The mineral matter in typical feed coals used in South African gasification processes and the ash derived from gasifying such coals have been investigated using a variety of mineralogical, chemical and electron microscope techniques. The mineral matter in the feed coals consists mainly of kaolinite, with minor proportions of quartz, illite, dolomite, calcite and pyrite plus traces of rutile and phosphate minerals. The calcite and dolomite occur in veins within the vitrinite macerals, and are concentrated in the floats fraction after density separation. Some Ca and Ti also appear to be present as inorganic elements associated with the organic matter. Electron microscope studies show that the gasification ash is typically made up of partly altered fragments of non-coal rock, bonded together by a slag-like material containing anorthite and mullite crystals and iron oxide particles, with interstitial vesicular glass of calcic to iron-rich composition. Ash formation and characteristics thus appear to be controlled by reactions at the particle scale, allowing the different types of particles within the feed coal to interact with each other in a manner controlled mainly by the modes of mineral occurrence. Integration of such techniques provides an improved basis for evaluating ash-forming processes, based on quantitative phase identification, bulk and particle chemistry, and the geometric forms in which the different phases occur. (C) 2011 Published by Elsevier B.V.