scholarly journals Heterogeneous Crystal Nucleation from the Melt in Polyethylene Oxide Droplets on Graphite: Kinetics and Microscopic Structure

Crystals ◽  
2021 ◽  
Vol 11 (8) ◽  
pp. 924
Author(s):  
Muhammad Tariq ◽  
Thomas Thurn-Albrecht ◽  
Oleksandr Dolynchuk
Keyword(s):  
Optical Microscopy ◽  
Polyethylene Oxide ◽  
Heterogeneous Nucleation ◽  
Polarized Light ◽  
Contact Angles ◽  
Nucleation Theory ◽  
Crystal Nucleation ◽  
Classical Nucleation Theory ◽  
Graphite Substrate ◽  
Nucleation Kinetics

It is well known that the crystallization of liquids often initiates at interfaces to foreign solid surfaces. In this study, using polarized light optical microscopy, atomic force microscopy (AFM), and wide-angle X-ray scattering (WAXS), we investigate the effect of substrate–material interactions on nucleation in an ensemble of polyethylene oxide (PEO) droplets on graphite and on amorphous polystyrene (PS). The optical microscopy measurements during cooling with a constant rate explicitly evidenced that the graphite substrate enhances the nucleation kinetics, as crystallization occurred at approximately an 11 °C higher temperature than on PS due to changes in the interactions at the solid interface. This observation allowed us to conclude that graphite induces heterogeneous nucleation in PEO. By employing the classical nucleation theory for analysis of the data with reference to the amorphous PS substrate, the obtained results indicated that the crystal nuclei with contact angles in the range of 100–117° were formed at the graphite interface. Furthermore, we show that heterogeneous nucleation led to a preferred orientation of PEO crystals on graphite, whereas PEO crystals on PS had isotropic orientation. The difference in crystal orientations on the two substrates was also confirmed with AFM, which showed only edge-on lamellae in PEO droplets on graphite compared to unoriented lamellae on PS.

scholarly journals Nucleation Behavior of a Single Al-20Si Particle Rapidly Solidified in a Fast Scanning Calorimeter

Materials ◽  
2021 ◽  
Vol 14 (11) ◽  
pp. 2920
Author(s):  
Qin Peng ◽  
Bin Yang ◽  
Benjamin Milkereit ◽  
Dongmei Liu ◽  
Armin Springer ◽  
...  
Keyword(s):  
Cooling Rate ◽  
Rapid Solidification ◽  
Heterogeneous Nucleation ◽  
Nucleation Theory ◽  
Classical Nucleation Theory ◽  
Solidification Behavior ◽  
Nucleation Kinetics ◽  
Nucleation Behavior ◽  
Nucleation Undercooling ◽  
Primary Si

Understanding the rapid solidification behavior characteristics, nucleation undercooling, and nucleation mechanism is important for modifying the microstructures and properties of metal alloys. In order to investigate the rapid solidification behavior in-situ, accurate measurements of nucleation undercooling and cooling rate are required in most rapid solidification processes, e.g., in additive manufacturing (AM). In this study, differential fast scanning calorimetry (DFSC) was applied to investigate the nucleation kinetics in a single micro-sized Al-20Si (mass%) particle under a controlled cooling rate of 5000 K/s. The nucleation rates of primary Si and secondary α-Al phases were calculated by a statistical analysis of 300 identical melting/solidification experiments. Applying a model based on the classical nucleation theory (CNT) together with available thermodynamic data, two different heterogeneous nucleation mechanisms of primary Si and secondary α-Al were proposed, i.e., surface heterogeneous nucleation for primary Si and interface heterogenous nucleation for secondary α-Al. The present study introduces a practical method for a detailed investigation of rapid solidification behavior of metal particles to distinguish surface and interface nucleation.

Nucleation and Glass Formation

1985 ◽  
Vol 57 ◽  
Author(s):  
D. R. Uhlmann ◽  
M. C. Weinberg
Keyword(s):  
Glass Formation ◽  
Nucleation Theory ◽  
Crystal Nucleation ◽  
Oxide Glass ◽  
Classical Nucleation Theory ◽  
Nucleation Kinetics ◽  
Formation Behavior ◽  
Homogeneous Crystal ◽  
Exponential Factors

AbstractThe role of nucleation kinetics in affecting glass formation behavior is discussed. Also considered are measurements of homogeneous crystal nucleation in a variety of liquids. For a number of oxide glass-forming liquids, available data indicate pre-exponential factors which are larger than those predicted from classical nucleation theory by factors of 1017 to 1049. Possible sources of this discrepancy are discussed.

