Abstract The nature of mineral matter in coal determines its transformation into ash during combustion and the nature of resulting ash (e.g. chemical composition and particle size distribution), and subsequently influences the ash deposition behaviour. The behaviour of mineral matter is primarily influenced by two parameters: the mineral grain size, and whether the mineral grains are within the coal matrix or not. Computer-controlled scanning electron microscopy (CCSEM) of coal provides such information on mineral matter in coal. CCSEM data are, therefore, processed to predict the fouling and slagging characteristics of several coals. The fraction of basic oxides in each mineral grain may be considered as an indicator of stickiness of the corresponding ash particle due to formation of low melting compounds. The cumulative mass fraction of mineral grains with certain basic oxides or viscosity of resulting ash particles from included and excluded minerals are proposed as alternative indices for ash deposition. The excluded mineral matter is in equilibrium with the combustion flue gases at the gas temperatures, whereas the included minerals are in equilibrium with the atmosphere within char at the burning char particle temperature. It is predicted from thermodynamic calculations based on this understanding that almost all the evaporation is either from the included mineral matter or from the atomically dispersed minerals in coal. This is due to the high temperature and reducing atmosphere inside the char particle. The release of the evaporated species is controlled by diffusion through the burning char particle and, therefore, may be estimated theoretically. The amount of mineral matter that is vaporized may then be related to fouling, whereas the melt phase present on the surface of large ash particles may be related to slagging. The theoretical speculations on the physical character of ash derived from these indices are compared with the experimental data obtained from combustion of coals in a drop-tube furnace.