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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 55 records · Page 3

Advances in the electron diffraction characterization of atomic clusters and nanoparticles

Nanoparticles and metallic clusters continue to make a remarkable impact on novel and emerging technologies. In recent years, there have been impressive advances in the controlled synthesis of clusters and their advanced characterization. One of the most common ways to determine the structures of nanoparticles and clusters is by means of X-ray diffraction methods. However, this requires the clusters to crystallize in a similar way to those used in protein studies, which is not possible in many cases. Novel methods based on electron diffraction have been used to efficiently study individual nanoparticles and clusters and these can overcome the obstacles commonly encountered during X-ray diffraction methods without the need for large crystals. These novel methodologies have improved with advances in electron microscopy instrumentation and electron detection. Here, we review advanced methodologies for characterizing metallic nanoparticles and clusters using a variety of electron diffraction procedures. These include selected area electron diffraction, nanobeam diffraction, coherent electron diffraction, precession electron diffraction, scanning transmission electron microcopy diffraction, and high throughput data analytics, which leverage deep learning to reduce the propensity for data errors and translate nanometer and atomic scale measurements into material data.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

In situ temperature synthesis and characterization of ferroelectric PZN-4.5PT nanoparticles’ thin films using synchrotron light source

Despite the excellent properties of Pb(Zn 1/3 Nb 2/3 )O 3 -4.5PbTiO 3 (PZN-4.5PT) single crystals, the greatest difficulty for their application on electronic devices is to make them to thin layers related to the difficulty to make them as ceramic materials. In this paper, we use the combined USAXS/SAXS/WAXS instrument at 9ID beamline at APS-ANL for in situ characterization of PZN-4.5PT inorganic perovskite nanoparticles thin films deposited on nanotextured silicon to understand the phase transitions and determine the observed microcrystals' structure. Here, the sample was annealed from ambient to 1000°C. The results revealed structure changes in the nanoparticles' thin films which could be explained by the new phase that can be assigned to the Pb 3 (PO 4 )2-based component. The peak at 31° indicates the presence of the rhombohedral phase perovskites assigned to the nanoparticles. WAXS characterization permitted to identification of many transitions during thermal annealing like dehydration or dihydroxylation of phosphorus gel -OH bonds and internal water.

36 MATERIALS SCIENCE↗

Towards Automated and High-Throughput Quantitative Sizing and Isotopic Analysis of Nanoparticles via Single Particle-ICP-TOF-MS

The work described herein assesses the ability to characterize gold nanoparticles (Au NPs) of 50 and 100 nm, as well as 60 nm silver shelled gold core nanospheres (Au/Ag NPs), for their mass, respective size, and isotopic composition in an automated and unattended fashion. Here, an innovative autosampler was employed to mix and transport the blanks, standards, and samples into a high-efficiency single particle (SP) introduction system for subsequent analysis by inductively coupled plasma–time of flight–mass spectrometry (ICP-TOF-MS). Optimized NP transport efficiency into the ICP-TOF-MS was determined to be >80%. This combination, SP-ICP-TOF-MS, allowed for high-throughput sample analysis. Specifically, 50 total samples (including blanks/standards) were analyzed over 8 h, to provide an accurate characterization of the NPs. This methodology was implemented over the course of 5 days to assess its long-term reproducibility. Impressively, the in-run and day-to-day variation of sample transport is assessed to be 3.54 and 9.52% relative standard deviation (%RSD), respectively. The determination of Au NP size and concentration was of <5% relative difference from the certified values over these time periods. Isotopic characterization of the 107 Ag/ 109 Ag particles (n = 132,630) over the course of the measurements was determined to be 1.0788 ± 0.0030 with high accuracy (0.23% relative difference) when compared to the multi-collector–ICP-MS determination.