Amorphous calcium phosphate phase-mediated crystal nucleation kinetics and pathway

2015 ◽  
Vol 179 ◽  
pp. 451-461 ◽  
Author(s):  
Shuqin Jiang ◽  
Haihua Pan ◽  
Yan Chen ◽  
Xurong Xu ◽  
Ruikang Tang
Keyword(s):  
Calcium Phosphate ◽  
Heterogeneous Nucleation ◽  
Amorphous Calcium Phosphate ◽  
Nucleation Theory ◽  
Crystal Nucleation ◽  
Nucleation Kinetics ◽  
Solution Interface ◽  
Precursor Phase ◽  
Phosphate Phase ◽  
Polymorph Transformation

Generally, a solution nucleation model is used to study biomineralization kinetics. However, we found that the amorphous calcium phosphate (ACP)-mediated hydroxyapatite (HAP) nucleation in simulated body fluids (SBF) had a different profile from the linear relationship between ln J and ln−2 S (J, nucleation rate; S, supersaturation). This behaviour was alternatively explained by a developed heterogeneous nucleation theory, which indicated that HAP was nucleated at the ACP–solution interface via a polymorph transformation. Based upon this new model, we demonstrated experimentally that the embedded polymer molecules inside ACP were inert on HAP nucleation kinetics; rather, the polymers adsorbed on ACP surface could inhibit HAP nucleation from ACP. It further confirmed the heterogeneous nucleation pathway of HAP on the precursor phase. The present study provides an in-depth understanding of HAP formation for ACP-mediated crystallization.

scholarly journals Pore-Scale Modeling of Mineral Growth and Nucleation in Reactive Flow

2022 ◽  
Vol 3 ◽  
Author(s):  
Vitalii Starchenko
Keyword(s):  
Reactive Transport ◽  
Surface Reaction ◽  
Nucleation Theory ◽  
Crystal Nucleation ◽  
Classical Nucleation Theory ◽  
Reactive Flow ◽  
Natural Environments ◽  
Pore Scale ◽  
Arbitrary Lagrangian Eulerian ◽  
Mineral Precipitation

A fundamental understanding of mineral precipitation kinetics relies largely on microscopic observations of the dynamics of mineral surfaces exposed to supersaturated solutions. Deconvolution of tightly bound transport, surface reaction, and crystal nucleation phenomena still remains one of the main challenges. Particularly, the influence of these processes on texture and morphology of mineral precipitate remains unclear. This study presents a coupling of pore-scale reactive transport modeling with the Arbitrary Lagrangian-Eulerian approach for tracking evolution of explicit solid interface during mineral precipitation. It incorporates a heterogeneous nucleation mechanism according to Classical Nucleation Theory which can be turned “on” or “off.” This approach allows us to demonstrate the role of nucleation on precipitate texture with a focus at micrometer scale. In this work precipitate formation is modeled on a 10 micrometer radius particle in reactive flow. The evolution of explicit interface accounts for the surface curvature which is crucial at this scale in the regime of emerging instabilities. The results illustrate how the surface reaction and reactive fluid flow affect the shape of precipitate on a solid particle. It is shown that nucleation promotes the formation of irregularly shaped precipitate and diminishes the effect of the flow on the asymmetry of precipitation around the particle. The observed differences in precipitate structure are expected to be an important benchmark for reaction-driven precipitation in natural environments.

The Effects of Si on the Nucleation Kinetics of Ferrite in Dual Phase Steels

2007 ◽  
Vol 26-28 ◽  
pp. 1307-1310 ◽  
Author(s):  
Sang Hwan Lee ◽  
Kyung Jong Lee
Keyword(s):  
Free Energy ◽  
Interfacial Energy ◽  
Free Energy Change ◽  
Nucleation Theory ◽  
Energy Change ◽  
Classical Nucleation Theory ◽  
Nucleation Kinetics ◽  
Kinetics Of ◽  
Volume Free Energy Change ◽  
Thermodynamic Factors

It is generally accepted that Si promotes kinetics of polygonal ferrite due to thermodynamic factors such as Ae3 and maximum amount of ferrite formed. However, in this study, it was found that the difference between the measured rates of ferrite formation in C-Mn steel and Si added steel was much larger than that expected considering only thermodynamic factors. The classical nucleation theory with pillbox model was adopted to figure out what is the most controlling factor in formation of ferrite. The volume free energy change was calculated by use of the dilute solution model. The diffusivity of carbon (DC) was formulated as functions of C, Mn and Si by using experimental data. It was found that the volume free energy change was still predominant but the kinetic factors such as interfacial energy and the diffusivity of carbon by addition of Si were not negligible at lower undercooling. However, with increasing undercooling, the diffusivity of C was the most effective on the ferrite kinetics, though the ambiguity of treating interfacial energy was not yet clear.

