Direct transitions among the allotropic forms of boron nitride at high pressures and temperatures

摘要

The direct transition behavior among the graphitic (hBN), wurtzitic (wBN), and zincblende (zBN) crystal forms of boron nitride is investigated as a function of temperature for pressures up to 130 kbar. At pressures in the 45 to 70 kbar range, direct transformation of both the hBN and wBN forms to the zincblende form are observed and at higher pressures (85 kbar and above) direct transformation of hBN to wBN is also observed. A pressure/temperature phase diagram is presented for pressures up to 130 kbar. In this pressure range, the thermodynamically stable solid phases are hBN and zBN, the experimental behavior indicating that wBN is not thermodynamically stable over this range. From temperature/time data, the activation energy for both the hBN to zBN and wBN to zBN transitions is estimated to be about 200 kcal/mole. From these high activation energies it is concluded that the direct conversion processes essentially require disruption of the hBN and wBN lattices before the atoms can rehyphen;form into the zincblende structure.