36 MATERIALS SCIENCE↗

Electron donation of non-oxide supports boosts O 2 activation on nano-platinum catalysts

Activation of O 2 is a critical step in heterogeneous catalytic oxidation. Here, the concept of increased electron donors induced by nitrogen vacancy is adopted to propose an efficient strategy to develop highly active and stable catalysts for molecular O 2 activation. Carbon nitride with nitrogen vacancies is prepared to serve as a support as well as electron sink to construct a synergistic catalyst with Pt nanoparticles. Extensive characterizations combined with the first-principles calculations reveal that nitrogen vacancies with excess electrons could effectively stabilize metallic Pt nanoparticles by strong p-d coupling. The Pt atoms and the dangling carbon atoms surround the vacancy can synergistically donate electrons to the antibonding orbital of the adsorbed O 2 . This synergistic catalyst shows great enhancement of catalytic performance and durability in toluene oxidation. The introduction of electron-rich non-oxide substrate is an innovative strategy to develop active Pt-based oxidation catalysts, which could be conceivably extended to a variety of metal-based catalysts for catalytic oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Core-Shell Rubber (CSR) Nanoparticles on the Fracture Toughness of an Epoxy Resin at Cryogenic Temperatures

This study investigates the effects of core-shell rubber (CSR) nanoparticles on the fracture toughness of an epoxy resin at liquid nitrogen (LN2) temperatures. Varying amounts of Kane Ace (Registered TradeMark) MX130 toughening agent were added to a commercially available EPON 862/W epoxy resin. Resulting fracture toughness was evaluated by the use of Charpy impact tests conducted on an instrumented drop tower. The size and distribution of the CSR nanoparticles were characterized using Transmission Electric Microscopy (TEM) and Small Angle X-ray Scattering (SAXS). Up to nominal 4.6% addition of the CSR nanoparticles, resulted in a nearly 5 times increase in the measured breaking energy. However, further increases in the amount of CSR nanoparticles had no appreciable affect on the breaking energy.

Wang, J.↗

Magnetic Nanoparticle Extraction of Lithium from Produced Waters - CRADA 483 (Final Report)

The demand for lithium in the energy production industry is expected to increase sharply, development of simple and cost-effective techniques for lithium production and recovery from various lithium sources is essential. In this project, core/shell magnetic nanoparticles were successfully designed to selectively extract lithium from aqueous lithium sources as an extension of Pacific Northwest National Laboratory’s magnetic nanofluid extraction technology. The core/shell magnetic nanoparticles are composed of manganese oxide-based lithium ion sieve shells, which allow selective lithium uptake from brines with multiple coexisting ions, over iron oxide cores, which can respond to external magnetic fields for effective recovery and reuse of adsorbents from a liquid. The synthesized lithium ion-sieves and core/shell magnetic nanoparticles were characterized using several techniques to reveal their crystallinity and morphology. The lithium uptake properties of the lithium ion-sieves and core/shell magnetic nanoparticles were evaluated in terms of lithium adsorption capacity, removal percentage, selectivity, and cycling performance in simulated and natural brines. Magnetic properties of the core/shell magnetic nanoparticles were tested by measuring magnetic saturation, and magnetic response of colloidal solutions containing the core/shell magnetic nanoparticles was tested with permanent magnets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Collaborative Research: Understanding Nanoparticle-Plasma Interactions in Dusty Non-Thermal Plasmas by Nanoparticle Probes and Online Aerosol Characterization

Research Objectives The goal of this research project is to understand the nature of charge interactions between plasmas and aerosol particles. Specifically, the project has the following objectives: 1) Study the effect of solid nanoparticles on properties of an atmospheric pressure plasma. 2) Study the influence of plasma density on the final charge of nanoparticles. 3) Develop a theoretical understanding of charge decay and charge dynamics in the spatial afterglow in support of experimental observations of the final charge of nanoparticles exiting a plasma.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Effects of Cryogenic Temperature on Fracture Toughness of Core-Shell Rubber (CSR) Toughened Epoxy Nanocomposites

This study investigated the effects of core-shell rubber (CSR) nanoparticles on the mechanical properties and fracture toughness of an epoxy resin at ambient and liquid nitrogen (LN2) temperatures. Varying amounts of Kane Ace MX130 toughening agent were added to a commercially available EPON 862/Epikure W epoxy resin. Elastic modulus was calculated using quasi-static tensile data. Fracture toughness was evaluated by the resulting breaking energy measured in Charpy impact tests conducted on an instrumented drop tower. The size and distribution of the CSR nanoparticles were characterized using Transmission Electron Microscopy (TEM) and Small Angle X-ray Scattering (SAXS). Scanning Electron Microscopy (SEM) was used to study the fracture surface morphology. The addition of the CSR nanoparticles increased the breaking energy with negligible change in elastic modulus and ultimate tensile stress (UTS). At ambient temperature the breaking energy increased with increasing additions of the CSR nanoparticles, while at LN2 temperatures, it reached a maximum at 5 wt% CSR concentration. KEY WORDS: liquid nitrogen (LN2) properties, fracture toughness, core-shell rubber (CSR).

