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At least 19 records

Normal and anomalous self-healing mechanism of crystalline calcium silicate hydrates

The origin of different stability of crystalline calcium silicate hydrates was investigated. The tobermorite crystal has been used as an analog of cement hydrate that is being mostly manufactured material on earth. Normal tobermorite is thermally unstable and transforms to amorphous at low pressure. Meanwhile, anomalous tobermorite with high Al content does not significantly transform under high pressure or high temperature. Conducted X-ray absorption spectroscopy explains the weak stability of normal tobermorite which was originally hypothesized by the role of zeolitic Ca ions in the cavities of silicate chains. Atomic simulations reproduced the experimentally observed trend of pressure behavior once the ideal structures were modified to account for the Al content as well as the chain defects. The simulations also suggested that the stability of tobermorite under stress could be rationalized as a self-healing mechanism in which the structural instabilities were accommodated by a global sliding of the CaO layer.

36 MATERIALS SCIENCE↗

Developing Flexible, High Performance Polymers with Self-Healing Capabilities

Flexible, high performance polymers such as polyimides are often employed in aerospace applications. They typically find uses in areas where improved physical characteristics such as fire resistance, long term thermal stability, and solvent resistance are required. It is anticipated that such polymers could find uses in future long duration exploration missions as well. Their use would be even more advantageous if self-healing capability or mechanisms could be incorporated into these polymers. Such innovative approaches are currently being studied at the NASA Kennedy Space Center for use in high performance wiring systems or inflatable and habitation structures. Self-healing or self-sealing capability would significantly reduce maintenance requirements, and increase the safety and reliability performance of the systems into which these polymers would be incorporated. Many unique challenges need to be overcome in order to incorporate a self-healing mechanism into flexible, high performance polymers. Significant research into the incorporation of a self-healing mechanism into structural composites has been carried out over the past decade by a number of groups, notable among them being the University of I1linois [I]. Various mechanisms for the introduction of self-healing have been investigated. Examples of these are: 1) Microcapsule-based healant delivery. 2) Vascular network delivery. 3) Damage induced triggering of latent substrate properties. Successful self-healing has been demonstrated in structural epoxy systems with almost complete reestablishment of composite strength being achieved through the use of microcapsulation technology. However, the incorporation of a self-healing mechanism into a system in which the material is flexible, or a thin film, is much more challenging. In the case of using microencapsulation, healant core content must be small enough to reside in films less than 0.1 millimeters thick, and must overcome significant capillary and surface tension forces to flow, mix and react to achieve healing. Vascular networks small enough to fit into such films must also overcome these same flow limitations. Self-healing has also been demonstrated in ionomeric substrates such as Surlyn , wherein the heat generated by a projectile impact triggers the latent ability of this substrate to flow back to its original shape. Recent work using Diels-Alder reactions have shown promise in bringing about actual reforming of broken chemical bonds to achieve self-healing [2]. All self-healing mechanisms that rely on the use of inherent latent substrate properties require some degree of polymer chain flow to achieve any significant level of healing.

Jolley, Scott T.↗

Assessment of Composite Delamination Self-Healing Via Micro-Encapsulation

Composite skin/stringer flange debond specimens manufactured from composite prepreg containing interleaf layers with a polymer based healing agent encapsulated in thin walled spheres were tested. As a crack develops and grows in the base polymer, the spheres fracture releasing the healing agent. The agent reacts with catalyst and polymerizes healing the crack. In addition, through-thickness reinforcement, in the form of pultruded carbon z-pins were included near the flange tips to improve the resistance to debonding. Specimens were manufactured with 14 plies in the skin and 10 plies in the stiffener flange. Three-point bend tests were performed to measure the skin/stiffener debonding strength and the recovered strength after healing. The first three tests performed indicated no healing following unloading and reloading. Micrographs showed that delaminations could migrate to the top of the interleaf layer due to the asymmetric loading, and hence, bypass most of the embedded capsules. For two subsequent tests, specimens were clamped in reverse bending before reloading. In one case, healing was observed as evidenced by healing agent that leaked to the specimen edge forming a visible "scar". The residual strength measured upon reloading was 96% of the original strength indicating healing had occurred. Hence, self-healing is possible in fiber reinforced composite material under controlled conditions, i.e., given enough time and contact with pressure on the crack surfaces. The micro-encapsulation technique may prove more robust when capsule sizes can be produced that are small enough to be embedded in the matrix resin without the need for using an interleaf layer. However, in either configuration, the amount of healing that can occur may be limited to the volume of healing agent available relative to the crack volume that must be filled.

