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Register a new userClassical nucleation theory predicts the shape of the nucleus in homogeneous solidification
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Macroscopic models of nucleation provide powerful tools for understanding activated phase transition processes. These models do not provide atomistic insights and can thus sometime lack material-specific descriptions. Here we provide a comprehensive framework for constructing a continuum picture from an atomistic simulation of homogeneous nucleation. We use this framework to determine the shape of the equilibrium solid nucleus that forms inside bulk liquid for a Lennard-Jones potential. From this shape, we then extract the anisotropy of the solid-liquid interfacial free energy, by performing a reverse Wulff construction in the space of spherical harmonic expansions. We find that the shape of the nucleus is nearly spherical and that its anisotropy can be perfectly described using classical models.
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In standard nucleation theory, the nucleation process is characterized by computing $DeltaOmega(V)$, the reversible work required to form a cluster of volume $V$ of the stable phase inside the metastable mother phase. However, other quantities besides the volume could play a role in the free energy of cluster formation, and this will in turn affect the nucleation barrier and the shape of the nucleus. Here we exploit our recently introduced mesoscopic theory of nucleation to compute the free energy cost of a nearly-spherical cluster of volume $V$ and a fluctuating surface area $A$, whereby the maximum of $DeltaOmega(V)$ is replaced by a saddle point in $DeltaOmega(V,A)$. Compared to the simpler theory based on volume only, the barrier height of $DeltaOmega(V,A)$ at the transition state is systematically larger by a few $k_BT$. More importantly, we show that, depending on the physical situation, the most probable shape of the nucleus may be highly non spherical, even when the surface tension and stiffness of the model are isotropic. Interestingly, these shape fluctuations do not influence or modify the standard Classical Nucleation Theory manner of extracting the interface tension from the logarithm of the nucleation rate near coexistence.
Nucleation is an out-of-equilibrium process, which can be strongly affected by the presence of external fields. In this letter, we report a simple extension of classical nucleation theory to systems submitted to an homogeneous shear flow. The theory involves accounting for the anisotropy of the critical nucleus formation, and introduces a shear rate dependent effective temperature. This extended theory is used to analyze the results of extensive molecular dynamics simulations, which explore a broad range of shear rates and undercoolings. At fixed temperature, a maximum in the nucleation rate is observed, when the relaxation time of the system is comparable to the inverse shear rate. In contrast to previous studies, our approach does not require a modification of the thermodynamic description, as the effect of shear is mainly embodied into a modification of the kinetic prefactor and of the temperature.
We investigated the homogenous nucleation of the stoichiometric B2 and B33 phases in the Ni50Zr50 alloy using the persistent embryo method and the classical nucleation theory. The two phases become very close competitors at large supercoolings, which is consistent with the experimental observations. In the case of the B2 phase, the linear temperature dependence of the solid-liquid interface (SLI) free energy extrapolated to the melting temperature leads to the same value as the one obtained from the capillarity fluctuation method (CFM). In the case of the B33 phases, the SLI free energy is also a linear function of temperature at large supercoolings but the extrapolation to the melting temperature leads to a value which is considerably different from the CFM value. This is consistent with the large anisotropy of the SLI properties of the B33 phase nearby the melting temperature observed in the simulation of the nominally flat interface migration.
Advanced phase-field techniques have been applied to address various aspects of polycrystalline solidification including different modes of crystal nucleation. The height of the nucleation barrier has been determined by solving the appropriate Euler-Lagrange equations. The examples shown include the comparison of various models of homogeneous crystal nucleation with atomistic simulations for the single component hard-sphere fluid. Extending previous work for pure systems (Granasy L, Pusztai T, Saylor D and Warren J A 2007 Phys. Rev. Lett. 98 art no 035703), heterogeneous nucleation in unary and binary systems is described via introducing boundary conditions that realize the desired contact angle. A quaternion representation of crystallographic orientation of the individual particles (outlined in Pusztai T, Bortel G and Granasy L 2005 Europhys. Lett. 71 131) has been applied for modeling a broad variety of polycrystalline structures including crystal sheaves, spherulites and those built of crystals with dendritic, cubic, rhombododecahedral, truncated octahedral growth morphologies. Finally, we present illustrative results for dendritic polycrystal-line solidification obtained using an atomistic phase-field model.
The homogeneous and heterogeneous nucleation of a Lennard-Jones liquid is investigated using the umbrella sampling method. The free energy cost of forming a nucleating droplet is determined as a function of the quench depth, and the saddle point nature of the droplets is verified using an intervention technique. The structure and symmetry of the nucleating droplets is found for a range of temperatures. We find that for deep quenches the nucleating droplets become more anisotropic and diffuse with no well defined core or surface. The environment of the nucleating droplets form randomly stacked hexagonal planes. This behavior is consistent with a spinodal nucleation interpretation. We also find that the free energy barrier for heterogeneous nucleation is a minimum when the lattice spacing of the impurity equals the lattice spacing of the equilibrium crystalline phase. If the lattice spacing of the impurity is different, the crystal grows into the bulk instead of wetting the impurity.
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