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At least 73 records · Page 4

A self-healing liquid metal anode with PEO-Based polymer electrolytes for rechargeable lithium batteries

In this study, a Ga-Sn liquid metal alloy material is demonstrated as a self-healing anode system due to its fluidity via operando synchrotron-based transmission X-ray microscopy and X-ray diffraction experiments. Cracks formed due to volume expansions can be recovered by the fluidity of the liquid metals. By incorporating with a poly(ethylene oxide) (PEO)-based electrolyte at 60°C, the Ga-Sn anode shows a reversible lithium insertion and extraction process with a high initial discharge specific capacity of 682 mAh g -1 , followed by delivering a capacity of 462 mAh g -1 in the second cycle at C/20 rate. Furthermore, compared with its solid counterparts, the Ga-Sn liquid metal anode demonstrates a better capability to maintain its mechanical integrity and better contact with PEO solid electrolytes due to its advantageous features of the liquid. This study suggests a potential strategy to use liquid metal alloys with polymer solid electrolyte to solve the anode challenges in rechargeable lithium batteries.

36 MATERIALS SCIENCE↗

Advanced Self-Healing Polymer-Cement Composites for Geothermal Wellbore Application at 300 °C

Polymer-cement composites were formulated using two base cements and three polymers and evaluated as potential alternatives to conventional geothermal wellbore cementitious material. To mimic geothermal conditions these cement composites were cured at 300 °C and their mechanical properties, including compressive strength, Young modulus, shear bond strength to steel casing, and self-healing and re-adhering (to steel) capability were tested. To test thermal stability the samples were cured at 300 °C for up to 30 days followed by analysis of their mineralogy and chemical composition by X-ray diffraction spectroscopy (XRD), 13C NMR, and total organic carbon (TOC). These tests showed that all polymer composites formulated were thermally stable as supported by almost 100% TOC of the 300 ?C cured samples and presence of all the polymer signals in 13C NMR permeability tests performed before and after healing a longitudinal fracture base cements and polymer-cement composites gave lower (2nd/1st) permeability ratios with respect to base cements which suggests that introduction polymers result in self-healing composite materials. Curing two of the best performing polymer-cement composites for a period of 30 days at 300 °C maintained the self-healing capability. These advanced polymer-cement composites with higher mechanical stability, ductility and self-healing capability are promising alternatives to wellbore cement materials for geothermal and fossil energy applications.

polymer-cement, composite, wellbore, self-healing,↗

Ionic-content-driven restructuring of spirobisindane ionene networks: implications for mechanics, self-healing, and gas transport

Polymers of intrinsic microporosity (PIMs) offer exceptional gas permeability but remain brittle and susceptible to physical aging, limiting their durability in separation applications. Here, we introduce a reconfigurable microporous polymer network that uniquely integrates permanent PIM microporosity with autonomous, intrinsic self-healing driven by imidazolium-based ionic motifs. Spirobisindane units generate the intrinsic free-volume architecture, while an imidazolium-containing polyamide ionene supplies dynamic ionic and hydrogen-bonding interactions that reorganize under mild activation. Incorporation of imidazolium-based ionic liquids further tunes cohesion, mobility, and densification, enabling the network to relax, re-associate, and retain microporosity without structural collapse. Through a comprehensive multiscale approach combining spectroscopy, scattering, thermal and mechanical characterization with all-atom molecular dynamics and density functional theory calculations, we elucidate how ionic content, as a single control parameter that reshapes free-volume distributions, modulates local coordination environments, and governs relaxation and healing kinetics. At intermediate ionic loadings, the networks achieve rapid, repeatable self-healing while maintaining CO$_2$ selectivity, demonstrating an optimal balance between segmental mobility and structural integrity. By establishing how hierarchical ionic interactions couple structure, dynamics, and transport in microporous ionene networks, this work provides generalizable design rules for adaptive soft-matter systems that require simultaneous mechanical resilience, reconfigurability, and selective gas transport.

