(Ba0.5Sr0.5)(Co0.8Fe0.2)O3−δ (BSCF) is a promising material with mixed ionic and electronic conductivity which is considered for oxygen separation membranes. Selective improvement of material properties, e.g. oxygen diffusivity or suppression of secondary phase formation, can be achieved by B-site doping. This study is concerned with the formation of Co-oxide precipitates in undoped BSCF at typical homogenization temperatures of 1,000°C, which act as undesirable nucleation sites for other secondary phases in the application-relevant temperature range. Y-doping successfully suppresses Co-oxide formation, whereas only minor improvements are achieved by Sc-doping. To understand the reason for the different behavior of Y and Sc, the lattice sites of dopant cations in BSCF were experimentally determined in this work. Energy-dispersive X-ray spectroscopy in a transmission electron microscope was applied to locate dopant sites exploiting the atom location by channeling enhanced microanalysis technique. It is shown that Sc exclusively occupies B-cation sites, whereas Y is detected on A- and B-cation sites in Y-doped BSCF, although solely B-site doping was intended. A model is presented for the suppression of Co-oxide formation in Y-doped BSCF based on Y double-site occupancy.

Alloy design has been a lifelong interest of Gareth Thomas, and modern design algorithms include atomistic parameters which are obtainable from new electron microscope techniques such as ALCHEMI. In this paper, we discuss the relevance of ALCHEMI site occupancy measurements to intermetallic alloys, and summarize prior work. The results are found to lie in regions of a site-occupancy diagram (SOC) relating ordering energies to occupancy, as predicted by the Bragg–Williams theory of short-range order. These predictions also explain previous inconsistencies in the ALCHEMI measurements. A diffraction camera and X-ray detector system of novel design is proposed for dedicated ALCHEMI analysis for substitutional and interstitial dopant site-occupancy measurement, and details of the design given. Using this novel hardware design, the data-collection times for two-dimensional ALCHEMI patterns should be reduced by an order of magnitude or more, and the full data collection process automated. The resulting occupancy information can provide essential input parameters for atomistic alloy design algorithms, and can provide entirely new information on interstitial occupancies in minerals, ceramics, semiconductors, and alloys.