Transition from the incommensurately modulated structure to the lock-in phase in Co-åkermanite

Abstract
The adaptation of the incommensurate structure modulation in Ca2CoSi2O7 (dicalcium cobalt disilicate) single crystals to decreasing temperature has been examined using in situ high-resolution transmission electron microscopy and electron diffraction. The transition from the incommensurate to the commensurate lock-in phase of Co-åkermanite exhibits a pronounced hysteresis of a highly strained metastable state with a characteristic microdomain morphology. A network of domain walls surrounding single orientation domains develops out of the room-temperature tartan pattern, the domains increase in size and their alignment changes from crystallographic to random. At 100 K the phase transition becomes almost complete. In parallel, the evolution of the modulation structure can be described by a change from a loose arrangement of octagonal tilings into a close-packed configuration of overlapping octagons in the commensurate low-temperature lock-in phase. Thereby, the octagon represents the ordered distribution of low-coordinated Ca clusters within a nanodomain extending over 4 × 4 subunits, on average [Riester et al. (2000). Z. Kristallogr. 215, 102–109]. The modulation wavevector was found to change from q 1,2 = 0.295 (a* ± b*) at 300 K to q 1,2 = 0.320 (a* ± b*) at 100 K.

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