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High Temperature Oxidation of Boron Nitride: Monolithic Boron Nitride - Part 1

High temperature oxidation of monolithic boron nitride (BN) is examined. Hot pressed BN and both low and high density CVD BN were studied. It is shown that oxidation rates are quite sensitive to microstructural factors such as orientation, porosity, and degree of crystallinity. In addition small amounts of water vapor lead to volatilization of the B2O3 oxide as H(x)B(y)O(z). For these reasons, very different oxidation kinetics were observed for each type of BN.

Jacobson, Nathan

Content of lithium, beryllium, boron, and titanium, and the isotopic composition of lithium, boron, and magnesium in Luna 16 regolith sample

The abundance of the following elements in the L 16-19 No. 118 regolith sample, zone V was determined by isotopic dilution using a mass spectrometer equipped with a scattering ion source: Li -- 9.8, Be -- 1.2, Be -- 2.6, and Ti -- 1.92 percent. For comparison, these same elements were measured in samples of surface material returned by Apollo 11, Apollo 12, and Apollo 14, and in the terrestrial reference standard diabase W-1. The content of Li, Be, and B in the Luna 16 sample is nearly the same as in the Apollo 11 surface material. The surface material returned by Apollo 12 and Apollo 14 contains two to four times more of these elements. However, the abundance ratios of Li, Be, and B are remarkably similar in the surface materials from the four different lunar regions. With respect to basaltic achondrites and especially with respect to chondrites, the lunar basalts are enriched in Li, Be, and B up to 100 times.

Eugster, O.

Hot isostatic pressing of silicon nitride with boron nitride, boron carbide, and carbon additions

Si3N4 test bars containing additions of BN, B4C, and C, were hot isostatically pressed in Ta cladding at 1900 and 2050 C to 98.9 percent to 99.5 percent theoretical density. Room-temperature strength data on specimens containing 2 wt pct BN and 0.5 wt pct C were comparable to data obtained for Si3N4 sintered with Y2O3, Y2O3 and Al2O3, or ZrO2. The 1370 C strengths were less than those obtained for additions of Y2O3 or ZrO2 but greater than those obtained from a combination of Y2O3 and Al2O3. SEM fractography indicated that, as with other types of Si3N4, room-temperature strength was controlled by processing flaws. The decrease in strength at 1370 C was typical of Si3N4 having an amorphous grain-boundary phase. The primary advantage of nonoxide additions appears to be in facilitating specimen removal from the Ta cladding.

Mieskowski, Diane M.

Initial design concepts for solid boron injection in ITER

As part of ITER’s consideration to change its first wall material from beryllium to tungsten, the ITER Organization has proposed studying the feasibility of real-time solid boron injection (SBI) into the plasma to coat the walls and divertor to supplement glow discharge boronization (GDB). Boron deposits getter oxygen and reduce sputtering of tungsten from plasma facing components (PFCs). Particularly in areas with significant plasma wall interactions, boron coatings are expected to be short-lived under high performance plasma conditions. The proposed SBI system aims to maintain boron layers in these areas to avoid excessive radiation from tungsten in the plasma as a risk mitigation to ensure ITER will be able to reach and sustain Q = 10 conditions. The system will be used sparingly, as redeposition of boron can lead to significant tritium retention, which must be minimized in ITER to comply with nuclear safety concerns. SBI is proposed to limit and precisely control the amount of boron injected in real-time during plasma operation. Here, some of the design requirements and initial concepts for an SBI system in ITER are presented based on previous results carried out with SBI systems on a number of tokamaks and stellarators around the world. Previous results using SBI systems installed by PPPL have injected boron particles from 5 µm–2 mm diameter at calibrated rates of 2–200 mg/s in real-time during plasma operation on AUG, DIII-D, EAST, KSTAR, LHD, TFTR, WEST, and W7-X, leading to improved wall conditions with reduced plasma impurity concentrations and radiated power and improved plasma performance. The boron is ionized in the plasma edge and then deposited on plasma-wetted surfaces. On AUG, EAST and WEST reduced tungsten sputtering sources were observed following several discharges with SBI. Extrapolation of these SBI results are presented to estimate the amount of boron needed for wall conditioning in ITER. Real-time SBI control requirements and plasma operation scenarios for ITER are also described.

