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Published online by Cambridge University Press: 10 February 2011
In materials that are subject to environmental reactions, one way to increase durability is to decrease the chemical interdiffusion rate. In metal systems, mass transport by diffusion is enhanced – if any change – with finer grained microstructures, because of the greater number of high diffusion interface and boundary paths. In non-metals, increased transport is not necessarily the case, as other mechanisms may control the overall diffusivity. C. Wagner [1] showed the theoretical basis of transport in certain nanocomposite cases based on space charge layers at interfaces.
In an oxide-in-oxide nanocomposite, one can use the tools of bulk analysis to study the near-interface effects on transport. The immiscible pair, TiO2-SiO2, was used as a model system. Nanophase powders (50 and 200 m2/g, respectively) from flame hydrolysis were dispersed with high shear, then freeze-dried and hot-pressed to near theoretical density. Transmission electron microscopy was used to show < 10 nm particles in the composites produced at the time of diffusivity measurement. The rate of change of four-point electrical conductivity in response to a change in oxygen partial pressure was used to estimate chemical diffusivity. The re-equilibration differences between TiO2 diffusivity for bars of about 10 times different square cross-section areas confirmed the interpretation of the conductance rate changes to be the result of bulk interdiffusion.
The interdiffusion rate in the nanoscale dispersoid composites was more than 5 times lower than for same SiO2-fraction composites after coarsening which were like TiO2 with no second-phase. Results are in qualitative agreement with models for impurity segregation to interfaces and for space charge layers near the dispersed nanoparticles.