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Simulation‐Assisted Evaluation of Acetylene Effect on Macromolecular Crosslinking Rate under Polyethylene Irradiation
Authors:Alexander Shyichuk  Galina Tokaryk
Abstract:Gel content data on acetylene accelerated radiation crosslinking (R.A. Jones, J. Polym. Sci., Part B: Polym. Phys. 1994 , 32, 2049) have been used to illustrate a new method to determine macromolecular crosslinking and scission yields. The sol‐gel analysis data have been plotted as log(sol) versus log(dose) resulting in quite linear plots having different slopes. The linear approximations with the least squares method resulted in gel‐points with a high accuracy. Computer simulations have shown the plot slope to be dependent on relative rate of competitive macromolecular scission. The scission/crosslink ratios have been found from the plot slopes using simulation software GelSim6. As a result acetylene gas has been found to be accelerating both crosslinking and scission rates: 60 times and 130 times, respectively. Obviously, the radiation yield of radicals is increased due to acetylene inhibiting the recombination of primarily induced radicals in a cage.
image

Gel content vs. irradiation dose data plotted as log(sol) versus log(dose). Numbers near the curves indicate concentrations of acetylene gas (mmol · kg?1).

Keywords:crosslinking  gels  macromolecule chain scission  radical polymerization  simulations
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