O'Brien, T. Kevin↗

Self-Healing Nanocomposites for Reusable Composite Cryotanks

Composite cryotanks, or composite overwrapped pressure vessels (COPVs), offer advantages over currently used aluminum-lithium cryotanks, particularly with respect to weight savings. Future NASA missions are expected to use COPVs in spaceflight propellant tanks to store fuels, oxidizers, and other liquids for launch and space exploration vehicles. However, reliability, reparability, and reusability of the COPVs are still being addressed, especially in cryogenic temperature applications; this has limited the adoption of COPVs in reusable vehicle designs. The major problem with composites is the inherent brittleness of the epoxy matrix, which is prone to microcrack formation, either from exposure to cryogenic conditions or from impact from different sources. If not prevented, the microcracks increase gas permeation and leakage. Accordingly, materials innovations are needed to mitigate microcrack damage, and prevent damage in the first place, in composite cryotanks. The self-healing technology being developed is capable of healing the microcracks through the use of a novel engineered nanocomposite, where a uniquely designed nanoparticle additive is incorporated into the epoxy matrix. In particular, this results in an enhancement in the burst pressure after cryogenic cycling of the nanocomposite COPVs, relative to the control COPVs. Incorporating a novel, self-healing, epoxy-based resin into the manufacture of COPVs allows repeatable self-healing of microcracks to be performed through the simple application of a low-temperature heat source. This permits COPVs to be reparable and reusable with a high degree of reliability, as microcracks will be remediated. The unique phase-separated morphology that was imparted during COPV manufacture allows for multiple self-healing cycles. Unlike single-target approaches where one material property is often improved at the expense of another, robustness has been introduced to a COPV by a combination of a modified resin and nanoparticle additives. Unique nanoparticles were used that have been surface-functionalized to be compatible with the resin. Both organic and inorganic components toughen the matrix and result in a more impact-resistant COPV. In one resin system containing an inorganic nanomaterial additive, a significant improvement in burst performance was observed after the COPV was cryo-impact-damaged and then self-healed, with a greater than 10% improvement in burst pressure after the self-healing process was performed. Initial cross-sectional analysis via microscopy showed good resin infiltration of the carbon fibers and without voids. To further enhance the capability between the nanomaterial additives and the resin, a surface modification was successfully performed. A second specialty epoxy resin was prepared using a surface modified nanomaterial additive, and COPVs were fabricated. Steps were taken to improve the mechanical properties of the COPVs by using a low-viscosity resin system that contained a different curing agent. This lower viscosity improves the processing of the COPV, and preliminary results show that the burst pressure of these new vessels is 20 to 25% higher than that of the original. The self-healing concept demonstrated in this research and development effort represents a platform technology, and the self-healing property is neither restricted to the particular epoxy system used here, nor to the COPV application. Self-healing is a direct result of a unique phase separated morphology created via the resin and is aided by the nanoparticles. The self-healing function can be introduced to other customer-specific resin systems in coating, bulk, or composite applications provided that the unique phase separated morphology can be enabled in those systems.

