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Challenges and Perspectives of the Polymer-Induced Liquid-Precursor Process: The Pathway from Liquid-Condensed Mineral Precursors to Mesocrystalline Products

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Abstract

The polymer-induced liquid-precursor (PILP) process falls within the category of nonclassical pathways of crystallization and proceeds in a colloid-mediated fashion via a liquid amorphous intermediate. By addition of tiny amounts of polyionic polymers like polyaspartate, polyamines or selected biomineralization proteins, classical nucleation of a solid crystalline phase is suppressed which, in turn, promotes the formation of a liquid-condensed phase of mineral precursor. This unusual ion-enriched liquid-amorphous phase becomes the crucial agent of the precipitation reaction; the process of mineralization is converted from a solution crystallization process to a pseudomorphic solidification process. This change of pathway provides efficient means to synthesize an impressive multitude of mineral morphologies, many of which mimic the features long considered enigmatic in biominerals. Mosaic and mesocrystalline thin films, replicas, hierarchical microspheres or fibrous mineral structures – all these non-equilibrium and non-facetted morphologies can be readily generated by means of the PILP process. In this chapter, we will review our current state of knowledge of this extraordinary crystallization pathway with a special regard to the as of yet unanswered questions. We will discuss the mechanistic foundations of the PILP process and highlight its ultimate provenance in the unexpected liquid/liquid phase separation of mineral solutions, which even occur under additive-free conditions, but do not seem suitable for morphosynthetic exploitation if generated in the absence of polymeric additives.

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Notes

  1. 1.

    Although often misinterpreted, the contribution of Faatz et al. does not claim spinodal decomposition. According to them, spinodal decomposition would lead to “ill-defined morphologies” whereas binodal decomposition to the observed monodisperse spheres. In subsequent contributions, they state their speculation about the binodal nature of this phase separation process much more clearly (Faatz 2005; Faatz et al. 2005).

  2. 2.

    Rieger pointed out that one should not interpret his findings as a claim for a spinodal demixing (see Faraday Discussion transcripts 2007).

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Acknowledgements

This material is based upon the work supported by the National Science Foundation (NSF) under Grant Number DMR-1309657 and by the National Institute of Diabetes and Digestive and Kidney Diseases (NIDDK) of the National Institutes of Health (NIH) under Award Number R01DK092311 and the National Institute of Dental and Craniofacial Research (NIDCR) Award Number 5R01DE016849-07. Any opinions, findings and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation or the National Institutes of Health.

SEW gratefully acknowledges financial support by an Emmy Noether research grant issued by the German Research Foundation (DFG, N° WO1712/3-1) and received further support by the Cluster of Excellence “Engineering of Advanced Materials—Hierarchical Structure Formation for Functional Devices” funded by the DFG (EXC 315).

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Authors and Affiliations

  1. Institute for Glass and Ceramics, Department of Materials Science and Engineering, Friedrich-Alexander University Erlangen-Nürnberg (FAU), Haberstrasse 9a, 91058, Erlangen, Germany

    Stephan E. Wolf

  2. Interdisciplinary Center for Functional Particle Systems (FPS), Friedrich-Alexander University Erlangen-Nürnberg (FAU), Haberstrasse 9a, 91058, Erlangen, Germany

    Stephan E. Wolf

  3. Department of Materials Science and Engineering, University of Florida, 210A Rhines Hall, Gainesville, FL, 32611-6400, USA

    Laurie B. Gower

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Correspondence to Stephan E. Wolf or Laurie B. Gower .

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Editors and Affiliations

  1. University Grenoble Alpes CNRS, ISTerre, Grenoble, France

    Alexander E.S. Van Driessche

  2. Material Physics, BASF SE, Ludwigshafen, Germany

    Matthias Kellermeier

  3. German Research Center for Geosciences, GFZ, Interface Geochemistry Section, Potsdam, Germany

    Liane G. Benning

  4. Department of Chemistry Physical Chemistry, University of Konstanz, Konstanz, Germany

    Denis Gebauer

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Wolf, S.E., Gower, L.B. (2017). Challenges and Perspectives of the Polymer-Induced Liquid-Precursor Process: The Pathway from Liquid-Condensed Mineral Precursors to Mesocrystalline Products. In: Van Driessche, A., Kellermeier, M., Benning, L., Gebauer, D. (eds) New Perspectives on Mineral Nucleation and Growth. Springer, Cham. https://doi.org/10.1007/978-3-319-45669-0_3

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