The Hidden Effect of Interface Energies in the Polymorphic Stability of Nanocrystalline Titanium Dioxide

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Abstract:

Rutile is the thermodynamically stable phase of coarsely crystalline titanium dioxide; however, metastable anatase is frequently present in TiO2 nanoparticles as a result of the lower surface (solid–vapor) energy of this last polymorph. Here, we show that the presence of a solid–solid interface (frequently present due to aggregation or sintering after synthesis and calcination procedures) also markedly influences the polymorphic stability of TiO2 at the nanoscale. By revisiting calorimetric data reported on TiO2 polymorphs, and using a different analysis approach, we derive both surface and interface energies for anhydrous and hydrous interfaces and redraw the stability diagram for anatase and rutile at the nanoscale including an interface term for the first time. The presence of the solid–solid interface (grain boundary) is observed to shift the critical size of the anatase–rutile transition. A similar approach is suggested to be required to provide a better understanding of reported calorimetric data on nanomaterials such as ZrO2 and Fe2O3.

Document Type: Research Article

DOI: http://dx.doi.org/10.1111/j.1551-2916.2010.04164.x

Affiliations: Peter A. Rock Thermochemistry Laboratory and NEAT ORU, University of California Davis, Davis, California 95616

Publication date: March 1, 2011

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