width, and induction period, it was found that the impurity dimethoxymethane would increase the solid–liquid interface energy and critical crystal size during the nucleation of Na2SO4. Ternary phase diagrams of the pseudo-ternary Na2SO4-NaCl-H2O systems in simulated wastewater were plotted in the temperature range of 303.15 to 333.15 K, indicating that a co-ionization effect existed between NaCl and Na2SO4, and NaCl had a strong salting out effect on Na2SO4. Finally, the nucleation rate and growth rate of Na2SO4 crystals under simulated wastewater conditions were determined by the intermittent dynamic method, and the crystallization kinetic models of Na2SO4 were established. The crystallization nucleation of Na2SO4 crystals was found to be secondary nucleation controlled by surface reactions. The basic theoretical research of crystallization in this study is expected to fundamentally promote the application of fractional crystallization to realize the resource utilization of high-salinity wastewater in the coal chemical industry. [ABSTRACT FROM AUTHOR]

In this work, we investigate the effects of convex surface roughness on heterogeneous ice nucleation through molecular dynamics simulations. Graphene surfaces with sawtooth structures are considered, and the ice nucleation rates are calculated by varying the vertex angle of the sawtooth structures. It is found that the ice nucleation rate is always suppressed by surface roughness regardless of the vertex angle. As the vertex angle is varied, the space between two adjacent ridges of the sawtooth roughness may or may not match the basic structure of ice, which leads to the variation in the free energy barrier for ice nucleation and, consequently, causes the ice nucleation rate to change by two orders of magnitude. [ABSTRACT FROM AUTHOR]

The experiment of Al‐deoxidized steel coupling with Mg treatment is conducted under three cooling methods to observe the size and morphology of MgAl2O4. Most of MgAl2O4 in the water‐cooled steel are sphere or ellipsoid‐like shape, in the furnace‐cooled steel are cubic or octahedral‐like shape, and in the air‐cooled steel are irregular shape. The quantity of inclusions in the size of 1–3 μm increases with the increasing cooling rate, whereas the quantity of the other size decreases with the increasing cooling rate. The result shows that the changing of cooling methods has little effect on the critical size and the nucleation rate of MgAl2O4. The growth of MgAl2O4 is effected by diffusion, Ostwald, and collision growth, and the increasing cooling rate leads to the decreasing growth time. The size of MgAl2O4 is decided by the diffusion of Mg and the growth time of MgAl2O4. Four possible morphological transformation paths of MgAl2O4 in steel are found, and the shape of MgAl2O4 can evolve from sphere or ellipsoid to octahedron via truncated octahedron or cubic‐like shape. The final morphology of MgAl2O4 is controlled by the transformation path which has a close relationship with the cooling rate. [ABSTRACT FROM AUTHOR]

We determine nucleation rates of hard spheres using brute-force molecular dynamics simulations. We overcome nucleation barriers of up to 28 kBT, leading to a rigorous test of nucleation rates obtained from rare-event methods and classical nucleation theory. Our brute-force nucleation rates show excellent agreement with umbrella sampling simulations by Filion et al. [J. Chem. Phys. 133, 244115 (2010)] and seeding simulations by Espinosa et al. [J. Chem. Phys. 144, 034501 (2016)]. [ABSTRACT FROM AUTHOR]