36 MATERIALS SCIENCE↗

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↗

Resilient Hydrogels from the Nanoscale to the Macroscale

Biological systems illustrate how a material composed of fragile molecular components can collectively be highly resilient. While the average protein, cell, or even tissue may not last more than a few weeks, many animals and plants live for more than a century. Continual component regeneration and multiple systems to resist mechanical and chemical damage together make this longetivity possible. This project sought to develop biomimetic methods to enable a specific type of material, a hydrogel, to resist damage across multiple scales using distinct, modular damage protection mechanisms. Because hydrogels share many features with biological tissues, they are an ideal substrate for exploring biomimetic strategies for designing resilience and self-repair. We specifically focused in this study on DNA-crosslinked hydrogels, which contain DNA strands that can serve as material to link it together or to control its current state or properties. We investigated how new tools from dynamic DNA nanotechnology could make it possible to actively recover from damage by continually growing and forming a materials shape, or by identifying damage and directing an adaptive response to that damage involving chemical synthesis to reconstruct a structure. We developed embedded molecular sensors able to detect and strain of the gel before damage occurred and react to counteract damage. We also developed methods to continually create shapes and patterns using chemical processes that will allow those patterns to reform when they are damaged. The ability to design resilient materials capable of self-repair has important implications for materials engineering. Instead of designing a material to withstand the worst stresses it may encounter, we could instead design a material to survive under average conditions, but self-repair or reconfigure to resist impending damage. Resilient, self-repairing hydrogels will also have diverse applications such as sensors or actuators.

36 MATERIALS SCIENCE↗

Understanding the Effect of Side Reactions on the Recyclability of Furan–Maleimide Resins Based on Thermoreversible Diels–Alder Network

We studied the effect of side reactions on the reversibility of epoxy with thermoreversible Diels–Alder (DA) cycloadducts based on furan and maleimide chemistry. The most common side reaction is the maleimide homopolymerization which introduces irreversible crosslinking in the network adversely affecting the recyclability. The main challenge is that the temperatures at which maleimide homopolymerization can occur are approximately the same as the temperatures at which retro-DA (rDA) reactions depolymerize the networks. Here we conducted detailed studies on three different strategies to minimize the effect of the side reaction. First, we controlled the ratio of maleimide to furan to reduce the concentration of maleimide groups which diminishes the effects of the side reaction. Second, we applied a radical-reaction inhibitor. Inclusion of hydroquinone, a known free radical scavenger, is found to retard the onset of the side reaction both in the temperature sweep and isothermal measurements. Finally, we employed a new trismaleimide precursor that has a lower maleimide concentration and reduces the rate of the side reaction. Our results provide insights into how to minimize formation of irreversible crosslinking by side reactions in reversible DA materials using maleimides, which is important for their application as novel self-healing, recyclable, and 3D-printable materials.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Self-repairing cement polymer composites and processes of making and using same

Examples of novel self-repairing cement-polymer composites and processes of making and using are detailed that address various problems in prior art cements. These matrices, compositions and materials that are more mechanically robust, thermally stable and chemically resistant and demonstrate better bonding to various structures and materials, than other self-healing cements known in the prior art. When in place under preselected conditions (the formulation of the slurry can be modified for optimal effectiveness under various conditions) the organic, cross linking and cement forming portions within the slurry form interconnecting chemical bonds and cures to form a self-repairing and self-re-adhering cement polymer composite matrix in the receiving location.

Fernandez, Carlos A.↗

Calcium-silicate-based porous particles, composition, method of making and use thereof

A method for synthesizing calcium-silicate-based porous particles (CSPPs) is described. Control over CSPP morphology and pore size is achieved through a refined solution-based synthesis, allowing loading of a variety of sealants. These particles, upon external stimuli, release the loaded sealant into the surrounding material. Methods of loading the CSPPs with loading sealant are described. The CSPPs may be used in pure form or mixed with another material to deliver self-healing, sealing and multi-functional properties to a physical structure. The composition of the CSPPs is described, along with methods of use of the CSPPs.

