Ground states in the diffusion-dominated regime.

We consider macroscopic descriptions of particles where repulsion is modelled by non-linear power-law diffusion and attraction by a homogeneous singular kernel leading to variants of the Keller-Segel model of chemotaxis. We analyse the regime in which diffusive forces are stronger than attraction between particles, known as the diffusion-dominated regime, and show that all stationary states of the system are radially symmetric non-increasing and compactly supported. The model can be formulated as a gradient flow of a free energy functional for which the overall convexity properties are not known. We show that global minimisers of the free energy always exist. Further, they are radially symmetric, compactly supported, uniformly bounded and C ∞ inside their support. Global minimisers enjoy certain regularity properties if the diffusion is not too slow, and in this case, provide stationary states of the system. In one dimension, stationary states are characterised as optimisers of a functional inequality which establishes equivalence between global minimisers and stationary states, and allows to deduce uniqueness.

Back-exchange: a novel approach to quantifying oxygen diffusion and surface exchange in ambient atmospheres.

A novel two-step Isotopic Exchange (IE) technique has been developed to investigate the influence of oxygen containing components of ambient air (such as H2O and CO2) on the effective surface exchange coefficient (k*) of a common mixed ionic electronic conductor material. The two step 'back-exchange' technique was used to introduce a tracer diffusion profile, which was subsequently measured using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The isotopic fraction of oxygen in a dense sample as a function of distance from the surface, before and after the second exchange step, could then be used to determine the surface exchange coefficient in each atmosphere. A new analytical solution was found to the diffusion equation in a semi-infinite domain with a variable surface exchange boundary, for the special case where D* and k* are constant for all exchange steps. This solution validated the results of a numerical, Crank-Nicolson type finite-difference simulation, which was used to extract the parameters from the experimental data. When modelling electrodes, D* and k* are important input parameters, which significantly impact performance. In this study La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF6428) was investigated and it was found that the rate of exchange was increased by around 250% in ambient air compared to high purity oxygen at the same pO2. The three experiments performed in this study were used to validate the back-exchange approach and show its utility.