Recyclable and Biobased Vitrimers for Carbon Fibre-Reinforced Composites-A Review.

Economic and environmental concerns over the accumulation of end-of-life carbon fibre composite waste have led to increased attention to sustainable materials with low environmental impact. Over decades of research, vitrimers, a modern class of covalent adaptable networks, have bridged the gap between thermoplastics and thermosets. With the distinguishing feature of dynamic covalent bonds, vitrimers can be rearranged and reprocessed within their existing network structures in response to external stimuli such as heat or light. This poses a unique solution to repairing damaged composites, extending their service life, and reducing post-consumer waste. However, the synthesis of vitrimers often requires petrochemical consumption, which increases their carbon footprint. Using bio-based materials could be a promising solution to reduce the reliance on petrochemicals and their related pollution. This review compiles the contemporary requirements for bio-based vitrimers regarding their properties, scalability, and recycling features. This article also presents a comprehensive overview of the pathways to produce sustainable bio-based vitrimers and an overview of promising studies showing the potential uses of bio-derived vitrimers on carbon fibre composite productions.

Review of Approaches to Minimise the Cost of Simulation-Based Optimisation for Liquid Composite Moulding Processes.

The utilisation of numerical process simulation has greatly facilitated the challenging task of liquid composite moulding (LCM) process optimisation, providing ease of solution evaluation at a significantly reduced cost compared to complete reliance on physical prototyping. However, due to the process complexity, such process simulation is still considerably expensive at present. In this paper, cost-saving approaches to minimising the computational cost of simulation-based optimisation for LCM processes are compiled and discussed. Their specific applicability, efficacy, and suitability for various optimisation/moulding scenarios are extensively explored in detail. The comprehensive analysation and assimilation of their operation alongside applicability for the problem domain of interest are accomplished in this paper to further complement and contribute to future simulation-based optimisation capabilities for composite moulding processes. The importance of balancing the cost-accuracy trade-off is also repeatedly emphasised, allowing for substantial cost reductions while ensuring a desirable level of optimization reliability.

Application of KNN and ANN Metamodeling for RTM Filling Process Prediction.

Process simulation is frequently adopted to facilitate the optimization of the resin transfer molding process. However, it is computationally costly to simulate the multi-physical, multi-scale process, making it infeasible for applications involving huge datasets. In this study, the application of K-nearest neighbors and artificial neural network metamodels is proposed to build predictive surrogate models capable of relating the mold-filling process input-output correlations to assist mold designing. The input features considered are the resin injection location and resin viscosity. The corresponding output features investigated are the number of vents required and the resultant maximum injection pressure. Upon training, both investigated metamodels demonstrated desirable prediction accuracies, with a low prediction error range of 5.0% to 15.7% for KNN metamodels and 6.7% to 17.5% for ANN metamodels. The good prediction results convincingly indicate that metamodeling is a promising option for composite molding applications, with encouraging prospects for data-intensive applications such as process digital twinning.

Magnetically Cured Macroradical Epoxy as Antimicrobial Coating.

The radical-bearing epoxy monomer could be the ideal embodiment of multifunctionality in epoxy-based materials. This study demonstrates the potential of macroradical epoxies as surface coating materials. A diepoxide monomer derivatized with a stable nitroxide radical is polymerized with a diamine hardener under the influence of a magnetic field. The magnetically oriented and stable radicals in the polymer backbone render the coatings antimicrobial. The unconventional use of magnets during polymerization proved crucial in correlating the structure-property relationships with antimicrobial performance inferred from oscillatory rheological technique, polarized macro-attenuated total reflectance - infrared (macro-ATR-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The magnetic thermal curing influenced the surface morphology, resulting in a synergy of the coating's radical nature with microbiostatic performance assessed using the Kirby-Bauer test and liquid chromatography - mass spectroscopy (LC-MS). Further, the magnetic curing of blends with a traditional epoxy monomer demonstrates that radical alignment is more critical than radical density in imparting biocidal behavior. This study shows how the systematic use of magnets during polymerization could pave for probing more significant insights into the mechanism of antimicrobial action in radical-bearing polymers.

