Oxygen reduction activity of Pt and Pt-Mn-Co electrocatalysts sputtered on nano-structured thin film support

We report on extensive measurements of oxygen reduction activity of Pt and Pt-Co-Mn electrocatalysts using the rotating ring-disk electrode (RRDE) method. The electrocatalysts were prepared by sputtering from Pt or Pt, Co and Mn targets onto 3M's nano-structured thin film support (NSTF) structures. The area specific activity of Pt/NSTF, measured in 0.1 M HClO₄ and at room temperature, is similar to that of bulk Pt. The area specific measurements show a 20 mV reduction in the Pt-Co-Mn/NSTF overpotential compared to Pt/NSTF. The corresponding kinetic gain in the area specific activity of the ternary alloy is about a factor of two. This ORR enhancement factor observed in the ternary Pt-Co-Mn/NSTF by RRDE measurements is similar to the results obtained in 50 cm² H₂/air fuel cells.     

Improvement of Crystallinity of KZr2P3O12 by Sol-Gel Synthesis

The X-ray diffraction pattern for potassium-zirconium phosphate is significantly improved when the material is prepared by the sol-gel route rather than the powder method. Peaks at high, low, and intermediate angles are presented and compared for the two methods. It is assumed that the more nearly homogeneous mixing of the elements in the sol-gel process is responsible for the significant improvement in crystallinity.     

Prediction of Experimental Methanol Decomposition Rates on Platinum from First Principles

A microkinetic model for methanol decomposition on platinum is presented. The model incorporates competitive decomposition pathways, beginning with both O–H and C–H bond scission in methanol, and uses results from density functional theory (DFT) calculations [Greeley and Mavrikakis, J. Am. Chem. Soc. 124 (2002) 7193, Greeley and Mavrikakis, J. Am. Chem. Soc. 126 (2004) 3910]. Results from reaction kinetics experiments show that the rate of H₂ production increases with increasing temperature and methanol concentration in the feed and is only nominally affected by the presence of CO or H₂ with methanol. The model, based on the values of binding energies, pre-exponential factors and activation energy barriers derived from first principles calculations, accurately predicts experimental reaction rates and orders. The model also gives insight into the most favorable reaction pathway, the rate-limiting step, the apparent activation energy, coverages, and the effects of pressure. It is found that the pathway beginning with the C–H bond scission (CH₃OH→H₂COH→HCOH→CO) is dominant compared with the path beginning with O–H bond scission. The cleavage of the first C–H bond in methanol is the rate-controlling step. The surface is highly poisoned by CO, whereas COH appears to be a spectator species.     

Influence of Amorphous Grain Boundary Phases on the Superplastic Behavior of 3-mol%-Yttria-Stabilized Tetragonal Zirconia Polycrystals (3Y-TZP)

Amorphous silicate grain boundary phases of varying chemistry and amounts were added to 3Y-TZP in order to determine their influence on the superplastic behavior between 1200° and 1300°C and on the room-temperature mechanical properties. Strain rate enhancement at high temperatures was observed in 3Y-TZP containing a glassy grain boundary phase, even with as little as 0.1 wt% glass. Strain rate enhancement was greatest in 3Y-TZP with 5 wt% glass, but the room-temperature hardness, elastic modulus, and fracture toughness were degraded. The addition of glassy grain boundary phases did not significantly affect the stress exponent of 3Y-TZP, but did lower the activation energy for superplastic flow. Strain rate enhancement was highest in samples containing the grain boundary phase with the highest solubility for Y₂O₃ and ZrO₂, but the strain rate did not scale inversely with the viscosity of the silicate phases. Grain boundary sliding accommodated by diffusional creep controlled by an interface reaction is proposed as the mechanism for superplastic deformation in 3Y-TZP with and without glassy grain boundary phases.     

Open annotations on multimedia Web resources

Many Web portals allow users to associate additional information with existing multimedia resources such as images, audio, and video. However, these portals are usually closed systems and user-generated annotations are almost always kept locked up and remain inaccessible to the Web of Data. We believe that an important step to take is the integration of multimedia annotations and the Linked Data principles. We present the current state of the Open Annotation Model, explain our design rationale, and describe how the model can represent user annotations on multimedia Web resources. Applying this model in Web portals and devices, which support user annotations, should allow clients to easily publish and consume, thus exchange annotations on multimedia Web resources via common Web standards.     