36 MATERIALS SCIENCE

Boron cosmochemistry

The assumption that boron is a moderately volatile element is examined. It was demonstrated that interior pieces of chondrites contain significantly less boron than had been thought to be indigenous to this type of meteorite. The mean and range of boron abundances in 16 internal pieces of 10 chondrites were significantly smaller than in 126 pieces of 40 chondrites with unknown terrestrial histories. A new value of the cosmic abundance of boron was determined using the geometric average of the results from interior pieces of 10 chondrites. Based upon the thermodynamic assessment of the cosmochemical properties of boron by Cameron, et al. Anders and Ebihara assumed that boron was a moderately volatile element. They renormalized the data of Curtis et al. to a chondrule free basis and thus inferred that the cosmic abundance of boron was about 3 times greater than that proposed by Curtis, et al. To resolve these differences in data, the relative abundances of several elements including boron were measured in 38 carefully prepared interior pieces of 26 different chondrites. Correlation between boron and sulfur abundances, indicate that, contrary to the conclusions of Cameron, et al., boron is not a moderately volatile element.

Curtis, D. B.

Removal of deuterium retained in boron powder by oxygen or high-temperature bakeout

Fuel retention in dust accumulated in fusion devices is a potential operational hazard. Boronization is one of the leading wall-conditioning candidates for future fusion devices. Fuel retention characteristics of boron dust must be studied to accurately understand the potential hazards of boron dust in fusion devices. We evaluated the retention of deuterium (D) in commercially available boron powder as a proxy for tritium retention in boron dust. Diffuse reflectance infrared Fourier transform spectroscopy revealed that boron powder between 300 and 500 K exposed to neutral hydrogen (H 2 ) gas retains H via B-H bonding. We utilized D 2 exposures of 17,400 L on the boron powder, which led to retention on the order of 0.5 g D per 100 kg B or 1.2 g D per m 2 B, as estimated from temperature programmed desorption measurements. We evaluated how powder bakeouts under ultra-high vacuum (UHV), or in an oxygen (O 2 ) or H 2 gas backfilled environment can remove the retained fuel. Bakeouts below 523 K under UHV exhibited poor D removal, promoting recapture of D 2 present as background gas in the chamber. Higher temperature bakeouts led to the removal of over 80% of the retained D within 3 days (623 K) or 1 h (723 K). Bakeouts at 423 K under an O 2 gas environment removed ∼150% more retained D from the boron powder, when compared to bakeouts conducted under UHV. These results suggest that efficient fuel removal from boron dust can be achieved by high-temperature bakeout (>623 K) or by bakeouts at lower temperature (423 K) under an O 2 environment.

Bakeout

Integrated modeling of boron powder injection for real-time plasma-facing component conditioning

An integrated modeling framework for investigating the application of solid boron (B) powder injection for real-time surface conditioning of plasma-facing components (PFCs) in tokamak environments is presented. Utilizing the DIII-D impurity powder dropper (IPD) setup, this study simulates B powder injection scenarios ranging from milligrams to tens of milligrams per second, corresponding to boron flux rates of 10 20 –10 21 B/s in standard L-mode conditions. The comprehensive modeling approach combines EMC3-EIRENE for simulating the deuterium plasma background and the Dust Injection Simulator (DIS) for the ablation and transport of the boron powder particles. EMC3 trace impurity fluid modeling results show substantial boron transport to the inboard lower divertor, predominantly influenced by the main ion plasma flow. The dependency on powder particle size (5-250 µm) was found to be insignificant for the scenario considered. The effects of erosion and redeposition were considered to reconcile the discrepancies with experimental observations, which saw substantial deposition on the outer divertor plasma-facing components. For this purpose, the WallDYN3D code was updated to include boron sources within the plasma domain and integrated into the modeling framework. The mixed-material migration modeling shows evolving boron deposition patterns, suggesting the formation of mixed B-C layers or predominantly B coverage depending on the powder mass flow rate. While the modeling outcomes at lower B injection rates tend to align with DIII-D experimental observations, the prediction of near-pure boron layers at higher rates has yet to be experimentally verified in the carbon environment of the DIII-D tokamak. The extensive reach of boron layers found in the modeling suggests the need for modeling that encompasses the entire wall geometry for more accurate experimental correlations. This integrated approach sets a precedent for analyzing and applying real-time in-situ boron coating techniques in advanced tokamak scenarios, potentially extendable to ITER.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY

