Search NASA⌕ Search

SEARCH · Search NASA

Results for “low energy electron diffraction”

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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Surface Amorphization of Vanadium Dioxide (B) for K-ion Battery

Given the merits of low cost, fast ionic transport in electrolyte, and high operating voltage, potassium ion batteries (PIBs) are promising alternatives to lithium-ion batteries. However, developing suitable electrode materials that can reversibly accommodate large potassium ions is a great challenge. In this paper, guided by density functional theory (DFT) calculations, it is demonstrated that the strategy of interfacial engineering via surface amorphization of VO 2 (B) nanorods (SA-VO 2 ), which results in the formation of a crystalline core/amorphous shell heterostructure, enables superior K + storage performance in terms of large capacity, outstanding rate capability, and long cycle stability working as an anode for PIBs. DFT calculations reveal that the created crystalline/amorphous heterointerface in SA-VO 2 can substantially lower the surface energy, narrow the band gap, and reduce the K + diffusion barrier of VO 2 (B). These conditions enable enhanced K + storage capacity and rapid K + /electron transfer, which result in large capacity and outstanding rate capability. Using in situ X-ray diffraction and in situ transmission electron microscopy complemented by ex situ microscopic and spectroscopic techniques, it is unveiled that the superior cycling stability originates from the excellent phase reversibility with negligible strain response and robust mechanical behavior of SA-VO 2 upon (de)potassiation.

25 ENERGY STORAGE↗
DOE OSTI2025

Polymorphism and Phase Control in Dion–Jacobson 2D 3-(Aminomethyl)piperidinium-Based Metal Iodide Perovskites

Two-dimensional halide perovskites exhibit rich structural diversity and tunable optoelectronic properties, making them promising materials for energy, sensing, and photonic applications. In this work, we report the structural mapping of four distinct polymorphs, γ (P2 1 /c), β (P4/mbm), α (P4/mmm), and δ (Cmcm) in the two-dimensional iodoplumbate, iodostannate, and iodogermanate perovskite so-called Dion-Jacobson series (3AMP)MI4 (M = Sn, Pb, Ge), where 3AMP is 3-(aminomethyl)piperidinium. The phases exhibit systematic evolution in octahedral distortion, lattice symmetry, and metal–halide geometry, enabling structural control over optoelectronic properties. Notably, the α-phase of (3AMP)SnI 4 represents a rare, ambient-stable, high-symmetry structure for Sn-based perovskites, without a phase transition down to 100 K. Variable-temperature single-crystal diffraction, powder x-ray diffraction (PXRD), and calorimetry reveal metal- and temperature-dependent polymorph interconversions, including the emergence of long range supercell reflections in Pb-rich compositions at low temperature. Optical spectroscopy and photoelectron yield spectroscopy confirm band gap tunability and band alignment trends, highlighting symmetry-dependent shifts and anomalous band gap bowing in mixed-metal systems, verified by electronic structure calculations. Calculations additionally indicate that the higher symmetry phases have reduced electron and hole effective masses compared to the lower symmetry phases.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Quantitative nanoscale tracking of oxygen vacancy diffusion inside single ceria grains by in situ transmission electron microscopy

