Carbon formation on steel has recently become an active research area with several important applications, using either carbon nanotubes (CNTs) or graphene structures. The production of vertically aligned CNT (VACNT) forests with combined metals has been explored with important results. Detailed kinetics is the best approach to understand a mechanism. The growth behavior seems complex but can be simplified through the knowledge of the three more common alternative reaction mechanisms/routes. The time required to optimize the production and properties might be reduced. The mechanistic proposal reported in 1971 was better explained recently. The volcano shape Arrhenius plot reported is observed only when Fe, Co, and Ni are used as reaction catalysts. Other metals are catalytically active at higher temperatures, following a different route, which does not require surface catalysis decomposition of the reactive gas. C2H2 and low olefins react well, but CH4 is not reactive via this surface catalysis route. Optimizing production of CNTs, research work is usually based on previous experience, but solid-state science-based studies are available.