Enhanced Crystallinity Through Melt Annealing of Thermoplastic Polyurethanes

ABSTRACT This study evaluated the influence of melt annealing on thermoplastic polyurethane (TPU) synthesized via reactive extrusion, aiming to enhance TPU melt crystallization behavior. The melt annealing process involved reprocessing the polymer in a twin‐screw extruder, leveraging a novel approach to manipulating crystallization behavior by optimizing melt annealing conditions to activate microphase separation. Differential scanning calorimetry analysis indicated increased nucleation density and a shift in peak crystallization temperature to higher values during cooling. Phase morphology was examined using scanning electron microscopy, while gel permeation chromatography was utilized to assess molecular weight changes. X‐ray diffraction provided insights into TPU microstructural modifications, and mechanical properties were evaluated via tensile tests. Fourier‐transform infrared spectroscopy was employed to analyze annealing‐induced changes in the hard segment structure and interpolymer bonding. The findings demonstrated that annealing enhances mechanical properties, promotes microphase separation, and increases the energy available for movement and realignment of hard segments, thereby improving TPU's thermal stability. Precise control of annealing temperature was critical to prevent adverse effects on polymer morphology or molecular weight reduction. Annealing at 210°C yielded the highest degree of crystallinity, optimizing mechanical properties and thermal stability.