Oxygen vacancy formation and migration in ceria is critical to its electrochemical and catalytic properties in systems for chemical and energy transformation, but its quantification is rather challenging especially at atomic-scale because of disordered distribution. Here we report a rational approach to track oxygen vacancy diffusion in single grains of pure and Sm-doped ceria at -20 °C to 160 °C using in situ (scanning) transmission electron microscopy ((S)TEM). To create a gradient in oxygen vacancy concentration, a small region (~30 nm in diameter) inside a ceria grain is reduced to the C-type CeO 1.68 phase by the ionization or radiolysis effect of a high-energy electron beam. The evolution in oxygen vacancy concentration is then mapped through lattice expansion measurement using scanning nano-beam diffraction or 4D STEM at a spatial resolution better than 2 nm; this allows direct determination of local oxygen vacancy diffusion coefficients in a very small domain inside pure and Sm-doped ceria at different temperatures. Further, the activation energies for oxygen transport are determined to be 0.59, 0.66, 1.12, and 1.27 eV for pure CeO 2 , Ce 0.94 Sm 0.06 O 1.97 , Ce 0.89 Sm 0.11 O 1.945 , and Ce 0.8 Sm 0.2 O 1.9 , respectively, implying that activation energy increases due to impurity scattering. The results are qualitatively supported by density functional theory (DFT) calculations. In addition, our in situ TEM investigation reveals that dislocations impede oxygen vacancy diffusion by absorbing oxygen vacancies from the surrounding areas and pinning them locally. With more oxygen vacancies absorbed, dislocations show extended strain fields with local tensile zone sandwiched between the compressed ones. Therefore, dislocation density should be reduced in order to minimize the resistance to oxygen vacancy diffusion at low temperatures.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Copper Electrode on Flexible Substrate by Intense Pulsed Light Sintering of Microsized Copper Particles

Metal electrodes deposited in a grid pattern onto flexible polymer substrates have been shown to be a viable alternative to replace indium tin oxide (ITO) as the transparent anode for organic photovoltaics. copper may be a better alternative in terms of cost and stability for large area low-cost solar modules, specifically on roll-to-roll platforms. These customized electrode patterns can be fabricated from copper nanoparticles through various printing techniques applicable to solution phase processing. The Intense Pulsed Light (IPL) technique has been used to sinter copper nanoparticles (~100nm) to fabricate conductive copper electrodes on flexible polymer substrates. However, compared to nanosized (~100 nm) copper particles, microsized (~2 um) copper is much cheaper. In this work, microsized (~2 um) copper is used to produce high conductive copper inks. The conductivity of the print can be adjusted through the use of surfactant. IPL sintering was optimized to obtain high conductivity copper films. In conclusion, several microscopic and electrical spectroscopic characterization techniques such as scanning electron microscopy (SEM), x-ray diffraction (XRD), 4-point probe resistivity measurements were employed to characterize the copper electrodes.

14 SOLAR ENERGY↗
DOE OSTI2023

Multimodal microscopy of extended defects in β-Ga 2 O 3 (010) EFG crystals

Beta-phase gallium oxide (β-Ga 2 O 3 ) has attracted attention in recent years as a potentially low cost, large area substrate and active layer material for high power, high temperature power electronics and sensing devices. However, growth of β-Ga 2 O 3 crystals is complicated by easily activated (100) and (001) cleavage planes, the presence of low angle grain boundaries (LAGBs) and twins, and the potential formation of polycrystalline grains. In this study, β-Ga 2 O 3 crystals were grown by the edge-defined film-fed growth technique with an (010) principal face. Two crystals with apparently randomly formed high angle grain boundaries (HAGBs) were selected and analyzed by electron backscatter diffraction, electron channeling contrast imaging, and cathodoluminescence to investigate the nature of the LAGBs and the source of the HAGB formation. It was discovered that planar LAGBs lying parallel to the (010) plane exist in the region immediately preceding the start of an HAGB. Increased misorientation across the LAGB was observed, approaching the initiation of a new grain. We present multimodal microscopy characterization, correlating misorientation and variation in optoelectronic properties with LAGBs and the associated dislocations.

