X-ray study of the α–β transformation of berlinite (AlPO4)

Abstract

The α–β transformation of berlinite (AlPO4) at 586 °C was studied by X-ray diffraction. Atomic displacements were obtained from results of least-squares refinement of data taken between room temperature and 600 °C using reflections whose intensity is unaffected by Dauphiné twinning. The results suggest a rotational motion of the PO4 and AlO4 tetrahedra around the two-fold axis together with a translational motion along the same axis as the transition is approached from below. The vibrational amplitudes of the atoms increase with temperature and have exceeded half of the separation between Dauphiné twin-related configurations at 500 °C. The final β-phase configuration is not achieved by this twinning due to the mismatch of the two configurational potential minima in the a direction. Analysis of the intensity vs. temperature data favours a single minimum model for the β phase configuration over an order–disorder model. The β-AlPO4 structure consists of alternate PO4 and AlO4 tetrahedra sharing all four corners with P—O and Al—O distances 1.505 and 1.694 Å respectively. The results are correlated with those obtained from temperature dependent studies by Raman scattering and by EPR on Fe3+-doped AlPO4.