A mechanistic study is detailed in which coal ash is heated with its shrinkage measured continuously up to a temperature of 1600°C. The temperatures corresponding to the rapid rate of shrinkage correspond to the formation of eutectics identified on phase diagrams. Samples were therefore heated to these temperatures, cooled rapidly and examined using a scanning electron microscope (SEM) to identify the associated chemical and physical changes. The progressive changes in the range of chemical composition (from SEM), the extent of undissolved ash particles and porosity were then quantified and related to homogenisation, viscosity and ash fusion mechanisms. Alternate ash fusion temperatures based on different levels of shrinkage have also been suggested to characterise the ash deposition tendency of the coals.