Evaluation of the Failure Mechanism in Polyamide Nanofibre Veil Toughened Hybrid Carbon/Glass Fibre Composites.

The interface of hybrid carbon/E-glass fibres composite is interlayered with Xantu.layr® polyamide 6,6 nanofibre veil to localise cracking to promote a gradual failure. The pseudo-ductile response of these novel stacking sequences examined under quasi-static three-point bending show a change to the failure mechanism. The change in failure mechanism due to the interfacial toughening is examined via SEM micrographs. The incorporation of veil toughening led to a change in the dominant failure mechanism, resulting in fibre yielding by localised kinking and reduced instances of buckling failure. In alternated carbon and glass fibre samples with glass fibre undertaking compression, a pseudo-ductile response with veil interlayering was observed. The localisation of the fibre failure, due to the inclusion of the veil, resulted in kink band formations which were found to be predictable in previous micro buckling models. The localisation of failure by the veil interlayer resulted in a pseudo-ductile response increasing the strain before failure by 24% compared with control samples.

High Performance Carbon Fiber Structural Batteries Using Cellulose Nanocrystal Reinforced Polymer Electrolyte.

In recent years, structural batteries have received great attention for future automotive application in which a load-bearing car panel is used as an energy storage. However, based on the current advances, achieving both high ionic conductivity and mechanical performance has remained a challenge. To address this challenge, this study introduces a cellulose nanocrystal (CNC) reinforced structural battery electrolyte (CSBE) consisting of CNC, triethylene glycol dimethyl ether (TriG) electrolyte containing a quasi-solid additive, e.g., cyclohexanedimethanol (CHDM), in a vinyl ester polymer. This green and renewable CSBE electrolyte system was in situ polymerized via reaction induced phase transition to form a high performance multidimensional channel electrolyte to be used in structural carbon fiber-based battery fabrication. The effect of various concentrations of CNC on the electrolyte ionic conductivity and mechanical properties was obtained in their relation to intermolecular interactions, interpreted by FTIR, Raman, Li NMR results. Compared to the neat SBE system, the optimized CSBE nanocomposite containing 2 wt % CNC shows a remarkable ionic conductivity of 1.1 × 10-3 S cm-1 at 30 °C, which reveals ∼300% improvement, alongside higher thermal stability. Based on the FTIR, Raman, Li NMR results, the content of CNC in the CSBE structure plays a crucial role not only in the formation of cellulose network skeleton but also in physical interaction with polymer matrix, providing an efficient Li+ pathway through the electrolyte matrix. The carbon fiber composite was fabricated by 2 wt % CNC reinforced SBE electrolyte to evaluate as a battery half-cell. The results demonstrated that by addition of 2 wt % CNC into SBE system, 7.6% and 33.9% improvements were achieved in specific capacity at 0.33 C and tensile strength, respectively, implying outstanding potential of ion conduction and mechanical load transfer between the carbon fibers and the electrolyte.

Characterising a Custom-Built Radio Frequency PECVD Reactor to Vary the Mechanical Properties of TMDSO Films.

Plasma-polymerised tetramethyldisiloxane (TMDSO) films are frequently applied as coatings for their abrasion resistance and barrier properties. By manipulating the deposition parameters, the chemical structure and thus mechanical properties of the films can also be controlled. These mechanical properties make them attractive as energy adsorbing layers for a range of applications, including carbon fibre composites. In this study, a new radio frequency (RF) plasma-enhanced chemical vapour deposition (PECVD) plasma reactor was designed with the capability to coat fibres with an energy adsorbing film. A key characterisation step for the system was establishing how the properties of the TMDSO films could be modified and compared with those deposited using a well-characterized microwave (MW) PECVD reactor. Film thickness and chemistry were determined with ellipsometry and X-ray photoelectron spectroscopy, respectively. The mechanical properties were investigated by nanoindentation and atomic force microscopy with peak-force quantitative nanomechanical mapping. The RF PECVD films had a greater range of Young's modulus and hardness values than the MW PECVD films, with values as high as 56.4 GPa and 7.5 GPa, respectively. These results demonstrated the varied properties of TMDSO films that could in turn be deposited onto carbon fibres using a custom-built RF PECVD reactor.

