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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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Synthesis of Lanthanide-Based Intermetallic Silicides

Lanthanide-containing materials are of interest because of their useful magnetic and electronic behavior. To study this intrinsic behavior, researchers need high-quality single crystals to avoid interference from grain boundaries or defects commonly found in polycrystalline samples. One method for growing single crystals is metal-flux synthesis, an approach that promotes crystal growth at lower reaction temperatures thus providing access to complex intermetallic phases. My project focuses on synthesizing novel lanthanide-containing intermetallic silicides related to previously reported f-element compounds with the Gd1??Fe4Si10?? structure type. I investigated reactions targeting lanthanum, praseodymium, neodymium, samarium, europium, and gadolinium-containing products, and used scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS) to identify promising lanthanide-containing phases. I prepared reactions by loading lanthanide oxides, Co, Si, Al, and Ga into alumina crucibles in a 0.2:1:1:10:10 Ln2O3/Co/Si/Al/Ga mmol ratio, where Ln = La, Nd, Pr, Sm, Eu, or Gd. The reactions were sealed in quartz tubes, heated in a furnace, and centrifuged to separate crystals from excess flux. Afterwards, I mechanically isolated single crystals and prepared them for characterization. Pr-, Nd-, and Sm-containing reactions were confirmed through SEM-EDS to have formed the targeted quaternary phase. Single crystal X-ray diffraction (SC-XRD) data showed the Nd-containing crystals exhibited a hexagonal unit cell associated with the Gd1??Fe4Si10?? structure type. La- and Eu-containing reactions instead formed competing Co(Al/Ga/Si)3 phase crystals. Single-crystal XRD, powder XRD, and magnetic susceptibility and heat-capacity measurements will be collected for the remaining lanthanide-containing crystals. This data will help determine the complete crystal structure of the lanthanide analogues, their phase purity and whether they exhibit localized magnetic behavior, magnetic ordering, or other electronic signatures that can be compared with the previously reported actinide analogues. The disordered structure of this intermetallic family is associated with unusual magnetic and electronic behavior meaning lanthanide analogues may show potential as thermoelectric materials. Developing new thermoelectric candidate materials is relevant to energy efficiency and waste-heat recovery, which supports DOE’s broader goal of advancing science and technology solutions for America’s energy needs.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2024

Real-Time Atomic-Scale Structural Analysis Resolves the Amorphous to Crystalline CaCO 3 Mechanism Controversy

Amorphous calcium carbonate (ACC) occurs as a precursor to geological and biogenic calcium carbonate (CaCO 3 ), yet its transformation pathways and reaction mechanisms remain inconsistent and controversial. In this study, we investigated the transformation of ACC to calcite under both solution and dry conditions, in the presence and absence of impurity ions, utilizing operando time-resolved synchrotron X-ray diffraction (TRXRD) and reactive transport modeling. Results demonstrate that TRXRD techniques allow us to differentiate dissolution-reprecipitation versus solid-state transformation mechanisms for amorphous to crystalline phase transitions. Specifically, we observe that in environments with abundant water, ACC transforms to calcite through a dissolution-reprecipitation mechanism. This features an activation energy of 63 ± 2 kJ/mol and unit cell volume contraction during calcite crystal growth. Conversely, under water-limited conditions, ACC to calcite transformation proceeds via a solid-state transformation mechanism, with an activation energy of 210 ± 2 kJ/mol, three times greater than the dissolution-reprecipitation route, and a unit cell expansion during crystalline calcite growth. Further, to illustrate the magnitude of these effects, the rates of calcite growth were similar during dissolution-reprecipitation at 3 °C [0.00207(35) s –1 ] and solid-state transformation at 280 °C [0.00134(11) s –1 ]. Moreover, the incorporation of an impurity, strontium, significantly retards the rate of calcite growth while expanding its unit cell but whose incorporation is history dependent. Reactive transport modeling of the dissolution–precipitation kinetics suggests that ACC must be dissolving as compact aggregates. These various transformation mechanisms drive diverse geological and biological carbonate formations, impacting their use as paleoenvironmental markers and functional materials synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

An Integrated Deposition and Passivation Strategy for Controlled Crystallization of 2D/3D Halide Perovskite Films

Abstract This work introduces a simplified deposition procedure for multidimensional (2D/3D) perovskite thin films, integrating a phenethylammonium chloride (PEACl)‐treatment into the antisolvent step when forming the 3D perovskite. This simultaneous deposition and passivation strategy reduces the number of synthesis steps while simultaneously stabilizing the halide perovskite film and improving the photovoltaic performance of resulting solar cell devices to 20.8%. Using a combination of multimodal in situ and additional ex situ characterizations, it is demonstrated that the introduction of PEACl during the perovskite film formation slows down the crystal growth process, which leads to a larger average grain size and narrower grain size distribution, thus reducing carrier recombination at grain boundaries and improving the device's performance and stability. The data suggests that during annealing of the wet film, the PEACl diffuses to the surface of the film, forming hydrophobic (quasi‐)2D structures that protect the bulk of the perovskite film from humidity‐induced degradation.