An industrial study of applying input space partitioning to test financial calculation engines

This paper presents results from an industrial study that applied input space partitioning and semi-automated requirements modeling to large-scale industrial software, specifically financial calculation engines. Calculation engines are used in financial service applications such as banking, mortgage, insurance, and trading to compute complex, multi-conditional formulas to make high risk financial decisions. They form the heart of financial applications, and can cause severe economic harm if incorrect. Controllability and observability of these calculation engines are low, so robust and sophisticated test methods are needed to ensure the results are valid. However, the industry norm is to use pure human-based, requirements-driven test design, usually with very little automation. The Federal Home Loan Mortgage Corporation (FHLMC), commonly known as Freddie Mac, concerned that these test design techniques may lead to ineffective and inefficient testing, partnered with a university to use high quality, sophisticated test design on several ongoing projects. The goal was to determine if such test design can be cost-effective on this type of critical software. In this study, input space partitioning, along with automation, were applied with the help of several special-purpose tools to validate the effectiveness of input space partitioning. Results showed that these techniques were far more effective (finding more software faults) and more efficient (requiring fewer tests and less labor), and the managers reported that the testing cycle was reduced from five human days to 0.5. This study convinced upper management to begin infusing this approach into other software development projects.     

Struktur und eigenschaften von ABS-polymeren. IX. Quantitative untersuchungen zur morphologie von ABS-polymerisaten

The technological properties of ABS polymers largely depend on the structure of the elastomer phase as well as on the elastomer/thermoplast interface. The morphological structure of such polymers can be determined from electron micrographs of ultramicrotome sections – after selective contrasting of the polybutadiene phase – or of replicas of fracture surfaces after selective chemical degradation. The various ABS polymers are classified by their manufacturing processes and their morphologies and characterized by electron micrographs. The degree and place of grafting are of particular importance. The quantitative determination of the surface- and internal grafting is achieved by combining the determination of the degree of grafting (extraction), the evaluation of the results obtained on particle counting, and a morphometric process. It is demonstrated that the morphometric process can in general be applied for the quantitative determination of the contrastable component in two-phase polymers.     

Lifetime assessment of epoxies by the kinetics of thermal degradation

The kinetics of thermal degradation of 4,4′‐diaminodiphenylsulfone (DDS)‐cured glycidylethers (DGBA) and glycidylamines (TGDDM) have been studied by isothermal annealing. Thermal degradation proceeds via first‐order kinetics with activation energies of 138 (DGBA/DDS) and 95 kJ/mol (TGDDM/DDS). From these data the temperature‐dependent lifetime can be calculated. Based on the heat distortion temperature and 20 years' service as criteria, the upper service temperature is found to be around 115–120°C. In spite of the different activation energies and bond stabilities, only marginal differences in the upper allowed service temperatures between these resins were found. Only slight improvements can be expected by optimizing the cure conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1881–1886, 2004     

Organolithium route to poly(arylsilane)s

Various poly(arylsilane)s The poly(carbosilane)s prepared in this way are of higher molecular weight than when prepared by the Wurtz-type condensation route previously reported. TG shows 40–50% overll weight loss attained at 500–600°C.     

β-Carotene transport in human lipoproteins. Comparisons with a-tocopherol

The purpose of this study was to investigate the temporal relationships of the transport of β-carotene in human lipoproteins. We administered 60 mg β-carotene with breakfast to nine fasting subjects, then blood samples were collected at intervals of up to 75 h, lipoproteins were isolated, and β-carotene was quantitated. β-Carotene concentrations in chylomicrons and very low density lipoproteins (VLDL) peaked at 6 and 9 h, respectively. Nonetheless, at all time points the majority of plasma β-carotene was contained in low density lipoproteins (LDL), while high density lipoproteins (HDL) carried a smaller portion (at 24 h, 73±8% in LDL as compared with 23±5% in HDL). In three subjects, transport of β-carotene was compred with the results of earlier studies on the transport of stereoisomers of α-tocopherol. Unlike plasmaRRR-α-tocopherol concentrations, which are maintained by the preferential incorporation ofRRR-α-tocopherol into VLDL by the liver, β-carotene increased and decreased in VLDL similarly toSRR-α-tocopherol, a stereoisomer whose concentrations are not maintained in plasma. In conclusion, β-carotene is primarily transported in the plasma in LDL, but its incorporation by the liver into lipoproteins does not appear to be enhanced.