Processing of Composite Thin Film Solid Oxide Fuel Cell Structures

A solid oxide fuel cell (SOFC) structure is proposed in which a composite thin film cathode substrate supports a dense thin film electrolyte with a thickness of less than 1 μm. The cathode substrate has a graded porosity achieved through the partial sintering of a spin-coated CeO₂ colloidal suspension. The resulting surface has a pore size and surface roughness which allowed a fully dense ZrO₂:16%Y (YSZ) electrolyte to be spin-coated directly from a polymeric precursor without capillary forces removing the precursor from the surface of the porous substrate. Using this process, fuel cell structures were constructed with temperatures not exceeding 800°C. The porous CeO₂ interlayer should allow for decreased ohmic losses, as well as decreased reactions between the YSZ and the cathode substrate. In addition, the nanocrystalline grain sizes should allow for increased catalytic activity on the cathode. Calculated ohmic losses indicated the resistance of the CeO₂ interlayer limited the power of the structure, which was minimized by impregnating the porous layer with a mixed-conducting perovskite. The final structure shows significantly reduced ohmic losses as calculated at 400°C.     

Catalytic combustion over platinum group catalysts: fuel-lean versus fuel-rich operation

Performance data are presented for methane oxidation on alumina-supported Pd, Pt, and Rh catalysts under both fuel-rich and fuel-lean conditions. Catalyst activity was measured in a micro-scale isothermal reactor at temperatures between 300 and 800 °C. Non-isothermal (near adiabatic) temperature and reaction data were obtained in a full-length (non-differential) sub-scale reactor operating at high pressure (0.9 MPa) and constant inlet temperature, simulating actual reactor operation in catalytic combustion applications.

Under fuel-lean conditions, Pd catalyst was the most active, although deactivation occurred above 650 °C, with reactivation upon cooling. Rh catalyst also deactivated above 750 °C, but did not reactivate. Pt catalyst was active above 600 °C. Fuel-lean reaction products were CO₂ and H₂O for all three catalysts.

The same catalysts tested under fuel-rich conditions demonstrated much higher activity. In addition, a ‘lightoff’ temperature was found (between 450 and 600 °C), where a stepwise increase in reaction rate was observed. Following ‘lightoff’ partial oxidation products (CO, H₂) appeared in the mixture, and their concentration increased with increasing temperature. All three catalysts exhibited this behavior.

High-pressure (0.9 MPa) sub-scale reactor and combustor data are shown, demonstrating the benefits of fuel-rich operation over the catalyst for ultra-low emissions combustion.     

Population balances for particulate processes—a volume approach

Population balance models have been used in chemical engineering since the 1960s and have evolved to become the most important tools for design and control of particulate processes. In this paper we show that the intrinsic particle parameter that determines changes in the process and should thus be included in the population balance is the particle volume. The basic population that is modeled should be the mass distribution, or the volume distribution if the density is constant. The population balance thus describes the change of the volume distribution of volume with time. Furthermore, we suggest that the “birth” and “death” terms that are often used to describe discrete events in particulate processes can almost always be replaced by a rate of change term.To design and control existing and future processes, a multi-dimensional population balance model is required. We propose a volume-based model in which the particle properties that are modeled are the volumes of solid, liquid, and air, respectively. In the most general case the model will consist of a properties vector and a distribution tensor. Depending on the complexity of the process, one or more of the properties may be omitted from the model. This is shown in three examples of increasing complexity: comminution, sintering, and granulation.     

