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Graphite to Diamond: Origin for Kinetics Selectivity.

Yao-Ping Xie1,2, Xiao-Jie Zhang1, Zhi-Pan Liu1

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Graphite transforms into hexagonal diamond, not cubic diamond, under mild compression. This surprising selectivity is explained by new atomic-level structures that facilitate hexagonal diamond formation and faster kinetics.

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Area of Science:

  • Materials Science
  • Solid-State Physics
  • Crystallography

Background:

  • The solid-phase transition of graphite to diamond under static compression is thermodynamically favored towards cubic diamond.
  • However, experimental observations show a preference for hexagonal diamond formation even under mild conditions (15 GPa).

Purpose of the Study:

  • To elucidate the atomic-level mechanisms governing the kinetics of the graphite to diamond phase transition.
  • To explain the preferential formation of hexagonal diamond over cubic diamond under mild static compression.

Main Methods:

  • Global exploration of potential energy surfaces to identify low-energy intermediate structures.
  • Quantitative kinetic analysis of the graphite-diamond transition pathways.

Main Results:

  • Identification of seven types of low-energy intermediate structures crucial for the transition kinetics.
  • Hexagonal diamond exhibits facile nucleation within the graphite matrix due to coherent graphite/hexagonal diamond interfaces.
  • Propagation kinetics for hexagonal diamond are significantly faster than for cubic diamond.

Conclusions:

  • The observed selectivity for hexagonal diamond is kinetically controlled, not thermodynamically driven.
  • Coherent interfaces promote rapid nucleation and growth of hexagonal diamond.
  • Cubic diamond formation is significantly slower due to a lack of coherent nucleation sites and is often mixed with hexagonal diamond growth.