Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Simulating micrometre-scale crystal growth from solution

Nature volume 438, pages 70–73 (2005)Cite this article

Abstract

Understanding crystal growth is essential for controlling the crystallization used in industrial separation and purification processes. Because solids interact through their surfaces, crystal shape can influence both chemical and physical properties1. The thermodynamic morphology can readily be predicted2, but most particle shapes are actually controlled by the kinetics of the atomic growth processes through which assembly occurs3. Here we study the urea–solvent interface at the nanometre scale and report kinetic Monte Carlo simulations of the micrometre-scale three-dimensional growth of urea crystals. These simulations accurately reproduce experimentally observed crystal growth. Unlike previous models of crystal growth4,5,6, no assumption is made that the morphology can be constructed from the results for independently growing surfaces or from an a priori specification of surface defect concentration. This approach offers insights into the role of the solvent, the degree of supersaturation, and the contribution that extended defects (such as screw dislocations) make to crystal growth. It also connects observations made at the nanometre scale, through in situ atomic force microscopy, with those made at the macroscopic level. If extended to include additives, the technique could lead to the computer-aided design of crystals.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Optical microscope and scanning probe microscope pictures of urea crystals.
Figure 2: Characterization of the local environment of a urea molecule.
Figure 3: Snapshots from the molecular dynamics simulations of the urea–solvent interface.
Figure 4: Comparison of the experimental and theoretical micrometre-scale crystal morphologies.

Similar content being viewed by others

References

  1. Winn, D. & Doherty, M. F. Modeling crystal shapes of organic materials grown from solution. Am. Inst. Chem. Eng. J. 46, 1348–1367 (2000)

    Article  CAS  Google Scholar 

  2. Gibbs, J. W. Collected Works (eds Longley, W. R. & van Name, R. G.) (Longman, New York, 1928)

    MATH  Google Scholar 

  3. Rodriguez-Hornedo, N. & Murphy, D. Significance of controlling crystallization mechanisms and kinetics in pharmaceutical systems. J. Pharm. Sci. 88, 651–660 (1999)

    Article  CAS  Google Scholar 

  4. Hartman, P. & Perdok, W. G. On the relations between structure and morphology of crystals. Acta Crystallogr. 8, 48–52 (1955)

    Google Scholar 

  5. Pina, C. M., Becker, U., Risthous, P., Bosbach, D. & Putnis, A. Molecular-scale mechanisms of crystal growth of barite. Nature 395, 483–486 (1998)

    Article  ADS  CAS  Google Scholar 

  6. Liu, X. Y., Boek, E. S., Briels, W. J. & Bennema, P. Prediction of crystal growth morphology based on structural analysis of the solid-fluid interface. Nature 374, 342–345 (1995)

    Article  ADS  CAS  Google Scholar 

  7. Davey, R. J., Mullin, J. W. & Whiting, M. J. L. Habit modification of succinic acid crystals grown from different solvents. J. Cryst. Growth 58, 304–312 (1982)

    Article  ADS  CAS  Google Scholar 

  8. Piana, S. & Gale, J. D. Understanding the barriers to crystal growth: Dynamical simulation of the dissolution and growth of urea from aqueous solution. J. Am. Chem. Soc. 127, 1975–1982 (2005)

    Article  CAS  Google Scholar 

  9. Wulff, G. Zur frage der geschwindigkeitb des wachsthums und der auflosung der krystallflachen. Z. Krist. 34, 449–530 (1901)

    CAS  Google Scholar 

  10. Gillespie, D. T. A general method for numerically simulating the stochastic time evolution of coupled chemical reactions. J. Comp. Phys. 22, 403–434 (1976)

    Article  ADS  MathSciNet  CAS  Google Scholar 

  11. Jónsson, H. Theoretical studies of atomic scale processes relevant to crystal growth. Annu. Rev. Phys. Chem. 51, 623–653 (2000)

