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Friction and Wear Properties of As-Deposited and Carbon Ion-Implanted Diamond Films

Recent work on the friction and wear properties of as-deposited and carbon ion-implanted diamond films was reviewed. Diamond films were produced by the microwave plasma chemical vapor deposition (CVD) technique. Diamond films with various grain sizes and surface roughnesses were implanted with carbon ions at 60 keV ion energy, resulting in a dose of 1.2 x 10(exp 17) carbon ions per cm(exp 2). Various analytical techniques, including Raman spectroscopy, proton recoil analysis, Rutherford backscattering, transmission and scanning electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction, were utilized to characterize the diamond films. Sliding friction experiments were conducted with a polished natural diamond pin in contact with diamond films in the three environments: humid air (40% relative humidity), dry nitrogen (less than 1 percent relative humidity), and ultrahigh vacuum (10(exp -7) Pa). The CVD diamond films indeed have friction and wear properties similar to those of natural diamond in the three environments. The as-deposited, fine-grain diamond films can be effectively used as self-lubricating, wear-resistant coatings that have low coefficients of friction (0.02 to 0.04) and low wear rates (10(exp -7) to lO(exp -8) mm(exp 3) N(exp -1) m(exp -1)) in both humid air and dry nitrogen. However, they have high coefficients of friction (1.5 to 1.7) and a high wear rate (10(exp -4) mm(exp 7) N(exp -1) m(exp -1)) in ultrahigh vacuum. The carbon ion implantation produced a thin surficial layer (less than 0.1 micron thick) of amorphous, non-diamond carbon on the diamond films. In humid air and dry nitrogen, the ion-implanted, fine and coarse-grain diamond films have a low coefficient of friction (around 0.1) and a low wear rate (10(exp -7) mm(exp 3) N(exp -1) m(exp-1)). Even in ultrahigh vacuum, the presence of the non-diamond carbon layer reduced the coefficient of friction of fine-grain diamond films to 0.1 or lower and the wear rate to 10(exp -6) mm(exp 3) N(exp -1) m(exp -1). Thus, the carbon ion-implanted, fine-grain diamond films can be effectively used as wear-resistant, self-lubricating coatings not only in air and dry nitrogen, but also in ultrahigh vacuum.

Miyoshi, Kazuhisa↗

Recreating Fuel Cell Catalyst Degradation in Aqueous Environments for Identical-Location Scanning Transmission Electron Microscopy Studies

The recent surge in interest of proton exchange membrane fuel cells (PEMFCs) for heavy-duty vehicles increases the demand on the durability of oxygen reduction reaction electrocatalysts used in the fuel cell cathode. This prioritizes efforts aimed at understanding and subsequently controlling catalyst degradation. Identical-location scanning transmission electron microscopy (IL-STEM) is a powerful method that enables precise characterization of degradation processes in individual catalyst nanoparticles across various stages of cycling. Recreating the degradation processes that occur in PEMFC membrane electrode assemblies (MEAs) within the aqueous cell used for IL-STEM experiments is vital for generating an accurate understanding of these processes. In this work, we investigate the type and degree of catalyst degradation achieved by cycling in an aqueous cell compared to a PEMFC MEA. While significant degradation is observed in IL-STEM experiments performed on a traditional Pt catalyst using the standard accelerated stress test potential window (0.6-0.95 VRHE), degradation of a PtCo catalyst designed for heavy-duty vehicle use is very limited compared to that observed in MEAs. We therefore explore various experimental parameters such as temperature, acid type, acid concentration, ionomer content, and potential window to identify conditions that reproduce the degradation observed in MEAs. We find that by extending the cycling potential window to 0.4-1.0 V RHE in an electrolyte containing Pt ions, the degraded particle size distribution and alloy composition better match that observed in MEAs. In particular, these conditions increase the relative contribution of Ostwald ripening, which appears to play a more significant role in the degradation of larger alloy particles supported on high-surface-area carbons than coalescence. Results from this work highlight the potential for discrepancies between ex situ aqueous experiments and MEA tests. While different catalysts may require a unique modification to the AST protocol, strategies provided in this work enable future in situ and identical-location experiments that will play an important role in the development of robust catalysts for heavy-duty vehicle applications.

