Brominated poly(isobutylene‐co‐para‐methylstyrene) (BIMS)‐clay nanocomposites: Synthesis and characterization

In this work, preparation and properties of different nanoclays modified by organic amines (octadecyl amine, a primary amine, and hexadecyltrimethylammonium bromide, a tertiary amine) and brominated polyisobutylene‐co‐paramethylstyrene (BIMS)‐clay nanocomposites are reported. The clays and the rubber nanocomposites have been characterized with the help of Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and X‐ray diffraction (XRD). The X‐ray diffraction peaks observed in the range of 3 °–10 ° for the modified clays disappear in the rubber nanocomposites. TEM photographs show predominantly exfoliation of the clays in the range of 12 ± 4 nm in the BIMS. In the FTIR spectra of the nanocomposites, there are common peaks of virgin rubber as well as those of the clays. Excellent improvement in mechanical properties like tensile strength, elongation at break, and modulus is observed on incorporation of the nanoclays in the BIMS. Structure‐property correlation in the above nanocomposites is attempted. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4489–4502, 2004     

Studies on crosslinking of EPDM-PE blends by thermoanalytical techniques

The effect of blend ratio and peroxide concentration on crosslinking characteristics of EPDM-PE blends were studied by Differential Scanning Calorimetry, Brabender plasticorder and Rheometer. Crosslinking of EPDM-PE blends follows first order reaction kinetics. The curing exotherm increases but activation energy decreases with increase in EPDM content in the blends. The same however increases with the increase in concentration of DCP upto a certain level, while the activation energy is almost independent of peroxide concentration. The cure rate increases whereas optimum cure time and energy consumption for curing decrease with increase in the EPDM-PE ratio. A method for determination of crosslinking efficiency in the case of blend systems was developed from high temperature modulus to predict the properties and the curing behaviour of the blends.

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Zusammenfassung Mittels DSC, Brabender Plasticorder und Rheometer wurde der Einfluß von Mischungsverhältnis und Peroxidkonzentration auf den Vernetzungsverlauf von EPDM-PE-Gemischen untersucht. Die Vernetzung von EPDM-PE-Gemischen verläuft nach einer Reaktion erster Ordnung. Je höher der Anteil von EPDM im Gemisch, um so exothermer ist die Vernetzung und um so kleiner ist die dazugehörige Aktivierungsenergie. Mit dem Anwachsen der DCP-Konzentration bis zu einem gewissen Niveau wächst der exotherme Charakter, während die Aktivierungsenergie fast unabhängig von der Peroxidkonzentration ist. Mit dem Anstieg des EPDM/PE-Verhältnisses wächst die vernetzungsgeschwindigkeit, während die optimale Vernetzungszeit und der Energieverbrauch für die Vernetzung sinken. Es wurde ein Verfahren zur Bestimmung der Vernetzungseffizienz bei Mischsystemen entwickelt, um Eigenschaften und Vernetzungsverhalten von Gemischen voraussagen zu können.

     

Silver (I)-promoted asymmetric halohydrin reaction of chiral N-enoyl-2-oxazolidinones: scope and limitations

The halohydrin reaction of chiral N-enoyl-2-oxazolidinones 1 by halogen (Br₂/I₂) and water were efficiently carried out in aqueous organic solvent promoted by silver(I) with high anti- and regioselectivity and moderate to good diastereoselectivities. The alkenoyl, cinnamoyl and electron-deficient cinnamoyl substrates smoothly underwent bromohydrin reaction in aqueous acetone but no iodohydrin reaction, where as electron-rich cinnamoyl substrates preferred to undergo iodohydrin reaction in aqueous acetone with moderate diastereoselectivity and enhanced diastereoselectivity was observed in aqueous THF.     

Degradation of rocket insulator at high temperature

The degradation of a rocket insulator compound based on ethylene propylene diene rubber (EPDM) containing asbestor, cork and iron oxide (Fe₂O₃) as fillers has been studied at high temperature (up to 600°) by using differential thermal analysis (DTA) and thermogravimetry (TG). The changes in physical properties on high-temperature aging are also reported. EPDM gum vulcanizates involving different types of diene, namely ethylidene norbornene (ENB), dicyclopentadiene (DCPD) and 1,4-hexadiene (HD), were used. In each case, the kinetic parameters for degradation have been evaluated. From these data, the lifetime of the rocket insulator compound has been found.

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Zusammenfassung Die Zersetzung einer Raketenisolator-Verbindung auf Äthylen-Propylen-Dien-Gummibasis (EPDM) mit Asbest, Kork und Eisenoxid (Fe₂O₃) als Füllstoffe wurden bei hohen Temperaturen (bis 600°) mittels Differentialthermalanalyse (DTA) und Thermogravimetrie (TG) untersucht. Die bei Hochtemperaturen eintretenden Veränderungen der physikalischen Eigenschaften sind ebenfalls angegeben. Verschiedene Typen von Dienen, nämlich Äthyliden-norbornen (ENB), Dicyclopentadien (DCPD) und 1,4-Hexadien (HD) enthaltenden EPDM-Gummivulkanisate waren Gegenstand der Untersuchung. In allen Fällen wurden die kinetischen Parameter der Zersetzung ermittelt. Aus diesen Daten wurde die Lebensdauer der Raketenisolator-Verbindung bestimmt.

