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Licensed Unlicensed Requires Authentication Published by De Gruyter (O) October 1, 2014

Synthesis and characterization of mullite-type (Al1-xGax)4B2O9

Kristin Hoffmann, M. Mangir Murshed, Reinhard X. Fischer, Hartmut Schneider and Thorsten M. Gesing


Mullite-type (Al1-xGax)4B2O9 compounds were synthesized using the glycerine method. The end members Al4B2O9 and Ga4B2O9 were produced at different temperatures. Starting from the Al4B2O9 composition the incorporation limit of Ga ranges between 60 and 70 mol-%, while starting from Ga4B2O9 the Al incorporation limit is 70 mol-% in the Ga4B2O9 structure. The crystal structures were refined from the X-ray powder diffraction data and analyzed by the Rietveld method. The positions of B atoms were determined by distance least squares modeling. The temperature-dependent investigations demonstrate that the stability of a given member is a function of Al/Ga ratio in the structure. The incorporation of Ga in the Al4B2O9 structures leads to a successive decrease of the decomposition temperatures. Pure Al4B2O9 decomposes above 1323 K, whereas pure Ga4B2O9 is stable up to 1073 K. The thermal expansions of the lattice parameters were fit using extended Grüneisen first-order approximation for the zero-pressure equation of state. Changes of the internal energy of the crystal were calculated by the Debye-Einstein-Anharmonicity model. The thermal stability of each member has been explained in terms of the obtained Debye temperature.

Corresponding author: Thorsten M. Gesing, Chemische Kristallographie fester Stoffe, Institut für Anorganische Chemie, Universität Bremen, Leobener Straße /NW2, 28359 Bremen, Germany, E-mail:


We gratefully thank L. Robben (Chemistry, University Bremen) for the evaluation of the decomposition temperatures using the autocorrelation analysis and the Deutsche Forschungsgemeinschaft (DFG) for the financial support of the projects GE1981/3-1 and 3-2, GE1981/5-1 and FI442/19-1.


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Received: 2014-7-1
Accepted: 2014-8-19
Published Online: 2014-10-1
Published in Print: 2014-10-1

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