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Thermodynamic Properties of the Amorphous and Crystalline Modifications of Carbon and the Metastable Synthesis of Diamond
Author(s) -
Guencheva V.,
Grantscharova E.,
Gutzow I.
Publication year - 2001
Publication title -
crystal research and technology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.377
H-Index - 64
eISSN - 1521-4079
pISSN - 0232-1300
DOI - 10.1002/1521-4079(200112)36:12<1411::aid-crat1411>3.0.co;2-8
Subject(s) - diamond , carbon fibers , metastability , materials science , isothermal process , amorphous carbon , amorphous solid , thermodynamics , supersaturation , glassy carbon , chemistry , composite number , crystallography , organic chemistry , metallurgy , composite material , electrochemistry , cyclic voltammetry , physics , electrode
The temperature dependencies of the thermodynamic properties of the little known (or even hypothetical) undercooled carbon melt and of the glasses that could be obtained from it at appropriate cooling rates are constructed. This is done using both a general thermodynamic formalism to estimate equilibrium properties of undercooled glass‐forming melts and the expected analogy in properties of Fourth Group Elements. A comparison of the hypothetical carbon glasses with amorphous materials, obtained by the pyrolisis of organic resins, usually called vitreous (or glassy) carbon, is made. It turns out that from a thermodynamic point of view existing vitreous carbon materials, although characterized by an amorphous, frozen‐ in structure, differ significantly from the carbon glasses, which could be obtained by a splat‐ cool‐quench of the carbon melt. It is shown also that the hypothetical carbon glasses should have at any temperature a thermodynamic potential, significantly higher than that of diamond. Thus they could be used as a source of constant supersaturation in metastable diamond synthesis. Existing amorphous carbon materials, although showing considerably lower thermodynamic potentials than the hypothetical carbon glasses, could also be used as sources of constant supersaturation in a process of isothermal diamond synthesis if their thermodynamic potential is additionally increased (e.g. by mechano‐ chemical treatment or by dispersion into nano‐size scale). Theoretical estimates made in terms of Ostwald's Rule of Stages indicate that in processes of metastable isothermal diamond synthesis additional kinetic factors (e.g. influencing the formation of sp 3 ‐ carbon structures in the ambient phase) and the introduction of active substrates (e.g. diamond powder) are to be of significance in the realization of this thermodynamic possibility.