A kinetic study of the formation of smectic phases in novel liquid crystal ionogens
[EN] 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 o…
Water absorption and hydrothermal performance of PHBV/sisal biocomposites
[EN] 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 d…
Hygrothermal ageing of reprocessed polylactide
[EN] 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 rearra…
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…
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 th…
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 …
Hydrothermal ageing of polylactide/sisal biocomposites. Studies of water absorption behaviour and Physico-Chemical performance
An accelerated hydrothermal degrading test was designed in order to analyse the synergic effect of water and temperature on PLA/sisal biocomposites with and without coupling agent. As well, the physicochemical properties of biocomposites were monitored along the hydrothermal test by means of Scanning Electron Microscopy, Size Exclusion Chromatography and Differential Scanning Calorimetry. The addition of fibre induced higher water absorption capability and promoted physical degradation, as observed in the surface topography. During the processing of biocomposites and throughout the hydrothermal ageing, a reduction of molecular weight due to chain scission was found. As a consequence, a fast…