In situ analysis of surfaces during high-flux plasma exposure represents a long-standing challenge in the study of plasma–material interactions. While post-mortem microscopy can provide a detailed picture of structural and compositional changes, in situ techniques can capture the dynamic evolution of the surface. In this study, we demonstrate how spectroscopic ellipsometry can be applied to the real-time characterization of W nanostructure (also known as “fuzz”) growth during exposure to low temperature, high-flux He plasmas. Strikingly, over a wide range of sample temperatures and helium fluences, the measured ellipsometric parameters (Ψ,Δ) collapse onto a single curve that can be directly correlated with surface morphologies characterized by ex situ helium ion microscopy. The initial variation in the (Ψ,Δ) parameters appears to be governed by small changes in surface roughness (<50 nm) produced by helium bubble nucleation and growth, followed by the emergence of 50 nm diameter W tendrils. This basic behavior appears to be reproducible over a wide parameter space, indicating that the spectroscopic ellipsometry may be of general practical use as a diagnostic to study surface morphologies produced by high-flux He implantation in refractory metals. An advantage of the methods outlined here is that they are applicable at low incident ion energies, even below the sputtering threshold. As an example of this application, we apply in situ ellipsometry to examine how W fuzz growth is affected both by varying ion energy and the temperature of the surface.
The passivation of polycrystalline nickel surfaces against hydrogen uptake by oxygen is investigated experimentally with low energy ion scattering (LEIS), direct recoil spectroscopy (DRS), and thermal desorption spectroscopy (TDS). These techniques are highly sensitive to surface hydrogen, allowing the change in hydrogen adsorption in response to varying amounts of oxygen exposure to be measured. The chemical composition of a nickel surface during a mixed oxygen and hydrogen exposure was characterized with LEIS and DRS, while the uptake and activation energies of hydrogen on a nickel surface with preadsorbed oxygen were quantified with TDS. By and large, these measurements of how the oxygen and hydrogen surface coverage varied in response to oxygen exposure were found to be consistent with predictions of a simple site-blocking model. This finding suggests that, despite the complexities that arise due to polycrystallinity, the oxygen-induced passivation of a polycrystalline nickel surface against hydrogen uptake can be approximated by a simple site-blocking model.
Metal oxides have been an attractive option for a range of applications, including hydrogen sensors, microelectronics, and catalysis, due to their reactivity and tunability. The properties of metal oxides can vary greatly on their precise surface structure; however, few surface science techniques can achieve atomistic-level determinations of surface structure, and fewer yet can do so for insulator surfaces. Low energy ion beam analysis offers a potential insulator-compatible solution to characterizing the surface structure of metal oxides. As a feasibility study, we apply low energy ion beam analysis to investigate the surface structure of a magnetite single crystal, Fe3O4(100). We obtain multi-angle maps using both forward-scattering low energy ion scattering (LEIS) and backscattering impact-collision ion scattering spectroscopy (ICISS). Both sets of experimental maps have intensity patterns that reflect the symmetries of the Fe3O4(100) surface structure. However, analytical interpretation of these intensity patterns to extract details of the surface structure is significantly more complex than previous LEIS and ICISS structural studies of one-component metal crystals, which had far more symmetries to exploit. To gain further insight into the surface structure, we model our experimental measurements with ion-trajectory tracing simulations using molecular dynamics. Our simulations provide a qualitative indication that our experimental measurements agree better with a subsurface cation vacancy model than a distorted bulk model.
The effect of nitrogen on the surfaces of polycrystalline ITER-grade tungsten and a tungsten single crystal were studied with low energy ion scattering (LEIS) and direct recoil spectroscopy (DRS). LEIS and DRS measurements on both tungsten surfaces were performed in an ultra-high vacuum system as various quantities of N2 were introduced into the chamber through a variable leak valve. The obtained ion energy spectra reveal that nitrogen was readily adsorbed onto the surface, in turn limiting the amount of hydrogen that could be adsorbed onto the surface. These results not only provide insight into how the presence of nitrogen on tungsten surfaces may play a role in hydrogen adsorption and retention, but also serve to benchmark models being developed to describe the H-N-W system.
