Performance of Methanol Oxidation Catalysts with Varying Pt:Ru Ratio as a Function of Temperature

This paper describes the effects of varying the Pt to Ru ratio in carbon-supported catalysts for methanol oxidation as a function of temperature. Previously these effects were studied in isolation, but now it is shown that the composition of a given catalyst as a function of temperature is extremely important for its activity towards methanol oxidation. Platinum rich 3:2 atomic ratio catalysts perform better than a 1:1 catalyst at 25 °C, where only Pt is believed to be active towards methanol dehydrogenation, since this process is a highly thermally activated process on Ru sites. This result is reversed at 65 °C, where the 1:1 catalyst displays much higher currents across the entire range of polarization. This may result from methanol dehydrogenation occurring on both Ru and Pt sites at higher temperatures. At an intermediate temperature, 45 °C, the 3:2 catalyst is seen to perform better at lower current values, while the 1:1 catalyst is superior at higher current densities, with the crossover occurring at 62 A g^–1. As a consequence, when designing fuel cell catalysts, the composition of the catalyst employed should be tailored with respect to the exact operating conditions, in order to promote optimum fuel cell performance.     

Hydrogenation of methyl sorbate and soybean esters with polymer-bound metal catalysts

New polymer-bound hydrogenation catalysts were made by complexing PdCl₂, RhCl₃·3H₂O, or NiCl₂ with anthranilic acid anchored to chloromethylated polystyrene. The Pd(II) and Ni(II) polymers were reduced to the corresponding Pd(O) and Ni(O) catalysts with NaBH₄. In the hydrogenation of methyl sorbate, these polymer catalysts were highly selective for the formation of methyl 2-hexenoate. The diene to monoene selectivity decreased in the order: Pd(II), Pd(O), Rh(I), Ni(II), Ni(O). Kinetic studies support 1,2-reduction of the Δ4 double bond of sorbate as the main path of hydrogenation. In the hydrogenation of soybean esters, the Pd(II) polymer catalysts proved superior because they were more active than the Ni(II) polymers and produced lesstrans unsaturation than the Rh(I) polymers. Hydrogenation with Pd(II) polymers at 50~100 C and 50 to 100 psi H₂ decreased the linolenate content below 3% and increasedtrans unsaturation to 10~26%. The linolenate to linoleate selectivity ranged from 1.6 to 3.2. Reaction parameters were analyzed statistically to optimize hydrogenation. Recycling through 2 or 3 hydrogenations of soybean esters was demonstrated with the Pd(II) polymers. In comparison with commercial Pd-on-alumina, the Pd(II) polymers were less active and as selective in the hydrogenation of soybean esters but more selective in the hydrogenation of methyl sorbate. Presented at ISF-AOCS Meeting, New York, April 1980.     

Asymmetric reverse osmosis and ultrafiltration membranes prepared from sulfonated polysulfone

The concept of solubility parameter, developed by Hansen, has been applied to the determination of solubility diagram of polysulfone and sulfonated polysulfone. Data showing the effect of various parameters such as thermodynamic quality of the solvent, casting solution composition and viscosity, solvent evaporation period and precipitation bath composition, on membrane structure and performance have been presented. By adjusting these parameters a wide variety of sulfonated polysulfone membranes useful for both ultrafiltration and reverse osmosis applications could be obtained.     

Inactivation of Staphylococcus hyicus lipase by hexadecylsulfonyl fluoride: evidence for an active site serine

The Staphylococcus hyicus lipase is an acyl hydrolase with broadsubstrate specificity including neutral glycerides and phospholipids.To obtain further insight into the mechanism of action of thisenzyme, we tested several sulfonyl fluorides as active site-directedinhibitors. The enzyme is resistant to the well-known serineprotease/esterase inhibitor phenylmethanesulfonyl fluoride (PMSF),but is rapidly inactivated by hexadecylsulfonyl fluoride. Thekinetics of inactivation were studied in Triton X-100 micelles.Inactivation is fast and the rate of inactivation is constantover the pH range where this lipase is active. Metal ions likeCa²⁺ and Sr²⁺ do not appreciably influence the rate of inactivation,although the enzymatic activity is significantly increased,suggesting a structural role for these ions. The S.hyicus lipasecontains a consensus sequence G-H/Y-S-X-G. Substitution by site-directedmutagenesis of this serine (Ser369) by a cysteine resulted ina mutant with only 0.2% residual activity. The activity of thismutant could not be inhibited with water-soluble sulfhydrylreagents either in the presence or absence of Triton X-100 micelles.In the presence of Triton X-100 micelles, inactivation of themutant occurred with 4-nitrophenylhexadecyl disulfide (t_1/2= 125 min) while the wild-type enzyme does not react at all.We conclude that Ser369 is the active site residue and thatin water this residue is inaccessible. Only after interfacialactivation Ser369 (or Cys369) becomes exposed and reacts withirreversible inhibitors.     

纳米粒子/环氧树脂复合材料的固化动力学研究

在纳米Al2O3、Si3N4、SiC填充环氧树脂复合材料体系中,纳米粒子表面活性及粒子与环氧树脂之间的相互作用影响着环氧树脂的固化过程.本文利用傅立叶红外光谱表征了纳米粒子与环氧树脂之间的化学作用情况,并利用差视扫描量热仪研究了不同纳米粒子/环氧树脂复合材料的固化动力学.结果表明,具有相对最强表面活性的纳米Al2O3粒子与基体之间的相互作用最强,同时该粒子对环氧树脂固化过程的促进作用最显著.     

