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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
NASA NTRS2013

Validation of Proposed Metrics for Two-Body Abrasion Scratch Test Analysis Standards

Abrasion of mechanical components and fabrics by soil on Earth is typically minimized by the effects of atmosphere and water. Potentially abrasive particles lose sharp and pointed geometrical features through erosion. In environments where such erosion does not exist, such as the vacuum of the Moon, particles retain sharp geometries associated with fracturing of their parent particles by micrometeorite impacts. The relationship between hardness of the abrasive and that of the material being abraded is well understood, such that the abrasive ability of a material can be estimated as a function of the ratio of the hardness of the two interacting materials. Knowing the abrasive nature of an environment (abrasive)/construction material is crucial to designing durable equipment for use in such surroundings. The objective of this work was to evaluate a set of standardized metrics proposed for characterizing a surface that has been scratched from a two-body abrasion test. This is achieved by defining a new abrasion region termed Zone of Interaction (ZOI). The ZOI describes the full surface profile of all peaks and valleys, rather than just measuring a scratch width. The ZOI has been found to be at least twice the size of a standard width measurement; in some cases, considerably greater, indicating that at least half of the disturbed surface area would be neglected without this insight. The ZOI is used to calculate a more robust data set of volume measurements that can be used to computationally reconstruct a resultant profile for de tailed analysis. Documenting additional changes to various surface roughness par ameters also allows key material attributes of importance to ultimate design applications to be quantified, such as depth of penetration and final abraded surface roughness. Further - more, by investigating the use of custom scratch tips for specific needs, the usefulness of having an abrasion metric that can measure the displaced volume in this standardized manner, and not just by scratch width alone, is reinforced. This benefit is made apparent when a tip creates an intricate contour having multiple peaks and valleys within a single scratch. The current innovation consists of a software- driven method of quantitatively evaluating a scratch profile. The profile consists of measuring the topographical features of a scratch along the length of the scratch instead of the width at one location. The digitized profile data is then fed into software code, which evaluates enough metrics of the scratch to reproduce the scratch from the evaluated metrics. There are three key differences between the current art and this innovation. First, scratch width does not quantify how far from the center of the scratch damage occurs (ZOI). Second, scratch width does not discern between material displacement and material removal from the scratch. Finally, several scratches may have the same width but different zones of interactions, different displacements, and different material removals. The current innovation allows quantitative assessment of all three.

Street, Kenneth W., Jr.↗
NASA NTRS2004

Low Earth Orbital Atomic Oxygen Interactions With Spacecraft Materials

Atomic oxygen, formed in Earth s thermosphere, interacts readily with many materials on spacecraft flying in low Earth orbit (LEO). All hydrocarbon based polymers and graphite are easily oxidized upon the impact of approx.4.5 eV atomic oxygen as the spacecraft ram into the residual atmosphere. The resulting interactions can change the morphology and reduce the thickness of these materials. Directed atomic oxygen erosion will result in the development of textured surfaces on all materials with volatile oxidation products. Examples from space flight samples are provided. As a result of the erosive properties of atomic oxygen on polymers and composites, protective coatings have been developed and are used to increase the functional life of polymer films and composites that are exposed to the LEO environment. The atomic oxygen erosion yields for actual and predicted LEO exposure of numerous materials are presented. Results of in-space exposure of vacuum deposited aluminum protective coatings on polyimide Kapton indicate high rates of degradation are associated with aluminum coatings on both surfaces of the Kapton. Computational modeling predictions indicate that less trapping of the atomic oxygen occurs, with less resulting damage, if only the space-exposed surface is coated with vapor deposited aluminum rather than having both surfaces coated.

Banks, Bruce A.↗
DOE OSTI2022

X-Ray Induced Chemical Reaction Revealed by In Situ X-Ray Diffraction and Scanning X-Ray Microscopy in 15 nm Resolution

