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At least 19 records

Monolayer Films of Binary Metal Oxide Nanoparticles for Carbon Nanotube Synthesis

Binary metal oxide nanoparticles (biMO-NPs) combining transition and main-group metals with well-organized atomic architectures have unique potential as robust and economical heterogeneous catalysts. Herein, metal oxide nanoparticles (CoAlxOy) using cobalt and aluminum were synthesized, and their structure, morphology, and chemical composition were investigated using various characterization techniques. The biMO-NPs, which had a Gaussian-type size distribution (∼6 nm), were assembled on plain silicon substrates modified chemically with linker molecules bearing suitable end groups. Surface analysis revealed an ordered, uniform, close-packed arrangement of biMO-NPs forming a monolayer architecture with nanoscale thickness (∼12 nm), high surface uniformity, and negligible defects. The nanoparticle monolayer film (NP-MF) was employed as a catalyst to grow carbon nanotube (CNT) forests via the thermal chemical vapor deposition (CVD) method, similar to those grown from catalyst thin films deposited by physical vapor deposition. Structural characterization confirmed the growth of a dense, uniform, high-quality vertically aligned carbon nanotube (VA-CNT) forest with a length of ∼125 µm, which is comparable to the VA-CNTs grown from expensive thin films. Thus, CNT growth was successfully catalyzed by the biMO-NPs, highlighting a simple and inexpensive alternative for catalyst deposition. In this innovative wet-chemistry approach, the catalyst and catalyst support are combined within a single nanoparticle before NP-MF assembly. Interestingly, this approach provides a scalable and cost-effective pathway for CNT growth, eliminating the need for expensive thin deposition techniques.

Regmi, Bishow [University of Cincinnati]

The impact of chromium coatings on Zircaloy cladding deformation behavior under reactivity-initiated accident-like mechanical loading conditions

A reactivity-initiated accident (RIA) occurs when a control rod ejection or control blade drop causes an increase in the fission rate. The injection of energy results in an increase in fuel temperature which in turn causes rapid thermal expansion of the fuel pellet. This thermal expansion may result in pellet-cladding mechanical interaction (PCMI) in which the fuel imparts a mechanical strain to the cladding. PCMI may cause the cladding to fail, and thus, the mechanical response of cladding due to PCMI must be investigated when characterizing new cladding materials. Chromium-coated Zircaloy-4 is a near-term accident-tolerant fuel cladding that exhibits improved high-temperature oxidation resistance. Modified burst testing was utilized to experimentally simulate the effects of PCMI on both uncoated and chromium-coated Zircaloy cladding samples at hot zero power conditions. Samples were coated using either cold spraying or physical vapor deposition to understand the differences in behavior that the coating application method may cause. Digital image correlation was used to analyze images of the deforming specimens to extract the in-situ strain behavior of the cladding. The uncoated specimens burst at hoop strains ranging from 8.8 % to 17.2 %. The cold-spray chromium-coated Zircaloy specimens burst at hoop strains of 7.0 % to 11.0 %. The physical vapor deposition coated tubes burst at hoop strains of 9.1 % to 11.5 %. These results indicate that the chromium coating causes a loss in the ductility of the cladding. Furthermore, the higher burst hoop strains of the physical vapor deposition-coated samples relative to the cold-spray samples indicate that the cold-spraying technique causes more of a loss in ductility than physical vapor deposition. All samples burst at higher hoop strains than those expected to occur in an RIA for fresh cladding.

Accident-tolerant fuel

High-rate deposition of ultrathick bismuth films by direct-current magnetron sputtering

Bismuth coatings deposited at room temperature by physical vapor deposition typically feature irregularly-shaped grains and a high density of voids, thereby preventing their use in many potential applications. Here, we demonstrate the deposition of low-stress, high-density 40-μm-thick Bi films by systematically studying the effect of the deposition rate and substrate tilt on the properties of Bi films deposited at room temperature by direct-current magnetron sputtering. Furthermore, results show that, with increasing deposition rate, the morphology, structure, and properties of Bi films greatly improve, while an increase in substrate tilt leads to a monotonic decrease in film thickness, density, and electrical conductivity.

