Grain-boundary-mediated kinetic arrest in graphite-to-diamond transformation

Abstract

The graphite-to-diamond transition exhibits striking variability under high-pressure, high-temperature (HPHT) conditions, producing diamond, graphitic phases, or metastable, mixed diamond-graphite nanocomposites despite similar synthesis conditions. Existing atomistic models, largely based on idealised single-crystal graphite, do not explain the persistence of partially transformed intermediate states under HPHT conditions. Here, using large-scale molecular dynamics simulations, we show that precursor grain structure governs graphite-to-diamond transformation pathways by decoupling diamond nucleation from cooperative transformation propagation. Grain boundaries first facilitate local sp$^3$ nucleation, after which diamond growth propagates within individual grains but becomes arrested at crystallographically mismatched grain boundaries. As a result, structurally heterogeneous graphite stabilizes kinetically arrested mixed sp$^2$-sp$^3$ states, whereas large or single-crystalline domains favour cooperative bulk transformation into diamond. Our findings identify structural heterogeneity as a missing control parameter alongside pressure and temperature, reframing metastable transformation products as kinetically trapped states arising from precursor microstructure rather than thermodynamic intermediates. Precursor crystallinity therefore emerges as a practical control parameter governing graphite-to-diamond transformation pathways.