2D/3D perovskites↗
DOE OSTI2026

Effects of Cooling Rates on Self-Reinforced Polyethylene Composites via Multiscale Experimental Characterizations

This study investigates cooling rate effects on self-reinforced polyethylene composites (PE-SRCs), focusing on macroscopic thermal and mechanical properties, and micro- to sub-micron morphologies. Unlike conventional fiber-reinforced composites (e.g., carbon and glass fiber based), cooling rate effects on SRCs remain less studied. PE-SRCs were fabricated from ultrahigh molecular weight polyethylene (UHMWPE) fabric and high-density polyethylene (HDPE) matrix with cooling rates from 0.76°C/min to 425°C/min. Tensile properties, including modulus (~9.5 GPa), strength (~360 MPa), and ultimate elongation (~6%), showed no significant cooling rate dependence. However, thermal analysis revealed melting temperature of HDPE matrix decreased from ~130°C to ~126.5°C with total crystallinity reducing from 84% to 75%. Wide-angle X-ray scattering confirmed decreasing crystallinity but at lower values (67%–59%), as thermal analysis might overestimate crystallinity. Small-angle X-ray scattering showed long period decreased from 24.3 to 17.4 nm, attributed to thinner lamellae and closer packing, suggesting limited crystal growth and faster nucleation. While cooling rates alter melting point and crystalline structures of HDPE matrix, these changes do not translate to substantial impact on macroscale mechanical properties of PE-SRCs. This insensitivity might be related to low interfacial shear strength at PE/PE interfaces, enabling process optimization while maintaining mechanical performance.

Cooling rate↗
DOE OSTI2022

Additive‐Free, Low‐Temperature Crystallization of Stable α‐FAPbI 3 Perovskite

Abstract Formamidinium lead triiodide (FAPbI 3 ) is attractive for photovoltaic devices due to its optimal bandgap at around 1.45 eV and improved thermal stability compared with methylammonium‐based perovskites. Crystallization of phase‐pure α‐FAPbI 3 conventionally requires high‐temperature thermal annealing at 150 °C whilst the obtained α‐FAPbI 3 is metastable at room temperature. Here, aerosol‐assisted crystallization (AAC) is reported, which converts yellow δ‐FAPbI 3 into black α‐FAPbI 3 at only 100 °C using precursor solutions containing only lead iodide and formamidinium iodide with no chemical additives. The obtained α‐FAPbI 3 exhibits remarkably enhanced stability compared to the 150 °C annealed counterparts, in combination with improvements in film crystallinity and photoluminescence yield. Using X‐ray diffraction, X‐ray scattering, and density functional theory simulation, it is identified that relaxation of residual tensile strains, achieved through the lower annealing temperature and post‐crystallization crystal growth during AAC, is the key factor that facilitates the formation of phase‐stable α‐FAPbI 3 . This overcomes the strain‐induced lattice expansion that is known to cause the metastability of α‐FAPbI 3 . Accordingly, pure FAPbI 3 p–i–n solar cells are reported, facilitated by the low‐temperature (≤100 °C) AAC processing, which demonstrates increases of both power conversion efficiency and operational stability compared to devices fabricated using 150 °C annealed films.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Stacking disorder in α – RuCl 3 investigated via x-ray three-dimensional difference pair distribution function analysis

The van der Waals layered magnet α-RuCl 3 offers tantalizing prospects for the realization of Majorana quasiparticles. Efforts to understand this are, however, hampered by inconsistent magnetic and thermal transport properties likely coming from the formation of structural disorder during crystal growth, postgrowth processing, or upon cooling through the first order structural transition. Here, we investigate structural disorder in α-RuCl 3 using x-ray diffuse scattering and three-dimensional difference pair distribution function (3D-ΔPDF) analysis. We develop a quantitative model that describes disorder in α-RuCl 3 in terms of rotational twinning and intermixing of the high and low-temperature structural layer stacking. As a result, this disorder may be important to consider when investigating the detailed magnetic and electronic properties of this widely studied material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Stimulated Raman Scattering Microscopy: Real-Time In-Situ Physical and Chemical Characterization of Reverse Osmosis Desalination Membrane Scaling

