Polyethylene crystallinity, irradiation

Similar effects are observed in y-irradiated n-C H (530 kGy) in the molten state. Three new structures are identified as a) one-bond crosslinks (H-structure), b) trans-vinylene groups and c) long branches (T- or Y-structure)144). However, highly crystalline polyethylene y-irradiated in the solid state at low doses (up to 40 kGy) yields predominantly the branched Y-structure. A failure to detect the cross-linked H-structure could arise from a) insufficient abundance of crosslinks to give a detectable signal and b) insufficient mobility of crosslinked chains in the polyethylene gel which results in very broad resonance lines, not observable during normal data acquisition in the solution 13C NMR experiment145). 

Many polymers, after irradiation at low temperature, give off light when allowed to warm. This phenomenon of thermoluminescence depends not only on the chemical structure but also on crystal morphology. In polyethylene, for example, peaks in the thermoluminescence glow curve correspond, respectively, to the crystalline and the amorphous regions (9, 19, 22) (Figure 2). 

Yahagi, K., K. Shinohara, and K. Mori y ray induced conductivity in polyethylene, effect of pre-irradiation and crystallinity. Rep. Prog. Polymer Phys., Japan 7, 313 (1964). 

The influence of the polymer structure on the irradiation grafting has been examined in the case of styrene to high pressure and low pressure polyethylene films (114). The most important factors which determine the efficiency of grafting are the degree of crystallinity, the thickness of the films and the dose rate. 

Just above the melting point the polymer is visually quite viscous and numerous observations have been made that the polymer exhibits a memory effect, that is to say, on recooling the melt crystallites will appear in the same sites where they had been before melting the polymer. Hartley, Lord and Morgan (1954) state It is reasonable to suppose that there will be a few localities in the crystalline polymer which have a very high degree of crystalline order, and therefore the melt can contain, even at considerable temperatures above the observed melting or collapse point, thermodynamically stable minute crystals of the polymer . Especially if the polymer has been irradiated so as to contain a few crosslinks as in irradiated polyethylene, then flow is inhibited and spherulites can be made to appear on recrystallization in the same sites that they had before the polymer was melted, Hammer, Brandt and Peticolas (1957). However, as mentioned above, the specific heat of irradiated polyethylene in the liquid state is identical with that of the unirradiated material, within the limits of experimental error. Dole and Howard (1957). 

For example, irradiation of either 2-naphthyl acetate (2-NA) or 2-naphthyl myristate (2-NM) in the rubbery state of a low density polyethylene (LDPE) or a high density polyethylene (HDPE) yields a variety of in-cage rearrangement products and 2-naphthol (2-NOL), a cage-escape product (Table 13.2). Both LDPE and HDPE consist of amorphous and crystalline regions LDPE has a larger volume... 

The mechanisms of the photooxidation of polyethylene and polypropylene have been discussed in depth with particular emphasis on the importance of hydroperoxides as the precursor to free radical formation . Both the kinetics and nature of the photooxidation products of the polymers are markedly controlled by these species especially polypropylene. On the other hand the density of polyethylene has been found to play an important role on the photooxidation rate of the polymer . Here the photostability of the polymer decreased with decreasing film density indicating that oxygen diffusion is impaired by the crystallites and therefore improves stability. In fact, other workers have found that the crystalline regions of polyethylene are unaffected by irradiation in air . These workers also found new crystalline regions are formed on irradiation due to the smaller polymer fragments... 

Experimental details solid-state photolysis 957 A crushed crystalline ketone (279a or 279b) ( 5 mg), suspended in hexane (3 ml), was placed between Pyrex microscope slides, sealed in a polyethylene bag under nitrogen and irradiated with a medium-pressure mercury lamp (450 W) at a distance of 10 cm from a water-cooled Pyrex immersion well (Figure 3.9) at either 20 or — 20 °C (cryostat ethanol bath). The product, a chiral organic salt, was derivatized to the corresponding methyl ester by treatment with excess diazomethane and purified by column chromatography. 

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