Photochemical Reactions in Supramolecular Assemblies of Gels: Dimerizations and Polymerizations via Pericyclic Reactions

Gel state reactions offer new direction for the reactivity of the organic molecules or metal‐organic materials upon photoirradiation with shorter reaction times and high yields compared to solid and solution states. The restricted molecular movement among the molecules in the soft solids control the stereoselectivity of the photoproducts in the gel state reactions. To date, most of the strategies based on self‐assembly have been demonstrated in the solid state, in particular for [2+2] reactions of olefins and polymerization reactions of diacetylenes via 1,4 addition. The soft materials are of emerging materials in recent days given their many applicative day‐to‐day aspects. This review gives a glimpse of recent reports on pericyclic reactions in the gel state that are designed based on the self‐assembly concept. Also it highlights how such reactions accompany the physical changes in the structure of the gels and stereo controlled products with high yields.     

Distribution of technetium in PUREX process streams

Extraction of technetium has been carried out from the aqueous medium containing nitric acid under different experimental conditions to investigate its extraction behaviour in 30% tri-n-butyl phosphate in n-dodecane. In order to study the distribution behaviour of technetium in different streams of PUREX process, experiments were carried out under process conditions. The distribution of technetium was also studied using anion-exchange resin. Based on these results, the path of technetium in the PUREX process streams has been established which will be useful in the development of an advanced PUREX flow-sheet for containment and isolation of technetium in an environmental friendly fuel cycle.     

Influence of phase modifiers on morphology and properties of thermoplastic elastomers prepared from ethylene propylene diene rubber and isotactic polypropylene

A series of thermoplastic elastomers (TPEs) were prepared from a binary blend of ethylene propylene diene rubber (EPDM) and isotactic polypropylene (iPP) using different types of phase modifiers. The influence of sulphonated EPDM, maleated EPDM, styrene‐ethylene‐co‐butylene‐styrene block copolymer, maleated PP, and acrylated PP as phase modifiers showed improved physico‐mechanical properties (like maximum stress, elongation at break, moduli, and tension set). Scanning electron and atomic force microscopy studies revealed better morphologies obtained with these phase modified EPDM‐iPP blends. The dependence of the phase modifier type and concentration was optimized with respect to the improvement in physical properties and morphology of the blends. Physical properties, dynamic mechanical properties, and morphology of these blends were explained with the help of interaction parameter, melt viscosity, and crystallinity of the blends. Theoretical modeling showed that Kerner, Ishai‐Cohen, and Paul models predicted the right morphology–property correlation for the prepared TPEs. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

Augmenting the performance of acrylonitrile–butadiene–styrene plastics for low‐noise dynamic applications

The main objective of this study was to enhance the performance of acrylonitrile–butadiene–styrene (ABS) plastics for dynamic structural applications, including those of automobile relevance. First, ABS was modified by blending with maleic anhydride grafted styrene–ethylene–butadiene–styrene block copolymer (MA‐g‐SEBS) in various proportions. Squeaking noise characteristics were evaluated by measurement of the frictional behavior in an in‐house fabricated friction testing apparatus, and the results are explained on the basis of the change in surface energy upon modification. Detailed dynamic mechanical analyses (strain, frequency, and temperature sweep) revealed significant improvements in the damping characteristics of the modified ABS, especially that modified with 10 wt % MA‐g‐SEBS, without much sacrifice in its mechanical strength. The modulus values predicted with Kerner's model of the blends were well correlated with the morphological changes upon modification. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Emulsifier‐free emulsion polymerization of acrylonitrile: Effect of in situ developed Cu(II)/glycine chelate complex initiated by monopersulfate

The catalytic effect of various Cu(II) salts and Cu(II) chelate complexes of certain amino acids on the emulsion polymerization of acrylonitrile in the absence of added emulsifier was investigated in experiments. The CuSO₄/glycine chelate complex was chosen for a detailed kinetic study of acrylonitrile polymerization. The polymerization was studied at varying concentrations of initiator, monomer, Cu(II), glycine, solvents, and TiO₂ over a temperature range of 30–60°C. The overall activation energy and the viscosity average molecular weight of the polymer were computed. From the kinetic and spectrophotometric studies, the mechanism of KHSO₅ decomposition by the Cu(II)/glycine complex and initiation of polymerization was suggested. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2785–2790, 1999     

An XPS Study with Depth Profiling for the Surface Oxide Layer Formed on Aluminides Produced on Superalloy 690 Substrates

Superalloy 690 substrates containing mainly Cr and Ni aluminides on the uppermost surface, formed by atmospheric plasma spraying and heat treatment, were oxidized at 1273 K in air for 2 h. Quantitative X-ray photoelectron spectroscopy (XPS) analyses indicated that the outermost surface layer formed on aluminides is composed of ~ 21.0 at.% Al⁺³ (as Al₂O₃), 17.0 at.% Al⁰ (elemental aluminium), 1.4 at.% Cr⁺³ (as Cr₂O₃) and 60.5 at.% O (in Al₂O₃ and Cr₂O₃ and also includes oxygen contaminant). Surface sputtering for 5 min exhibited splitting of Cr2p_3/2 peak into a doublet comprising Cr⁺³ (0.9 at.%) and Cr⁰ (0.4 at.%) with the presence of 1.15 at.% Ni⁰ in the surface layer that mainly contained ~ 37.3 at.% Al⁺³, 7.3 at.% Al⁰ and 52.9 at.% O. Surface sputtering for 15 min indicated surface composition similar to surface sputtered for 5 min but with a marked reduction in ratio of Al⁺³/Al⁰ (32.2 at.% Al⁺³/11.90 at.% Al⁰) in the surface layer.     

Investigation of Pt and Pd Modified WO<Subscript>3</Subscript> and ZnO Based Thin Film Sensors for Ethanol Sensing

Ethanol sensors based on different WO₃ and ZnO structures are studied in the present work. The XRD and SEM processes are used to characterize the sensing layer’s surface morphology which reveals the presence of nanoparticle in sensing layer. Further reducing the nanoparticle diameter by the addition of palladium (Pd) and platinum (Pt) for both the sensors (ZnO and WO₃) gives good results on sensitivity, operating temperature, response time and recovery time. Nanoparticle diameter for undoped WO₃, Pd-modified WO₃ and Pt-modified WO₃ based sensors is 11.8, 6 and 5.4 nm, whereas nanoparticle diameter for undoped, Pd-modified and Pt-modified ZnO based sensors is 20, 14 and 11 nm, respectively. Analysis of dynamic response of the sensors when exposed to different concentrations of ethanol vapour (from 500 to 10,000 ppm) and various temperatures indicate the improvement in sensitivity up to 77.2% for WO₃ and 74.6% for ZnO based sensors.