Shahsavari, Rouzbeh↗

Autogenous healing of Engineered Cementitious Composites (ECC) based on MgO-fly ash binary system activated by carbonation curing

Developing self-healing of concrete cracks represents a critical approach for extending material longevity. If demonstrated on concretes with CO 2 stored through carbonation curing, self-healing can further mitigate infrastructure lifecycle emissions. In this study, the self-healing process is investigated on novel Engineered Cementitious Composites (ECC) based on binary blends of reactive MgO cement and siliceous fly ash activated by carbonation. The self-healing was observed under cyclic wetting and drying exposures and was characterized by measurements of resonance frequency, optical microscopy and X-ray computed microtomography (XCT). Thermogravimetric analysis, X-ray powder diffraction and scanning electron microscopy were employed to assist in identifying healing products and mechanisms. It was found that micro-cracks could be autogenously filled in 7 wet-dry cycles, as evidenced by over 95% recovery of resonance frequency and healed crack appearance under optical microscopic observation. Nevertheless, the composite mechanical performance, particularly tensile strength and ductility, did not fully recover with respect to the uncracked specimens. The inadequate post-healing mechanical properties were consistent with XCT observations that indicated low material densities in the cracked area. Based on the chemical and microstructural characterizations, it was determined that nesquehonite crystallites were responsible for the crack filling. Although the nesquehonite filled cracks will be less permeable to invasion of reactive fluids, novel strategies are needed to establish more robust healing capability to completely restore the crack bridging and composite tensile performance.

36 MATERIALS SCIENCE↗

Reconfigurable structure and tunable transport in synchronized active spinner materials

Ensembles of actuated colloids are excellent model systems to explore emergent out-of-equilibrium structures, complex collective dynamics, and design rules for the next generation materials. Here, we demonstrate that ferromagnetic microparticles suspended at an air-water interface and energized by an external rotating magnetic field spontaneously form dynamic ensembles of synchronized spinners in a certain range of the excitation field parameters. Each spinner generates strong hydrodynamic flows, and collective interactions of the multiple spinners promote a formation of dynamic lattices. On the basis of experiments and simulations, we reveal structural transitions from liquid to nearly crystalline states in this novel active spinner material and demonstrate that dynamic spinner lattices are reconfigurable, capable of self-healing behavior and that the transport of embedded inert cargo particles can be remotely tuned by the parameters of the external excitation field. Our findings provide insights into the behavior of active spinner materials with reconfigurable structural order and tunable functionalities.

36 MATERIALS SCIENCE↗

Polymer Chemistry

This viewgraph presentation describes new technologies in polymer and material chemistry that benefits NASA programs and missions. The topics include: 1) What are Polymers?; 2) History of Polymer Chemistry; 3) Composites/Materials Development at KSC; 4) Why Wiring; 5) Next Generation Wiring Materials; 6) Wire System Materials and Integration; 7) Self-Healing Wire Repair; 8) Smart Wiring Summary; 9) Fire and Polymers; 10) Aerogel Technology; 11) Aerogel Composites; 12) Aerogels for Oil Remediation; 13) KSC's Solution; 14) Chemochromic Hydrogen Sensors; 15) STS-130 and 131 Operations; 16) HyperPigment; 17) Antimicrobial Materials; 18) Conductive Inks Formulations for Multiple Applications; and 19) Testing and Processing Equipment.

