Start‐Up Characteristics of Segmented‐In‐Series Tubular SOFC Power Modules Improved by Catalytic Combustion at Cathodes

For large‐scale SOFC power generation systems, a shorter start‐up time of SOFC cell stacks with relatively large heat capacity is one of the most important technological issues to determine the flexibility in SOFC system operation. In this study, start‐up procedures have been examined to shorten the start‐up time period. The conventional heating procedure using pre‐heated hot air and self‐heating by SOFC operation at low temperatures had a difficulty to shorten the start‐up time period because of the limitation in power generation at lower temperatures. In this study, as an alternative start‐up procedure, catalytic combustion at the SOFC cathodes is, for the first time, demonstrated to be useful on the system level. The applicability of the catalytic combustion to shorten the start‐up time period has been verified numerically as well as experimentally by using a large‐scale cell stack cartridge. This unique start‐up procedure enables to operate SOFC‐based large‐scale power generation systems.     

Improvement of the Electrochemical Performance of Ln0.58Sr0.4Fe0.8Co0.2O3 – δ IT‐SOFC Cathodes by Ternary Lanthanide Combinations (La‐Pr‐Sm)

Active perovskite‐based SOFC cathodes have been developed through lanthanide combination in the (La_{1 – x – y}Pr_xSm_y)_0.58Sr_0.4Fe_0.8Co_0.2O_{3 – δ} system following a ternary mixture experimental design. These compositions were prepared through a sol–gel method and characterised by electrochemical impedance spectroscopy (EIS) as symmetrical cells on GDC‐electrolyte samples in the 450–650 °C temperature range. The electrochemical properties of the single lanthanide‐based Ln_0.58Sr_0.4Fe_0.8Co_0.2O_{3 – δ} compounds were enhanced when different lanthanides were combined together in the same crystalline structure. The observed improvement does not follow a mere additional effect of the performance from the parent Ln_0.58Sr_0.4Fe_0.8Co_0.2O_{3 – δ} compounds, i.e. it does not follow a linear behaviour, and the better performance is ascribed to synergetic catalytic effects among lanthanide cations. A reduction in electrode polarisation resistance with respect to non‐substituted compositions is stated for most Ln_0.58Sr_0.4Fe_0.8Co_0.2O_{3 – δ} electrode compositions combining two or three lanthanides. Samarium addition to the electrode material involves a substantial reduction in the activation energy and the reduction degree is directly dependant on the samarium amount incorporated in the lattice. The best performing composition comprises a praseodymium‐rich lanthanum‐based electrode material. The experimental data derived from the ternary mixture design were modelled using nonlinear functions and this modelling allowed finding an electrode composition minimising the polarisation resistance while maintaining the activation energy at reduced values. Selected cathode compositions were tested in fully assembled anode‐supported cells and electrochemical characterisation supports the cooperative effect of lanthanide combination.     

Modeling of a Tubular‐SOFC: The Effect of the Thermal Radiation of Fuel Components and CO Participating in the Electrochemical Process

A mathematical model based on first principles is developed to study the effect of heat and electrochemical phenomena on a tubul solid oxide fuel cell (SOFC). The model accounts fordiffusion, inherent impedance, transport (momentum, heat and mass transfer) processes, internal reforming/shifting reaction, electrochemical processes, and potential losses (activation, concentration, and ohmic losses). Thermal radiation of fuel gaseous components is considered in detail in this work in contrast to other reported work in the literature. The effect of thermal radiation on SOFC performance is shown by comparing with a model without this factor. Simulation results indicate that at higher inlet fuel flow pressures and also larger SOFC lengths the effect of thermal radiation on SOFC temperature becomes more significant. In this study, the H₂ and CO oxidation is also studied and the effect of CO oxidation on SOFC performance is reported. The results show that the model which accounts for the electrochemical reaction ofCO results in better SOFC performance than other reported models. This work also reveals that at low inlet fuel flow pressures the CO and H₂ electrochemical reactions are competitive and significantly dependent on the CO/H₂ ratio inside the triple phase boundary.     

Microstructural Change of Ni–GDC Cermet Anode in the Electrolyte‐supported Disk‐type SOFC upon Daily Start‐up and Shout‐down Operations

The daily start‐up and shut‐down operations were carried out for the 1 kW‐class solid oxide fuel cell stack composed of 46 electrolyte‐supported disk‐type planar cells made by Mitsubishi Materials Corporation and Kansai Electric Power Company. The representative Ni–gadolinia doped ceria cermet anodes in the deteriorated cells were analyzed by the dual‐beam focused ion beam‐scanning electron microscope. The anode microstructures were reconstructed and the microstructural parameters such as triple phase boundary (TPB) length were quantified. The surface area of nickel phase decreased with an increase in the deterioration rate, leading to a reduction in the TPB length. Furthermore, the TPB length had a strong correlation with the voltage deterioration rate.     

