By J. F. Jackson, Bruce Johnson (auth.), Roger S. Porter, Julian F. Johnson (eds.)
Read or Download Analytical Calorimetry: Proceedings of the Symposium on Analytical Calorimetry at the meeting of the American Chemical Society, held in Chicago, Illinois, September 13–18, 1970 PDF
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Additional resources for Analytical Calorimetry: Proceedings of the Symposium on Analytical Calorimetry at the meeting of the American Chemical Society, held in Chicago, Illinois, September 13–18, 1970
The very little changed original maximum at l29 0 Cshould be connected with the remaining old lamellae which were not yet destroyed by rolling. The increase of intensity of the low temperature shoulder centering about l2S o C is very likely caused by a new maximum characteristic for tie molecules invulnerable to RND3 attack and generated during rolling. Such a higher temperature maximum corresponds to tie molecules. Tie molecules are also formed in quenched rolled samples as seen by the new maximum at the high temperature side of the thermogram at 12S o C.
The introduction of bromine on the surface then acts as a site from which melting can initiate. Hence the introduction of bromine again causes an increase in the amount of material melting out at the lower temperature. It is apparent from the heat of fusion measurements of the 85°C crystals that bromination does not disrupt the crystal lattice. 50C crystals are not as complete, they do seem to indicate similar results. 50C crystals has been associated with an annealing process. 50C crystals containin~ less than one bromine per fold does not incorporate bromine atoms in the lattice.
There exists conflicting evidence f~ 1~~ effect of heating rate on the rearrangement of single crystals ' ) It has been reported that rearrangement takes place at heating rates of 15 0 /min. or less, but no superheating ~f folded chain crystals takes place from 15°/ min. up to 3000 0min. 13) However the majority of heats of fusion reported are measured at 5 or 100 /min. Lamellae thickening may BROMINATION EFFECTS IN POLYETHYLENE CRYSTALS 29 also be prevented by irradiation induced cross-linking.