BRANCHING IN POLYETHYLENE
The principal purpose of this paper is to present the current status, as viewed by the authors, of our knowledge of branching in polyethylene and the effects of branching on its properties. Another purpose is to present some speculative material, and some challenging observations, in an attempt to stimulate, in some measure, future work on the structure and chemistry of polyethylene. In endeavoring to achieve these aims, the authors have drawn heavily upon their own work and liberally from the literature, particularly the published results of R. B. Richards and his collaborators. Polyethylene resins are made by polymerizing ethylene at elevated temperatures and high pressures.’, The polymer molecules formed under these conditions are branched hydrocarbon chains3* 4 . 6 * and their average molecular size varies from approximately 50 carbon atoms per molecule, for the greasy products, to more than 1000 carbon atoms per molecule for rigid resins. The degree of branching in polyethylene has been shown to play an important role in determining the properties of the resin.’ In fact, it is now generally recognized that degree of branching and molecular weight are the most important molecular variables in polyethylene resins. In this paper, degree of branching is defined as the number of branches per 100 carbon atoms, and the number of branches per molecule is defined as the number of -CH3 groups per molecule more than two. Although some chains and branches are terminated by vinyl groups (-CH=CHJ, the concentration of these is very small compared to the concentration of methyl groups. Side chain methylene groups (RR’C=CHZ) may be regarded as short branches but, as such, represent not more than 15 per cent, and generally a much smaller proportion, of the total number of branches. As a result, this configuration is not considered significant for the purposes of this paper.
Molekulargewicht und Polymolekularität
Neben dem im vorigen Abschn. 2.1 behandelten chemischen Aufbau der Makromolekule und den daraus resultierenden zwischenmolekularen Kraften (2.6) bestimmen Molekulargewicht und Polymolekularitat (d. h. die Molekulgrosenverteilung) die physikalischen Eigenschaften der hochmolekularen Stoffe und sind daher fur deren Verhalten beim Einsatz in der Praxis von erheblicher Bedeutung. Der vorliegende Abschnitt bringt eine Ubersicht uber die grundlegenden Erscheinungen; zahlreiche Beispiele zeigen die Zusammenhange mit den makroskopischen Eigenschaften.
Neutron Residual Stress Measurements on Rail Sections for Different Production Conditions
Rail sectioning with subsequent neutron diffraction experiments has been used to assess residual stresses in the rails. In this study we present the results of neutron stress measurements performed at the NIST Center for Neutron Research (NCNR) on rail sections from rails that were produced under various conditions. Specifically, these are air-cooled, air-cooled and roller-straightened, head-hardened and head-hardened and roller-straightened. More significantly, a head-hardened and roller-straightened rail was also studied after service to elucidate evolution of the service-induced residual stresses. In the latter case both a transverse-cut slice and the central region of a 0.53 m long piece were studied. Measurements on this piece are the first in which triaxial stresses have been determined for an intact rail. Neutron strain measurements with 3×3×3 mm3 spatial resolution were successfully employed for transversally cut slices to verify the difference in the stress state depending on the production process. Although examination of slices allows determination of only two-dimensional stresses in the plane of the slice, additional measurements on obliquely-cut slices, which were also carried out, and utilization of FEM gives the possibility of reconstructing the full triaxial stress distribution. Together, these approaches provide a better understanding of rail fabrication and the possibility of improving the durability and safety of rails in the future.Copyright © 2004 by ASME