The detection sensitivity of synchrotron-based X-ray techniques has been largely improved due to the ever-increasing source brightness, which has significantly advanced ex situ and in situ research for energy materials such as lithium-ion batteries. However, the strong beam–material interaction arising from the high beam flux can substantially modify the material structure. The beam-induced parasitic effect inevitably interferes with the intrinsic material property, making the interpretation of the experimental results difficult and requiring comprehensive assessments. Here, we present a quantitative study of the beam effect on an electrode material Ag 2 VO 2 PO 4 using four different X-ray characterization methods with different radiation dose rates. The material system exhibits interesting and reversible radiation-induced thermal and chemical reactions, further evaluated under electron microscopy to illustrate the underlying mechanism. Further, the work will provide a guideline for using synchrotron X-rays to distinguish the intrinsic behavior from extrinsic structure change of materials induced by X-rays.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Thermohydraulic Design Analysis of the Target Assembly in the Material Plasma Exposure Experiment Facility

The Material Plasma Exposure eXperiment (MPEX) project seeks to design a steady-state linear plasma facility at Oak Ridge National Laboratory that will be used to study plasma-material interactions (PMIs) at fusion prototypic levels, supporting the evaluation and development of materials for the next generation of fusion devices. This study is focused on PMI exposure of small-size neutron-irradiated specimens, which are clamped onto an actively cooled component. A thermohydraulic evaluation of a new MPEX target assembly design to assess the appropriate operation during MPEX operation is presented. To further guide the design and assess the structural integrity of the components under expected loads, preliminary thermomechanical stress analyses were also conducted. To ensure good thermal contact between the components, thermal interface materials, such as silver flexible graphite, were used in the assembly. It was found that the maximum target temperatures of 1572, 1463, and 1315 K were obtained for Grafoil thicknesses of 0.61, 0.38, and 0.25 mm, respectively. The distribution of the axial deformation at high heat fluxes showed that there are no gaps between components, indicating good contact at material interfaces. Moreover, the contact pressure between the target and other components indicated that very good contact was established at these interfaces. Furthermore, the stress-strain conditions for the target will be further used to assess the appropriate operation during MPEX experiments and gain insight into materials science phenomena during PMI experiments.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1978

Fabrics for fire resistant passenger seats in aircraft

The essential elements of the problem and of approaches to improved fire resistance in aircraft seats are reviewed. The performance requirements and availability of materials, delay in the ignition of upholstery fabric by a small source are considered a realistic objective. Results of experimental studies on the thermal response of fabrics and fabric/foam combinations suggest significant conclusions regarding: (1) the ignition behavior of a commercial 90/10 wool/nylon upholstery fabric relative to fabrics made from thermally stable polymers; (2) the role of the foam backing; (3) the behavior of seams. These results, coupled with data from other sources, also confirm the importance of materials' interactions in multicomponent assemblies, and the need for system testing prior to materials' selection. The use of an interlinear or thermal barrier between upholstery fabric and foam is a promising and viable approach to improved fire resistance of the seat assembly, but experimental evaluation of specific combinations of materials or systems is an essential part of the selection process.

Tesoro, G. C.↗
NASA NTRSDate not supplied

Investigating Material Behavior in Atmospheric Entry Conditions: Arc-Jet Testing Insights from Meteorite Ablation to High-Temperature Coatings.

Arc-jet testing is an indispensable tool in elucidating the complex interactions materials undergo when subjected to the extreme thermal and mechanical stresses of atmospheric entry. By replicating these harsh conditions, arc-jets enable researchers to explore critical phenomena such as ablation, melting, and spallation, generating invaluable data that informs the development of sophisticated, physics-based models. These models are pivotal not only in predicting material performance for spacecraft re-entry systems but also in assessing the threat posed by celestial bodies as they encounter Earth’s atmosphere. One of the leading facilities for such investigations is the Hypersonic Materials Environmental Test System (HyMETS) at NASA’s Langley Research Center. A pioneering test campaign conducted at HyMETS focused on unraveling the ablation mechanisms of an ordinary chondrite meteorite (Tamdakht H5) and a terrestrial analog (basalt). These studies unveiled distinct material behaviors: Tamdakht demonstrated a remarkably stable melt flow, with mass loss primarily driven by the volatilization of elements such as iron and sodium, whereas basalt exhibited more aggressive surface degradation due to the rapid decomposition of hydrated minerals, culminating in significant spallation and surface material ejection. Beyond meteorite analysis, HyMETS has also been integral in the exploration of advanced Thermal Protection Systems (TPS) such as Phenolic Impregnated Carbon Ablator (PICA), a material with extensive flight heritage in missions like Stardust, Mars Science Laboratory, Mars 2020, and Osiris-REx. PICA, when coated with NuSil CV-1144-0—a polysiloxane resin designed to prevent particle shedding—undergoes a remarkable transformation upon heating. The resin pyrolyzes to form a thin, oxidation-resistant silicon oxycarbide layer that profoundly influences the material’s thermal response through a sophisticated four-stage process. Initially, the silicon oxycarbide acts as a formidable barrier, impeding reactive interactions with the PICA char and effectively suppressing surface temperature rise and material recession. However, as the heating persists, the protective layer decomposes via carbothermal reduction, exposing the underlying char, which in turn leads to a dramatic spike in surface temperature and accelerated material erosion. In the final stage, equilibrium is reached, with recession rates aligning with those of the virgin material. This intricate understanding of PICA-NuSil behavior under extreme conditions offers valuable insights, enhancing material response models and advancing the development of next-generation TPS for space exploration.

