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A study has been undertaken of the characteristics exhibited by mullite-rich plasma electrolytic oxide coatings grown on aluminium alloys by using silicate-rich electrolytes. It is found that they can be grown at a higher rate, and to a greater thickness, than alumina PEO coatings on aluminium. The thermal conductivity of these coatings has been measured using a steady-state method. It is shown to be of the order of 0.5 W m- 1 K- 1, which may be compared with (similar to) 1.5 W m- 1 K- 1 for pure alumina PEO coatings and (similar to) 10-15 W m- 1 K- 1 for dense polycrystalline mullite. Coupled with excellent substrate adhesion and good mechanical properties, this relatively low conductivity makes these coatings attractive for thermal barrier applications. Furthermore, they are shown to exhibit a relatively low global stiffness ((similar to) 40 GPa), which will reduce the magnitude of thermally-induced stresses and improve the resistance to spallation during temperature changes.