The mechanism of action of crosslinking additives in polyethylene vulcanisation: an EPR investigation

The nature and kinetics of the free radicals intermediates in the peroxide induced thermal vulcanisation of low density polyethylene and the mechanism of action of two crosslinking co-agents with the structure of alkenyl aromatic hydrocarbons have been elucidated by EPR spectroscopy. At low peroxide concentration, the crosslinking mechanism in the pure low density polyethylene (LDPE) matrix is based, as expected, on the H abstraction from the chains and the coupling of the resulting macroalkyl radicals. The latter reaction takes place in competition with the disproportionation causing the formation of chain unsaturations that accumulate with the reaction time. At relatively large (>2%) peroxide concentrations, such unsaturations reach high enough levels to scavenge all the initiating and macroalkyl radicals giving macroallyl radicals as the dominant intermediates and determining changes in the structure of the crosslinks during the course of the reaction. At the concentration used, the activities of the co-agents 1,3-diisopropenylbenzene and 2,4-diphenyl-4-methyl-1-pentene are sufficient to scavenge all the initiating and macroalkyl radicals by double bond addition; this mechanism, when involving macroalkyl radicals, leads to the attachment of saturated and unsaturated pendants on the LDPE chains respectively. The unsaturated pendants are thought to be responsible for the crosslinking promotion effect by the 1,3 diisopropenylbenzene coagent. The lack of the second unsaturation causes 2,4-diphenyl-4-methyl-1-pentene to act essentially as a mild antiscorch agent.     

Analysis of high-order-accurate fluctuation splitting schemes for steady advection

This article provides an analysis of high-order-accurate two-dimensional fluctuation splitting schemes for steady advection. Using Lagrangian elements, a residual distribution scheme is formulated and its properties are assessed. Distributing the residuals over the sub-triangles of each element allows one to obtain a well-posed scheme. It is also shown that the standard elemental approach is ill-posed, insofar as it produces an undetermined linear system. A steady scalar-advection problem is used to verify that the numerical schemes do obey the analysis.     

Thermal decomposition of the tris-(o-phen) complexes of some first transition group elements

Journal of Thermal Analysis and Calorimetry - A series of complexes of transition metalsM(o-phen) 3 X 2, whereM=Fe 2+,Co 2+,Ni 2+,Cu 2+,Zn 2+, andX=Cl ?,Br ?, has been studied using TG,...