Chemistry↗
DOE OSTI2023

Material Plasma Exposure eXperiment High Heat Flux Microwave Absorber Design, Manufacture, and Articles Test

The Material Plasma Exposure eXperiment (MPEX) at Oak Ridge National Laboratory is in the final design phase. MPEX will be capable of exposing neutron-irradiated materials to plasmas for the study of plasma-material interaction. This facility will provide information about the complex effects of plasmas on materials and contribute to examining new materials that can withstand high heat fluxes and high ion fluences for future fusion devices. MPEX plasma is heated by 70-GHz or 105-GHz electron Bernstein wave/electron cyclotron heating (ECH), and the high-frequency microwaves are prone to scattering microwave power, which can have detrimental effects, especially on diagnostic components. A large portion of the injected ECH power is expected to be absorbed by plasma, but the remainder requires that microwave absorbers be placed immediately upstream and downstream of the ECH launcher to minimize stray microwaves leaving the ECH region. These microwaves can inadvertently heat components that cannot be shielded or otherwise protected. The microwave absorber design is based on an array of pyramid-shaped ceramic tiles brazed to a water-cooled explosion-bonded heat sink and a stainless steel plate to produce one tile module. Computational fluid dynamics and structural analyses were performed to optimize and validate the design. Multiple test coupons were produced to validate the process for brazing the two different tile materials to the Glidcop AL-15 baseplate. The articles were tested to evaluate the reliability and thermal performance through exposure to an electron beam with a heat flux of up to 1.5 MW/m2. Nondestructive testing was performed before and after testing to identify voids or separations that may have been introduced by the high heat flux. This paper discusses the details of high heat flux microwave absorber design, manufacturing details and associated challenges, and test results, demonstrating the effectiveness of the proposed design.

Hussain, Aftab↗
DOE OSTI2022

Development of self-sensing materials for extreme environments based on metamaterial concept and additive manufacturing

Structural health monitoring of an engineered component in a harsh environment is critical for multiple DOE missions including nuclear fuel cycle, subsurface energy production/storage, and energy conversion. Supported by a seeding Laboratory Directed Research & Development (LDRD) project, we have explored a new concept for structural health monitoring by introducing a self-sensing capability into structural components. The concept is based on two recent technological advances: metamaterials and additive manufacturing. A self-sensing capability can be engineered by embedding a metastructure, for example, a sheet of electromagnetic resonators, either metallic or dielectric, into a material component. This embedment can now be realized using 3-D printing. The precise geometry of the embedded metastructure determines how the material interacts with an incident electromagnetic wave. Any change in the structure of the material (e.g., straining, degradation, etc.) would inevitably perturbate the embedded metastructures or metasurface array and therefore alter the electromagnetic response of the material, thus resulting in a frequency shift of a reflection spectrum that can be detected passively and remotely. This new sensing approach eliminates complicated environmental shielding, in-situ power supply, and wire routing that are generally required by the existing active-circuit-based sensors. The work documented in this report has preliminarily demonstrated the feasibility of the proposed concept. The work has established the needed simulation tools and experimental capabilities for future studies.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Defect Characterization Using Positron Annihilation Spectroscopy on Laser-Ablated Surfaces

