Quantitative interpretation of impedance spectroscopy data on porous LSM electrodes using X-ray computed tomography and Bayesian model-based analysis.

It is broadly understood that strontium-doped lanthanum manganate (LSM) cathodes for solid oxide fuel cells (SOFCs) have two pathways for the reduction of oxygen: a surface-mediated pathway culminating in oxygen incorporation into the electrolyte at the triple-phase boundary (TPB), and a bulk-mediated pathway involving oxygen transfer across the electrode-electrolyte interface. Patterned electrode and thin film experiments have shown that both pathways are active in LSM. Porous electrode geometries more commonly found in SOFCs have not been amenable for precise measurement of active electrode width because of the difficulty in precisely measuring the electrode geometry. This study quantitatively compares a reaction-diffusion model for the oxygen reduction reaction in LSM to the impedance spectrum of an experimental LSM porous electrode symmetric button cell on a yttria-stabilized zirconia (YSZ) electrolyte. The porous microstructure was characterized using computed tomography (nano-CT) and Bayesian model-based analysis (BMA) was used to estimate model parameters. BMA produced good fits to the data, with higher than expected values for the interfacial capacitance at the LSM-YSZ interface and vacancy diffusion activation energy; these results may indicate that the active width of the electrode is on a similar scale with that of the space-charge width at the LSM-YSZ interface. The analysis also showed that the active width and proportion of current moving through the bulk pathway is temperature dependent, in accordance with patterned electrode results.

Molecular dynamics simulation study of P (VP-co-HEMA) hydrogels: effect of water content on equilibrium structures and mechanical properties.

Poly (N-vinyl-2-pyrrolidone-co-2-hydroxyethyl methacrylate) (P(VP-co-HEMA)) hydrogel system with a composition of VP:HEMA=37:13 was studied using molecular dynamics simulations in order to investigate the effect of the water content on the equilibrium structures and the mechanical properties. The degree of randomness of the monomer sequence for the random and the blocky copolymers, were 1.170 and 0.104, respectively, and the degree of polymerization was fixed at 50. The equilibrated density of the hydrogel was found to be larger for the random sequence than for the blocky sequence at low water contents (<40 wt%), but this density difference decreased with increasing water content. The pair correlation function analysis shows that VP is more hydrophilic than HEMA and that the random sequence hydrogel is solvated more than the blocky sequence hydrogel at low water content, which disappears with increasing water content. Correspondingly, the water structure is more disrupted by the random sequence hydrogel at low water content but eventually develops the expected bulk water-like structure with increasing water content. From mechanical deformation simulations, stress-strain analysis showed that the VP is found to relax more efficiently, especially in the blocky sequence, so that the blocky sequence hydrogel shows less stress levels compared to the random sequence hydrogel. As the water content increases, the stress level becomes identical for both sequences. The elastic moduli of the hydrogels calculated from the constant strain energy minimization show the same trend with the stress-strain analysis.

Effect of monomeric sequence on mechanical properties of P(VP-co-HEMA) hydrogels at low hydration.

We have used molecular modeling of both random and blocky hydrogel networks of poly (N-vinyl-2-pyrrolidone-co-2-hydroxyethyl methacrylate) with VP:HEMA=37:13 composition to investigate the effect of the monomeric sequence on the mechanical properties. The degrees of monomer sequence randomness for the random and the blocky copolymers were 1.170 and 0.104, respectively, and the degree of polymerization was set as 50. The equilibrated density of the dry gel network was 0.968+/-0.007 and 0.911+/-0.007 g/cm3 for the random and the blocky sequences, respectively. In the partially hydrated state with 10 wt % water content, the effect of the monomeric sequence causes more distinct differences in density of 1.004+/-0.007 and 0.916+/-0.009 g/cm3 for the random and the blocky copolymer network, respectively. We observed that in such networks, the water molecules are associated more closely with the N-vinyl-2-pyrrolidone than with the hydroxyethyl methacrylate moieties, which is consistent with results from quantum mechanical solvation free energy calculations. By simulating a compressive deformation of the dry gels up to 80% strain, we found that the random sequence network develops higher stress levels than the blocky network. We also found that stress reduction occurs in the random sequence network due to the hydration, which is not evident in the blocky sequence network. This difference in stress reduction between the random and the blocky sequence networks is due to the difference in the structural rearrangement of monomers in the presence of water during deformation. The random sequence network is able to undergo much more efficient rearrangement of HEMA units than in the blocky sequence network.