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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Self-healing, self-assembling islanded power systems using only local measurements

This SAND report collects the results from the LDRD project “SHAZAM”, which aimed to push the limits of performance for self-healing, self-assembling power systems whose sectionalizing and load-control agents rely on local measurements only (i.e., only what they can measure at their own terminals, with no data sharing between agents). This work includes self-networking microgrids. The key objectives of this work were a) to demonstrate how high the performance of local-measurement-only self-assembling power systems can be; and b) to solve certain technical problems associated with such systems, such as their inability to prevent the accidental formation of closed loops and their tendency to thermally overload some conductors. “SHAZAM” investigators a) demonstrated that the performance of such systems can be surprisingly high, b) demonstrated that such systems are quite robust to all kinds of variations, and c) developed and demonstrated solutions to several key challenges associated with this type of system.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Structural and chemical changes from CO2 exposure to self-healing polymer cement composites for geothermal wellbores

Wellbore cement is subjected to a number of mechanical, thermal and chemical stress regimes over its lifetime. Therefore, next generation wellbore cement formulations need to be evaluated in conditions relevant to these environments. In this work, we investigate the mechanism of the alteration of a novel self-healing polymer-cement composite recently reported by our group after exposure to a CO2-rich environment by using synchrotron based X-ray Fluorescence (XRF) and X-ray absorption near edge structure (XANES) and scanning electron microscopy coupled with energy dispersive spectroscopy. Results showed that chemical alteration of the polymer-cement follows the rim carbonation mechanism, similar to conventional cement although carbonation takes place to a lesser extent in polymer-cements despite the higher porosity. Along with detailed mechanistic insights on carbonation in polymer-cement composite, the performance of these in CO2-rich environment is further studied using standard compressive strength analysis.

Elbakhshwan, Mohamed↗

Well-Tunable, 3D-printable, and Fast Autonomous Self-Healing Elastomers

Self-healing elastomers provide extended longevity of functional materials, due to their unique adaptability and durability. However, a major scientific challenge remains in developing materials with a rapid healing process combined with decent mechanical properties, that can be prepared by a relatively simple synthesis approach. Herein, we report a versatile design approach on self-healing elastomers by incorporating two different hydrogen bonding containing monomers, i.e., 2-[[(butylamino)carbonyl]oxy]ethyl acrylate (BCOE) and 2-ureido-4[1H]pyrimidinone (UPy) functionalized ethyl methacrylate. Poly(BCOE-r-UPy)s are synthesized by reversible addition-fragmentation chain-transfer (RAFT) polymerization, and controlling the ratio of two monomers enables well-tunable mechanical properties with tensile strength ranging from 0.04 to 6.3 MPa and tensile strain up to 3,000 %. The characteristic dissociation energy is calculated from a temperature dependence of terminal relaxation followed by subtracting the segmental relaxation. The rapid autonomous self-healing is achieved when the molar composition of Poly(BCOE-r-UPy) is tailored to BCOE/UPy = 99/1. The self-healing process is monitored in situ by a helium-ion microscope, and its macroscopic study using tensile tests indicates that Poly(BCOE-r-UPy1) with 1 % molar ratio of UPy recovers 70 % of its original toughness at ambient temperature within 10 mins. 3D printing of Poly(BCOE-r-UPy) affords a self-healable 3D structure, demonstrating the adaptability of Poly(BCOE-r-UPy) for on-demand fabrication. The simplicity of synthesis, well-tunable mechanical properties, unique self-healability, and 3D printing capability of Poly(BCOE-r-UPy)s indicate their potential for a range of applications.

36 MATERIALS SCIENCE↗

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↗

Subsurface Spectroscopy in Heterogeneous Materials Using Self-Healing Laser Beams

Self-healing optical beams are a class of propagation modes that can recover their beam shapes after distortion or partial blockage. This self-healing property makes them attractive for use in applications involving turbid media as they can—in theory—penetrate further into these materials than standard Gaussian beams. In this paper, we characterize the propagation of two different self-healing beams (Bessel and Airy) through a solid scattering material with different scatterer concentrations and find that both beams do recover after scattering for samples below a threshold scatterer concentration. Additionally, we test the applicability of both beam shapes for improved sub-surface spectroscopy in heterogeneous materials using fluorescent particles and find that there is an average fluorescence intensity enhancement of 1.3× using self-healing beams versus a standard Gaussian beam.