Computational predictions of the polymorphic outcomes of a crystallization process, referred to as polymorph selection, can accelerate the process development for manufacturing solid products with targeted properties. Polymorph selection requires understanding the interplay between the thermodynamic and kinetic factors that drive nucleation. Moreover, post-nucleation events, such as crystal growth and polymorphic transformation, can affect the resulting crystal structures. Here, the nucleation kinetics of the Lennard-Jones (LJ) fluid from the melt is investigated with a focus on the competition between FCC and HCP crystal structures. Both molecular dynamics (MD) simulations and 2D free energy calculations reveal that polymorph selection occurs not during nucleation but when the cluster sizes exceed the critical cluster size. This result contrasts with the classical nucleation mechanism, where each polymorph is assumed to nucleate independently as an ideal bulk-like cluster, comprised only of its given structure. Using the 2D free energy surface and the MD simulation-derived diffusion coefficients, a structure-dependent nucleation rate is estimated, which agrees with the rate obtained from brute force MD simulations. Furthermore, a comprehensive population balance modeling (PBM) approach for polymorph selection is proposed. The PBM combines the calculated nucleation rate with post-nucleation kinetics while accounting for the structural changes of the clusters after nucleation. When applied to the LJ system, the PBM predicts with high accuracy the polymorphic distribution found in a population of crystals generated from MD simulations. Due to the non-classical nucleation mechanism of the LJ system, post-nucleation kinetic events are crucial in determining the structures of the grown crystals. [ABSTRACT FROM AUTHOR]

Magic clusters are metastable faceted nanoparticles that are thought to be important and, sometimes, observable intermediates in the nucleation of certain faceted crystallites. This work develops a broken bond model for spheres with a face-centered-cubic packing that form tetrahedral magic clusters. With just one bond strength parameter, statistical thermodynamics yield a chemical potential driving force, an interfacial free energy, and free energy vs magic cluster size. These properties exactly correspond to those from a previous model by Mule et al. [J. Am. Chem. Soc. 143, 2037 (2021)]. Interestingly, a Tolman length emerges (for both models) when the interfacial area, density, and volume are treated consistently. To describe the kinetic barriers between magic cluster sizes, Mule et al. invoked an energy parameter to penalize the two-dimensional nucleation and growth of new layers in each facet of the tetrahedra. According to the broken bond model, barriers between magic clusters are insignificant without the additional edge energy penalty. We estimate the overall nucleation rate without predicting the rates of formation for intermediate magic clusters by using the Becker–Döring equations. Our results provide a blueprint for constructing free energy models and rate theories for nucleation via magic clusters starting from only atomic-scale interactions and geometric considerations. [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]

Arguably, the main challenge of nucleation theory is to accurately evaluate the work of formation of a critical embryo in the new phase, which governs the nucleation rate. In Classical Nucleation Theory (CNT), this work of formation is estimated using the capillarity approximation, which relies on the value of the planar surface tension. This approximation has been blamed for the large discrepancies between predictions from CNT and experiments. In this work, we present a study of the free energy of formation of critical clusters of the Lennard-Jones fluid truncated and shifted at 2.5σ using Monte Carlo simulations, density gradient theory, and density functional theory. We find that density gradient theory and density functional theory accurately reproduce molecular simulation results for critical droplet sizes and their free energies. The capillarity approximation grossly overestimates the free energy of small droplets. The incorporation of curvature corrections up to the second order with the Helfrich expansion greatly remedies this and performs very well for most of the experimentally accessible regions. However, it is imprecise for the smallest droplets and largest metastabilities since it does not account for a vanishing nucleation barrier at the spinodal. To remedy this, we propose a scaling function that uses all relevant ingredients without adding fitting parameters. The scaling function reproduces accurately the free energy of the formation of critical droplets for the entire metastability range and all temperatures examined and deviates from density gradient theory by less than one kBT. [ABSTRACT FROM AUTHOR]

Molecule- and particle-based simulations provide the tools to test, in microscopic detail, the validity of classical nucleation theory. In this endeavor, determining nucleation mechanisms and rates for phase separation requires an appropriately defined reaction coordinate to describe the transformation of an out-of-equilibrium parent phase for which myriad options are available to the simulator. In this article, we describe the application of the variational approach to Markov processes to quantify the suitability of reaction coordinates to study crystallization from supersaturated colloid suspensions. Our analysis indicates that collective variables (CVs) that correlate with the number of particles in the condensed phase, the system potential energy, and approximate configurational entropy often feature as the most appropriate order parameters to quantitatively describe the crystallization process. We apply time-lagged independent component analysis to reduce high-dimensional reaction coordinates constructed from these CVs to build Markov State Models (MSMs), which indicate that two barriers separate a supersaturated fluid phase from crystals in the simulated environment. The MSMs provide consistent estimates for crystal nucleation rates, regardless of the dimensionality of the order parameter space adopted; however, the two-step mechanism is only consistently evident from spectral clustering of the MSMs in higher dimensions. As the method is general and easily transferable, the variational approach we adopt could provide a useful framework to study controls for crystal nucleation. [ABSTRACT FROM AUTHOR]

