A key challenge in the fabrication of ferromagnetically filled carbon-nanotube buckypapers in the presence of Cl-radicals is the achievement of a preferential horizontal nanotube-alignment.

We report the synthesis of ultrathin buckypapers comprising carbon nanostructures filled with Fe ₃ C, FeCo, FeNi, CoNi, Co and Ni by pyrolysis of single or combined metallocenes with very low quantities of dichlorobenzene.

Novel cm-size free-standing buckypapers of bucky-onions filled with a single-phase of ferromagnetic Fe₃C single crystals were serendipitously discovered.

One of the challenges in the field of carbon nanotubes (CNTs) is the encapsulation of a single crystalline phase of ferromagnetic α-Fe. The formation of additional γ-Fe and Fe₃C phases during CNT-growth generally limits the direct encapsulation of these crystals in the form of a single phase. A solution, the use of post-synthesis annealing, has been considered; however oxidation of the encapsulated metal-phases is commonly found due to the elevated temperatures (T) necessary for the phase-conversion. Here we investigate the dynamics of γ-Fe to α-Fe transition by T-dependent X-ray diffraction in vacuum. We show that a direct γ-Fe to α-Fe transition is present already below 200 °C and becomes significantly fast in the T-range of 300–399 °C. In such a T-range no metal oxidation is found. Rietveld refinement analyses also show that a T-dependent increase in the unit-cell c-axis value of the graphitic CNT-walls is present.