A. Martínez-Felipe

Liquid crystal polymers and ionomers for membrane applications

Transport phenomena through polymeric composite membranes depend on several complex factors, involving not only their chemical composition but also their microstructure. Due to the combination of mesomorphic and macromolecular behaviour, thermotropic liquid crystal polymers (LCP) may enhance the transport properties in membranes by improving parameters related to the order, orientation, connectivity and distribution of the different domains arising from phase separation. This paper provides an overview of some existing and potential applications of liquid crystals (LC) in polymeric membranes as effective structure-directing templates or as components providing a dynamic response to external stimuli. The first part is a description of the composition and phase behaviour of LCP containing ionic and ionogenic groups, the so-called liquid crystal ionomers (LCI). The second part is focused on the description of LCP and LCI used in transport applications, such as proton-conducting films in fuel cells, ionic polymer transducers and hydrogels. The paper highlights the relationships between the composition and the LC properties of the materials and their potential as membranes for ionic and solvent transport, with particular attention paid to covalently linked materials prepared by copolymerisation, due to their higher versatility and stability.

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.

New insights into the transitional behaviour of methyl-6-O-(n-dodecanoyl)-α-D-glucopyranoside using variable temperature FTIR spectroscopy and X-ray diffraction

The liquid crystalline behaviour of methyl-6-O-(n-dodecanoyl)-α-D-glucopyranoside, 1, has been characterised using X-ray diffraction and variable temperature Fourier transform infrared (FTIR spectroscopy). 1 exhibits a monotropic interdigitated smectic A phase consisting of bilayers in which the alkyl chains are overlapped. The crystal–isotropic transition is accompanied by a pronounced decrease in the strength of the hydrogen bonding network involving the sugar groups resulting in a marked change in the environment of the alkyl chains. The isotropic phase consists of disordered smectic-like domains stabilised via hydrogen bonding between the sugar groups. At the transition to the smectic A phase, a subtle change in hydrogen bonding is observed which is manifested by a change in the temperature dependence of the OH stretching peak position in the FTIR spectrum. On crystallisation, the strong hydrogen bonding network is re-established accompanied by a change in the conformational distribution of the alkyl chains. A model is proposed in which a combination of hydrogen bonding (enthalpic effects) and conformational arrangements (entropic effects) promotes initially the formation of smectic-like domains in the isotropic phase and subsequently stabilises the smectic A phase by inhibiting the microphase separation leading to the crystal phase.

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 O(2). 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.