Bismuth

Domain-Dependent Electronic Properties of 2D Copper Boride Synthesized from Reversible Subsurface Diffusion on Cu(111)

Emerging boron-based 2D materials hold properties with potential applications ranging from electronic devices to catalysis and energy storage. Using physical vapor deposition, 2D copper borides are formed on Cu(111) at elevated temperatures. However, the as-prepared surfaces often contain boron clusters that compromise structural homogeneity, and the dynamics of their formation is not yet fully understood. Through in situ low-energy electron microscopy (LEEM), Auger electron spectroscopy (AES), and scanning tunneling microscopy/spectroscopy (STM/STS), we show that cluster-free 2D CuB x is synthesized via reversible subsurface diffusion of boron atoms. The resolved regular atomic structure aligns with the previously calculated Cu 8 B 14 model. In a rare case, possibly due to surface strain and a change of orientation, a second domain of CuB x was observed with a pronounced change in electronic properties, yet electronic states remain delocalized in both domains. In conclusion, these findings demonstrate the sensitivity of electronic properties to domain structure and highlight a potential opportunity to tune 2D CuB x for diverse applications.

77 NANOSCIENCE AND NANOTECHNOLOGY

Investigating the impact of preparation routes on the properties of copper-decorated silicon particles as anode materials for lithium-ion batteries

In recent years, the calendar life of Si has been recognized as a significant issue that must be addressed prior to technology deployment: The carbon conductive additive is a potential source of parasitic side reactions. However, carbon remains essential due to the low electronic conductivity of Si. In this study, we investigate the use of Cu as a conductive additive and potential alternative to carbon. Some Cu-decorated silicon particles (Si Cu ) were prepared using physical vapor deposition (PVD) via sputtering and high-energy milling. Other Si Cu particles were prepared by using a solution method and examined briefly. The milling method caused Cu to appear as island-like features on the Si surface, whereas the PVD method initially produced similar island-like features that gradually developed into a continuous coating around the Si as sputtering time increased. Electrodes fabricated from Si Cu exhibited lower overall resistivity, demonstrating the beneficial effect of Cu in improving electronic percolation through the electrode. Electrochemical tests showed that the milled SiCu exhibited higher capacity retention, improved rate capability, and lower overpotential. Furthermore, Si Cu coupled with an NMC811 cathode exhibited lower leakage currents compared with the baseline silicon, indicating that incorporating Cu provided an additional advantage of minimizing parasitic currents in the cells.

25 ENERGY STORAGE

Microstructural Assessment of Molybdenum Disulfide Coatings Using Nanoindentation Hardness

MoS 2 coatings are used extensively in aerospace and defense applications due to their ultralow friction and high wear resistance. Burnished and resin-bonded MoS 2 coatings are commonly used in these applications due to simplicity in deposition and history of use, despite issues with consistency in coating properties and performance. Physical vapor deposition (PVD) of MoS 2 thin films has emerged as a process alternative in the past 50 years, promising far greater control over film structure and composition but at a greater cost. Despite PVD’s benefits, hesitance to adoption persists in high-consequence applications, not only due to increased costs but variability in resulting coating properties. These variations in properties and subsequent performance are in part due to the complexity of the PVD process and the sensitive interplay between coating process-structure-property relationships. This work aims to demystify the remaining uncertainties of the process-structure-property relationships in PVD MoS 2 . The microstructure and mechanical and tribological properties of 61 different PVD pure MoS 2 coatings are examined herein. Emphasis has been placed on developing performance-based (i.e., hardness, modulus) metrics that can assess microstructural changes (density, orientation, and crystallinity) and be utilized to accelerate process development and coating optimization. Relationships established within suggest that nanoindentation hardness can be used to infer coating performance (i.e., wear rate) and properties (i.e., density, crystalline texture, and stoichiometry). Furthermore, this work demonstrates that PVD MoS 2 coatings close to the theoretical density of MoS 2 consistently have the best tribological performance and can be reliably identified by their hardness.

