Effect of Ti on the properties of diamond microcrystals synthesized in C–O–H supercritical fluid at high pressure and high temperature

Abstract

Diamond micropowders 1–10 μm were synthesized at 7.5 GPa, 1300–1500 °C, and 3–6 s. Detonation nanodiamonds and pentaerythritol (C5H8(OH)4) with the addition of Ti were used as the reaction medium. The total nitrogen concentration, determined by electron paramagnetic resonance (EPR) and infrared (IR) spectroscopies, in diamonds synthesized without the addition of Ti was 1700 ppm. In diamonds synthesized with the addition of Ti, there are no 2N (A-center) and N3VH0 centers as well as oxygen-related functional groups, and the total concentration of nitrogen centers is reduced to 640 ppm. The addition of Ti leads to an increase in the synthesis temperature by 100–200 °C.Thermodynamics model calculations of the equilibrium compositions of the reaction medium at a pressure of 7.5. GPa and temperatures of 500, 1000 and 1500 °C were performed. The Gibbs free energy of possible reactions between the components of the reaction medium was calculated. It has been shown that under equilibrium conditions and a reaction medium corresponding to the synthesis conditions, the formation of TiN is thermodynamically possible. This leads to a decrease in the nitrogen concentration in diamonds. However, the formation of TiO2 is a competing reaction that can lead to a decrease in the concentration of oxygen-related functional groups.