Eberly, Daniel↗

A Self‐Healing System for Polydicyclopentadiene Thermosets

Self-healing offers promise for addressing structural failures, increasing lifespan, and improving durability in polymeric materials. Implementing self-healing in thermoset polymers faces significant manufacturing challenges, especially due to the elevated temperature requirements of thermoset processing. To introduce self-healing into structural thermosets, the self-healing system must be thermally stable and compatible with the thermoset chemistry. This article demonstrates a self-healing microcapsule-based system stable to frontal polymerization (FP), a rapid and energy-efficient manufacturing process with a self-propagating exothermic reaction (≈200 °C). A thermally latent Grubbs-type complex bearing two N-heterocyclic carbene ligands addresses limitations in conventional G2-based self-healing approaches. Under FP's elevated temperatures, the catalyst remains dormant until activated by a Cu(I) co-reagent, ensuring efficient polymerization of the dicyclopentadiene (DCPD) upon damage to the polyDCPD matrix. The two-part microcapsule system consists of one capsule containing the thermally latent Grubbs-type catalyst dissolved in the solvent, and another capsule containing a Cu(I) coagent blended with liquid DCPD monomer. Using the same chemistry for both matrix fabrication and healing results in strong interfaces as demonstrated by lap-shear tests. In an optimized system, the self-healing system restores the mechanical properties of the tough polyDCPD thermoset. Self-healing efficiencies greater than 90% via tapered double cantilever beam tests are observed.

36 MATERIALS SCIENCE↗

The effect of shear strain and shear localization on fault healing

The seismic cycle of repeated earthquake failure requires that faults regain frictional strength during the interseismic phase, when the fault is locked or undergoing quasi-static creep. Fault healing plays a central role in determining earthquake stress drop, recurrence interval, elastic radiation frequency and other source parameters. In particular, the longer a fault remains quasi-stationary, the stronger it becomes and the larger the potential stress drop can be for the next event. Here, we address the role of shear strain and strain localization on fault healing and healing rate. We performed slide-hold-slide friction experiments on quartz gouge in the double-direct shear configuration for shear strain up to 25 and hold times from 10 to 1000 s. The results show that both healing and healing rate increase nonlinearly with increasing shear strain. Frictional healing scales with volumetric strain within the laboratory fault zone. Using the volumetric strain upon reshear as a proxy for strain localization, we demonstrate that the capacity of a fault to heal is directly proportional to shear bandwidth and degree of strain localization. The more the deformation is localized, the higher are the healing and healing rate, and thus, the fault strength. Our data provide a framework for understanding variations in fault strength over the seismic cycle and the role of brecciation and strain localization on spatiotemporal variations in fault strength.

58 GEOSCIENCES↗

Hydrogel-assisted self-healing of biomineralized living building materials

Living building materials (LBMs) are an emergent class of structural materials that leverage the biomineralization capability of microorganisms within sand-hydrogel scaffolds to produce living, load-bearing structures. Here we produced LBMs using a physically crosslinkable sand-hydrogel scaffold and two microorganisms with different biomineralization pathways - Synechococcus sp. PCC 7002 (photosynthetic) and S. pasteurii (ureolytic) - and investigated their self-healing capacity. Our results reveal that both Synechococcus sp. PCC 7002 and S. pasteurii demonstrated exceptional viability within all LBMs for more than 20 days. Damaged LBMs containing Synechococcus sp. PCC 7002 exhibited 103% and 112% of their original compressive and flexural strengths, respectively, after three days of healing at 50% relative humidity (RH) (i.e., ambient conditions). In contrast, LBMs containing S. pasteurii exhibited 71% and 66% of their original compressive and flexural strengths, respectively, after three days of healing at 50% RH. The compressive and flexural strengths of all LBMs rebounded to 93-100% after seven days of healing at 50% RH. Data substantiate that the self-healing ability of the hydrogel plays a critical role in facilitating healing of LBMs, as evidenced by the 82-118% rebounds in compressive and flexural strengths by the sand-hydrogel scaffold alone after three or seven days of healing at 50% RH. Healing was less effective at 100% RH for all LBMs investigated herein.

36 MATERIALS SCIENCE↗

Postmortem and Antemortem Forensic Assessment of Pediatric Fracture Healing from Radiographs and Machine Learning Classification

A timeline of pediatric bone healing using fracture healing characteristics that can be assessed solely using radiographs would be practical for forensic casework, where the fracture event may precede death by days, months, or years. However, the dating of fractures from radiographs is difficult, imprecise, and lacks consensus, as only a few aspects of the healing process are visible on radiographs. Multiple studies in both the clinical and forensic literature have attempted to develop a usable scale to assess pediatric bone healing on radiographs using various healing characteristics. In contrast to the orthopedic definition, a fracture in forensic casework is only considered to be healed when the area around the fracture has been remodeled to the point that the fracture is difficult to detect on a radiograph or on the surface of the bone itself, a process that can take several years. We subjectively assessed visible characteristics of healing in radiograms of fractures occurring in 942 living children and adolescents. By dividing these assessments into learning and test (validation) sets, the accuracy of a newly proposed fracture healing scale was compared to a previous study. Two machine learning models were used to test predictions of the new scale. All three models produced similar estimates with substantial imprecision. Results corroborate the Malone model with an independent dataset and support the efficacy of using less complex models to estimate fracture age in children.

