A Comparative Study on Crystallisation for Virgin and Recycled Polyethylene Terephthalate (PET): Multiscale Effects on Physico-Mechanical Properties.

Poly(Ethylene Terephthalate) (PET) is one of the most used polymers for packaging applications. Modifications induced by service conditions and the means to make this matter circular have to be understood to really close the loop (from bottle to bottle for example). Physico-chemical properties, crystalline organisation, and mechanical behaviour of virgin PET (vPET) are compared with those of recycled PET (rPET). Using different combined experimental methods (Calorimetry, Small Angle X-ray Scattering [SAXS], Atomic Force Microscopy [AFM], Dynamic Mechanical Analysis [DMA], and uniaxial tensile test), it has been proven that even if there is no change in the crystallinity of PET, the crystallisation process shows some differences (size and number of spherulites). The potential impact of these differences on local mechanical characterisation is explored and tends to demonstrate the development of a homogeneous microstructure, leading to well-controlled and relevant local mechanical property characterisation. The main contribution of the present study is a better understanding of crystallisation of PET and recycled PET during forming processes such as thermoforming or Injection Stretch Blow Moulding (ISBM), during which elongation at the point of breaking can depend on the microstructure conditioned by the crystallisation process.

Influence of Polymer Processing on the Double Electrical Percolation Threshold in PLA/PCL/GNP Nanocomposites.

For the first time, the double electrical percolation threshold was obtained in polylactide (PLA)/polycaprolactone (PCL)/graphene nanoplatelet (GNP) composite systems, prepared by compression moulding and fused filament fabrication (FFF). Using scanning electron microscopy (SEM) and atomic force microscopy (AFM), the localisation of the GNP, as well as the morphology of PLA and PCL phases, were evaluated and correlated with the electrical conductivity results estimated by the four-point probe method electrical measurements. The solvent extraction method was used to confirm and quantify the co-continuity in these samples. At 10 wt.% of the GNP, compression-moulded samples possessed a wide co-continuity range, varying from PLA55/PCL45 to PLA70/PCL30. The best electrical conductivity results were found for compression-moulded and 3D-printed PLA65/PCL35/GNP that have the fully co-continuous structure, based on the experimental and theoretical findings. This composite owns the highest storage modulus and complex viscosity at low angular frequency range, according to the melt shear rheology. Moreover, it exhibited the highest char formation and polymers degrees of crystallinity after the thermal investigation by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), respectively. The effect of the GNP content, compression moulding time, and multiple twin-screw extrusion blending steps on the co-continuity were also evaluated. The results showed that increasing the GNP content decreased the continuity of the polymer phases. Therefore, this work concluded that polymer processing methods impact the electrical percolation threshold and that the 3D printing of polymer composites entails higher electrical resistance as compared to compression moulding.

Characterization of Optimized Ternary PLA/PHB/Organoclay Composites Processed through Fused Filament Fabrication and Injection Molding.

The aim of this study was to investigate the structure-properties relationship of ternary blends of polylactide/polyhydroxybutyrate (PLA/PHB)/organo-modified layered silicate (OMLS). Morphological, thermal, rheological, and mechanical characterizations were performed to understand the influence of OMLS on PLA/PHB (70/30 wt%) formulations optimized through modifications with an epoxy-based chain extender, the use of a plasticizer, as well as the influence of the type of processing route: injection molding or fused filament fabrication. The addition of OMLS allowed the blend compatibility to be improved, with the appearance of a single melting peak on DSC thermograms at 146 °C, as well as the reduction in the size of the nodules for the injected molded specimens. Concerning the printed samples, AFM analysis revealed a coalescence of the PHB minor phase due to its degradation. This phenomenon was dramatically enhanced in the presence of OMLS and has been ascribed to the degradation of both the organo-modifier and the PHB minor phase in the blend. Rheological and mechanical tests (17% decrease in Young's modulus and 13% decrease in elongation at break) confirmed this degradation that would have occurred during the manufacturing of the filaments and the printing of specimens due to additional thermal and cooling steps.