14 SOLAR ENERGY↗
DOE OSTI2023

Multiscale Imaging of Nuclear Deformation at the Electron-Ion Collider

We show within the Color Glass Condensate framework that exclusive vector meson production at high energy is sensitive to the geometric deformation of the target nucleus at multiple length scales. Studying e+U collisions and varying the deformation of the uranium target, we demonstrate that larger deformations result in enhanced incoherent vector meson production cross sections. Further, different multipole deformation parameters affect different regions of transverse momentum transfer. Employing JIMWLK evolution to study the Bjorken-x dependence of our results, we find that the ratio of incoherent to coherent cross sections decreases with decreasing x, largely independently of the quadrupole deformation of the target. Comparing results for the same process using 20 Ne targets with 16 O targets, we find that differences in deformation are clearly visible in the incoherent cross section. These findings show that certain observables at the Electron-Ion Collider are very sensitive to nuclear structure. Consequently, deformations need to be taken into account when interpreting experimental results. More importantly, this also means that |t|-differential diffractive vector meson production could become a powerful tool, enabling the most direct measurements of nuclear structure at different length scales, ranging from nuclear deformation at low |t| to nucleon and subnucleon-size scales at higher |t|.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Thermoelectric power generation in the core of a nuclear reactor

Thermoelectric energy converters offer a promising solution to generate electrical power using heat in the nuclear reactor core. Despite significant improvements in thermoelectric efficiency of nanostructured materials, the performance of these advanced materials has yet to be demonstrated in the harsh radiation environment of a reactor core. Herein, we demonstrate a thermoelectric generator (TEG) made from nanostructured bulk half-Heusler (HH) materials generating stable electrical power density > 1140 W/m 2 after 30 days in the MIT Nuclear Research Reactor under an unprecedented fast-neutron (>1 MeV) fluence of 1.5 × 10 20 n/cm 2 . Despite an initial degradation due to irradiation damage when operating under relatively low temperatures, our TEG showed a 20-fold increase in power output when operating under high temperature due to in-situ annealing and resulting thermoelectric property recovery. First-principles modeling indicates that a chemically disordered metallic phase was formed under irradiation at lower temperatures, resulting in a drastic degradation in thermoelectric properties, while at sufficiently high temperatures the system returned to the initial chemically ordered HH phase and the thermoelectric properties recovered. Transmission electron microscopy and electron diffraction demonstrated that the chemically disordered phase was formed upon ion irradiation, confirming the prediction from first-principles simulations. Furthermore, the results suggest that with proper control over the TEG operating temperatures, the nanostructured bulk TEGs could produce stable electrical power and operate indefinitely in the core of a nuclear reactor.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

RCSB Protein Data Bank: powerful new tools for exploring 3D structures of biological macromolecules for basic and applied research and education in fundamental biology, biomedicine, biotechnology, bioengineering and energy sciences

Abstract The Research Collaboratory for Structural Bioinformatics Protein Data Bank (RCSB PDB), the US data center for the global PDB archive and a founding member of the Worldwide Protein Data Bank partnership, serves tens of thousands of data depositors in the Americas and Oceania and makes 3D macromolecular structure data available at no charge and without restrictions to millions of RCSB.org users around the world, including >660 000 educators, students and members of the curious public using PDB101.RCSB.org. PDB data depositors include structural biologists using macromolecular crystallography, nuclear magnetic resonance spectroscopy, 3D electron microscopy and micro-electron diffraction. PDB data consumers accessing our web portals include researchers, educators and students studying fundamental biology, biomedicine, biotechnology, bioengineering and energy sciences. During the past 2 years, the research-focused RCSB PDB web portal (RCSB.org) has undergone a complete redesign, enabling improved searching with full Boolean operator logic and more facile access to PDB data integrated with >40 external biodata resources. New features and resources are described in detail using examples that showcase recently released structures of SARS-CoV-2 proteins and host cell proteins relevant to understanding and addressing the COVID-19 global pandemic.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

An Atom-Precise Approach to Damp First-Order Phase Transitions and Its Implications for Neuromorphic Signal Processing

