Hydrothermal ageing of polylactide/sisal biocomposites. Studies of water absorption behavior and physicochemical performance.

The performance of biocompositesof polyhydroxybutyrate-co-valerate (PHBV) and sisal fibre subjected to hydrothermal tests at different temperatures above the glass transition of PHBV (TH= 26, 36 and 46 ºC) 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 was assessed by Fourier-Transform Infrared Analysis, Size-Exclusion Chromatography, Differential Scanning Calorimetry and Scanning Electron Microscopy. It was found that the diffusion rate increased withboth 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 inherent to hydrolytical degradation, the physical performance was considerably affected, due to the swelling of fibres, which internally blow-up the PHBV matrix, provoking cracks and fibre detachment.

The influence of the combined exposure to water and temperature on the behaviour of polylactide/sisal biocomposites coupled with maleic acid anhydride was assessed through accelerated hydrothermal ageing. The biocomposites were immersed in water at temperatures from 65 to 85 ºC, between the glass transition and cold crystallisation of the PLA matrix. The results showed that the most influent factor for water absorption was the percentage of fibres, followed by the presence of coupling agent, whereas the effect of the temperature was not significant. Deep assessment was devoted to biocomposites subjected to hydrothermal ageing at 85 ºC, since it represents the extreme degrading condition. The morphology and crystallinity of the biocomposites were evaluated by means of X-Ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). The viscoelastic and thermal performance were assessed by means of dynamic-mechanical-thermal analysis (DMTA) and thermogravimetry (TGA). The presence of sisal generally diminished the thermal stability of the biocomposites, which was mitigated by the addition of the coupling agent. After composite preparation, the effectiveness of the sisal fibre was improved by the crystallisation of PLA around sisal, which increased the storage modulus and reduced the dampening factor. The presence of the coupling agent strengthened this effect. After hydrothermal ageing, crystallisation was promoted in all biocomposites therefore showing more fragile behaviour evidencing pores and cracks. However, the addition of coupling agent in the formulation of biocomposites contributed in all cases to minimise the effects of hydrothermal ageing.

The dielectric properties of virgin polylactide (PLA) and its reinforced composites with different weight amounts of sisal fibres were assessed at broad temperature (from-130ºC to 130ºC) and frequency ranges (from 10-2 to 10 7 Hz), before and after being subjected to accelerated hydrothermal ageing. The synergetic effects of both the loading of sisal and hydrothermal ageing were analysed by means of dielectric relaxation spectra. The relaxation time functions were evaluated by the Havriliak-Negami model, substracting the ohmic contribution of conductivity. The intramolecular and intermolecular relaxations were respectively analysed by means of Arrhenius and Vogel-Fulcher-Tammann-Hesse thermal activation models. The addition of fibre increased the number of hydrogen bonds, which incremented the dielectric permittivity and mainly hindered the non-cooperative relaxations of the biocomposites by increasing the activation energy. Hydrothermal ageing enhanced the formation of the crystalline phase at the so-called transcrystalline region along sisal. This fact hindered the movement of the amorphous PLA fraction, and consequently decreased the dielectric permittivity and increased the dynamic fragility.

The eco-design considers the factors to prepare biocomposites under an end-of-life scenario. PLA/sisal biocomposites were obtained from amorphous polylactide and sisal loadings of 10, 20 and 30 wt% with and without coupling agent, and subjected to biodegradation in soil according to standard ISO846. Mass-loss, differential scanning calorimetry and size-exclusion chromatography were used for monitoring biodegradation. A statistical factorial analysis based on the molar mass Mn and crystallinity degree XC pointed out the relevance and interaction of amount of fibre and use of coupling agent with the time of burial in soil. During the preparation of biocomposites, chain scission provoked a similar reduction of Mn for coupled and noncoupled biocomposites. The amount of fibre was relevant for the increase of XC due to the increase of nucleation sites. The coupling agent accelerated the evolution of both factors: reduction of Mn and the consequent increase of XC, mainly during biodegradation in soil. Both factors should be balanced to facilitate microbial assimilation of polymer segments, since bacterial digestion is enhanced by chain scission but blocked by the promotion of crystalline fractions.

Empty fruit bunch oil palm (EFBOP) fibres were surface modified by four different methods, propionylation, vinyltrimethoxy silanization, PPgMA dissolution modification, and PPgMA blending, and integrated into a polypropylene (PP) matrix. The designed biocomposites were subjected to an absorption process at different temperatures. Their water uptake behaviour was compared with the unmodified fibre biocomposites. An increased fibre content and temperature resulted in increased water uptake for all of the biocomposites. The biocomposites containing modified fibres showed a reduction in water uptake, rate of diffusion, sorption, and permeation in comparison with unmodified fibre composites. Comparing the 20 wt% fibre composites at ambient temperature, the performance in water absorption followed the sequence silanization < propionylation < PPgMA dissolution modification < PPgMA blending < no modification. Furthermore, the lowest water absorption was obtained from the silanized fibre/PP composite with 40% fibre content at ambient temperature. Dissolution or blending of PPgMA gave similar water uptake results. The reduction of diffusion, sorption, and permeation confirmed that the modification of fibres was potentially effective at resisting water penetration into the composites.

The decomposition behaviours of composites made of poly(3-hydroxybutyrate-co-3hydroxyvalerate) (PHBV) and sisal were assessed in terms of thermal stability and decomposition kinetics, under inert and oxidative conditions, by means of multi-rate linear non-isothermal thermogravimetric experiments. A Statistical Design of Experiments was applied to study the influence of the addition of sisal (0 %wt-30 %wt), the presence coupling agent (Yes/No) and the applied conditions of work (inert or oxidative). An improvement of the thermal and thermooxidative stability of PHBV with the addition of sisal was observed for all cases. An accurate methodology based on iso-conversional methods was applied to simulate the potential of thermal recovery technologies, such as pyrolysis and controlled combustion, to use these biocomposites after the end of their service life. The mathematical descriptions of both thermo-chemical reactions were helpful in the evaluation of the eventual optimal operational conditions to carry out a suitable energetic valorisation. A minimum of 240 °C and 137 kJ/mol of activation energy in inert conditions and 236 °C and 118 kJ/mol in oxidative conditions ensured the feasibility of the reactions regardless the composition of the PHBV/sisal biocomposites, which may ease the operability of further energy valorisation with the aim to turn biowaste into new fuels.

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