The effects of Cl-induced alloying in Pt–Sn/Al2O3 catalysts on butane/H2 reactions

The effects of oxidation/reduction regeneration treatments, with and without 1,2-dichloropropane present as a chlorinating agent, on the structure of Pt(3%)–Sn(4.5%)/Al₂O₃ catalysts have been correlated with selectivities for butane/H₂ reactions. Particles of Pt⁰ fin Cl-free catalysts were partly covered by Sn⁰, but retained exposed ensembles of Pt atoms which were active for isomerisation, hydrogenolysis and dehydrogenation reactions, the latter becoming dominant at high reaction temperatures. Coking reduced Pt ensemble size and, hence, also favoured high selectivities for dehydrogenation as hydrogenolysis and isomerisation sites became poisoned. In contrast, the addition of 1,2-dichloropropane in an oxychlorination step before reduction promoted 1:1 Pt⁰–Sn⁰ alloy formation after reduction, the proportion of the total Pt in alloy being enhanced by increasing 1,2-dichloropropane concentration and oxychlorination temperature. The alloy surfaces were inactive for isomerisation and hydrogenolysis reactions, giving dehydrogenation as the sole catalytic reaction.     

Self‐regulation during e‐learning: using behavioural evidence from navigation log files

The current paper examined the relationship between perceived characteristics of the learning environment in an e‐module in relation to test performance among a group of e‐learners. Using structural equation modelling, the relationship between these variables is further explored in terms of the proposed double mediation as outlined by Ning and Downing. These authors initially proposed that motivation and self‐regulation strategies are mediators between the perception of the learning environment and performance. In our replication and extension study, we substituted self‐reported self‐regulation with behavioural indicators of self‐regulation using navigation log files and focused on test‐taking rather than general motivation. We proposed that navigational patterns captured using log files can also help deduce self‐regulation in e‐modules and provide information in the absence of self‐reports. Path analyses provide partial support for our navigational hypotheses and the model. Implications of our results for the use of e‐module data and conclusions based on navigation are discussed.     

A New Level-Set Model for the Representation of Non-Smooth Geometries

In Starinshak et al. (J Comput Phys 262(1):1–16, 2014), we proposed a new level-set model for representing multimaterial flows in multiple space dimensions. Rather than associating each level-set function with the boundary of a material, the new model associates each level-set function with a pair of materials and the interface that separates them. In this paper, we extend the model to represent geometries with non-smooth boundaries. The model uses multiple level-set functions to describe the shape boundary, typically with one level-set function per smooth boundary segment. Sign information is collected from all level-set functions and a voting algorithm is used to determine the interior/exterior of the geometric shape. The model is well suited for representing boundaries with singularities; it offers significant improvement over standard level-set approaches, both in shape preservation and area conservation; and it eliminates the need for costly redistancing of the level-set function. Numerical examples illustrate the superior performance of the proposed model.     

Interval type-2 fuzzy weighted support vector machine learning for energy efficient biped walking

An interval type-2 fuzzy weighted support vector machine (IT2FW-SVM) is proposed to address the problem of high energy consumption for biped walking robots. Different from the traditional machine learning method of ‘copy learning’, the proposed IT2FW-SVM obtains lower energy cost and larger zero moment point (ZMP) stability margin using a novel strategy of ‘selective learning’, which is similar to human selections based on experience. To handle the uncertainty of the experience, the learning weights in the IT2FW-SVM are deduced using an interval type-2 fuzzy logic system (IT2FLS), which is an extension of the previous weighted SVM. Simulation studies show that the existing biped walking which generates the original walking samples is improved remarkably in terms of both energy efficiency and biped dynamic balance using the proposed IT2FW-SVM.     

Bulk and suspension polymerization of styrene in the presence of n-pentane. An evaluation of monofunctional and bifunctional initiation

The plasticizing effect of n-pentane on the rate of bulk free radical polymerization of styrene and molecular weight distribution development has been modeled on the basis of the free volume theory for both monofunctional and bifunctional initiation. A strong decrease in the reaction rate in the late stages of the polymerization, due to the displacement of the onset of the gel effect, has been observed for both types of initiation. This decrease in the polymerization rate limited the terminal conversion to values well below 100% for mono-functional initiation. However, in bifunctionally initiated polymerization, terminal conversions close to 100% were obtained in spite of the decrease in reaction rate. Contrary to what was expected, the molecular weight distribution obtained at terminal conversion was almost completely insensitive to these changes in polymerization rate. This phenomenon is explained in terms of limited transfer to monomer reactions when n-pentane is present in the system. In suspension polymerization, the limiting conversion and plasticizing effects of n-pentane in monofunctionally initiated systems, caused enhanced coalescence leading to suspension set-up. In bifunctionally initiated systems this enhanced coalescence was completely overcome by the short duration of the particle growth stage, owing to high polymerization rates, and stable suspensions were achieved. For these systems the particle size distributions obtained were similar to that of suspension polystyrene without n-pentane. © 1993 John Wiley & Sons, Inc.     

Monomeric N-hydroxyethylated amides

Oxyethylated amides that are good wetting agents have been prepared as mixtures by allowing amides to react with ethylene oxide under base catalysis. Individual components of such mixtures can be synthesized by allowing 1-alkylaziridines to react with p-toluenesulfonic acid in monomethylethers of di-, tri- and tetraethylene glycol used as solvents. The aminoethers are then acylated, and the methylether group is removed with trimethylsilyliodide from the resulting amide ethers. The sequence should allow the synthesis of specific wetting agents of quite varied structure (alkyl, aryl groups) with an option for isotopic labeling for more detailed analysis of the wetting properties.     

