The elasticity of MgAl2O4–MnAl2O4 spinels by Brillouin scattering and an empirical approach for bulk modulus prediction
-
Enrico Bruschini
,
Sergio Speziale
Abstract
The elastic constants Cij of a set of synthetic single crystals belonging to the join MgAl2O4-MnAl2O4 (spinel sensu stricto-galaxite) were determined by Brillouin spectroscopy at ambient conditions. The C11 component tends to remain constant for Mg-rich compositions (XMn < 0.5) and decreases in Mn-rich compositions, whereas C12 increases and C44 decreases almost linearly from MgAl2O4 to MnAl2O4. The bulk modulus KS is weakly dependent upon Mg-Mn substitution within experimental uncertainties, whereas the shear modulus G decreases with increasing Mn2+ content. For MnAl2O4, C11 = 271.3(1.3) GPa, C12 = 164.8(1.3) GPa, C44 = 124.9(5) GPa, KS = 200(1) GPa, and G = 88.7(5) GPa.
Based on the “polyhedral approach,” we developed a model that describes the crystal bulk moduli of the MgAl2O4-MnAl2O4 spinels in terms of their cation distribution and the polyhedral bulk moduli of the different cations. We refined a set of values for the effective polyhedral bulk modulus of Mg, Mn2+, and Al in tetrahedral (T) and octahedral (M) sites, which span from 153 to 270 GPa ranking as follows: KMMn < KMMg < KTMg ≈ KTMn < KMAl << KTAl.
Crystal bulk modulus was perfectly reproduced within 0.1% for all Mn2+-bearing samples. We also found a high linear correlation between the effective polyhedral bulk modulus and the ionic potential, IP, of the coordinating cations: Kji (GPa) = 20(2) IP + 108(10) (where i indicates the cation and j the polyhedral site). We tested this simple correlation by calculating the specific effective polyhedral bulk modulus of several cations in T and M coordination and then predicting the crystal bulk modulus for several spinel compositions. The success of our simple correlation in modeling the bulk modulus of spinels outside the MgAl2O4-MnAl2O4 system is encouraging, and suggests that the relationships between chemical composition, cation distribution and elastic properties in spinel-structured minerals and materials can indeed be expressed by relatively simple models.
© 2015 by Walter de Gruyter Berlin/Boston
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