Abstract
Many crystallization processes of great importance, including frost heave, biomineralization, the synthesis of nanomaterials, and scale formation, occur in small volumes rather than bulk solution. Here, the influence of confinement on crystallization processes is described, drawing together information from fields as diverse as bioinspired mineralization, templating, pharmaceuticals, colloidal crystallization, and geochemistry. Experiments are principally conducted within confining systems that offer well-defined environments, varying from droplets in microfluidic devices, to cylindrical pores in filtration membranes, to nanoporous glasses and carbon nanotubes. Dramatic effects are observed, including a stabilization of metastable polymorphs, a depression of freezing points, and the formation of crystals with preferred orientations, modified morphologies, and even structures not seen in bulk. Confinement is also shown to influence crystallization processes over length scales ranging from the atomic to hundreds of micrometers, and to originate from a wide range of mechanisms. The development of an enhanced understanding of the influence of confinement on crystal nucleation and growth will not only provide superior insight into crystallization processes in many real-world environments, but will also enable this phenomenon to be used to control crystallization in applications including nanomaterial synthesis, heavy metal remediation, and the prevention of weathering.
Highlights
We present a review of the effects of confinement on crystallization—and the origins of these—where our goal has Crystallization is a hugely important phenomenon that under- been to create a comprehensive picture of this phenomenon pins processes as diverse as the production of nanomaterials, by bringing together information from these diverse fields.ceramics, and pharmaceuticals, the generation of bones, teeth, Together, these demonstrate that confinement can influence and seashells, ice formation and weathering in our environ- factors including nucleation rates, melting and freezing points, ment, and the formation of scale in kettles and oil wells
We describe confining systems of increasing geometrical complexity including cylindrical pores, mesoporous solids, wedgeshaped pores, and manufactured reaction chambers, where these demonstrate how effects operate over different length scales and geometries
Insight into the effects of confinement on crystallization has been gained from diverse systems offering length scales varying from the nanoscale to hundreds of micrometers, and geometries including sponge-like networks of pores and finite droplets
Summary
We present a review of the effects of confinement on crystallization—and the origins of these—where our goal has Crystallization is a hugely important phenomenon that under- been to create a comprehensive picture of this phenomenon pins processes as diverse as the production of nanomaterials, by bringing together information from these diverse fields. We describe confining systems of increasing geometrical complexity including cylindrical pores, mesoporous solids, wedgeshaped pores, and manufactured reaction chambers, where these demonstrate how effects operate over different length scales and geometries This is followed by an overview of crystallization within heterogeneous porous media, where this is offered from the perspective of the geosciences, and we finish with a description of the crystallization of colloidal particles in constrained volumes, where this can provide valuable insight into the behavior of crystals of atomic and molecular species. His current research is focused on the crystallization of inorganic compounds in nanoporous media with an emphasis on crystal morphology, polymorph control, and the influence of pore surface chemistry
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