30 DIRECT ENERGY CONVERSION↗

An Analytical Model for the Prediction of a Micro-Dosimeter Response Function

A rapid analytical procedure for the prediction of a micro-dosimeter response function in low Earth orbit (LEO), correlated with the Space Transportation System (STS, shuttle) Tissue Equivalent Proportional Counter (TEPC) measurements is presented. The analytical model takes into consideration the energy loss straggling and chord length distribution of the detector, and is capable of predicting energy deposition fluctuations in a cylindrical micro-volume of arbitrary aspect ratio (height/diameter) by incoming ions through both direct and indirect (ray) events. At any designated (ray traced) target point within the vehicle, the model accepts the differential flux spectrum of Galactic Cosmic Rays (GCR) and/or trapped protons at LEO as input. On a desktop PC, the response function of TEPC for each ion in the GCR/trapped field is computed at the average rate of 30 seconds/ion. The ionizing radiation environment at LEO is represented by O'Neill fs GCR model (2004), covering charged particles in the 1 less than or equal to Z less than or equal to 28. O'Neill's free space GCR model is coupled with the Langley Research Center (LaRC) angular dependent geomagnetic cutoff model to compute the transmission coefficient in LEO. The trapped proton environment is represented by a LaRC developed time dependent procedure which couples the AP8MIN/AP8MAX, Deep River Neutron Monitor (DRNM) and F10.7 solar radio frequency measurements. The albedo neutron environment is represented by the extrapolation of the Atmospheric Ionizing Radiation (AIR) measurements. The charged particle transport calculations correlated with STS 51 and 114 flights are accomplished by using the most recent version (2005) of the LaRC deterministic High charge (Z) and Energy TRaNsport (HZETRN) code. We present the correlations between the TEPC model predictions (response function) and TEPC measured differential/integral spectra in the lineal energy (y) domain for both GCR and trapped protons, with the conclusion that the model correctly accounts for the increase in flux at low y values where energetic ions are the primary contributor. We further discuss that, even with the incorporation of angular dependency in the cutoffs, comparison of the GCR differential/integral flux between STS 51 and 114 TEPC measured data and current calculations indicates that there still exists an underestimation by the simulations at low to mid range y values. This underestimation is partly related the exclusion of the secondary pion particle production from the current version of HZETRN.

Badavi, Francis F.↗

Microstructure, stored energy, and stability of H/He-filled nanocavities in low temperature irradiated Inconel 718

The microstructure, trapped transmutation gases, stored energy, and mechanical behavior of samples from an irradiated Inconel 718 proton beam window were characterized using transmission electron microcopy, thermal desorption spectrometry (TDS), differential scanning calorimetry (DSC), and tensile testing. In the as-irradiated condition the microstructure contained a high number density of 1–3 nm gas-filled nanocavities. Emissions of trapped gases, H and He, during TDS correlated with peaks of the energy release curves from DSC examinations, which suggest these gases were likely stored in highly stable defect traps. The stored energy from radiation damage saturated at doses of a few dpa and did not increase with increasing radiation dose, but the amount of stored H and He increased with increasing dose. Effects of post-irradiation annealing were studied as well. After exposure to 700 °C, the nanocavities grew only slightly to 2–4 nm in diameter, but after exposure to 900 °C, the cavities grew to 10–20 nm in diameter and electron energy-loss spectroscopy showed these cavities contained a core of He surrounded by a shell of H. Further, this study demonstrated that the irradiation defect structures containing H and He were remarkably stable during irradiation and after exposure up to 700 °C. The effect of the irradiation temperature, defect mobility, and interaction of H, He, and irradiation defects on mechanical behavior provides insight into the processes responsible for the unusual recovery in ductility with increasing radiation dose observed in Inconel 718 after high energy proton and spallation neutron irradiation.

36 MATERIALS SCIENCE↗

A profile monitor for proton radiography experiments at the Los Alamos Neutron Science Center

The Proton Radiography (pRad) facility at the Los Alamos Neutron Science Center utilizes pulses of protons delivered by the 800 MeV linear accelerator to produce a series of radiographic images to study the dynamic behavior of materials under extreme conditions. Radiographs taken with an empty field of view, or beam pictures, are used to normalize transmission. However, because the center of the proton beam shifts between pulses, an in situ method for measuring beam position is required to normalize images for beam movement to perform absolute radiography. The beam profile monitor described here uses an array of scintillating fibers positioned in the beam path to produce light proportional to beam intensity across the beam cross section. This light is detected using fast photodiodes and a digital oscilloscope, providing a response time of several nanoseconds—suitable for measuring the 50-ns proton pulses used in pRad. The profile monitor achieves a measured position precision of 40 μm and an intensity precision of 0.7%, allowing for beam movement corrections to be applied to images, thereby improving data accuracy and image quality.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Electrochemical Evolution of Fuel Cell Platinum Nanocatalysts on Carbon Nanotubes at the Atomic Scale

