Cation self-diffusion and the isotope effect in Mn1−δO

Diffusion of ⁵⁴Mn in Mn_1?δO single crystals has been measured by a serial sectioning technique as a function of temperature (1000–1500°C) and deviation from stoichiometry (0.00003 < δ < 0.12). The value of m in the expression varies from about 6 at low Po₂ at all temperatures to a value approacing 2 at high Po₂ and high temperatures, thus suggesting that diffusion occurs by doubly charged vacancies at low Po₂ with increasing contributions from singly charged and neutral vacancies as Po₂ (and vacancy concentration) increases. For δ near 0.1, the values of D fall below the values extrapolated from smaller defect concentrations. The isotope effect for cation self-diffusion was measured by simultaneous diffusion of ⁵²Mn and ⁵⁴Mn in Mn_1?δO (0.0004 < δ < 0.116) at 1300 and 1500°C. The measured values of fΔK are independent of temperature within experimental error, and decrease from a value of 0.70 at low defect concentrations to 0.37 for large values of δ. The isotope-effect results suggest that diffusion occurs by single non-interacting vacancies at low defect concentrations; defect-defect interactions become important for δ ? 0.01. The defect-defect interactions may involve essentially individual defects or may result in defect clusters; the similarity between the present isotope-effect results and those for Fe_1?δ0 suggests that defect clustering plays a significant role in mass transport in Mn_1?δO at large values of δ.