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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Electrolyte–Electrocatalyst Interfacial Effects of Polymeric Materials for Tandem CO 2 Capture and Conversion Elucidated Using In Situ Electrochemical AFM

Integrating CO 2 capture and electrochemical conversion has been proposed as a strategy to reduce the net energy required for CO 2 regeneration in traditional CO 2 capture and conversion schemes and can be coupled with carbon-free renewable electricity. Polyethylenimine (PEI)-based materials have been previously studied as CO 2 capture materials and can be integrated in these reactive capture processes. PEI-based electrolytes have been found to significantly increase the CO 2 loading, and impact selectivity and rate of product formation when compared to the conventional aqueous electrolytes. However, the influence of these materials at the catalyst–electrode interface is currently not well understood. In this study, PEI-based electrolytes were prepared and their impact on the morphology of a silver electrode performing electrochemical CO 2 reduction (CO 2 R) was studied using in situ electrochemical atomic force microscopy (EC-AFM). The presence of PEI on the electrode surface could be distinguished based on nanomechanical properties (DMT modulus), and changes were observed as negative polarization was applied, revealing a reorganization of the PEI chains due to electrostatic interactions. These changes were impacted by the electrolyte composition, including the addition of supporting electrolyte KHCO 3 salt, as well as CO 2 captured by the PEI-based electrolyte, which minimized the change in surface mechanical properties and degree of PEI alignment on the electrode surface. The changes in surface mechanical properties were also dependent on the PEI polymer length, with higher molecular weight PEI showing different reconfiguration than the shorter polymer brushes. The study highlights that the choice of polymer material, the electrolyte composition, and CO 2 captured impact the nearelectrode environment, which has implications for CO 2 R, and presents EC-AFM as a new tool that can be used to probe the dynamic behavior of these interfaces during electrocatalysis.

36 MATERIALS SCIENCE↗
DOE OSTI2024

In Situ TEM for Structural and Chemical Evolutions of Bimetallic Pt–Ni Nanoparticles at Elevated Temperatures: Implications for Heterogeneous Catalysis

Platinum-based bimetallic nanoparticles (NPs) are of great interest for their applications in catalysis. The catalytic properties of these NPs are significantly dependent on their morphology, structure, and composition, whose response to thermal input remains challenging to be fully understood. This study investigates the thermally induced structural and chemical evolutions of single-crystalline Pt-Ni NPs using in situ transmission electron microscopy. The observed morphological evolution includes the facet development from a truncated octahedron to a spherical-like isotropic shape, followed by the formation of pancake-like ellipsoid shape at high temperatures due to surface atom migration and interfacial wetting enabled by the particle-substrate interaction. Comparative investigations by in situ scanning transmission electron microscopy with energy dispersive X-ray spectroscopy mapping elucidate that the solid-solution compositional configuration can be retained over a large temperature range, while core-shell NPs undergo irreversible solid-solution transitions through chemical homogenization at elevated temperatures. Finally, these findings elucidate the effect of thermal input on structural evolution and compositional redistribution of Pt-Ni bimetallic NPs, offering valuable insights into the design of heterogeneous catalysts.

25 ENERGY STORAGE↗
DOE OSTI2020

Morphological and nanomechanical changes in tungsten in high heat flux conditions

Abstract Morphological and nanomechanical alteration of tungsten in extreme environments, like those in edge localized modes in nuclear fusion environments, up to 46.3 GWm −2 heat fluxes were experimentally simulated using electrothermal plasma. Surface and subsurface damage to the tungsten is seen mainly in the form of pore formation, cracks, and resolidified melt instabilities. Mirco voids, rosette-type microfeatures, core-shell structure, particle enrichment, and submicron channels all manifest in the damaged subsurface. The formation of voids in the subsurface was determined to originate from the ductile fracture of hot tungsten by plastic flow but not developed to cracking. The voids were preferentially settled in grain boundaries, interfaces. The directionality of elongated voids and grains is biased to the heat flow vector or plasma pathway, which is the likely consequence of the thermally driven grain growth and sliding in the high-temperature conditions. The presence of a border between the transient layer and heat-affected zone is observed and attributed to plasma shock and thermal spallation of fractural tungsten at high temperature. Plasma peening-like hardening effects in tungsten were observed in the range of 22.7–46.3 GWm −2 but least in the case of the lowest heat flux, 12.5 GWm −2 .

