Phase transformations in prototype high strength polycrystalline nickel-based superalloys of varying Ti/Nb ratio are studied using time-resolved, high resolution X-ray synchrotron diffractometry. The dissolution kinetics of the ordered phase Ni-3(Al, Ti, Nb, Ta) upon heating to the solutioning temperature of similar to 1200 degrees C and its reprecipitation on cooling are deduced; effects of varying Nb and Ti alloy composition on the reaction kinetics are identified. Heating to 800 degrees C does not alter substantially the fraction of the strengthening phase Ni-3(Al, Ti, Nb, Ta) but further heating causes its rapid dissolution. At higher temperatures, evidence is provided for the formation of further ordered phases; Ni-3(Ti, Ta) is proposed and possibly Ni0.45Ta0.55; cooling causes their dissolution and reprecipitation of Ni-3(Al, Ti, Nb, Ta), so that it seems probable that the reactions are coupled. The unforeseen high temperature precipitation of further ordering by phases other than Ni-3(Al, Ti, Nb, Ta) implies the possibility of a contribution by them to the high temperature mechanical behaviour of these materials, which until now has been thought to be solely due to Ni-3(Al, Ti, Nb, Ta). The MC carbide, probably TiC, is stable even at the solution heat treatment temperature; no evidence of reactions involving other carbides such as M23C6 is found. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).