Investigation of LSM/8YSZ cathode within an all-ceramic SOFC,Part II: Optimization of performance and co-sinterability

This paper focuses on the cathode and current collector layers of a co-sintered, all-ceramic solid oxide fuel cell (SOFC) concept. Challenges to reach good electrochemical performance have to be overcome, due to more demanding manufacturing conditions, including a relatively high co-sintering temperature. Master sintering curves show that the sintering activity of lanthanum strontium manganite (LSM) is significantly higher than that of 8-mol% yttria stabilized zirconia (8YSZ). By applying a double-layered cathode and a current collector with optimized microstructures the best electrochemical performance of the cathode is 0.26 $\mathrm{\Omega }$cm${}^2$ at 800 $°$C, evaluated from polarization resistances of 8YSZ electrolyte-supported symmetric cells post-sintered at 1150 $°$C $<T<1250$ $°$C. The cathode and current collector materials are adapted to fit the co-sintering process by adjustment of the paste compositions. Half-cells consisting of silicate mechanical support, LSM current collector, LSM mixed with 8YSZ composite cathode and 8YSZ electrolyte are co-sintered porous and defect-free at 1150 $°$C $<T<1250$ $°$C.     

Differentiating seawater and groundwater sulfate attack in Portland cement mortars

The study reported in this article deals with understanding the physical, chemical and microstructural differences in sulfate attack from seawater and groundwater. Portland cement mortars were completely immersed in solutions of seawater and groundwater. Physical properties such as length, mass, and compressive strength were monitored periodically. Thermal analysis was used to study the relative amounts of phases such as ettringite, gypsum, and calcium hydroxide, and microstructural studies were conducted by scanning electron microscopy. Portland cement mortars performed better in seawater solution compared to groundwater solution. The difference in performance could be attributed to the reduction in the quantity of the expansive attack products (gypsum and ettringite). The high Cl concentration of seawater could have played an important role by binding the C₃A to form chloroaluminate compounds, such as Friedel's salt (detected in the microstructural studies), and also by lowering the expansive potential of ettringite. Furthermore, the thicker layer of brucite forming on the specimens in seawater could have afforded better protection against ingress of the solution than in groundwater.     

Optimization of cathode catalyst layer for direct methanol fuel cells: Part I. Experimental investigation

The cathode catalyst layer (CL) in direct methanol fuel cells (DMFCs) has been optimized through a balance of ionomer and porosity distributions, both playing important roles in affecting proton conduction and oxygen transport through a thick CL of DMFC. The effects of fabrication procedure, ionomer content, and Pt distribution on the microstructure and performance of a cathode CL under low air flowrate are investigated. Electrochemical methods, including electrochemical impedance, cyclic votammetry and polarization curves, are used in conjunction with surface morphology characterization to correlate electrochemical characteristics with CL microstructure. CLs in the form of catalyst-coated membrane (CCM) have higher cell open circuit voltages (OCVs) and higher limiting current density; while catalyzed-diffusion-media (CDM) CLs display better performance in the moderate current density region. The CL with a composite structure, consisting both CCM and CDM, shows better performance in both kinetic and mass-transport limitation region, due to a suitable ionomer distribution across the CL. This composite cathode is further evaluated in a full DMFC and the cathode performance loss due to methanol crossover is discussed.     

Carbon aerogel spheres prepared via alcohol supercritical drying

We have developed a method that would allow for the fabrication of carbon aerogel (CA) spheres. The inverse phase suspension polymerization of resorcinol and formaldehyde monomers with Na₂CO₃ as a catalyst followed by supercritical drying was explored. The effects of the chemical formulation and processing procedures and the conditions of the structures of organic and related carbon aerogels were studied. The experimental results indicated that it was easy to avoid the accumulation of polymerization heat during gelation, and easy to take out the products from the reaction container, through this fabrication method. Sol-gel microspheres with diameters ranging from about 30-1000μm could be obtained. After drying the sol-gel spheres under alcohol supercritical drying conditions, aerogel spheres with a bulk density of 0.8-1.0 g/cm³were prepared, and by subsequently pyrolyzing them, CA spheres with surface areas of 250-650 m²/g were obtained. The resultant CA spheres could be used as the electrode materials of supercapacitors. The specific capacitance of the CA spheres was as high as 215 F/g, and the equivalent series resistance at 48 Hz was about 1 Ω.     

Synthesis and characterization of organic-inorganic hybrid thin films from poly(acrylic) and monodispersed colloidal silica

Hybrid thin films containing nano-sized inorganic domain were synthesized from poly(acrylic) and monodispersed colloidal silica with coupling agent. The 3-(trimethoxysilyl)propyl methacrylate (MSMA) was bonded with colloidal silica first, and then polymerized with acrylic monomer to form a precursor solution. Then, the precursor was spin coated and cured to form the hybrid films. The silica content in the hybrid thin films was varied from 0 to 50 wt%. The experimental results showed that the coverage area of silica particle by the MSMA decreased with increasing silica content and resulted in the aggregation of silica particle in the hybrid films. Thus, the silica domain in the hybrid films was varied from 20 to 35 nm by the different mole ratios of MSMA to silica. The results of scanning electron microscope, transmission electron microscope, and elemental analysis support the above results. The prepared hybrid films from the crosslinked acrylic polymer moiety showed much better film uniformity, thermal stability and mechanical properties than the poly(methyl methacrylate) (PMMA) based hybrid materials. Large pin-holes were found in the PMMA-silica hybrid films probably due to the significant difference on thermal properties between the two moieties or the evaporation of solvent. The refractive index decreased linearly with increasing the silica fraction in the hybrid films. Excellent optical transparence was obtained in the prepared hybrid films. These results show that the hybrid thin films have potential applications as passive films for optical devices.     

