Epoxy Vitrimer Materials by Lipase-Catalyzed Network Formation and Exchange Reactions.

The preparation and reprocessing of an epoxy vitrimer material is performed in a fully biocatalyzed process wherein network formation and exchange reactions are promoted by a lipase enzyme. Binary phase diagrams are introduced to select suitable diacid/diepoxide monomer compositions overcoming the limitations (phase separation/sedimentation) imposed by curing temperature inferior than 100 °C, to protect the enzyme. The ability of lipase TL, embedded in the chemical network, to catalyze efficiently exchange reactions (transesterification) is demonstrated by combining multiple stress relaxation experiments at 70-100 °C and complete recovery of mechanical strength after several reprocessing assays (up to 3 times). Complete stress relaxation ability disappears after heating at 150 °C, due to enzyme denaturation. Transesterification vitrimers thus designed are complementary to those involving classical catalysis (e.g., using the organocatalyst triazabicyclodecene) for which complete stress relaxation is possible only at high temperature.

Lipase-Catalyzed Epoxy-Acid Addition and Transesterification: from Model Molecule Studies to Network Build-Up.

Commercially available lipase from Pseudomonas stutzeri (lipase TL) is investigated as a biocatalyst for the formation of an acid-epoxy chemical network. Molecular model reactions are performed by reacting 2-phenyl glycidyl ether and hexanoic acid in bulk, varying two parameters: temperature and water content. Characterizations of the formed products by 1H NMR spectroscopy and gas chromatography-mass spectrometry combined with enzymatic assays confirm that lipase TL is able to simultaneously promote acid-epoxy addition and transesterification reactions below 100 °C and solely the acid-epoxy addition after denaturation at T > 100 °C. A prototype bio-based chemical network with ß-hydroxyester links was obtained using resorcinol diglycidyl ether and sebacic acid as monomers with lipase TL as catalyst. Differential scanning calorimetry, attenuated total reflection, and swelling analysis confirm gelation of the network.

Direct-Write Piezoelectric Transducers on Carbon-Fiber-Reinforced Polymer Structures for Exciting and Receiving Guided Ultrasonic Waves.

Advancements in the structural health monitoring (SHM) technology of composite materials are of paramount importance for early detection of critical damage. In this work, direct-write transducers (DWTs) were designed for the excitation and reception of selective ultrasonic guided waves and fabricated by spraying 25- [Formula: see text]-thick piezoelectric poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-TRFE)] coating with a comb-shaped electrode on carbon fiber-reinforced polymer (CFRP) plates. The characteristics and performance of the ultrasonic DWTs were benchmarked with the state-of-the-art devices, discrete lead zirconate titanate (PZT) ceramic transducers surface-mounted on the same CFRP plates. The DWTs exhibited improved Lamb wave mode excitation (A0 or S0 mode) relative to the discrete PZT transducers. Moreover, high signal-to-noise ratio was obtained by effectively canceling other modes and enhancing the directivity with the periodic comb-shaped electrode design of the DWTs, despite the smaller signal amplitudes. The enhanced directivity overcompensates for lower amplitude attenuation, making DWT a good candidate for locally monitoring critical stress hot spot regions in the CFRP structure prone to early damage initiation. It is shown that pairing a DWT sensor with a discrete PZT actuator could further achieve balanced performance in both wave mode selection and signal amplitudes, making this combination really attractive for ultrasonic SHM.

Patterned, morphing composites via maskless photo-click lithography.

Morphing materials, also known as smart materials are attracting increasing attention as sensors, actuators and in soft robotic applications. In this work bilayered morphing composites were created by exploiting the thiol-ene photoclick reaction via maskless digital light processing (DLP). This technique allows for gradients and patterns of near infrared (nIR)-triggered materials to be efficiently crosslinked to substrates, with suitable interfacial adhesion to realise complex morphing. Photo-thermally responsive composites are produced by DLP patterning of reduced graphene oxide-filled chitosan-methacrylamide (rGO-chitosan-MA) on thiolated polydimethylsiloxane substrates via thiol-ene photoclick reaction. Morphing composites with parallel striped patterns and box-like hinges were printed via DLP to realise self-rolling and self-folding behaviours. Bilayered structures, with gradient rGO-chitosan-MA thicknesses (2-8 µm), were produced by controlling the light intensity from the DLP device. These gradient bilayered structures enable photothermal-triggered gradient bending and morphing exemplified here by a "walking worm" and a kirigami-inspired "opening flower". Thermo-mechanical calculations were performed to estimate bending angles, and finite element analysis applied to simulate self-folding and bending. The difference between simulation and measurements is in the range 0.4-7.6%, giving confidence to the assumptions and simplifications applied in design.

