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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 109 records · Page 6

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↗

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↗

Light-Mediated Synthesis and Reprocessing of Dynamic Bottlebrush Elastomers under Ambient Conditions

We introduce a novel grafting-through polymerization strategy to synthesize dynamic bottlebrush polymers and elastomers in one step using light to construct a disulfide-containing backbone. The key starting material—α-lipoic acid (LA)—is commercially available, inexpensive, and biocompatible. When installed on the chain end(s) of poly(dimethylsiloxane) (PDMS), the cyclic disulfide unit derived from LA polymerizes under ultraviolet (UV) light in ambient conditions. Significantly, no additives such as initiator, solvent, or catalyst are required for efficient gelation. Formulations that include bis-LA-functionalized cross-linker yield bottlebrush elastomers with high gel fractions (83–98%) and tunable, supersoft shear moduli in the ~20–200 kPa range. An added advantage of these materials is the dynamic disulfide bonds along each bottlebrush backbone, which allow for light-mediated self-healing and on-demand chemical degradation. These results highlight the potential of simple and scalable synthetic routes to generate unique bottlebrush polymers and elastomers based on PDMS.

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↗

Irradiation-induced shift in the thermodynamic stability of phases and the self-healing effect in transformative high entropy alloys

Here, this work investigated Fe 40 Mn 20 Cr 15 Co 20 Si 5 high entropy alloy (CS-HEA), which exhibits transformation induced plasticity (TRIP) from γ-fcc → ε-hcp, as a probable candidate for nuclear applications. CS-HEA is an extensively-explored, low stacking fault energy alloy with superior strength, ductility, fatigue resistance, and corrosion resistance. This study delved into the effect of irradiation on the shift in thermodynamic stability of the phases and thus radiation tolerance. The evolution of phases, lattice parameters, and transformation volume, V γ→ε , were evaluated from X-ray diffraction experiments along with the mechanical response from nanoindentation. The alloy exhibited a recently-proposed novel self-healing mechanism possible due to the TRIP effect to minimize irradiation damage by restraining the γ-fcc → ε-hcp transformation via thermal aid; this self-healing mechanism was confirmed by transmission electron microscopy. The results were corroborated by a negative change in V γ→ε and a low |V γ→ε |, which is an important criterion for recovery of parent γ-fcc phase. Thus, this alloy was deemed a good radiation-tolerant candidate for nuclear application.

36 MATERIALS SCIENCE↗

Application of the core shell model for strengthening polymer filament interfaces

While surface segregation has been intensively studied in thin films, relatively little has been investigated in filament geometries. In contrast to thin films, the filament surface forms a continuum, with interactions both at the free air and internal filament interface, which makes it difficult to achieve an equilibrium configuration. This asymmetry has become particularly apparent with the increasing use of additive manufacturing where entire structures are constructed via layered deposition of filamentous layers from a moving thermal nozzle. In addition, this process is highly non-equilibrated with poor thermal retention and is responsible for insufficient filament–filament interfacial fusion and internal pore formation along the printing direction. These features all contribute to poor mechanical and structural properties, which are exacerbated in semi-crystalline polymers, such as Polylactic Acid (PLA), where the melting point, T m , is much higher than the glass transition, T g . Even though system is liquid the molecules become ordered within the crystal structure and this ordering interferes with interdiffusion, which in turn prevents proper interfacial fusion. Capitalizing on the differential in surface tension, we show that addition of less than 1%, or trace amounts, of longer chain polymers, an oriented core shell structure, will be formed with a self-limiting thickness of three time the radius of gyration, R g , of the tracer chains. The lower T g of the tracers and their orientation makes them poised for interdiffusion when subsequent layers are deposited producing structures with significant improvement of the mechanical properties and internal structural integrity.