The evolution of Pt nanoparticles supported on carbon nanotubes is analyzed before and after electrochemical potential cycling, using identical location aberration-corrected transmission electron microscopy, for applications in proton exchange membrane fuel cells. The work is focused on the half-cell accelerated stress test protocol of potential cycles ranging between 1.0 and 1.5 V RHE to represent the start-up/shutdown settings of a fuel cell vehicle. The research work reveals that particle migration and coalescence are key mechanisms for a reduction in the Pt nanoparticle surface area at the early stages of potential cycling. Further, the mechanism for particle movement and coalescence is attributed to carbon corrosion, catalyzed either by Pt or by bulk corrosion of the carbon nanotubes. Carbon corrosion results in the appearance of carbon vacancies at the carbon nanotube/Pt nanoparticle interface during cycling, as well as the formation of edge and surface defects. During cycling, the concentration of the dissoluble Pt increases. As soon as a significant amount is reached, subnanometer/atomic clusters emerge on the carbon nanotube support, which can move and coalesce, or redeposit on the surface of larger particles through Ostwald ripening.

25 ENERGY STORAGE↗

Dark field proton radiography

A pre- and post-collimation scheme has been applied to high energy proton radiography to establish a dark field condition, which defaults to a state of no transmission until a scatterer is placed at the object plane. This technique, dark field proton radiography, provides two additional capabilities to a standard proton radiography setup. First, protons with a high degree of angular dispersion are removed from the beam, reducing the effects of chromatic aberrations and decreasing noise. Second, protons below the same threshold are removed from the beam downstream of the objects, effectively making the transmission highly sensitive to small amounts of scatter at the object plane. Finally, initial results indicate that the system is highly sensitive to the presence of thinner materials and improves sensitivity to subtle areal density variations in thick objects.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Reaction Mechanism of Electrodeposited ε-MnO 2 : A Proton-Centered Pathway in Aqueous Zn-Ion Systems

Aqueous Zn/MnO 2 batteries have garnered significant interests owing to their abundance, high theoretical specific capacity, safety, and low cost. However, large-scale application of these systems is limited by the incomplete understanding of the MnO 2 reaction chemistry. The different crystal lattice structures among MnO 2 polymorphs contribute to the variations in reported reaction mechanisms. Among them, ε-MnO 2 polymorph, the dominant phase in electrolytic manganese dioxide (EMD), is notably observed during the charge cycles of aqueous Zn/MnO 2 batteries. Here, in this work, we investigate the electrochemical behavior of an ε-MnO 2 cathode synthesized via electrodeposition from a ZnSO 4 and MnSO 4 electrolyte, onto a 3-dimensional carbon cloth substrate. Proton intercalation emerges as the dominant charge storage mechanism, critically enabling the reversibility of ε-MnO 2 during cycling, as revealed by operando synchrotron X-ray diffraction and X-ray absorption spectroscopy. Additionally, a proton-coupled dissolution/redeposition pathway operates alongside minor Zn 2+ intercalation, as quantified by Rietveld refinement. Morphological and chemical heterogeneities are studied by transmission X-ray microscopy further validates this reaction mechanism. These mechanistic insights provide the foundation for rationally designing Zn/MnO 2 batteries with optimized proton dynamics and charge transfer, advancing these systems as a viable solution for safe, cost-effective grid-scale energy storage.

36 MATERIALS SCIENCE↗

Single-layer graphene as a highly selective barrier for vanadium crossover with high proton selectivity

In this paper, we report near-zero crossover for vanadium cross-permeation through single-layer graphene immobilized at the interface of two Nafion® polymer electrolyte membranes. Vanadium ion diffusion and migration, including proton mobility through membrane composites, were studied with and without graphene under diffusion and migration conditions. Single-layer graphene was found to effectively inhibit vanadium ion diffusion and migration under specific conditions. The single-layer graphene composites also enabled remarkable ion transmission selectivity improvements over pure Nafion® membranes, with proton transport being four orders of magnitude faster than vanadium ion transport. Resistivity values of 0.02 ± 0.005 Ω cm 2 for proton and 223 ± 4 Ω cm 2 for vanadium ion through single atomic layer graphene are reported. This high selectivity may have significant impact on flow battery applications or for other electrochemical devices where proton conductivity is required, and transport of other species is detrimental. Our results emphasize that crossover may be essentially completely eliminated in some cases, enabling for greatly improved operational viability.