The interaction of water with different substances in the earth's atmosphere lies at the heart of many processes that influence our climate. However, it is still unclear how different species interact with water on the molecular level and in which ways this interaction contributes to the water vapor phase transition. Here, we report the first measurements of water–nonane binary nucleation in the 50–110 K temperature range, along with unary nucleation data of both. The time-dependent cluster size distribution in a uniform post-nozzle flow was measured by time-of-flight mass spectrometry coupled with single-photon ionization. From these data, we extract experimental rates and rate constants for both nucleation and cluster growth. The observed mass spectra of water/nonane clusters are not or only slightly affected by the introduction of the other vapor, and the formation of mixed clusters was not observed during nucleation of the mixed vapor. Additionally, the nucleation rate of either substance is not much affected by the presence (or absence) of the other species, i.e., the nucleation of water and nonane proceeds independently, indicating that hetero-molecular clusters do not play a role during nucleation. Only at the lowest temperature of our experiment (i.e., 51 K) do the measurements suggest that interspecies interaction slows water cluster growth. The findings here are in contrast to our earlier work in which we showed that vapor components in other mixtures, e.g., CO2 and toluene/H2O, can interact to promote nucleation and cluster growth in a similar temperature range. [ABSTRACT FROM AUTHOR]

Until quite recently, in almost all papers on crystal nucleation in glass-forming substances, it was assumed that nucleation proceeds in a completely relaxed supercooled liquid and, hence, at constant values of the critical parameters determining the nucleation rate for any given set of temperature, pressure, and composition. Here, we analyze the validity of this hypothesis for a model system by studying nucleation in a lithium silicate glass treated for very long times (up to 250 days) in deeply supercooled states, reaching 60 K below the laboratory glass transition temperature, Tg. At all temperatures in the considered range, T < Tg, we observed an enormous difference between the experimental number of nucleated crystals, N(t), and its theoretically expected value computed by assuming the metastable state of the relaxing glass has been reached. Analyzing the origin of this discrepancy, we confirmed that the key parameters determining the nucleation rates change with time as a result of the glass relaxation process. Finally, we demonstrate that, for temperatures below 683 K, this particular glass almost fully crystallizes prior to reaching the ultimate steady-state nucleation regime (e.g., at 663 K, it would take 176 years for the glass to reach 99% crystallization, while 2600 years would be needed for complete relaxation). This comprehensive study proves that structural relaxation strongly affects crystal nucleation in deeply supercooled states at temperatures well below Tg; hence, this phenomenon has to be accounted for in any crystal nucleation model. [ABSTRACT FROM AUTHOR]

The high density of aluminum nanocrystals (>1021 m−3) that develop during the primary crystallization in Al-based metallic glasses indicates a high nucleation rate (∼1018 m−3 s−1). Several studies have been advanced to account for the primary crystallization behavior, but none have been developed to completely describe the reaction kinetics. Recently, structural analysis by fluctuation electron microscopy has demonstrated the presence of the Al-like medium range order (MRO) regions as a spatial heterogeneity in as-spun Al88Y7Fe5 metallic glass that is representative for the class of Al-based amorphous alloys that develop Al nanocrystals during primary crystallization. From the structural characterization, an MRO seeded nucleation configuration is established, whereby the Al nanocrystals are catalyzed by the MRO core to decrease the nucleation barrier. The MRO seeded nucleation model and the kinetic data from the delay time (τ) measurement provide a full accounting of the evolution of the Al nanocrystal density (Nv) during the primary crystallization under isothermal annealing treatments. Moreover, the calculated values of the steady state nucleation rates (Jss) predicted by the nucleation model agree with the experimental results. Moreover, the model satisfies constraints on the structural, thermodynamic, and kinetic parameters, such as the critical nucleus size, the interface energy, and the volume-free energy driving force that are essential for a fully self-consistent nucleation kinetics analysis. The nucleation kinetics model can be applied more broadly to materials that are characterized by the presence of spatial heterogeneities. [ABSTRACT FROM AUTHOR]