scholarly journals Entropy and the Tolman Parameter in Nucleation Theory

Entropy ◽  
2019 ◽  
Vol 21 (7) ◽  
pp. 670 ◽  
Author(s):  
Jürn W. P. Schmelzer ◽  
Alexander S. Abyzov ◽  
Vladimir G. Baidakov
Keyword(s):  
Surface Tension ◽  
Size Dependence ◽  
Nucleation Theory ◽  
Crystal Nucleation ◽  
Alternative Methods ◽  
Classical Nucleation Theory ◽  
Component Systems ◽  
Bulk Parameters ◽  
Curvature Dependence ◽  
Gibbs Theory

Thermodynamic aspects of the theory of nucleation are commonly considered employing Gibbs’ theory of interfacial phenomena and its generalizations. Utilizing Gibbs’ theory, the bulk parameters of the critical clusters governing nucleation can be uniquely determined for any metastable state of the ambient phase. As a rule, they turn out in such treatment to be widely similar to the properties of the newly-evolving macroscopic phases. Consequently, the major tool to resolve problems concerning the accuracy of theoretical predictions of nucleation rates and related characteristics of the nucleation process consists of an approach with the introduction of the size or curvature dependence of the surface tension. In the description of crystallization, this quantity has been expressed frequently via changes of entropy (or enthalpy) in crystallization, i.e., via the latent heat of melting or crystallization. Such a correlation between the capillarity phenomena and entropy changes was originally advanced by Stefan considering condensation and evaporation. It is known in the application to crystal nucleation as the Skapski–Turnbull relation. This relation, by mentioned reasons more correctly denoted as the Stefan–Skapski–Turnbull rule, was expanded by some of us quite recently to the description of the surface tension not only for phase equilibrium at planar interfaces, but to the description of the surface tension of critical clusters and its size or curvature dependence. This dependence is frequently expressed by a relation derived by Tolman. As shown by us, the Tolman equation can be employed for the description of the surface tension not only for condensation and boiling in one-component systems caused by variations of pressure (analyzed by Gibbs and Tolman), but generally also for phase formation caused by variations of temperature. Beyond this particular application, it can be utilized for multi-component systems provided the composition of the ambient phase is kept constant and variations of either pressure or temperature do not result in variations of the composition of the critical clusters. The latter requirement is one of the basic assumptions of classical nucleation theory. For this reason, it is only natural to use it also for the specification of the size dependence of the surface tension. Our method, relying on the Stefan–Skapski–Turnbull rule, allows one to determine the dependence of the surface tension on pressure and temperature or, alternatively, the Tolman parameter in his equation. In the present paper, we expand this approach and compare it with alternative methods of the description of the size-dependence of the surface tension and, as far as it is possible to use the Tolman equation, of the specification of the Tolman parameter. Applying these ideas to condensation and boiling, we derive a relation for the curvature dependence of the surface tension covering the whole range of metastable initial states from the binodal curve to the spinodal curve.

scholarly journals Multiple pathways of crystal nucleation in an extremely supersaturated aqueous potassium dihydrogen phosphate (KDP) solution droplet

2016 ◽  
Vol 113 (48) ◽  
pp. 13618-13623 ◽  
Author(s):  
Sooheyong Lee ◽  
Haeng Sub Wi ◽  
Wonhyuk Jo ◽  
Yong Chan Cho ◽  
Hyun Hwi Lee ◽  
...  
Keyword(s):  
Deep Level ◽  
Potassium Dihydrogen Phosphate ◽  
Nucleation Theory ◽  
Crystal Nucleation ◽  
Classical Nucleation Theory ◽  
Dihydrogen Phosphate ◽  
High Concentration ◽  
Liquid Phases ◽  
Nucleation Sites ◽  
Solution Studies

Solution studies have proposed that crystal nucleation can take more complex pathways than previously expected in classical nucleation theory, such as formation of prenucleation clusters or densified amorphous/liquid phases. These findings show that it is possible to separate fluctuations in the different order parameters governing crystal nucleation, that is, density and structure. However, a direct observation of the multipathways from aqueous solutions remains a great challenge because heterogeneous nucleation sites, such as container walls, can prevent these paths. Here, we demonstrate the existence of multiple pathways of nucleation in highly supersaturated aqueous KH2PO4(KDP) solution using the combination of a containerless device (electrostatic levitation), and in situ micro-Raman and synchrotron X-ray scattering. Specifically, we find that, at an unprecedentedly deep level of supersaturation, a high-concentration KDP solution first transforms into a metastable crystal before reaching stability at room temperature. However, a low-concentration solution, with different local structures, directly transforms into the stable crystal phase. These apparent multiple pathways of crystallization depend on the degree of supersaturation.

