Detection of polymer transition temperatures by infrared absorption spectrometry

Infrared bands in the 900–1100 cm −1 region are sensitive to thermal energy. These bands can result from intermolecular coupling, producing the crystal lattice, or from intramolecular coupling of the various atomic groups in a regular helix or coiled chain. In either case an increase in temperature will disrupt the coupling mode, resulting in a form of structural relaxation and a reduction in the integrated absorbance. It is proposed that the temperature at which the peak areas begin to decrease be assigned as the T g . This is measured by continuously scanning a selected peak in the infrared spectrum of a polymer film while it is heated at a rate of about 1°C/min. Using this technique polyamides (nos. 6,66, and 610) exhibited transitions in the 30–50°C range, and by studying the increase in the free NH region (3440 cm −1 ) of nylon 66 two other transitions were detected at 80 and 137°C; the latter represents a change in the nylon 66 crystal state. An amorphous film of poly(ethylene terephthalate) displayed a transition at 58–68°C ( T g ) and at 85°C, which is the crystallization temperature. Films of poly(vinyl acetate) and polystyrene exhibited transitions at 25–37°C and at 70°C, respectively.