Williams, Martha↗

Nature-Inspired Motivation for Developing Self-Healable Electrical Insulation

Polymeric aircraft electrical insulation normally degrade by partial discharge with increasing voltage, which causes excessive localized Joule heating in the material and ultimately leads to dielectric failure of the insulator through thermal breakdown. Self-healing insulation may be a viable option to mitigate permanent mechanical degradation, thus increasing the longevity of the material. Instead of relying on catalyst and monomer-filled microcapsules to crack, flow, and cure at the damaged sites described in well-published mechanisms, self-healing through establishment of ionic crosslinks allows for multiple healing events to occur as well as achieving full recovery strength under certain thermal environments. Surlyn®, a commercial ionically-crosslinked material, was investigated as a self-healing insulation candidate based on prior demonstrations of self-healing behavior. Thin films of varying thicknesses were investigated and the effects of thickness on the dielectric strength were evaluated and compared to representative polymer insulators. The effects of thermal conditioning on the recovery strength and healing were observed as a function of time following dielectric breakdown. Moisture absorption was studied to determine if moisture absorption rates in Surlyn® were lower than that of common polyimide insulators. Preliminary data showed that when cut, Surlyn® films lost nearly 60 percent of its original dielectric strength. However, when Surlyn® was cut and subsequently annealed, the films not only re-mended, but also recouped approximately 93 percent of its original dielectric strength, along with 90-97 percent of its mechanical strength.

electrical↗

NASA Subsonic Rotary Wing Project - Structures and Materials Discipline

The Structures & Materials Discipline within the NASA Subsonic Rotary Wing Project is focused on developing rotorcraft technologies. The technologies being developed are within the task areas of: 5.1.1 Life Prediction Methods for Engine Structures & Components 5.1.2 Erosion Resistant Coatings for Improved Turbine Blade Life 5.2.1 Crashworthiness 5.2.2 Methods for Prediction of Fatigue Damage & Self Healing 5.3.1 Propulsion High Temperature Materials 5.3.2 Lightweight Structures and Noise Integration The presentation will discuss rotorcraft specific technical challenges and needs as well as details of the work being conducted in the six task areas.

Halbig, Michael C.↗

Self-Healing Behavior of Ethylene-Based Ionomers

The self-healing behavior of poly(ethylene-co-methacrylic acid) (EMAA)-based ionomers holds tremendous potential for use in a wide variety of unique applications. However, to effectively utilize this self-healing behavior and to design novel materials which possess this ability, the mechanism by which they heal must first be understood ionomers are a class of polymers that can be described as copolymers containing less than 15 mol% ionic content whereby the bulk properties are governed by ionic interactions within the polymer. These ionic groups aggregate into discrete regions known as multiplets which overlap forming clusters that act as physical cross-links profoundly influencing the bulk physical properties. These clusters possess an order-disorder transition (T(sub i)) where the clustered regions may rearrange themselves given time and stimuli. Recognizing the strong influence of these ionic regions on other well understood ionomer properties, their role in self-heating behavior will be assessed. The self-healing behavior is observed following projectile puncture. It has been suggested that during impact energy is passed to the ionomer material, heating it to the melt state. After penetration, it is proposed that the ionic regions maintain their attractions and flow together patching the hole. Thus, the importance of this ionic character and is unique interaction must be established. This will be accomplished through examination of materials with varying ionic content and through the analysis of the T(sub i). The specific ionomer systems examined include a number of ethylene-based materials. Materials of varying ionic content, including the non-ionic base copolymers, will be examined by peel tests, projectile impact and DSC analysis. The information will also be compared with some basic data on LDPE material.

Kalista, Stephen J., Jr.↗

Self–Healing and Stretchable Molecular Ferroelectrics with High Expandability

The interplay between crystal ordering and stretchability is frequently encountered in contemporary materials science, particularly in the case of ferroelectrics. The inherent dilemma arises when these materials need to withstand repetitive mechanical deformations or stretching without sacrificing their crystal integrity, all while retaining their remarkable ferroelectric properties and even exhibiting self-healing capabilities. This complexity further presents a significant challenge in the design and engineering of mechanically rigid molecular ferroelectric crystals, particularly for applications where both precise crystalline structure and mechanical adaptability are crucial. In this study, the humidity-controlled expansion and contraction, dissolution, and recrystallization of a self-assembled molecular ferroelectric-in-hydrogel framework are reported. Self-healing ferroelectric-in-hydrogel networks exhibit a recyclable humidity-tailored ionic conductivity from 2.86 × 10 –6 to 1.36 × 10 –5 S cm –1 , facilitating the stretchable piezoelectric sensing. Additionally, the dynamic bond reforming interactions are observed, leading to the tailoring of Young's modulus from 452 to 170 MPa, maintaining ferroelectricity under a strain of 20% with a piezoelectric coefficient of 15.7 pC N –1 . Upon lattice contraction, the molecular contacts undergo reforming, leading to the restoration of stretchable ferroelectrics/piezoelectrics and paving the way for stretchable bioelectronics for full-body motion monitoring. The capabilities highlighted here open avenues for stretchable and self-healing ferroelectric-in-hydrogel bioelectronic technologies.