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The authors are grateful to the Indian Space Research Organization for funding, and acknowledge the help and suggestions from Mr. T. S. Ram and Mr. Baby John, R.P.P., V.S.S.C., Trivandrum. The authors are also grateful to Prof. S. K. De, Rubber Technology Centre, and Prof. R. Ghosh, Chemistry Department, I.I.T., Kharagpur.

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The authors thank Mr. Asutosh Ghosh, Indian Association for the Cultivation of Science, for experimental assistance.     

Numerical investigation on the effect of magnetic field on natural convection heat transfer from a pair of embedded cylinders within a porous enclosure

The present work examines the influence of magnetohydrodynamic field on natural convection phenomena inside a porous square enclosure with a pair of embedded hot circular cylinders. Numerical investigations are performed to understand the effects of interspacing distance between the embedded cylinders, Hartmann number, Rayleigh number and Darcy number on the thermal transport process and the total irreversibility generation. It is observed that the isotherm distribution is strongly affected by the presence of magnetic field although the distribution of streamlines remains independent of the strength of magnetic field. This underlines the fact that magnetic field strongly influences the heat transfer process and entropy generation characteristics. It reveals that the natural convection is suppressed in the presence of a higher magnetic field as evident from the reduction in Nusselt number. It is observed that an increase in the spacing between the cylinders increases the heat transfer rate, and moreover, the effect of the magnetic field on heat transfer is more pronounced at higher interspacing distance between the embedded cylinders. The heat transfer rate increases significantly with the increase in the permeability of the medium. The entropy generation rate is independent of the strength of applied magnetic field. Further, the contribution of the entropy generation owing to friction is found to be negligible in total irreversibility obtained at lower values of Rayleigh number irrespective of Darcy number. However, the contribution of irreversibility owing to heat transfer is found to be minimal at higher values of Rayleigh number.

     

XNBR/LDH nanocomposites: Effect of vulcanization and organic modifier on nanofiller dispersion and strain‐induced crystallization

In elastomer/organo clay nanocomposites, the morphological characteristics, and hence the mechanical properties, of the vulcanizates are strongly influenced by the organic modifier and the vulcanization process. When the elastomer itself undergoes strain‐induced crystallization, both the organic modifier and the dispersed filler particles could significantly influence the crystallization process. These phenomena are very common in case of natural rubber‐based vulcanizates. In this study, the similar effects have been demonstrated with carboxylated nitrile rubber (XNBR) and organically modified layered double hydroxide (O‐LDH)‐based nanocomposites. The effect of size of the organic modifier was obviously visible on the interlayer distance of O‐LDH and also on the morphological reorganization of the dispersed O‐LDH particles during vulcanization process. The strain‐induced crystallization of the XNBR was found to be strongly dependent on the morphological change that occurs during vulcanization process. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Sulfonation of metallocene‐based polyolefinic elastomers and its influence on physicomechanical properties: Effect of reaction parameters,styrene grafting,and pendant chain length

Direct sulfonation and styrene‐mediated sulfonation were carried out onto metallocene‐based poly(ethylene‐co‐octene) (POE) and poly(ethylene‐co‐butene) (PBE) elastomers to impart polarity on the completely nonpolar rubbery matrices and to prepare a new class of elastomer. The influence of styrene‐grafting and pendant chain length on the degree of sulfonation was also studied. The effects of sulfonation, styrene grafting and styrene‐mediated sulfonation at their optimized levels on various physicomechanical properties were thoroughly investigated, and the resultant properties were correlated with structures of the modified elastomers. Higher extent of sulfonic acid groups were introduced through direct sulfonation in comparison with the styrene‐mediated sulfonation, whereas better thermal and mechanical properties were obtained through styrene‐mediated sulfonation in comparison with the direct sulfonation process. PBE had shown higher degree of sulfonation and percentage grafting than POE. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8023–8040, 2008     

Number-theoretic interpretation and construction of a digital circle

This paper presents a new interpretation of a digital circle in terms of the distribution of square numbers in discrete intervals. The number-theoretic analysis that leads to many important properties of a digital circle succinctly captures the original perspectives of digital calculus and digital geometry for its visualization and characterization. To demonstrate the capability and efficacy of the proposed method, two simple algorithms for the construction of digital circles, based on simple number-theoretic concepts, have been reported. Both the algorithms require only a few primitive operations and are completely devoid of any floating-point computation. To speed up the computation, especially for circular arcs of high radii, a hybridized version of these two algorithms has been given. Experimental results have been furnished to elucidate the analytical power and algorithmic efficiency of the proposed approach. It has been also shown, how and why, for sufficiently high radius, the number-theoretic technique can expedite a circle construction algorithm.