36 MATERIALS SCIENCE↗
DOE OSTI2024

The Effect of Sulfuric Acid Anodization on the Electrochemical Properties of Aluminum Alloy AlSi 10 Mg Prepared by Selective Laser Melting

Aluminum alloy, AlSi 10 Mg, prepared by selective laser melt (SLM) fabrication was anodized in 9.8% sulfuric acid (Type II) at 15 V for a total of 23 min. Experiments were performed to study the potentiostatic anodization process and its effects on the oxide coating morphology, thickness, and electrochemical properties of the alloy. Prior to anodization, the alloy microstructure is composed of aluminum cells encapsulated in a silicon network. Anodizing the abraded and polished AlSi 10 Mg surface produced a porous oxide layer with a thickness of 5μm. The oxide coating weight was 698 ± 29 mg/ft 2 . The oxide coating forms in the aluminum cells that are isolated from one another by the silicon eutectic phase. In electrochemical tests, the anodic and cathodic potentiodynamic polarization currents were suppressed by factors of 15× and 215×, respectively, as compared to the unanodized controls. The data indicate the anodic oxide coating suppresses the cathodic more than the anodic reaction rate. Linear polarization resistance (R p ) values increased by 279× after anodization. The corrosion current density values (j corr ) decreased by 133× after anodization. Taken together, the electrochemical data indicate the anodic oxide coating (unsealed) increases the corrosion resistance of the SLM alloy by two orders of magnitude.

Electrochemistry↗
DOE OSTI2023

Experimental and Computational Studies of Stress Corrosion Cracking of Alloys 308/309 and 82/182 Weldments in Corrosive and Radiation Environment

The goal of the project was to determine factors that influence SCC and IASCC in weldments found in LWR nuclear power plants. We focused on a SA508-304L SS weldment fabricated by EPRI using gas tungsten arc welding and used an aggressive BWR normal water chemistry (NWC) immersion environment. This weldment used 309L butter and 308L groove filler material. The microstructure of the 309L butter was non-uniform, exhibiting a 20–30μm thick martensitic layer closest to the SA508 interface, a 1–4 mm thick single γ austenite phase dilution zone, and a γ–δ duplex region extending to the 308L groove filler. The 308L groove filler had an entirely γ–δ duplex microstructure. Two approximately 1-inch thick 304L and SA508 plates approximately 12 by 6 square inches were joined using standard nuclear grade welding techniques. This included a post weld heat treatment of the 309L butter after application, a 0.32 cm fit-up root opening, and 57 bead lines of 308L groove filler applied in 18 layers. A 60 degree weld bevel angle was used and the 309L butter was 1.5 cm thick. Displacement cascade damage was induced using proton irradiation at the Michigan Ion Beam Laboratory. The incident proton energy was 2 MeV, the sample temperature was 360 ºC, and the calculated dpa value at 10 μm (60% of the Bragg peak depth of ~18 μm) was 5 dpa using the quick Kinchin-Pease model. Proton irradiation to this damage level required approximately 125 hours of beam time. Two types of samples were irradiated, tensile specimens and TEM bars. Samples were selected from all regions of the weldment, including the SA508-309L butter interface, the 309L-308L interface, and 308L-304L interface. The stainless steel alloys (304L, 308L, and 309L) within the heat affected zone are characterized by a duplex skeletal morphology of δ-ferrite and γ-austenite resulting from the recrystallization associated with weld fabrication. Approximately 7 to 8 mm of length along the specimen was irradiated. The gauge volume surfaces were mechanically polished and then electro-polished to remove mechanical damage from the mechanical polishing step prior to irradiation. Immersion tests were performed in a recirculating autoclave under BWR NWC conditions (2000 ppb wt. dissolved oxygen, neutral pH, 288 ºC, 10 MPa, and inlet water conductivity <100 nS/cm) to accelerate corrosion. Constant strain rate tests were performed either to failure or to approximately 5% strain. Strain rates of 10 -7 to 10 -6 mm/mm/s were used and typical immersion testing required four to six weeks to achieve failure or strains near 5%. Analysis primarily used advanced electron microscopy techniques of FIB lift out specimens.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Local Electric Field Effects on Water Dissociation in Bipolar Membranes Studied Using Core–Shell Catalysts