Fire Behavior of Polyamide 12/Rubber Formulations Made by Laser Sintering.

In the present work, the processability and fire behavior of parts made by the laser sintering (LS) of polyamide 12/rubber powder blends is studied. In order to evaluate some of the interactions that could take place during LS, three acrylonitrile butadiene rubbers (NBRs) were used, which included two that had different acrylonitrile (AN) contents, and one that had carboxylated rubber. The results show that the flowability of the powders is strongly dependent on the rubber used. For the carboxylated rubber, a good flowability of the blend was observed, whereas the use of rubbers with different AN contents led to significant changes in the powder flowability, with a heterogeneous powder bed, and differences in the porosity as a function of the AN content. Furthermore, the addition of rubbers to polyamide 12 (PA12) entails an increase in the sintering window and, in particular, a change in the melting temperature of PA12 is noticed. Even though some changes in the crystallization and melting temperatures are observed, formulations containing 10 and 20 wt.% of rubbers could be processed using the same process parameters as PA12. Furthermore, the formulations containing carboxylated rubber show improved fire behavior, which is measured by a cone calorimeter, with reductions of about 45 and 65% in the peak of the heat release rate, compared to the PA12. Moreover, almost all of the samples evaluated in this study are classed as "Good" by the Flame Retardancy Index. This result can be partially explained by the formation of an amide linkage between the polyamide and NBR during processing, which could result in increases in the melt viscosities of these samples.

Fabrication of PLA/PCL/Graphene Nanoplatelet (GNP) Electrically Conductive Circuit Using the Fused Filament Fabrication (FFF) 3D Printing Technique.

For the purpose of fabricating electrically conductive composites via the fused filament fabrication (FFF) technique whose properties were compared with injection-moulded properties, poly(lactic acid) (PLA) and polycaprolactone (PCL) were mixed with different contents of graphene nanoplatelets (GNP). The wettability, morphological, rheological, thermal, mechanical, and electrical properties of the 3D-printed samples were investigated. The microstructural images showed the selective localization of the GNPs in the PCL nodules that are dispersed in the PLA phase. The electrical resistivity results using the four-probes method revealed that the injection-moulded samples are insulators, whereas the 3D-printed samples featuring the same graphene content are semiconductors. Varying the printing raster angles also exerted an influence on the electrical conductivity results. The electrical percolation threshold was found to be lower than 15 wt.%, whereas the rheological percolation threshold was found to be lower than 10 wt.%. Furthermore, the 20 wt.% and 25 wt.% GNP composites were able to connect an electrical circuit. An increase in the Young's modulus was shown with the percentage of graphene. As a result, this work exhibited the potential of the FFF technique to fabricate biodegradable electrically conductive PLA-PCL-GNP composites that can be applicable in the electronic domain.

Peculiar Morphologies Obtained for 80/20 PLA/PA11 Blend with Small Amounts of Fumed Silica.

This work highlights the possibility of obtaining peculiar morphologies by adding fumed silica into 80/20 polylactic acid/polyamide11 (PLA/PA11) blends. Two kinds of fumed silica (A200 and trimethoxyoctylsilane modified R805 fumed silica) were dispersed (by twin-screw extrusion, TSE) at a weight amount of 5% in neat PLA, neat PA11 and a 80/20 PLA/PA11 blend. Thermal Gravimetric Analysis (TGA) was used to verify this 5 wt % amount. Oscillatory shear rheology tests were conducted on all the formulations: (1) on neat polymer nanocomposites (PLASi5, PLASiR5, PA11Si5, PA11SiR5); and (2) on polymer blend nanocomposites (PLA80Si5 and PLA80SiR5). Scanning Electron Microscope (SEM), Scanning Transmission Electron Microscope (STEM), Atomic Force Microscopy (AFM) characterizations and laser granulometry were conducted. Microscopic analysis performed on polymer blend nanocomposites evidenced a localization of A200 silica in the PA11 dispersed phase and R805 silica at the PLA/PA11 interface. Frequency sweep tests on neat polymer nanocomposites revealed a pronounced gel-like behavior for PLASi5 and PA11SiR5, evidencing a high dispersion of A200 in PLA and R805 in PA11. A yield behavior was also evidenced for both PLA80Si5 and PLA80SiR5 blends. For the blend nanocomposites, PA11 dispersed phases were elongated in the presence of A200 silica and a quasi-co-continuous morphology was observed for PLA80Si5, whereas PLA80SiR5 exhibits bridges of silica nanoparticles between the PA11 dispersed phases.