Subcritical crack growth and threshold in borosilicate glass

The crack-growth behaviour of borosilicate glass was investigated by use of lifetime measurements on Knoop-damaged specimens. The threshold behaviour in particular was observed, and the influence of residual wedging stresses and preloading below the threshold value were studied in detail. A threshold ofK _lth = 0.38 MPam^1/2 was found. The residual stress intensity factor caused by the Knoop indentations was found to beK _lres,0 0.1 MPam^1/2. In a static test performed below the threshold, the threshold value was increased by K _lth 0.15MPam^1/2.     

The influence of training level on manual flight in connection to performance,scan pattern,and task load

This work focuses on the analysis of pilots’ performance during manual flight operations in different stages of training and their influence on gaze strategy. The secure and safe operation of air traffic is highly dependent on the individual performances of the pilots. Before becoming a pilot, he/she has to acquire a broad set of skills by training to pass all the necessary qualification and licensing standards. A basic skill for every pilot is manual control operations, which is a closed-loop control process with several cross-coupled variables. Even with increased automation in the cockpit, the manual control operations are essential for every pilot as a last resort in the event of automation failure. A key element in the analysis of manual flight operations is the development over time in relation to performance and visual perception. An experiment with 28 participants (including 11 certified pilots) was conducted in a Boeing 737 simulator. For defined flight phases, the dynamic time warping method was applied to evaluate the performance for selected criteria, and eye-tracking methodology was utilized to analyze the gaze-pattern development. The manipulation of workload and individual experience influences the performance and the gaze pattern at the same time. Findings suggest that the increase of workload has an increased influence on pilots depending on the flight phase. Gaze patterns from experienced pilots provide insights into the training requirements of both novices and experts. The connection between workload, performance and gaze pattern is complex and needs to be analyzed under as many differing conditions. The results imply the necessity to evaluate manual flight operations with respect to more flight phases and a detailed selection of performance indications.

     

XPS investigations of electrochemically formed passive layers on Fe/Cr-alloys in 0.5 M H2SO4

Passive layers on Fe20Cr and Fe15Cr were prepared by anodic oxidation in 0.5 M H₂SO₄ and were investigated by X-ray photoelectron spectroscopy. The preparation of the sputter-cleaned samples and their transfer to the ultrahigh vacuum was performed under protection of purified argon without any contact to the laboratory atmosphere. The prepassive layer consists of a homogeneous film with Cr(III)hydroxide and Cr(III)-sulphate with a low content of Fe(II). In the passive potential range a bilayer structure with enrichment of Cr(III)-oxides with an outer hydroxide and an inner oxide part is formed. Iron exists only in a bivalent oxidation state. In the transpassive potential range a pronounced change of the layer composition was observed: The outer part of the transpassive layer is formed predominantly by Fe(III) species whereas the inner part still contains a strong enrichment of Cr₂O₃.     

Development of a new indicator of pollutant loads and its application to the Chesapeake Bay watershed

Pollutant load reductions are often required to restore aquatic ecosystems experiencing eutrophication. Loads can be estimated using watershed models or data from monitoring stations, however data availability can limit the timeliness or comprehensiveness of the load estimates. We developed an approach to address this challenge that used watershed model results to estimate the proportion of annual nonpoint source nitrogen (N), phosphorus (P) and sediment (Sed) loads derived from unmonitored catchments. This proportion was multiplied by the nonpoint portion of United States Geological Survey (USGS) estimated annual river loads to account for annual variation in hydrologic conditions. Total loads were calculated as the sum of measured river loads, reported point sources from unmonitored areas and the estimated nonpoint source loads from unmonitored catchments. We applied this approach to the Chesapeake Bay because of its socio‐economic and ecological importance. Median watershed loads for N, P and Sed were 140, 6.4 and 3030 Mg year^?1, respectively (1990–2004). Nonpoint source loads from the monitored areas constituted the greatest source of N, P and Sed (55, 47 and 74% respectively) to the Bay. The high N, P and Sed yield rates (7.3, 0.38 and 99 kg ha^?1 year^?1, respectively) from nonpoint loads originating from unmonitored areas near the Bay resulted in 25, 32 and 26% (N, P and Sed, respectively) of the Bay's total loads (excluding direct atmospheric deposition, shoreline erosion and oceanic inputs). Disproportionately high loads of P and Seds were associated with years that experienced elevated discharge whereas N loads were directly related to discharge. Error estimates indicated that our methods were most reliable for N (±6%) but reasonable for P (±22%) and provide an effective technique for the timely estimation of pollutant loads from watersheds with unmonitored catchments. Management strategies that decrease N deposition and reduce runoff to control P and Sed transport will effectively reduce pollutant loads. Published in 2010 by John Wiley & Sons, Ltd.     

Zur personellen Verankerung der IT-Funktion im Vorstand börsennotierter Unternehmen: Ergebnisse einer inhaltsanalytischen Betrachtung

On the Rate of Board Members with IT Responsibilities in Firms Listed on the Stock Exchange: Results of a Content Analysis: This article reports on a content analysis that investigates the rate of board members with IT responsibilities in firms listed on the stock exchange in the German speaking countries. Furthermore, the study ascertains the correlation of six factors – which become evident through content analysis – with the rate of board members with IT responsibilities. A total of 679 annual reports of German, Austrian, and Swiss corporations have been analyzed. The results show that in Germany and Switzerland 26 percent of the firms investigated have a board member with IT responsibilities, in Austria the rate is 23 percent. Additionally, the results show that turnover and number of employees are highly positively correlated with the rate of board members with IT responsibilities. Furthermore, the data show a correlation between industry and the rate of board members with IT responsibilities.