Abstract
Dynamical and structural heterogeneities have long been thought to play a key role in a unified picture of solidification in view of the two competitive processes of crystallization and vitrification. Here, we study these heterogeneities by means of a combination of dynamic and static light-scattering techniques applied to the simplest model system exhibiting crystallization and vitrification: the colloidal hard-sphere system. Our method enables us to quantify and correlate the temporal evolution of the amount of ordered clusters (precursors) and the amount of slow particles. Our analysis shows that their temporal evolutions are closely related and that there is an intimate link between structural and dynamic heterogeneities, crystal nucleation and the non-crystallization transition.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$209.00 per year
only $17.42 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Berthier, L. & Biroli, G. Theoretical perspective on the glass transition and amorphous materials. Rev. Mod. Phys. 83, 587–645 (2011).
Richert, R. Heterogeneous dynamics in liquids: fluctuations in space and time. J. Phys. Condens. Matter 14, R703–R738 (2002).
Widmer-Cooper, A. & Harrowell, P. On the relationship between structure and dynamics in a supercooled liquid. J. Phys. Condens. Matter 17, S4025–S4034 (2005).
van Megen, W. & Bryant, G. Dynamical heterogeneity and the freezing transition in hard-sphere suspensions: further analysis of the mean square displacement and the velocity autocorrelation function. Phys. Rev. E 76, 021402 (2007).
Taffs, J., Williams, S. R., Tanaka, H. & Royall, C. P. Structure and kinetics in the freezing of nearly hard spheres. Soft Matter 9, 297–305 (2013).
Kawasaki, T. & Tanaka, H. Formation of a crystal nucleus from liquid. Proc. Natl Acad. Sci. USA 107, 14036–14041 (2010).
Schöpe, H. J., Bryant, G. & van Megen, W. Two-step crystallization kinetics in colloidal hard-sphere systems. Phys. Rev. Lett. 96, 175701 (2006).
Schilling, T., Schöpe, H. J., Oettel, M., Opletal, G. & Snook, I. Precursor-mediated crystallization process in suspensions of hard spheres. Phys. Rev. Lett. 105, 025701 (2010).
Sanz, E. et al. Avalanches mediate crystallization in a hard-sphere glass. Proc. Natl Acad. Sci. USA 111, 75–80 (2014).
Ediger, M. D. Spatially heterogeneous dynamics in supercooled liquids. Annu. Rev. Phys. Chem. 51, 99–128 (2000).
Kawasaki, T. & Tanaka, H. Structural origin of dynamic heterogeneity in three-dimensional colloidal glass formers and its link to crystal nucleation. J. Phys. Condens. Matter 22, 232102 (2010).
Widmer-Cooper, A. & Harrowell, P. Predicting the long-time dynamic heterogeneity in a supercooled liquid on the basis of short-time heterogeneities. Phys. Rev. Lett. 96, 185701 (2006).
Brito, C. & Wyart, M. Geometric interpretation of previtrification in hard sphere liquids. J. Chem. Phys. 131, 024504 (2009).
Matharoo, G. S., Razul, M. S. G. & Poole, P. H. Structural and dynamical heterogeneity in a glass-forming liquid. Phys. Rev. E 74, 050502(R) (2006).
Speck, T., Malins, A. & Royall, C. P. First-order phase transition in a model glass former: coupling of local structure and dynamics. Phys. Rev. Lett. 109, 195703 (2012).
Weeks, E. R. & Weitz, D. A. Properties of cage rearrangements observed near the colloidal glass transition. Phys. Rev. Lett. 89, 095704 (2002).
Conrad, J. C., Starr, F. W. & Weitz, D. A. Weak correlations between local density and dynamics near the glass transition. J. Phys. Chem. B 109, 21235–21240 (2005).
Royall, C. P., Williams, S. R., Ohtsuka, T. & Tanaka, H. Direct observation of a local structural mechanism for dynamic arrest. Nature Mater. 7, 556–561 (2008).
Leocmach, M. & Tanaka, H. Roles of icosahedral and crystal-like order in the hard spheres glass transition. Nature Commun. 3, 1974 (2012).
Hocky, G. M., Coslovich, D., Ikeda, A. & Reichman, D. R. Correlation of local order with particle mobility in supercooled liquids is highly system dependent. Phys. Rev. Lett. 113, 157801 (2014).
Kegel, W. K. & van Blaaderen, A. Direct observation of dynamical heterogeneities in colloidal hard sphere suspensions. Science 287, 290–293 (2000).
