A self-healing microvascular polymeric foam has been developed to improve the resilience of rigid foam core materials for sandwich structures. We investigated the healing of brittle polyisocyanurate ...(PIR) foam after mode-I crack separation in a 3-point single edge notch bend (SENB) specimen. A two-part healing chemistry based on a commercially available polyurethane (PUR) foam formulation is employed to rebond the interface. Both components are initially sequestered in separate channels in a vascularized SENB geometry. Upon loading and subsequent crack propagation through the network, the healing agents are released and polymerize on contact to create new foam material in the crack plane. An attractive feature of this system is the volumetric expansion of the healing chemistry, demonstrating the ability to repair macro-scale damage. The foaming reaction occurs on the order of minutes at room temperature, enabling rapid in-situ healing. Furthermore, by using a vascular delivery technique, multiple damage–recovery cycles are achieved at consistently high healing efficiencies. Through repeated mechanical testing, we have demonstrated over 100% recovery in fracture toughness for this new class of bioinspired, self-healing cellular materials.
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The addition of liquid-filled urea-formaldehyde (UF) microcapsules to an epoxy matrix leads to significant reduction in fatigue crack growth rate and corresponding increase in fatigue life. Mode-I ...fatigue crack propagation is measured using a tapered double-cantilever beam (TDCB) specimen for a range of microcapsule concentrations and sizes: 0, 5, 10, and 20% by weight and 50, 180, and 460 μm diameter. Cyclic crack growth in both the neat epoxy and epoxy filled with microcapsules obeys the Paris power law. Above a transition value of the applied stress intensity factor ΔKT, which corresponds to loading conditions where the size of the plastic zone approaches the size of the embedded microcapsules, the Paris law exponent decreases with increasing content of microcapsules, ranging from 9.7 for neat epoxy to approximately 4.5 for concentrations above 10 wt% microcapsules. Improved resistance to fatigue crack propagation, indicated by both the decreased crack growth rates and increased cyclic stress intensity for the onset of unstable fatigue-crack growth, is attributed to toughening mechanisms induced by the embedded microcapsules as well as crack shielding due to the release of fluid as the capsules are ruptured. In addition to increasing the inherent fatigue life of epoxy, embedded microcapsules filled with an appropriate healing agent provide a potential mechanism for self-healing of fatigue damage.
Microencapsulated healing agents that possess adequate strength, long shelf-life and excellent bonding to the host material are required for self-healing materials. Urea-formaldehyde microcapsules ...containing dicyclopentadiene were prepared by in situ polymerization in an oil-in-water emulsion that meet these requirements for self-healing epoxy. Microcapsules of 10-1000 microm in diameter were produced by appropriate selection of agitation rate in the range of 200-2000 rpm. A linear relation exists between log(mean diameter) and log(agitation rate). Surface morphology and shell wall thickness were investigated by optical and electron microscopy. Microcapsules are composed of a smooth 160-220 nm inner membrane and a rough, porous outer surface of agglomerated urea-formaldehyde nanoparticles. Surface morphology is influenced by pH of the reacting emulsion and interfacial surface area at the core-water interface. High yields (80-90%) of a free flowing powder of spherical microcapsules were produced with a fill content of 83-92 wt% as determined by CHN analysis.
Incorporating self-healing functionality in a polysiloxane elastomer successfully retards the growth of fatigue cracks under torsional fatigue loading. The fully in situ self-healing material ...consists of a microencapsulated vinyl-terminated poly(dimethylsiloxane) resin containing platinum catalyst compounds and a microencapsulated initiator (methylhydrosiloxane), embedded in a poly(dimethylsiloxane) elastomer matrix. A torsion fatigue test protocol is adopted to assess the self-healing performance of two different elastomeric matrices. Significant recovery of torsional stiffness occurs after approximately 5h, the time required to achieve a measurable degree of cure of the healing agents. Total fatigue crack growth in a self-healing specimen is reduced by 24% in comparison to relevant controls. The retardation of growing fatigue cracks is attributed, in part, to a sliding-crack-closure mechanism, where polymerized healing agent shields the crack tip from the applied far-field stress.