60 APPLIED LIFE SCIENCES↗

ELASTOMERIC MICROVASCULAR SELF-HEALING MATERIALS

Damaged elastomeric diaphragms within pneumatic controllers used in the oil and gas industry lead to an unintended release of methane. Self-healing microvascular materials capable of healing various types of damage have been fabricated. These microvascular materials are designed to replace currently available commercial diaphragms found in pneumatic controllers and provide a solution to reduce unintended methane leaks. Poly(dimethylsiloxane) (PDMS) was used as the main matrix material, with additional testing conducted on polyurethane and flexibilised epoxy materials. Microvascular networks were implemented into the elastomeric membranes to act as ves- sels to deliver healing agents to the damaged areas. The complex, interdigitated channel networks were created using a 3D printed custom compounded filament composed of polylactic acid (PLA) and tin(II) oxalate. Two-part liquid casting polymers were poured around the channels into a mould to create samples with the scaffolding of the microvascular channels intact. Hollow microvascular networks were created by placing the samples within a vacuum oven at 250◦C which causes the thermal depolymerisation of PLA into its gaseous monomers. The manufactured materials were placed in test stands and pressurized using nitrogen gas to determine their healing and mechanical behaviour. Self-healing behaviour was demonstrated using PDMS matrix materials and healing chemistries within a pressure test cell. This test cell was designed to detect any damage to a sample by record- ing an outlet pressure. Damages including puncture holes, diagonal cuts and star-shaped central iv cuts were applied to the samples and a reduction in the outlet pressure was recorded for all sam- ples. A variation in channel spacing and diameter was studied to determine the optimal design of the microvascular network for self-healing performance. The mechanical performance of elastomeric membrane materials within a diaphragmatic pressurised stand was observed. Deformations and strains around the channels and channel inter- sections at the midplane of the materials were recorded using digital image correlation. Normal stresses were calculated using Hooke’s law and the material properties of the PDMS matrix. A reduction in leak rate, implying the success of self-healing, was recorded within manu- factured diaphragm samples tested within a commercial valve. PDMS is the favourable material when compared to polyurethane and flexibilised epoxy for creating

03 NATURAL GAS↗

Recent Advances in Thermoplastic Puncture-Healing Polymers

Self-healing materials provide a route for enhanced damage tolerance in materials for aerospace applications. In particular, puncture-healing upon impact has the potential to mitigate significant damage caused by high velocity micrometeoroid impacts. This type of material also has the potential to improve damage tolerance in load bearing structures to enhance vehicle health and aircraft durability. The materials being studied are those capable of instantaneous puncture healing, providing a mechanism for mechanical property retention in lightweight structures. These systems have demonstrated healing capability following penetration of fast moving projectiles -- velocities that range from 9 mm bullets shot from a gun (approx.330 m/sec) to close to micrometeoroid debris velocities of 4800 m/sec. In this presentation, we report on a suite of polymeric materials possessing this characteristic. Figure 1 illustrates the puncture healing concept. Puncture healing in these materials is dependent upon how the combination of a polymer's viscoelastic properties responds to the energy input resulting from the puncture event. Projectile penetration increases the temperature in the vicinity of the impact. Self-healing behavior occurs following puncture, whereby energy must be transferred to the material during impact both elastically and inelastically, thus establishing two requirements for puncture healing to occur: a.) The need for the puncture event to produce a local melt state in the polymer material and b.) The molten material has to have sufficient melt elasticity to snap back and close the hole. 1,2 Previous ballistic testing studies revealed that Surlyn materials warmed up to a temperature approx.98 C during projectile puncture (3 C higher than it s melting temperature). 1,2 The temperature increase produces a localized flow state and the melt elasticity to snap back thus sealing the hole. Table 1 lists the commercially polymers studied here, together with their physical properties. The polymers were selected based on chemical structure, tensile strengths, tensile moduli, glass transition temperature, melting temperatures, and impact strength. The thermal properties of the polymers were characterized by Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA). Mechanical properties were assessed by a Sintech 2W instron according to ASTM D1708 or D638 at crosshead speeds of 5.08 cm/min. 7.6 cm x 7.6 cm panels of the different materials were prepared and ballistic testing was performed at various temperatures. The panels were shot with a .223 caliber semiautomatic rifle from a distance of 23 meters at various temperatures. Chronographs were used to measure initial and final bullet velocity. Temperatures at the site of impact were measured using a FLIR ThermaCAM S60 thermal camera. A Vision Research model Phantom 9 high speed video camera was used to capture high speed video footage of ballistics testing.