Catalysis of gasification of coal-derived cokes and chars

Calcium is the most important in-situ catalyst for gasification of US coal chars in O₂, CO₂ and H₂O. It is a poor catalyst for gasification of chars by H₂. Potassium and sodium added to low-rank coals by ion exchange and high-rank coals by impregnation are excellent catalysts for char gasification in O₂, CO₂ and H₂O. Carbon monoxide inhibits catalysis of the CH₂O reaction by calcium, potassium and sodium; H₂ inhibits catalysis by calcium. Thus injection of synthesis gas into the gasifier will inhibit the CH₂O reaction. Iron is not an important catalyst for the gasification of chars in O₂, CO₂ and H₂O, because it is invariably in the oxidized state. Carbon monoxide disproportionates to deposit carbon from a dry synthesis gas mixture (3 vol H₂ + 1 vol CO) over potassium-, sodium- and iron-loaded lignite char and a raw bituminous coal char, high in pyrite, at 1123 K and 0.1 MPa pressure. The carbon is highly reactive, with the injection of 2.7 kPa H₂O to the synthesis gas resulting in net carbon gasification. The effect of traces of sulphur in the gas stream on catalysis of gasification or carbon-forming reactions by calcium, potassium, or sodium is not well understood at present. Traces of sulphur do, however, inhibit catalysis by iron.     

Quantitative31P nuclear magnetic resonance analysis of the phospholipids of erythrocyte membranes using detergent

³¹P Nuclear magnetic resonance (NMR) spectra of human erythrocyte lysates dissolved in sodium cholate were acquired. The narrow resonances of phospholipids were mostly well resolved, allowing identification and accurate quantitative analysis of phospholipid classes of the erythrocyte membranes. The ether-linked phosphatidylethanolamine components of the erythrocyte membranes were identified, based on the removal of plasmalogens by acidolysis and of diacyl phospholipid species by degradation using phospholipase A₁. It was also shown that the introduction of double bonds on the acyl chains of phosphatidylcholine shifted the³¹P NMR resonances to lower frequencies. Quantitative analyses of phospholipids from the spectra were based on their apparent molar concentrations. The recoveries of phospholipids from erythrocytes were significantly higher than those using conventional extraction procedures.     

Structure/property relationships in flexible alkoxysilane automotive coatings

Flexible automotive coatings are susceptible to scratch and mar damage, especially during finishing and assembly operations. One-component (1K) flexible clearcoats exhibit very good scratch and mar resistance, but unfortunately suffer from poor durability and environmental etch resistance. Two-component clearcoats offer improvements in both etch and durability, but at the expense of scratch and mar. In this paper, the concept and properties of 1K flexibilized silane clearcoats for use on automotive plastics will be introduced and their structure/property relationships examined as they apply to scratch and mar. The role of coating crosslink density, toughness, glass transition temperature (T_g), and surface profile on the scratch damage of coated plastic substrates will be described. In addition, a new scratch methodology, termed Scratcho, is utilized to determine relative scratch performance and is compared to conventional scratch resistance testing. Results to date indicate that hardness, as affected by the glass transition temperature, and crosslink density, as it contributes to higher essential work values, both affect resultant scratch propensity of the flexible coatings. The relative ranking of different coating systems employing alternate crosslinkers (e.g., isocyanate and melamine) is also presented and compared to the newly developed silane crosslinked coatings. Presented at the 28th International Waterborne, High-Soids, and Powder Coatings Symposium, Feb. 21–23, 2001, in New Orleans. LA. 377 Fairall St., Ajax, Ont., L1S 1R7, Canada. 401 Southfield Rd., P.O. Box 6231, Dearborn, MI 48121-6231.     

Diets,population structure,and seasonal activity patterns of mudpuppies (Necturus maculosus) in an urban,Great Lakes coastal habitat

Freshwater species native to the Laurentian Great Lakes region face numerous environmental stressors, and the conservation status and ecological relationships of many remain poorly understood. One such species, the mudpuppy (Necturus maculosus), is declining, but better information on their natural history and development of more effective population monitoring techniques is needed. We assessed seasonal variation in capture success, biases in capture techniques, and feeding ecology of mudpuppies in Wolf Lake, a highly perturbed and urban former estuarine wetland complex to Lake Michigan. Trapping periods of ≥ 3 consecutive nights occurred from January to May 2015, and October 2015 to March 2016. Overall trapping success differed among trapping periods (p = 0.01) and declined precipitously at water temperatures above 14.1 °C (p < 0.001). Mudpuppies in traps (mean 26.9 ± 0.5 cm) were larger than those caught with hand nets (mean 14.7 ± 0.8 cm, p < 0.0001), suggesting that multiple methods may be needed to accurately assess demographics. Stomach contents obtained through gastric lavage included mollusks, leeches, insects, isopods, amphipods, crayfish, fish, a frog, and a juvenile conspecific. Invasive species, including rusty crayfish (Orconectes rusticus), round gobies (Neogobius melanostomus), and zebra/quagga mussels (Dreissena spp.) were present in guts, suggesting mudpuppy foraging has changed along with aquatic communities in the region. Prey community analyses revealed differences in overall diet among size classes of mudpuppies (p = 0.001), but relatively weak similarity within size classes. Results suggest that mudpuppies in lake ecosystems occupy a broad niche that changes as they grow.