Wang, J.↗

Effects of Core-Shell Rubber (CSR) Nanoparticles on the Cryogenic Fracture Toughness of CSR Modified Epoxy

This study investigated the effects of core-shell rubber (CSR) nanoparticles on the mechanical properties and fracture toughness of an epoxy resin at ambient and liquid nitrogen (LN2) temperatures. Varying amounts of Kane Ace(Registered TradeMark) MX130 and Kane Ace(Registered TradeMark) MX960 toughening agent were added to a commercially available EPON 862/Epikure W epoxy resin. Elastic modulus was calculated using quasi-static tensile data. Fracture toughness was evaluated by the resulting breaking energy measured in Charpy impact tests conducted on an instrumented drop tower. The size and distribution of the CSR nanoparticles were characterized using Transmission Electron Microscopy (TEM) and Small Angle X-ray Scattering (SAXS). Scanning Electron Microscopy (SEM) was used to study the fracture surface morphology. The addition of the CSR nanoparticles increased the breaking energy with negligible change in elastic modulus and ultimate tensile stress (UTS). At ambient temperature the breaking energy increased with increasing additions of the CSR nanoparticles up to 13.8wt%, while at LN2 temperatures, it reached a plateau at much lower CSR concentration.

Wang, Jun↗

Enhancing the Multifunctional Photocatalytic Activity of Sustainable Magnetic Nanoparticles

The development of efficient photocatalytic materials has intensified in response to increasing emphasis on sustainable energy conversion and environmental restoration. However, the excessive use and indiscriminate release of heavy metals from photocatalytic nanoparticles pose potential environmental risks. This study provides insights into optimizing visible-light-active photocatalysts to enhance their photocatalytic properties and stability. Specifically, cobalt doping and controlled pH modulation are employed on the modified Fe 3 O 4 , forming two distinct samples: Co@Fe 3 O 4 -B (base-treated) and Co@Fe 3 O 4 -A (acid-treated) nanoparticles. Microscopic characterization reveals that Co@Fe 3 O 4 -A undergoes a phase transition to hematite, whereas Co@Fe 3 O 4 -B retains its mixed-phase configuration. Spectroscopic analyses confirm that the cobalt dopants decorate the outskirts of each nanoparticle, forming a core–shell structure. However, Co@Fe 3 O 4 -B exhibit Co 2+ states with a high oxygen vacancy content, whereas Co@Fe 3 O 4 -A contain mixed Co 2+/3+ states. The high density of defect states in the Co@Fe 3 O 4 -B results in superior photocatalytic efficiency, achieving near-complete oxidation of furfuraldehyde (97% conversion) and 5-hydroxymethylfurfural (94% conversion), as well as effective degradation of toluene (78% conversion). This study demonstrates that the combined approach of doping and pH treatment is promising for the surface-defect engineering of photocatalysts, enhancing their multifunctional performance and reusability for sustainable energy conversion.

