Search NASA⌕ Search

SEARCH · Search NASA

Results for “nanocrystalline”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Revealing the Structural Evolution of Green Rust Synthesized in Ionic Liquids by In Situ Molecular Imaging

Abstract Ionic liquids are green solvents that have wide applications in material synthesis, catalysis, and separation. A model switchable ionic liquid (SWIL) consisting of 1,8‐diazabicycloundec‐7‐ene (DBU) and 1‐hexanol with carbon dioxide (CO 2 ) as the trigger gas is chosen to synthesize nanocrystalline green rust. Under anoxic conditions, by adding iron (II) acetate (Fe(C 2 H 3 O 2 ) 2 ) and methanol to the degassed SWIL, a nanoparticulate green rust with carbonate (nano‐GR) is synthesized. More importantly, the molecular structural change of the ionic liquid resulting in green rust crystallines is first characterized using in situ liquid using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) coupled with the system for analysis at the liquid vacuum interface (SALVI), a vacuum compatible microfluidic reactor in this work. Dimers and ionic clusters consisting ferric and ferrous ions are identified in liquid ToF‐SIMS spectra. Spectral principal component analysis is used to confirm that these ion pairs including dimers and cluster ions are different from nonionic liquids. The results show that liquid ToF‐SIMS can be a useful tool to study complex liquids at the molecular level providing insights into predicative synthesis of nanomaterials using environmentally friendly green solvents and giving unique visualization of the evolving material interface due to nucleation.

Shen, Yanjie↗
DOE OSTI2025

Ligand‐Induced Crystallization Control in MAPbBr 3 Hybrid Perovskites for High Quality Nanostructured Films

AbstractControlling the formation of hybrid perovskite thin films is crucial in obtaining high‐performance optoelectronic devices, since factors like morphology and film thickness have a profound impact on a film's functionality. For light‐emitting applications grain sizes in the sub‐micrometer‐range have previously shown enhanced brightness. It is therefore crucial to develop simple, yet reliable methods to produce such films. Here, a solution‐based synthesis protocol for the on‐substrate formation of MAPbBr3 (MA = methylammonium) nanostructures by adding the bifunctional rac‐3‐aminobutyric acid to the precursor solution is reported. This synthesis route improves key optical properties such as photoluminescence quantum yields and life times of excited states by inducing a controlled slow‐down of the film formation and suppressing agglomeration effects. In situ spectroscopy reveals a delayed and slowed down crystallization process, which achieves synthesis of perovskite structures with much reduced defect densities. Further, aggregation can be controlled by the amount of amino acid added and adjusting the synthesis protocol allows to produce cubic crystallites with targeted size from nanometer to micrometer scales. The nanocrystalline MAPbBr3 samples show enhanced amplified spontaneous emission (ASE) intensities, reduced ASE thresholds and purer ASE signals, compared to pristine films, even under intense optical driving, making them promising structures for lasing applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Non‐Linear Kinetics of The Lithium Metal Anode on Li 6 PS 5 Cl at High Current Density: Dendrite Growth and the Role of Lithium Microstructure on Creep

Abstract Interfacial instability, viz., pore formation in the lithium metal anode (LMA) during discharge leading to high impedance, current focusing induced solid–electrolyte (SE) fracture during charging, and formation/behaviour of the solid–electrolyte interphase (SEI), at the anode, is one of the major hurdles in the development of solid‐state batteries (SSBs). Also, understanding cell polarization behaviour at high current density is critical to achieving the goal of fast‐charging battery and electric vehicle. Herein, via in situ electrochemical scanning electron microscopy (SEM) measurements, performed with freshly deposited lithium microelectrodes on transgranularly fractured fresh Li6PS5Cl (LPSCl), the LiǀLPSCl interface kinetics are investigated beyond the linear regime. Even at relatively small overvoltages of a few mV, the LiǀLPSCl interface shows non‐linear kinetics. The interface kinetics possibly involve multiple rate‐limiting processes, i.e., ion transport across the SEI and SE|SEI interfaces, as well as charge transfer across the LiǀSEI interface. The total polarization resistance R P of the microelectrode interface is determined to be ≈ 0.8 Ω cm 2 . It is further shown that the nanocrystalline lithium microstructure can lead to a stable LiǀSE interface via Coble creep along with uniform stripping. Also, spatially resolved lithium deposition, i.e., at grain surface flaws, grain boundaries, and flaw‐free surfaces, indicates exceptionally high mechanical endurance of flaw‐free surfaces toward cathodic load (>150 mA cm −2 ). This highlights the prominent role of surface defects in dendrite growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Silicon Anodes with Improved Calendar Life Enabled By Multivalent Additives

