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Structural polymer composites for high-performance applications are amongst the most difficult materials to recycle effectively. It is foreseen that the end-of-life scenario of materials and products will have an increasingly more prominent role in material selection. Therefore it is crucial that circular recycling solutions are developed for both the resin and the fibrous/particulate phase of thermoset composite materials. In achieving this goal, thermosets with degradable or dynamic covalent bonds can fulfill an important role as they allow for a certain mobility of the matrix phase. The inclusion of these bonds theoretically allows for the effective separation of the different composite phases. These recyclable thermosets can be subdivided into degradable, associative and dissociative systems based on the molecular linkages that facilitate the stimuli-triggered recycling process. This article will highlight the most illustrative and advanced examples of the different types of recyclable thermoset composites developed throughout the years. In order to contribute to a circular material economy it is important that the thermoset resins are developed from renewable resources. Therefore special attention is given to composite matrices that are (partially) biobased and the chemical pathways that are required to synthesize them.

The outstanding performance of conventional thermosets arising from their covalently cross-linked networks directly results in a limited recyclability. The available commercial or close-to-commercial techniques facing this challenge can be divided into mechanical, thermal, and chemical processing. However, these methods typically require a high energy input and do not take the recycling of the thermoset matrix itself into account. Rather, they focus on retrieving the more valuable fibers, fillers, or substrates. To increase the circularity of thermoset products, many academic studies report potential solutions which require a reduced energy input by using degradable linkages or dynamic covalent bonds. However, the majority of these studies have limited potential for industrial implementation. This review aims to bridge the gap between the industrial and academic developments by focusing on those which are most relevant from a technological, sustainable and economic point of view. An overview is given of currently used approaches for the recycling of thermoset materials, the development of novel inherently recyclable thermosets and examples of possible applications that could reach the market in the near future.

This work reports on the development of a novel polymer blend with thermally triggered shape memory and self-healing properties. Blends were prepared by mixing a self-healing ionomer (Surlyn 9520) and polycyclooctene (with and without crosslinking agent) in different ratios. The regions of thermal activation were determined by thermogravimetric analysis, differential scanning calorimetry and oscillatory shear rheology. Consecutively, the shape memory and self-healing behaviour were investigated by a torsion procedure and tensile testing respectively. It was found that ionomer/crosslinked polycyclooctene blends of 70/30 wt% lead to polymers showing partial macroscopic healing and repeatable shape memory characteristics. The new polymer system shows both dual and triple shape memory behaviour and a near to 100% stiffness recovery after healing of crosscuts at standard ionomer healing conditions. Furthermore, the relation between terminal relaxation and self-healing in blends is shown. This study introduces a triple shape memory polymer with self-healing properties by a blending strategy thereby clearing the path for more durable materials based on shape memory properties.

A comparative study is performed on the monitoring of delamination healing in CFRP-ionomer sandwich composites by non-destructive techniques and destructive compression testing. Artificial delaminations of various areal dimensions and nature were introduced during production of the composites. The extent of the delamination and the healing thereof was monitored in both air and water-coupled ultrasonic C-scan experiments as well as by the frequency shift of the local defect resonance (LDR). It is shown that the LDR approach can be used to detect the early stage healing of the delaminations while ultrasonic C-scanning techniques are very effective to determine the extent of healing in the final stages of the repair process. A quasi-linear relation was observed between the delaminated area measured with ultrasonic C-scan and the compressive failure strength in destructive testing. This correlation shows the beneficial effect on the compression strength of the delaminated area reduction by on-demand healing.

This article presents development of a novel self-healing technology for asphalt pavements, where asphalt binder rejuvenator is encapsulated within the compartmented alginate fibres. The key objective of the study was to optimise the compartmented alginate fibre design, i.e., maximising amount of rejuvenator encapsulated within the fibre. The results demonstrate that optimum rejuvenator content in the alginate fibre is of 70:30 rejuvenator/alginate ratio. The fibres are of sufficient thermal and mechanical strength to survive harsh asphalt mixing and compaction processes. Furthermore, results illustrate that zeer open asfalt beton (ZOAB) asphalt mix containing 5% of 70:30 rejuvenator/alginate ratio compartmented alginate fibres has higher strength, stiffness and better healing properties in comparison to the control asphalt mix, i.e., mix without fibres, and mix containing fibres with lower rejuvenator content. These results show that compartmented alginate fibres encapsulating bitumen rejuvenator present a promising new approach for the development of self-healing asphalt pavement systems.

This work reports on the healing of early stage fatigue damage in ionomer/nano-particulate composites. A series of poly(ethylene-co-methacrylic acid) zinc ionomer/Fe3O4 nanoparticle composites with varying amounts of ionic clusters were developed and subjected to different levels of fatigue loading. The initiated damage was healed upon localized inductive heating of the embedded nanoparticles by exposure of the particulate composite to an alternating magnetic field. It is here demonstrated that healing of this early stage damage in ionomer particulate composites occurs in two different steps. First, the deformation is restored by the free-shrinkage of the polymer at temperatures below the melt temperature. At these temperatures, the polymer network is recovered thereby resetting the fatigue induced strain hardening. Then, at temperatures above the melting point of the polymer phase, fatigue-induced microcracks are sealed, hereby preventing crack propagation upon further loading. It is shown that the thermally induced free-shrinkage of these polymers does not depend on the presence of ionic clusters, but that the ability to heal cracks by localized melting while maintaining sufficient mechanical integrity is reserved for ionomers that contain a sufficient amount of ionic clusters guaranteeing an acceptable level of mechanical stability during healing.

Self-healing is a smart and promising way to make materials more reliable and longer lasting. In the case of structural or functional composites based on a polymer matrix, very often mechanical damage in the polymer matrix or debonding at the matrix–filler interface is responsible for the decrease in intended properties. This review describes the healing behavior in structural and functional polymer composites with a so-called intrinsically self-healing polymer as the continuous matrix. A clear similarity in the healing of structural and functional properties is demonstrated which can ultimately lead to the design of polymer composites that autonomously restore multiple properties using the same self-healing mechanism.

This paper addresses the various strategies to induce self-healing behaviour in fibre reinforced polymer based composites. A distinction is made between the extrinsic and intrinsic healing strategies. These strategies can be applied at the level of the fibre, the fibre/matrix interface or at the level of the matrix. It is shown that the degree of healing depends on the type of damage and the testing mode used and examples are given both for extrinsic and for intrinsic healing systems. The conclusion is drawn that self-healing in fibre reinforced composites is possible yet unlikely to become a commercial reality in the near future.

This paper explores the potential use of compartmented alginate fibres as a new method of incorporating rejuvenators into asphalt pavement mixtures. The compartmented fibres are employed to locally distribute the rejuvenator and to overcome the problems associated with spherical capsules and hollow fibres. The work presents proof of concept of the encapsulation process which involved embedding the fibres into the asphalt mastic mixture and the survival rate of fibres in the asphalt mixture. To prove the effectiveness of the alginate as a rejuvenator encapsulating material and to demonstrate its ability survive asphalt production process, the fibres containing the rejuvenator were prepared and subjected to thermogravimetric analysis and uniaxial tensile test. The test results demonstrated that fibres have suitable thermal and mechanical strength to survive the asphalt mixing and compaction process. The CT scan of an asphalt mortar mix containing fibres demonstrated that fibres are present in the mix in their full length, undamaged, providing confirmation that the fibres survived the asphalt production process. In order to investigate the fibres physiological properties and ability to release the rejuvenator into cracks in the asphalt mastic, the environmental scanning electron microscope and optical microscope analysis were employed. To prove its success as an asphalt healing system, compartmented alginate fibres containing rejuvenator were embedded in asphalt mastic mix. The three point bend tests were performed on the asphalt mastic test samples and the degree to which the samples began to self-heal in response was measured and quantified. The research findings indicate that alginate fibres present a promising new approach for the development of self-healing asphalt pavement systems.

We report the development of an intrinsic healing glass fibre reinforced polymer (GFRP) composite based on a disulphide-containing organic-inorganic thermoset matrix. Thermomechanical experiments showed that the newly developed matrix has a combination of a Young's modulus value in the range of (800-1200 MPa), the ability to multiple thermally induced healing delamination (70-85 degrees C), and processability by conventional vacuum infusion process that is not yet reported in literature. The composite mechanical properties and the extent of healing were determined by flexural, fracture and low-velocity impact testing. Small sized (cm(2)) damage, by increasing the healing pressure provided the location of the primary damage is concentrated within the matrix phase. The polymer matrix composite introduced here represents a significant step forward from the often mechanically inferior intrinsically self-healing composites towards structural self-healing composites. (C) 2017 Elsevier Ltd. All rights reserved.