36 MATERIALS SCIENCE↗

A recyclable self-healing composite with advanced sensing property

Polymer-based composites frequently encounter damage, often lurking beneath the surface and proving challenges to their early detection and repair. While material-based sensors show promise for encoding self-sensing properties within these composites, their in situ healing and reprocessability remain significant challenges. Therefore, the overarching goal of this study is the creation of a reprocessable polymeric composite encoded with self-healing attributes and the ability to autonomously sense damage. At the core of this innovation are vitrimers, a polymeric material characterized by a covalently adaptive dynamic network responsive to external factors such as heat. They combine thermoset-like resilience with thermoplastic-like flowability on demand under external stimuli. We nanoengineer a polyester-based vitrimeric polymer by incorporating piezoresistive carbon nanotubes (CNTs) as reinforcing elements that not only enhance its mechanical strength but also create a percolation network within the composite, thereby enabling piezoresistive self-sensing properties, all the while preserving the intrinsic self-healing capabilities offered by the vitrimeric matrix. The fabrication process of the composite involves a solvent-free in situ polymerization method that combines epoxy and anhydride-containing monomers with ~ 0.1 wt.% of CNTs. Once it was established that the introduction of CNTs into the polymeric matrix did not compromise the mechanical properties of the composite, their strain-sensing properties were characterized by applying cyclic loading while measuring their electrical resistance. Strikingly, CNT-enhanced vitrimer composite consistently retains its mechanical and sensing properties through repeated cycles of reshaping and reprocessing, underscoring its potential as a robust distributed strain sensor. This polyester-based vitrimeric composite is also easily recyclable without harsh chemical treatments. Preliminary findings from this study conclusively demonstrate that the bulk composite boasts both self-sensing capabilities and in situ detect healing properties, charting a promising course towards the development of a mechanically resilient multifunctional composite that seamlessly integrates selfsensing and healing capabilities.

Rohewal, Sargun Singh↗

Mitigating Damage to Hybrid Perovskites Using Pulsed-Beam TEM

Using a pulsed-beam transmission electron microscope, we discover a reduction in damage to methylammonium lead iodide (MAPbI3) as compared to conventional beams delivered at the same dose rates. For rates as low as 0.001 e·Å –2 ·s –1 , we find up to a 17% reduction in damage at a total dose of 10 e·Å –2 . We systematically study the effects of number of electrons in each pulse and the duration between pulse arrival. Damage increases for both, though the number of electrons per pulse has a larger effect. A crossover is identified, where a pulsed beam causes more damage than a conventional one. Although qualitatively similar to previous findings, the degree to which damage is reduced in MAPbI3 is less than that observed for other materials (e.g., C36H74), supporting the hypothesis that the effects are material- and damage-mechanism-dependent. Despite this, the observation here of damage reduction for relatively large electron packets (up to 200 electrons per pulse) suggests that MAPbI3 is in fact less susceptible to irradiation than C36H74, which may be related to reported self-healing effects. This work provides insights into damage processes and durability in hybrid perovskites and also illustrates the viability of using pulsed-beam TEM to explore the associated molecular-level routes to degradation, analogous to laser-accelerated energetic pulsed electron beams and the study of damage to biomolecules, cells, and tissues in radiobiology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