I. Okazaki et B. Wunderlich, REVERSIBLE MELTING IN POLYMER CRYSTALS DETECTED BY TEMPERATURE-MODULATED DIFFERENTIAL SCANNING CALORIMETRY, Macromolecules, 30(6), 1997, pp. 1758-1764
A small amount of locally reversible melting and crystallization in po
ly(ethylene terephthalate) (PET) has been detected by temperature-modu
lated differential scanning calorimetry (TMDSC). Extended-time TMDSC w
as used in the quasi-isothermal mode. Studied were melt-crystallized,
quenched, and a biaxially-oriented film of PET in temperature steps of
2 K from 320 to 560 K. The integral of the endothermic and exothermic
latent heat contributions to the reversible melting and crystallizati
on is less than 10% of the total heat of fusion and decreases further
with time over many hours. The new observations support the concept th
at ''molecular nucleation'' is the reversible and rate-determining ste
p in crystallization. On TMDSC, partially-melted chains remain on the
surface of higher-melting crystals to permit crystallization during th
e cooling cycle without supercooling.