Microstructure and Mechanical Properties of the Ductile Al–Ti–Mo–Nb–V Refractory High Entropy Alloys

Metallurgical and Materials Transactions A - A number of non-equimolar refractory high entropy alloys (RF HEAs) from the Al–Ti–Mo–Nb–V system are synthesized, with the...     

Synthetic applications of nonmetal catalysts for homogeneous oxidations

Nonmetal oxidation catalysts have gained much attention in recent years. The reason for this surge in activity is 2-fold: On one hand, a number of such catalysts has become readily accessible; on the other hand, such catalysts are quite resistant toward self-oxidation and compatible under aerobic and aqueous reaction conditions. In this review, we have focused on five nonmetal catalytic systems which have attained prominence in the oxidation field in view of their efficacy and their potential for future development; stoichiometric cases have been mentioned to provide overview and scope. Such nonmetal oxidation catalysts include the alpha-halo carbonyl compounds 1, ketones 2, imines 3, iminium salts 4, and nitroxyl radicals 5. In combination with a suitable oxygen source (H2O2, KHSO5, NaOCl), these catalysts serve as precursors to the corresponding oxidants, namely, the perhydrates I, dioxiranes II, oxaziridines III, oxaziridinium ions IV, and finally oxoammonium ions V. A few of the salient features about these nonmetal, catalytic systems shall be reiterated in this summary. The first class entails the alpha-halo ketones, which catalyze the oxidation of a variety of organic substrates [figure: see text] by hydrogen peroxide as the oxygen source. The perhydrates I, formed in situ by the addition of hydrogen peroxide to the alpha-halo ketones, are quite strong electrophilic oxidants and expectedly transfer an oxygen atom to diverse nucleophilic acceptors. Thus, alpha-halo ketones have been successfully employed for catalytic epoxidation, heteroatom (S, N) oxidation, and arene oxidation. Although high diastereoselectivities have been achieved by these nonmetal catalysts, no enantioselective epoxidation and sulfoxidation have so far been reported. Consequently, it is anticipated that catalytic oxidations by perhydrates hold promise for further development, especially, and should ways be found to transfer the oxygen atom enantioselectively. The second class, namely, the dioxiranes, has been extensively used during the last two decades as a convenient oxidant in organic synthesis. These powerful and versatile oxidizing agents are readily available from the appropriate ketones by their treatment [figure: see text] with potassium monoperoxysulfate. The oxidations may be performed either under stoichiometric or catalytic conditions; the latter mode of operation is featured in this review. In this case, a variety of structurally diverse ketones have been shown to catalyze the dioxirane-mediated epoxidation of alkenes by monoperoxysulfate as the oxygen source. By employing chiral ketones, highly enantioselective (up to 99% ee) epoxidations have been developed, of which the sugar-based ketones are so far the most effective. Reports on catalytic oxidations by dioxiranes other than epoxidations are scarce; nevertheless, fructose-derived ketones have been successfully employed as catalysts for the enantioselective CH oxidation in vic diols to afford the corresponding optically active alpha-hydroxy ketones. To date, no catalytic asymmetric sulfoxidations by dioxiranes appear to have been documented in the literature, an area of catalytic dioxirane chemistry that merits attention. A third class is the imines; their reaction with hydrogen peroxide or monoperoxysulfate affords oxaziridines. These relatively weak electrophilic oxidants only manage to oxidize electron-rich substrates such as enolates, silyl enol ethers, sulfides, selenides, and amines; however, the epoxidation of alkenes has been achieved with activated oxaziridines produced from perfluorinated imines. Most of the oxidations by in-situ-generated oxaziridines have been performed stoichiometrically, with the exception of sulfoxidations. When chiral imines are used as catalysts, optically active sulfoxides are obtained in good ee values, a catalytic asymmetric oxidation by oxaziridines that merits further exploration. The fourth class is made up by the iminium ions, which with monoperoxysulfate lead to the corresponding oxaziridinium ions, structurally similar to the above oxaziridine oxidants except they possess a much more strongly electrophilic oxygen atom due to the positively charged ammonium functionality. Thus, oxaziridinium ions effectively execute besides sulfoxidation and amine oxidation the epoxidation of alkenes under catalytic conditions. As expected, chiral iminium salts catalyze asymmetric epoxidations; however, only moderate enantioselectivities have been obtained so far. Although asymmetric sulfoxidation has been achieved by using stoichiometric amounts of isolated optically active oxaziridinium salts, iminium-ion-catalyzed asymmetric sulf-oxidations have not been reported to date, which offers attractive opportunities for further work. The fifth and final class of nonmetal catalysts concerns the stable nitroxyl-radical derivatives such as TEMPO, which react with the common oxidizing agents (sodium hypochlorite, monoperoxysulfate, peracids) to generate oxoammonium ions. The latter are strong oxidants that chemoselectively and efficiently perform the CH oxidation in alcohols to produce carbonyl compounds rather than engage in the transfer of their oxygen atom to the substrate. Consequently, oxoammonium ions behave quite distinctly compared to the previous four classes of oxidants in that their catalytic activity entails formally a dehydrogenation, one of the few effective nonmetal-based catalytic transformations of alcohols to carbonyl products. Since less than 1 mol% of nitroxyl radical is required to catalyze the alcohol oxidation by the inexpensive sodium hypochlorite as primary oxidant under mild reaction conditions, this catalytic process holds much promise for future practical applications.     

