The catalyzed hydrosilation reaction: substituent effects

Ab initio electronic structure calculations using MP2 wavefunctions have been used to investigate a reaction path for the hydrosilation reaction catalyzed by divalent titanium [modeled by TiH₂, TiCl₂, and Ti(C₅H₅)₂]. Optimized structures and energies are presented. All model reactions predict a barrierless reaction path compared to a barrier of 78 kcal/mol for the uncatalyzed reaction. Received: 11 August 1998 / Accepted: 3 September 1998 / Published online: 23 February 1999     

Muonium formation in xenon and argon up to 60 atmospheres

Results of muon polarization studies in xenon and argon up to 60 atm are reported. In argon for pressures up to 10 atm, the muon polarization is best explained by an epithermalcharge exchange model. Above this pressure, the decrease inP _D and increase inP _L are ascribed to charge neutralization and spin exchange reactions, respectively, in the radiolysis track. Measurements with Xe/He mixtures with a xenon pressure of 1 atm indicate that the lost polarization in the pure xenon at this pressure is due to inefficient moderation of the muon. As the pressure in pure xenon is increased above 10 atm, we find thatP _L remains roughly constant andP _D begins to increase. The lost fraction may be due to the formation of a XeMu Van der Waals type complex, whileP _D is ascribed to XeMu⁺ formation. This suggests that spur processes appear to be less important in xenon than in argon.     

Millimeter wave backscatter measurements in support of collision avoidance applications

Millimeter-wave short range radar systems have unique advantages in surface navigation applications, such as military vehicle mobility, aircraft landing assistance, and automotive collision avoidance. In collision avoidance applications, characterization of clutter due to terrain and roadside objects is necessary in order to maximize the signal-to-clutter ratio (SCR) and to minimize false alarms. The results of two types of radar cross section (RCS) measurements at 95 GHz are reported in this paper. The first set of measurements presents data on the normalized RCS (NRCS) as well as clutter distributions of various terrain types at low grazing angles of 5° and 7.5°. The second set of measurements presents RCS data and statistics on various types of roadside objects, such as metallic and wooden sign posts. These results are expected to be useful for designers of short-range millimeter-wave collision avoidance radar systems. Brett Snuttjer is presently an Air Force Lieutenant at Rome Laboratory, Rome, NY 13441     

Remarks on product

Well known results related to the compactness of Hankel operators of one complex variable are extended to little Hankel operators of two complex variables. Critical to these considerations is the result of Ferguson and Lacey (2002) characterizing the boundedness of the little Hankel operators in terms of the product BMO of S.-Y. Chang and R. Fefferman (1985), (1980).

     

Thermal boundary condition effects on heat transfer in turbulent rough-wall boundary layers

Measurements and predictions are presented which investigate the effects of thermal boundary condition on heat transfer in the turbulent rough-wall boundary layer. Stanton number measurements are reported for the turbulent flow of air over rough plates with a variety of thermal boundary conditions on two separate rough surfaces. The cases considered are constant wall temperature, constant wall heat flux, step wall temperature, and piecewise linear wall temperature distributions. These measurements and data from other sources are compared with predictions using finite difference solutions of the discrete element roughness model and with superposition solutions. The predictions and the measurements are in good to excellent agreement.In dieser Arbeit werden Messungen und Berechnungen gezeigt, die den Einfluß der thermischen Randbedingungen auf die Wärmeübertragung in turbulenten Grenzschichten an rauhen Wänden untersuchen. Es werden Messungen der Stanton Zahl für turbulente Luftströmung über rauhe Platten an zwei separaten Oberflächen unter einer Reihe von thermischen Randbedingungen dargestellt. Die betrachteten Fälle sind konstante Wandtemperatur, konstanter Wärmestrom durch die Wand, abgestufte Wandtemperatur und stückweise konstante Wandtemperatur. Diese Messungen, sowie Daten anderer Untersuchungen, werden mit Berechnungen durch Finite-Differenzen Lösungen des Diskrete-Elemente-Rauhheits-Modells und Superpositionslösungen verglichen. Berechnungen und Messungen liegen in guter bis ausgezeichneter Übereinstimmung.     

Electrochemical sensors and biosensors based on redox polymer/carbon nanotube modified electrodes: A review

The aim of this review is to present the contributions to the development of electrochemical sensors and biosensors based on polyphenazine or polytriphenylmethane redox polymers together with carbon nanotubes (CNT) during recent years. Phenazine polymers have been widely used in analytical applications due to their inherent charge transport properties and electrocatalytic effects. At the same time, since the first report on a CNT-based sensor, their application in the electroanalytical chemistry field has demonstrated that the unique structure and properties of CNT are ideal for the design of electrochemical (bio)sensors. We describe here that the specific combination of phenazine/triphenylmethane polymers with CNT leads to an improved performance of the resulting sensing devices, because of their complementary electrical, electrochemical and mechanical properties, and also due to synergistic effects. The preparation of polymer/CNT modified electrodes will be presented together with their electrochemical and surface characterization, with emphasis on the contribution of each component on the overall properties of the modified electrodes. Their importance in analytical chemistry is demonstrated by the numerous applications based on polymer/CNT-driven electrocatalytic effects, and their analytical performance as (bio) sensors is discussed.     

Ultra-high surface area and mesoporous N-doped carbon derived from sheep bones with high electrocatalytic performance toward the oxygen reduction reaction

A nitrogen (N)-doped mesoporous carbon material exhibiting ultra-high surface area was successfully synthesized from sheep bones via a facile and low-cost method. The obtained carbon material had an ultra-high specific surface area of 1961 m² g^?1 and provided rich active sites for the oxygen reduction reaction (ORR), which in turn resulted in high electrocatalytic activity. It was found that the pore size distribution for the newly prepared carbonaceous material fell in the range of 1–4 nm. Benefiting from its high surface area and the presence of pyridine-N and quaternary-N species, the as-prepared carbon material exhibited excellent ORR activity in an oxygen-saturated 0.1 M KOH solution, compared to commercial Pt/C (10 wt%). Due to its high ORR catalytic activity, stability and low-cost, using sheep bone as C and N precursors to produce N-doped carbon provides an encouraging step toward the goal of replacing commercial Pt/C as fuel cell cathode electrocatalyst.     

Elements of Design‐Based Science Activities That Affect Students' Motivation

The primary purpose of this study was to examine the ways in which a 12‐week afterschool science and engineering program affected middle school students' motivation to engage in science and engineering activities. We used current motivation research and theory as a conceptual framework to assess 14 students' motivation through questionnaires, structured interviews, and observations. Students reported that during the activities they perceived that they were empowered to make choices in how to complete things, the activities were useful to them, they could succeed in the activities, they enjoyed and were interested in the hands‐on activities and some presentations, they felt cared for by the facilitators and received help when they were stuck or confused, and they put forth effort. Based on our examination of data across our three data sources, we identified motivating opportunities that were provided to students during the activities. These motivating opportunities can serve as examples to help both formal and informal science educators better connect motivation theory to practice so that they can create motivating opportunities for students. Furthermore, this study provides a methodological example of how students' motivation can be examined during the context of authentic science and engineering instruction.