Controlling the crystal morphology of high-hardness TPU through two pre-crystallization processes and its impact on physical foaming behavior

Clarifying the relationship between crystal evolution and the physical foaming behavior of high-hardness thermoplastic polyurethane (HD-TPU) is essential for preparing HD-TPU foams with controllable cellular morphology. In this study, two thermal treatment methods, isothermal annealing and isothermal crystallization, were utilized to control the crystal structure of HD-TPU. The effect of crystals on the physical foaming behavior of HD-TPU foams was examined. The annealing process produced mainly lamellae and Form Ⅰ structure, while isothermal crystallization primarily led to Form Ⅱ spherulites. Foams based on original and pre-treated HD-TPU were prepared by pressure quench foaming. The evolution of foam density and cell morphology was discussed. At low foaming temperatures, crystals induced the heterogeneous nucleation. Realizing a uniform cell structure at high foaming temperatures could be challenging when the spherulite size was large. When the size of the spherulite was small but loosely distributed, larger cells with thinner cell walls could be obtained. However, if the spherulite distribution was dense, the spherulites hindered cell growth, resulting in unevenly distributed and deformed cells.