2D nanomaterial↗

Radiation Transport Properties of Potential In Situ-Developed Regolith-Epoxy Materials for Martian Habitats

We will evaluate the radiation transport properties of epoxy-martian regolith composites. Such composites, which would use both in situ materials and chemicals fabricated from elements found in the martian atmosphere, are candidates for use in habitats on Mars. The principal objective is to evaluate the transmission properties of these materials with respect to the protons and heavy charged particles in the galactic cosmic rays which bombard the martian surface. The secondary objective is to evaluate fabrication methods which could lead to technologies for in situ fabrication. The composites will be prepared by NASA Langley Research Center using simulated martian regolith. Initial evaluation of the radiation shielding properties will be made using transport models developed at NASA-LaRC and the results of these calculations will be used to select the composites with the most favorable radiation transmission properties. These candidates will then be empirically evaluated at particle accelerators which produce beams of protons and heavy charged particles comparable in energy to the radiation at the surface of Mars.

Miller, J.↗

Schematic model for induced fission in a configuration-interaction approach

We model fission at barrier-top energies in a simplified model space that permits comparison of different components of the residual nucleon-nucleon interaction. The model space is built on particle-hole excitations of reference configurations. These are Slater determinants of uniformly spaced orbitals characterized only by their quantum numbers and orbital energies. The residual interaction in the Hamiltonian includes the diabatic interaction connecting similar orbitals at different deformations, the pairing interaction between like nucleons, and a schematic off-diagonal neutron-proton interaction. We find that the fission reaction probability is sensitive to the off-diagonal neutron-proton interaction much more than to the pairing and the diabatic interactions. In particular, the transmission coefficients become insensitive to the strength of the pairing interaction when the neutron-proton interaction is large. Here, we also find that the branching ratio is insensitive to the final-state scission dynamics, as is assumed in the well-known Bohr-Wheeler theory.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Demonstration of transmission high energy electron microscopy

Charged particle radiography with 800 MeV protons has been used for decades at LANL and developed around the world to study dynamic material properties. Recently, charged particle radiography has been demonstrated with the use of high-energy electrons. Because of the difference in the mass of the electron compared to the mass of the proton, the radiographic processes are substantially different and well suited to the study of fast dynamic processes in relatively thin systems. This presentation will show the layout required for such measurements, along with data collected from this recent demonstration performed with 14 GeV electrons generated at the SLAC National Accelerator Laboratory. The radiographic performance for flash measurements will be presented, along with the limitations of this measurement technique.

Merrill, F. E.↗

Anisotropic growth of Ni 2 (Cr,Mo) ordered phase in proton irradiated Ni-Cr-Mo alloys

Ni-Cr-Mo alloys are widely used in the nuclear industry as structural materials due to their high temperature strength and corrosion resistance. Ni-based alloys containing around 33 at.% (Cr+Mo) developed a long-range ordered Ni 2 (Cr,Mo) phase after thermal aging and/or irradiation. The ordering mechanism for thermally-aged Ni 2 (Cr,Mo) phase is well-understood, characterized to be sluggish, homogeneous, and isotropic. The ordering mechanism for irradiation-induced Ni 2 (Cr,Mo) phase is not fully understood, characterized as having rapid formation and demonstrating anisotropic precipitation. Here, this work elucidates the anisotropic precipitation and anisotropic precipitation mechanism of Ni 2 (Cr,Mo) after proton irradiation in Ni-Cr-Mo alloys. Selected area electron diffraction and bright-field scanning transmission electron microscopy imaging are used to image superlattice reflections from the ordered phase and irradiation-induced defects, respectively. A higher degree of anisotropic precipitation is observed with increasing dislocation loop and void size; a phenomenon not observed in thermally aged samples.

