Diffusion - Forsiden - Universitetet i Oslo：扩散forsiden - universitetet我奥斯陆.pptVIP

Factors that affect diffusivity We have seen that the random diffusion coefficient can be expressed in terms of jump distance s and jump rate Γ (number of jumps n per time t): We shall now analyse the jump rate in more detail. It contains a number of factors: The vibration frequency The ratio of vibrations sufficiently energetic to make the jump The number of neighbouring sites to jump to The chance (ratio) that the jumping particle is free to jump. The chance (ratio) that the site jumped to can receive it. Attempt frequency Defect concentration enters here when applicable a0 Diffusion by vacancy mechanism Jump rate is proportional to the attempt frequency, number of neighbouring sites to jump to, and the concentration (fraction) of vacancies (defects) The diffusivity thus becomes Example: bcc structure: Z = 8, s = √3 a0/2. In general, we collect all geometrical factors in a parameter α: (For bcc and fcc, α = 1) Diffusion by interstitial mechanism Diffusion of an interstitially dissolved foreign atom The chance that the atom is interstitial is unity. The chance that the neighbouring (interstitial) position is vacant is close to unity when the concentration of interstitials is small. Diffusion of a component species by interstitial mechanism In this case, the chance that a component atom is interstitial, Nd, enters. Thus, for component species, the defect concentration enters either way! How does D vary with T and pO2? We start by analysing the influence from the concentration of defects. Example:Vacancies in an elemental solid: Example: Oxide ion vacancies in a non-stoichiometric oxide, e.g. MaOb-δ: Example: Oxide ion vacancies in an acceptor-doped oxide, e.g. Ca-doped ZrO2-δ: Temperature dependency of ω The rate of sufficiently energetic vibrations contains vibration frequency ν (”nu”) Gibbs energy of the activated saddle point complex Activation entropy Activation enthalpy It is common to disregard the entropy and consider the ent