Evolving Strategies for Producing Multiscale Graphene-Enhanced Fiber-Reinforced Polymer Composites for Smart Structural Applications.

Graphene has become an important research focus in many current fields of science including composite manufacturing. Developmental work in the field of graphene-enhanced composites has revealed several functional and structural characteristics that promise great benefits for their use in a broad range of applications. There has been much interest in the production of multiscale high-performance, lightweight, yet robust, multifunctional graphene-enhanced fiber-reinforced polymer (gFRP) composites. Although there are many reports that document performance enhancement in materials through the inclusion of graphene nanomaterials into a matrix, or its integration onto the reinforcing fiber component, only a few graphene-based products have actually made the transition to the marketplace. The primary focus of this work concerns the structural gFRPs and discussion on the corresponding manufacturing methodologies for the effective incorporation of graphene into these systems. Another important aspect of this work is to present recent results and highlight the excellent functional and structural properties of the resulting gFRP materials with a view to their future applications. Development of clear standards for the assessment of graphene material properties, improvement of existing materials and scalable manufacturing technologies, and specific regulations concerning human health and environmental safety are key factors to accelerate the successful commercialization of gFRPs.

Influence of Different Nanocellulose Additives on Processing and Performance of PAN-Based Carbon Fibers.

Nanocellulose, as a biobased versatile nanomaterial that can be derived with tailorable surface functionalities, dimensions, and morphologies, has considerable implications for modifying the rheology, mechanical reinforcement, and influencing the carbonization efficiency in the production of polyacrylonitrile (PAN)-based carbon fibers. Herein, we report the influence of three different nanocellulose types, varying in the derivatization method, source, and aspect ratio, on the mechanical properties and thermal transformations of solution-spun PAN/nanocellulose nanocomposite fibers into carbon fibers. The incorporation of 0.1 wt % nanocellulose into solution-spun PAN fibers led to a 7-19% increase in tensile modulus and 0-27% increase in tensile strength in the solution-spun fibers, compared to a control PAN fiber. These improvements varied depending on the nanocellulose type. After low-temperature carbonization at 1200 °C, improvements in the mechanical properties of the nanocellulose-reinforced carbon fibers, compared with a PAN fiber, were also observed. In contrast to the precursor fibers, the improvement % in the carbonized fibers was found to be dependent on the nanocellulose morphology and was linearly correlated with increasing aspect ratio of nanocellulose. For example, in carbon fibers with a cotton-derived low-aspect-ratio cellulose nanocrystal and spinifex-derived high-aspect-ratio CNC and nanofiber, up to 4, 87, and 172% improvements in tensile moduli were observed, respectively. Due to the processing methods used, the nanocellulose aspect ratio and crystallinity are inversely related, and as such, the increase in the carbon fiber mechanical properties was also related to a decrease in crystallinity of the nanocellulose reinforcers. Raman spectra and electron microscopy analysis suggest that mechanical improvement after carbonization is due to internal reinforcement by highly ordered regions surrounding the carbonized nanocellulose, within the turbostratic carbon fibers.

Graphene based room temperature flexible nanocomposites from permanently cross-linked networks.

Graphene based room temperature flexible nanocomposites were prepared using epoxy thermosets for the first time. Flexible behavior was induced into the epoxy thermosets by introducing charge transfer complexes between functional groups within cross linked epoxy and room temperature ionic liquid ions. The graphene nanoplatelets were found to be highly dispersed in the epoxy matrix due to ionic liquid cation-π interactions. It was observed that incorporation of small amounts of graphene into the epoxy matrix significantly enhanced the mechanical properties of the epoxy. In particular, a 0.6 wt% addition increased the tensile strength and Young's modulus by 125% and 21% respectively. The electrical resistance of nanocomposites was found to be increased with graphene loading indicating the level of self-organization between the ILs and the graphene sheets in the matrix of the composite. The graphene nanocomposites were flexible and behave like ductile thermoplastics at room temperature. This study demonstrates the use of ionic liquid as a compatible agent to induce flexibility in inherently brittle thermoset materials and improve the dispersion of graphene to create high performance nanocomposite materials.

Mechanical property and structure of covalent functionalised graphene/epoxy nanocomposites.