Helium ion beam interactions with materials have important implications for magnetic confinement fusion, material modification, and helium ion microscopy. These interactions depend on the precise physics of how helium ions channel into the materials, which can vary greatly based on the local crystalline orientation. In this work, we performed a dedicated experiment to investigate helium ion channeling in a well-characterized tungsten single crystal. Time-of-flight impact-collision ion scattering spectroscopy was used to obtain multi-angle maps of the backscattering intensity for 3 keV He+ → W(111). We found that the backscattering intensity profile arising from helium ion channeling could be well described by a shadow cone analysis. This analysis revealed that subsurface W atoms as deep as the ninth monolayer contributed to the backscattering intensity profile. Binary collision approximation simulations were performed with MARLOWE to model the experimental maps with sufficient accuracy to allow for quantitative comparisons using reliability factors. These quantitative comparisons were applied to investigate how the W lattice structure and He-W interatomic potential affect the multi-angle maps.
In this report, we summarize preliminary surface characterization results for Nb surfaces, using low energy ion scattering, direct recoil spectrometry, and Auger electron spectroscopy. While most surface analysis tools cannot detect hydrogen, the low energy ion beam techniques described here are among the few techniques that are directly sensitive to it. For this study, we examined chemisorption using both molecular and atomic hydrogen (using an heated tungsten capillary to dissociate the hydrogen.) To complement these results, we have been performing ex-situ spectroscopic ellipsometry as a means of detecting the surface oxide.
Low energy ion scattering (LEIS) and direct recoil spectroscopy (DRS) are among the few experimental techniques that allow for the direct detection of hydrogen on a surface. The interpretation of LEIS and DRS measurements, however, is often made difficult by complexities that can arise from complicated scattering processes. Previously, these complexities were successfully navigated to identify the exact binding configurations of hydrogen on a few surfaces using a simple channeling model for the projectile ion along the surface. For the W(111) surface structure, this simple channeling model breaks down due to the large lateral atomic spacing on the surface and small interlayer spacing. Instead, our observed hydrogen recoil signal can only be explained by considering not just channeling along the surface but also scattering from subsurface atoms. Using this more complete model, together with molecular dynamics (MD) simulations, we determine that hydrogen adsorbs to the bond-centered site for the W(111)+H(ads) system. Additional MD simulations were performed to further constrain the adsorption site to a height h=1.0±0.1Å and a position dBC=1.6±0.1Å along the bond between neighbors in first and second layers. Our determination of the hydrogen adsorption site is consistent with density functional theory simulation results in the literature.
Atmospheric ice affects Earth's radiative properties and initiates most precipitation. Growing ice typically requires a particle, often airborne mineral dust, e.g., to catalyze freezing of supercooled cloud droplets. How chemistry, structure and morphology determine the ice - nucleating ability of minerals remains elusive. Not surprisingly, poor understanding of a erosol - cloud interactions is a major source of uncertainty in climate models. In this project, we combine d optical microscopy with atomic force microscopy t o explore the mechanisms of initial ice formation on alkali feldspar, a mineral proposed to dominate ice nucleation in Earth's atmosphere. When cold air becomes supersaturated with respect to water, we discovered that supercooled liquid water condenses at steps without having to overcome a nucleation barrier, and subsequently freezes quickly. Our results imply that steps, common even on macroscopically flat feldspar surfaces, can accelerate water condensation followed by freezing, thus promoting glaciation and dehydration of mixed - phase clouds. Motivated by the fact that current climate simulations do not properly account for feldspar's extreme efficiency to nucleate ice, we modified DOE's climate model, the Energy Exascale Earth System Model (E3SM), to i ncrease the activation of ice nucleation on feldspar dust. This included add ing a new aerosol tracer into the model and updat ing the ice nucleation parameterization, based on Classical Nucleation Theory, for multiple mineral dust tracers. Although t he se m odifications have little impact on global averages , predictions of regional averages can be strongly affected .
Tungsten, the material used in the plasma-facing components (PFCs) of nuclear fusion reactors, develops a fuzz-like surface morphology under typical reactor operating conditions. This fragile 'fuzz' surface nanostructure adversely affects reactor performance and operation. Developing predictive models, capable of simulating the spatiotemporal scales relevant to the fuzz formation process is essential for understanding the growth of such extremely complex surface features and improving PFC and reactor performance. Here, we report the development of an atomistically-informed, continuous-domain model for the onset of fuzz formation in helium plasma-irradiated tungsten and validate the model by comparing its predictions with measurements from carefully designed experiments. Our study demonstrates that fuzz forms in response to stress induced in the near-surface region of PFCs as a result of plasma exposure and helium gas implantation. Our model sets the stage for detailed descriptions of this complex fuzz formation phenomenon and similar phenomena observed in other materials.