Neuromorphic computing inspired by mammalian intelligence aims to emulate the nonlinear dynamics of biological neurons and synapses to achieve fast, low-energy, and highly efficient information processing. Brain-inspired computing relies on the design and discovery of materials exhibiting nonlinear current–voltage profiles, frequently underpinned by electronic state transitions, to achieve spiking neurons and dynamically tunable synapses. A signature challenge in the design of artificial neurons is controlling the steepness of first-order transitions in active elements, as abrupt transitions are at risk of driving unstable voltage and temperature oscillations, which result in catastrophic device failure. A critical knowledge gap is the lack of structure–function correlations mapping the composition and atomistic structure of crystalline solids to nonlinear dynamical response characteristics. Here, we address the key question of how modification of atomistic structure correlates with alteration of neuron-like functionality. Constructing oscillator circuits from millimeter-scale single crystals enables high-resolution atomic structure solutions, which we use to demonstrate that the selective positioning of Pb cations modifies charge ordering along a one-dimensional CuxV2O5 framework even at low insertion stoichiometries, thereby providing an atom-precise design parameter for damping first-order transitions. We use temperature-variant X-ray diffraction and X-ray spectroscopy to elucidate the suppression of Cu-ion shuttling based on the precise positioning of Pb ions in seven-coordinated tunnel interstitial sites as the mechanistic basis for transition broadening, thus bridging a critical gap between statistical mechanics and quantum chemical descriptions of phase transitions. Such mechanistic understanding thus paves the way to site-selective modification strategies for modulating the sharpness of first-order transitions, with an exemplary demonstration here in tuning neuronal signal processing.

Crystal structure↗
DOE OSTI2025

High-Speed and High-Quality Field Welding Repair Based on Advanced Non-Destructive Evaluation and Numerical Modeling

Creep strength-enhanced ferritic (CSEF) steels such as Grade 91 (9Cr-1Mo-V) and Grade 92 (Fe-9Cr-2W-0.5Mo) steels are widely used in the fossil-fuel-fired and nuclear power plants. The weld integrity of these steels is crucial for power plants' safe and reliable operations. Due to harsh service conditions, the steel weld can become susceptible to environmental degradation. Field welding repair is used to restore the degraded weld’s performance where a controlled temper-bead welding technique is commonly used to temper the freshly formed martensite during welding. However, knowledge of weld repairability is limited and experimental trial and error optimization to achieve desired microstructure and joint properties is expensive and time-consuming. Many existing computational models, e.g., finite element models, are limited to solving heat conduction equation and ignoring convective heat transfer due to molten metal flow. These models can result in over-prediction of peak temperatures of weld pool and heat-affected zone (HAZ), which in turn can affect the accuracy of tempering prediction. Moreover, these finite element models require an input of the deposit profiles in advance and thus limits the usability of these models. Here, a molten pool-based, multi-pass multi-layer model has been developed based on computational fluid dynamics (CFD) approach with the Volume of Fluid (VOF) method. The model calculates the bead formation, thereby eliminating the need for pre-determined bead profiles required by finite element models. For computational efficiency, a coordinate system attached to the moving heat source is utilized. A subroutine is developed to convert the temperature profiles in the reference frame stationary to the heat source to that stationary to the workpiece. The converted thermal cycles are then imported into a microstructure model to compute the tempering kinetics and resultant hardness using a Johnson-Mehl-Avrami-Kolmogorov (JMAK), and modified Grange-Baughman parameter. The modeling approach is first developed and validated on single- and multi-pass deposition of stainless steel filler metal onto a SA-533 high strength steel substrate. The models are then applied to a multi-pass V-groove repair weld of Grade 91 steel plate as well as directed energy deposition of Grade 92 steel. Non-destructive characterization of microstructures was performed on Grade 91 and 92 steel welds. Two welding processes, cold metal transfer (CMT) and flux-cored arc welding (FCAW), were investigated for the Grade 91 steel weld samples. For the Grade 92 weld samples, three different heat inputs (low, medium, and high) of gas tungsten arc welding (GTAW) were utilized to replicate traditional field welding processes. The non-destructive evaluation (NDE) method used for this research was immersion ultrasonic testing (UT) using a micro-resolution ultrasonic imaging methodology specifically designed to operate in the through-transmission configuration operating at 20 MHz of frequency. The system used a focused ultrasonic beam spot size diameter between 250-300 μm, and a 6 μm laser vibrometer spot size for detection, to produce highly defined images with longitudinal and mode-converted shear waves. From the micro-resolution ultrasonic C-scan images, three microstructural regions, i.e., weld metal (WM), HAZ, and base metal (BM), were clearly identifiable. Various levels of ultrasonic amplitudes distributed over the three regions were correlated with electron beam backscattered diffraction (EBSD) images using grain size, grain boundaries, and dislocation densities. The results showed that areas with relatively higher ultrasonic amplitude levels were associated with smaller grains and higher dislocation densities, while areas with lower amplitude levels were associated with larger grains and lower dislocation densities. In addition, ultrasonic velocity data obtained across the three different weld microstructural regions of Grade 91 test samples were correlated with optical metallographic images and hardness measurements. The results showed distinctive decreases in ultrasonic velocity and hardness over the HAZ region, where weld failures often occur during service.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Direct Deposition of Nonaqueous SnO 2 Dispersion by Blade Coating on Perovskites for the Scalable Fabrication of p–i–n Perovskite Solar Cells

