The microstructure of commercially available electrodeposited and thermally aged Ni-W layers with a composition of 18 at.% W was studied by means of field ion microscopy and the tomographic atom probe. In comparison with standard Ni-P or hard chrome coatings, Ni-W layers have a promising application field owing to their specific tribological and electro-erosion properties and in particular because they are manufactured at low cost without harm to the environment. The as-plated state is characterized by the presence of nanocrystalline grains of the Ni-rich fcc phase, with the nanocrystalline structure being preserved up to 700 degreesC. At this temperature the formation of the ordered Ni4W-phase (D1a structure) is observed and finally, after aging at 800 degreesC the specimens are completely ordered. Whereas in Ni-P the continuous segregation of P and the grain boundaries is responsible for the thermal stability, in Ni-W grain growth is inhibited by the low mobility of the W atoms. (C) 2002 Elsevier Science B.V. All rights reserved.