Synthesis and self-association in aqueous media of poly(ethylene oxide)/poly(ethyl glycidyl carbamate) amphiphilic block copolymers

New temperature sensitive AB, ABA, and BAB amphiphilic block copolymers consisting of hydrophilic poly(ethylene oxide) and hydrophobic poly(ethyl glycidyl carbamate) blocks were synthesized by anionic polymerization followed by chemical modification reactions. The self-association of the block copolymers in aqueous media was studied by UV-vis spectroscopy and dynamic and static light scattering. The obtained block copolymers spontaneously form micelles in aqueous media. The critical micellization concentration varied from 0.5 to 4 g/L depending on the copolymer architecture and composition. The influence of the temperature upon the self-association of the block copolymers was investigated. The increase of temperature did not affect the value of the critical micellization concentration, but led to the formation of better defined micelles with narrow size distribution.     

Interactions in compatible polymer systems

Summary Dynamic mechanical measurements on polystyrene — poly(vinylmethylether) blends are demonstrating that the relaxation processes in the blends are mainly connected with the motions of the poly(vinylmethylether) chain.Concerning the effect of mixing on topological properties of the blends, an increase of the polydispersity of the relaxation processes is detected in blends with high molecular weight polystyrene while low molecular weight polystyrene exerts an effect of dilution upon the relaxation of the high molecular poly(vinylmethylether) chains.From these measurements as well as from thermoanalytical data it results that the energetic interaction is more pronounced in the blends with oligomeric than with high molecular weight polystyrene. The glass transition temperature shows a larger deviation from additivity for blends with high molecular polystyrene than for those with oligomeric polystyrene.Herrn Prof. Dr. M. Kryszewski zum 60. Geburtstag herzlichst gewidmet     

Upgrading a Granular Computing Based Data Mining Framework to a Relational Case

One of the popular methods to develop an algorithm for mining data stored in a relational structure is to upgrade an existing attribute‐value algorithm to a relational case. Current approaches to this problem have some shortcomings such as (1) a dependence on the upgrading process of the algorithm to be extended, (2) complicated redefinitions of crucial notions (e.g., pattern generality, pattern refinement), and (3) a tolerant limitation of the search space for pattern discovery. In this paper, we propose and evaluate a general methodology for upgrading a data mining framework to a relational case. This methodology is defined in a granular computing environment. Thanks to our relational extension of a granular computing based data mining framework, the three above problems can be overcome.     

