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The structure and properties of blends of a novel polyethylene terephthalate copolymer (COPET) obtained by chemical recycling of commercial PET with high-molar-mass poly-L-lactide (PLLA) are investigated and compared to corresponding composites with chopped flax fibres. The focus is on the morphology at nano- and micro-scales, on the thermal characteristics and on the mechanical behaviour. The blends are immiscible, as evidenced by virtually unchanged glass transition temperatures of the blend components compared to the neat polymers (49 °C for COPET and 63 °C for PLLA by DSC). At low PLLA content, the blends display a sea–island morphology with sub-micron to micron droplet sizes. As the composition approaches 50/50, the morphology transitions to a coarser co-continuous elongated structure. The blends and composites show strongly improved stiffness compared to COPET above its glass transition temperature, e.g., from melt behaviour at 60 °C for COPET alone to almost 600 MPa for the 50/50 blend and 500 MPa for the 20% flax composite of the 80/20 COPET/PLLA blend. The flax fibres increase the crystallisation rate of PLLA in blends with dispersed PLLA morphology. The evidence of cavitation on the fracture surfaces of blends shows that despite the immiscibility of the components, the interfacial adhesion between the phases is excellent. This is attributed to the presence of aliphatic ester spacers in COPET. The tensile strength of the 80/20 blend is around 50 MPa with a Young’s modulus of 2250 MPa. The corresponding 20% flax composite has similar tensile strength but a high Young’s modulus equal to 6400 MPa, which results from the individual dispersion and strong adhesion of the flax fibres and leads close to the maximum possible reinforcement of the composite, as demonstrated by tensile tests and nano-indentation. The Ashby approach to eco-selection relying on the embodied energy (EE) further clarifies the eco-friendliness of the blends and their composites, which are even better positioned than PLLA in a stiffness versus EE chart.

A major societal issue of disposal and environmental pollution is raised by the enormous and fast-growing production of single-use polyethylene terephthalate (PET) bottles, especially in developing countries. To contribute to the problem solution, an original route to recycle PET in the form of value-added environmentally friendly thermoplastic composites with banana fibres (Musa acuminata) has been developed at the laboratory scale. Banana fibres are a so far undervalued by-product of banana crops with great potential as polymer reinforcement. The melt-processing constraints of commercial PET, including used bottles, being incompatible with the thermal stability limits use of natural fibres; PET has been modified with bio-sourced reactants to produce co-polymers with moderate processing temperatures below 200 °C. First, commercial PET were partially glycolyzed with 1.3-propanediol to produce co-oligomers of about 20 repeating units, which were next chain extended with succinic anhydride and post-treated in a very unusual “soft solid state” process at temperatures in the vicinity of the melting point to generate co-polymers with excellent ductility. The molar mass build-up reaction is dominated by esterification of the chain ends and benefits from the addition of succinic anhydride to rebalance the acid-to-hydroxyl end-group ratio. Infra-red spectroscopy and intrinsic viscosity were extensively used to quantify the concentration of chain ends and the average molar mass of the co-polymers at all stages of the process. The best co-polymers are crystallisable, though at slow kinetics, with a Tg of 48 °C and a melting point strongly dependent upon thermal history. The composites show high stiffness (4.8 GPa at 20% fibres), consistent with the excellent dispersion of the fibres and a very high interfacial cohesion. The strong adhesion can be tentatively explained by covalent bonding involving unreacted succinic anhydride in excess during solid stating. A first approach to quantify the sustainable benefits of this PET recycling route, based on a rational eco-selection method, gives promising results since the composites come close to low-end wood materials in terms of the stiffness/embodied energy balance. Moreover, this approach can easily be extended to many other natural fibres. The present study is limited to a proof of concept at the laboratory scale but is encouraging enough to warrant a follow-up study toward scale-up and application development.

An original wet recycling method is developed for large carbon-fibers reinforced-polymers composite panels, addressed through a proof-of-concept fabrication of a new composite part based on recycled fibers. The recycling process relies on formic acid as separation reagent at room temperature and under atmospheric pressure conditions. Electron microscopy and thermal analysis indicate that the recycled fibers are covered by a thin layer of about 10wt.% of residual resin, alternating with few small particles, as compared to the virgin fibers exhibiting a smooth surface. The mechanical properties of composites based on neat and recycled fibers are determined from interlaminar shear strength, compression, compression after impact and Iosipescu shear tests. The recycled composites show promising shear and strength values with a deterioration of performances limited to about 10 to 33% depending on the property as compared to the reference. The recycled carbon fibers can thus be reused for structural applications requiring moderate to high performances. The loss of properties is attributed to a lower adhesion between fresh epoxy resin and recycled carbon fibers having lost their sizing, partly compensated by a good interface between fresh and residual cured epoxy thanks to mechanical anchoring as well as chemical reactions.