MoS2

Ferroelectricity in Atomic Layer Deposited Wurtzite Zinc Magnesium Oxide Zn 1– x Mg x O

Conformal deposition of wurtzite ferroelectrics, which is needed for their use in scaled nonvolatile memories, is challenging using current physical vapor deposition techniques. To overcome the conformality barrier, this work demonstrates ferroelectricity in wurtzite Zn 1− x Mg x O thin films prepared by plasma-enhanced atomic layer deposition, which is a non-line-of-sight deposition method. Films ranging in composition from x = 0.00 to x = 0.58 are predominantly wurtzite phase and exhibit a (0001)-texture. Increasing the magnesium content decreases the c/a ratio, increases the optical bandgap energy, increases the piezoelectric response, and enables polarization reversal. Clear polarization switching is demonstrated in 50 nm thick Zn 1− x Mg x O films by piezoresponse force microscopy in compositions containing x = 0.46 and x = 0.58.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Industrial deposition of wavelength-shifting films for liquid argon photon detection systems

The Deep Underground Neutrino Experiment (DUNE) Phase-II Far Detector is considering an approximately 2000 m 2 photon detection system to achieve a target mean light yield of 180 PE/MeV. Meeting this requirement demands scalable, cost-effective, and high-quality wavelength-shifter (WLS) coatings capable of converting 127 nm liquid-argon scintillation light into visible photons with controlled and reproducible optical performance. We report on the successful realization of an industrial physical vapor deposition (PVD) process forp-terphenyl (pTP) coatings, adapted from vacuum deposition techniques developed for OLED display manufacturing, to produce uniform WLS layers on large-area inorganic substrates, a task traditionally challenged by adhesion and uniformity issues at organic-inorganic interfaces. Surface characterization by profilometry and spectroscopic measurements demonstrates edge-region thickness variation below 10% and emission spectra consistent with high-quality pTP reference samples. The industrial process demonstrates reproducibility, scalability, and significantly reduced production time compared to laboratory-based methods, while maintaining optical characteristics consistent with established pTP reference samples. These results establish a viable pathway for mass production of high-performance pTP coatings for DUNE FD3 and future neutrino experiments, from a coating manufacturing and process standpoint. Detector-level performance validation, including quantitative VUV conversion efficiency measurements at 127 nm, is identified as future work.

47 OTHER INSTRUMENTATION

New Trends in Coatings Developments for Turbine Blades: Materials Processing and Repair

Turbine engines for aeronautic applications now have to face strenuous requirements concerning not only operating performances but also reliability and repairability. This evolution of the specifications induces important consequences regarding the choice and the design of turbine blade protective coatings. This paper presents several key features concerning the deposition techniques and the real-life behavior of such coatings: (1) complex aluminides well suited to the protection against high temperature oxidation and hot corrosion of directionally solidified nickel-base superalloy turbine blades; (2) ceramic coatings used as thermal barriers - they have to exhibit both high resistance to thermomechanical fatigue and adequate smoothness; (3) processing techniques for thermal barriers, including plasma spraying, electron beam physical vapor deposition and plasma enhanced chemical vapor deposition; and (4) blades and coatings repair techniques.

