Municipal solid waste (MSW) flue gas residues require further treatment prior to disposal or reuse, and vitrification is one of the main solidification-stabilization processes. This paper investigates the high temperature behavior of MSW flue gas residues, performed in laboratory experiments up to 1400 degrees C, and coupled with thermogravimetric analyses, X-ray diffraction, chemical and electron microprobe analyses. Melting temperatures of electrostatic precipitator (ESP) ash are in the range of 1202-1272 degrees C, whereas semi-dry scrubber residues melt between 1900 and 2300 degrees C. We show that the mean liquidus temperature of flue gas residues can be simply evaluated from their CaO content, by using the CaO-SiO2-Al2O3 ternary diagram. For ESP ash, the liquidus phase is a Zn-rich aluminous spinel, followed by anorthite at 1225 degrees C, and melilite at 1190 degrees C. The total mass loss reaches 18 wt.% at 1300 degrees C. Moreover, 90% of evaporation takes place below 1000 degrees C, linked to evaporation of C, Cl, S, Na, K, and of the toxic metals Hg, Cd, Pb, Cu. Due to the high partial pressure of chlorine during heating, chloride is the most probable form of evaporation for Cd, Pb, and Cu. However, most of Zn, Cr, Ni, Sb and Sn remain in the vitrified product. (C) 2007 Elsevier B.V. All rights reserved.