Argon diffusivities and solubilities in single gem-quality crystals of corundum
were determined from experiments conducted under 0.5 to ~6000bar Ar pressures
at 425 to 1200C. Surface-sensitive analyses were conducted in order to confirm
that the near-surface regions of the crystals were crystalline, unreacted and free
from structural damage. Polished single-crystal slabs and specimens with natural
facets were placed in open containers and exposed to an Ar atmosphere in a
pressure vessel or in a gas-flow tube furnace at near-atmospheric pressure. The Ar
atoms from the pressure medium diffused into the crystals to produce near-surface
concentration gradients which were directly profiled using Rutherford backscattering
spectrometry. The Arrhenius relationship was:
D (m2/s) = 1.2 x 10-20exp[-33(kJ/mol)/RT]
The activation energy was probably an apparent one which was a combination of
the effects of the lattice diffusion of Ar atoms, with trapping in point-defect
vacancies. There were no discernible differences in Ar diffusion in different
crystallographic directions, and the diffusivity did not vary as a function of the
intrinsic oxygen fugacity of the experimental vessel. The uptake gradients also
yielded lattice solubilities of argon, as represented by the concentrations at the
mineral surfaces. The solubility was of the order of 2000ppm[wt]. The Ar
solubilities were independent of the Ar pressure above 1bar, but were slightly
lower at 0.5 to 1bar. This suggested that all of the sites capable of accommodating
Ar atoms were filled at Ar pressures of ~1bar. The Ar appeared to be compatible;
although the degree of compatibility was expected to depend upon assumptions
concerning the minimum Ar fugacity required to fully populate the available
vacancies.
Lattice Diffusion and Solubility of Argon in Forsterite, Enstatite, Quartz and
Corundum. J.B.Thomas, D.J.Cherniak, E.B.Watson: Chemical Geology, 2008,
253[1-2], 1-22