Electron-beam radiation copolymers

R i and R2 are substituents other than hydrogen) are expected to degrade predominantly upon electron beam radiation. Copolymers containing MA do not conform with this structure since MA contains one hydrogen on each olefinic carbon. 

PBS (Figure 30) is an alternating copolymer of sulfur dioxide and 1-butene. It undergoes efficient main chain scission upon exposure to electron beam radiation to produce, as major scission products, sulfur dioxide and the olefin monomer. Exposure results first in scission of the main chain carbon-sulfur bond, followed by depolymerization of the radical (and cationic) fragments to an extent that is temperature dependent and results in evolution of the volatile monomers species. The mechanism of the radiochemical degradation of polyolefin sulfones has been the subject of detailed studies by O Donnell et. al. (.41). 

Figure 41. A plot of sensitivity to Mo (5.4k) x-ray radiation and 20 kV electron beam radiation for several resists. EPB is epoxidized polybutadiene, P(GMA-EA) is a copolymer of glycidyl methacrylate and ethyl acrylate (COP), PGMA is poly (glycidyl methacrylate), PBS is poly (butene-1 -sulfone), FBM-1 is poly (2,2,3,3-tetrafluoropropyl methacrylate), P(MMA-MA) is a copolymer of methyl methacrylate and methacrylic acid, PMMA is poly (methyl methacrylate). (Reproduced with permission from Ref. 56J...

There is some reason to expect that conversion of the anhydride to a half-ester might reduce the sensitivity of the copolymers. Hiraoka (10) determined the relative sensitivities of PMMA, PMA (polymethacrylic acid) and PMA AN (polymethacrylic anhydride) by measuring the gaseous products (CO, C02, and H2) given off when these polymers were exposed to electron beam radiation of 2.5 keV at 297 °K. He found that the G values (number of chemical events produced per 100 eV of absorbed radiation) for the removal of side groups are 2.0, 7.4 and 16 for PMMA, PMA and PMA AN, respectively. Anderson (11) found a similar relative order of sensitivity. For copolymers of methylmethacryate with 25% dimethylitaconate, 25% monomethyl itaconate or 25% itaconic acid (or anhydride) the G(s) values were 1, 2, 3, respectively. For the copolymer of alpha-methylstyrene and monomethyl maleate, on the other hand, we find an increase in sensitivity by a factor of 2.5 over the corresponding anhydride as described below. 

Heat-resistant [218] soft foams were prepared from the blends of hdPE with E-P random copolymers. The azodicarbanamide acts as a thermal antioxidant and the crosslinking of the blend was increased by electron beam radiations and foamed at 225 °C with 2320% expansion. A blend of 35 wt.% PE-PP (8 92), 15 wt.% E-P block copolymers, and 50 wt.% EPDM showed accelerated weathering resitance [219] 1000 h probably due to crosslinking between constituents of the block copolymer, polyblend and EPDM. The effect of filler and thermodynamic compatibility on kaolin-filled PE-PP blend was studied by Lipatov and coworkers [220]. The thermodynamic interaction parameter (%) decreased and thermodynamic stability increased by filler addition, the degree of crystallinity decreased with increasing thermodynamic compatibility of the components due to sharp decrease in the phase separation rate during cooling. 

Crosslinking of polyethylen and its copolymers EPM, EPDM, and EVA is mainly carried out by radicals generated from organic peroxides. Other crosslinking methods like electron-beam radiation and grafting of vinylsUanes assume a smaller role in this process. 

Chain-Scission Yields of Methacrylate Copolymers Under Electron Beam Radiation... 

Ethylene Chlorotrifluoroethylene Copolymer (ECTFE) 2-8 Chlorinated Polyvinyl Chloride (CPVC) Electron Beam Radiation 9 Polyester, PBT Polyethersulfone (PES) 8-9 8... 

EFFECT OF ELECTRON BEAM RADIATION ON THE MELT RHEOLOGY OF POLYVINYLIDENE FLUORIDE AND ITS COPOLYMERS... 

C The Epoxy Resists. The first negative tone electron beam resist materials with useful sensitivity were based on utilizing the radiation chemistry of the oxirane or epoxy moiety. The most widely used of these materials, COP (Figure 32) is a copolymer of glycidyl methacrylate and ethyl acrylate and was developed at Bell Laboratories (43,44). COP has found wide applicability in the manufacturing of photomasks. The active element... 

Acrylate resists such as polymethylmethacrylate (PMMA) have been used extensively in electron beam lithography because of their excellent resolution and contrast, despite their limited dry etch resistance and low sensitivity (1). Copolymers of PMMA, containing chemical groups more sensitive to radiation induced degradation, have also been studied and have shown up to a four-fold improvement in sensitivity (2). One approach has been to form a crosslinked gel, in-situ on the wafer, which contains radiation sensitive crosslinks and leads to improved sensitivity and improved contrast during development (3-7). 

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