Thermo-oxidative ageing of photo-crosslinked polyethylene pipes for thermal energy storage

This study presents a comprehensive evaluation of the thermo-oxidative stability of crosslinked polyethylene (PEX) pipes designed for borehole thermal energy storage (BTES) systems, with a particular focus on a novel PEX type produced via a photo-initiated crosslinking process (PEX-e). Two formulations, PEX-e1 and PEX-e2, were assessed and compared to commercial peroxide-crosslinked polyethylene (PEX-a) and bimodal polyethylene (PE100) pipes. The pipes were aged in distilled water at the intended BTES service temperature for 210 days, with periodic analyses conducted to monitor antioxidant (AO) depletion and the formation of degradation products. Advanced analytical techniques were employed, including Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy, gel content analysis, colorimetry, differential scanning calorimetry (DSC), oxidation induction time (OIT), and dynamic mechanical analysis (DMA). FTIR analysis revealed the presence of degradation-related peaks on the pipe surfaces, while the formation of oxidation products in the bulk material was limited. Phase composition analysis showed that physical ageing dominated during the first 30 days, leading to increased crystallinity and enhanced lamellar thickness. Over time, chain scission emerged as the primary degradation mechanism, resulting in molecular weight reductions, with PEX-a being the most severely affected. No abrupt changes in phase composition or mechanical properties were observed after 210 days of ageing, indicating that the pipes remained in the induction phase of degradation. Interestingly, despite their high OIT levels, both PEX-e formulations exhibited accelerated AO depletion during prolonged exposure, suggesting the need for further optimization of PEX-e formulations to ensure long-term stability under demanding BTES conditions. • Chain scission was the main degradation mechanism in the degradation of PEX pipes. • Ageing led to decrease in molecular weight and increase in amorphous phase mobility. • Oxidation was detected on the surface of the pipes before depletion of additives. • Photo-crosslinked polyethylene was less prone to chain scission. • PEX-e formulations tested exhibited rapid depletion of antioxidant additives.