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Onset of heterogeneous crystal nucleation in colloidal suspensions

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Abstract

The addition of small ‘seed’ particles to a supersaturated solution can greatly increase the rate at which crystals nucleate. This process is understood, at least qualitatively, when the seed has the same structure as the crystal that it spawns1,2. However, the microscopic mechanism of seeding by a ‘foreign’ substance is not well understood. Here we report numerical simulations of colloidal crystallization seeded by foreign objects. We perform Monte Carlo simulations to study how smooth spherical seeds of various sizes affect crystallization in a suspension of hard colloidal particles. We compute the free-energy barrier associated with crystal nucleation3,4. A low barrier implies that nucleation is easy. We find that to be effective crystallization promoters, the seed particles need to exceed a well-defined minimum size. Just above this size, seed particles act as crystallization ‘catalysts’ as newly formed crystallites detach from the seed. In contrast, larger seed particles remain covered by the crystallites that they spawn. This phenomenon should be experimentally observable and can have important consequences for the control of the resulting crystal size distribution.

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Figure 1: The spontaneous crystallizations of hard-sphere colloids on seed particles.
Figure 2: Plot of the smallest pressure P that causes complete crystallization as a function of the seed curvature κ.
Figure 3: Free-energy barriers for crystal nucleation in a system of hard spheres with a smooth spherical seed.
Figure 4: Snapshot sequence of crystal nucleation on spherical seeds.

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Acknowledgements

The work of the FOM Institute is part of the research program of FOM and is made possible by financial support from the Netherlands Organization for Scientific Research (NWO).

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  1. S. Auer

    Present address: Department of Chemistry, Cambridge University, Lensfield Road, Cambridge, CB2 1EW, UK

Authors and Affiliations

  1. FOM Institute for Atomic and Molecular Physics, Kruislaan 407, 1098 SJ, Amsterdam, The Netherlands

    A. Cacciuto

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  1. A. Cacciuto
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  2. S. Auer
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  3. D. Frenkel
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Correspondence to A. Cacciuto.

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Cacciuto, A., Auer, S. & Frenkel, D. Onset of heterogeneous crystal nucleation in colloidal suspensions. Nature 428, 404–406 (2004). https://doi.org/10.1038/nature02397

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