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The effects of thermal oxidation on the‐ molecular structure and on the morphology of a series of high‐density polyethylene pipes have been studied “as received” or after service. The existence of a 40 to 170 μm thick oxidation skin was established, the structure and morphology of which were characterized by gloss measurements, scanning electron microscopy, polarized microscopy, infrared spectroscopy, gel measurements, and differential scanning calorimetry. The skin surface frequent contained craterlike structures, 25‐50 μm in diameter, whereas small‐scale structures occurred much less frequently than in non‐oxidized surfaces, and the gloss increased significantly. The presence of a carbonyl concentration gradient through the skin was established, and the gel measurements also indicated a crosslink gradient. The skin was found to be composed of a top layer with a mainly non‐spherulitic structure of very low crystallinity and melting point and a large‐scale spherulitic layer with a crystallinity and melting point slightly below the corresponding bulk values. The formation of this brittle surface layer and its effect on the long‐term fracture performance of the pipe are discussed.

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