The local electric field strength is thought to affect the rate of water dissociation (WD) in bipolar membranes (BPMs) at the catalyst–nanoparticle surfaces. Here, we study core–shell nanoparticles, where the core is metallic, semiconducting, or insulating, to understand this effect. The nanoparticle cores were coated with a WD catalyst layer (TiO2 or HfO2) via atomic layer deposition (ALD), and the morphology was imaged with transmission electron microscopy. Irrespective of the core material, these core–shell catalysts displayed comparable WD overpotentials at optimal mass loading, despite the hypothesized differences in the electric field strength across the catalyst particle suggested by continuum electrostatic simulations. Substantial atomic interdiffusion between the core and shell was ruled out by X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and diffuse reflectance optical measurements. However, the optimal mass loading of catalyst was roughly 1 order of magnitude higher for the conductive and high dielectric core materials than for the low dielectric insulating cores. These findings are consistent with the hypothesis that electric field screening within the core material focuses the electric field drop between particles such that larger film thicknesses can be tolerated. Collectively, these data support the idea that it is the local electric field at the molecular level that controls proton-transfer rates and that the metal core/dielectric-shell constructs introduced here modulate that field. Further materials and synthetic design may enable optimization of the electric field strength across the proton-transfer trajectory at the material surface.

Sarma, Prasad V↗
DOE OSTI2025

Root architectural plasticity optimizes nutrient acquisition in switchgrass under variable phosphorus forms

Aims Understanding the influence of different forms of phosphorus (P) over the different root traits and how those traits are related to increasing the efficiency of nutrient acquisition strategies. Methods Investigation of switchgrass (Panicum virgatum L.) root morphology responses to inorganic P (Pi) soluble (Potassium-P), insoluble (Aluminum-P), and organic P (Po) (Inositol Hexa-Phosphate, IHex-P) in rhizoboxes. Roots were traced over the root box and scanned using WinRhizoTM. The CRootbox model was employed to simulate root growth. Results Significant plasticity observed under IHex-P treatment, with a 46% increase in root branching, leading to a 74% rise in total root length and a 65% increase in root surface area compared to inorganic P forms. IHex-P resulted in a 73% higher root biomass than Aluminum-P and a 26% increase compared to Potassium-P. Most of the differences were attributed to the elongation of root branches. Conclusions Here, the study emphasizes the dynamic nature of switchgrass root architecture and morphology in response to varying P forms in the soil. The absence of Pi in the soil triggered increased plasticity in root traits, facilitating root access to Po and uptake of P. These findings offer valuable insights into the adaptive mechanisms of perennial plants, with significant implications for optimizing nutrient acquisition strategies in both agricultural and natural ecosystems.

Organic phosphorus↗
DOE OSTI2026

Metal Foam Morphology Affects the Run to Run Reproducibility of OER Using Nickel Catalysts

Nickel (Ni) foam-based electrodes are excellent catalysts for the oxygen evolution reaction; however, we found that the random pore-size distribution of Ni foams contributes to a significant variability in electrochemically active surface area, compromising experimental reproducibility. We provide insights into quantifying this critical material property, verified by four electrochemical laboratories.

