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Accelerated aging of polyethylene materials at high oxygen pressure characterized by photoluminescence spectroscopy and established aging characterization methods

Grabmayer, Klemens, Wallner, Gernot M., Beißmann, Susanne, Braun, Ulrike, Steffen, Ronald, Nitsche, David, Röder, Beate, Buchberger, Wolfgang, Lang, Reinhold W.
Polymer degradation and stability 2014 v.109 pp. 40-49
accelerated aging, antioxidants, crystal structure, differential scanning calorimetry, discoloration, high performance liquid chromatography, infrared spectroscopy, mechanical properties, oxidation, oxygen, photoluminescence, polyethylene, quinones, temperature, ultraviolet-visible spectroscopy
Two commercial polyethylene grades were exposed to water at elevated temperatures and enhanced oxygen pressure. To characterize their aging behavior laser-induced photoluminescence spectroscopy was applied. Additionally, aging characterization was performed by established methods such as tensile testing, infrared (IR) spectroscopy, high performance liquid chromatography (HPLC), differential scanning calorimetry (DSC) and UV–VIS spectroscopy. During the initial stages of aging, the overall concentration of phenolic antioxidants as well as oxidation onset temperatures decreased exponentially. Simultaneously, significant discoloration due to the formation of conjugated degradation products from phenolic antioxidants (e.g., quinone methides) was detected. After the consumption of antioxidants, photoluminescence started to grow continuously presumably due to the formation of photoluminescent unsaturated carbonyls. In the final stages of aging, embrittlement of the materials as characterized by the degradation of mechanical properties (i.e., loss in ductility) coincided with rising carbonyl index values as well as an increase in crystallinity due to chemicrystallization. Between integrated photoluminescence intensity and carbonyl index, a linear correlation was established. In the induction period, the photoluminescence method exhibited a significantly higher sensitivity to reflect aging induced material changes.