47 OTHER INSTRUMENTATION↗

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↗

Water accelerated self-healing of hydrophobic copolymers

Previous studies have shown that copolymer compositions can significantly impact self-healing properties. This was accomplished by enhancement of van der Waals (vdW) forces which facilitate self-healing in relatively narrow copolymer compositional range. In this work we report the acceleration of self-healing in alternating/random hydrophobic acrylic-based copolymers in the presence of confined water molecules. Under these conditions competing vdW interactions do not allow H 2 O-diester H-bonding, thus forcing nBA side groups to adapt L-shape conformations, generating stronger dipole-dipole interactions resulting in shorter inter-chain distances compared to ‘key-and-lock’ associations without water. The perturbation of vdW forces upon mechanical damage in the presence of controllable amount of confined water is energetically unfavorable leading the enhancement of self-healing efficiency of hydrophobic copolymers by a factor of three. The concept may be applicable to other self-healing mechanisms involving reversible covalent bonding, supramolecular chemistry, or polymers with phase-separated morphologies.

36 MATERIALS SCIENCE↗

Autonomous Self-Healing Elastomers with Unprecedented Adhesion Force

Self-healable elastomers are extremely attractive due to their ability to prolong product lifetime. An additional function that could further expand their applications is strong adhesion force to clean and dusty surfaces. This study reports a series of autonomous self-healable and highly adhesive elastomers (ASHA-Elastomer) that are fabricated via a simple, efficient, and scalable process. The obtained elastomers exhibit outstanding mechanical properties with elongation at break up to 2102% and toughness (modulus of toughness) of 1.73 MJ m -3 . The damaged ASHA-Elastomer can autonomously self-heal with full recovery of functionalities, and the healing process is not affected by the presence of water. The elastomers are found to possess an ultrahigh adhesion force up to 3488 N m -1 , greatly outperforming previously reported self-healing adhesive elastomers. Furthermore, the adhesion force of the ASHA-Elastomer is negligibly affected by dust on the surface, in stark contrast with regular adhesive polymers that have adhesion strengths extremely sensitive to dust. The successful development of high-toughness, autonomous self-healable, and ultra-adhesive elastomers will enable a wide range of applications with enhanced longevity and versatility, including their use in sealants, adhesives, and stretchable devices.

36 MATERIALS SCIENCE↗

Degradation and Self-Healing in Perovskite Solar Cells

Organic–inorganic halide perovskites are well-known for their unique self-healing ability. In the presence of strong external stimuli, such as light, temperature, and moisture, high-energy defects are created which can be healed by removing the perovskite from the degradation source. Furthermore, this self-healing ability has been showcased in devices with recoverable performance and day-and-night cycling operation to dramatically extend the device lifetime and even mechanical durability. However, to date, the mechanistic details and theory around this captivating trait are sparse and convoluted by the complex nature of perovskites. With a clear understanding of the intrinsic self-healing property, perovskite solar cells with extended lifetimes and durability can be designed to realize the large-scale commercialization of perovskite solar cells. Here, we spotlight the relevant degradation and self-healing literature and then propose design strategies to help conceptualize future research.

14 SOLAR ENERGY↗

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↗

Effect of chloride ingress on self-healing recovery of smart cementitious composite incorporating crystalline admixture and MgO expansive agent

Highlights: • Crack closure under wet/dry cycles in chloride solution is higher than the one in distilled water. • Element analysis shows that calcium is vital for crack healing either in water or chloride solution. • AFm is consumed by chloride ion to form Fs, and Fs were decomposed to AH{sub 3} by carbonation. • Soluble reactive silica reacts with calcium hydrate to form C-S-H gel to heal concrete cracks. • Expansion of magnesium hydroxide facilitates crack self-healing by interconnected network. In this study, the effect of chloride environment containing various concentrations of chloride ion (Cl{sup −}) on self-healing performance of pre-cracked cementitious composite containing crystalline admixture (CA) and MgO expansive agent (MEA) was investigated under wet-dry cycles in chloride solutions. The results revealed that the Cl{sup −} changed the mineralogy of self-healing products, and consequently, affected the crack closure ratio and mechanical strength recovery. When self-healing occurred in distilled water, a large amount of ettringite (AFt) were detected, whereas in Cl{sup −} solution, monosulfate (AFm) was consumed by Cl{sup −} to form Friedel's salt (Fs), and then the Fs was decomposed to Al(OH){sub 3}(AH{sub 3}) due to carbonation. During the multiphase conversion process, hydroxide (OH{sup −}) was released into crack solution, therefore the dissolved carbon dioxide (CO{sub 2}) concentration was increased. The carbonation of the crystals formed in cracks was accelerated with the volume expansion, which achieved rapid crack sealing but contributed little to the mechanical performance recovery.

36 MATERIALS SCIENCE↗

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)↗

Synthesis of multiphase self-healing polymers from commodity monomers

A self-healing polymer material that includes a multiphase copolymer, and a method of making the copolymer, are provided. The multiphase copolymer includes one or more hydrogen bond-forming copolymer segments, each segment including a polymerized acrylamide monomer and a polymerized acrylic monomer. The polymerized acrylamide monomer includes functional groups that form hydrogen bonds in the multiphase copolymer, and is present in the one or more copolymer segments in an amount sufficient for self-healing of the multiphase copolymer.