This study examines channeling, multiple scattering, and neutralization/re-ionization of ions scattered along the stepped Al(332) plane. Our experimental approach involves probing the surface with 1–2 keV He+ and Ne+ beams, and then systematically mapping the scattered ion fluxes over a large solid angle. This provides comprehensive ion channeling information over all directions, rather than along a few low-index azimuths, as is common practice in ion scattering spectroscopy. We first probe the surface with 2 keV He+ at near-normal incidence, and then map the backscattered particle flux (both ions and neutrals) via time of flight (TOF) spectrometry. The features contained in these maps can be correlated with axial and inter-planar channeling effects, and are reproduced well via binary collision simulations. Sensitivity to the stepped surface topography is heightened considerably for oblique ion incidence in the forward-scattering direction. In this geometry, we used 2 keV Ne+ to probe the surface and mapped the corresponding scattered fluxes of both single and multiply-charged ions. In both cases, the scattering intensity depends strongly on the precise trajectory taken along the surface, and is particularly sensitive to how extensively the incident ions interact with the step edges. We interpret the information contained in these maps by considering several mechanisms for charge transfer and double ion production. The formation of Ne++ appears to be correlated with a previously observed inelastic mechanism that occurs when the collision apsis, Rmin, is less than 0.65 Å. This contributes to an energy loss of 48 ± 8 eV for Ne+ undergoing single scattering; the Rmin threshold for this inelastic step coincides with the emergence of a distinct Ne++ peak. Using the information gained from the maps, we propose methods for extending this approach to chemisorbed layers.
Herein, we investigate the saturation limits of hydrogen on the (110) and (100) surfaces of tungsten via Density Functional Theory (DFT) and complement our findings with experimental measurements. We present a detailed study of the various stable configurations that hydrogen can adopt upon the surfaces at coverage ratios starting below 1.0, up to the point of their experimental coverage ratios, and beyond. We provide the many low-energy configurations that exist at all coverages along with the energy landscape they form. Our findings allow us to estimate that the saturation limit on each surface exists with one monolayer of hydrogen atoms adsorbed. In the case of (110) this corresponds to a coverage ratio of one hydrogen atom per tungsten atom, while in the case of (100) a full monolayer is present at a coverage ratio of 2.0 hydrogen atoms per tungsten atoms. Preliminary Low Energy Ion Scattering (LEIS) and Direct Recoil Spectroscopy (DRS) measurements complement this work on the W(110) surface. These results and some previously published measurements obtained on the W(100) surface confirm the findings obtained by DFT. In particular, the saturation limits on each surface, the preferred adsorption sites on both surfaces up to saturation, and the reconstruction of the bare and unsaturated (100) surface.
The Sandia HyMARC team continued its development of new synthetic, modeling, and diagnostic tools that are providing new insights into all major classes of storage materials, ranging from relatively simple systems such as PdHx and MgH2, to exceptionally complex ones, such as the metal borohydrides, as well as materials thought to be very well-understood, such as Ti-doped NaAlH4. This unprecedented suite of capabilities, capable of probing all relevant length scales within storage materials, is already having a significant impact, as they are now being used by both Seedling projects and collaborators at other laboratories within HyMARC. We expect this impact to grow as new Seedling projects begin and through collaborations with other scientists outside HyMARC. In the coming year, Sandia efforts will focus on the highest impact problems, in coordination with the other HyMARC National Laboratory partners, to provide the foundational science necessary to accelerate the discovery of new hydrogen storage materials.