Development of high-performance liquid chromatography criteria for determination of grades of commercial olive oils. Part I. The normal ranges for the triacylglycerols

Criteria for authentic olive oils were developed from isocratic high-performance liquid chromatography analyses of 99 olive oils from the major Mediterranean producers in the 1983–1986 crop years. Authentic olive oils include extra virgin, virgin and pure or refined oils, but exclude all reesterified and adulterated oils. The extra virgin through pure grades will have a combined area for the LOO (C_18:2C_18:1C_18:1), LOP (C_18:2C_18:1C_16:0), OOO (C_18:1C_18:1C_18:1), POO (C_16:0C_18:1C_18:1), POP (C_16:0C_18:1C_18:1), and SOO (C_18:0C_18:1C_18:1) peaks between 82.0 and 92.6% of the total area (L, linoleic; O, oleic; P, palmitic; S, stearic). Authentic oils will have ratios of LOO/LOP and OOO/POO that coincide with a line defined by OOO/POO=0.7844(LOO/LOP)+0.0968; correlation coefficient is 0.885. Authentic oils will not have a trilinolein (LLL) peak over 0.5% in area. Neither triolein (OOO) nor any other single peak suffices to characterize an olive oil sample as one of the authentic grades.     

Synthetic hydrogels: 3. Hydroxyalkyl acrylate and methacrylate copolymers: surface and mechanical properties

The surface and mechanical properties of copolymers of hydroxyalkyl acrylates and methacrylates have been examined by a variety of techniques. This work is complementary to earlier parts of this series which describe the effect of copolymer structure on water binding properties. Water structure has been demonstrated to exert a profound effect upon mechanical properties whether measured in compression or in tension. In particular, water that is characterized by differential scanning calorimetry as ‘freezing’ water is observed to have a marked plasticizing effect upon the gel, whereas ‘non-freezing’ water has little such effect. Similarly, the ‘freezing’ water produces a more marked effect on thermally induced transitions. Two distinct transition points are observed as a result of its presence. One corresponds to the freezing point of water and the other to a glass transition temperature, whose value depends upon the proportion of ‘freezing’ or ‘plasticizing’ water in the gel. Several predictive and direct measurement techniques have been used to study the surface properties of the copolymers in both hydrated and dehydrated states. Taken together they have established a sound understanding of the way in which polar and dispersive components of surface free energy vary as a function of copolymer composition and water content. Use of protein adsorption and fibroblast cell interaction techniques demonstrate that biological phenomena respond to changes at a molecular level which current macroscopic surface energy techniques are unable to discern.     

Preparation of segmented, high molecular weight, aliphatic poly(ether-urea) copolymers in isopropanol. In-situ FTIR studies and polymer synthesis

The use of isopropanol (IPA) as the reaction solvent for the preparation of high molecular weight segmented polyether-urea copolymers based on cycloaliphatic diisocyanates was investigated. Reactivity of IPA with bis(4-isocyanatohexyl)methane (HMDI) and isophorone diisocyanate (IPDI) was studied between 0 and 40 °C using in-situ FTIR spectroscopy. HMDI, which has secondary isocyanate groups, shows a very slow reaction with a large excess of IPA at 0 and 23 °C. Analysis of the kinetic data indicates an activation energy of 51 kJ/mol for the reaction between HMDI and IPA. As expected, IPDI, which has both a primary and a secondary isocyanate (NCO) group, reacts faster with IPA compared with HMDI, which only has secondary NCO groups. However, the rate of reaction of IPDI with IPA at 0 °C is extremely slow (approximately 1% consumption of isocyanate in 60 min) thus allowing the use of IPA as the reaction solvent for polyether-urea synthesis. Preparation of high molecular weight, high-strength HMDI and IPDI based polyether-urea segmented copolymers in IPA has been demonstrated. Thermal analysis and stress-strain analyses were used to characterize the products.     