Hierarchical thermoplastic biocomposites reinforced with flax fibres modified by xyloglucan and cellulose nanocrystals.

This work is focused on the modification of the interphase zone in short flax fibres / polypropylene (PP) composites by a bio-inspired modification of fibres called "nanostructuration" that uses the adsorption of biomass by-products, i.e. cellulose nanocrystals (CNC) and xyloglucan (XG), to create hierarchical flax fibres. The wettability and interfacial adhesion study reveals a strong decrease in the polar character of CNC modified flax fibres, hence increasing the work of adhesion with PP. Moreover, combining XG/CNC modified interphases with MAPP coupling agent enhances the ultimate mechanical properties of biocomposites with higher tensile strength and work of rupture, and modifies failure mechanisms as revealed by in situ micro-mechanical tensile SEM experiments. Bio-based hierarchical composites inspired by naturally occurring nanostructures open a new path for the development of sustainable composites with enhanced structural properties.

Influence of Sepiolite and Lignin as Potential Synergists on Flame Retardant Systems in Polylactide (PLA) and Polyurethane Elastomer (PUE).

A comparison of the influence of sepiolite and lignin as potential synergists for fire retardant (FR) systems based on ammonium polyphosphate (APP) has been carried out in polyurethane elastomer and polylactide. Different ratios of kraft lignin and sepiolite were tested in combination with APP in both polymers. The thermal stability and the fire behavior of the corresponding composites were evaluated using Thermogravimetric Analysis (TGA), a Pyrolysis Combustion Flow Calorimeter (PCFC) and Cone Calorimeter (CC). The mechanisms of flame retardancy imparted by APP and other components were investigated. Synergistic effects were highlighted but only for specific ratios between APP and sepiolite in polyurethane elastomer (PUE) and polylactide (PLA) on one hand, and between APP and lignin in PLA on the other hand. Sepiolite acts as char reinforcement but through the formation of new phosphorus compounds it is also able to form a protective layer. Conversely, only complementary effects on fire performance were noted for lignin in PUE due to a dramatic influence on thermal stability despite its action on char formation.

Wicking Tests for Unidirectional Fabrics: Measurements of Capillary Parameters to Evaluate Capillary Pressure in Liquid Composite Molding Processes.

During impregnation of a fibrous reinforcement in liquid composite molding (LCM) processes, capillary effects have to be understood in order to identify their influence on void formation in composite parts. Wicking in a fibrous medium described by the Washburn equation was considered equivalent to a flow under the effect of capillary pressure according to the Darcy law. Experimental tests for the characterization of wicking were conducted with both carbon and flax fiber reinforcement. Quasi-unidirectional fabrics were then tested by means of a tensiometer to determine the morphological and wetting parameters along the fiber direction. The procedure was shown to be promising when the morphology of the fabric is unchanged during capillary wicking. In the case of carbon fabrics, the capillary pressure can be calculated. Flax fibers are sensitive to moisture sorption and swell in water. This phenomenon has to be taken into account to assess the wetting parameters. In order to make fibers less sensitive to water sorption, a thermal treatment was carried out on flax reinforcements. This treatment enhances fiber morphological stability and prevents swelling in water. It was shown that treated fabrics have a linear wicking trend similar to those found in carbon fabrics, allowing for the determination of capillary pressure.