Thermally reduced graphene nanoplatelets were covalently functionalised via Bingel reaction to improve their dispersion and interfacial bonding with an epoxy resin. Functionalised graphene were characterized by microscopic, thermal and spectroscopic techniques. Thermal analysis of functionalised graphene revealed a significantly higher thermal stability compared to graphene oxide. Inclusion of only 0.1 wt% of functionalised graphene in an epoxy resin showed 22% increase in flexural strength and 18% improvement in storage modulus. The improved mechanical properties of nanocomposites is due to the uniform dispersion of functionalised graphene and strong interfacial bonding between modified graphene and epoxy resin as confirmed by microscopy observations.

Individual dispersion of carbon nanotubes in epoxy via a novel dispersion-curing approach using ionic liquids.

The effective dispersion of carbon nanotubes (CNTs) in a thermoset was achieved using ionic liquid as the dispersion-curing agent. We preferentially dispersed multiwalled carbon nanotubes (MWCNTs) down to individual tube levels in epoxy resin. Here the dispersion is ruled by the depletion of physical bundles within the MWCNT networks, for which molecular ordering of ionic liquids is considered responsible. The quantitative analyses using ultra small angle X-ray scattering (USAXS) confirmed the dispersion of individual MWCNTs in the matrix. The distance between the dispersed nanotubes was calculated at different nanotube loadings using the power law fitting of the USAXS data. The fine dispersion and subsequent curing, both controlled by ionic liquid, lead to composites with substantially enhanced fracture mechanical and thermomechanical properties with no reduction in thermal properties. Merging processing techniques of nanocomposites with ionic liquid for efficient dispersion of nanotubes and preferential curing of thermosets facilitates the development of new, high performance materials.

Overcoming interfacial affinity issues in natural fiber reinforced polylactide biocomposites by surface adsorption of amphiphilic block copolymers.

This work demonstrates that the interfacial properties in a natural fiber reinforced polylactide bio-composite can be tailored through surface adsorption of amphiphilic and biodegradable poly (ethylene glycol)-b-poly(l-lactide) (PEG-PLLA) block copolymers. The deposition from solvent solution of PEG-PLLA copolymers onto the fibrous substrate induced distinct mechanisms of molecular organization at the cellulosic interface, which are correlated to the hydrophobic/hydrophilic ratios and the type of solvent used. The findings of the study evidenced that the performance of the corresponding biocomposites with polylactide were effectively enhanced by using these copolymers as interfacial coupling agents. During the fabrication stage, diffusion of the polylactide in the melt induced a change in the environment surrounding block copolymers which became hydrophobic. It is proposed that molecular reorganization of the block copolymers at the interface occurred, which favored the interactions with both the hydrophilic fibers and hydrophobic polylactide matrix. The strong interactions such as intra- and intermolecular hydrogen bonds formed across the fiber-matrix interface can be accounted for the enhancement in properties displayed by the biocomposites. Although the results reported here are confined, this concept is unique as it shows that by tuning the amphiphilicity and the type of building blocks, it is possible to control the surface properties of the substrate by self-assembly and disassembly of the amphiphiles for functional materials.

The Effect of a Rapid Heating Rate, Mechanical Vibration and Surfactant Chemistry on the Structure-Property Relationships of Epoxy/Clay Nanocomposites.

The role of processing conditions and intercalant chemistry in montmorillonite clays on the dispersion, morphology and mechanical properties of two epoxy/clay nanocomposite systems was investigated in this paper. This work highlights the importance of employing complementary techniques (X-ray diffraction, small angle X-ray scattering, optical microscopy and transmission electron microscopy) to correlate nanomorphology to macroscale properties. Materials were prepared using an out of autoclave manufacturing process equipped to generate rapid heating rates and mechanical vibration. The results suggested that the quaternary ammonium surfactant on C30B clay reacted with the epoxy during cure, while the primary ammonium surfactant (I.30E) catalysed the polymerisation reaction. These effects led to important differences in nanocomposite clay morphologies. The use of mechanical vibration at 4 Hz prior to matrix gelation was found to facilitate clay dispersion and to reduce the area fraction of I.30E clay agglomerates in addition to increasing flexural strength by over 40%.