Guan, Zhibin↗

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↗

Dual Function Solid State Battery with Self-Forming Self-Healing Electrolyte and Separator (Final Scientific/Technical Report)

Over the course of this program, we have demonstrated an improved rechargeable Li/I2 battery with reduced impedance, improved cyclability, improved Coulombic Efficiency, and the ability to “self-heal” during shorting events. Multi-year efforts have led to the development and improvements in the composition, fabrication, and preparation of the solid state electrolyte, the role of the interface, and design of appropriate test conditions. These investigations have led to significant improvements in Coulombic efficiency. By systematic development of a composite solid state electrolyte, this system is able to self-form upon charge, thus lending itself to long shelf life before use. The initial project objective was to demonstrate a solid-state rechargeable battery based on a Li-metal anode and iodine cathode with a self-forming, self-healing electrolyte and separator with high gravimetric and volumetric energy density. The final deliverables of this project build on a multi-year effort beginning with materials development and design to generate a suitable solid state electrolyte composite with demonstrated higher ionic conductivity compared to the baseline (LiI). Development in cell design and interface modification leading to the generation of rechargeable solid electrolyte cells with Coulombic efficiency improvements of ~3X over initial tests, as well as demonstration of self-healing behavior, where the cells retained their ability to continue extended cycling after shorting events. The hypothesis put forward as part of the initial concept for the project was that the cell chemistry would be self-healing. For example, if a lithium dendrite formed during charge of the cell and reached the iodine cathode, the reaction of the lithium dendrite with the iodine would consume the tip of the dendrite to form lithium iodide, more of the solid electrolyte. The formation of the solid electrolyte would allow the cell to recover and continue to function. This type of self-healing during cycling has been demonstrated and has the potential to improve on safety considerations that stem from shorting events in other Li- containing systems.

25 ENERGY STORAGE↗

Self-healing barrier films for vacuum insulation panels

A self-healing vacuum insulation panel and a method of manufacture are provided. The vacuum insulation panel includes a self-healing, multi-layer barrier film including a separator between a curing agent and a curable resin. Upon damage to the separator, the curing agent penetrates the separator due to a pressure differential across the barrier film and reacts with the curable resin to seal any cuts or punctures. The curing agent and the curable resin can be selected to have long term stability and a short reaction time with no need for external stimuli. As a result, the multi-layer barrier film can retain the internal vacuum and maintain a desirably low thermal conductivity using low-cost, commercially available epoxies and curing agents.

Biswas, Kaushik↗

Confinement-Driven Segregation Enables Glassy Polymer Hybrid Materials Featuring Disordered Hyperuniformity and Integrated Self-Healing

The blending of glassy copolymer-brush modified colloids with a viscoelastic linear copolymer featuring intrinsic self-healing enabled disordered hyperuniform hybrid materials that combined mechanical robustness with structural color, processability, environmental stability, and the ability to recover structure and properties after incurring physical damage via ‘integrated self-healing’. Symmetric linear n-butyl acrylate/methyl methacrylate (BA/MMA) were co-assembled with asymmetric glassy BA/MMA statistical copolymer brush (silica) particles. ‘Confinement-driven segregation’ resulted in a microphase-separated morphology in which the linear copolymer resided within the interstitial regions of a rigid (∼1 GPa) copolymer brush particle template with disordered hyperuniform microstructure. Diffusion of the self-healing copolymer additive into damage regions drove the recovery after damage, along with the restoration of structural color due to the materials hyperuniform microstructure. The synergistic action of intrinsic and extrinsic healing mechanisms could provide a versatile platform for the bottom-up fabrication of multifunctional hybrid materials with increased damage resistance and functional longevity.

36 MATERIALS SCIENCE↗

Progress and Challenges in Self-Healing Cementitious Materials

Concrete is the most used man-made material today consisting of a mixture of aggregates (sand, gravel, crashed rock) and paste. The paste component, made up of cement and water, cracks with time. Despite this shortcoming, research towards next-generation cement and concrete has only taken a boost in the past 10-15 years. In particular, self-healing cementitious materials is a research area that has attracted a great deal of attention. A number of reported novel formulations have demonstrated an increase in mechanical and chemical stability with respect to conventional Portland cement, through the addition of inorganic, organic, and even biological additives. This review reports on the latest advances in cement research related to the synthesis of self-healing cements applied in concrete structures. These include geopolymers, engineered cementitious materials (ECC), bacterial cement composites, microencapsulated self-healing materials, shape memory alloys (SMA), and polymer-cement composites. This work describes the performance of each cementitious material and the mechanism responsible for self-healing, including a section on the latest computational modeling studies towards this end. A detailed understanding of these various self-healing cement technologies, including their strengths and weaknesses, is critical at the time of determining the type of structures that these materials could be used for.

Fernandez, Carlos A.↗