Tin(IV) oxide materials have been extensively used as electron transport materials in n–i–p perovskite solar cells (PSCs) due to their superior optoelectronic properties, low-temperature processability, and high chemical stability. However, solvent incompatibility and processing temperature have limited the direct deposition of fully solution-processed SnO 2 in p–i–n devices. In this study, we overcome this limitation by the functionalization of SnO 2 nanoparticles with acetate through ligand exchange, allowing their dispersion in anhydrous ethanol. The SnO 2 dispersion was deposited on the perovskite absorber by blade coating without damaging the underlying perovskite layer, as determined by X-ray diffraction and scanning electron microscopy. Photoluminescence spectroscopy confirmed effective electron extraction. The champion device shows 14.1% initial power conversion efficiency (PCE) which is unprecedented for a p–i–n device employing solution-phase SnO 2 . Finally, PSCs stored for 40 days in a nitrogen flow box retained an average of 95.8% of the initial PCE.

14 SOLAR ENERGY↗
DOE OSTI2024

Chemical and Electrochemical Characterization of Hot–Pressed Li 6 PS 5 Cl Solid State Electrolyte: Operating Pressure–Invariant High Ionic Conductivity

Sulfide solid state electrolytes (SSE) are among the most promising materials in the effort to replace liquid electrolytes, largely due to their comparable ionic conductivities. Among the sulfide SSEs, Argyrodites (Li 6 PS 5 X, X=Cl, Br, I) further stand out due to their high theoretical ionic conductivity (~1×10 –2 S cm –1 ) and interfacial stability against reactive metal anodes such as lithium. Generally, solid state electrolyte pellets are pressed from powder feedstock at room temperature, however, pellets fabricated by cold pressing consistently result in low bulk density and high porosity, facilitating interfacial degradation reactions and allowing dendrites to propagate through the pores and grain boundaries. Here, we demonstrate the mechanical and electrochemical implications of hot-pressing standalone LPSCl SSE pellets with near-theoretical ionic conductivity, superior cycling performance, and enhanced mechanical stability. X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and x-ray diffraction spectroscopy (XRD) analysis reveal no chemical changes to the Argyrodite surface after hot pressing up to 250°C. Furthermore, we use electrochemical impedance spectroscopy (EIS) to understand mechanical stability of Argyrodite SSE pellets as a function of externally applied pressure, demonstrating for the first time pressed standalone Argyrodite pellets with near-theoretical conductivities at external pressures below 14 MPa.