Silicon is widely recognized as the most promising upgrade for graphite anodes due to its much higher capacity, natural abundance, and ability to be directly applied in the slurry-based, roll-to-roll production lines. However, in addition to the fast capacity decay, silicon anodes also suffer from inferior calendar life in practical applications due to the unstable solid-electrode interface (SEI). Until now, strategies to effectively improve the calendar life by tailored SEIs remain largely unclear, especially in high-Si content, zero-graphite anodes. Here, silicon anodes with superior calendar life are developed by adding small concentrations of multivalent salts into the baseline electrolyte. The Ca additive reacts with the F ions in the electrolyte, forming a layer of nanocrystalline CaF 2 that is closely coated around the silicon particles. The CaF 2 -enabled new SEI is strong and dense, which effectively protects the silicon core from side reactions, leading to lower capacity decay after calendar aging at high voltage. More importantly, the Ca additive is effective universally for all available commercial silicon or SiO sources. This study provides a feasible and low-cost solution for developing silicon anodes with long calendar life, paving the way towards commercially viable silicon anodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Twinning Enhances Efficiencies of Metallic Catalysts toward Electrolytic Water Splitting

Twinning is demonstrated to be an effective way of enhancing efficiencies of metallic catalysts toward electrolytic water splitting. Dendritic Cu possessing dense coherent nanotwin (NT) boundaries (NTCu-5nm) is successfully prepared with an organic-assisted electrodeposition at high pulse current densities. NT boundaries significantly improve electrocatalytic efficiencies and stability of NTCu-5nm over nanocrystalline Cu (NCCu), reducing overpotentials at 10 mA cm -2 for the oxygen evolution reaction (OER) from 378 to 281 mV and from 235 to 88 mV for the hydrogen evolution reaction (HER), with a small chronoamperometric decay of 5% after 100 h continuous overall water splitting at an ultrahigh initial current density of 500 mA cm -2 , largely outperforming the large chronoamperometric decay of 27% for only 1 h operation of the NCCu//NCCu couple. The defective twin boundaries enable formation of active Cu III O 2 - at low overpotentials, thus enhancing OER performance. Furthermore, the synergistic geometric and electronic effects induced by the twin boundaries result in shifts in Gibbs free energies of hydrogen adsorption (ΔG H ) toward the apex of a volcano plot of exchange current density versus ΔG H , leading to the remarkable improvement in HER activity.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2023

Grain Boundary Phases in NbFeSb Half‐Heusler Alloys: A New Avenue to Tune Transport Properties of Thermoelectric Materials

Abstract Many thermoelectric materials benefit from complex microstructures. Grain boundaries (GBs) in nanocrystalline thermoelectrics cause desirable reduction in the thermal conductivity by scattering phonons, but often lead to unwanted loss in the electrical conductivity by scattering charge carriers. Therefore, modifying GBs to suppress their electrical resistivity plays a pivotal role in the enhancement of thermoelectric performance, zT . In this work, different characteristics of GB phases in Ti‐doped NbFeSb half‐Heusler compounds are revealed using a combination of scanning transmission electron microscopy and atom probe tomography. The GB phases adopt a hexagonal close‐packed lattice, which is structurally distinct from the half‐Heusler grains. Enrichment of Fe is found at GBs in Nb 0.95 Ti 0.05 FeSb, but accumulation of Ti dopants at GBs in Nb 0.80 Ti 0.20 FeSb, correlating to the bad and good electrical conductivity of the respective GBs. Such resistive to conductive GB phase transition opens up new design space to decouple the intertwined electronic and phononic transport in thermoelectric materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Nanocrystal‐Enabled Perovskite Heterojunctions in Photovoltaic Applications and Beyond