S Alpérine

Thin-Film Embedded Sensors for Battery Health Monitoring

Hybrid or all-electric aircraft are being developed as the next generation of aircraft to both allow new forms of aviation and decrease environmental impact. Since these types of aircraft are based on high-capacity battery technology, safe operation of these batteries becomes increasingly important. In particular, the potential for battery failure due to uncontrolled chemical reactions resulting in thermal runaway, catastrophic failure, and battery fires must be addressed in order for such battery technology to have the level of safety needed for standard aviation implementation. Efforts to ensure battery safety often involve engineering solutions that seek to contain rather than prevent such events by early detection. Such approaches increase the system weight and decrease the power per unit mass provided by the battery system. Existing methods for measuring battery parameters to determine the battery state-of-health are limited. These methods include electrical measurements of the cell current and/or voltage output as well as temperature measurements taken externally on the cell surface. Such external temperature measurements are limited in their ability to provide early warning of impending battery failure. In response, an effort to develop sensors operating internal to battery for health monitoring has been ongoing in the NASA Sensor-based Prognostics to Avoid Runaway Reactions & Catastrophic Ignition (SPARRCI) project. The basic approach associated with this sensor work is the deposition of thin film sensors on the battery separator located between the anode and cathode of the battery. These thin film sensors are then monitored to determine changes in battery parameters and health. Microfabrication techniques are employed to minimize the overall impact of the sensors on battery operation through the implementation of sensors with minimal size, weight, and power consumption. The thickness of the films, which are fabricated through physical vapor deposition (sputtering), are on the order of thousands of angstroms and can have minimal surface area. Thin film sensors for system health management have been implemented for a many decades on complex components for aerospace applications. However, the application of thin films of this type on a battery separator for internal battery monitoring applications has not previously been demonstrated to our knowledge. This paper describes the development of sensors for the internal battery monitoring through the use of thin film sensor technology. Thin metal films were successfully deposited on a battery separator polymer material with good adherence and electrical continuity. Multiple types of sensors have been deposited, as well as lead connections from the sensor to the edge of the separator material. The ability of these thin film sensors immersed in electrolyte to perform multiple types of battery parameter measurements has been demonstrated. For example, a multiparameter sensor system measured multiple properties simultaneously inside of a pouch cell over a wide temperature range. Further, real time measurement of interior temperature changes in a battery pouch cell with an integrated interior temperature sensor was demonstrated. These changes include detecting a fault in the battery (shorting) in situ with rapid response time (less than a minute) corresponding to a more limited response by a temperature sensor mounted externally. Other aspects of monitoring battery health were also explored, such as real-time measurement of simulated dendrite growth/metal deposition by sensor on separator material demonstrated. Future efforts will include improvements in the durability of the sensor structure to allow introduction of the approach into standard battery fabrication techniques. Overall, this work is a step forward in providing a method to prevent catastrophic battery failures and provide a foundation for safer, lighter, and higher energy batteries for the electric aircraft industry.

thin film battery health

Active Learning for Rapid Targeted Synthesis of Compositionally Complex Alloys

The next generation of advanced materials is tending toward increasingly complex compositions. Synthesizing precise composition is time-consuming and becomes exponentially demanding with increasing compositional complexity. An experienced human operator does significantly better than a novice but still struggles to consistently achieve precision when synthesis parameters are coupled. The time to optimize synthesis becomes a barrier to exploring scientifically and technologically exciting compositionally complex materials. This investigation demonstrates an active learning (AL) approach for optimizing physical vapor deposition synthesis of thin-film alloys with up to five principal elements. We compared AL-based on Gaussian process (GP) and random forest (RF) models. The best performing models were able to discover synthesis parameters for a target quinary alloy in 14 iterations. We also demonstrate the capability of these models to be used in transfer learning tasks. RF and GP models trained on lower dimensional systems (i.e., ternary, quarternary) show an immediate improvement in prediction accuracy compared to models trained only on quinary samples. Furthermore, samples that only share a few elements in common with the target composition can be used for model pre-training. We believe that such AL approaches can be widely adapted to significantly accelerate the exploration of compositionally complex materials.

Chemistry

The mechanism of hydroxyapatite coatings degradation at high substrate temperatures

Physical vapor deposition methods used for hydroxyapatite (HA) coatings typically require elevated substrate temperatures and post-deposition annealing to induce crystallization. However, such thermal treatments can degrade both the mechanical integrity and bioactivity of the coating, particularly when substrate temperatures exceed 500 °C. The mechanisms underlying these phenomena remain insufficiently understood. In this study, HA thin films were deposited on silicon and Ti6Al4V substrates using pulsed laser deposition and were systematically characterized to elucidate these mechanisms. XPS and SIMS analyses revealed a temperature-dependent loss of OH − and PO 4 3− groups, an increased Ca/P ratio, and the formation of interfacial oxides, all of which contribute to weakened adhesion. To clarify the temperature-dependent decline in bioactivity, protein adsorption behavior was analyzed using a Kramers-type kinetic framework; the fitted desorption kinetics indicate that coatings deposited near ∼500 °C provide the most stable protein attachment, whereas higher temperatures accelerate desorption due to dehydroxylation and carbonate substitution. Together, these findings provide mechanistic insight into the thermal degradation of HA coatings and offer a framework for optimizing deposition parameters to preserve stoichiometry, adhesion, and bioactivity for long-term biomedical applications.