Full-torus impurity transport simulation in boron powder injection experiments in the Large Helical Device

The toroidal distribution of boron deposition on plasma-facing components (PFCs) in boron powder injection using an impurity power dropper (IPD) was investigated by full-torus simulation and observations in a systematic plasma density-scan experiment. The images of the ablation of dropped boron powders observed with a visible CCD camera were consistently explained by the simulations of the ablation positions of the boron powders considering the size distribution. Simulations assuming full-torus boron deposition on the PFCs did not reproduce the observed intensity profile of boron emission lines for higher plasma densities. It indicated that the density of boron deposited on PFCs installed toroidally far from the IPD was low for higher plasma densities due to the change in the ablation positions of the boron powders toward the outboard side. The experimental results verified the previous full-torus simulation of the toroidal distribution of the boron deposition in both lower and higher plasma densities.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY

First result of boronization assisted by the ICWC on EAST with full metal wall

Boron (B), a low-Z (atomic number) material, has been widely utilized in wall conditioning to improve plasma performance in fusion devices. In 2023, boronization was successfully conducted on EAST featuring an ITER-like tungsten divertor and fully metallic first wall. The process employed predischarge coating with carborane (C 2 B 10 H 12 ) as the working material, assisted by ion cyclotron wall conditioning (ICWC). After one time 12 g boronization, it was found the thickness of B film was approximately 120 nm. Post-boronization observations indicated that substantial hydrogen (H) release during initial plasma discharges compared with the consumed W/B wall, attributed to H co-deposition during the ICWC-boronization processing, which led to uncontrollable divertor neutral pressure and plasma density. The H/(H + D) ratio demonstrated a gradual reduction from ∼85% to 30% over more than 1850 s of deuterium plasma, with a cumulative injected energy of 2325 MJ. The B coating significantly enhanced the stored energy in plasma and improved confinement performance. The stored energy in plasma showed an increase of about 20%, primarily due to a reduction in impurity radiation, including oxygen (O) and heavy impurities such as tungsten (W), iron (Fe), and copper (Cu). The effective ion charge (Z eff ) decreased from 2.3 to 2.0. Following ICWC-boronization, the line-integrated radiation profile decreased by nearly 35% in the plasma core, plasma density and electron temperature exhibited an increase of ∼7% and 12% due to enhanced wall fueling and reduced impurity radiation. The lifetime of boronization, as evaluated by the line emissions from boron and other impurity radiation, was about 1700 s of deuterium plasma, with a cumulative injected energy of 2125 MJ on EAST. These findings provide significant insights for evaluating ICWC-boronization applicability in ITER with full W wall structure.

