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

The adaptation of the incommensurate structure modulation in Ca(2)CoSi(2)O(7) (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 x 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.