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Hexagonal → Cubic Transition in Ag: Prototype for a General Mechanism for Irreversible Solid-Solid Structural Transformations
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DOI：10.1021/acs.jpcc.9b04727.png)
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Using the hexagonal -> cubic transition in Ag as a prototype, we provide a simple, mechanistic model for a large class of irreversible solid-solid structural transformations. Our conclusions are based on a detailed study of the effects of spatial confinement on the kinetically arrested, metastable hexagonal (4H) polymorph of Ag, as it undergoes a structural phase transition to the stable, cubic (3C) form. The phase transition was monitored using in situ, hot-stage X-ray diffraction and transmission electron microscopy. 4H-Ag was synthesized in the form of thick films (bulk phase) and also confined within the pores of alumina templates with different mean pore diameters. With an increase in the degree of confinement, the transition is progressively retarded. Finally, it is almost completely arrested within pores of diameter approximate to 37 nm. Our data indicate unequivocally that the phase transformation occurs via thermal aggregation and growth of the crystallites, a process that is inherently irreversible. In all cases where the initial metastable phase is stabilized by size reduction, the irreversible transformation may be expected to follow a similar route. These results should have important implications for a large class of size-stabilized, technologically attractive materials including gamma-Fe2O3, gamma-Al2O3, anatase-TiO2, tetragonal ZrO2, tetragonal HfO2, and cubic Cu2O.
Keyword:
MAGNETIC-PROPERTIES
OPTICAL-PROPERTIES
CRYSTAL-STRUCTURE
SIZE
PHASE
NANOPARTICLES
ZIRCONIA
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期刊
IF:
3.2
论文数:
5.6W
被引数:
15.0W
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