We introduce a stimulated Raman scattering (SRS) methodology designed for rapid, real-time, and in situ monitoring of RO membrane scaling adapted for bench-scale desalination flow cells. The methodology can provide new insights into membrane scaling dynamics by offering time-resolved reflection imaging of inorganic crystal growth, coupled with chemical identification from Raman spectral data. These capabilities allow for direct local measurement of the membrane surface area covered by different scalants as well as an approximation of the scalant volume using three-dimensional, integrated Raman intensity. The 2D and 3D SRS results obtained from CaSO 4 scaling experiments are compared to and are in reasonable agreement with those provided by confocal microscopy. The real-time physical and chemical characterization capabilities presented here could be extended to study combinations of inorganic, organic, and biological fouling. Overall, the SRS methodology represents an advancement in real-time sensing of membrane fouling that offers the potential for improved operation, lower cost, and more resilient RO membrane systems for sustainable water management.

42 ENGINEERING↗
DOE OSTI2025

Evolution of Structural Order and Magnetic Anisotropy in Yb 0.5 (Co 1– x Fe x ) 3 Ge 3 through Doping of a Kagome Lattice

Kagome materials provide fruitful grounds for exploring the intersection of topology and magnetism. In this article, the single crystal growth of Yb 0.5 (Co 1–x Fe x ) 3 Ge 3 (x = 0.00, 0.25, 0.50, 0.75, and 1.00) is reported. As Fe is substituted into the Co-containing kagome net, the structure transforms from the disordered Y 0.5 Co 3 Ge 3 /CoSn-type hybrid structure to the ordered HfFe 6 Ge 6 -type structure. Diffusive scattering is observed in all doped concentrations that eventually converge to a single reflection in the Fe end member, ultimately doubling the unit cell along the c-axis. Anisotropic magnetic measurements were performed to evaluate how the magnetism of the kagome lattice is influenced by Fe substitution. Magnetic interactions are primarily observed along the c-axis. Additionally, a reorientation of the magnetic easy axis is observed with increasing Fe incorporation, highlighting how the magnetism of this material can be chemically tuned. Resistivity with unusual behavior observed in the doped compositions is also reported. Furthermore, the rationale behind the structural evolution from disordered to ordered is discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Assessment of Blocking Contacts in Suppressing Polarization Effects in CsPbBr 3 Perovskite Detectors

The CsPbBr 3 perovskite has garnered significant attention as a room-temperature semiconductor for hard radiation detection due to straightforward synthesis, scalable crystal growth, low cost, and excellent energy resolution. However, despite these advantages, at ambient temperature, CsPbBr 3 devices may experience performance deterioration and irreversible failure due to “polarization” induced by electromigration of ions to electrical connections on the device. In this study, we tested several contact materials and their optimization deposition techniques to assess the stability of high-performance CsPbBr 3 γ-ray detectors. Metals, with low work functions (Ti, In, Sn, Sb, Pb, Bi, Al, Au, and TiC) and high-work-function (Au or Pt) contacts, were used to form different Schottky junctions using vacuum thermal evaporation, electron-beam evaporation, and sputtering methods. These detectors were tested in intermittent and continuous modes to assess their stability. Among the tested detectors, the Bi/CLB/Pt electrode configuration demonstrated superior stability, operating effectively for 11 months under periodic testing and 16 days under continuous testing. In contrast, other configurations functioned only for a few months under intermittent conditions. Upon incorporating a ~40-nm-thick TiC passivation layer on the anode side (Bi/TiC/CLB/Pt), the CLB device operated continuously for 36 days without degradation. In many cases, the failure mode of the devices was due to the degradation of the anode. Here, the chemical changes in the fresh and deteriorated anodes were characterized using scanning electron microscopy and energydispersive X-ray spectroscopy

CsPbBr3 perovskite↗
DOE OSTI2025

Single Crystalline Na 0.67 Ni 0.33 Mn 0.67 O 2 Positive Electrode Material via Molten Salt Synthesis for Sodium Ion Batteries

