Résumé : We report a detailed structural and chemical characterisation of aluminium silicon manganese nitrides that act as grain growth inhibitors in industrially processed grain-oriented (GO) electrical steels. The compounds are characterised using energy dispersive X-ray spectrometry (EDX) and energy filtered transmission electron microscopy (EFTEM), while their crystal structures are analysed using X-ray diffraction (XRD) and TEM in electron diffraction (ED), dark-field, high-resolution and automated crystallographic orientation mapping (ACOM) modes. The chemical bonding character is determined using electron energy loss spectroscopy (EELS). Despite the wide variation in composition, all the precipitates exhibit a hexagonal close-packed (h.c.p.) crystal structure and lattice parameters of aluminium nitride. The EDX measurement of ~ 900 stoichiometrically different precipitates indicates intermediate structures between pure aluminium nitride and pure silicon manganese nitride, with a constant Si/Mn atomic ratio of ~ 4. It is demonstrated that aluminium and silicon are interchangeably precipitated with the same local arrangement, while both Mn2 + and Mn3 + are incorporated in the h.c.p. silicon nitride interstitial sites. The oxidation of the silicon manganese nitrides most likely originates from the incorporation of oxygen during the decarburisation annealing process, thus creating extended planar defects such as stacking faults and inversion domain boundaries. The chemical composition of the inhibitors may be written as (AlN)x(SiMn0.25N yOz)1 - x with x ranging from 0 to 1. © 2013 Elsevier Inc.