X-ray photoelectron spectroscopy (XPS) has been used to investigate the changes in surface composition of three steels as they have undergone heating. The steels were mild steel, and two austenitic stainless steels, commonly designated 304 and 316 stainless steels. XPS measurements were made on the untreated samples, and then following heating for 30 min in vacuo and in a 1 x 10(-6) Torr partial pressure of air, at temperatures between 100 degrees C and 600 degrees C. Mild steel behaves differently to the two stainless steels under the heating conditions. In mild steel the iron content of the surface increased, with oxygen and carbon decreasing, as a function of increasing temperature. The chemical state of the iron also changed from oxide at low temperatures, to metallic at temperatures above 450 degrees C. In both stainless steels the amount of iron present in the surface decreased with increasing temperature. The decrease in iron at the surface was accompanied by an increase in the amount of chromium at the steel surface. At temperatures above 450 degrees C the iron in both 304 and 316 stainless steels showed significant contributions from metallic iron, whilst the chromium present was in an oxide state. In 316 stainless steel heated to 600 degrees C there was some metallic chromium present in the surface layer. The surfaces heated in air showed the least variation in composition, with the major change being the loss of carbon from the surfaces following heating above 300 degrees C. There was also a minor increase in the concentration of chromium present on both the stainless steels heated under these conditions. There was also little change in the oxidation state of the iron and chromium present on the surface of these steels. There was some evidence of the thickening of the surface oxides as seen by the loss of the lower binding energy signal in the iron or chromium core level scans. The surfaces heated in vacuum showed a similar trend in the concentration of carbon on the surfaces, however the overall concentration of oxygen decreased throughout the heating of these steels. There were also significant changes in the oxidation state of the iron and chromium on these surfaces with significant amounts or iron and chromium present in the metallic form following heating up to 600 degrees C. It appears that the carbon contamination on the surfaces plays an important role in the fate of the surface oxide layer for all of the steels heated in a vacuum environment. (C) 2011 Elsevier B.V. All rights reserved.