Abstract Heterojunctions are used to tailor the properties of semiconductors in optoelectronic devices, yet for emerging devices composed of metal halide perovskites, fabricating perovskite/perovskite heterojunctions has proved challenging due to solvent incompatibilities and rapid homogenization due to ion migration. Recent studies have demonstrated various strategies for using perovskite nanocrystals as a component to fabricate perovskite/perovskite heterojunctions, either with a perovskite thin film or a second nanocrystal layer. Heterojunctions such as these can impart many advantages of both bulk and nanocrystalline perovskite morphologies. This perspective focuses on recent developments of solution‐processed perovskite heterojunctions for solar cells and novel optoelectronic devices, in particular, highlighting the demonstrated and potential advantages of nanocrystal‐enabled fabrication strategies. A central tenet of this perspective is that the synthesis and dispersion of perovskite nanocrystals in non‐polar organic solvents offers a key processing advantage over traditional perovskite precursor solutions in polar solvents since the former allows for layer‐by‐layer deposition without dissolving an underlying perovskite film or crystal. This processing advantage, coupled with nanocrystal size control and ligand chemistry, enables perovskite heterojunctions with highly tunable optical and electrical properties. Such heterojunctions may enable disruptive technological advances in broad classes of devices such as solar cells, photodetectors, sensors, and (in)coherent photon sources with tunable polarization.

14 SOLAR ENERGY↗
DOE OSTI2020

Reduced type-A carbohydrate-binding module interactions to cellulose I leads to improved endocellulase activity

Dissociation of nonproductively bound cellulolytic enzymes from cellulose is hypothesized to be a key rate-limiting factor impeding cost-effective biomass conversion to fermentable sugars. However, the role of carbohydrate-binding modules (CBMs) in enabling nonproductive enzyme binding is not well understood. Here, we examine the subtle interplay of CBM binding and cellulose hydrolysis activity for three models type-A CBMs (Families 1, 3a, and 64) tethered to multifunctional endoglucanase (CelE) on two distinct cellulose allomorphs (i.e., cellulose I and III). We generated a small library of mutant CBMs with varying cellulose affinity, as determined by equilibrium binding assays, followed by monitoring cellulose hydrolysis activity of CelE–CBM fusion constructs. Finally, kinetic binding assays using quartz crystal microbalance with dissipation were employed to measure CBM adsorption and desorption rate constants kon and koff, respectively, towards nanocrystalline cellulose derived from both allomorphs. Overall, our results indicate that reduced CBM equilibrium binding affinity towards cellulose I alone, resulting from increased desorption rates (koff) and reduced effective adsorption rates (nkon), is correlated to overall improved endocellulase activity. Future studies could employ similar approaches to unravel the role of CBMs in nonproductive enzyme binding and develop improved cellulolytic enzymes for industrial applications.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Engineering and characterization of carbohydrate‐binding modules for imaging cellulose fibrils biosynthesis in plant protoplasts

Abstract Carbohydrate binding modules (CBMs) are noncatalytic domains that assist tethered catalytic domains in substrate targeting. CBMs have therefore been used to visualize distinct polysaccharides present in the cell wall of plant cells and tissues. However, most previous studies provide a qualitative analysis of CBM‐polysaccharide interactions, with limited characterization of engineered tandem CBM designs for recognizing polysaccharides like cellulose and limited application of CBM‐based probes to visualize cellulose fibrils synthesis in model plant protoplasts with regenerating cell walls. Here, we examine the dynamic interactions of engineered type‐A CBMs from families 3a and 64 with crystalline cellulose‐I and phosphoric acid swollen cellulose. We generated tandem CBM designs to determine various characteristic properties including binding reversibility toward cellulose‐I using equilibrium binding assays. To compute the adsorption ( nk on ) and desorption ( k off ) rate constants of single versus tandem CBM designs toward nanocrystalline cellulose, we employed dynamic kinetic binding assays using quartz crystal microbalance with dissipation. Our results indicate that tandem CBM3a exhibited the highest adsorption rate to cellulose and displayed reversible binding to both crystalline/amorphous cellulose, unlike other CBM designs, making tandem CBM3a better suited for live plant cell wall biosynthesis imaging applications. We used several engineered CBMs to visualize Arabidopsis thaliana protoplasts with regenerated cell walls using confocal laser scanning microscopy and wide‐field fluorescence microscopy. Lastly, we also demonstrated how CBMs as probe reagents can enable in situ visualization of cellulose fibrils during cell wall regeneration in Arabidopsis protoplasts.

