The Nanocrystalline SnO 2 –TiO 2 System‒Part II: Surface Energies and Thermodynamic Stability

Miagava, Joice; da Silva, Andre L.; Navrotsky, Alexandra; Castro, Ricardo H. R.; Gouvêa, Douglas; Rohrer, ed., G.

doi:10.1111/jace.13954

The Nanocrystalline SnO ₂ –TiO ₂ System‒Part II: Surface Energies and Thermodynamic Stability

Journal Article · Thu Oct 15 00:00:00 EDT 2015 · Journal of the American Ceramic Society

DOI:https://doi.org/10.1111/jace.13954· OSTI ID:1401402

Miagava, Joice ^[1]; da Silva, Andre L. ^[2]; Navrotsky, Alexandra ^[2]; Castro, Ricardo H. R. ^[2]; Gouvêa, Douglas ^[3]; Rohrer, ed., G.

Peter A. Rock Thermochemistry Laboratory &, NEAT ORU University of California Davis California 95616, Department of Metallurgical and Materials Engineering University of São Paulo São Paulo 05508‐030 Brazil
Peter A. Rock Thermochemistry Laboratory &, NEAT ORU University of California Davis California 95616
Department of Metallurgical and Materials Engineering University of São Paulo São Paulo 05508‐030 Brazil

The thermodynamic stability of nanocrystalline SnO ₂ –TiO ₂ solid solutions was studied experimentally. Microcalorimetry of water adsorption revealed a systematic decrease in the surface energy with increasing Ti ⁴⁺ content in the SnO ₂ ‐rich compositions, consistent with previous reports of Ti ⁴⁺ segregation on the surface. The surface energy change was accompanied by an increase in the magnitude of the heat of water adsorption, also indicating a modification of the SnO ₂ surface by Ti ⁴⁺ . Supporting the water adsorption data, calculations using high‐temperature oxide melt solution calorimetry data also suggest a decrease in the interface energies. A thermodynamic analysis showed that the observed surface energy decrease is responsible for an increase in the stability of solid solutions in the nanophase regime. Although a miscibility gap is expected in this system from bulk phase diagrams, the surface energy contribution modifies the bulk trend and promotes extensive solid solutions when the surface area is above a critical value dependent on the surface energy and the bulk enthalpy of mixing.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

OSTI ID:: 1401402

Journal Information:: Journal of the American Ceramic Society, Journal Name: Journal of the American Ceramic Society Journal Issue: 2 Vol. 99; ISSN 0002-7820

Publisher:: Wiley-BlackwellCopyright Statement

Country of Publication:: United States

Language:: English

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The Nanocrystalline SnO 2 –TiO 2 System‒Part II: Surface Energies and Thermodynamic Stability

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The Nanocrystalline SnO ₂ –TiO ₂ System‒Part II: Surface Energies and Thermodynamic Stability