Thermal analysis applied to the characterization of degradation in soil of polylactide: II. On the thermal stability and thermal decomposition kinetics

The disposal stage of polylactide (PLA) was assessed by burying it in active soil following an international standard. Degradation in soil promotes physical and chemical changes in the polylactide properties. The characterization of the extent of degradation underwent by PLA was carried out by using Thermal Analysis techniques. In this paper, studies on the thermal stability and the thermal decomposition kinetics were performed in order to assess the degradation process of a commercial PLA submitted to an accelerated soil burial test by means of multi-linear-non-isothermal thermogravimetric analyses. Results have been correlated to changes in molecular weight, showing the same evolution as that described by the parameters of thermal stability temperatures and apparent activation energies. The decomposition reactions can be described by two competitive different mechanisms: Nucleation model (A2) and Reaction Contracting Volume model (R3). The changes in the kinetic parameters and kinetic models are in agreement with the calorimetric and dynamic-mechanical-thermal results, presented in the Part I of the study

Thermal analysis applied to the characterization of degradation in soil of polylactide: I. Calorimetric and viscoelastic analyses

An accelerated soil burial test has been performed on a commercial polylactide (PLA) for simulating non-controlled disposal. Degradation in soil promotes physical and chemical changes in polylactide properties, which can be characterized by Thermal Analysis techniques. Physical changes occurred in polylactide due to the degradation in soil were evaluated by correlating their calorimetric and viscoelastic properties. It is highly remarkable that each calorimetric scan offers specific and enlightening information. Degradation in soil affects the polylactide chains reorganization. A multimodal melting behavior is observed for buried PLA, degradation in soil also promotes the enlarging the lamellar thickness distribution of the population with bigger average size. Morphological changes due to degradation in soil lead to an increase in the free volume of the polylactide chains in the amorphous phase that highly affected the bulk properties. Thermal Analysis techniques provide reliable indicators of the degradation stage of polylactide induced by degradation in soil, as corroborated by molecular weight analysis

Thermal and thermo-oxidative stability of reprocessed poly(ethylene terephthalate)

An exhaustive assessment of the behaviour of virgin and mechanically reprocessed poly(ethylene terephthalate) (PET) facing thermal and thermo-oxidative decomposition processes is presented in this work, as an approach for the energetic valorisation of post-consumer PET goods. Multi-rate linear-non-isothermal thermogravimetric (TGA) experiments under inert (Ar) and reactive (O2) conditions were performed to virgin PET and its recyclates in order to simulate the thermal behaviour of the materials facing pyrolysis and combustion processes. The release of gases was monitored by evolved gas analysis of the fumes of the TGA experiment, by in-line Fourier-transform infrared (IR) analysis, with the aid of 2D-correlation IR characterisation. A kinetic analysis methodology, consisting in the combination of six different methods (namely Flynn-Wall-Ozawa, Kissinger-Akahira-Sunose, Vyazovkin, Master-Curves and Perez-Maqueda criterion along with Coats-Redfern equation) was applied. Its validity for being used for both constant and variable kinetic parameters was discussed. The kinetic model that described both thermal and thermo-oxidative decompositions of PET and its recyclates was of the type An: nucleation and growth of gas bubbles in the melt. Novel parameters and functions were proposed to characterise the thermal stability along the reprocessing cycles, as well as the variation of the activation energy and the pre-exponential factor during thermal and thermo-oxidative decompositions. The reliability of a simplified kinetic triplet with constant activation parameters was suitable only under thermal decomposition. The usability of PET after reprocessing showed a threshold in the thermal performance from the second recyclate on. During thermal and thermo-oxidative processes, reprocessed PET behaved similarly to virgin PET, and thus current energetic valorisation technologies could be assimilable for all materials

Hygrothermal ageing of reprocessed polylactide

The influence of an accelerated hygrothermal ageing simulation test on a commercial PLA and its three subsequent mechanically-reprocessed materials was studied. The analysis was focused on the water diffusion kinetics and the physico-chemical changes induced by the hygrothermal degradation. Water diffusion proceeded faster than chain relaxation processes, as defined by a Case II absorption model. It was proved that the water diffusion rate decreased with subsequent reprocessing cycles and increased with higher hygrothermal ageing temperatures. Hydrolytic chain scission provoked significant molar mass decays and consequent general losses of thermal and mechanical performance. The rearrangement into crystalline fractions of shorter chains provoked by hygrothermal ageing was qualitatively and quantitatively followed by both Fourier-Transform Infrared Spectroscopy and Differential Scanning Calorimetry. The microstructural changes were monitored by the cold-crystallization temperature, the crystallinity degree XC and the absorbance intensity ratio I921/I955. A Weibull model showed that the crystallites were formed faster at higher reprocessing cycles and at lower hygrothermal ageing temperatures. All these effects were particularly significant for PLA reprocessed more than one time

Water absorption and hydrothermal performance of PHBV/sisal biocomposites

The performance of biocomposites of poly(hydroxybutyrate-co-valerate) (PHBV) and sisal fibre subjected to hydrothermal tests at different temperatures above the glass transition of PHBV (TH = 26, 36 and 46 °C) was evaluated in this study. The influences of both the fibre content and presence of coupling agent were focused. The water absorption capability and water diffusion rate were considered for a statistical factorial analysis. Afterwards, the physico-chemical properties of water-saturated biocomposites were assessed by Fourier-Transform Infrared Analysis, Size Exclusion Chromatography, Differential Scanning Calorimetry and Scanning Electron Microscopy. It was found that the water diffusion rate increased with both temperature and percentage of fibre, whereas the amount of absorbed water was only influenced by fibre content. The use of coupling agent was only relevant at the initial stages of the hydrothermal test, giving an increase in the diffusion rate. Although the chemical structure and thermal properties of water-saturated biocomposites remained practically intact, the physical performance was considerably affected, due to the swelling of fibres, which internally blew-up the PHBV matrix, provoking cracks and fibre detachment