Gordon, K. L.↗

Self-healing cable for extreme environments

Self-healing cable apparatus and methods disclosed. The self-healing cable has a central core surrounded by an adaptive cover that can extend over the entire length of the self-healing cable or just one or more portions of the self-healing cable. The adaptive cover includes an axially and/or radially compressible-expandable (C/E) foam layer that maintains its properties over a wide range of environmental conditions. A tape layer surrounds the C/E layer and is applied so that it surrounds and axially and/or radially compresses the C/E layer. When the self-healing cable is subjected to a damaging force that causes a breach in the outer jacket and the tape layer, the corresponding localized axially and/or radially compressed portion of the C/E foam layer expands into the breach to form a corresponding localized self-healed region. The self-healing cable is manufacturable with present-day commercial self-healing cable manufacturing tools.

Huston, Dryver R.↗

A high-efficiency self-healing cementitious material based on supramolecular hydrogels impregnated with phosphate and ammonium

High-efficiency self-healing cementitious materials using hydroxyapatites as healing product were described. Supramolecular hydrogels impregnated with phosphate and ammonium ions were designed. Morphology of the supramolecular hydrogel and its capability to release phosphate in solution, the structure of healing products and the self-healing efficiency were characterized with a range of analytical techniques. Cracks in the cementitious materials with width up to 1 mm are closed and completely healed. The healing product in the cracks without ammonium ions was brushite with a sponge-like morphology. Released ammonium ions reacted with calcium hydroxide in the cement matrix, increasing the concentration of soluble calcium ions up to 300 times that in reference pore solution. Ammonium ions facilitated the formation and aggregation of healing products which were converted into hydroxyapatites, improving the maximum healable crack width.

36 MATERIALS SCIENCE↗

SELF-HEALING PNEUMATIC ACTUATOR DIAPHRAGMS

In the oil and gas industry, damaged diaphragms in pneumatic actuators can lead to unintended methane leaks, increasing emissions. In this work, replacement self-healing diaphragms are manufactured for a commercial pneumatic actuator. To enable self-healing, hollow microvascular networks are created within the diaphragms using sacrificial 3D printed PLA w/ tin(II) oxalate. These microvascular networks are filled with healing chemistries and, upon damage, rupture. After rupturing, the healing chemistries mix and cure to “heal” the damage and reduce leaks. Separate actuator test stands using nitrogen gas and using natural gas were developed to assess the healing performance of diaphragms. A fatigue stand was also developed to evaluate the effects of the different microvascular network geometries on the fatigue life of diaphragms. Our results demonstrate self-healing in diaphragms subjected to damage and tested for leaks. In fatigue testing, our results indicate that the introduction of microvascular networks does not influence the fatigue life.