Graphene-aramid nanocomposite fibres via superacid co-processing.

The development of graphene-polymer nanocomposite materials has been hindered by issues such as poor colloidal stability of graphene in liquid media, weak interactions between graphene and the host polymers as well as the lack of scalable and economical graphene synthesis routes. Chlorosulfonic acid (CSA) can spontaneously disperse graphene without the need for mechanical agitation, chemical functionalisation or surfactant stabilisation,1 however is incompatible with most polymers and organic materials. Here, we demonstrate how poly(p-phenylene terephthalamide) (PPTA) - the polymer which constitutes Kevlar - can be co-processed with graphene in CSA and wet-spun into nanocomposite fibres with minimal aggregation of graphene.

Early Damage Detection in Composites during Fabrication and Mechanical Testing.

Fully integrated monitoring systems have shown promise in improving confidence in composite materials while reducing lifecycle costs. A distributed optical fibre sensor is embedded in a fibre reinforced composite laminate, to give three sensing regions at different levels through-the-thickness of the plate. This study follows the resin infusion process during fabrication of the composite, monitoring the development of strain in-situ and in real time, and to gain better understanding of the resin rheology during curing. Piezoelectric wafer active sensors and electrical strain gauges are bonded to the plate after fabrication. This is followed by progressive loading/unloading cycles of mechanical four point bending. The strain values obtained from the optical fibre are in good agreement with strain data collected by surface mounted strain gauges, while the sensing regions clearly indicate the development of compressive, neutral, and tensile strain. Acoustic emission event detection suggests the formation of matrix (resin) cracks, with measured damage event amplitudes in agreement with values reported in published literature on the subject. The Felicity ratio for each subsequent loading cycle is calculated to track the progression of damage in the material. The methodology developed here can be used to follow the full life cycle of a composite structure, from manufacture to end-of-life.

Thermal Diffusivity Mapping of Graphene Based Polymer Nanocomposites.

Nanoparticle dispersion is widely recognised as a challenge in polymer nanocomposites fabrication. The dispersion quality can affect the physical and thermomechanical properties of the material system. Qualitative transmission electronic microscopy, often cumbersome, remains as the 'gold standard' for dispersion characterisation. However, quantifying dispersion at macroscopic level remains a difficult task. This paper presents a quantitative dispersion characterisation method using non-contact infrared thermography mapping that measures the thermal diffusivity (α) of the graphene nanocomposite and relates α to a dispersion index. The main advantage of the proposed method is its ability to evaluate dispersion over a large area at reduced effort and cost, in addition to measuring the thermal properties of the system. The actual resolution of this thermal mapping reaches 200 µm per pixel giving an accurate picture of graphene nanoplatelets (GNP) dispersion. The post-dispersion treatment shows an improvement in directional thermal conductivity of the composite of up to 400% increase at 5 wt% of GNP. The Maxwell-Garnet effective medium approximation is proposed to estimate thermal conductivity that compare favourably to measured data. The development of a broadly applicable dispersion quantification method will provide a better understanding of reinforcement mechanisms and effect on performance of large scale composite structures.

Transverse Crack Detection in 3D Angle Interlock Glass Fibre Composites Using Acoustic Emission.

In addition to manufacturing cost and production rates, damage resistance has become a major issue for the composites industry. Three-dimensional (3D) woven composites have superior through-thickness properties compared to two-dimensional (2D) laminates, for example, improved impact damage resistance, high interlaminar fracture toughness and reduced notch sensitivity. The performance of 3D woven preforms is dependent on the fabric architecture, which is determined by the binding pattern. For this study, angle interlock (AI) structures with through-thickness binding were manufactured. The AI cracking simulation shows that the transverse component is the one that leads to transverse matrix cracking in the weft yarn under tensile loading. Monitoring of acoustic emission (AE) during mechanical loading is an effective tool in the study of damage processes in glass fiber-reinforced composites. Tests were performed with piezoelectric sensors bonded on a tensile specimen acting as passive receivers of AE signals. An experimental data has been generated which was useful to validate the multi-physics finite element method (MP-FEM), providing insight into the damage behaviour of novel 3D AI glass fibre composites. MP-FEM and experimental data showed that transverse crack generated a predominant flexural mode A0 and also a less energetic extensional mode S0.