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↗

Liquid metal walls

Here, the plasma performance of fusion devices depends strongly on the chosen wall materials. Solid plasma-facing components (PFCs) are predominantly used in present devices, and are the most investigated candidates for fusion designs. High-Z materials such as tungsten (W) are the leading solid PFC material candidates. To date, a material choice that scales to steady-state reactor conditions has not been identified. Moreover, if plasma transient events such as edge-localized modes and disruptions cannot be altogether avoided or sufficiently mitigated, the projected peak heat and particle loads far exceed the power exhaust capabilities of solids. Liquid metal (LM) PFCs represent an intrinsic self-healing boundary that are both resilient to surface damage from transients, and that could handle high steady-state heat and particle fluxes. Flowing LM PFCs can be designed to remove “slag,” the buildup of material erosion due to plasma-material interactions, including charge exchange sputtering in the main chamber. Further, LM offer the prospect to manage hydrogenic species otherwise retained in the PFCs, which is important from a safety and inventory standpoint. The two most promising LMs are lithium (Li) and tin (Sn), although Sn–Li eutectics may be considered. While Sn offers a higher temperature window with low vapor pressure and low hydrogen retention, Li offers the prospect of enhanced energy confinement and higher acceptable core contamination limits, and this section focuses on Li PFCs. An LM PFC development research program developed LM PFC concepts for a nuclear fusion device via engineering design calculations, single-effect experiments, and staged prototypical experiments. A self-consistent design window was identified with liquid Li flow speeds ~5–10 m/s; plasma contamination was negligible for predicted Li evolution rates. While these preconceptual designs hold promise, there is substantial R&D needed to advance the technical readiness levels of LM PFCs for application to fusion power plants.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Operando Interaction and Transformation of Metastable Defects in Layered Oxides for Na‐Ion Batteries

Non-equilibrium defects often dictate the macroscopic properties of materials. They largely define the reversibility and kinetics of processes in intercalation hosts in rechargeable batteries. Recently, imaging methods have demonstrated that transient dislocations briefly appear in intercalation hosts during ion diffusion. Despite new discoveries, the understanding of impact, formation and self-healing mechanisms of transient defects, including and beyond dislocations, is lacking. Here, operando X-ray Bragg Coherent Diffractive Imaging (BCDI) and diffraction peak analysis capture the stages of formation of a unique metastable domain boundary, defect self-healing, and resolve the local impact of defects on ionic diffusion in Na x Ni 1-y MnyO 2 intercalation hosts in a charging sodium-ion battery. Results, applicable to a wide range of layered intercalation materials due to the shared nature of framework layers, elucidate new dynamics of transient defects and their connection to macroscopic properties, and suggest how to control the nanostructure dynamics.

36 MATERIALS SCIENCE↗

Anisotropic Dynamics and Mechanics of Macromolecular Crystals Containing Lattice-Patterned Polymer Networks

The mechanical and functional properties of many crystalline materials depend on cooperative changes in lattice arrangements in response to external perturbations. However, the flexibility and adaptiveness of crystalline materials are limited. Additionally, the bottom-up, molecular-level design of crystals with desired dynamic and mechanical properties at the macroscopic level remains a considerable challenge. To address these challenges, we had previously integrated mesoporous, cubic ferritin crystals with hydrogel networks, resulting in hybrid materials (polymer integrated crystals or PIX) which could undergo dramatic structural changes while maintaining crystalline periodicity and display efficient self-healing. Here, the dynamics and mechanics of these ferritin-PIX were devoid of directionality, which is an important attribute of many molecular and macroscopic materials/devices. In this study, we report that such directionality can be achieved through the use of ferritin crystals with anisotropic symmetries (rhombohedral or trigonal), which enable the templated formation of patterned hydrogel networks in crystallo. The resulting PIX expand and contract anisotropically without losing crystallinity, undergo prompt bending motions in response to stimuli, and self-heal efficiently, capturing some of the essential features of sophisticated biological devices like skeletal muscles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A linked-scale coupled model of mass erosion and redistribution in plasma-exposed micro-foam surfaces

Surface evolution due to exposure to harsh environments is of importance in many scientific and technological applications. In plasma-exposed materials, the surface receives charged particles from the plasma, leading to a series of processes that drive the system far from equilibrium and may lead to the severe deterioration of the surface properties. Although surface morphological changes are driven by atomic collisions taking place over picoseconds and nanometers, these processes result in mass loss and redistribution of matter over much larger length and time scales. This necessitates a multi-scale approach capable of capturing the range of processes linking primary atomic collision events with engineering-level surface geometry changes. In this paper, we develop a computational model to simulate the morphological evolution and effective erosion rate of micro-architected tungsten foams during low-energy plasma ion bombardment. Furthermore, the model acts on several length scales, with the energy and angular dependence of the sputtering yield of flat tungsten surfaces determined using the SRIM code based on the binary collision approximation. This information is introduced into a low-fluence, short-term Monte Carlo raytracing model, and further into a high-fluence, long-term particle transport model. In the latter, material particles representing billions of atoms are described in a digitized 3-D representation of the foam structure from X-ray tomography data, and are sputtered off and redeposited using the atomistic information. We show that the redeposition of sputtered atoms leads to partial self-healing in the bottom layers with a sharp reduction in the sputtering coefficient of low density foams, roughly 25% of the solid W value. This is in qualitative agreement with recent experiments on low porosity W structures. At high fluence, the foam structure degrades considerably as there are fewer ligaments available to recapture sputtered atoms and, consequently, the sputtering rate increases again.