Weeks, E. R., Crocker, J. C., Levitt, A. C., Schofield, A. & Weitz, D. A. Three-dimensional direct imaging of structural relaxation near the colloidal glass transition. Science 287, 627–631 (2000).
Courtland, R. E. & Weeks, E. R. Direct visualization of ageing in colloidal glasses. J. Phys. Condens. Matter 15, S359–S365 (2003).
Conrad, J. C., Dhillon, P. P., Weeks, E. R., Reichman, D. R. & Weitz, D. A. Contribution of slow clusters to the bulk elasticity near the colloidal glass transition. Phys. Rev. Lett. 97, 265701 (2006).
Valeriani, C. et al. From compact to fractal crystalline clusters in concentrated systems of monodisperse hard spheres. Soft Matter 8, 4960–4970 (2012).
Schöpe, H. J., Bryant, G. & van Megen, W. Effect of polydispersity on the crystallization kinetics of suspensions of colloidal hard spheres when approaching the glass transition. J. Chem. Phys. 127, 084505 (2007).
Franke, M., Golde, S. & Schöpe, H. J. Solidification of a colloidal hard sphere like model system approaching and crossing the glass transition. Soft Matter 10, 5380–5389 (2014).
Tan, P., Xu, N. & Xu, L. Visualizing kinetic pathways of homogeneous nucleation in colloidal crystallization. Nature Phys. 10, 73–79 (2014).
Pusey, P. N. & van Megen, W. Phase-behavior of concentrated suspensions of nearly hard colloidal spheres. Nature 320, 340–342 (1986).
Kasper, A., Bartsch, E. & Silescu, H. Self-diffusion in concentrated colloidal suspensions studied by digital video microscopy of core–shell tracer particles. Langmuir 14, 5004–5010 (1998).
Flenner, E., Zhang, M. & Szamel, G. Analysis of a growing dynamic length scale in a glass-forming binary hard-sphere mixture. Phys. Rev. E 83, 051501 (2011).
Golde, S., Franke, M. & Schöpe, H. J. Space-resolved dynamic light scattering probing inhomogeneous dynamics in soft matter. AIP Conf. Proc. 1518, 304–307 (2013).
Harland, J. L. & van Megen, W. Crystallization kinetics of suspensions of hard colloidal spheres. Phys. Rev. E 55, 3054–3067 (1997).
Pusey, P. N. & van Megen, W. Dynamic light-scattering by non-ergodic media. Phys. A 157, 705–741 (1989).
van Megen, W. & Underwood, S. M. Glass-transition in colloidal hard spheres—measurement and mode-coupling-theory analysis of the coherent intermediate scattering function. Phys. Rev. E 49, 4206–4220 (1994).
Martinez, V. A., Bryant, G. & van Megen, W. Slow dynamics and aging of a colloidal hard sphere glass. Phys. Rev. Lett. 101, 135702 (2008).
Schöpe, H. J., Marnette, O., van Megen, W. & Bryant, G. Preparation and characterization of particles with small differences in polydispersity. Langmuir 23, 11534–11539 (2007).
Acknowledgements
We are pleased to thank G. Bryant and M. Franke for helpful discussions and E. Bartsch for the particle synthesis. We gratefully acknowledge financial support by the Deutsche Forschungsgemeinschaft (DFG) (Pa459/13, Pa459/16, and SCHO 1054/3-3). S.G. is a recipient of a fellowship through the Excellence Initiative (DFG/GSC 266).
Author information
Authors and Affiliations
Contributions
H.J.S. designed the research and set-up. S.G. and H.J.S. realized the set-up. S.G. performed the research. S.G. and H.J.S. analysed data. S.G., T.P. and H.J.S. contributed to writing this paper.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Supplementary information
Supplementary information
Supplementary information (PDF 2536 kb)
Rights and permissions
About this article
Cite this article
Golde, S., Palberg, T. & Schöpe, H. Correlation between dynamical and structural heterogeneities in colloidal hard-sphere suspensions. Nature Phys 12, 712–717 (2016). https://doi.org/10.1038/nphys3709
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nphys3709
This article is cited by
-
Structure determines where crystallization occurs in a soft colloidal glass
Nature Physics (2021)
-
Spatial coherence of light inside three-dimensional media
Nature Communications (2021)
-
Demonstration of variable angle super-heterodyne dynamic light scattering for measuring colloidal dynamics
Colloid and Polymer Science (2021)
-
Network structure and dynamics heterogeneities in Al2O3 system: insight from visualization and analysis of molecular dynamics data
Indian Journal of Physics (2019)
-
Breakdown of diffusivity–entropy scaling in colloidal glass-forming liquids
Communications Physics (2018)