Many phase change materials (PCMs) are found to crystallize without exhibiting a glass transition endotherm upon reheating. In this paper, we review experimental evidence revealing that these PCMs and likely other hyperquenched molecular and metallic systems can crystallize from the glassy state when reheated at a standard rate. Among these evidences, PCMs annealed below the glass transition temperature Tg exhibit slower crystallization kinetics despite an increase in the number of sub-critical nuclei that should promote the crystallization speed. Flash calorimetry uncovers the glass transition endotherm hidden by crystallization and reveals a distinct change in kinetics when crystallization switches from the glassy to the supercooled liquid state. The resulting Tg value also rationalizes the presence of the pre-Tg relaxation exotherm ubiquitous of hyperquenched systems. Finally, the shift in crystallization temperature during annealing exhibits a non-exponential decay that is characteristic of structural relaxation in the glass. Modeling using a modified Turnbull equation for nucleation rate supports the existence of sub-Tg fast crystallization and emphasizes the benefit of a fragile-to-strong transition for PCM applications due to a reduction in crystallization at low temperature (improved data retention) and increasing its speed at high temperature (faster computing). [ABSTRACT FROM AUTHOR]

Clotrimazole (CMZ) is a classical antifungal drug for studying crystallization. In this study, a new CMZ polymorph (Form 2) was discovered during the process of nucleation and growth rate determination in the melt. High-quality single crystals were grown from melt microdroplets to determine the crystal structure by x-ray diffraction. Form 2 is metastable and exhibits a disordered structure. The crystal nucleation and growth kinetics of the two CMZ polymorphs were systematically measured. Form 2 nucleates and grows faster than the existing form (Form 1). The maximum nucleation rate of Forms 1 and 2 was observed at 50 °C (1.07 Tg). The summary of the maximum nucleation rate temperature of CMZ and the other six organic compounds indicates that nucleation near Tg in the supercooled liquid is a useful approach to discovering new polymorphs. This study is relevant for the discovering new drug polymorphs through an understanding of nucleation and growth kinetics during melt crystallization. [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]

Nucleation is a key step in the synthesis of a new material from a solution. The well-established lattice-gas models can be used to gain insight into the basic physics of nucleation pathways involving a single nucleus type. In many situations, a solution is supersaturated with respect to more than one precipitating phase. This can generate a population of both stable and metastable nuclei on similar timescales and, hence, complex nucleation pathways involving a competition between the two. In this study, we introduce a lattice-gas model based on two types of interacting dimers representing the particles in a solution. Each type of dimer nucleates to a specific space-filling structure. Our model is tuned such that stable and metastable phases nucleate on a similar timescale. Either structure may nucleate first, with a probability sensitive to the relative rate at which a solute is replenished from their respective reservoirs. We calculate these nucleation rates via forward flux sampling and demonstrate how the resulting data can be used to infer the nucleation outcome and pathway. Possibilities include direct nucleation of the stable phase, domination of long-lived metastable crystallites, and pathways in which the stable phase nucleates only after multiple post-critical nuclei of the metastable phase have appeared. [ABSTRACT FROM AUTHOR]

