Structural states of Mg-cordierite I: Order parameters from synchrotron X-ray and NMR data

The hexagonal to orthorhombic phase transition in synthetic Mg-cordierite has been studied by (i) measuring the spontaneous strain associated with the transition using Synchrotron X-ray powder diffraction and (ii) measuring the degree of Al, Si order in terms of the number of Al-O-Al bonds per formula unit using solid state NMR spectroscopy. This defines the two order parameters Q and Q_odrespectively, and their relationship as a function of annealing temperature and time is used to define the structural states of cordierite during the ordering sequence. The formation of modulated hexagonal cordierite within which a high degree of Al, Si order can be attained, results in a strongly non-linear relationship between Q and Q_od.The transition from modulated to orthorhombic cordierite is strongly first-order under all temperature conditions studied and involves a large step in Q, while Q_odchanges continuously throughout the ordering sequence with no marked discontinuity at the phase transition. The lattice distortion, traditionally defined in cordierite by the Δ index provides no full information on the degree of Al, Si order in anhydrous Mg-cordierite, and both order parameters must be used to define its structural state. Transmission electron microscopy has been used to study the mechanism of the transformation from hexagonal to modulated to orthorhombic cordierite.