25 ENERGY STORAGE↗
DOE OSTI2022

In situ Bragg coherent X-ray diffraction imaging of corrosion in a Co–Fe alloy microcrystal

Corrosion is a major concern for many industries, as corrosive environments can induce structural and morphological changes that lead to material dissolution and accelerate material failure. The progression of corrosion depends on nanoscale morphology, stress, and defects present. Experimentally monitoring this complex interplay is challenging. Here we implement in situ Bragg coherent X-ray diffraction imaging (BCDI) to probe the dissolution of a Co-Fe alloy microcrystal exposed to hydrochloric acid (HCl). By measuring five Bragg reflections from a single isolated microcrystal at ambient conditions, we compare the full three-dimensional (3D) strain state before corrosion and the strain along the [111] direction throughout the corrosion process. We find that the strained surface layer of the crystal dissolves to leave a progressively less strained surface. Interestingly, the average strain closer to the centre of the crystal increases during the corrosion process. We determine the localised corrosion rate from BCDI data, revealing the preferential dissolution of facets more exposed to the acid stream, highlighting an experimental geometry effect. These results bring new perspectives to understanding the interplay between crystal strain, morphology, and corrosion; a prerequisite for the design of more corrosion-resistant materials.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Formation of zinc carbonate phases on dissolving calcite, aragonite, and vaterite in acidic aqueous solutions

Calcium carbonate (CaCO 3 ) minerals serve as a major sink to retain metal ions through mineral-water interfacial reactions in which the capacity and long-term stability of contaminant uptake are influenced by coupled dissolution and precipitation reactions of both primary and secondary carbonate minerals (i.e., mineral replacement). Notably, recent studies of calcite reactivity in acidic solutions containing high levels of metal ions demonstrated complex behavior under conditions of sustained disequilibrium. Here, we explored the reactivity of three CaCO 3 polymorphs (calcite, aragonite, and vaterite) with acidic Zn 2+ -containing aqueous solutions using a suite of imaging techniques including optical and scanning electron microscopies, synchrotron-based micro X-ray fluorescence, and transmission X-ray microscopy. Zn uptake by calcite occurred through a two-step process: the formation of a thin layer of the zinc precipitate on the substrate surface followed by the growth of fibrous and radiating hydrozincite particles from the layer. In contrast, Zn uptake by aragonite occurred by mineral replacement where the secondary Zn carbonate phase preserved the external morphology of the original crystal (i.e., a pseudomorph). The replacement of vaterite by hydrozincite occurred within the confined space beneath the porous shell of vaterite, signifying that the primary mechanism driving Zn carbonate precipitation was chemical exchange through the pores. When multiple CaCO 3 polymorphs coexisted, the replacement of aragonite and vaterite occurred preferentially over that of calcite. These results demonstrate the distinct morphological and mineralogical controls over the reactivities of calcium carbonate minerals with Zn 2+ under acidic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Microstructure-Sensitive modeling of surface roughness and notch effects on extreme value fatigue response

Fatigue life knockdown due to surface roughness induces local stress concentrations. Physical fatigue experiments are crucial to qualify materials for use but are limited in their capability to examine the mechanisms underlying the fatigue crack formation driving force due to these stress concentrations. Microstructure-sensitive computational models can aid in this regard and are employed in this work to examine the effects of surface roughness in Al 7075-T6. Digital microstructure models are subjected to crystal plasticity finite element method (CPFEM) simulations to examine the combined effects of microstructure and grain scale asperities on the driving force for fatigue crack formation. Following elastic–plastic shakedown, mesoscale volume-averaged fatigue indicator parameters (FIPs) are computed within fatigue damage process zones of grains. An increase in the intensity of realistic surface roughness profiles corresponds accordingly to larger FIPs but it is difficult to precisely interpret the mechanisms and effects of this intensification. We thus parametrically investigate surface asperities that couple with microstructure and lack of constraint on slip at the free surface to describe microstructure-sensitive surface roughness knockdown effects on fatigue resistance. The depth of a single valley (i.e., notch) due to surface roughness is found to be more detrimental to fatigue resistance than the radius (i.e., notch width, not to be confused with notch acuity). Finally, we also find that different crystallographic textures, grain morphologies, and number of sampled grains have a limited effect on the depth of influence of these notches.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Navigating thermal stability intricacies of high-nickel cathodes for high-energy lithium batteries