36 - MATERIALS SCIENCE↗

A TOPAS model for lens-based proton radiography

Abstract Objective. Proton Radiography can be used in conjunction with proton therapy for patient positioning, real-time estimates of stopping power, and adaptive therapy in regions with motion. The modeling capability shown here can be used to evaluate lens-based radiography as an instantaneous proton-based radiographic technique. The utilization of user-friendly Monte Carlo program TOPAS enables collaborators and other users to easily conduct medical- and therapy- based simulations of the Los Alamos Neutron Science Center (LANSCE). The resulting transport model is an open-source Monte Carlo package for simulations of proton and heavy ion therapy treatments and concurrent particle imaging. Approach. The four-quadrupole, magnetic lens system of the 800-MeV proton beamline at LANSCE is modeled in TOPAS. Several imaging and contrast objects were modelled to assess transmission at energies from 230–930 MeV and different levels of particle collimation. At different proton energies, the strength of the magnetic field was scaled according to βγ, the inverse product of particle relativistic velocity and particle momentum. Main results. Materials with high atomic number, Z, (gold, gallium, bone-equivalent) generated more contrast than materials with low-Z (water, lung-equivalent, adipose-equivalent). A 5-mrad collimator was beneficial for tissue-to-contrast agent contrast, while a 10-mrad collimator was best to distinguish between different high-Z materials. Assessment with a step-wedge phantom showed water-equivalent path length did not scale directly according to predicted values but could be mapped more accurately with calibration. Poor image quality was observed at low energies (230 MeV), but improved as proton energy increased, with sub-mm resolution at 630 MeV. Significance. Proton radiography becomes viable for shallow bone structures at 330 MeV, and for deeper structures at 630 MeV. Visibility improves with use of high-Z contrast agents. This modality may be particularly viable at carbon therapy centers with accelerators capable of delivering high energy protons and could be performed with carbon therapy.

60 APPLIED LIFE SCIENCES↗

Impact of post-irradiation annealing on mechanical performance of irradiated 718 alloy

Here, the effect of post-irradiation annealing on solution-annealed 718 alloy was investigated using advanced mechanical testing, fractography, scanning electron microscopy, and transmission electron microscopy. Specimens were extracted from a proton beam window operated at the Spallation Neutron Source, irradiated with 940 MeV protons to a maximum dose of approximately 9.7 displacements per atom (dpa) at a calculated temperature not exceeding 110 °C while in service. Helium and hydrogen concentrations reached about 1700 and 6900 atomic parts per million (appm), respectively. Despite irradiation and high tensile strength (yield stress over 1 GPa), the material exhibited significant ductility. Annealing at 500 °C, 700 °C, and 900 °C for 30 min resulted in an appreciable decrease in yield strength and an increase in ductility for annealing treatments at 500 °C and 900 °C relative to the strength and ductility of the as-irradiated material. The presence of helium and hydrogen led to cavity formation and cleavage-like brittle features on fractured surfaces; however, high-magnification imaging revealed the presence of small-scale ductile dimples, indicating that the fracture mechanism remained mixed. The annealed specimens retained total elongation levels of 14–33 %, and there was no sudden drop in ductility after heat treatments. The ductility level in the irradiated and annealed material is notable despite the presence of helium and hydrogen.

36 MATERIALS SCIENCE↗

Introduction to Radiation Issues for International Space Station Extravehicular Activities

The International Space Station (ISS) provides significant challenges for radiation protection of the crew due to a combination of circumstances including: the extended duration of missions for many crewmembers, the exceptionally dynamic nature of the radiation environment in ISS orbit, and the necessity for numerous planned extravehicular activities (EVA) for station construction and maintenance. Radiation protection requires accurate radiation dose measurements and precise risk modeling of the transmission of high fluxes of energetic electrons and protons through the relatively thin shielding provided by the space suits worn during EVA. Experiments and analyses have been performed due to the necessity to assure complete radiation safety for the EVA crew and thereby ensure mission success. The detailed characterization described of the material and topological properties of the ISS space suits can be used as a basis for design of space suits used in future exploration missions. In radiation protection practices, risk from exposure to ionizing radiation is determined analytically by the level of exposure, the detrimental quality of the radiation field, the inherent radiosensitivity of the tissues or organs irradiated, and the age and gender of the person at the time of exposure. During low Earth orbit (LEO) EVA, the relatively high fluxes of low-energy electrons and protons lead to large variations in exposure of the skin, lens of the eye, and tissues in other shallow anatomical locations. The technical papers in this publication describe a number of ground-based experiments that precisely measure the thickness of the NASA extravehicular mobility unit (EMU) and Russian Zvezda Orlan-M suits using medical computerized tomography (CT) X-ray analysis, and particle accelerator experiments that measure the minimum kinetic energy required by electrons and photons to penetrate major components of the suits. These studies provide information necessary for improving the understanding of the current ISS space suits and provide insights into improved approaches for the design of future suits. This chapter begins with a summary of the dynamic ionizing radiation environment in LEO space and introduces the concepts and quantities used to quantify exposure to space radiation in LEO. The space suits used for EVA and the experimental partial human phantom are described. Subsequent chapters report results from measured charged particle fields before and after incident protons and secondary particles are transported through the space suits and into organs and tissues.

Shavers, M. R.↗