Impact fracture behavior of clay-reinforced polypropylene nanocomposites

The micromechanism of plastic deformation during impact loading of polypropylene-clay nanocomposites is examined and compared with the unreinforced polypropylene under identical conditions of processing to underscore the determining role of clay. The addition of clay to polypropylene increases the impact strength in the temperature range of 0 to +70 °C. Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and transmission electron microscopy (TEM), wide-angle X-ray diffraction (WAXD) and scanning electron microscopy (SEM) techniques provided an understanding of the micromechanism of plastic deformation in terms of the response of the polymer matrix, nucleating capability of the reinforcement, crystal structure, percentage crystallinity, lamellae thickness, and particle-matrix interface. The enhancement of toughness on reinforcement of polypropylene with nanoclay is associated with change in the primary mechanism of plastic deformation from crazing and vein-type in neat polypropylene to microvoid-coalescence-fibrillation process in the nanocomposite.     

Thermal gas effusion from diamond-like carbon films

Good-quality diamond-like carbon films (6 at.% H₂, 2400 kgf/mm² microhardness, 2.7 eV bandgap, higly insulating) have been obtained by the DC glow discharge decomposition of acetylene. Mass spectroscopic thermal effusion measurements were carried out on the films deposited under different deposition conditions. Analyses of hydrogen in conjunction with hydrocarbon effusing species yield information on the microstructure and nature of C---H bonding configurations. It is shown to be a useful analytical tool to study hydrogenated amorphous carbon films of different microstructures varying from polymer-like to diamond-like.     

Characterizing herring bone structures in carbon nanofibers using selected area electron diffraction and dark field transmission electron microscopy

The use of selected area electron diffraction and centered dark field imaging using a transmission electron microscope is demonstrated for studying the herringbone structure of carbon nanofibers (CNFs). The experimental method is described and illustrated with CNFs that were grown via a chemical vapor deposition method with a nickel catalyst. It is demonstrated that this method gives the angle of the herringbone with great accuracy and gives insight into the uniformity of graphitic elements in the herringbone structure. It was found that the Ni catalyst could be removed from the fiber-tips by treatment in HNO₃, without affecting the carbon structure. These electron microscopy results were confirmed by XRD. The parameters that can be determined by application of this characterization method are expected to be useful to study and optimize growth conditions for carbon nanofibers grown by chemical vapor deposition.     

Gas-phase residence time distribution in a falling-film microreactor

Industrial-scale performance of gas-liquid reactors can be difficult to optimise for very rapid or highly exothermic reactions. Microstructured reactors for laboratory measurements offer new opportunities for the study of these reactions by enabling precise heat management and fine control of reactor operating conditions. For accurate experimental study, characterisation of the flow conditions within these new reactor devices is essential.The present study examines experimental residence time distributions for the gas phase through a microstructured falling-film reactor, in order to develop an appropriate flow model for further study of gas-phase mass-transfer characteristics in the system. For the gas-phase residence time distribution experiments, the detection system involves a flow of oxygen containing ozone as a tracer gas with continuous monitoring of the concentration by UV-light absorption. The experimental results are used to model the flow behaviour in the gas volume over the gas-liquid contact zone as a series of continuous stirred tank reactors whose number is a simple function of the gas Reynolds number.The experimental results are compared with computational fluid dynamics calculations of the gas flow within the reactor. The comparison indicates a clear correlation of the flow model behaviour with the appearance of recirculation loops in the reaction chamber and the effect of the gas jet at the entrance of the gas-liquid contact zone.     

Microstructure of Pd/CeO2 catalyst: Effect of high temperature reduction in hydrogen

The effect of high temperature reduction (HTR) in hydrogen (up to 1180 K) on the microstructure of 9 wt.-% Pd/CeO₂ catalyst was studied by HRTEM and XRD methods. Reduction of the catalyst at or above 973 K caused severe recrystallization of CeO₂ and Pd with simultaneous strong interaction between the two components appearing as three phenomena: epitaxial growth of small Pd particles on CeO₂ (most frequently with [111]Pd[111]CeO₂); decoration of large Pd particles with ordered CeO₂ overlayer and expansion of the lattice parameter of Pd (by 2.1%). The origin of the Pd lattice expansion is discussed and diffusion of Ce species into the Pd lattice seems to be the most probable one. HTR caused also phase transformations in the ceria support. At 973 K and 1100 K, whole CeO₂ was transformed into oxygen deficient CeO_x phase exhibiting the same or similar structure but with expanded lattice parameter (by 2.8%). At 1180 K most ceria was transformed into hexagonal A-Ce₂₃. The CeO_x phase appeared to be stable in hydrogen and in vacuum at room temperature, but upon exposure to air at room temperature it rapidly reoxidised to CeO₂. Ce₂O₃ also reoxidised to CeO₂ but much slower. Another consequence of HTR at or above 773 K was formation of pits in CeO₂ crystallites, mainly on (112)-type crystal faces. The pits (1–10 nm) exhibited well defined walls parallel to CeO₂ lattice fringes and they could possibly constitute nucleation sites for strongly bonded, epitaxial oriented Pd particles.