Molecular Dynamics Simulation of Nano Cluster-Seed Effects on Heterogeneous Nucleation

2009 ◽  
Author(s):  
Donguk Suh ◽  
Seung-chai Jung ◽  
Woong-sup Yoon
Keyword(s):  
Molecular Dynamics ◽  
Heterogeneous Nucleation ◽  
Three Dimensional ◽  
Seed Mass ◽  
Nucleation Theory ◽  
Dynamics Simulation ◽  
Classical Nucleation Theory ◽  
Supersaturation Ratio ◽  
Order Of Magnitude ◽  
Nano Cluster

A three-dimensional heterogeneous nucleation is simulated by classical molecular dynamics, where the Lennard-Jones gas and solid nano cluster-seed molecules have argon and aluminum properties, respectively. All dimensions of the wall are periodic and a soft core carrier gas within the system controls the temperature rise induced by latent heat of condensation. There are three shapes of cluster-seeds being cube, rod, and sphere, three classes of masses, and the simulation took place under nine supersaturation ratios, making a total of 81 calculations. An analysis of variance was performed under a three-way layout to analyze the cluster-seed and supersaturation ratio effects on the system. For supersaturation ratios above the critical value nucleation rates were evaluated, below growth rates, and overall liquefaction rates were each defined and calculated. Results show that the supersaturation ratio dominantly controls all rates, but seed characteristics are important for the growth of the largest cluster under the critical supersaturation ratio. Overall liquefaction increases subject to an escalation of supersaturation ratio and seed mass. However, the significance of the supersaturation ratio for overall liquefaction suggests that thermal diffusion is more dominant than mass interactions for this system. Homogeneous characteristics are also compared with the heterogeneous system to find that though nucleation may occur for an insufficient supersaturation ratio when a seed is within the system, the addition of a seed does not in fact facilitate the increase in rates of the phenomena at high supersaturation ratios. Finally a comparison with the classical nucleation theory asserts a 3 to 4 order of magnitude difference, which is within the lines of deviation when it comes to theory and molecular simulations.

scholarly journals Immersion freezing of water and aqueous ammonium sulfate droplets initiated by humic-like substances as a function of water activity

2013 ◽  
Vol 13 (13) ◽  
pp. 6603-6622 ◽  
Author(s):  
Y. J. Rigg ◽  
P. A. Alpert ◽  
D. A. Knopf
Keyword(s):  
Water Activity ◽  
Active Sites ◽  
Melting Curve ◽  
Contact Angles ◽  
Ice Nucleation ◽  
Nucleation Theory ◽  
Classical Nucleation Theory ◽  
Surface Areas ◽  
Immersion Freezing ◽  
Freezing Temperatures

Abstract. Immersion freezing of water and aqueous (NH4)2SO4 droplets containing leonardite (LEO) and Pahokee peat (PP) serving as surrogates for humic-like substances (HULIS) has been investigated. Organic aerosol containing HULIS are ubiquitous in the atmosphere; however, their potential for ice cloud formation is uncertain. Immersion freezing has been studied for temperatures as low as 215 K and solution water activity, aw, from 0.85 to 1.0. The freezing temperatures of water and aqueous solution droplets containing LEO and PP are 5–15 K warmer than homogeneous ice nucleation temperatures. Heterogeneous freezing temperatures can be represented by a horizontal shift of the ice melting curve as a function of solution aw by Δaw = 0.2703 and 0.2466, respectively. Corresponding hetrogeneous ice nucleation rate coefficients, Jhet, are (9.6 ± 2.5)×104 and (5.4 ± 1.4)×104 cm−2 s−1 for LEO and PP containing droplets, respectively, and remain constant along freezing curves characterized by Δaw. Consequently predictions of freezing temperatures and kinetics can be made without knowledge of the solute type when relative humidity and ice nuclei (IN) surface areas are known. The acquired ice nucleation data are applied to evaluate different approaches to fit and reproduce experimentally derived frozen fractions. In addition, we apply a basic formulation of classical nucleation theory (α(T)-model) to calculate contact angles and frozen fractions. Contact angles calculated for each ice nucleus as a function of temperature, α(T)-model, reproduce exactly experimentally derived frozen fractions without involving free-fit parameters. However, assigning the IN a single contact angle for the entire population (single-α model) is not suited to represent the frozen fractions. Application of α-PDF, active sites, and deterministic model approaches to measured frozen fractions yield similar good representations. Furthermore, when using a single parameterization of α-PDF or active sites distribution to fit all individual aw immersion freezing data simultaneously, frozen fraction curves are not reproduced. This implies that these fitting formulations cannot be applied to immersion freezing of aqueous solutions, and suggests that derived fit parameters do not represent independent particle properties. Thus, from fitting frozen fractions only, the underlying ice nucleation mechanism and nature of the ice nucleating sites cannot be inferred. In contrast to using fitted functions obtained to represent experimental conditions only, we suggest to use experimentally derived Jhet as a function of temperature and aw that can be applied to conditions outside of those probed in laboratory. This is because Jhet(T) is independent of time and IN surface areas in contrast to the fit parameters obtained by representation of experimentally derived frozen fractions.

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