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Re-entrant solidification in polymer–colloid mixtures as a consequence of competing entropic and enthalpic attractions

Nature Materials volume 14, pages 61–65 (2015)Cite this article

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Abstract

In polymer–colloid mixtures1,2, non-adsorbing polymers dispersed with much larger colloids provide a universal yet specific entropic attraction between the colloids3,4,5,6,7,8. Such so-called depletion interaction2,3 arises from an osmotic-pressure imbalance caused by the polymers and is considered to be independent of temperature. Here we show that, for the most commonly used polymer–colloid depletion systems5,6, the polymer undergoes a crossover from non-adsorbing to adsorbing9 and that, consequently, the effective colloidal interactions depend on temperature. We also find that a combination of the enthalpic (polymer bridging10,11,12) and entropic (polymer exclusion2,3,4) interactions, both attractive, leads to a re-entrant regime where the colloids are dispersed and form solids both on heating and on cooling. We provide a simple model to explain the observed transitions and to fill the theoretical gap at the polymer-adsorption crossover2,9. Our findings open possibilities for colloidal self-assembly5,13, the formation of colloidal crystals14,15 and glasses16, and the behaviour of temperature-controlled viscoelastic materials.

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Figure 1: Re-entrant phase transitions from depletion interactions.
Figure 2: Phase behaviour of the polymer–colloid system.
Figure 3: Simple theoretical model and intercolloid distance test.
Figure 4: Temperature-dependent adsorption energy.
Figure 5: Protocol-dependent optic-elastic material.

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Acknowledgements

We would like to thank A. Grosberg, D. Grier, A. Hollingsworth, G. Hunter, K. Edmond and D. Kraft for fruitful discussions. This work is supported partially by the NSF MRSEC Program under Grant No. DMR-0820341 for materials, and NASA NNX08AK04G for microscopy. L.F., B.L. and P.C. acknowledge support from DOE-BES-DE-SC0007991 for thermal and optical measurements, data acquisition and analysis.

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Author notes

  1. Lang Feng

    Present address: Present address: Corporate Strategic Research, ExxonMobil Research and Engineering, 1545 Route 22 East, Annandale, New Jersey 08801, USA.,

  2. Lang Feng and Bezia Laderman: These authors contributed equally to this work.

Authors and Affiliations

  1. Physics Department, Center for Soft Matter Research, New York University, 4 Washington Place, New York New York 10003, USA,

    Lang Feng, Bezia Laderman, Stefano Sacanna & Paul Chaikin

  2. Chemistry Department, New York University, 100 Washington Square East, New York New York 10003, USA,

    Stefano Sacanna

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  1. Lang Feng
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Contributions

L.F. and P.C. initiated the project. L.F., B.L. and S.S. performed the experiments. L.F., B.L. and P.C. developed the theoretical model. All authors analysed the data and wrote the paper.

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Correspondence to Lang Feng.

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The authors declare no competing financial interests.

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Feng, L., Laderman, B., Sacanna, S. et al. Re-entrant solidification in polymer–colloid mixtures as a consequence of competing entropic and enthalpic attractions. Nature Mater 14, 61–65 (2015). https://doi.org/10.1038/nmat4109

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