Rutile precipitation within alumina scales grown on coated nickel-based superalloy CMSX-4 has been found to occur preferentially at grain boundaries within the scale. Misorientation analysis using Rodrigues–Frank space has revealed clustering of the misorientation between neighboring grains of corundum and rutile about the established 〈0 0 0 1〉_c{1 1 2¯ 0}_c//〈0 1 0〉_r{1 0 1}_r orientation relationship observed in Ti-containing sapphire crystals. The fraction of interfaces found to exist in this configuration is sufficient to explain the nucleation of rutile from a single corundum grain abutting the rutile grain. The diffusive behavior of Ti has been observed to vary considerably within three commercially used coatings, a plain aluminide coating, a plat-aluminide coating and a diffused platinum coating. Titanium diffusion is enhanced by the presence of Pt. However this did not lead to the precipitation of more rutile, which although observed in all three coatings, was present in sufficient quantity to be detected using XRD only within the plain aluminide coated samples.The work was carried out under the financial support provided by Rolls-Royce plc and Engineering and Physical Sciences Research Councils, UK under the Rolls-Royce/ESPRC Strategic Partnership (EP/M005607/1 & EP/H022309/1). This study was also supported by Nanotechnology Platform Project (NIMS Nanofabrication Platform) sponsored by the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan. Financial support was also received from the Seventh Framework Programme of the European Commission: ESTEEM2, contract number 312483. Requests for access to the underlying research data should be directed to the corresponding author and will be considered against commercial interests and data protection.This is the author accepted manuscript. The final version is available from Elsevier at http://www.sciencedirect.com/science/article/pii/S1359645415002281