Constraints on oxygen fugacity within metal capsules

Experiments were conducted with olivine encapsulated or wrapped in five different metals (Pt, Ni, Ni70, Fe30, Fe, and Re) to determine the oxygen fugacity in the interior of large capsules used for deformation and seismic property experiments. Temperature (1200° C), pressure (300 MPa), and duration (24 h) were chosen to represent the most common conditions in these experiments. The oxygen fugacity was determined by analysing the Fe content of initially pure Pt particles that were mixed with the olivine powder prior to the experiments. Oxygen fugacities in the more oxidizing metal containers are substantially below their respective metal-oxide buffers, with the fO2 of sol–gel olivine in Ni about 2.5 orders of magnitude below Ni–NiO. Analysis of olivine and metal blebs reveals three different length-, and hence diffusive time scales: (1) Fe loss to the capsule over ~100 µm, (2) fO2 gradients at the sample–capsule interface up to 2 mm into the sample, and (3) constant interior fO2 values with an ordering corresponding to the capsule material. The inferred diffusive processes are: Fe diffusion in olivine with a diffusivity ~ 10^-14 m/m/s, diffusion possibly of oxygen along grain boundaries with a diffusivity ~ 10^-12 m/m/s, and diffusion possibly involving pre-existing defects with a diffusivity~ 10^-10 m/m/s. The latter, fast adjustment to changing fO2 may consist of a rearrangement of pre-existing defects, representing a metastable equilibrium, analogous to decoration of pre-existing defects by hydrogen. Full adjustment to the external fO2 requires atomic diffusion.This work was, in part, funded by NSF Grant EAR 1321889 to U.F. and ARC Grant DP130103848 to I.J, A.B., U.F., and S. Karato