Poly l-Lactide (PLLA) composites with short flax fibers (from 0 to 10 wt/wt%)with close to maximum theoretical stiffness are prepared by melt-compounding and injection-molding followed by a two-step isothermal crystallization protocol that fully separates the nucleation and growth stages (Tammann). The use of fast chip scanning calorimetry for thermal characterization avoids the complicating issues of crystal reorganization during the cooling and heating steps between the isothermal stages. Flax fibers are very efficient and selective nucleating agents of PLLA favoring the ordered 𝜶 form. The resulting morphology exhibits trans-crystallization on the fibers surface, predominantly at fiber defects, with a clear reduction of crystal size and a very strong fiber matrix cohesion. Efficient nucleation further leads to a large reduction of the overall crystallization time. Avrami analysis evidences a reduction of crystal growth dimensionality, consistent with both optical and scanning electron microscopy. The high modulus of the composites is unambiguously related to the strong orientation of the fibers in the tensile direction, to their high aspect ratio and to the excellent matrix-fibers cohesion. On the other hand, the tensile strength and hardness appear isotropic within experimental uncertainty and are unfavorably influenced by the presence of the fibers and by the two-stage annealing.

A remarkable synergistic increase in fracture toughness by 130% is demonstrated for a CFRP high performance epoxy composite when adding an equal weight combination of phenoxy thermoplastic and core-shell rubber (CSR) toughening agents, as compared to a single toughener at a comparable total concentration of around 10 wt%. The dual-toughened matrix exhibits an unusual morphological arrangement of the two toughener agents. The interlaminar shear strength of the composites is also synergistically improved by about 75% as compared to the reference while the compression modulus reduction and viscosity increase are significantly smaller than for the single phenoxy toughened system. A partial filtering of the CSR particles by the dense CF fabric during pre-pregging leads to a less than optimum CSR dispersion in the composites, showing that the synergy can be further optimized, possibly to the same level as the unreinforced systems.

The hybrid assembling of thermoplastics with thermosets through controlled interdiffusion is an attractive approach towards integrated structural composite bonding. The fracture toughness of the interphase between the high Tg thermoplastic polyetherimide and the RTM6 epoxy is found to be four times higher than the corresponding RTM6 value under specific curing cycle. The origin of this remarkable cracking resistance is elucidated by analyzing the crack path in relationship with the morphology and local elastoplastic and fracture properties of the interphase. The crack is trapped inside a morphological gradient involving a relatively low PEI concentration. Uniaxial compression and nanoindentation tests on homogenous blends exhibit an unexpected softening in this PEI content window. This efficient crack trapping mechanism originates thus from a synergistic coupling between a lower local strength and higher local fracture toughness. This finding opens to many new options for interface toughening beyond the system addressed in this research.

A new block copolymer-thermoplastic dual toughening concept for high performance RTM6 epoxy matrix composites is elaborated through a comprehensive microstructural study of well-defined model systems. A blend of phenoxy and MAM (copolymer of poly(methyl methacrylate) and poly(butyl acrylate)) increases the toughness of the corresponding carbon fiber reinforced composite by 125%, a five-fold synergistic improvement over the situation where the tougheners are used alone at the same total concentration. Selective intercalation of blended toughener thin films in the preform gives rise to a diffusion-induced composition gradient during the RTM process, which generates a morphology gradient upon curing. The observed microstructures results from MAM self-assembly in the miscible mixture of phenoxy and the epoxy resin precursor, followed by reaction induced phase separation, forming wormlike micelles, interconnected micelles and co-continuous morphologies. The resulting microstructures activate different toughening mechanisms responsible for the observed synergy.

The mechanical properties of an unmodified reference composite panel based on a highly crosslinked epoxy resin are compared with several corresponding toughened versions, all containing the same amount of representative hard or soft tougheners. The panels are prepared and tested under identical conditions. In terms of tougheners, soft MAM block copolymers and CTBN rubber are compared with two high glass transition temperature (Tg) amorphous thermoplastics, PES and phenoxy. The high Tg thermoplastic tougheners yield considerable improvements of the composites mechanical properties, especially the interlaminar fracture toughness, as compared to the reference panel. On the contrary, MAM and CTBN modification are much less effective. The analysis of the morphology strongly suggests that effective toughening of composite panels based on densely crosslinked epoxy resins requires the combination of at least two key factors: (i) a fine dispersion of the toughener and (ii) strong matrix-toughener and matrix-carbon fibers interfaces. The study provides valuable insights for the choice of suitable tougheners for high performance epoxy systems, based on the link with the physical toughening mechanisms.

