Abstract
Monodisperse colloidal suspensions of micrometre-sized spheres are playing an increasingly important role as model systems to study, in real space, a variety of phenomena in condensed matter physics—such as glass transitions and crystal nucleation1,2,3,4. But to date, no quantitative real-space studies have been performed on crystal melting, or have investigated systems with long-range repulsive potentials. Here we demonstrate a charge- and sterically stabilized colloidal suspension—poly(methyl methacrylate) spheres in a mixture of cycloheptyl (or cyclohexyl) bromide and decalin—where both the repulsive range and the anisotropy of the interparticle interaction potential can be controlled. This combination of two independent tuning parameters gives rise to a rich phase behaviour, with several unusual colloidal (liquid) crystalline phases, which we explore in real space by confocal microscopy. The softness of the interaction is tuned in this colloidal suspension by varying the solvent salt concentration; the anisotropic (dipolar) contribution to the interaction potential can be independently controlled with an external electric field ranging from a small perturbation to the point where it completely determines the phase behaviour. We also demonstrate that the electric field can be used as a pseudo-thermodynamic temperature switch to enable real-space studies of melting transitions. We expect studies of this colloidal model system to contribute to our understanding of, for example, electro- and magneto-rheological fluids.
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References
Grier, D. G. & Murray, C. A. The microscopic dynamics of freezing in supercooled colloidal fluids. J. Chem. Phys. 100, 9088–9095 (1994)
van Blaaderen, A. & Wiltzius, P. Real-space structure of colloidal hard-sphere glasses. Science 270, 1177–1179 (1995)
Kegel, W. K. & van Blaaderen, A. Direct observation of dynamical heterogeneities in colloidal hard-sphere suspensions. Science 287, 290–293 (2000)
Gasser, U., Weeks, E. R., Schofield, A., Pusey, P. N. & Weitz, D. A. Real-space imaging of nucleation and growth in colloidal crystallization. Science 292, 258–262 (2001)
Antl, L., Goodwin, J., Hill, R., Ottewill, R. & Waters, J. The preparation of poly(methyl methacrylate) latices in non-aqueous media. Colloids Surf. 17, 67–78 (1986)
van Blaaderen, A. & Vrij, A. Synthesis and characterization of colloidal dispersions of fluorescent, monodisperse silica spheres. Langmuir 8, 2921–2931 (1992)
Dhont, J. K. G., Smits, C. & Lekkerkerker, H. N. W. A time resolved static light-scattering study on nucleation and crystallization in a colloidal system. J. Colloid Interf. Sci. 152, 386–401 (1992)
Russel, W. B., Chaikin, P. M., Zhu, J., Meyer, W. V. & Rogers, R. Dendritic growth of hard sphere crystals. Langmuir 13, 3871–3881 (1997)
Palberg, T. Crystallization kinetics of repulsive colloidal spheres. J. Phys. Condens. Matter 11, R323–R360 (1999)
Harland, J. L. & vanMegen, W. Crystallization kinetics of suspensions of hard colloidal spheres. Phys. Rev. E 55, 3054–3067 (1997)
Gast, A. P. & Russel, W. B. Simple ordering in complex fluids—Colloidal particles suspended in solution provide intriguing models for studying phase transitions. Phys. Today 51, 24–30 (1998)
Pham, K. N. et al. Multiple glassy states in a simple model system. Science 269, 104–106 (2002)
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)
Pusey, P. N. & van Megen, W. Phase behaviour of concentrated suspensions of nearly hard colloidal spheres. Nature 320, 340–342 (1986)
Russel, W. B., Schowalter, W. R. & Saville, D. A. Colloidal Dispersions (Cambridge Univ. Press, Cambridge, 1999)
Parthasarathy, M. & Klingenberg, D. J. Electrorheology: mechanisms and models. Mater. Sci. Eng. R17, 57–103 (1996)
Tao, R. & Jiang, Q. Simulation of structure formation in an electrorheological fluid. Phys. Rev. Lett. 73, 205–208 (1994)
Martin, J. E., Odinek, J. & Halsey, T. C. Evolution of structure in a quiescent electrorheological fluid. Phys. Rev. Lett. 69, 1524–1527 (1992)
Martin, J. E., Anderson, R. A. & Tigges, C. P. Simulation of the athermal coarsening of composites structured by a uniaxial field. J. Chem. Phys. 108, 3765–3787 (1998)
Dassanayake, U., Fraden, S. & van Blaaderen, A. Structure of electrorheological fluids. J. Chem. Phys. 112, 3851–3858 (2000)
Bosma, G. et al. Preparation of monodisperse, fluorescent PMMA-latex colloids by dispersion polymerization. J. Colloid Interf. Sci. 245, 292–300 (2002)
de Hoog, E. H. A., Kegel, W. K., van Blaaderen, A. & Lekkerkerker, H. N. W. Direct observation of crystallization and aggregation in a phase-separating colloid-polymer suspension. Phys. Rev. E 64, 021407 (2001)
Pronk, S. & Frenkel, D. Can stacking faults in hard-sphere crystals anneal out spontaneously? J. Chem. Phys. 110, 4589–4592 (1999)
Robbins, M. O., Kremer, K. & Grest, G. S. Phase diagram and dynamics of Yukawa systems. J. Chem. Phys. 88, 3286–3312 (1988)
Sirota, E. B. et al. Complete phase-diagram of a charged colloidal system - A synchrotron X-ray scattering study. Phys. Rev. Lett. 62, 1524–1527 (1989)
Monovoukas, Y. & Gast, A. P. The experimental phase diagram of charged colloidal suspensions. J. Colloid Interf. Sci. 128, 533–548 (1989)
El Azhar, F., Baus, M., Ryckaert, J.-P. & Meijer, E. J. Line of triple points for the hard-core Yukawa model: A computer simulation study. 112, 5121–5126 (2000).
Halsey, T. C. & Toor, W. Structure of electrorheological fluids. Phys. Rev. Lett. 65, 2820–2823 (1990)
Holtz, J. H. & Asher, S. A. Polymerized colloidal crysal hydrogel films as intelligent chemical sensing materials. Nature 389, 829–832 (1997)
O'Brien, R. W. & White, L. R. Electrophoretic mobility of a spherical colloidal particle. J. Chem. Soc. Faraday Trans. II 74, 1607–1626 (1978)
Acknowledgements
We thank G. Bosma for particle synthesis, C. van Kats for electrophoresis measurements, H. Wisman for technical support, K. van Walree for the suggestion of TCAB salt, and discussion of charge mechanisms, and J. Hoogenboom, S. Auer and D. Frenkel for discussion. We also thank M. Dijkstra and G. Patey for a critical reading of the manuscript. This work is part of the research program of the ‘Stichting voor Fundamenteel Onderzoek der Materie (FOM)’, which is financially supported by the ‘Nederlandse organisatie voor Wetenschappelijke Onderzoek (NWO)’.
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Yethiraj, A., van Blaaderen, A. A colloidal model system with an interaction tunable from hard sphere to soft and dipolar. Nature 421, 513–517 (2003). https://doi.org/10.1038/nature01328
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DOI: https://doi.org/10.1038/nature01328
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