Correlation between anisotropy and lattice distortions in single crystal calcite nanowires grown in confinement.

Growing nanostructures in confinement allows for the control of their shape, size and structure, as required in many technological applications. We investigated the crystal structure and morphology of calcite nanowires, precipitated in the pores of track-etch membranes, by employing transmission electron microscopy and selected area electron diffraction (SAED). The data showed that the nanowires show no preferred growth orientation and that the crystallographic orientation rotated along the length of the nanowire, with lattice rotation angles of several degrees per micrometer. Finite element calculations indicated that the rotation is caused by the anisotropic crystallographic nature of the calcite mineral, the nanoscale diameter of the wires and the confined space provided by the membrane pore. This phenomenon should also be observed in other single crystal nanowires made from anisotropic materials, which could offer the potential of generating nanostructures with tailored optical, electronic and mechanical properties.

Microstructural evolution and nanoscale crystallography in scleractinian coral spherulites.

One of the most important aspects in the research on reef-building corals is the process by which corals accrete biogenic calcium carbonate. This process leads to the formation of a mineral/organic composite and it is believed that the development of the nano- and microstructure of the mineral phase is highly sensitive to the growth conditions. Transmission electron microscopy (TEM) analysis of large-scale (10×30µm) focused ion beam (FIB) prepared lamellae was performed on adult and juvenile scleractinian coral skeleton specimens. This allowed for the investigation of the nano and microstructure and the crystallographic orientation of the aragonite mineral. We found the following microstructural evolution in the adult Porites lobata specimens: randomly oriented nanocrystals with high porosity, partly aligned nanocrystals with high porosity and areas of dense acicular crystals of several micrometers extension, the latter two areas are aligned close to the [001] direction (Pmcn space group). To the best of our knowledge, for the first time the observed microstructure could be directly correlated with the dark/bright bands characteristic of the diurnal growth cycle. We hypothesize that this mineral structure sequence and alignment in the adult specimen is linked to the photosynthetic diurnal cycle of the zooxanthellea regulating the oxygen levels and organic molecule transport to the calcifying medium. These observations reveal a strong control of crystal morphology by the organism and the correlation of the accretion process. No indication for a self-assembly of nanocrystalline units, i.e., a mesocrystal structure, on the micrometer scale could be found.