The aim of this work is to encapsulate a self-healing photo-polymerisable material for aerospace applications. To meet the technical requirements of space applications - low and high temperatures: -120 °C (dark side) to +250 °C (solar side); UV radiations: 200-400 nm; low pressure: 10(-4 )Pa - we chose trimethylolpropane triacrylate as healing agent. This monomer polymerises at 190 °C. To avoid its earlier thermal polymerisation, an inhibitor was added to the monomer/photo-initiator formulation. Moreover, among several microencapsulation techniques tested, we chose the sol-gel process to form silica microcapsules containing the self-healing formulation. These microcapsules were characterised by different analysis (scanning electron microscopy (SEM), thermo gravimetric analysis (TGA), Fourier transform infra-red spectroscopy (FTIR), etc.) and satisfied our requirements (size 1-30 μm, thermal stability >250 °C). After the microcapsules breakage, the generation of poly(TMPTA) film by radical photopolymerisation of the released TMPTA monomer was proved by disappearance of the IR peak at 1635 cm(-1) (assigned to TMPTA). The obtained film has a thermal stability above 300 °C.

The specific influence of polyethersulfone (PES) endfunctionalization with chlorine or hydroxyl end groups at same molar mass on PES-epoxy composites based on a high-performance tetra-epoxide with di-amine hardener resin (RTM6) is investigated in terms of morphology,thermal behavior, and toughness. A model study on PES filaments embedded in epoxy precursor is first performed to compare the interdiffusion and resulting morphology upon curing. PES-OH shows a larger interdiffusion distance compared to PES-Cl in the model systems and the laminates. This effect is more pronounced at high heating rate. Cross sections and fracture surfaces of composite panels are analyzed by scanning electron microscopy (SEM) coupled with energy dispersive X-ray (EDX) spectroscopy to establish the link between the microstructures and fracture mechanisms. The toughness of PES-OH-modified epoxy composites is doubled compared to unmodified reference panels, whereas the PES-Cl shows no improvement. The favorable influence of PES-OH is ascribed to enhanced miscibility, interfacial adhesion and morphology, resulting from the better affinity between hydroxyl-terminated PES and the epoxy-resin.

The use of phenoxy nanocomposite films as carriers of nanofillers involving multiwalled carbon nanotubes and nanoclays is successfully demonstrated for application in epoxy carbon fibers reinforced composites (CFRC) processed by RTM. Model studies on individual nanocomposite filaments embedded in epoxy precursors show that the nanofillers are passively transported by the interdiffusion gradient during heating over distance around 800 lm. A morphology gradient is generated after reaction induced phase separation and the nanofillers end up in the epoxy, despite their initial dispersion in the phenoxy. The proof of concept is extended to CFRC panels where nanocomposite phenoxy films are prepositioned between every odd carbon layer of the preform. Carbon nanotubes are filtered by the carbon fabrics, which limits their full diffusion and that of phenoxy through the preform. This has negative consequences on fracture toughness (GIc). For nanoclay, GIc is rather slightly improved although the origin is not fully clear.

We explore the influence of the interdiffusion of two thermoplastic tougheners and RTM6 epoxy resin precursors on the resulting morphologies after curing and the consequences on delamination toughness of the corresponding carbon fiber reinforced composites. Two thermoplastics with contrasting Tg and compatibility, i.e. poly(ether sulfone) (PES) and phenoxy are compared. The dramatic improvement of the interlaminar fracture toughness (GIC) found for the phenoxy-RTM6 system as compared to the pure thermoset reference can be ascribed to the broad morphology gradient only observed for that system. By contrast, the PES-RTM6 system is characterized by a steep morphology gradient and a corresponding decrease of as compared to the reference.

The interdiffusion between a low and a high viscosity epoxy resin was studied on model systems representing the novel composite manufacturing process called “Same Qualified-Resin Transfer Molding” (SQ-RTM). Neat resin model systems were first characterized after curing by Raman spectroscopy, energy dispersive X-ray microscopy, and nano-indentation, all methods reveal an interdiffusion distance of about 700–900 µm. Transmission electron microscopy further revealed a complex morphological gradient structure in the interdiffusion zone. The interdiffusion distance was about 800 µm in the absence of carbon fibers, reducing down to 500 µm when the viscous resin was replaced by the corresponding prepreg, due to the geometrical constraints imposed by the fibers. Moreover, some asymmetry was observed in the interdiffusion profile because of the viscosity difference between the resins. The results obtained on the model systems were found to match very well the interdiffusion profiles generated in real SQ-RTM composites processed with the same combination of resins. POLYM. ENG. SCI. 56:1061–1069, 2016. © 2016 Society of Plastics Engineers