Ceramics of strontium barium niobate (Sr0.6Ba0.4Nb2O6, SBN40), having the tetragonal tungsten bronze (TTB) structure, were prepared by a conventional processing route; sintering at temperatures in the range 1573–1723 K yielded products with three types of microstructure. Incommensurate superstructures were investigated by transmission electron microscopy (TEM). Modulation of the incommensurate superstructure (ICS) depended on microstructural development. The lowest-order ICS modulation was a common feature in all the SBN40 ceramics, regardless of microstructure. (h+1/2,h+1/2,l) reflections and unusually low δ (incommensurability parameter) were observed in SBN40 specimens having abnormally large grains and thus a certain degree ofA-site ordering was expected. Transparent SBN40 ceramics which exhibited large homogeneous grains were characterized by a shortenedcaxis, intense [001] X-ray diffraction reflections, a multiplication of (110) and (001) cell spacings and the appearance of higher-order ICS reflections. Planar defects, having the thickness of one d_{110} spacing, were observed aligned along \{110\}. The development of a higher-order structural modulation and of ICS reflections is believed to reduce the structural energy; the development of planar defects appears to stabilize the incommensurate phase.
