Oxy-fuel combustion of coal is a promising technology for cost-effective power production with carbon capture and sequestration that has ancillary benefits of emission reductions and lower flue gas cleanup costs. To fully understand the results of pilot-scale tests of oxy-fuel combustion and to accurately predict scale-up performance through CFD modeling, fundamental data are needed concerning coal and coat char-combustion properties under these unconventional conditions. In the work reported here, the ignition and devolatilization characteristics of both a high-volatile bituminous coal and a Powder River Basin subbituminous coal were analyzed in detail through single-particle imaging at a gas temperature of 1700 K over a range of 12-36 vol % O-2 in both N-2 and CO2 diluent gases. The bituminous coal images show large,)lot soot cloud radiation whose size and shape vary with oxygen concentration and, to a lesser extent, with the use of N-2 versus CO2 diluent gas. Subbituminous coal images show cooler, smaller emission signals during devolatilization that have the same characteristic size as the coal particles introduced into the flow (nominally 100 full). The measurements also demonstrate that the use of CO2 diluent retards the onset of ignition and increases the duration of devolatilization, once initiated. For a given dilUent gas, a higher oxygen concentration yields shorter ignition delay and devolatilization times. The effect of CO2 oil coal particle ignition is explained by its higher molar specific heat and its tendency to reduce the local radical pool. The effect OF O-2 on coal particle ignition results from its effect on the local mixture reactivity. CO2 decreases the rate of devolatilization because of the lower mass diffusivity of volatiles in CO2 mixtures, whereas higher O-2 concentrations increase the mass flux of oxygen to the volatiles flame and thereby increase the rate of devolatilization. (C) 2009 The Combustion Institute. Published by Elsevier Inc. All rights reserved.