Extended‐chain crystals. VI. Annealing of polyethylene under elevated pressure

Abstract

Abstract Polyethylene crystals of different degrees of perfection were annealed at 5.1 kb pressure for 20 hr at various temperatures and analyzed by electron microscopy, thermal analysis, and density determination. No annealing took place until the temperature was close to the melting point of the starting material. Up to 235°C increasing solidstate annealing was observed. Mixed crystals of up to 0.989 g/cm 3 density and 1500 Å thickness in the chain direction could be produced. At slightly higher temperature recrystallization to extended‐chain crystals rather than annealing occurred. The annealing process at atmospheric pressure seems to be similar in nature, but takes much longer for comparable perfection. From a comparison of annealing and crystallization it is concluded that polymer crystallization goes through a stage of internally imperfect order during which most of the observed chain extension occurs. Estimates of this outer imperfect layer of a growing crystal place its depth at 30,000 Å.