09 BIOMASS FUELS↗
DOE OSTI2020

Quantized Grain Boundary States Promote Nanoparticle Alignment During Imperfect Oriented Attachment

Oriented attachment (OA) has become a well-recognized mechanism for the growth of metal, ceramic, and biomineral crystals. While many computational and experimental studies of OA have shown that particles can attach with some misorientation then rotate to remove adjoining grain boundaries, the underlying atomistic pathways for this “Imperfect OA” process remain the subject of debate. In this paper, molecular dynamics and in situ TEM were used to probe the crystallographic evolution of up to 30 gold and copper nanoparticles during aggregation. It was found that Imperfect OA occurs because (1) grain boundaries become quantized when their size is comparable to the separation between constituent dislocations and (2) kinetic barriers associated with the glide of grain boundary dislocations are small. In support of these findings, TEM experiments show the formation of a single crystal aggregate after annealing 9 initially misoriented, agglomerated particles with evidence of dislocation slip and twin formation during particle/grain alignment. These observations motivate future work on assembled nanocrystals with tailored defects and call for a revision of Read-Shockley models for grain boundary energies in nanocrystalline materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Nanostructured Conductive Metal Organic Frameworks for Sustainable Low Charge Overpotentials in Li–Air Batteries

Lithium-oxygen batteries are among the most attractive alternatives for future electrified transportation. However, their practical application is hindered by many obstacles. Due to the insulating nature of Li 2 O 2 product and the slow kinetics of reactions, attaining sustainable low charge overpotentials at high rates becomes a challenge resulting in the battery's early failure and low round trip efficiency. Herein, outstanding characteristics are discovered of a conductive metal organic framework (c-MOF) that promotes the growth of nanocrystalline Li 2 O 2 with amorphous regions. This provides a platform for the continuous growth of Li 2 O 2 units away from framework, enabling a fast discharge at high current rates. Moreover, the Li 2 O 2 structure works in synergy with the redox mediator (RM). The conductivity of the amorphous regions of the Li 2 O 2 allows the RM to act directly on the Li 2 O 2 surface instead of catalyst edges and then transport through the electrolyte to the Li 2 O 2 surface. This direct charge transfer enables a small charge potential of <3.7 V under high current densities (1-2 A g -1 ) sustained for a long cycle life (100-300 cycles) for large capacities (1000-2000 mAh g -1 ). These results open a new direction for utilizing c-MOFs towards advanced energy storage systems.

25 ENERGY STORAGE↗
DOE OSTI2022

Entrapped Molecule‐Like Europium‐Oxide Clusters in Zinc Oxide with Nearly Unaffected Host Structure

Abstract Nanocrystalline ZnO sponges doped with 5 mol% EuO 1.5 are obtained by heating metal–salt complex based precursor pastes at 200–900 °C for 3 min. X‐ray diffraction, transmission electron microscopy, and extended X‐ray absorption fine structure (EXAFS) show that phase separation into ZnO:Eu and c ‐Eu 2 O 3 takes place upon heating at 700 °C or higher. The unit cell of the clean oxide made at 600 °C shows only ≈0.4% volume increase versus undoped ZnO, and EXAFS shows a ZnO local structure that is little affected by the Eu‐doping and an average Eu 3+ ion coordination number of ≈5.2. Comparisons of 23 density functional theory‐generated structures having differently sized Eu‐oxide clusters embedded in ZnO identify three structures with four or eight Eu atoms as the most energetically favorable. These clusters exhibit the smallest volume increase compared to undoped ZnO and Eu coordination numbers of 5.2–5.5, all in excellent agreement with experimental data. ZnO defect states are crucial for efficient Eu 3+ excitation, while c ‐Eu 2 O 3 phase separation results in loss of the characteristic Eu 3+ photoluminescence. The formation of molecule‐like Eu‐oxide clusters, entrapped in ZnO, proposed here, may help in understanding the nature of the unexpected high doping levels of lanthanide ions in ZnO that occur virtually without significant change in ZnO unit cell dimensions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Automated High‐Throughput Fatigue Testing of Freestanding Thin Films

Abstract Mechanical testing at small length scales has traditionally been resource‐intensive due to difficulties with meticulous sample preparation, exacting load alignments, and precision measurements. Microscale fatigue testing can be particularly challenging due to the time‐intensive, tedious repetition of single fatigue experiments. To mitigate these challenges, this work presents a new methodology for the high‐throughput fatigue testing of thin films at the microscale. This methodology features a microelectromechanical systems‐based Si carrier that can support the simultaneous and independent fatigue testing of an array of samples. To demonstrate this new technique, the microscale fatigue behavior of nanocrystalline Al is efficiently characterized via this Si carrier and automated fatigue testing with in situ scanning electron microscopy. This methodology reduces the total testing time by an order of magnitude, and the high‐throughput fatigue results highlight the stochastic nature of the microscale fatigue response. This manuscript also discusses how this initial capability can be adapted to accommodate more samples, different materials, new geometries, and other loading modes.