P2-layered Na 0.67 Ni 0.33 Mn 0.67 O 2 (NNMO) has emerged as a promising positive electrode material for sodium ion batteries due to its appealing electrochemical properties. Synthesis of polycrystalline NNMO (PC-NNMO) materials through conventional calcination of solid precursors remains the prevailing method, where heating occurs in a dry environment with air or O 2 . On the other hand, the molten salt method, where precursors are submerged in molten salt medium during calcination, emerged in recent years to be a scalable technique for more controlled crystal growth and uniform morphology in a variety of materials. Here, we utilize the molten salt method to synthesize single crystalline NNMO (SC-NNMO) materials with enhanced electrochemical properties. The SC-NNMO material exhibits an initial specific discharge capacity of 95 mAh g –1 at a 0.1C rate, retaining approximately 88.5% of its capacity after 100 cycles over a wide voltage range of 2.0–4.2 V. Furthermore, SC-NNMO maintains a capacity retention of 83.9% after 300 cycles at a 1C rate compared to 66.6% for PC-NNMO, indicating excellent long-term cycling stability. This stability is further confirmed by the performance of an SC-NNMO//hard carbon full cell, which retains 90.3% of its capacity after 200 cycles at 1C within a voltage window of 1.9–4.1 V. The enhancement in stability of the SC-NNMO sample is attributed to the single crystalline structure suppressing the undesired P2–O2 phase transition at high voltage. This study also presents an easy, efficient, and straightforward molten salt process for SC-NNMO material synthesis, offering valuable insights into the potential application of such methodology for the large-scale, cost-effective production of various sodium-layered transition metal oxide positive electrode materials for SIBs.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2020

Blading Phase–Pure Formamidinium–Alloyed Perovskites for High–Efficiency Solar Cells with Low Photovoltage Deficit and Improved Stability

Currently, blade-coated perovskite solar cells (PSCs) with high power conversion efficiencies (PCEs), i.e. greater than 20%, normally employ methylammonium lead tri-iodide with a sub-optimal bandgap. Alloyed perovskites with formamidinium (FA) cation have narrower bandgap and thus enhance device photocurrent. However, FA-alloyed perovskites show low phase stability and high moisture sensitivity. Here, we report that incorporating 0.83 molar percent organic halide salts (OHs) into the perovskite inks enables phase-pure, highly crystalline FA-alloyed perovskites with extraordinary optoelectronic properties. Here, the OH molecules modulate the crystal growth, enhance the phase stability, passivate ionic defects at the surface and/or grain boundaries, and enhance the moisture stability of the perovskite film. We demonstrate a high efficiency of 22.0% under 1 sun illumination for blade-coated PSCs with an open-circuit voltage of 1.18 V, corresponding to a very small voltage deficit of 0.33 V, and significantly improved operational stability with 96% of the initial efficiency retained under one sun illumination for 500 hours.

14 SOLAR ENERGY↗
DOE OSTI2022

Electroactive ZnO: Mechanisms, Conductivity, and Advances in Zn Alkaline Battery Cycling

Zinc oxide is of great interest for advanced energy devices because of its low cost, wide direct bandgap, non-toxicity, and facile electrochemistry. In zinc alkaline batteries, ZnO plays a critical role in electrode passivation, a process that hinders commercialization and remains poorly understood. Here, novel observations of an electroactive type of ZnO formed in Zn-metal alkaline electrodes are disclosed. The electrical conductivity of battery-formed ZnO is measured and found to vary by factors of up to 10 4 , which provides a first-principles-based understanding of Zn passivation in industrial alkaline batteries. Simultaneous with this conductivity change, protons are inserted into the crystal structure and electrons are inserted into the conduction band in quantities up to ≈10 20 cm –3 and ≈1 mAh gZnO –1 . Electron insertion causes blue electrochromic coloration with efficiencies and rates competitive with leading electrochromic materials. The electroactivity of ZnO is evidently enabled by rapid crystal growth, which forms defects that complex with inserted cations, charge-balanced by the increase of conduction band electrons. Furthermore, this property distinguishes electroactive ZnO from inactive classical ZnO. Knowledge of this phenomenon is applied to improve cycling performance of industrial-design electrodes at 50% zinc utilization and the authors propose other uses for ZnO such as electrochromic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2025

De Nive Quinquangula: Pentagonal Snowflake Metal Nanocrystals as an Example of Emergence Phenomenon in Nanotechnology Complex Systems

