Magnetic and EPR studies of edge-localized spin paramagnetism in multi-shell nanographites derived from nanodiamonds

Prolonged (up to 2 h) heat treatment at 1600 °C of nanodiamond particles (5 nm) leads to their conversion to the mixture of quasi-spherical carbon onions and multi-shell polyhedral nanographites. Structural and magnetic properties of two (A and B) series of nanographite samples obtained at various annealing intervals were studied. XRD data show that both multi-shell nanographite samples have practically the same crystalline structures. HRTEM evidences that the most of particles obtained by short time (7 min) annealing have a spherical like shape whereas the long time (~ 2 h) annealing leads to the majority of particles having a polyhedral shape with a hollow inside. Electronic and magnetic properties of these nanocarbons were investigated by magnetic susceptibility and EPR. Annealing results in entire transformation of the EPR signal of nanodiamond to new EPR signals of various line shapes and widths. These signals are extremely sensitive to ambient oxygen. Concentrations for all EPR active spins vary from ~ 1 × 10¹⁹ spins/g (7 min) to ~ 2 × 10¹⁹ spins/g (2 h). Temperature dependences of EPR spectra' parameters were obtained for vacuum-processed samples within the range 4?600 K. Intensity vs. T plots may be well-fitted by the combination of Curie–Weiss and temperature-independent Pauli susceptibility contributions. The latter one increases on heat treatment. Significant extension of electron spin-lattice relaxation time on decreasing temperature was found.