Kylychbekov, Salizhan [Univ. of Oxford (United Kin

Harnessing Machine Learning to Predict MoS 2 Solid Lubricant Performance

Physical vapor deposited (PVD) molybdenum disulfide (MoS 2 ) solid lubricant coatings are an exemplar material system for machine learning methods due to small changes in process variables often causing large variations in microstructure and mechanical/tribological properties. Here, in this work, a gradient boosted regression tree machine learning method is applied to an existing experimental data set containing process, microstructure, and property information to create deeper insights into the process-structure–property relationships for molybdenum disulfide (MoS 2 ) solid lubricant coatings. The optimized and cross-validated models show good predictive capabilities for density, reduced modulus, hardness, wear rate, and initial coefficients of friction. The contribution of individual deposition variables (i.e., argon pressure, deposition power, target conditioning) on coating properties is highlighted through feature importance. The process-property relationships established herein show linear and non-linear relationships and highlight the influence of uncontrolled deposition variables (i.e., target conditioning) on the tribological performance.

MoS2

Understanding the high-temperature behavior and corrosion resistance of Cr-Nb coated cladding for BWRs

While Cr-coated Accident Tolerant Fuel has proven successful in Pressurized Water Reactors, its dissolution in high dissolved oxygen Boiling Water Reactor environments represents a major technological barrier. Here, this study presents a comprehensive evaluation of novel Cr-Nb alloys as a coating breakthrough solution for Accident Tolerant Fuel cladding in Boiling Water Reactors. We systematically investigated Physical Vapor Deposited Cr-Nb coatings with 13% and 24 at% Nb content on commercial Zr-based cladding through rigorous testing under both normal and accident conditions. Our results demonstrate Cr-Nb coatings remained completely intact during extended Boiling Water Reactor autoclave testing, while pure Cr coatings failed catastrophically due to oxide dissolution. Under Loss-of-Coolant Accident conditions at 1100°C, Cr-Nb coatings maintained protective capability for 45 min. At 800°C, the alloy coatings matched pure Cr's excellent corrosion resistance. Despite microstructural changes during prolonged high-temperature exposure, no coating delamination occurred, ensuring continued protection of the underlying Zr substrate. These findings establish Cr-Nb coatings as a viable Accident Tolerant Fuel solution for Boiling Water Reactors.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Ternary and Quaternary Nickel-Iron-Oxide-Based Thin Films as Oxygen Evolution Reaction Catalysts in Alkaline Media

Alkaline water electrolyzers are a promising technology for energy storage and conversion through the electrochemical production of hydrogen, however the slow kinetics of the oxygen evolution reaction (OER) pose a major challenge. The alkaline environment enables the use of non-Pt-group metals as OER catalysts, in particular NiFe-based materials. In this study, Mn and/or Cr were elementally mixed with NiFe to further improve the OER catalyst properties through a controlled, systematic synthesis process involving thin films prepared by electron beam-induced physical vapor deposition (PVD). By exploring both simultaneous co-deposition and serial deposition of the different metals, the OER performance was investigated as a function of both the location of Mn or Cr in the multi-metal NiFe-based catalysts and the difference between surface versus bulk mixing. The distinct differences in the redox dynamics, surface oxidation, and stability of the seven studied catalysts reveal metal Cr- and/or Mn-overlayers as a promising synthesis approach for fine-tuning of catalyst properties and improving the OER performance.