The formation of snowflakes (SFL) is one of the most captivating phenomena in nature. The fabrication of multimetallic gold (Au) nanoparticles containing copper (Cu) and iron (Fe) is reported, which adopt snowflake-like morphology after nanoparticle aggregation. The synthesis of these snowflake-like Au microcrystals occurs mainly by kinetic control. In this process, a surfactant-assisted salt reduction method is employed on a heated substrate. Here, the metal salts react within seconds to form nanoparticles. This process results in a hierarchical structure with pseudo-pentagonal symmetry and chiroptical activity. We discuss how large superstructures emerge from nanoparticle aggregation, resembling natural snowflakes. However, unlike ice snowflakes, which exhibit hexagonal symmetry, the Au snowflakes display pentagonal symmetry. It is proposed that the formation of these snowflake-like microcrystals is the result of the complexity involved in the crystal growth process and represents an example of the phenomenon of emergence, which has become very significant in several fields of modern science, including physics, biology, chemistry, economics, philosophy, and poetry. The term emergent is used to evoke the collective behavior of a large number of microscopic constituents that is qualitatively different than the behaviors of the individual constituents.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Uniaxial compression of [001]-oriented CaFe 2 As 2 single crystals:the effects of microstructure and temperature on superelasticity Part I: Experimental observations

Micropillar compression experiments on [001]-oriented CaFe 2 As 2 single crystals have recently revealed the existence of superelasticity with a remarkably high elastic limit of over 10%. The collapsed tetragonal phase transition, which is a uni-axial contraction process in which As-As bonds are formed across an intervening Ca-plane, is the main mechanism of superelasticity. Usually, superelasticity and the related structural transitions are affected strongly by both the microstructure and the temperature. As such, in this study, we investigated how the microstructure and temperature affect the superelasticity of [001]-oriented CaFe 2 As 2 micropillars cut from solution-grown single crystals, by performing a combination of in-situ cryogenic micromechanical testing and transmission electron microscopy studies. Our results show that the microstructure of CaFe 2 As 2 is influenced strongly by the crystal growth conditions and by subsequent heat treatment. The presence of Ca and As vacancies and FeAs nanoprecipitates affect the mechanical behavior significantly. In addition, the onset stress for the collapsed tetragonal transition decreases gradually as the temperature decreases. These experimental results are discussed primarily in terms of the formation of As-As bonds, which is the essential feature of this mechanism for superelasticity. Our research outcomes provide a more fundamental understanding of the superelasticity exhibited by CaFe 2 As 2 under uni-axial compression.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Citation for the 2019 Victor M. Goldschmidt award to Donald J. DePaolo

Perhaps the comments most commonly heard when a colleague receives professional recognition are “well-deserved” and “long-overdue”. As such, it is my pleasure to introduce Donald DePaolo as the recipient of this year’s Goldschmidt Award as it is both long-overdue and so well-deserved. While Don has received many honors over the course of his career, the Goldschmidt best recognizes his broad impact on geochemistry. There are few who have contributed as much to geochemistry as Don DePaolo. Finally, his scientific contributions are voluminous and broad, ranging from pioneering efforts to establish the Sm/Nd isotopic system, and its applications to mantle evolution and basalt petrogenesis, to studies of magma mixing, assimilation and crystal fractionation, to evolution of the lower crust and granite petrogenesis, to chemical oceanography, diagenesis and seafloor alteration, to reactive transport accompanying rock-water interaction, and to kinetic isotopic fractionation associated with crystal growth, diffusion and evaporation.

58 GEOSCIENCES↗
DOE OSTI2023

Effects of particle shape and surface roughness on van der Waals interactions and coupling to dynamics in nanocrystals

The van der Waals interaction between colloids and nanoparticles is one of the key components to understanding particle aggregation, attachment, and assembly. While the ubiquity of anisotropic particle shapes and surface roughness is well-recognized in nanocrystalline materials, the effect of both on van der Waals forces and torques has not been adequately investigated. Here, in this study, we develop a numerical scheme and determine the van der Waals forces and torques between cubic particles with multiple configurations and relative orientations. Our results show that the van der Waals torque due to anisotropic particle shapes is appreciable at nearly all configurations and mutual angles, outcompeting Brownian motion for various materials systems and conditions. The effect of surface roughness increases this shape effect, resulting in stronger van der Waals interactions ascribed to protrusions in the rough surfaces. Moreover, a scaling analysis indicates that the surface roughness alters the separation dependence of the van der Waals force and, more importantly, significantly influences the dynamics of two approaching particles. Our results clearly demonstrate that surface roughness and anisotropic shape play a crucial role in the energetics and kinetics of various particle-scale and emergent phenomena, such as crystal growth by oriented attachment, nanomaterials synthesis and assembly, mud flow rheology, as well as the deposition of natural nanocrystals within the subsurface.

Arbitrary configurations↗