EAST

Boron Abundances in A and B-type Stars

Boron abundances in A- and B-type stars may be a successful way to track evolutionary effects in these hot stars. The light elements - Li, Be, and B - are tracers of exposure to temperatures more moderate than those in which the H-burning CN-cycle operates. Thus, any exposure of surface stellar layers to deeper layers will affect these light element abundances. Li and Be are used in this role in investigations of evolutionary processes in cool stars, but are not observable in hotter stars. An investigation of boron, however, is possible through the B II 1362 A resonance line. We have gathered high resolution spectra from the IUE database of A- and B-type stars near 10 solar mass for which nitrogen abundances have been determined. The B II 1362 A line is blended throughout; the temperature range of this program, requiring spectrum syntheses to recover the boron abundances. For no star could we synthesize the 1362 A region using the meteoritic/solar boron abundance of log e (B) = 2.88; a lower boron abundance was necessary which may reflect evolutionary effects (e.g., mass loss or mixing near the main-sequence), the natal composition of the star forming regions, or a systematic error in the analyses (e.g., non-LTE effects). Regardless of the initial boron abundance, and despite the possibility of non-LTE effects, it seems clear that boron is severely depleted in some stars. It may be that the nitrogen and boron abundances are anticorrelated, as would be expected from mixing between the H-burning and outer stellar layers. If, as we suspect, a residue of boron is present in the A-type supergiants, we may exclude a scenario in which mixing occurs continuously between the surface and the deep layers operating the CN-cycle. Further exploitation of the B II 1362 A line as an indicator of the evolutionary status of A- and B-type stars will require a larger stellar sample to be observed with higher signal-to-noise as attainable with the Hubble Space Telescope.

Lambert, David L.

Spatial Burnout in Water Reactors with Nonuniform Startup Distributions of Uranium and Boron

Spatial burnout calculations have been made of two types of water moderated cylindrical reactor using boron as a burnable poison to increase reactor life. Specific reactors studied were a version of the Submarine Advanced Reactor (sAR) and a supercritical water reactor (SCW) . Burnout characteristics such as reactivity excursion, neutron-flux and heat-generation distributions, and uranium and boron distributions have been determined for core lives corresponding to a burnup of approximately 7 kilograms of fully enriched uranium. All reactivity calculations have been based on the actual nonuniform distribution of absorbers existing during intervals of core life. Spatial burnout of uranium and boron and spatial build-up of fission products and equilibrium xenon have been- considered. Calculations were performed on the NACA nuclear reactor simulator using two-group diff'usion theory. The following reactor burnout characteristics have been demonstrated: 1. A significantly lower excursion in reactivity during core life may be obtained by nonuniform rather than uniform startup distribution of uranium. Results for SCW with uranium distributed to provide constant radial heat generation and a core life corresponding to a uranium burnup of 7 kilograms indicated a maximum excursion in reactivity of 2.5 percent. This compared to a maximum excursion of 4.2 percent obtained for the same core life when w'anium was uniformly distributed at startup. Boron was incorporated uniformly in these cores at startup. 2. It is possible to approach constant radial heat generation during the life of a cylindrical core by means of startup nonuniform radial and axial distributions of uranium and boron. Results for SCW with nonuniform radial distribution of uranium to provide constant radial heat generation at startup and with boron for longevity indicate relatively small departures from the initially constant radial heat generation distribution during core life. Results for SAR with a sinusoidal distribution rather than uniform axial distributions of boron indicate significant improvements in axial heat generation distribution during the greater part of core life. 3. Uranium investments for cylindrical reactors with nonuniform radial uranium distributions which provide constant radial heat generation per unit core volume are somewhat higher than for reactors with uniform uranium concentration at startup. On the other hand, uranium investments for reactors with axial boron distributions which approach constant axial heat generation are somewhat smaller than for reactors with uniform boron distributions at startup.

Fox, Thomas A.

Molecular dynamics simulations of reflection and sputtering behavior of boron under deuterium ion irradiation

