Six kinds of industrial alloys, SUS316, FCH2, Invar, Permalloy, Inconel, and Nichrome, and three kinds of pure metals, Fe, Ni, and Cr, were used for substrates on which multi-walled carbon nanotubes (MWCNTs) were directly synthesized from ethylene. To activate their surfaces for the MWCNT formation, their surfaces were modified by two steps, (1) oxidation step in Ar-O-2 mixture gas and (1) following reduction step in Ar-H-2 mixture gas. It was discovered that Cr is a key component to realize the catalytic growth of MWCNTs on Fe and Ni emerged from the alloys. Using SUS316 to observe the influence of oxidation duration on MWCNT diameter, it was seen that increasing the oxidation duration resulted in the increase of the MWCNT diameter. This tendency can be explained by diffusion of Fe through Cr-rich layer, which causes the increase of catalyst particle diameters. The excess Fe diffusion through the Cr-rich layer resulted in the formation of a unique mushroom structure. These effects seen in the observation on the oxidation duration did not appear when reduction duration was prolonged because the Cr-rich layer could inhibit the Fe diffusion. Instead, the length of the MWCNTs can became maximum by employing an appropriate reduction duration. (C) 2014 Elsevier B.V. All rights reserved.