Barrios, Alejandro↗
DOE OSTI2022

Virtual texture analysis to investigate the deformation mechanisms in metal microstructures at the atomic scale

Understanding the deformation behavior of metallic materials at high strain rates requires the characterization of plasticity contributors such as twins, phase transformed regions, and dislocations. However, predicting the contributions from phase transformation and twinning relies on a complete understanding of the selection of variants for various loading orientations and the evolution of their volume fractions. This manuscript presents a new virtual texture (VirTex) analysis approach to characterize phase transformation and twinning variants in deformed microstructures generated using molecular dynamics (MD) simulations. Furthermore, the VirTex method involves the construction of a rotation matrix to calculate the angle/axis pairs and misorientation angles for each atom in the microstructure. Any changes in the orientation angle from angle/axis pairs and/or structure types are analyzed to determine the nucleation and evolution of variants in the microstructure. The study uses shock deformed single-crystal Fe, Ta, and Cu to analyze the variant selections for phase transformation or twinning or both in BCC and FCC systems. In addition, the VirTex analysis is able to characterize the phase transformation and twinning variants in nanocrystalline Fe and Ta microstructures. Besides characterizing variants, orientation mapping also provides an accelerated and on-the-fly approach for quantifying twin fractions in MD microstructures.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The heterogeneous nature of mechanically accelerated grain growth

Abstract While grain growth is traditionally viewed as a purely thermally driven process, nanocrystalline metals can undergo grain growth under mechanical loads, even at room temperature. We performed a detailed atomistic study of the heterogeneous nature of mechanically accelerated grain growth in a polycrystalline Pt nanowire. Using molecular dynamics simulations, we compared the grain-growth behavior of individual grains during tensile and shear cyclic loading, for three different equivalent strain levels, and at two temperatures. Pure thermal grain growth with no mechanical loading provided a baseline reference case. On average, grains that were already susceptible to thermal grain growth were stimulated to grow faster with mechanical loading, as expected. However, when analyzed on a grain-by-grain basis, the results were far more complex: grains that grew fastest under one stimuli were less accelerated under other stimuli. Even when the magnitude of loading changed, the relative growth of individual grains was distorted. We interpret this complexity from the perspective of superimposed growth mechanisms.

Chen, Elton Y.↗
DOE OSTI2020

Development of a heterogeneous nanostructure through abnormal recrystallization of a nanotwinned Ni superalloy

This work explores the development of a heterogeneous nanostructured material through leveraging abnormal recrystallization, which is a prominent phenomenon in coarse-grained Ni-based superalloys. Additionally, through synthesis of a sputtered Inconel 725 film with a heterogeneous distribution of stored energy and subsequent aging treatments at 730°C, a unique combination of grain sizes and morphologies was observed throughout the thickness of the material. Three distinct domains are formed in the aged microstructure, where abnormally large grains are observed in-between a nanocrystalline and a nanotwinned region. In order to investigate the transitions towards a heterogeneous structure, crystallographic orientation and elemental mapping at interval aging times up to 8 h revealed the microstructural evolution and precipitation behavior. From the experimental observations and the detailed analysis of this study, the current methodology can be utilized to further expand the design space of current heterogeneous nanostructured materials.

36 MATERIALS SCIENCE↗
DOE OSTI2020

He ion irradiation response of a gradient T91 steel

Metallic materials with a gradient microstructure usually exhibit excellent mechanical properties. How- ever, the radiation response of gradient structural materials is less well understood. In this work, room- temperature He ion irradiation up to ~4.5 dpa with ~10 at% He injection was performed on a gradient T91 steel processed by surface severe plastic deformation. In comparison to the coarse-grained ferritic T91, the gradient T91 with the nanocrystalline layers shows improved radiation tolerance in terms of less bubble swelling and radiation hardening. Additionally, bubble distribution along grain boundaries depends on misorientation angle suggesting a strong capacity of non-equilibrium grain boundaries in storing He atoms. The present study provides insight into the design of radiation tolerant gradient steels for nuclear industry applications.

36 MATERIALS SCIENCE↗