This is a review on the long‐term behavior of polyolefin pipes used in hot‐water environments. Included in the review is work done on pipes of crosslinked polyethylene, isotactic poly(butene‐1), isotactic polypropylene and medium‐density polyethylene, and in particular the extensive work performed at Studsvik, Sweden. A collective view of the changes in antioxidant concentration profiles and molecular/physical structure accompanying hot‐water exposure is presented. Failure at high stress levels is preceded by gross deformation (Stage I failure), whereas at lower stresses fracture is brittle either without any signs of thermal oxidation (Stage II) or induced by a strong and spatially concentrated thermal oxidation (Stage III). It is shown that the Stage III lifetime can be divided into three phases, denoted Regimes A, B, and C. They involve internal precipitation of antioxidant from a supersaturated solution (Regime A), diffusion‐controlled migration of antioxidant to the surrounding media (Regime B), and degradation of the polymer by thermal oxidation (Regime C). For hitherto reported cases the Regime B life constitutes 80% to 90% of the entire life. A presentation is also made of current lifetime extrapolation methods.
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