Fe3 O4 nanoparticles↗

Biosynthesis of Zinc Oxide Nanoparticles using Fungal Filtrates

Fungi produce and excrete various proteins, enzymes, and polysaccharides, which may be used for the synthesis of nanoparticles. This study investigated the effect an anion species on the synthesis of ceramic nanoparticles using fungal filtrates. In this work, ceramic zinc oxide (ZnO) nanoparticles ranging between 1 nm and 1000 nm were successfully synthesized using three different filamentous fungi: Aspergillus sp., Penicillium sp., and Paecilomyces variotti. Each fungus was cultured, and the filtrate was extracted and individually exposed to zinc nitrate, zinc sulfate, or zinc chloride. The formation of nanoparticles was characterized using UV-visible spectrophotometry (UV-Vis), fluorescence microscopy, and with transmission electron microscopy (TEM) analyses. UV-Vis spectra exhibited broad increases in the absorption across the range of 200 nm - 800 nm, which corresponded to the formation of ZnO nanoparticles under various conditions. Nanoparticle formation was confirmed with fluorescence microscopy and TEM analysis and determined to form particles with an irregular spherical shape. To date, our work demonstrates that the ability of fungi to synthesize ZnO nanoparticles is not genus/species-specific but is dependent on the starting composition of a given metal salt.

59 BASIC BIOLOGICAL SCIENCES↗

Low-Energy Ion Scattering Intensities from Supported Nanoparticles: The Spherical Cap Model

Supported nanoparticles are of great importance to many technologies like fuel processing and chemical synthesis using catalysts and electrocatalysts, energy storage and generation using fuel cells and batteries, electrochemistry, magnetic information storage, and more. Low-energy ion scattering spectroscopy (LEIS) with noble gas ions like He+ is a powerful tool for the characterization of nanoparticles dispersed across flat support surfaces due to its ability to probe the elemental composition in the topmost atomic layer of a surface, providing quantitative information regarding the size and number density of nanoparticles. In this work, we present a derivation of the LEIS intensities expected from nanoparticles and the support material as a function of the average particle size, their number per unit area, and their contact angle with the support when modeled as spherical caps of the nanoparticle material dispersed over the surface of a flat support. The model assumes that the ion intensities are determined only by the physical blocking of linear ion trajectories and independent of the tilt angle of the local surface relative to the incident and scattered ion directions, an assumption we support by quantitative modeling of published data which tested tilt-angle effects. The model is a generalization to arbitrary contact angles of the hemispherical cap model, which assumes 90° contact angle and has been widely used to model spectroscopic signals in LEIS (and also in Auger and photoelectron spectroscopies) during nanoparticle growth. Here, this new model quantitatively reveals how LEIS signals are sensitive not only to the diameter and number density of the nanoparticle but also to their contact angle (or height/diameter ratio). With the use of additional data (e.g., from microscopy or adsorption microcalorimetry), the model presented here will enable more accurate determination of the average size, shape, and number density of supported nanoparticles based on LEIS intensity measurements.

99 GENERAL AND MISCELLANEOUS↗

Nanosized Organo-Silica Particles with “Built-In” Surface-Initiated Atom Transfer Radical Polymerization Capability as a Platform for Brush Particle Synthesis

A facile synthetic method was developed to prepare sub-5 nm organo-silica (oSiO 2 ) nanoparticles through the self-condensation of ATRP-initiator-containing silica precursors. The obtained oSiO 2 nanoparticles were characterized by a combination of nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), dynamic light scattering (DLS) and small-angle neutron scattering (SANS). The accessibility of the surface -Br initiating sites was evaluated by the polymerization of poly(methyl methacrylate) (PMMA) ligands from the surface of the oSiO 2 nanoparticles using surface-initiated atom transfer radical polymerization (SI-ATRP). Here, the ultra-small size, tunable composition and ease of surface modification may render these organosilica nanoparticle systems with built-in SI-ATRP capability an interesting alternative to conventional silica nanoparticles for functional material design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Monitoring Structural and Electronic Changes of Supported Metal Catalysts Using Combined X‐Ray Techniques

Supported metal nanoparticle catalysts have become increasingly crucial for many catalytic applications. However, long-term catalyst stability remains a problem due to catalyst deactivation caused by coke formation and sintering. The deposition of a thin overcoating via atomic layer deposition (ALD) onto metal-supported nanoparticles has shown to greatly inhibit catalyst deactivation. This work utilizes a model catalyst system comprised of Pt nanoparticles supported on Al 2 O 3 to demonstrate the effect of an atomically thin overcoating on supported metal nanoparticles. Continuous operando small-angle X-ray scattering (SAXS) and X-ray absorption near edge spectroscopy (XANES) monitor structural and electronic changes to the catalyst and overcoating during calcination. SAXS data fitting reveals the formation of nanopores in the overcoating at high temperatures, while XANES monitors the oxidation state of the Pt catalyst. Herein, the usefulness of combined X-ray techniques is demonstrated to characterize supported metal catalysts to further understanding of the synergistic effects of the ALD overcoating to aid in the design of new catalyst materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Collaborative Research: Understanding Nanoparticle-Plasma Interactions in Dusty Non-Thermal Plasmas by Nanoparticle Probes and Online Aerosol Characterization (Final Technical Report)

