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The bulk density of graphitized ultradisperse diamond (UDD) was measured by a gamma-ray attenuation method at 1370–1870 K. These data combined with small angle x-ray scattering and true density measurements of the samples heated at various fixed temperatures were used to study the graphitization kinetics of the UDD. The reaction rate was modeled as a migration rate of the interface between the developing graphite-like carbon and the remaining diamond phase. A “reducing sphere” model was used to obtain the rates from the changes in densities. The estimated kinetic parameters in an Arrhenius expression, namely the activation energy, E=45±4 kcal/mol, and the pre-exponential factor, A=74±5 nm/s, allow quantitative calculations of the diamond graphitization rates in and around the indicated temperature range. The calculated graphitization rates agree well with the graphitization rates of diamonds with different dispersity estimated from high-resolution transmission electron microscopy data. The large difference between the rates and the kinetic parameters obtained in this study and those estimated by G. Davies and T. Evans [Proc. R. Soc. London 328, 413 (1972)] for the temperature range 2150–2300 K indicates that there are different graphitization mechanisms operating in the “low” and “high” temperatures regions.

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In recent high resolution transmission electron microscopic studies we have found that high temperature vacuum annealing (1200–1800 K) of ultradispersed (2–5 nm) and micron size diamond produces fullerene-like graphitic species, namely, onion-like carbon and closed curved graphite structures (multilayer nanotubes and nanofolds), respectively. Here we undertake theoretical studies to help in the understanding of the experimental data for these systems. (1) Calculations of cluster models by a standard semiempirical method (MNDO a software package) are used to explain the preferential exfoliation of {111} planes over other low index diamond planes. (2) The same approach suggests the likelihood that the graphitization is initiated by a significant thermal displacement of a single carbon atom at temperatures close to the Debye temperature. (3) At the diamond–graphite interface we have observed the formation of two curved graphitic sheets from three diamond {111} planes. We suggest that the evolution of this interface proceeds by a “zipper”-like migration mechanism with the carbon atoms of the middle diamond layer being distributed equally between the two growing graphitic sheets. (4) The observed mosaic packaging of closed curved graphite structures during the diamond surface graphitization is suggested to be a self-assembling process. This process is explained in terms of the “stretching” of a bowed graphite hexagonal network. The stretch is due to the fact that, if relaxed, the network would be smaller than the initially transformed hexagonal diamond (111), and to the increased separation between the separated sheet and the surface. The initial phase of the process is studied quantitatively using a molecular mechanics simulation.

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