In recent years, short, pulsed laser ablation has been gaining popularity for machining small-scale test geometries from bulk samples and for efficient serial sectioning. These laser-based techniques are being added to the toolbox in material science, which makes it necessary to understand the changes in the material that occur from the laser–material interaction. Positron annihilation spectroscopy is a unique, nondestructive technique to investigate small defects in materials difficult to investigate by other tools. In this work, Doppler broadening and positron lifetime annihilation spectroscopy are utilized to help quantify the damage in materials treated with short, pulsed lasers. Using a femtosecond laser on single crystal silicon, this manuscript shows that clusters of vacancy-like defects and small voids increase systematically with laser power. Lastly, the damage induced by the laser can also reach to micrometer depths.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Understanding non-stochiometric deposition of multi-principal elemental NiCoCr thin films

Multi-principal elemental NiCoCr thin films with compositional flexibility have potential applications as a thermal barrier, corrosion-resistant coatings, and functional energy materials. In this study, the non-stochiometric multi-principal element alloy thin film formation behavior from an equiatomic ablation target of NiCoCr using pulsed laser deposition has been reported. Here, the effect of varying laser fluence on compositions of constituent elements in the NiCoCr thin films is systematically investigated. The increase in laser fluence typically increases the likelihood of acquiring undesirable particulates in thin films. Therefore, to maintain the film quality the laser fluences are adjusted within the range of 1.3–3.3 J·cm -2 , while the film thicknesses are kept constant at ~30 nm. Results show that the constituent elements are well-distributed in the formed NiCoCr thin films, however, having average atomic percentages of Ni and Cr twice as high as Co irrespective of the equiatomic composition of individual elements in the ablation target. This stochiometric alteration in the as-deposited thin films is governed by the rate of ablation and subsequent evaporation of each element, which is facilitated by the optical properties and vapor pressure of individual constituent elements. Additionally, electron energy-loss spectroscopy and x-ray absorption spectroscopy analysis reveal that the thin films have partially oxidized, with the Cr oxidation contributing the most to the O-K edge in comparison to Ni and Co. Finally, this study presents a laser-assisted pathway for fabricating compositionally flexible NiCoCr thin films and develops an understanding of the non-equilibrium laser-material interactions and how the intrinsic properties of constituent elements affect the stoichiometric flow of materials from the target to the final film deposition.

36 MATERIALS SCIENCE↗
DOE OSTI2025

In situ Detection of Plasma Induced Surface Interaction based on Deep Learning based Visual Diagnostics (Technical Report)

It is characteristic for many plasma devices to undergo plasma-material interaction leading to surface erosion. These processes, often not easily detectable, lead to changes in device performance and lifespan. State-of-the-art lifetime tests and wear experiments require over 1000s hours. A self-consistent model for accurately predicting the erosion's effects is not available. In situ detection of these processes is not a trivial task since the surface variations at the early stages have a micron scale. Such limitations not only restrict testing and prediction capabilities but also slow the development of new thrusters and limit mission duration. To address these challenges, an in-situ diagnostic for real-time erosion assessment has been developed, aiming to expedite lifetime testing and broaden experimental campaigns. Several works were dedicated to real-time and in situ monitoring of material erosion during plasma exposure using laser holography, microscopy, and with telemicroscopes. However, the applicability of these approaches is limited due to complexity, cost and less flexibility as they often require placing diagnostic equipment inside the vacuum chamber. In collaboration with Princeton Collaborative Research Facility (PCRF), Princeton Plasma Physics Laboratory (PPPL), a new diagnostic approach is developed, where geometry modifications to the ceramic channel walls were introduced that would result in accelerated channel erosion. We employed Long-distance microscope (LDM) imagery, combined with Deep-Learning based Shape from focus or depth from focus (DFF or SFF) approach, that provides an accessible and cost-effective solution. LDM employs focus variation techniques to continuously capture multiple images of the target object at distinct focal planes. DFF, an optical focus variation method, generates a 3D topographical surface depth map from a sequence of variably focused images. Combined with the developed diagnostic, this approach offers a controllable means to study erosion under accelerated conditions. In this work, we develop Neural Network-based DFF algorithm applicable for LDM data to quantitatively evaluate plasma induced surface modification from LDM data. Next, we develop Deep Learning-based super-resolution depth map image reconstruction technique to increase the resolution of depth maps obtained from DFF algorithm to improve the accuracy of erosion measurements. Thirdly, we develop several image processing techniques to remove noise and improve the quality of depth map image. Here we report the results of initial tests for this approach. An experimental setup designed and built in PPPL was employed that consists of a 3-cm gridded ion source that produces a neutralized argon beam with energies up to 600 eV. A hexagonal boron nitride (h-BN) ceramic target, designed based on computational predictions, was used. Tests were conducted to reconstruct the complex geometry of the target under the lighting conditions of the operated ion source.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Physical and technical basis of Materials Plasma Exposure eXperiment from modeling and Proto-MPEX results *

