Metal forming constitutes a group of industrially important processes to form metallic components to net shape. When forming aluminium and other materials that tend to stick to the tools, problems associated with material transfer, e.g. galling, may occur. In a previous study by the present authors, in situ observations of aluminium transfer during sliding contact in the SEM revealed that the surface topography and chemical composition of the tool steel counter surface have a strong impact on the initial material transfer tendency. Even if carefully polished to a very smooth surface (Ra<50 nm), transfer of aluminium was found to immediately take place on a very fine scale and preferentially to the surface irregularities presented by the slightly protruding M(C,N) particles (height 15 nm) in the tool steel. In contrast, the less protruding M6C carbides, as well as the martensitic steel matrix exhibited very little initial transfer. The mechanism behind the preferential pick-up tendency displayed by the M(C,N) particles was not fully understood and it was not possible to determine if the decisive mechanism operates on the microstructural scale, the nanoroughness scale or the chemical bonding scale. In the present study, these mechanisms have been further investigated and analysed by comparing the very initial stages of material transfer onto different types of tool steels in sliding contact with aluminium in the SEM. The tool steels investigated cover conventional ingot cast and powder metallurgy steel grades, selected to possess a range of different types, amounts and sizes of hard phase particles, including MC, M(C,N), M7C3 and M6C. The transfer mechanisms are investigated using high resolution SEM, and the differences between the different microstructures and carbide types are carefully analysed. The implications for real metal forming are discussed.