Thermal Decomposition of Radiation-Damaged Polystyrene

The radiation-damaged polystyrene (given the identification name of 'polycube') was fabricated by mixing high-density polystyrene material ("Dylene Fines # 100") with plutonium and uranium oxides. The polycubes were used in the 1960s for criticality studies during processing of spent nuclear fuel. The polycubes have since been stored for almost 40 years at the Hanford Plutonium Finishing Plant (PFP) after failure of two processes to reclaim the plutonium and uranium oxides from the polystyrene matrix. Thermal decomposition products from this highly cross-linked polystyrene matrix were characterized using Gas Chromatograph/Mass Spectroscopy (GC/MS) system coupled to a horizontal furnace. The decomposition studies were performed in air and helium atmospheres at about 773 K. The volatile and semi-volatile organic products for the radiation-damaged polystyrene were different compared to virgin polystyrene. The differences were in the number of organic species generated and their concentrations. In the inert (i.e., helium) atmosphere, the major volatile organic products identified (in order of decreasing concentrations) were styrene, benzene, toluene, ethylbenzene, xylene, nathphalene, propane, .alpha.-methylbenzene, indene and 1,2,3-trimethylbenzene. But in air, the major volatile organic species identified changed slightly. Concentrations of the organic species in the inert atmosphere were significantly higher than those for the air atmosphere processing. Overall, 38 volatile organic species were identified in the inert atmosphere compared to 49 species in air. Twenty of the 38 species in the inert conditions were also products in the air atmosphere. Twenty-two oxidized organic products were identified during thermal processing in air