Structural changes in poly(ethylene terephthalate) induced by mechanical milling

Poly(ethylene terephthalate) (PET) has been subjected to high-energy ball milling (mechanical milling, MM) at three different temperatures. The resulting milled powder is characterized by molecular weight measurements, differential scanning calorimetry and wide-angle Xray scattering. Regardless of the initial degree of crystallinity or milling temperature employed, MM apparently yields an "oriented amorphous" PET morphology in which the PET chains are locally aligned but rotationally disordered. This conclusion is based on the persistence of the (100) peak in otherwise amorphous x-ray patterns from milled PET. Thermograms of milled PET exhibit a small, broad crystallization exotherm and a large melting endotherm. The unusually small crystallization enthalpy is attributed to the local orientation of PET molecules present in the oriented amorphous morphology. Only minor rotations and translations of oriented PET molecules are needed to put the chains into register and, hence, the crystalline state. Evidence is also presented to suggest that extended-chain crystals of PET are produced upon crystallization of mechanically milled PET. (C) 2000 Elsevier Science Ltd. All rights reserved.