Molecules at a liquid/vapor interface have different organizations and mobilities from those in the bulk. These differences potentially influence the rate of crystal nucleation, but the effect remains imperfectly understood. We have measured the crystal nucleation rates at the surface and in the bulk of amorphous poscaconazole, a rod-like molecule known to have a preferred interfacial orientation. We find that surface nucleation is vastly enhanced over bulk nucleation, by ∼9 orders of magnitude, and selects a different polymorph (II) from bulk nucleation (I). This phenomenon mirrors the recently reported case of D-arabitol and stems from the similarity of anisotropic surface molecular packing to the structure of the surface-nucleating polymorph. In contrast to these two systems, the surface enhancement of nucleation is weaker (though still significant) in acetaminophen and in water and does not select a different polymorph. Together, the systems investigated to date all feature surface enhancement, not suppression, of crystal nucleation, and those showing a polymorphic change feature (1) structural reconstruction at the surface relative to the bulk and (2) existence of a different polymorph that can take advantage of the surface environment to nucleate. These results help predict the effect of a liquid/vapor interface on crystal nucleation and polymorph selection, especially in systems with a large surface/volume ratio, such as atmospheric water and amorphous particles. [ABSTRACT FROM AUTHOR]

Prediction of nucleation rates in first order phase transitions requires the knowledge of the barrier associated with the free energy profile W. Molecular simulations offer a direct route through W = −kT ln pa, where k is Boltzmann's constant, T is temperature, and pa is the probability distribution of the size of any nucleus. However, in practice, the extremely scarce spontaneous occurrence of large nuclei impedes the full determination of pa, and a numerical bias must be introduced, which is generally done on the size of the largest nucleus in the system, leading to the probability size distribution of the largest nucleus pl. Although pl is known to be system size dependent, unlike pa, it has extensively been used as an approximation for pa. This communication demonstrates an improved relation between pa and pl, which cures this approximation and allows an accurate calculation of free energy barriers from biased simulations. [ABSTRACT FROM AUTHOR]

We calculate bubble nucleation rates in a Lennard-Jones fluid through explicit molecular dynamics simulations. Our approach—based on a recent free energy method (dubbed reweighted Jarzynski sampling), transition state theory, and a simple recrossing correction—allows us to probe a fairly wide range of rates in several superheated and cavitation regimes in a consistent manner. Rate predictions from this approach bridge disparate independent literature studies on the same model system. As such, we find that rate predictions based on classical nucleation theory, direct brute force molecular dynamics simulations, and seeding are consistent with our approach and one another. Published rates derived from forward flux sampling simulations are, however, found to be outliers. This study serves two purposes: First, we validate the reliability of common modeling techniques and extrapolation approaches on a paradigmatic problem in materials science and chemical physics. Second, we further test our highly generic recipe for rate calculations, and establish its applicability to nucleation processes. [ABSTRACT FROM AUTHOR]

Nucleation of particles into crystalline structures can be observed in a wide range of systems from metallic and metal–organic compounds to colloidal and polymeric patch particles. Here, we perform kinetic Monte Carlo simulations to study the nucleation kinetics of particles with different ligancies z at constant supersaturation s. This approach allows one to determine several physico-chemical quantities as a function of s, including the growth probability P(n), the critical nucleus size n*, and the stationary nucleation rate Js. Our numerical results are rationalized in terms of a self-consistent nucleation theory where both n* and Js present a non-trivial dependence on s, but which can be determined from the values of effective z-dependent parameters. [ABSTRACT FROM AUTHOR]

Quantifying the active surface area of Mars‐van‐Krevelen catalysts is paramount for the elucidation of structure‐property relationships and the knowledge‐based catalyst development. Different cerium oxides were prepared via precipitation‐based techniques. By altering conditions during precipitation, materials with a wide span of material properties were prepared. The influence of temperature during ammonia‐based precipitation was investigated. When using Ce(IV) precursors an increase in precipitation temperature decreases the crystallite size while increasing specific surface area, attributed to an increase in nucleation rate. Sintering stability is also increased for materials precipitated at higher temperature. Measuring the total oxygen storage capacity (TOSC) values of the prepared materials showed that the TOSC is not strictly a function of BET surface area. Our results suggest that crystallites with a domain size under a certain threshold are not reduced via oxygen release but rather hydroxyl formation. A method was proposed with which the redox active surface area for polycrystalline ceria can be estimated on basis of the domain size obtained from Rietveld refinement. These findings were corroborated by CO oxidation light‐off experiments in which the light‐off temperature was found to correlate with the surface that can release oxygen reversibly, the Mars‐van‐Krevelen active surface area, rather than BET surface area. [ABSTRACT FROM AUTHOR]

