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The role of nanopore shape in surface-induced crystallization

Nature Materials volume 10, pages 867–871 (2011)Cite this article

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Abstract

Crystallization of a molecular liquid from solution often initiates at solid–liquid interfaces1,2,3, and nucleation rates are generally believed to be enhanced by surface roughness4,5. Here we show that, on a rough surface, the shape of surface nanopores can also alter nucleation kinetics. Using lithographic methods, we patterned polymer films with nanopores of various shapes and found that spherical nanopores 15–120 nm in diameter hindered nucleation of aspirin crystals, whereas angular nanopores of the same size promoted it. We also show that favourable surface–solute interactions are required for angular nanopores to promote nucleation, and propose that pore shape affects nucleation kinetics through the alteration of the orientational order of the crystallizing molecule near the angles of the pores. Our findings have clear technological implications, for instance in the control of pharmaceutical polymorphism and in the design of ‘seed’ particles for the regulation of crystallization of fine chemicals.

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Figure 1: Fabrication of polymer films with spherical nanopores by NpIL.
Figure 2: Angular nanopores on AA-co-DVB polymer films and their templates.
Figure 3: Effect of the nanopore shape in AA-co-DVB polymer films on the nucleation kinetics of aspirin: spherical pores versus hexagonal pores and square pores of the same size.
Figure 4: Angle-directed nucleation of aspirin crystals induced by angular nanopores.
Figure 5: Effect of polymer surface chemistry on the kinetics of angular nanopore-induced nucleation of aspirin: AA-co-DVB versus AM-co-DVB.

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Acknowledgements

We acknowledge the Novartis-MIT Center for Continuous Manufacturing for funding. We are grateful to T. Savas at MIT Research Laboratory of Electronics for fabricating the imprint mould with Si square nanopillars and to K. Gleason for use of her equipment for plasma treatment and glass silanization.

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Author notes

  1. Takuya Harada

    Present address: Present address: Nanotechnology Center, Yokohama R&D Laboratories, Furukawa Electric Co., Ltd., 2-4-3, Okano, Nishi-ku, Yokohama 220-0073, Japan,

Authors and Affiliations

  1. Department of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Massachusetts 02139, E19-502b, Cambridge, USA

    Ying Diao, Takuya Harada, Allan S. Myerson, T. Alan Hatton & Bernhardt L. Trout

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  1. Ying Diao
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  2. Takuya Harada
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  3. Allan S. Myerson
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Contributions

Y.D. designed, carried out the experiments and wrote the manuscript. B.L.T., T.A.H. and A.S.M. supervised the work, guided and revised the manuscript. T.H. synthesized and characterized the Fe3O4 magnetic nanoparticles and co-wrote the Supplementary Information.

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Correspondence to Takuya Harada or Bernhardt L. Trout.

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Diao, Y., Harada, T., Myerson, A. et al. The role of nanopore shape in surface-induced crystallization. Nature Mater 10, 867–871 (2011). https://doi.org/10.1038/nmat3117

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