Effect of Carbohydrate on the Rheological Parameters of Paste Extrusion

Carbohydrates are often key components in the formulation of extrusion pastes, yet the reasons for selection are presently empirical. The influence on paste extrusion of various types of carbohydrates, such as starch, dextrin, lactose, and glucose, have been studied and related to their water retention capacities. The bulk yield stress and the surface shear stress both decrease as the moisture content increases; however, the way in which the water that is present interacts with the carbohydrate has an important influence. The behavior of some carbohydrates can be substantially accounted for by a consideration of packing effects; however, dextrin behaves differently. The carbohydrates function not only as a binder but also as a means of retaining the liquid phase.     

Glass Formation and Crystallization Behavior of a Novel GeS2–Sb2S3–PbS Chalcogenide Glass System

In the present work, a large glass-forming region was found in the novel GeS₂–Sb₂S₃–PbS system, in which up to 58 at.% PbS could be incorporated without deteriorating the thermal and physical properties of glasses. Infrared (IR) transmitting glass ceramics with a large amount of small-sized crystals (<100 nm) were then produced by choosing sub-stable compositions and annealing at fairly low temperatures (15°–30°C above T _g) for long durations (up to 100 h). Crystals were identified by X-ray diffraction as Pb₂GeS₄, PbGeS₃, PbS, PbSb₂S₄, etc., depending on base glass compositions. Compared with base glasses, glass ceramics showed much improved thermal shock resistance and fracture toughness, making them good candidate materials for IR optics.     

Modifying milk fat composition of dairy cows to enhance fatty acids beneficial to human health

There is increased consumer awareness that foods contain microcomponents that may have beneficial effects on health maintenance and disease prevention. In milk fat these functional food components include EPA, DHA, and CLA. The opportunity to enhance the content of these FA in milk has improved as a result of recent advances that have better defined the interrelationships between rumen fermentation, lipid metabolism, and milk fat synthesis. Dietary lipids undergo extensive hydrolysis and biohydrogenation in the rumen. Milk fat is predominantly TG, and de novo FA synthesis and the uptake of circulating FA contribute nearly equal amounts (molar basis) to the FA in milk fat. Transfer of dietary EPA and DHA to milk fat is very low (<4%); this is, to a large extent, related to their extensive biohydrogenation in the rumen, and also partly due to the fact that they are not transported in the plasma lipid fractions that serve as major mammary sources of FA uptake (TG and nonesterified FA). Milk contains over 20 isomers of CLA but the predominant one is cis-9,trans-11 (75–90% of total CLA). Biomedical studies with animal models have shown that this isomer has anticarcinogenic and anti-atherogenic activities. cis-9,trans-11-CLA is produced as an intermediate in the rumen biohydrogenation of linoleic acid but not of linolenic acid. However, it is only a transient intermediate, and the major source of milk fat CLA is from endogenous synthesis. Vaccenic acid, produced as a rumen biohydrogenation intermediate from both linoleic acid and linolenic acid, is the substrate, and Δ9-desaturase in the mammary gland and other tissues catalyzes the reaction. Diet can markedly affect milk fat CLA content, and there are also substantial differences among individual cows. Thus, strategies to enhance milk fat CLA involve increasing rumen outflow of vaccenic acid and increasing Δ9-desaturase activity, and through these, several-fold increases in the content of CLA in milk fat can be routinely achieved. Overall, concentrations of CLA, and to a lesser extent EPA and DHA, can be significantly enhanced through the use of diet formulation and nutritional management of dairy cows.     

Scalable Realistic Rendering with Many‐Light Methods

Recent years have seen increasing attention and significant progress in many‐light rendering, a class of methods for efficient computation of global illumination. The many‐light formulation offers a unified mathematical framework for the problem reducing the full lighting transport simulation to the calculation of the direct illumination from many virtual light sources. These methods are unrivaled in their scalability: they are able to produce plausible images in a fraction of a second but also converge to the full solution over time. In this state‐of‐the‐art report, we give an easy‐to‐follow, introductory tutorial of the many‐light theory; provide a comprehensive, unified survey of the topic with a comparison of the main algorithms; discuss limitations regarding materials and light transport phenomena and present a vision to motivate and guide future research. We will cover both the fundamental concepts as well as improvements, extensions and applications of many‐light rendering.