High-temperature X-ray investigation of natural columbites

Structural investigations at high temperature were carried out on natural columbite samples across the join Fe(Nb0.95Ta0.05)2O6–Mn(Nb0.95Ta0.05)2O6. The samples were preliminarily annealed to attain the complete cation-ordered state and avoid the superimposition of the effects of cation ordering during high-temperature studies. Unit-cell parameters of three columbites with different XFe content were measured at regular intervals in the temperature range 25–900 °C using single-crystal X-ray diffraction techniques. The crystal structures of completely ordered ferrocolumbite and manganocolumbite were also refined from intensity data collected at room temperature, 300 and 600 °C. Structural thermal expansion coefficients show positive, linear expansion of a, b, c lattice constants and cell volume. In general, slightly higher expansion occurs along a and c directions. However, anisotropy decreases sharply with decreasing Fe content. Reversibility of thermal expansion in the investigated temperature range was checked by high-temperature diffraction studies under heating-up and cooling-down conditions. Impurities do not play an important role in thermal expansion of columbites; expansion coefficients measured on two crystals of the same sample characterized by different Ti content are in fact almost identical. Structural changes with temperature essentially affect bond lengths: volumes of both A and B octahedral sites increase linearly with temperature, whereas interpolyhedral geometrical parameters do not vary significantly.