Thermal degradation behavior and kinetic analysisof poly(L-lactide) in nitrogen and air atmosphere

The non-isothermal and isothermal degradation behaviors and kinetics of poly(L-lactide) (PLLA) were studied by using thermogravimetry analysis (TGA) in nitrogen and air atmosphere, respectively. At lower heating rate ((5–10)°C/min), PLLA starts to decompose in air at lower temperature than those in nitrogen atmosphere; however, at higher heating rate ((20–40)°C/min), the starting decomposition temperature in air are similar to those in nitrogen atmosphere, not only showing that PLLA has better thermal stability in nitrogen than in air atmosphere, but also suggesting that the faster heating rate will decrease the decomposition of PLLA in thermal processing. Whether in air or in nitrogen atmosphere, the decomposition of PLLA has only one-stage degradation with a first-order decomposed reaction, suggesting that the molecular chains of PLLA have the similar decomposed kinetics. The average apparent activation energy of non-isothermal thermal degradation (Ē_non) calculated by Ozawa theory are 231.7kJ·mol⁻¹ in air and 181.6kJ·mol⁻¹ in nitrogen; while the average apparent activation energy of isothermal degradation (Ē_iso) calculated by Flynn method are 144.0kJ·mol⁻¹ in air and 129.2kJ·mol⁻¹ in nitrogen, also suggesting that PLLA is easier to decompose in air than in nitrogen. Moreover, the decomposed products of PLLA are also investigated by using thermogravimetry-differential scanning calorimetry-mass spectrometry (TG-DSC-MS). In air atmosphere the volatilization products are more complex than those in nitrogen because the oxidation reaction occurring produces some oxides groups.