In this work, we examine the response of an ultra-fine grained (UFG) tungsten material to high-flux deuterium plasma exposure. UFG tungsten has received considerable interest as a possible plasma-facing material in magnetic confinement fusion devices, in large part because of its improved resistance to neutron damage. However, optimization of the material in this manner may lead to trade-offs in other properties. We address two aspects of the problem in this work: (a) how high-flux plasmas modify the structure of the exposed surface, and (b) how hydrogen isotopes become trapped within the material. The specific UFG tungsten considered here contains 100 nm-width Ti dispersoids (1 wt%) that limit the growth of the W grains to a median size of 960 nm. Metal impurities (Fe, Cr) as well as O were identified within the dispersoids; these species were absent from the W matrix. To simulate relevant particle bombardment conditions, we exposed specimens of the W-Ti material to low energy (100 eV), high-flux (> 1022 m− 2 s− 1) deuterium plasmas in the PISCES-A facility at the University of California, San Diego. To explore different temperature-dependent trapping mechanisms, we considered a range of exposure temperatures between 200 °C and 500 °C. For comparison, we also exposed reference specimens of conventional powder metallurgy warm-rolled and ITER-grade tungsten at 300 °C. Post-mortem focused ion beam profiling and atomic force microscopy of the UFG tungsten revealed no evidence of near-surface bubbles containing high pressure D2 gas, a common surface degradation mechanism associated with plasma exposure. Thermal desorption spectrometry indicated moderately higher trapping of D in the material compared with the reference specimens, though still within the spread of values for different tungsten grades found in the literature database. For the criteria considered here, these results do not indicate any significant obstacles to the potential use of UFG tungsten as a plasma-facing material, although further experimental work is needed to assess material response to transient events and high plasma fluence.
Current austenitic stainless steel storage reservoirs for hydrogen isotopes (e.g. deuterium and tritium) have performance and operational life-limiting interactions (e.g. embrittlement) with H-isotopes. Aluminum alloys (e.g.AA2219), alternatively, have very low H-isotope solubilities, suggesting high resistance towards aging vulnerabilities. This report summarizes the work performed during the life of the Lab Directed Research and Development in the Nuclear Weapons investment area (165724), and provides invaluable modeling and experimental insights into the interactions of H isotopes with surfaces and bulk AlCu-alloys. The modeling work establishes and builds a multi-scale framework which includes: a density functional theory informed bond-order potential for classical molecular dynamics (MD), and subsequent use of MD simulations to inform defect level dislocation dynamics models. Furthermore, low energy ion scattering and thermal desorption spectroscopy experiments are performed to validate these models and add greater physical understanding to them.
In this work, we examine how deuterium becomes trapped in plasma-exposed tungsten and forms near-surface platelet-shaped precipitates. How these bubbles nucleate and grow, as well as the amount of deuterium trapped within, is crucial for interpreting the experimental database. Here, we use a combined experimental/theoretical approach to provide further insight into the underlying physics. With the Tritium Plasma Experiment, we exposed a series of ITER-grade tungsten samples to high flux D plasmas (up to 1.5 × 1022m-2s-1) at temperatures ranging between 103 and 554 °C. Retention of deuterium trapped in the bulk, assessed through thermal desorption spectrometry, reached a maximum at 230 °C and diminished rapidly thereafter for T > 300 °C. Post-mortem examination of the surfaces revealed non-uniform growth of bubbles ranging in diameter between 1 and 10 μm over the surface with a clear correlation with grain boundaries. Electron back-scattering diffraction maps over a large area of the surface confirmed this dependence; grains containing bubbles were aligned with a preferred slip vector along the <111> directions. Focused ion beam profiles suggest that these bubbles nucleated as platelets at depths of 200 nm-1 μm beneath the surface and grew as a result of expansion of sub-surface cracks. To estimate the amount of deuterium trapped in these defects relative to other sites within the material, we applied a continuum-scale treatment of hydrogen isotope precipitation. In addition, we propose a straightforward model of near-surface platelet expansion that reproduces bubble sizes consistent with our measurements. For the tungsten microstructure considered here, we find that bubbles would only weakly affect migration of D into the material, perhaps explaining why deep trapping was observed in prior studies with plasma-exposed neutron-irradiated specimens. We foresee no insurmountable issues that would prevent the theoretical framework developed here from being extended to a broader range of systems where precipitation of insoluble gases in ion beam or plasma-exposed metals is of interest.