Boronization is a commonly used method of wall conditioning in fusion reactors. The application of boron films to the plasma-facing materials results in enhanced plasma performance due to the reduction of intrinsic impurities. This is primarily driven by a reduction in oxygen content that is chemically trapped in the boron film. The reactive nature of these boron films also raises questions concerning interactions with hydrogen isotopes. In this work, boron-deuterium interactions were studied using molecular dynamics (MD). Reactive force field potentials were used to model the chemical interactions between B and D. An amorphous boron substrate was irradiated by D atoms at varying incident energies, 10 eV < E i < 150 eV and angles, 0° < α < 85°. The reflection probability was calculated and compared to results from the commonly-used binary collision approximation (BCA) method. This comparison found that the BCA underestimated the reflection probability at E i < 35 eV and α > 45 ∘ . The source of this discrepancy was found to be the surface binding energy model. The BCA calculation with an isotropic surface binding energy model was more closely aligned to the MD result. This, in combination with a correction function based on the MD results allows for corrections to the reflection probability of deuterium impinging on boron surfaces. The sputtering of the substrate material was also studied. While this study did not contain sufficient events to quantitatively describe the sputtering behavior, some qualitative results emerged: namely, chemical sputtering of B and D-containing molecules (BD, BD 2 , BD 3 ) at low ( < 20 eV) incident deuterium energies. This result suggests that chemical sputtering could be a significant factor in limiting boron coating lifetime when exposed to lower ion energies, such as those in detached plasmas. The results show that chemical interactions should be taken into account when modeling the interactions between D ions and B surfaces.

Boron

Uncovering the linear boron environment in Na 3 BP 2 through solid-state 11 B NMR spectroscopy

Boron-based compounds exhibit a wide range of structural diversity, with potential applications spanning organic and inorganic chemistry. Herein, we focus on the characterization of the linear boron-phosphorus unit P═B═P in Na 3 BP 2 using solid-state nuclear magnetic resonance (ssNMR) spectroscopy and density functional theory (DFT) calculations. High-resolution 11 B ssNMR spectra were recorded at two fields, and key parameters such as chemical shift anisotropy (CSA), quadrupolar coupling constants (C Q ), and electric field gradient (EFG) tensors were extracted. The 11 B NMR results revealed a distinct chemical environment for the two-coordinate boron atom, with a CSA span (Ω) of 280 ppm and a C Q of 3.0 MHz. These values were further validated through periodic plane-wave DFT calculations, which showed good agreement with experimental results. The obtained spectral parameters are compared to other linear boron units, such as the BO 2 motif, providing a broader context for understanding boron coordination in inorganic compounds. This work expands the body of NMR knowledge on boron-containing materials, particularly for linear boron motifs. The findings contribute to the growing field of boron chemistry and its potential applications in advanced materials.

Porter, Andrew P. [Ames Laboratory (AMES), Ames, I

Hybrid-PIC Modeling of the Transport of Atomic Boron in a Hall Thruster

Computational analysis of the transport of boron eroded from the walls of a Hall thruster is performed by implementing sputter yields of hexagonal boron nitride and velocity distribution functions of boron within the hybrid-PIC model HPHall. The model is applied to simulate NASA's HiVHAc Hall thruster at a discharge voltage of 500V and discharge powers of 1-3 kW. The number densities of ground- and 4P-state boron are computed. The density of ground-state boron is shown to be a factor of about 30 less than the plasma density. The density of the excited state is shown to be about three orders of magnitude less than that of the ground state, indicating that electron impact excitation does not significantly affect the density of ground-state boron in the discharge channel or near-field plume of a Hall thruster. Comparing the rates of excitation and ionization suggests that ionization has a greater influence on the density of ground-state boron, but is still negligible. The ground-state boron density is then integrated and compared to cavity ring-down spectroscopy (CRDS) measurements for each operating point. The simulation results show good agreement with the measurements for all operating points and provide evidence in support of CRDS as a tool for measuring Hall thruster erosion in situ.

Materials Engineering

Synthesis of boron-carbide aerogels

We present the synthesis of boron carbide aerogels utilizing nano-boron powder and resorcinol–formaldehyde (RF) organic aerogels as precursors. Monolithic aerogels were fabricated from suspensions of boron nanoparticles and RF via an organic sol-gel process, enabling effective distribution of boron in the gel network. The resulting gels underwent supercritical drying, thermal reduction, and subsequent heat treatment to yield boron carbide aerogels with densities ranging from 37 to 55 mg/cm³. By tuning the boron-to-carbon ratio, heat treatment temperature, and dwell time, surface areas up to 53 m²/g were obtained. X-ray diffraction analysis confirmed the formation of the boron carbide phase and detected the presence of residual carbon within the structure.

Materials science