25 ENERGY STORAGE↗
DOE OSTI2021

Room-temperature large magnetoelectricity in a transition metal doped ferroelectric perovskite

There is increasing interest in novel magnetoelectric (ME) materials that exhibit robust ME coupling at room-temperature (RT) for advanced memory, energy, spintronics, and other multifunctional device applications, by making use of the ability to control polarization with a magnetic field and/or magnetization via an electric field. Obtaining ME materials with strong ME coupling, understanding the origin, and manipulating its processing along with composition to realize large ME coefficients at RT constitute an important step in multiferroic research. To address this, we have investigated the multiferroic and ME properties of Ni-doped Pb(Zr 0.20 Ti 0.80 )O 3 (PZT). We find that the ferroelectric (T C ~ 700 K) and weak ferromagnetic (~ 602 K) phase transitions of Ni-doped PZT are well above RT, leading to a strong ME coupling coefficient (α E,31 ) of 11.7 mVcm -1 Oe -1 (H ac = 1 Oe and f = 1 kHz). While X-ray diffraction suggests a single-phase material, high resolution transmission electron microscopy reveals regions with and without Ni present; thus magnetoelectric coupling between two phases is possible. First-principle calculations suggest the (Ni Pb ) × defect is likely to be responsible for the experimental observed magnetism and ME coupling in Ni-doped PZT. Furthermore, we demonstrate that Ni-doped PZT exhibits low loss tangent, low leakage current, large saturation polarization and weak ferromagnetism. Ultimately, our work demonstrates that Ni-doped PZT is a cost-effective RT multiferroic with strong ME coupling.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Linker-Free Magnetite-Decorated Gold Nanoparticles (Fe3O4-Au): Synthesis, Characterization, and Application for Electrochemical Detection of Arsenic (III)

Linker-free magnetite nanoparticles (Fe3O4NPs)-decorated gold nanoparticles (AuNPs) were grown using a new protocol that can be used as a new platform for synthesis of other intact metal–metal oxide nanocomposites without the need for linkers. This minimizes the distance between the metal and metal oxide nanoparticles and ensures the optimum combined effects between the two material interfaces. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy confirmed the successful synthesis of the Fe3O4-Au nanocomposite, without any change in the magnetite phase. Characterization, using transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy, revealed the composite to consist of AuNPs of 70 ± 10 nm diameter decorated with tiny 10 ± 3 nm diameter Fe3O4NPs in Au:Fe mass ratio of 5:1. The prepared Fe3O4-Au nanocomposite was embedded in ionic liquid (IL) and applied for the modification of glassy carbon electrode (GCE) for the electrochemical detection of As(III) in water. By combining the excellent catalytic properties of the AuNPs with the high adsorption capacity of the tiny Fe3O4NPs towards As(III), as well as the good conductivity of IL, the Fe3O4-Au-IL nanocomposite showed excellent performance in the square wave anodic stripping voltammetry detection of As(III). Under the optimized conditions, a linear range of 1 to 100 μg/L was achieved with a detection limit of 0.22 μg/L (S/N = 3), and no interference from 100-fold higher concentrations of a wide variety of cations and anions found in water. A very low residual standard deviation of 1.16% confirmed the high precision/reproducibility of As(III) analysis and the reliability of the Fe3O4-Au-IL sensing interface. Finally, this proposed sensing interface was successfully applied to analyzing synthetic river and wastewater samples with a 95–101% recovery, demonstrating excellent accuracy, even in complex synthetic river and wastewater samples containing high concentrations of humic acid without any sample pretreatments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Enhanced Low-Temperature Thermoelectric Performance in (PbSe) 1+δ (VSe 2 ) 1 Heterostructures due to Highly Correlated Electrons in Charge Density Waves

