Transformation of topologically close-packed beta-W to body-centered cubic alpha-W: Comparison of experiments and computations
K Barmak and JX Liu and LA Harlan and PH Xiao and J Duncan and G Henkelman, JOURNAL OF CHEMICAL PHYSICS, 147, 152709 (2017).
The enthalpy and activation energy for the transformation of the metastable form of tungsten, beta-W, which has the topologically close- packed A15 structure (space group Pm<(3)overbar>n), to equilibrium alpha-W, which is body-centered cubic (A2, space group Im (3) over barm), was measured using differential scanning calorimetry. The beta-W films were 1 mu m-thick and were prepared by sputter deposition in argon with a small amount of nitrogen. The transformation enthalpy was measured as -8.3 +/- 0.4 kJ/mol (-86 +/- 4 meV/atom) and the transformation activation energy as 2.2 +/- 0.1 eV. The measured enthalpy was found to agree well with the difference in energies of alpha and beta tungsten computed using density functional theory, which gave a value of -82 meV/atom for the transformation enthalpy. A calculated concerted transformation mechanism with a barrier of 0.4 eV/atom, in which all the atoms in an A15 unit cell transform into A2, was found to be inconsistent with the experimentally measured activation energy for any critical nucleus larger than two A2 unit cells. Larger calculations of eight A15 unit cells spontaneously relax to a mechanism in which part of the supercell first transforms from A15 to A2, creating a phase boundary, before the remaining A15 transforms into the A2 phase. Both calculations indicate that a nucleation and growth mechanism is favored over a concerted transformation. More consistent with the experimental activation energy was that of a calculated local transformation mechanism at the A15-A2 phase boundary, computed as 1.7 eV using molecular dynamics simulations. This calculated phase transformation mechanism involves collective rearrangements of W atoms in the disordered interface separating the A15 and A2 phases. Published by AIP Publishing.
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