36 MATERIALS SCIENCE↗

A Domestic Program for Liquid Metal PFC Research in Fusion

While high-Z solid plasma-facing components (PFCs) are the leading candidates for reactors, it is unclear that they can survive the intense plasma material interaction (PMI). Liquid metals (LM) PFCs offer potential solutions since they are not susceptible to the same type of damage, and can be “self-healing”. Following the Fusion Energy System Study on Liquid Metal Plasma Facing Components study that recently was completed by Kessel et al. (Fusion Sci Technnol 75:886, 2019) a domestic LM PFC design program has been initiated to develop reactor-relevant LM PFC concepts. This program seeks to evaluate LM PFC concepts for a Fusion Nuclear Science Facility (FNSF) or a Compact Pilot Plant via engineering design calculations, modeling of PMI and PFC components and laboratory experiments. The latter involves experiments in dedicated test stands and confinement devices and seeks to identify and answer open questions in LM PFC design. The new national LM PFC program is first investigating lithium as the plasma facing material for a flowing divertor PFC concept. Several flow speeds will be evaluated, ranging from ~ cm/s to m/s. The surface temperature will initially be held below the strongly evaporative limit in the first design; higher temperatures with strong evaporation will be considered in future concepts. Other topics of interest include: understanding of the hydrogen and helium interaction with the liquid lithium; single effect experiments on wetting, compatibility and embrittlement; and prototypical experiments for control and characterization of flowing LM. A path to plasma and future tokamak exposure of these concepts will be developed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

A Self-Healing, Flowable, Yet Solid Electrolyte Suppresses Li-Metal Morphological Instabilities

In this article, lithium metal (Li 0 ) solid-state batteries encounter implementation challenges due to dendrite formation, side reactions, and movement of the electrode–electrolyte interface in cycling. Notably, voids and cracks formed during battery fabrication/operation are hot spots for failure. Here, a self-healing, flowable yet solid electrolyte composed of mobile ceramic crystals embedded in a reconfigurable polymer network is reported. This electrolyte can auto-repair voids and cracks through a two-step self-healing process that occurs at a fast rate of 5.6 µm h -1 . A dynamical phase diagram is generated, showing the material can switch between liquid and solid forms in response to external strain rates. The flowability of the electrolyte allows it to accommodate the electrode volume change during Li 0 stripping. Simultaneously, the electrolyte maintains a solid form with high tensile strength (0.28 MPa), facilitating the regulation of mossy Li 0 deposition. The chemistries and kinetics are studied by operando synchrotron X-ray and in situ transmission electron microscopy (TEM). Solid-state NMR reveals a dual-phase ion conduction pathway and rapid Li + diffusion through the stable polymer-ceramic interphase. This designed electrolyte exhibits extended cycling life in Li 0 –Li 0 cells, reaching 12 000 h at 0.2 mA cm -2 and 5000 h at 0.5 mA cm -2 . Furthermore, owing to its high critical current density of 9 mA cm -2 , the Li 0 –LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) full cell demonstrates stable cycling at 5 mA cm -2 for 1100 cycles, retaining 88% of its capacity, even under near-zero stack pressure conditions.

25 ENERGY STORAGE↗

Autonomous Changes in Polymer Materials Driven by Chemical Fuels

Time-dependent properties in polymer materials can be achieved through coupling to out-of-equilibrium chemical fuel reactions that mimic biological processes. Through transient changes in bonding in polymers, transient gelation, changes in mechanical stiffness, swelling, self-healing, or self-assembly can be achieved. Recent advances in these categories are discussed. These out-of-equilibrium behaviors enable applications ranging from smart adhesives to actuators for soft robotics. However, challenges remain, including waste accumulation, bio-compatibility, and achieving functionally useful performance. Addressing these issues is essential for advancing the practical use of chemically driven polymer materials and unlocking their full potential for future technologies.

36 MATERIALS SCIENCE↗

Ce nanoparticles and sol-gel hybrid organic-inorganic coatings maximize corrosion protection in the anodized AA2024-T3

Herein we demonstrate that the corrosion resistance of the AA2024-T3 alloy can be maximized with the application of top protective sol-gel hybrid organic-inorganic coatings. Samples combining Ce nanoparticles within the pores of the anodic layer with the top sol-gel coatings were observed to outperform samples featuring only the coating. This research unravels the self-healing capability against corrosion of the sol-gel coating when Ce nanoparticles are present, as well as a good coverage of defective regions within the oxide by the hybrid layer. This research opens a paradigm aiming at maximizing the corrosion resistance for non-ferrous anodized alloys.

36 MATERIALS SCIENCE↗