Abstract
Microcapsules containing a liquid metal alloy core of gallium-indium (Ga-In) are prepared via in situ urea-formaldehyde (UF) microencapsulation. The capsule size, shape, thermal properties, ...and shell wall thickness are investigated. We prepare ellipsoidal capsules with major and minor diameter aspect ratios ranging from 1.64 to 1.08 and with major diameters ranging from 245 µm to 3 µm. We observe that as the capsule major diameter decreases, the aspect ratio approaches 1. The thermal properties of the prepared microcapsules are investigated by thermogravimetric (TGA) and differential scanning calorimetry (DSC). Microcapsules are shown to survive incorporation into an epoxy matrix and to trigger via mechanical damage to the cured matrix. Microcapsules containing liquid metal cores may have diverse applications ranging from self-healing to contrast enhancement or the demonstration of mechano-adaptive circuitry.
An emerging strategy for creating self-healing materials relies on embedded vascular networks of microchannels to transport reactive fluids to regions of damage. Here we investigate the use of active ...pumping for the pressurized delivery of a two-part healing system, allowing a small vascular system to deliver large volumes of healing agent. Different pumping strategies are explored to improve the mixing and subsequent polymerization of healing agents in the damage zone. Significant improvements in the number of healing cycles and in the overall healing efficiency are achieved compared with prior passive schemes that use only capillary forces for the delivery of healing agents. At the same time, the volume of the vascular system required to achieve this superior healing performance is significantly reduced. In the best case, nearly full recovery of fracture toughness is attained throughout 15 cycles of damage and healing, with a vascular network constituting just 0.1 vol% of the specimen.
Microvascular networks show promise for applications such as self-healing, self-cooling, and structural damage sensing. Fluid-filled micro-scale channels have been investigated extensively in the ...field of microfluidics, but three-dimensional networks in polymeric structural materials have been achieved only recently. The purpose of microvascular network integration is to provide a vehicle for the distribution and replenishment of active fluids throughout a matrix material enabling multifunctional operation. This perspective seeks to examine the advances in fabrication techniques, characterization, and new theoretical and computational tools for guiding design that are leading to systems with greater functionality and complexity.
A protocol is described to assess self-healing of crack damage in a polymer coating deposited on a substrate containing a microvascular network. The bio-inspired coating/substrate design delivers ...healing agent to cracks in the coating via a three-dimensional microvascular network embedded in the substrate. Through capillary action, monomer flows from the network channels into the crack plane where it is polymerized by a catalyst embedded in the coating. The healing efficiency of this materials system is assessed by the recovery of coating fracture toughness in a four-point beam bending experiment. Healing results for the microvascular networks are compared to data for a coating containing microencapsulated healing agents. A single crack in a brittle epoxy coating is healed as many as seven times in the microvascular systems, whereas microcapsule-based healing occurs for only one cycle. The ability to heal continuously with the microvascular networks is limited by the availability of catalyst in the coating.
A materials system for autonomic healing of epoxy vinyl esters is demonstrated. The system is comprised of wax microspheres containing Grubbs' catalyst and microcapsules containing ...exo‐dicyclopentadiene (DCPD) embedded together in an epoxy vinyl ester matrix. Healing is triggered when damage in the form of a crack ruptures the microcapsules, causing DCPD to be released into the crack plane where it comes in contact and mixes with the catalyst microspheres initiating ring opening metathesis polymerization (ROMP). The chemical compatibility of the catalyst with the matrix is investigated and wax protection of the catalyst via microspheres of a sufficient size (34–98 μm) is shown to provide a suitable barrier for protecting the catalyst from free radicals generated in situ during the curing of the epoxy vinyl ester resin. Wax protection of the catalyst also allows uninhibited curing of the matrix to proceed at room temperature. Concentration of self‐healing components is varied with a view towards optimization of the recovery of virgin mechanical properties. Efficient self‐healing is observed with microspheres that are smaller than those used in previous polymer matrices. Significant recovery of virgin mechanical properties is observed within 2.5 min of healing time at room temperature and the mechanical properties of healed samples after 24 h of healing time match those of existing ROMP‐based self‐healing systems.
The autonomic healing of epoxy vinyl esters at ambient temperatures is demonstrated by the incorporation of wax protected Grubbs' catalyst and microencapsulated DCPD into the vinyl ester matrix. Fracture testing shows that this material is capable of recovering up to 50 % of resin peak fracture load.
A method for fabricating microvascular networks in fiber‐reinforced composites is presented. The method relies on sacrificial fibers woven into fiber preforms that, when removed by depolymerization ...and volatilization, create 3D microvascular networks inside the composite material. By circulation of functional liquids in the resulting channels, a diverse set of new functionality is demonstrated. Simplicity, robustness, scalability, and reliance on readily available components make this method compatible with composite manufacturing methods.
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