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Structural changes induced by cation ordering in ferrotapiolite

Dipartimento di Scienze della Terra, Università di Pavia, Via Ferrata 1, 27100 Pavia, Italy

^* E-mail: michele.zema{at}unipv.it

Structural modifications as a function of the degree of order (Q) in FeTa₂O₆ ferrotapiolite have been characterized by means of single-crystal X-ray diffraction (SC-XRD). A total of 26 datasets covering the range of Q between 0.154 and 1 have been obtained by thermal treatments followed by quenching of natural tapiolite crystals. Ordering of Fe²⁺ at the A sites and of Ta⁵⁺ at the B sites causes a linear increase in the a/c lattice constants ratio, as a consequence of a linear decrease of the c dimension and only slight modifications of the a parameter. Calibration of a/c vs. Q represents a very useful tool for a rapid determination of the degree of order of tapiolite samples. Polyhedral volumes of the two octahedral sites vary linearly with Q as a consequence of the different ionic radii of the two species. Both the sites remain almost regular at all Q values but the B site shows an increasing off-centre displacement of the cation with increasing Q. Observed structure factors of supercell reflections, characterized by l 3n, increase linearly as a function of Q, thus representing a further tool for a quick evaluation of the degree of order.

KEYWORDS: tapiolite, order-disorder, single-crystal X-ray diffraction