Air-thermal oxidation of diamond nanopowders obtained by the methods of mechanical grinding and detonation synthesis

In this work, using the methods of X-ray phase analysis, transmission electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy, the features of the impact of annealing in air within the temperature range of t = 200÷÷550 °C on the morphology, elemental and phase composition, chemical state and structure of primary particles of nanopowders obtained by grinding natural diamond and the method of detonation synthesis are studied. It is shown that heat treatment in air at given values of temperature and heating time does not affect the elemental composition and atomic structure of primary particles of nanopowders obtained both by the methods of detonation synthesis (DND) and natural diamond grinding (PND). Using XPS, Raman spectroscopy, and transmission electron microscopy, it has been found that annealing in air within the temperature range of 400–550 °C results in the effective removal of amorphous and graphite-like carbon atoms in the sp2- and sp3-states from diamond nanopowders by oxidation with atmospheric oxygen. In the original DND nanopowder, containing about 33.2 % of non-diamond carbon atoms of the total number of carbon atoms, after annealing for 5 h at a temperature of 550 °C, the relative number of nondiamond carbon atoms in the sp2-state decreased to ~21.4 %. In this case, the increase in the relative number of carbon atoms in the sp3-state (in the lattice of the diamond core) and in the composition of oxygen-containing functional groups ranged from ~39.8 % to ~46.5 % and from ~27 % to ~32.1 %, respectively. In the PND nanopowder, which prior to annealing contains about 10.6 % of non-diamond carbon atoms in the sp2-state of the total number of carbon atoms, after annealing under the same conditions as the DND nanopowder, their relative number decreased to 7.1 %. The relative number of carbon atoms in the sp3-state  increased from 72.9 % to 82.1 %, and the proportion of carbon atoms in the composition of oxygen-containing functional groups also slightly increased from 10.2 % to 10.8 %. It is demonstrated that the annealing of PND and DND nanopowders in air leads to a change in their color, they become lighter as a result of oxidation of non-diamond carbon by atmospheric oxygen. The maximum effect is observed at a temperature of 550 °C and an annealing time of 5 h. In this case, the weight loss of PND and DND nanopowders after annealing was 5.37 % and 21.09 %, respectively. The significant weight loss of DND nanopowder compared to PND is primarily caused by the high content of non-diamond carbon in the initial state and the high surface energy of primary particles due to their small size.