High-nickel oxide cathodes, LiNi x M 1−x O 2 (x ≥ 0.8), are preferred in automotive lithium batteries, but they face thermal instability challenges. Inconsistent literature reports and unstandardized testing protocols further complicate quantitative assessments of the thermal stability of these cathodes. Here, we present here a statistical thermal analysis based on the differential scanning calorimetry measurements of 15 representative cathode materials with different compositions, morphologies and states of charge. The findings reveal that each cathode has a critical state of charge that defines its safe operating limit, which is affected by the metal–oxygen bond strength and surface reactivity. The thermal runaway temperature is dictated by the layered Li 1−x NiO 2 to LiNi 2 O 4 spinel-like phase transition, which is thermodynamically determined by the metal–oxygen bond covalency and kinetically influenced by the cation mixing and particle size. Raman spectroscopy is used to predict the thermal runaway temperature on the basis of the linear relationship between them. Finally, we propose a thermal stability index to quantify cathode thermal stability as a guide for developing safer high-nickel cathodes.

batteries↗
DOE OSTI2023

Multidimensional visualization of the dynamic evolution of Li metal via in situ/operando methods

The growing demands for high-energy density electrical energy storage devices stimulate the coupling of conversion-type cathodes and lithium (Li) metal anodes. While promising, the use of these “Li-free” cathodes brings new challenges to the Li anode interface, as Li needs to be dissolved first during cell operation. In this study, we have achieved a direct visualization and comprehensive analysis of the dynamic evolution of the Li interface. The critical metrics of the interfacial resistance, Li growth, and solid electrolyte interface (SEI) distribution during the initial dissolution/deposition processes were systematically investigated by employing multidimensional analysis methods. They include three-electrode impedance tests, in situ atomic force microscopy, scanning electrochemical microscopy, and cryogenic scanning transmission electron microscopy. The high-resolution imaging and real-time observations show that a loose, diffuse, and unevenly distributed SEI is formed during the initial dissolution process. This leads to the dramatically fast growth of Li during the subsequent deposition, deviating from Fick’s law, which exacerbates the interfacial impedance. The compactness of the interfacial structure and enrichment of electrolyte species at the surface during the initial deposition play critical roles in the long-term stability of Li anodes, as revealed by operando confocal Raman spectroscopic mapping. In conclusion, our observations relate to ion transfer, morphological and structural evolution, and Li (de)solvation at Li interfaces, revealing the underlying pathways influenced by the initial dissolution process, which promotes a reconsideration of anode investigations and effective protection strategies.

25 ENERGY STORAGE↗
DOE OSTI2020

Structural breakdown in high power GaN-on-GaN p-n diode devices stressed to failure

The morphology of GaN-on-GaN vertical p-i-n diode devices after reverse-bias electrical stressing to breakdown has been investigated. All failed devices had irreversible structural damage, showing large surface craters that were ∼15–35 μm deep with lengthy surface cracks. Cross-sectional electron micrographs of failed devices showed substantial concentrations of threading dislocations around the cracks and near the crater surfaces. Progressive ion-milling across damaged devices revealed high densities of threading dislocations and the presence of voids beneath the surface cracks; these features were not observed in any unstressed devices. These results should serve as a useful reference for future reliability studies of vertical high-power GaN devices.