Ferroelectric wurtzite‐type aluminum scandium nitride (Al1−xScxN) presents unique properties that can enhance the performance of non‐volatile memory technologies. The realization of the full potential of Al1−xScxN requires a comprehensive understanding of the mechanism of polarization reversal and domain structure dynamics involved in the ferroelectric switching process. In this work, transient current integration measurements performed by a pulse switching method are combined with domain imaging by piezoresponse force microscopy (PFM) to investigate the kinetics of domain nucleation and wall motion during polarization reversal in Al0.85Sc0.15N capacitors. In the studied electric field range (from 4.4 to 5.6 MV cm−1), ferroelectric switching proceeds via domain nucleation and wall movement. The currently available phenomenological models are shown to not fully capture all the details of the complex dynamics of polarization reversal in Al0.85Sc0.15N. PFM reveals a non‐linear increase of both domain nucleation rate and lateral wall velocity during the switching process, as well as the dependency of the domain pattern on the polarization reversal direction. A continuously faster N‐ to M‐polar switching upon cycling is reported and ascribed to an increasing number of M‐polar nucleation sites and density of domain walls. [ABSTRACT FROM AUTHOR]

The polar sulfonate groups in cationic dyeable polyester (CDP) lead to complex crystallization behavior, affecting CDP production's stability. In this study, cationic dyeable polyesters (CDP) with different sulfonate group contents were prepared via one-step feeding of sodium isophthalic acid-5-sulfonate (SIPA), terephthalic acid (PTA), and ethylene glycol (EG). The non-isothermal crystallization behavior of these copolyesters was analyzed by differential scanning calorimetry (DSC). Results show that the crystallization temperature of the sample shifts to lower values with the increase in SIPA content. The relaxation behavior of the molecular chain is enhanced due to the ionic aggregation effect of sulfonate groups in CDP. Therefore, at low cooling rates (2.5 °C/min and 5 °C/min), some molecular chain segments in CDP are still too late to orderly stack into the lattice, forming metastable crystals, and melting double peaks appear on the melting curve after crystallization. When the cooling rate increases (10–20 °C/min), the limited region of sulfonate aggregation in CDP increases, resulting in more random chain segments, and a cold crystallization peak appears on the melting curve after crystallization. The non-isothermal crystallization behavior of all samples was fitted and analyzed by the Jeziorny equation, Ozawa equation, and Mo equation. The results indicate that the nucleation density and nucleation growth rate of CDP decrease with the increase in SIPA content. Meanwhile, analysis of the Kissinger equation reveals that the activation energy of non-isothermal crystallization decreases gradually with the increase in SIPA content, and the addition of SIPA makes CDP crystallization more difficult. [ABSTRACT FROM AUTHOR]

