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Crystallization by particle attachment is a colloidal assembly process

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Abstract

The nucleation of crystals has long been thought to occur through the stochastic association of ions, atoms or molecules to form critical nuclei, which will later grow out to crystals1. Only in the past decade has the awareness grown that crystallization can also proceed through the assembly of different types of building blocks2,3, including amorphous precursors4, primary particles5, prenucleation species6,7, dense liquid droplets8,9 or nanocrystals10. However, the forces that control these alternative pathways are still poorly understood. Here, we investigate the crystallization of magnetite (Fe3O4) through the formation and aggregation of primary particles and show that both the thermodynamics and the kinetics of the process can be described in terms of colloidal assembly. This model allows predicting the average crystal size at a given initial Fe concentration, thereby opening the way to the design of crystals with predefined sizes and properties.

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Fig. 1: Cryo-TEM of different stages of magnetite formation.
Fig. 2: Quantitative analysis of the TEM images.
Fig. 3: Thermodynamic model.
Fig. 4: Model of the CPA process.

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Data availability

All data are available from the authors upon reasonable request.

Code availability

All Python and Mathematica scripts used for the theoretical modelling are available from the authors upon reasonable request.

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Acknowledgements

We thank R. Tuinier and J. Landman for useful discussions. A.I. thanks the Python community for their effort in developing open-source scientific resources. The work of G.M. is supported by the Technology Foundation STW, Applied Science Division of the Netherlands Organization for Scientific Research (NWO). The work by A.A. was supported by a Grant-in-Aid for Scientific Research (B) (no. 18H01794) from the Japan Society for the Promotion of Science (JSPS).

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Author notes

  1. Nico A. J. M. Sommerdijk

    Present address: Department of Biochemistry, Radboud Institute for Molecular Life Sciences, Radboud University Medical Center, Nijmegen, the Netherlands

  2. These authors contributed equally: Giulia Mirabello, Alessandro Ianiro.

Authors and Affiliations

  1. Laboratory of Materials and Interface Chemistry and Center of Multiscale Electron Microscopy, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, the Netherlands

    Giulia Mirabello, Paul H. H. Bomans, Heiner Friedrich, Gijsbertus de With & Nico A. J. M. Sommerdijk

  2. Institute for Complex Molecular Systems, Eindhoven University of Technology, Eindhoven, The Netherlands

    Giulia Mirabello, Alessandro Ianiro, Paul H. H. Bomans, Heiner Friedrich & Nico A. J. M. Sommerdijk

  3. Laboratory of Physical Chemistry, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Eindhoven, the Netherlands

    Alessandro Ianiro

  4. Division of Biotechnology and Life Science, Institute of Engineering, Tokyo University of Agriculture and Technology, Tokyo, Japan

    Takuto Yoda & Atsushi Arakaki

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  1. Giulia Mirabello
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Contributions

N.A.J.M.S. and G.M. conceived and designed the experiments. G.M. performed the synthetic experiments. G.M., H.F. and P.H.H.B. conceived and designed the TEM and cryo-TEM experiments. G.M. and P.H.H.B. performed the TEM and cryo-TEM acquisition and analysis. A.I. developed the theoretical model. G.d.W. supervised the theoretical modelling. A.A. and T.Y. performed the vibrating sample magnetometry analysis. N.A.J.M.S., G.d.W., G.M. and A.I. contributed to writing the manuscript.

Corresponding author

Correspondence to Nico A. J. M. Sommerdijk.

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Supplementary Information

Supplementary materials, discussions 1–3, Tables 1–3, Figs. 1–9 and references.

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Mirabello, G., Ianiro, A., Bomans, P.H.H. et al. Crystallization by particle attachment is a colloidal assembly process. Nat. Mater. 19, 391–396 (2020). https://doi.org/10.1038/s41563-019-0511-4

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