Methyl 3-[4-(4-nitro-benz-yloxy)phen-yl]propano-ate.

The title compound, C(17)H(17)NO(5), crystallizes with two mol-ecules (A and B) in the asymmetric unit. The conformational structures of the two mol-ecules show small but significant differences in the dihedral angles between the two aryl rings with values of 18.8 (1)° for mol-ecule A and 7.5 (1)° for mol-ecule B. In mol-ecule A, the propano-ate group is twisted out of the plane of the benzene group [C(ar)-C(ar)-C-C torsion angle = -44.9 (2)°], while for mol-ecule B, this group lies closer to the plane [C(ar)-C(ar)-C-C torsion angle = 8.6 (3)°]. C-H⋯O inter-actions characterize the crystal-packing inter-actions in this compound.

Enhanced permanganate chemiluminescence.

The significant enhancement of acidic potassium permanganate chemiluminescence by Mn(II) results from the concomitant presence of permanganate and Mn(III) in the reagent solution, which enables rapid production of the excited Mn(II) emitter with a wide range of analytes. Furthermore, the key Mn(III) co-reactant can be quickly generated by reducing permanganate with sodium thiosulfate, instead of the slow (~24 h) equilibration required when Mn(ii) is used. The emission from reactions with analytes such as tyrosine and fenoterol was over two orders of magnitude more intense than with the traditional permanganate reagent.

Toughening of a Carbon-Fibre Composite Using Electrospun Poly(Hydroxyether of Bisphenol A) Nanofibrous Membranes Through Inverse Phase Separation and Inter-Domain Etherification.

The interlaminar toughening of a carbon fibre reinforced composite by interleaving a thin layer (~20 microns) of poly(hydroxyether of bisphenol A) (phenoxy) nanofibres was explored in this work. Nanofibres, free of defect and averaging several hundred nanometres, were produced by electrospinning directly onto a pre-impregnated carbon fibre material (Toray G83C) at various concentrations between 0.5 wt % and 2 wt %. During curing at 150 °C, phenoxy diffuses through the epoxy resin to form a semi interpenetrating network with an inverse phase type of morphology where the epoxy became the co-continuous phase with a nodular morphology. This type of morphology improved the fracture toughness in mode I (opening failure) and mode II (in-plane shear failure) by up to 150% and 30%, respectively. Interlaminar shear stress test results showed that the interleaving did not negatively affect the effective in-plane strength of the composites. Furthermore, there was some evidence from DMTA and FT-IR analysis to suggest that inter-domain etherification between the residual epoxide groups with the pendant hydroxyl groups of the phenoxy occurred, also leading to an increase in glass transition temperature (~7.5 °C).

Exploring molecular changes at the surface of polypropylene after accelerated thermomolecular adhesion treatments.

A central composite rotatable design (CCRD) method was used to investigate the performance of the accelerated thermomolecular adhesion process (ATmaP), at different operating conditions. ATmaP is a modified flame-treatment process that features the injection of a coupling agent into the flame to impart a tailored molecular surface chemistry on the work piece. In this study, the surface properties of treated polypropylene were evaluated using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). All samples showed a significant increase in the relative concentration of oxygen (up to 12.2%) and nitrogen (up to 2.4%) at the surface in comparison with the untreated sample (0.7% oxygen and no detectable nitrogen) as measured by XPS. ToF-SIMS and principal components analysis (PCA) showed that ATmaP induced multiple reactions at the polypropylene surface such as chain scission, oxidation, nitration, condensation, and molecular loss, as indicated by changes in the relative intensities of the hydrocarbon (C(3)H(7)(+), C(3)H(5)(+), C(4)H(7)(+), and C(5)H(9)(+)), nitrogen and oxygen-containing secondary ions (C(2)H(3)O(+), C(3)H(8)N(+), C(2)H(5)NO(+), C(3)H(6)NO(+), and C(3)H(7)NO(+)). The increase in relative intensity of the nitrogen oxide ions (C(2)H(5)NO(+) and C(3)H(7)NO(+)) correlates with the process of incorporating oxides of nitrogen into the surface as a result of the injection of the ATmaP coupling agent.