Abstract In this work, we apply low energy ion beam analysis to examine directly how the adsorbed hydrogen concentration and binding configuration on W(1 0 0) depend on temperature. We exposed the tungsten surface to fluxes of both atomic and molecular H and D. We then probed the H isotopes adsorbed along different crystal directions using 1-2 keV Ne+ ions. At saturation coverage, H occupies two-fold bridge sites on W(1 0 0) at 25°C. The H coverage dramatically changes the behavior of channeled ions, as does reconstruction of the surface W atoms. For the exposure conditions examined here, we find that surface sites remain populated with H until the surface temperature reaches 200°C. After this point, we observe H rapidly desorbing until only a residual concentration remains at 450°C. Development of an efficient atomistic model that accurately reproduces the experimental ion energy spectra and azimuthal variation of recoiled H is underway.
Increasingly, basic models such as density functional theory and molecular dynamics are being used to simulate different aspects of hydrogen recycling from plasma facing materials. These models provide valuable insight into hydrogen diffusion, trapping, and recombination from surfaces, but their validation relies on knowledge of the detailed behavior of hydrogen at an atomic scale. Despite being the first wall material for ITER, basic single crystal beryllium surfaces have been studied only sparsely from an experimental standpoint. In prior cases researchers used electron spectroscopy to examine surface reconstruction or adsorption kinetics during exposure to a hydrogen atmosphere. While valuable, these approaches lack the ability to directly detect the positioning of hydrogen on the surface. Ion beam techniques, such as low energy ion scattering (LEIS) and direct recoil spectroscopy (DRS), are two of the only experimental approaches capable of providing this information. In this study, we applied both LEIS and DRS to examine how hydrogen binds to the Be(0001) surface. Our measurements were performed using an angle-resolved ion energy spectrometer (ARIES) to probe the surface with low energy ions (500 eV - 3 keV He{sup +} and Ne{sup +}). We were able to obtain a 'scattering maps' of the crystal surface, providing insight on how low energy ions are focused along open surface channels. Once we completed a characterization of the clean surface, we dosed the sample with atomic hydrogen using a heated tungsten capillary. A distinct signal associated with adsorbed hydrogen emerged that was consistent with hydrogen residing between atom rows. To aid in the interpretation of the experimental results, we developed a computational model to simulate ion scattering at grazing incidence. For this purpose, we incorporated a simplified surface model into the Kalypso molecular dynamics code. This approach allowed us to understand how the incident ions interacted with the surface hydrogen, providing confirmation of the preferred binding site.
Chemical vapor deposited (CVD) silicon carbide (SiC) has superior resistance to tritium permeation even after irradiation. Prior work has shown Ultrametfoam to be forgiving when bonded to substrates with large CTE differences. The technical objectives are: (1) Evaluate foams of vanadium, niobium and molybdenum metals and SiC for CTE mitigation between a dense SiC barrier and steel structure; (2) Thermostructural modeling of SiC TPB/Ultramet foam/ferritic steel architecture; (3) Evaluate deuterium permeation of chemical vapor deposited (CVD) SiC; (4) D testing involved construction of a new higher temperature (> 1000 C) permeation testing system and development of improved sealing techniques; (5) Fabricate prototype tube similar to that shown with dimensions of 7cm {theta} and 35cm long; and (6) Tritium and hermeticity testing of prototype tube.
Under appropriate conditions, uranium will form a hydride phase when exposed to molecular hydrogen. This makes it quite valuable for a variety of applications within the nuclear industry, particularly as a storage medium for tritium. However, some aspects of the U+H system have been characterized much less extensively than other common metal hydrides (particularly Pd+H), likely due to radiological concerns associated with handling. To assess the present understanding, we review the existing literature database for the uranium hydride system in this report and identify gaps in the existing knowledge. Four major areas are emphasized: {sup 3}He release from uranium tritides, the effects of surface contamination on H uptake, the kinetics of the hydride phase formation, and the thermal desorption properties. Our review of these areas is then used to outline potential avenues of future research.
Overview of Plasma Materials Interaction (PMI) activities are: (1) Hydrogen diffusion and trapping in metals - (a) Growth of hydrogen precipitates in tungsten PFCs, (b) Temperature dependence of deuterium retention at displacement damage, (c) D retention in W at elevated temperatures; (2) Permeation - (a) Gas driven permeation results for W/Mo/SiC, (b) Plasma-driven permeation test stand for TPE; and (3) Surface studies - (a) H-sensor development, (b) Adsorption of oxygen and hydrogen on beryllium surfaces.