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Formation of porous crystals via viscoelastic phase separation

Nature Materials volume 16, pages 1022–1028 (2017)Cite this article

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Abstract

Viscoelastic phase separation of colloidal suspensions can be interrupted to form gels either by glass transition or by crystallization. With a new confocal microscopy protocol, we follow the entire kinetics of phase separation, from homogeneous phase to different arrested states. For the first time in experiments, our results unveil a novel crystallization pathway to sponge-like porous crystal structures. In the early stages, we show that nucleation requires a structural reorganization of the liquid phase, called stress-driven ageing. Once nucleation starts, we observe that crystallization follows three different routes: direct crystallization of the liquid phase, the Bergeron process, and Ostwald ripening. Nucleation starts inside the reorganized network, but crystals grow past it by direct condensation of the gas phase on their surface, driving liquid evaporation, and producing a network structure different from the original phase separation pattern. We argue that similar crystal-gel states can be formed in monatomic and molecular systems if the liquid phase is slow enough to induce viscoelastic phase separation, but fast enough to prevent immediate vitrification. This provides a novel pathway to form nanoporous crystals of metals and semiconductors without dealloying, which may be important for catalytic, optical, sensing, and filtration applications.

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Figure 1: Phase behaviour.
Figure 2: Percolated network structures.
Figure 3: Structural evolution at late times.
Figure 4: Stress-driven ageing.
Figure 5: Characterization of the crystal gel.
Figure 6: Crystal-gel formation.

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Acknowledgements

This study was partly supported by Grants-in-Aid for Scientific Research (S) (Grand No. 21224011) and Specially Promoted Research (Grand No. 25000002) from the Japan Society for the Promotion of Science (JSPS). Collaboration between M.L. and H.Tanaka has been funded by CNRS through Projet international de coopération scientifique no. 7464.

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Authors and Affiliations

  1. Institute of Industrial Science, University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505, Japan

    Hideyo Tsurusawa, John Russo & Hajime Tanaka

  2. School of Mathematics, University of Bristol, Bristol BS8 1TW, UK

    John Russo

  3. Univ Lyon, Université Claude Bernard Lyon 1, CNRS, Institut Lumière Matière, F-69622 Villeurbanne, France

    Mathieu Leocmach

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  1. Hideyo Tsurusawa
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H.Tsurusawa and J.R. contributed equally to this work. H.Tanaka conceived and supervised the project, H.Tsurusawa performed experiments, J.R. analysed the data, M.L. linked experiments and analysis, and all the authors discussed and wrote the manuscript.

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Correspondence to Hajime Tanaka.

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Tsurusawa, H., Russo, J., Leocmach, M. et al. Formation of porous crystals via viscoelastic phase separation. Nature Mater 16, 1022–1028 (2017). https://doi.org/10.1038/nmat4945

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