A kinetic study of the formation of smectic phases in novel liquid crystal ionogens

A multi-rate non-isothermal kinetic analysis of the isotropic-melt to liquid crystalline phase transition of novel liquid crystalline ionogenic copolymers, LCIs, the 10-(4-methoxyazobenzene-4′-oxy)decyl methacrylate]-co-2-(acrylamido-2-methyl-1-propanesulfonic acid)s, 10-MeOAzB/AMPS, copolymers, has been performed by means of calorimetric experiments. An analytical methodology which includes the study of the phase transition rate parameter, the determination of the activation energies by using Kissinger and Flynn-Wall-Ozawa models, and the study of the phase transition kinetics by the use of the Avrami theory, has been applied. The formation of the mesophases from the isotropic state occurred close to thermodynamic equilibrium. The results evidence the presence of several individual processes in the formation of liquid crystalline phases from the melt and a strong dependence of phase transition rates and activation energies with acid contents. A decrease in the phase transition rate, related to a decrease in the overall change of the transition entropy, has been observed. The final inhibition of the liquid crystal (LC) behaviour is ascribed to an exponential increase in the activation energy of the phase transition, promoted by strong acid aggregation. An optimum composition of the 10-MeOAzB/AMPS copolymers to achieve the dual characteristics of LCIs (ionogenic and liquid crystalline behaviour) requires acid concentrations capable of promoting structure-forming effects on the LC phases and the evolution of phase separated morphologies

Reprocessed polylactide: Studies of thermo-oxidative decomposition

The combustion process of virgin and reprocessed polylactide (PLA) was simulated by multi-rate linear non-isothermal thermogravimetric experiments under O2. A complete methodology that accounted on the thermal stability and emission of gases was thoroughly developed. A new model, Thermal Decomposition Behavior, and novel parameters, the Zero-Decomposition Temperatures, were used to test the thermal stability of the materials under any linear heating rate. The release of gases was monitored by Evolved Gas Analysis with in-line FT-IR analysis. In addition, a kinetic analysis methodology that accounted for variable activation parameters showed that the decomposition process could be driven by the formation of bubbles in the melt. It was found that the combustion technologies for virgin PLA could be transferred for the energetic valorization of its recyclates. Combustion was pointed out as appropriate for the energetic valorization of PLA submitted to more than three successive reprocessing cycles

A methodology to assess the energetic valorization of bio-based polymers from the packaging industry: Pyrolysis of reprocessed polylactide

The energetic valorization process of bio-based polymers is addressed in this study, taking polylactide (PLA) as model. The pyrolysis of virgin and multiple-injected PLA was simulated by means of multi-rate linear-non-isothermal thermogravimetric experiments. A complete methodology, involving control of gases, thermal stability and thermal decomposition kinetics was proposed. The release of gases was monitored by Evolved Gas Analysis of the fumes of pyrolysis, by in-line FT-IR, with the aid of 2D-correlation IR characterization. A novel model to establish the thermal stability of PLAs under any linear heating profile was proposed. A kinetic strategy was methodically applied to assess the thermal decomposition in terms of activation energy and kinetic model. It was found that the pyrolysis technologies for virgin PLA could be straightforwardly transferred for the valorization of its recyclates

Dielectric spectroscopy of recycled polylactide

The effects of multiple mechanical recycling on amorphous polylactide (PLA) were simulated by means of five successive injection-grinding cycles. The influence of the induced thermo-mechanical degradation on the dielectric properties of PLA was analysed. The relaxation spectra were studied in terms of the complex dielectric permittivity (ε0 and ε00) and the dielectric loss tangent, tg(d) in the frequency range from 102 to 107 Hz over the temperature interval from 0 C to 140 C. It was possible to distinguish two relaxations zones, one at low temperatures and high frequencies (b relaxation) and another at higher temperatures and lower frequencies (a relaxation). The individual relaxations were characterised using the HavriliakeNegami model and the effect of conductivity at high temperatures was subtracted. The thermal activation of the b relaxations was explained on an Arrhenius model basis while the a relaxation was modelled using VogeleFulchereTammanneHesse (VFTH) equations. The study of the segmental dynamics showed a decrease in the fragility parameters, connected with the decrease of molar mass, along with an increase in the free volume, the higher the number of reprocessing cycles were applied, particularly up to the second reprocessing step. 2014 Elsevier Ltd. All rights reserved.The authors would like to acknowledge the Spanish Ministry of Economy and Competitiveness, through the Research Project ENE2011-28735-C02-01. The Vice-Rectorate for Research, Innovation and Technology Transfer of Universitat Politecnica de Valencia is also thanked for additional support through PAID-06-SP20120581 project.Badía Valiente, JD.; Monreal Mengual, L.; Sáenz De Juano Arbona, V.; Ribes Greus, MD. (2014). Dielectric spectroscopy of recycled polylactide. Polymer Degradation and Stability. 107:21-27. https://doi.org/10.1016/j.polymdegradstab.2014.04.023S212710