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Metastable and unstable cellular solidification of colloidal suspensions

Abstract

Colloidal particles are often seen as big atoms that can be directly observed in real space. They are therefore becoming increasingly important as model systems to study processes of interest in condensed-matter physics such as melting, freezing and glass transitions. The solidification of colloidal suspensions has long been a puzzling phenomenon with many unexplained features. Here, we demonstrate and rationalize the existence of instability and metastability domains in cellular solidification of colloidal suspensions, by direct in situ high-resolution X-ray radiography and tomography observations. We explain such interface instabilities by a partial Brownian diffusion of the particles leading to constitutional supercooling situations. Processing under unstable conditions leads to localized and global kinetic instabilities of the solid/liquid interface, affecting the crystal morphology and particle redistribution behaviour.

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Figure 1: Experimental observations of the development of global interface instabilities and their impact on the crystal structure, for 0.2-μm particles.
Figure 2: Experimental conditions for the development of global instabilities: ice-crystal stability and structure diagrams.
Figure 3: Particle and crystal arrangement and definition of the interface locations close to the crystal tips.
Figure 4: Proposed mechanism for the development of instabilities: particle concentration, temperature and freezing-point profile, for metastable and unstable situations.
Figure 5: Experimental observations of the particle-concentration profile under unstable conditions, for 0.4-μm particles.
Figure 6: Schematic sequence of the development of the instabilities, with nucleation and growth of crystals in the constitutionally supercooled freezing zone and diffusion layer ahead of the crystal tip.

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Acknowledgements

We acknowledge the European Synchrotron Radiation Facility for the provision of synchrotron radiation beam time and we would like to thank E. Boller and J.-P. Valade for their irreplaceable assistance in using beamline ID19. Financial support was provided by the National Research Agency (ANR), project NACRE in the non-thematic BLANC programme, reference BLAN07-2_192446.

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Contributions

S.D. and Ch.G. designed the research project, S.D. and E.M. designed the experiments, S.D., E.M., A.L., J.L., Ca.G. and A.B. carried out the experiments, S.D. and G.B.-G. analysed the data, S.D., E.M. and G.B.-G. wrote the paper. All authors discussed the results and implications and commented on the manuscript at all stages.

Corresponding author

Correspondence to Sylvain Deville.

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Deville, S., Maire, E., Bernard-Granger, G. et al. Metastable and unstable cellular solidification of colloidal suspensions. Nature Mater 8, 966–972 (2009). https://doi.org/10.1038/nmat2571

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