    Article  ADS  Google Scholar 

  12. Boerrigter, S. X. M. et al. MONTY: Monte Carlo crystal growth on any crystal structure in any crystallographic orientation; application to fats. J. Phys. Chem. A 108, 5894–5902 (2004)

    Article  CAS  Google Scholar 

  13. Davey, R., Fila, W. & Garside, J. The influence of biuret on the growth kinetics of urea crystals from aqueous solutions. J. Cryst. Growth 79, 607–613 (1986)

    Article  ADS  CAS  Google Scholar 

  14. Land, T. A., Martin, T. L., Potapenko, S., Palmore, G. T. & de Yoreo, J. J. Recovery of surfaces from impurity poisoning during crystal growth. Nature 399, 442–445 (1999)

    Article  ADS  CAS  Google Scholar 

  15. Fleming, S. D. & Rohl, A. L. GDIS: a visualization program for molecular and periodic systems. Z Krist. 220, 1–5 (2005)

    Google Scholar 

  16. Swaminathan, S., Craven, B. M., Spackman, M. A. & Stewart, R. F. Theoretical and experimental studies of the charge density in urea. Acta Crystallogr. B 40, 398–404 (1984)

    Article  Google Scholar 

  17. Lindhal, E., Hess, B. & van der Spoel, D. GROMACS 3.0: a package for molecular simulation and trajectory analysis. J. Mol. Modeling 7, 306–317 (2001)

    Article  Google Scholar 

  18. Smith, L. J., Berendsen, H. J. C. & van Gusteren, W. F. Computer simulation of urea-water mixtures: A test of force field parameters for use in biomolecular simulation. J. Phys. Chem. B 108, 1065–1071 (2004)

    Article  CAS  Google Scholar 

  19. van Gusteren, W. F., et al. Biomolecular Simulation: the GROMOS96 Manual and User Guide 1–1024 (Vdf Hochschulverlag AG an der ETH Zurich, Zurich, 1996)

    Google Scholar 

  20. Essman, U. et al. A smooth particle mesh Ewald method. J. Chem. Phys. 103, 8577–8593 (1995)

    Article  ADS  Google Scholar 

  21. Pinck, L. A. & Kelly, M. A. The solubility of urea in water. J. Am. Chem. Soc. 47, 2170–2172 (1925)

    Article  CAS  Google Scholar 

  22. Boomadevi, S., Dhanasekaran, R. & Ramasamy, P. Investigations on nucleation and growth kinetics of urea crystals from methanol. Cryst. Res. Technol. 37, 159–168 (2002)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We are grateful to A. Rohl for discussions, and to T. Dincer for assistance with the optical microscope. S.P. acknowledges financial support from an Australian Research Fellowship, while S.P. and J.D.G. both gratefully acknowledge the support of the Government of Western Australia through the Premiers Research Fellowship programme. Author Contributions S.P. performed all the calculations and the optical microscopy, M.R. produced the atomic force microscope images, J.D.G. conceived the project and wrote the manuscript with S.P.

Author information

Authors and Affiliations

  1. Nanochemistry Research Institute, Department of Applied Chemistry, Curtin University of Technology, GPO Box U1987, 6845, Western, Perth, Australia

    Stefano Piana, Manijeh Reyhani & Julian D. Gale

Authors
  1. Stefano Piana
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Manijeh Reyhani
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Julian D. Gale
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Julian D. Gale.

Ethics declarations

Competing interests

Reprints and permissions information is available at npg.nature.com/reprintsandpermissions. The authors declare no competing financial interests.

Supplementary information

Supplementary Notes

This contains Supplementary Methods, Supplementary Tables (including tabulations of the rate constants derived from the molecular dynamics and used in the kinetic Monte Carlo simulations) and additional references. (DOC 300 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Piana, S., Reyhani, M. & Gale, J. Simulating micrometre-scale crystal growth from solution. Nature 438, 70–73 (2005). https://doi.org/10.1038/nature04173

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature04173

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing