Improving solvent-based self-healing materials through shape memory alloys

Healing of epoxy resins can be accomplished using a combination of embedded ethyl phenylacetate (EPA) solvent loaded capsules and shape memory alloy (SMA) wires. Upon crack formation, the EPA solvent diffuses in the resin and induces swelling which tends to close the crack, while the SMA wires upon heating reduce the crack gap and foster residual epoxy cure. The kinetics of EPA diffusion in the epoxy matrix were measured so as to evaluate the swelling thickness versus time, and concentration at saturation. The largest healable crack gap was found to be 30 mu m after 24 h. EPA solvent was shown to lower the curing reaction kinetics and the glass transition temperature (T-g) of the epoxy, as well as its stiffness and strength. Healing efficiency was assessed using long-groove tapered double cantilever beam (TDCB) test samples, with embedded SMA wires across the crack plane. The healing efficiency greatly improved when the crack gap was reduced to 30 pm, from 24% for samples without SMA wires to 78% for samples with SMA wires activated according to an optimized scenario. (C) 2011 Elsevier Ltd. All rights reserved.

Tailored Capsule Based Self-Healing for Epoxy Matrix Composites

Sam Neuser

Self-healing materials are a novel class of materials able to repair structural or, more generally, functional damage to a part. They hence have the potential to improve reliability and cost effectiveness, because failure or loss of functionality may be postponed or completely avoided. This concept has been applied to all classes of materials, but is particularly suited to polymers and their composites. Indeed, it was first demonstrated for epoxies containing capsules of dicyclopentadiene and dispersed Grubbs’ catalyst. However, the high cost of the catalyst precludes commercial use of this self-healing system. In the present thesis, two alternative approaches to self-healing of an epoxy matrix were investigated: (1) a solvent based self-healing epoxy; (2) a two-component epoxy/amine self-healing system using a novel encapsulation technique. The solvent-based system showed efficient healing in an under-cured epoxy matrix. The solvent in question was ethyl phenylacetate (EPA) encapsulated with urea-formaldehyde (UF) or UF-polyurethane. It was demonstrated that during a crack event, the solvent diffused into the epoxy matrix following a non-Fickian case II profile, with a geometrical swelling of the surface layer of the crack. For a healing time of 24h, a critical crack gap of 30μm was identified, beyond which the swelling was insufficient to bridge the crack faces and the healing efficiency was limited to around 25%. For smaller crack gaps, solvent swelling led to intimate contact of the crack faces and reaction of residual functional groups through a reduction of the glass transition temperature Tg of the epoxy, resulting in improved healing efficiency. The use of shape memory alloys (SMA) that are strained during the fracture event and subsequently heated to reduce the crack opening was also investigated. High healing efficiencies were observed and it was found that longer SMA wire activation times further improved the healing efficiency up to almost 80% through improved crack closure and an increased degree of polymerization. The behavior of this material during aging was then investigated in partially cracked samples, guaranteeing small crack gaps. It was found that the premature diffusion of the solvent through the microcapsule membrane into the epoxy matrix led to a decrease in healing efficiency from around 75% in fresh samples, to about 15% in samples aged for 75 days. Increasing the thickness of the polymeric shell of the capsules did not significantly improve performance. Moreover, moisture uptake by the epoxy also contributed to the reduced healing efficiency. Because the healing agent is hydrophobic, a higher water content in the epoxy matrix limited solvent diffusion into the epoxy and hence the extent of healing. A potential solution to the problem of premature diffusion of solvent into the epoxy is suggested to be the use of other shell materials or additional coatings on the capsules. The response of the solvent based self-healing system to dynamic fatigue was also studied. While in static testing, matrix swelling governs crack healing, a different mechanism was observed in the case of dynamic loading. In contrast to the unmodified epoxy, which showed rapid crack propagation under all the conditions investigated, in the presence of the solvent, crack arrest was observed for stress intensities of up to 0.48 MPam1/2. This phenomenon was attributed to crack pinning owing to diffusion of the solvent into the matrix surrounding the crack tip. The elongation at break of the solvated epoxy increased threefold, and the Young’s modulus decreased by more than 50%. Using finite element analysis (FEM) to model the stress distribution around the solvent-infused crack tip, it was shown that the local crack tip stress was reduced by 43%, accounting for this novel toughening effect. While solvent healing performed well in an under-cured matrix and interesting phenomena were observed, a fully cured matrix with a two-component self-healing system may be preferable for real applications because it avoids issues pertaining to premature solvent diffusion. The possibility of encapsulating an amine curing agent in a core-shell structure was therefore investigated as an alternative. A microfluidic glass chip was used to encapsulate a hydrophilic amine/water based curing agent in an acrylate resin shell using ex-situ exposure to UV light. Low viscosity epoxy was encapsulated with UF using a modified agitated emulsion encapsulation technique. Successful self-healing was demonstrated for epoxy specimens containing these microcapsules, along with embedded SMA wires, with healing efficiencies of up to 100% and 40% for low and high temperature curing epoxy, respectively. Overall, this work represents a significant step towards affordable epoxy self-healing materials, the feasibility of solvent and epoxy/amine healing having been successfully demonstrated for an epoxy matrix. The epoxy/amine self-healing system is thought to be particularly promising, considering the early stage of development. Furthermore, the integration of SMA wires proved to improve healing efficiencies dramatically, especially with the epoxy/amine microcapsules. With further optimization and scale-up of the microfluidic encapsulation method, a new low cost self-healing system, and hence potentially compatible with a wide range of polymeric materials, including composites, is therefore within reach because it is based on a commonly used epoxy/amine adhesive.

EPFL2013

Fatigue Response of Solvent-Based Self-Healing Smart Materials

Véronique Michaud, Sam Neuser

We investigated the healing of epoxy resins with embedded ethyl phenylacetate (EPA) solvent loaded capsules and shape memory alloy (SMA) wires under fatigue loading in tapered double cantilever beam (TDCB) mode. Under cyclic loading, the kinetics of solvent diffusion are in competition with the rate of damage propagation. We showed that the active mechanism of self-healing under continuous loading is different from that in quasi-static testing. Crack arrest was observed after some initial crack growth, resulting from the diffusion of EPA solvent into the crack tip, involving local plasticization of the epoxy. Finite element analysis confirmed that the lower modulus and higher elongation at break of the solvated epoxy reduced the stresses at the crack tip. This effect combined with the well-studied microcapsule toughening effect, tremendously increased the toughness of plain epoxy. For epoxy with embedded SMA wires, completely fractured samples, healed using SMA activation, showed similar fatigue resistance as virgin samples. Furthermore, SMA activation during a 10 min break also stabilized crack progression, compared to at least 2 h needed to reach the same effect without SMA wires.

Springer Verlag2014

Functional composites with damage control and repair

Amaël Maximilien Cohades

Fibre Reinforced Polymer (FRP) composite structures are subjected during service to low energy impacts or unexpected loads, leading to damage. Microcracks are generally first formed in the matrix and can reach up to several hundred microns in thickness. In many living systems, an initial self-sealing phase followed by self-healing of the original tissue leads to highly effective repair of minor damage events. A bio-inspired strategy for the efficient healing of microcracks in FRPs is hence to: (i) autonomously close cracks whose thickness is above a certain threshold to ensure better crack faces registry; (ii) use a healing matrix with structural properties close to that of a conventional FRP matrix, that is able to expand and fill the cracked regions repeatedly after multiple damage events. This strategy was investigated in the present work through (i) the use of Shape Memory Alloy wires (SMAs) as stitches in FRPs and (ii) a healing matrix based on thermoset-thermoplastic phase-separated blends. Blends composed of epoxy resin and different thermoplastics (PCL, PLA and PMMA) were evaluated for their potential as healing matrix, based on their room temperature toughness, stiffness and their capacity to heal when subjected to a moderate heating cycle. Three types of blend morphology resulted from polymerisation-induced phase separation during cure, depending on the thermoplastic content, including an interconnected particulate epoxy phase and a co-continuous thermoplastic phase at high thermoplastic contents. An optimal composition was found for epoxy-25vol%PCL blends. The PCL phase expands by 14% in volume upon melting at 150 °C, therefore enabling filling of small cracks. When further integrated to FRPs (with an adapted vacuum infusion moulding process), this healing matrix led to composites with similar stiffness and strength to that of pure epoxy composites, but also to full recovery of compression after impact strength for low damage extent (impacts of 8.5 J). To provide healing for larger damage extent, NiTiCu SMA wires, with a diameter of 150µm, were stitched in the dry fabric before processing. After damage and upon heating at 150 °C, SMA stitches, that have been stretched and partly debonded upon crack propagation, efficiently closed the cracks. This procedure demonstrated the capacity of the wires to close 200 µm thick cracks in the FRPs and led to fully heal impact damage events up to 17 J, corresponding to the main concern of maintenance activities in the composite industry (e.g. tools dropped from 1-2 m height). Finally, as an alternative to blends, PCL electrospun nanofibrous veils were interleaved into fabrics, infused with epoxy and cured to reach a microstructure combining both phase-separated domains as well as intact nanofibre regions. Interlaminar crack propagation demonstrated up to 48% toughness increase as compared to reference specimens. However, healing was prevented due to reduced flow of PCL in the fine channels resulting from phase separation, showing the limitation of this approach as compared to the use of blends and stitches. Phase-separated epoxy-PCL composites (with or without stitched SMA wires), considering their manufacturing feasibility through conventional industrial processes, their acceptable mechanical properties and their ability to fully heal low-velocity impact damage, demonstrated their relevance for composite structures that are subjected to moderate loads and not easily accessible to repair.