Abstract The Materials Plasma Exposure eXperiment (MPEX) is a steady-state linear plasma device that will address plasma-material interaction (PMI) science and enable testing of fusion reactor-relevant divertor plasma-facing materials. The MPEX source concept consists of a helicon plasma source to generate the plasma, electron cyclotron heating (ECH) for electron heating, and ion cyclotron heating (ICH) for ion heating. The MPEX source plasma is then transported axially to the PMI material target region to test material samples in fusion reactor-relevant divertor conditions. This paper will summarize the physical and technical basis of MPEX. The paper will first define the MPEX parameters and scenarios at the target relevant to PMI science for various fusion reactor-relevant divertor conditions and show plasma transport modeling results to set the MPEX source parameters. Recent experimental and modeling results from Proto-MPEX, a short-pulse experiment to develop the plasma production, heating, and transport physics for MPEX, will be shown. From these results, it will be shown that MPEX can reach its desired scenarios. The MPEX physical and technical basis will also determine important functional requirements for magnetic field, radiofrequency (RF) power, RF frequency, and neutral pressure in the helicon, ECH, ICH, and PMI regions that are required to achieve the desired MPEX scenarios. The necessity for key in-vessel components such as skimmers, limiters, and microwave absorbers will also be highlighted.

Lau, C. (ORCID:0000000285765867)↗
DOE OSTI2024

Nonequilibrium Phenomena in Plasmas in Contact with Liquids

Plasma-liquid interaction is a low-temperature plasma science frontier involving fundamental issues in plasma-materials interaction, multiphase kinetics, and collective effects. Plasmas in contact with liquids present two distinctive types of nonequilibrium: kinetic - across the interface - involving complex physical and chemical kinetics; and dissipative - along the interface - comprising superficial transport that is often conducive to instabilities and the formation of dissipative structures such as spot patterns. The project investigated dissipative and kinetic nonequilibrium phenomena concurrently in plasmas in contact with liquid water electrodes. The project’s objective was to determine the properties of dissipative (macroscopic) and kinetic (microscopic) nonequilibrium phenomena, and the interrelation between them, in low-temperature atmospheric-pressure plasmas in contact with liquid electrodes.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Energy-dependent implementation of secondary electron emission models in continuum kinetic sheath simulations

The plasma-material interactions present in multiple fusion and propulsion concepts between the flow of plasma through a channel and a material wall drive the emission of secondary electrons. This emission is capable of altering the fundamental structure of the sheath region, significantly changing the expected particle fluxes to the wall. The emission spectrum is separated into two major energy regimes, a peak of elastically backscattered primary electrons at the incoming energy, and cold secondary electrons inelastically emitted directly from the material. The ability of continuum kinetic simulations to accurately represent the secondary electron emission is limited by relevant models being formulated in terms of monoenergetic particle interactions which cannot be applied directly to the discrete distribution function. As a result, rigorous implementation of energy-dependent physics is often neglected in favor of simplified, constant models. We present here a novel implementation of semi-empirical models in the boundary of continuum kinetic simulations which allows the full range of this emission to be accurately captured in physically-relevant regimes.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Evaluation of the interaction between SiC, pre-oxidized FeCrAlMo with aluminized and pre-oxidized Fe-8Cr-2W in flowing PbLi

We report dissimilar materials interactions are a major concern when liquid metals are used as a working fluid. To simulate a dual-coolant PbLi blanket, chemical vapor deposited (CVD) SiC, pre-oxidized FeCrAlMo (APMT) and pre-oxidized aluminized coating on Fe-8Cr-2 W (F82H) specimens were exposed to flowing commercial Pb-17at.%Li with a peak temperature of 650 °C in a pre-oxidized APMT thermal convection loop (TCL) for 1000 h. Similar to prior results in static PbLi, the coated F82H showed small mass changes and limited degradation of room-temperature tensile properties. After exposure, the α-Al 2 O 3 on the surface coated F82H reacted with the PbLi to form LiAlO 2 . However, no significant Al coating loss or interdiffusion was observed. Mass transfer was observed between the APMT, TCL and the SiC specimens. Fe, Cr and Ni were dissolved into the molten flowing PbLi and transported through the TCL to react with the SiC specimens. Compared to a prior experiment with a majority of bare FeCrAl specimens that were exposed in a TCL with a peak temperature of 700 °C for 1000 h, the SiC reaction was reduced to only a few microns of carbides and silicides. Oxygen dissolved in the molten PbLi sustained the formation of an Al 2 O 3 scale on the surface of the coating and induced the formation of a thin surface SiO 2 layer on the surface of the SiC.

