Development of a novel pyrolysis-gas chromatography/mass spectrometry method for the analysis of poly(lactic acid) thermal degradation products

Thermal degradation of PLA is a complex process since it comprises many simultaneous reactions. The use of analytical techniques, such as differential scanning calorimetry (DSC) and thermogravimetry (TGA), yields useful information but a more sensitive analytical technique would be necessary to identify and quantify the PLA degradation products. In this work the thermal degradation of PLA at high temperatures was studied by using a pyrolyzer coupled to a gas chromatograph with mass spectrometry detection (Py-GC/MS). Pyrolysis conditions (temperature and time) were optimized in order to obtain an adequate chromatographic separation of the compounds formed during heating. The best resolution of chromatographic peaks was obtained by pyrolyzing the material from room temperature to 600 °C during 0.5 s. These conditions allowed identifying and quantifying the major compounds produced during the PLA thermal degradation in inert atmosphere. The strategy followed to select these operation parameters was by using sequential pyrolysis based on the adaptation of mathematical models. By application of this strategy it was demonstrated that PLA is degraded at high temperatures by following a non-linear behaviour. The application of logistic and Boltzmann models leads to good fittings to the experimental results, despite the Boltzmann model provided the best approach to calculate the time at which 50% of PLA was degraded. In conclusion, the Boltzmann method can be applied as a tool for simulating the PLA thermal degradation.

Impedance spectroscopy study of the effect of environmental conditions in the microstructure development of OPC and slag cement mortars

In this work, the microstructure of mortars made with an ordinary Portland cement and slag cement has been studied. These mortars were exposed to four different constant temperature and relative humidity environments during a 180-day period. The microstructure has been studied using impedance spectroscopy, and mercury intrusion porosimetry as a contrast technique. The impedance spectroscopy parameters make it possible to analyze the evolution of the solid fraction formation for the studied mortars and their results are confirmed with those obtained using mercury intrusion porosimetry. The development of the pore network of mortars is affected by the environment. However, slag cement mortars are more influenced by temperature while the relative humidity has a greater influence on the OPC mortars. The results show that slag cement mortars hardened under non-optimal environments have a more refined microstructure than OPC mortars for the studied environmental conditions.