Radiation, cross-linking

Cross-linking of polyethylene can be accomphshed either chemically or by high energy radiation. Radiation cross-linking is usually accomphshed by x-rays (44) or electrons (45,46). Chemical cross-linking of polyethylene is accomphshed with dicumyl peroxide (47), d4-tert-huty peroxide (48), or other peroxides. Radiation cross-linking (49) is preferred for thin foams, and chemical cross-linking for the thicker foams. 

There has been interest, particularly in Japan, in the production of cross-linked low-density polyethylene foam. Some processes, such as the Furukawa process and the Hitachi process, use chemical cross-linking techniques whilst others, such as the Sekisui process, involve radiation cross-linking. 

The radiation-treated cables find wide applications in control instmmentation of nuclear power reactors, particle accelerators, aviation, and telephone equipments. Usually PE and PVC are radiation cross-linked for production of such cables. The heat shrinkable foils are widely used in packaging, electrical and electronic industries. The radiation cross-linked PE possesses the property of elastic memory which is utilized to produce heat shrinkable products. 

The effect of antioxidants such as hindered phenohcs, secondary amine, and thioester on the radiation cross-linking efficiency of LDPE has been reported [260]. Amount of cross-linking at a given dose decreases with aU the antioxidants, the thioester being the most effective. IR absorption spectroscopy has been used to demonstrate dose-rate dependence of trani -vinylene unsaturation in irradiated Marlex 50 PE [261]. When the irradiated polymer is stored in vacuum a decrease is observed in trani-vinylene absorbance over a period of several weeks. After high dose-rate irradiation the decay is preceded by an initial increase. These phenomena have been ascribed to the reaction of trapped radicals. 

Radiation cross-linking of PVC in the absence of additives has been reported by several authors [20,21,267,268]. PVC by itself is not readily cross-linkable by EB radiation. In the study of radiation chemistry of PVC, it is known that the oxidation takes place in the presence of atmospheric oxygen during irradiation [269] and hydroperoxide groups are produced on oxidation. The formation of carbonyl group along with the elimination of HCl from PVC on irradiation in air has also been reported [270,271]. 

To improve the dimensional stability of the oligoethyleneoxy phosphazene/ metal salt complexes, some attempts have been reported which concern the chemical modification of the parent polymers, their chemical or radiation cross-linking, or the use of blends. 

Poly[bis(methylamino)phosphazene], for instance,has been radiation cross-linked [640] for the preparation of phosphazene-based membranes. MEEP, a... 

Figure 9. SANS measurements of R /Rt° and RL/R ° for stretched radiation cross-linked polystyrene. is determined by measurements in which the neutron is parallel (iso) and perpendicular (aniso) to the stretching direction. Mc is molecular weight between crosslinks. Theoretical curves 2 and 3 are drawn for tetrafunctional networks. Data from Ref. 21.

Since the excellent work of Moore and Watson (6, who cross-linked natural rubber with t-butylperoxide, most workers have assumed that physical cross-links contribute to the equilibrium elastic properties of cross-linked elastomers. This idea seems to be fully confirmed in work by Graessley and co-workers who used the Langley method on radiation cross-linked polybutadiene (.7) and ethylene-propylene copolymer (8) to study trapped entanglements. Two-network results on 1,2-polybutadiene (9.10) also indicate that the equilibrium elastic contribution from chain entangling at high degrees of cross-linking is quantitatively equal to the pseudoequilibrium rubber plateau modulus (1 1.) of the uncross-linked polymer. 

Figure I. Dependence of the water permeability coefficient on pressure (radiation cross-linked, 86,000 mol wt, 100% hydrolyzed PVA )...

Figure 4. Pressure dependence of water fluxes through PVA membranes as determined by Ehra-Lima and Paul (6) and in this work ( ) Ebra-Lima and Paul s data at 24°C ( = SSg/n) (O) data for radiation cross-linked, 115,000 mol wt, 100% hydrolyzed PVA (X = 4.0 /im).

Figure 5. Temperature dependence of the water permeability of radiation cross-linked PVA membranes under various pressure differentials ( ) AP = 200 psi ...

Although radical cations are generated in some electron-irradiated monomers (e.g., vinyl ethers or epoxies), efficient cationic polymerization is not observed. Under certain conditions (addition of iodonium, sulfonium, or sulfoxonium salts, cationic polymerization with the use of electron beam irradiation can be induced. Several studies on radiation cross-linking of elastomers support the concept of ionic mechanism. ... 

Experiments on cross-linking by irradiahon have revealed that in many cases the cross-link densities equivalent to those obtained by conventional methods of cross-linking require relatively high radiation doses. Therefore, a great deal of experimental work has been done on the use of additives, which promote cross-linking by irradiation. Such compounds are called radiation cross-link promoters or prorads. 

Enhanced radiation cross-linking in polyethylene, polypropylene, and poly-isobutylene and in copolymers of ethylene and propylene was found when nitrous oxide was incorporated into the polymer matrix. Mechanisms of fhis process have been proposed by several workers. ... 

The higher crystalline fraction of the radiation cross-linked polyethylene even after a melt-freeze cycle has great technological merit for the heat-shrink packaging and electrical connector products. ... 

Compared with chemical cross-linking of PE, radiation curing produces a different product in many respects. The chemical cross-linking is done at temperatures near 125°C (257°F), where the polymer is in the molten state. Consequently, the cross-link density in the chemically cross-linked polyethylene is almost uniformly distributed, while there are relatively few cross-links in the crystalline fraction of the radiation cross-linked PE. The crystalline fraction of the radiation-processed polyethylene is greater than that in the chemically cured product. ... 

Radiation cross-linking of polyethylene requires considerably less overall energy and less space, and is faster, more efficient, and environmentally more acceptable. Chemically cross-linked PE contains chemicals, which are by-products of the curing system. These often have adverse effects on the dielectric properties and, in some cases, are simply not acceptable. The disadvantage of electron beam cross-linking is a more or less nonuniform dose distribution. This can happen particularly in thicker objects due to intrinsic dose-depth profiles of electron beams. Another problem can be a nonuniformity of rotation of cylindrical objects as they traverse a scanned electron beam. However, the mechanical properties often depend on the mean cross-link density. ... 

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