Minerals form in natural systems from solutions with varying ratios of their lattice ions, yet non‐stoichiometric conditions have generally been overlooked in investigations of new formation (nucleation) of ionic crystals. Here, we investigated the influence of cation:anion ratio in the solution on the initial steps of nucleation by studying positively and negatively charged triple ion complexes and subsequent particle size evolution. Our model systems are carbonates and sulfates of calcium and barium, as it was recently shown that solution stoichiometry affects the timing and rate of their nucleation. Molecular dynamics (MD) simulations and dynamic light scattering (DLS) flow experiments show that nucleation correlates with the stability and lifetime of the initial complexes, which were significantly impacted by the cation:anion stoichiometry and ion type. Specifically, BaSO422- ${{\rm B}{\rm a}{\left({{\rm S}{\rm O}}_{4}\right)}_{2}^{2-}}$ was found to have higher association constants and its lifetime was twofold longer than Ba2SO42+ ${{{\rm B}{\rm a}}_{2}{{\rm S}{\rm O}}_{4}^{2+}}$. Similar trends were observed for BaCO3 ${{{\rm B}{\rm a}{\rm C}{\rm O}}_{3}}$ and CaSO4 ${{{\rm C}{\rm a}{\rm S}{\rm O}}_{4}}$. Contrastingly, for CaCO3 ${{{\rm C}{\rm a}{\rm C}{\rm O}}_{3}}$ , CaCO322- ${{\rm C}{\rm a}{\left({{\rm C}{\rm O}}_{3}\right)}_{2}^{2-}}$ was found to have lower association constants and its lifetime was shorter than Ca2CO32+ ${{{\rm C}{\rm a}}_{2}{{\rm C}{\rm O}}_{3}^{2+}}$. These trends in stability and lifetime follow the same asymmetrical behaviour as observed experimentally for particle formation using techniques like DLS. This suggests a causal relationship between the stability and lifetime of the initial charged complexes and the nucleation under non‐stoichiometric conditions. [ABSTRACT FROM AUTHOR]

The precipitation of nonstoichiometric crystals (of different composition from the parent glass) motivated us to study the stoichiometric Na2O•2CaO•3SiO2 (N2CS3) glass-forming system comprehensively. The concentration profiles of Na and Ca in the diffusion zone around Na4+2xCa4-x[Si6O18], 0 < x < 1, crystals in an N2C3S glass were characterized by energy-dispersive spectroscopy and were then theoretically described. We show that the diffusion zone is formed because of the rejection of part of calcium by the growing crystal. The radial variation of the Ca concentrations and the crystal nucleation rate through the diffusion zone were analyzed simultaneously.We found that the nucleation rate in the diffusion zone near the crystal--glass interface drastically decreases due to the increase in the work of critical cluster formation resulting from the composition change. In contrast, the diffusion activation barrier remains practically constant. Moreover, the Ca diffusion coefficients, DCa, inNa2O•2CaO•3SiO2 and CaO•SiO2 glasses show the same Arrhenius dependence, demonstrating that (surprisingly) DCa does not depend on the glass composition in the CaO•SiO2--Na2O•SiO2 metasilicate joint. This work provides the quantitative spatial distribution of chemical components in a partially crystallized glass, shedding light on solid solution crystallization in a glass-forming liquid and its consequences. [ABSTRACT FROM AUTHOR]

In this study, the austenite formation behavior is investigated for the ferrite–pearlite initial microstructure, considering the influence of ferrite recrystallization and cementite distribution. Special attention is also given to the effect of recrystallization state on cementite distribution for varied heating routes. Austenite nucleation for varied recrystallization state is elucidated in terms of activation energy evaluation and post microstructural characterization, and the austenite transformation kinetics are modeled and experimentally validated. In the uncrystallized state, austenite forms on the original pearlite colonies quickly due to the short carbon diffusion path. The high activation energy leads to the exceptionally difficult nucleation at the ferrite–cementite interface inside ferrite matrix. Once recrystallization occurs partially, priority of austenite nucleation is on those ferrite boundaries (both recrystallized and unrecrystallized boundaries) decorated by cementite. With complete recrystallization, preferential nucleation sites are found to be junctions of ferrite–cementite interface on recrystallized ferrite boundaries. Austenite transformation kinetics is well predicted by considering the varied nucleation density due to different recrystallization state, showing a good agreement with experimental data. It is demonstrated directly by experimental evidence that proceeding of recrystallization postpones the austenite transformation kinetics, while getting rid of the interference of heating rate and nucleation location. [ABSTRACT FROM AUTHOR]