Alkaline Water Electrolysis

Growth of Low-Defect WSe 2 Film via High-Purity van der Waals Crystal Precursor

Two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs) exhibit exceptional electrical and optical properties, empowering their promising prospects for future nanoelectronics. Despite major advances in n-type 2D semiconductors, the field has yet to synthesize high-mobility p-type 2D TMDs, in particular WSe 2 , and systematically query the influence of defects. In this study, we unveil the pivotal role of substitutional impurity defects vis-à-vis the precursor used and growth method employed in defining the quality of 2D p-type WSe 2 . Density functional theory calculations suggest the adverse effect of Fe-, Co-, Ni- and Si-substituted W impurity defects on the mobility of WSe 2 , whereas defects such as O-, S-substituted Se and Mo-substituted W pose negligible impact. Guided by the theory, we pinpoint van der Waals (vdW) crystals, commonly used in mechanical exfoliation, as the optimal precursor, and develop a facile vdW crystal physical vapor deposition (PVD) method to grow high-purity monolayer 2D WSe 2 film (VPVD-WSe 2 ) that is continuous across a centimeter scale. A suite of spectroscopies confirms the markedly reduced defect density of the as-synthesized WSe 2 compared to those by typical chemical vapor deposition methods, and by PVD with commercial or hydrothermal precursors. Scanning tunneling microscopy further evidence the ultralow substitutional impurity defect density of VPVD-WSe 2 , greatly outperforming the control samples and approaching the mechanically exfoliated counterparts. The VPVD-WSe 2 based field-effect transistors exhibit notable electrical performance with record-high field-effect hole mobility up to 112 cm 2 V –1 s –1 at room temperature, exceeding the best-reported monolayer WSe 2 synthesized by chemical vapor deposition and rivaling the mechanically exfoliated 2D WSe 2 flakes.

WSe2

NiFeCo-based catalysts in high current zero-gap anion exchange membrane water electrolyzers

Understanding degradation mechanisms in pure water anion exchange membrane water electrolyzers is essential for developing durable and precious metal-free hydrogen production systems, yet electronic, chemical, and transport-driven pathways often occur simultaneously at the anode. To separate these effects, we establish a morphology invariant Ni/Fe/Co thin film model catalyst platform using physical vapor deposition and systematically compare composition-dependent behavior under both pure water and 0.1 M KOH feeds. Devices were operated under industrially relevant current density conditions, galvanostatically at 1 A cm −2 for 24 hours; metal dissolution, ionomer oxidation, and resistance growth were quantified using inductively coupled plasma mass spectrometry, X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy. Under pure-water operation, Ni-rich films showed voltage increases that correlated with rising total cell resistance (ΔV ≈ 243 mV, ΔR ≈ 0.17 Ω cm 2 ). Co-rich films maintained near constant voltages with minimal resistance change (ΔV < 10 mV, ΔR ≈ 0.03 Ω cm 2 ) but induced pronounced ionomer oxidation observed by XPS. In 0.1 M KOH, ionomer oxidation is suppressed, and impedance growth is minimized (<0.08 Ω cm 2 ) across all compositions, consistent with reduced transport limitations and improved ionic conduction relative to pure-water feeds. These results demonstrate how a controlled thin film model platform can isolate composition electrolyte relationships and provide mechanistic design principles for stable pure water anion exchange membrane electrolyzers.

Milenia Rojas Mendoza, B. [Stanford Univ., CA (Uni

The effect of high-power transient events on tungsten and tungsten coatings used for radio frequency launcher applications

High-temperature plasma-facing material coatings used for radio frequency (RF) launchers need to be robust enough to survive RF breakdown arcing or other transient events from the plasma (e.g., an edge localized mode) without causing a catastrophic failure of the coating. High-power transient effects are being explored by using an RF-induced vacuum arc to determine the robustness of tungsten coatings made by a variety of manufacturing methods. A 1/4-wavelength resonant section of vacuum transmission line terminated with an open circuit electrode structure with a well-defined electric field (30-60 kV/mm) produces repeatable arcing conditions. The initial focus is on tungsten as a plasma-facing material, including sintered tungsten, tungsten coatings on steel produced via physical vapor deposition (PVD), and functionally graded tungsten/steel coatings deposited by low-pressure plasma-spraying (LPPS). Thin PVD coatings (1-2 microns) fail catastrophically from an arc and result in severe delamination of the coating. The arc-induced damage of thicker coatings, such as those made via LPPS, tend to be restricted to the top few microns of the surface. Arcing often initiates on sharp surface microstructures and causes localized melting of tungsten at the surface of all the materials studied and results in resolidified melt pools with surface cracks. The resolidified surface results in a reduction in overall deuterium retention when exposed to typical RF plasma sheath conditions.

Caughman, John [ORNL] (ORCID:0000000206091164)