We explore the effect of charge density wave (CDW) on the in-plane thermoelectric transport properties of (PbSe) 1+δ (VSe 2 ) 1 and (PbSe) 1+δ (VSe 2 ) 2 heterostructures. In (PbSe) 1+δ (VSe 2 ) 1 we observe an abrupt 86% increase in the Seebeck coefficient, 245% increase in the power factor, and a slight decrease in resistivity over the CDW transition. This behavior is not observed in (PbSe) 1+δ (VSe 2 ) 2 and is rather unusual compared to the general trend observed in other materials. The abrupt transition causes a deviation from the Mott relationship through correlated electron states. Raman spectra of the (PbSe) 1+δ (VSe 2 ) 1 material show the emergence of additional peaks below the CDW transition temperature associated with VSe 2 material. Temperature-dependent in-plane X-ray diffraction (XRD) spectra show a change in the in-plane thermal expansion of VSe 2 in (PbSe) 1+δ (VSe 2 ) 1 due to lattice distortion. Here, the increase in the power factor and decrease in the resistivity due to CDW suggest a potential mechanism for enhancing the thermoelectric performance at the low temperature region.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Conversion, Stability, and Selectivity Improvements Through Catalyst Development for the Reductive Etherification Reaction

Economical pathways from lignocellulosic non-food biomass feedstocks to biofuels with appropriate fuel properties are necessary for displacing fossil-fuel derived diesel use in medium-/heavy duty vehicles. Oxygenated compounds have recently shown promise due to low sooting tendencies and autoignition properties and molecules with sufficiently high carbon numbers can meet the requisite standards for water solubility and flash point. Coupling waste biomass derived small molecules into bioblendstock targets through the reductive etherification reaction shows potential for increasing molecular weight without losing the advantages of oxygenates. However, the transition to industrial viability for this process is limited by strong catalyst deactivation in typical flow reactor systems. Strong acid resins such as Amberlyst-15 (A-15) show excellent activity in batch reactions but are limited to low temperatures and are poisoned by the side-product, water. In this talk, I will describe our recent work in catalyst synthesis and testing to select superior options with improved aqueous and thermal stability in reductive etherification flow reactions. Water-tolerant solid acid catalysts have potential to improve the conversion and selectivity to the ether target at temperatures above the degradation point of A-15. Analysis techniques such as physisorption, chemisorption, x-ray diffraction and transmission electron microscopy are being used to characterize the active sites. These techniques are also being used to evaluate degradation of the catalyst after extensive flow reactions in addition to comparative efficiency testing with standardized cyclohexene hydrogenation reactions. Finally, I will discuss a demonstration of the full pathway from bio-derived butyric acid to the performance-advantaged ether product and the additional obstacles from side-products and purification limitations in the preliminary upgrading reactions.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2025

Revealing the Crystalline Architecture of Semicrystalline Ion Exchange Membranes for the Design of Conductive and Durable Alkaline Anion Exchange Membranes

Alkaline anion exchange membrane (AAEM) fuel cells offer a cost-effective alternative to proton exchange membrane (PEM) fuel cells by eliminating the need for expensive precious metal catalysts. In both PEMs and AAEMs, semicrystalline polymers are a common choice, as the crystalline domains can act as mechanical reinforcements that limit swelling and promote mechanical durability in the material. However, spatially resolved characterization of crystalline organization in ion exchange membranes beyond ensemble-averaged X-ray scattering is underrepresented, likely in part due to ionization damage limitations in soft materials. Here, in this study, we resolve the nanometer-size crystallites in semicrystalline ion exchange membranes by applying cryogenic four-dimensional scanning transmission electron microscopy (cryo-4D-STEM) along with data-processing algorithms designed to optimize signals at a low dose to minimize radiation damage. We investigate the effects of synthesis components, including molecular weight and thermal treatment, on a model system of AAEMs in comparison to Nafion, the most commonly used and commercially successful PEM today. We find that excess water uptake in polymer membranes, a property directly associated with weak mechanical durability and with possible negative impacts on ion conductivity, can be reduced by over 30% by varying the polymer's crystalline morphology through changes in synthesis parameters such as molecular weight and thermal history. Our results indicate that this improvement is correlated with smaller crystalline domains with a more homogeneous distribution. More broadly, these results demonstrate how the crystalline architecture of polymer membranes can be tuned through their chemistry and thermal treatment in order to improve their conductivity and durability for commercial fuel cell performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