This report describes results from the University of Minnesota’s contribution to studies performed under the award DE-SC0018202 (principal Investigator: Christopher J. Hogan Jr.. This award is a collaborative research grant with support equally provided to Case Western Reserve University and to the University of Illinois (with principal investigator R. Mohan Sankaran). To date ten peer-reviewed published papers have resulted from the studies performed with University of Minnesota personnel contributing; this report describes the results of these studies as well as several unpublished studies, grouped into seven separate study types. The overarching goal of the carried out studies was to understand nanoparticle behavior and dynamics in non-thermal plasma synthesis reactors, specifically adapting aerosol measurement technology to provide online measurements of particle size, charge, and structure in plasma reactor systems.

42 ENGINEERING↗

Resolving Nonequilibrium Shape Variations among Millions of Gold Nanoparticles

Nanoparticles, exhibiting functionally relevant structural heterogeneity, are at the forefront of cutting-edge research. Now, high-throughput single-particle imaging (SPI) with X-ray free-electron lasers (XFELs) creates opportunities for recovering the shape distributions of millions of particles that exhibit functionally relevant structural heterogeneity. To realize this potential, three challenges have to be overcome: (1) simultaneous parametrization of structural variability in real and reciprocal spaces; (2) efficiently inferring the latent parameters of each SPI measurement; (3) scaling up comparisons between 10 5 structural models and 10 6 XFEL-SPI measurements. Here, we describe how we overcame these three challenges to resolve the nonequilibrium shape distributions within millions of gold nanoparticles imaged at the European XFEL. These shape distributions allowed us to quantify the degree of asymmetry in these particles, discover a relatively stable “shape envelope” among nanoparticles, discern finite-size effects related to shape-controlling surfactants, and extrapolate nanoparticles’ shapes to their idealized thermodynamic limit. Ultimately, these demonstrations show that XFEL SPI can help transform nanoparticle shape characterization from anecdotally interesting to statistically meaningful.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A versatile machine learning workflow for high-throughput analysis of supported metal catalyst particles

Accurate and efficient characterization of nanoparticles (NPs), particularly regarding particle size distribution, is essential for advancing our understanding of their structure-property relationship and facilitating their design for various applications. In this study, we introduce a novel two-stage artificial intelligence (AI)-driven workflow for NP analysis that leverages prompt engineering techniques from state-of-the-art single-stage object detection and large-scale vision transformer (ViT) architectures. This methodology is applied to transmission electron microscopy (TEM) and scanning TEM (STEM) images of heterogeneous catalysts, enabling high-resolution, high-throughput analysis of particle size distributions for supported metal catalyst NPs. The model's performance in detecting and segmenting NPs is validated across diverse heterogeneous catalyst systems, including various metals (Ru, Cu, PtCo, and Pt), supports (silica (SiO 2 ), γ-alumina (γ-Al 2 O 3 ), and carbon black), and particle diameter size distributions with mean and standard deviations ranging from 1.6 ± 0.2 nm to 9.7 ± 4.6 nm. The proposed machine learning (ML) methodology achieved an average F1 overlap score of 0.91 ± 0.01 and demonstrated the ability to disentangle overlapping NPs anchored on catalytic support materials. The segmentation accuracy is further validated using the Hausdorff distance and robust Hausdorff distance metrics, with the 90th percent of the robust Hausdorff distance showing errors within 0.4 ± 0.1 nm to 1.4 ± 0.6 nm. In conclusion, our AI-assisted NP analysis workflow demonstrates robust generalization across diverse datasets and can be readily applied to similar NP segmentation tasks without requiring costly model retraining.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