The nature of the structural phase transition from the hexagonal (4H) phase to the cubic (3C) phase of silver

The phase transition from the hexagonal 4H polytype of silver to the commonly known 3C (fcc) phase was studied in detail using x-ray diffraction, electron microscopy, differential scanning calorimetry and Raman spectroscopy. The phase transition is irreversible and accompanied by extensive microstructural changes and grain growth. Detailed scanning and isothermal calorimetric analysis suggests that it is an autocatalytic transformation. Though the calorimetric data suggest an exothermic first-order phase transition with an onset at 155.6 °C (for a heating rate of 2 K min−1) and a latent heat of 312.9 J g−1, the microstructure and the electrical resistance appear to change gradually from much lower temperatures. The 4H phase shows a Raman active mode at 64.3 cm−1 (at 4 K) that undergoes mode softening as the 4H → 3C transformation temperature is approached. A first-principles density functional theory calculation shows that the stacking fault energy of 4H-Ag increases monotonically with temperature. That 4H-Ag has a higher density of stacking faults than 3C-Ag, implies the metastability of the former at higher temperatures. Energetically, the 4H phase is intermediate between the hexagonal 2H phase and the 3C ground state, as indicated by the spontaneous transformation of the 2H to the 4H phase at −4 °C. Our data appear to indicate that the 4H-Ag phase is stabilized at reduced dimensions and thermally induced grain growth is probably responsible for triggering the irreversible transformation to cubic Ag.