38 research outputs found
Nucleation mechanism for the direct graphite-to-diamond phase transition
Graphite and diamond have comparable free energies, yet forming diamond from
graphite is far from easy. In the absence of a catalyst, pressures that are
significantly higher than the equilibrium coexistence pressures are required to
induce the graphite-to-diamond transition. Furthermore, the formation of the
metastable hexagonal polymorph of diamond instead of the more stable cubic
diamond is favored at lower temperatures. The concerted mechanism suggested in
previous theoretical studies cannot explain these phenomena. Using an ab initio
quality neural-network potential we performed a large-scale study of the
graphite-to-diamond transition assuming that it occurs via nucleation. The
nucleation mechanism accounts for the observed phenomenology and reveals its
microscopic origins. We demonstrated that the large lattice distortions that
accompany the formation of the diamond nuclei inhibit the phase transition at
low pressure and direct it towards the hexagonal diamond phase at higher
pressure. The nucleation mechanism proposed in this work is an important step
towards a better understanding of structural transformations in a wide range of
complex systems such as amorphous carbon and carbon nanomaterials
Understanding the nature of "superhard graphite"
Numerous experiments showed that on cold compression graphite transforms into
a new superhard and transparent allotrope. Several structures with different
topologies have been proposed for this phase. While experimental data are
consistent with these models, the only way to solve this puzzle is to find
which structure is kinetically easiest to form. Using state-of-the-art
molecular-dynamics transition path sampling simulations, we investigate kinetic
pathways of the pressure-induced transformation of graphite to various
superhard candidate structures. Unlike hitherto applied methods for elucidating
nature of superhard graphite, transition path sampling realistically models
nucleation events necessary for physically meaningful transformation kinetics.
We demonstrate that nucleation mechanism and kinetics lead to -carbon as the
final product. -carbon, initially competitor to -carbon, is ruled out by
phase growth. Bct-C structure is not expected to be produced by cold
compression due to less probable nucleation and higher barrier of formation
Ultrahard carbon film from epitaxial two-layer graphene
Atomically thin graphene exhibits fascinating mechanical properties, although
its hardness and transverse stiffness are inferior to those of diamond. To
date, there hasn't been any practical demonstration of the transformation of
multi-layer graphene into diamond-like ultra-hard structures. Here we show that
at room temperature and after nano-indentation, two-layer graphene on SiC(0001)
exhibits a transverse stiffness and hardness comparable to diamond, resisting
to perforation with a diamond indenter, and showing a reversible drop in
electrical conductivity upon indentation. Density functional theory
calculations suggest that upon compression, the two-layer graphene film
transforms into a diamond-like film, producing both elastic deformations and
sp2-to-sp3 chemical changes. Experiments and calculations show that this
reversible phase change is not observed for a single buffer layer on SiC or
graphene films thicker than 3 to 5 layers. Indeed, calculations show that
whereas in two-layer graphene layer-stacking configuration controls the
conformation of the diamond-like film, in a multilayer film it hinders the
phase transformation.Comment: Published online on Nature Nanotechnology on December 18, 201