Peri, Prudhvi (ORCID:000000022338441X)↗
DOE OSTI2024

Chemo-Mechanical Instabilities in Lithium Cobalt Oxide at Higher State-Of-Charge in Li-Ion Batteries

Transition metal oxide cathodes are widely used in commercial Li-ion batteries. However, their practical charge capacity is limited due to severe chemo-mechanical instabilities at higher charge voltage, and state-of-charge condition. Here, in situ stress and strain measurements were synchronized to probe mechanical deformations in the lithium cobalt oxide (LCO) cathode via a multi-beam stress sensor and digital image correlation, respectively. In situ mechanical measurements revealed how Li removal from the electrode structure induces deformations on the LCO composite cathodes during cycling. The structure and morphology of the LCO cathodes were further investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies. Two distinct electrochemical and mechanical behaviors were identified when the LCO was charged up to 4.65 V. The LCO undergoes a compressive stress generation when charged up to 4.2 V and surface fractures on the LCO particles were detected by SEM. LCO cathode experienced significantly large contractions (negative strains) when charged up to 4.65 V, where intergranular crack formation and phase transformation were detected on the LCO particles via SEM and XRD, respectively. Overall, the study bridges complicated structural deformations with in situ analysis of mechanical degradations in LCO cathodes charged at higher voltages. The correlation is vital to understanding instability mechanisms in transition metal oxides at high voltages for alkali metal ion batteries.

higher state-of-charge↗
DOE OSTI2026

Morphology-driven oxygen evolution performance of NiO x nanostructures and implications for hole transport in perovskite solar cells

Morphology-controlled nanostructures provide an effective strategy to modulate both oxygen evolution reaction (OER) activity and photovoltaic performance in perovskite solar cells (PSCs). However, achieving low OER overpotentials and high power conversion efficiency (PCE) simultaneously through morphology engineering remains challenging. In this work, nickel oxide (NiO x ) nanostructures with spindle-like (NiO x -NS) and plate-like (NiO x -NP) morphologies were synthesized and evaluated as bi-functional OER catalysts and hole transport layers (HTLs) in inverted PSCs. Structural and thermal analyses reveal that NiO x -NS crystallizes into a cubic phase at a lower temperature (300 °C), whereas NiO x -NP requires higher calcination temperatures, reflecting differences in precursor microstructure. Electrochemical measurements indicate that NiO x -NS calcined at 300 °C delivers the lowest OER overpotential (395 mV at 10 mA cm −2 ), outperforming NiO x -NP calcined at 400 °C (565 mV) and 500 °C (474 mV). This enhanced activity is ascribed to favorable surface strain, increased defect density, and advantageous facet exposure. When used as HTLs, NiO x -NS also delivers the highest PCE (13.25%) among all tested devices, exceeding those based on NiO x -NP and commercial NiO x , owing to improved hole extraction and interfacial contact. Overall, this study highlights the importance of morphology control and thermal processing in tailoring NiO x for multifunctional nanomaterials in electrocatalytic and photovoltaic applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Probing the Mechanical Performance of Micro-architected Porous Structures Through In Situ Characterization and Analysis

Micropores play critical roles in both natural and man-made materials. Such pores take on a variety of shapes and sizes ranging from spherical to irregular sphere-like voids with diameters spanning from the nanometer to millimeter scales. When porous structures are mechanically loaded, the pores direct the stress around their free surfaces, altering the material’s mechanical response relative to fully dense materials. In this study, for the first time, we create micro-architected porous samples using nanolithography and investigate the role of pore morphology by conducting a series of in situ micropillar compression tests in scanning electron microscopy. The findings demonstrate that porosity is the primary factor influencing the mechanical response of these micro-architected materials, as often seen on a macroscopic level. Additionally, we observed that pore geometry had a significant impact on Young’s modulus, yield stress, and strain energy density as a secondary parameter. Then, the extracted Young’s modulus was compared to macroscopic empirical models and determined the analytical models sufficiently described the impact of porosity in the microscopic scale but failed to capture the impact of second-order parameters. Furthermore, these results suggest how porous materials can be tailored to achieve desired mechanical properties based on the engineering applications of interest.

36 MATERIALS SCIENCE↗