Ten samples originating from different boiler FBC systems burning petroleum coke and one laboratory sample were chosen to perform a study on the development, structure, and composition of deposits formed by agglomeration in various locations. The work focused on examination by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) analysis. The possibility of a contribution of liquid phases in the adherence to solid surfaces and in agglomeration was discussed and checks by SEM, EDX, and analysis by neutron activation were performed; no evidence could be found either for liquid phases or for any role of vanadium or alkaline element compounds. The agglomerations result from the continued sintering of CaSO4 particles until they build up a strong framework that is indefinitely extended, into which particles of different and complex compositions are bound, without contributing to the cohesion. Chemical sintering occurring by the sulphation of CaO into CaSO4 appears to be an important contribution while CaO is still available, but sintering also occurs by mass transfer mechanisms and continues after the depletion of CaO. Deposits formed in regions only reached by fly ash (convection section), and also in in-bed deposits, grow from particles < 50 mum, mostly in the range of 10 mum or less. In regions collecting bed ash (e.g., J-valves), the deposit grows from the sintering together of particles on the order of 100-300 mum (originally bed ash particles), which themselves appear as conglomerates of extensively sintered smaller particles. (C) 2003 Published by Elsevier Science B.V