Structural chemistry of synthetic cordierite: Evidence for solid solutions and disordered compositional domains in Bi-flux-grown Mg-cordierites

The structure, crystal chemistry, and microstructure of disordered and ordered Mg-cordierites synthesized in a bismuth oxide flux system have been studied by a combination of x-ray and neutron powder diffraction and quantitative x-ray microanalysis using analytical electron microscopy. Microchemical data obtained on Bi-flux cordierites using energy-dispersive x-ray analysis is interpreted through comparison with data collected on stoichiometric Mg₂Al₄Si₅O₁₈ glass and α- and β-cordierite samples synthesized by subsolidus crystallization of the glass. Bi-flux cordierites crystallize in both the hexagonal and orthorhombic polymorphs and contain 5 to 10 at% occupancy of bismuth on the C1 and C2 channel sites. The microstructure of Bi-flux α-cordierite is characterized by the existence of local domains of disordered cordierite solid solutions with variable composition and significant vacancy concentrations on the octahedral site. The β-cordierites have a more homogeneous microstructure but are still Al-deficient, Si-rich solid solutions.