36 MATERIALS SCIENCE↗
DOE OSTI2024

The development of an augmented machine learning approach for the additive manufacturing of thermoelectric materials

Through the integration of machine learning (ML) techniques alongside additive manufacturing (AM) experimentation, we demonstrate an iterative process to rapidly predict laser-material interactions and melt pool geometries throughout the build parameter space for a bismuth telluride thermoelectric (TE) material. In doing so, we determined process parameters that created crack-free, highly dense (>99 %) n-type bismuth telluride (Bi 2 Te 2.7 Se 0.3 ) parts through laser powder bed fusion (LPBF). Furthermore, the ML-assisted understanding of the processing space allowed for the identification of build parameters that successfully yielded geometrically enhanced Bi 2 Te 2.7 Se 0.3 parts with reduced build times and no increase in experimental effort.

36 MATERIALS SCIENCE↗
NASA NTRS1993

An overview of the Evaluation of Oxygen Interaction with Materials-third phase (EOIM-3) experiment: Space Shuttle Mission 46

The interaction of the atomic oxygen (AO) component of the low earth orbit (LEO) environment with spacecraft materials has been the subject of several flight experiments over the past 11 years. The effect of AO interactions with materials has been shown to be significant for long-lived spacecraft such as Space Station Freedom and has resulted in materials changes for externally exposed surfaces. The data obtained from previous flight experiments, augmented by limited ground-based evaluation, have been used to evaluate hardware performance and select materials. Questions pertaining to the accuracy of this data base remain, resulting from the use of long-term ambient density models to estimate the O-atom fluxes and fluences needed to calculate materials reactivity in short-term flight experiments. The EOIM-3 flight experiment was designed to produce benchmark AO reactivity data and was carried out during STS-46. Ambient density measurements were made with a quadrupole mass spectrometer which was calibrated for AO measurements in a unique ground-based test facility. The combination of these data with the predictions of ambient density models allows an assessment of the accuracy of measured reaction rates on a wide variety of materials, many of which had never been tested in LEO before. The mass spectrometer is also used to obtain a better definition of the local neutral and plasma environments resulting from interaction of the ambient atmosphere with various spacecraft surfaces. In addition, the EOIM-3 experiment was designed to produce information on the effects of temperature, mechanical stress, and solar exposure on the AO reactivity of a wide range of materials. An overview of the EOIM-3 methods and results are presented.

Leger, Lubert J.↗
DOE OSTI2020

Plasmon-Mediated Intramolecular Methyl Migration with Nanoscale Spatial Control

Plasmonic materials interact strongly with light to focus and enhance electromagnetic radiation down to nanoscale volumes. Due to this localized confinement, materials that support localized surface plasmon resonances are capable of driving energetically unfavorable chemical reactions. In certain cases, the plasmonic nanostructures are able to preferentially catalyze the formation of specific photoproducts, which offers an opportunity for the development of solar-driven chemical synthesis. Here, using plasmonic environments, we report inducing an intramolecular methyl migration reaction, forming 4-methylpyridine from N-methylpyridinium. Using both experimental and computational methods, we were able to confirm the identity of the N-methylpyridinium by making spectral comparisons against possible photoproducts. This reaction involves breaking a C–N bond and forming a new C–C bond, highlighting the ability of plasmonic materials to drive complex and selective reactions. Additionally, we observe that the product yield depends strongly on optical illumination conditions. This is likely due to steric hindrance in specific regions on the nanostructured plasmonic substrate, providing an optical handle for driving plasmonic catalysis with spatial specificity. Furthermore, this work adds yet another class of reactions accessible by surface plasmon excitation to the ever-growing library of plasmon-mediated chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