Radiation effects crosslinking

Much research into radiation effects on polymers is done with samples sealed under vacuum. However, polymer materials may, in practical applications, be subjected to irradiation in air. The effect of irradiation is usually substantially different in air, with increased scission at the expense of crosslinking, and the formation of peroxides and other oxygen-containing structures. Diffusion rates control the access of oxygen to radicals produced by the radiation, and at high dose rates, as in electron beams, and with thick samples, the behaviour may be similar to irradiation in vacuum. Surface changes may be quite different from bulk due to the relative availability of oxygen. 

Polyethylene is known as one of the typical polymers which crosslink under the influence of ionizing radiation. The radiation-induced crosslinking (the formation of C-C covalent bonds between polymer chains) of polyethylene has long attracted the interest of a large number of research workers, because this polymer has the most simple chemical structure for the fundamental study of radiation effects on polymers, and also because the irradiation with ionizing radiation is a practically important means of modifying the mechanical and thermal properties of polyethylene. 

The major industrial applications of this technology in the field of polymers are based on (i) polymerization, (ii) crosslinking, (iii) scission, and (iv) sterilization of medical disposables. Radiation processing of polymer blends can lead to crosslinking or scission of one or more components, or even to inter-phase (inter-polymer) crosslinking. These effects modify the blends properties. 

In 1959, Miller (1959a,fc) reported that radiation polymerization of a plasticized PVC containing a divinyl monomer could be used to crosslink PVC effectively without seriously affecting thermal stability. Three monomers were used poly(ethylene glycol dimethacrylate) (PEGDMA), ethylene glycol... 

The radiation effects on ethylene-propylene rubber (EPR) are modestly dependent on the ethylene content [63]. As the ethylene content is increased a shift to a larger yield for crosslinking occurs and the polymer is less prone to scission, the relationship is not linear since similar results for yields are found at 42 and 69% ethylene. 

Seguchi, T., Hayakawa, N., Yoshida, K., and Tamura, N., Fast neutron irradiation effect. II. Crosslinking of polyethylene, ethylene-propylene copolymer, and tetra-fluoroethylene-propylene copolymer, Radiat. Phys. Chem., 26, 221-225 (1985). Keller, A., and Ungar, G., Radiation effects and crystallinity in polyethylene, Radiat. Phys. Chem., 22, 155-181 (1983). 

There is not enough space here to give a detailed classification, but only to delineate the major families from which resins for industrial coatings may be selected. Resins may be divided into two groups according to their modes of film formation which may or may not involve a chemical reaction. In the first, the components must react together to form a crosslinked structure which may require heat, radiation or catalysis to effect the reaction. The bulk of resins used in industrial finishes are of this type. They are commonly referred to as chemically convertible or, simply, convertible. 

Unsaturated polyester finishes of this type do not need to be stoved to effect crosslinking, but will cure at room temperature once a suitable peroxide initiator cobalt salt activator are added. The system then has a finite pot life and needs to be applied soon after mixing. Such a system is an example of a two-pack system. That is the finish is supplied in two packages to be mixed shortly before use, with obvious limitations. However, polymerisation can also be induced by ultra violet radiation or electron beam exposure when polymerisation occurs almost instantaneously. These techniques are used widely in packaging, particularly cans, for which many other unsaturated polymers, such as unsaturated acrylic resins have been devised. 

The very first studies with radiation crosslinked polyethylene oxide (PEO) have shown that SAH is able to substantially reduce the sensitivity of plants to water shortage [7], to promote their growth, particularly, under conditions of water deficiency [8], to improve seedling survival and the final crop [9], These results stimulated a more detailed analysis of the effects of SAH in the water balance of... 

For extensive studies of the effects of 254 nm radiation on acrylates and methacrylates, the reader is referred to the work of Morimoto and Suzuki(14) and of Grassie (15,16). In 1964, Oster reported on the crosslinking of these and other polymers by the near ultraviolet, sensitized by the presence of 2-methylanthraquinone (17). 

A substantial intramolecular protective effect by phenyl groups in polymers is shown by the low G values for Hz and crosslinking in polystyrene (substituent phenyl) and in polyarylene sulfones (backbone phenyl), as well as many other aromatic polymers. The relative radiation resistance of different aromatic groups in polymers has not been extensively studied, but appears to be similar, except that biphenyl provides increased protection. Studies on various poly(amino acid)s indicate that the phenol group is particularly radiation resistant. 

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