Theoretical Model for the Optimal Design of Air Cooling Systems of Polymer Electrolyte Fuel Cells. Application to a High‐Temperature PEMFC

The cooling system of a high‐temperature PEM fuel cell with a nominal electric power of 1.5 kW for a combined heat and power unit (CHP) has been designed using a thermochemical model. The 1D model has been developed as a simple, predictive, and useful tool to evaluate, design, and optimize cooling systems of PEM fuel cells. As proved, it can also be used to analyze the influence of different operational and design parameters, such as the number and geometry of the channels, or the air flow rate, on the overall performance of the stack. To validate the model, predicted results have been compared with experimental measurements performed in a commercial 2 kW air‐forced open‐cathode stack. The model has then been applied to calculate the air flow required by the designed prototype stack as a function of the power output, as well as to analyze the influence of the cooling channels configuration (cross‐section geometry and number) on the heat management. Results have been used to select the optimum air‐fan cooling system, which is based on compact axial fans.     

Saturation‐specific pattern of acquired colour vision deficiency in two clinical populations revealed by the method of triads

Subjective colour spaces were reconstructed for persons occupationally exposed to mercury (Hg) and patients with diabetes mellitus type 2, two groups at risk for acquired colour‐vision deficiency, and compared with healthy normal trichromats. Judgments of colour dissimilarity were collected with the method of triads, applied to a composite assortment of colour samples. These were drawn from two widely used colour arrangement tests—10 hues from the Farnsworth D‐15 test and five from the Lanthony Desaturated D‐15d test, ensuring that the assortment sampled two levels of lightness and saturation. The data were analyzed with maximum‐likelihood multidimensional scaling (MDS) and within a novel individual‐differences MDS model to estimate subject‐specific parameters. The MDS solutions for the two clinical groups showed a compression along a blue‐yellow axis, limited however to desaturated hues. This result was confirmed by the individual‐differences model. In addition, the clinical groups were found to place significantly higher weights on the lightness differences between stimuli, conceivably to compensate for their reduced chromatic discrimination. The specific form of colour‐space distortion in the clinical groups indicated an increase in their thresholds for blue‐yellow signals, providing insights into the nature of impairment mechanisms. The results have implications for stimuli and diagnostic procedures for testing individual differences in color vision, and for analyzing the responses. This approach is sensitive to distinctive patterns of subtle colour‐vision impairment underestimated by the conventional D‐15d test. © 2013 Wiley Periodicals, Inc. Col Res Appl, 39, 125–135, 2014     

Water diffusion and permeability in unsaturated polyester resin films characterized by measurements performed with a water‐specific permeameter: Analysis of the transient permeation

A water‐specific permeameter was developed to study water diffusion in an unsaturated polyester; these polyesters are often used as high‐barrier materials. Low water enrichment of a dry sweeping gas is measured via the dew point temperature, with two hygrometers, one of which is used because of its fast response and the other because of its accuracy. This high‐performance device is just as suited to pervaporation as to permeation tests and allows the transient and stationary fluxes to be characterized. At first sight, the experimental data seem in good agreement with D = D₀e^γC. However, a more thorough study has shown a time‐dependence of D. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3380–3395, 1999     

Immobilization of a functionalized poly(ethylene glycol) onto β‐cyclodextrin‐coated surfaces by formation of inclusion complexes: Application to the coupling of proteins

The aim of this study was the immobilization of COOH‐modified poly(ethylene glycol) (PEG) layers onto β‐cyclodextrin‐coated surfaces by formation of inclusion complexes, in view of biosensors applications. To this end, PEGs with one phenyladamantyl and one carboxylic end group (Ad‐PEG‐COOH) were prepared according to a three‐step procedure. After modification of PEG with 4‐toluenesulfonylchloride, the reaction of the tosyl intermediate with the alcoholate of 4‐(1‐adamantyl)‐phenol was carried out in tetrahydrofuran to avoid the formation of by‐products. Then, it was shown by high performance liquid chromatography that the association between β‐cyclodextrin cavities and Ad‐PEG‐COOH polymers was not hindered by the presence of the COOH group. Last, the Ad‐PEG‐COOH polymer was immobilized onto β‐cyclodextrin‐coated gold surfaces by formation of inclusion complexes. The immobilization was performed in water, at room temperature, with a rapid kinetics. After activation of COOH groups with N‐hydroxysuccinimide, β‐lactoglobulin was coupled to the biocompatible PEG layer. Functionalization of the gold surface with β‐cyclodextrin cavities, immobilization of Ad‐PEG‐COOH onto the surface, and coupling of the protein to the reactive PEG layer were followed in real time by surface plasmon resonance imaging system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2362–2370, 2006