Crystallization studies of semi-crystalline polymers under oscillatory shear using the rheometrics mechanical spectrometer

A method has been developed on the Rheometrics mechanical spectrometer using the eccentric rotating disks mode to study the crystallization kinetics of different semi-crystalline polymers (polyethylene, polypropylene, poly(butylene terephthalate) and Nylon 11) under oscillatory shear. Dynamic shear moduli (storage G′ and loss G″), loss tangent (tan δ), and dynamic viscosity (η′) were simultaneously, monitored during the crystallization process. The onset and completion of crystallization were characterized by the initial rise and final levelling off of G′, while the peak time, of crystallization (t_p) is calculated from the time elapsed between the onset and peak of crystallization which is indicated by the G″ or η′ maximum. In the case of polypropylene, going from a low frequency of ?0.1 rad/s, to higher frequencies of up to 10 rad/s, there is a monotonic decrease in peak time of crystallization (t_p) together with a progressive decrease in spherulitic morphology. The observed acceleration in crystallization is due predominantly to the increase in nucleation rate and orientation of chains in melt crystalline aggregate. The progressive disappearance of the spherulitic morphology is attributed to the disruption of the spherulite superstructure at higher frequencies of shear.     

Direct Measurement of Transformation Zone Strains in Toughened Zirconia

Residual strains responsible for crack tip shielding have been measured within transformation zones surrounding cracks in Mg-PSZ. Two techniques were used for strain measurement: moiré interferometry and high-resolution image matching. Both methods provide maps of differential in-plane displacements within the specimen surface intersected by the crack, the latter method with the higher resolution. The results are compared with finite-element analysis to assess surface relaxation effects, and the measured strains are used to evaluate the crack tip shielding stress intensity factor. Calculations based on the assumption that the unconstrained transformation strain is hydrostatic dilatation yielded results that were significantly smaller than the measured toughness increases.     

Determination of Both Mesopores and Macropores in Three-Dimensional Ordered Porous Materials by Nitrogen Adsorption

Three-dimensionally ordered silica structures containing both mesopores and macropores are created using polystyrene coacervate spheres with a diameter of ca. 146 nm. The close-packed polystyrene coacervate spheres are intercalated with tetraethyl orthosilicate. The spheres are removed by calcination leaving an inverse silica replica with a spherical macropore cavity diameter of 110 nm. Due to the nature of these porous structures, pores leading into the macropore cavity are in the mesopore regime, 40 nm in diameter. The nitrogen adsorption data described in the following paper gives a pore size for both the macropore cavity and the mesopore openings leading into the cavity. The pore sizes as determined by nitrogen sorption are in good agreement with the pore sizes observed by scanning electron microscopy. Mercury intrusion porosimetry results confirm the size of the mesopore openings leading into the macropore cavity, however due to destruction of the sample upon intrusion, extrusion results can not be obtained to determine main cavity diameters. As a result, nitrogen sorption may be a viable option for determining pore sizes with these three-dimensionally ordered materials containing both mesopores and macropores.     

The circadian cycles of plasma corticosterone and adrenal cholesteryl esters in the normal and EFA-deficient female rat

In female rats subjected to a 12 hr light-12 hr darkness schedule and fed a semipurified diet containing 10% corn oil, plasma corticosterone concentration showed a monophasic circadian cycle with minimum and maximum concentrations at the start of the light and dark periods, respectively. Adrenal total cholesteryl ester concentration was inversely related to plasma corticosterone, as were those of several of the individual esters; changes in cholesteryl ester concentration appeared to follow rather than precede changes in plasma corticosterone. There was preferential depletion of the cholesteryl esters of 18∶1, 18∶2ω6, and 20∶4ω6 during glucocorticoid secretion. [Abbreviations: EFA, essential fatty acid (s);X:YωZ, fatty acid with X carbon atoms and Y olefinic bonds with the terminal double bond Z carbon atoms from the methyl group.] In female rats fed hydrogenated coconut oil (EFA-deficient), a monophasic cycle for plasma corticosterone was also observed, but the peak was much broader than that recorded for rats fed corn oil, although minima and maxima occurred at similar times for the two groups. No significant cycle of adrenal total cholesteryl esters was evident in the deficient rats, but the 20∶3ω9 and 22∶3ω9 esters did decrease significantly during the period of high plasma corticosterone concentration. Preferential net decreases in adrenal cholesteryl esters during corticosteroidogenesis were more apparent in normal than in EFA-deficient rats.