Self-healing, pneumatic actuator↗

Self-healing carbon fiber/epoxy laminates with particulate interlayers of a low-melting-point alloy

In order to prolong the service life of fiber-reinforced polymer composites, the implementation of self-healing ability with the micro-encapsulated healing agent has been extensively studied. However, such microcapsule-based self-healing composites typically suffer from degraded mechanical properties due to the liquid-phase inclusions, thereby limiting their proliferation. Here, in this study, a low-melting-point alloy is utilized as the particulate inclusions of carbon fiber/epoxy laminated composites. Field's Metal particles (melting point: 62 °C) are distributed between woven carbon fiber preforms followed by the resin impregnation to realize laminated composites with a Field's Metal-enhanced interlayer(s). The resulting laminated composites demonstrate the autonomic repair of interlaminar failure with a 40 % of healing efficiency. Most of all, the mechanical properties of these self-healing laminated composites are comparable to the conventional laminated composites attributed to the rigid inclusions that can be compressed to increase the fiber volume. Since the Field's Metal particle inclusions can bestow polymer composites with self-healing ability and the potential increase in mechanical properties, Field's Metal-enhanced fiber-reinforced polymer composites are expected to unlock the practical utility of self-healing composites.

A. polymer-matrix composites (PMCs)↗

Assessment of Composite Delamination Self-Healing Under Cyclic Loading

Recently, the promise of self-healing materials for enhanced autonomous durability has been introduced using a micro-encapsulation technique where a polymer based healing agent is encapsulated in thin walled spheres and embedded into a base polymer along with a catalyst phase. For this study, composite skin-stiffener flange debonding specimens were manufactured from composite prepreg containing interleaf layers with a polymer based healing agent encapsulated in thin-walled spheres. Constant amplitude fatigue tests in three-point bending showed the effect of self-healing on the fatigue response of the skin-stiffener flange coupons. After the cycling that created debonding, fatigue tests were held at the mean load for 24 hours. For roughly half the specimens tested, when the cyclic loading was resumed a decrease in compliance (increase in stiffness) was observed, indicating that some healing had occurred. However, with continued cycling, the specimen compliance eventually increased to the original level before the hold, indicating that the damage had returned to its original state. As was noted in a prevoius study conducted with specimens tested under monotonically increasing loads to failure, healing achieved via the micro-encapsulation technique may be limited to the volume of healing agent available relative to the crack volume.

O'Brien, T. Kevin↗

Enhanced Photoluminescence and Prolonged Carrier Lifetime through Laser Radiation Hardening and Self-Healing in Aged MAPbBr3 Perovskites Encapsulated in NiO Nanotubes

Organic-inorganic perovskites hold great promise as optoelectronic semiconductors for pure color light emitting and photovoltaic devices. However, challenges persist regarding their photostability and chemical stability, which limit their extensive applications. This paper investigates the laser radiation hardening and self-healing-induced properties of aged MAPbBr3 perovskites encapsulated in NiO nanotubes (MAPbBr3@NiO) using photoluminescence (PL) and fluorescence lifetime imaging (FLIM). After deliberately subjecting the MAPbBr3@ NiO to atmospheric conditions for two years, the sample remains remarkably stable. It exhibits no changes in PL wavelength during UV laser irradiation and self-healing. Furthermore, exposure to UV light at 375 nm enhances the PL of the self-healed MAPbBr3@NiO. FLIM analysis sheds light on the mechanism behind photodegradation, self-healing, and PL enhancement. The results indicate the involvement of many carrier-trapping states with low lifetime events and an increase in peak lifetime after self-healing. The formation of trapping states at the perovskite/nanotube interface is discussed and tested. This study provides new insights into the dynamics of photo-carriers during photodegradation and self-healing in organic-inorganic perovskites.

36 MATERIALS SCIENCE↗

The Role of Clay in Limiting Frictional Healing in Fault Gouges

Abstract Frictional healing is fundamental to the seismic cycle and plays a role in the energy balance, dynamics, and recurrence interval of earthquakes and slow slip events. Although the healing behavior of quartz has been studied extensively, the role of clay content is less understood. We tested synthetic mixtures of quartz and smectite (10%–100% smectite) in a double‐direct shear configuration to measure frictional healing. We show that the magnitude and rate of healing decreases systematically with higher clay content (from 0.008/decade at 10% smectite to 0.002/decade at 100% smectite). Healing scales with both the magnitude of stress relaxation during holds and layer‐normal compaction of the gouge. We suggest this reflects the alignment of clay minerals, leading to saturation of the real area of contact that limits restrengthening during holds. The low healing rates of clay‐rich faults—together with rate‐neutral to rate‐strengthening friction—should promote frequent, small failures or stable sliding.

58 GEOSCIENCES↗