Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Enrichment”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Distribution of rare earth elements in fly ash derived from the combustion of Illinois Basin coals

This study examined rare earth element (REE) trends for Illinois Basin coal-sourced fly ashes, with the goal of understanding the elemental composition and resource potential for various fly ash fractions. Illinois Basin coals have a high volatile C through A bituminous rank with a moderate ash content (slightly>12% ash (dry basis)), about 3% sulfur, and, in general, lower concentrations of hazardous and other trace elements than many Central Appalachian coals. Fly ash from the combustion of Illinois Basin coals tends to have a high Fe 2 O 3 content owing to the amount of pyrite in the feed coals. The rare earth element (REE) concentrations in Illinois Basin coal-sourced fly ashes are less than that for fly ashes from the combustion of Central Appalachian coals. The Upper continental crust-corrected fly ashes show an H-type enrichment, a positive Eu N /Eu N * , and, in some cases, a sharp Gd peak. For comparison, a suite of fly ashes from the combustion of a blend of eastern Kentucky coals had an H-type enrichment, a positive Eu N /Eu N * , but only a minimal Gd peak. In contrast, fly ash from the combustion of the Fire Clay coal, a REE-rich coal, had a negative Eu N /Eu N * and a sharp Gd peak. Finally, these results highlight the importance of feed coal composition on trace element contents of respective combustion fly ash fractions and also the unique REE enrichment patterns of the Illinois Basin fly ashes relative to the better studied fly ashes of eastern Kentucky and Central Appalachia.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2022

Nickel-rich, volatile depleted iron meteorites: Relationships and formation processes

Ungrouped iron meteorites Tishomingo, Willow Grove, and Chinga, and group IVB iron meteorites, are Ni-rich. Similarities include enrichments of 10–100 × CI for some refractory siderophile elements, and equivalent depletions in more volatile siderophile elements. Superimposed on the overall enrichment/depletion trend, certain siderophile elements (P, W, Fe, Mo) are depleted relative to elements of similar volatility. All three ungrouped irons derive from parent bodies formed in the early Solar System. Willow Grove and Chinga are characterized by cosmic ray exposure corrected 182 W/ 184 W consistent with metal-silicate segregation on their parent bodies within 1–3 Myr of Solar System formation, within the age range determined for segregation of magmatic iron meteorite parent bodies, including group IVB irons. Tishomingo is characterized by a younger model age 4–5 Myr subsequent to Solar System formation, reflecting either late stage melting resulting from 26 Al decay, or an impact resetting. The discovery of stishovite in Tishomingo, indicating exposure to a minimum shock pressure of 8–9 GPa, is consistent with the latter. Stishovite in Tishomingo and chromite included in troilite-daubréelite in IVB irons allows oxygen isotopic composition comparison between these meteorites. Different mass independent oxygen isotopic compositions of IVB irons and Tishomingo indicate genetically distinct parent bodies. By contrast, mass independent Mo isotopic compositions overlap within analytical uncertainties, indicating a similar, carbonaceous chondrite (CC) type genetic heritage. Molybdenum and 183 W isotopic data for Chinga and Willow Grove indicate derivation from CC type parent bodies. Willow Grove shares Mo and 183 W isotopic compositions with the Ni-rich South Byron Trio (SBT) grouplet and the Milton pallasite. These Ni-rich meteorites likely formed in the same general nebular environment as other CC planetesimals, likely the outer Solar System. Highly siderophile element (HSE) abundances of Willow Grove and Tishomingo are similar to some IVB meteorites, consistent with formation by moderate degrees of fractional crystallization from initial metallic melts with low S and P, and modestly fractionated HSE. The comparable HSE abundances of Tishomingo and Willow Grove to some IVB irons, yet substantially higher Ni concentrations, indicate formation on parent bodies with lower bulk HSE abundances or HSE concentration in proportionally smaller volumes of metal. HSE abundances in Chinga are considerably lower than in IVB irons, highly fractionated, and processes responsible for these remain elusive. For IVB irons and these ungrouped irons, high temperature condensation likely dominated the enrichment and depletion of the refractory and volatile siderophile elements, respectively. Parent body degassing may have also played a role. Relative depletion of volatile siderophile elements is not, however, a universal feature of high-Ni meteorites. The SBT and Milton pallasite are Ni-rich, but less depleted in the more volatile siderophile elements. Nickel enrichment was likely driven by oxidation of Fe metal during parent body accretion or core segregation. Oxidation of the Tishomingo and Willow Grove parent bodies may have occurred at ~ IW + 1, indicated by relative Mo and W depletions due to metal/water reaction during differentiation. Late-stage reduction, indicated by the presence of Cr-bearing sulfides in Tishomingo and IVB irons, may have resulted from exhaustion of the oxidant.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Contributions of anoxic microsites to soil carbon protection across soil textures

Anoxic microsites, zones of oxygen depletion in otherwise oxic soils, may slow soil C turnover. However, the abundance of anoxic microsites and their contribution to soil C protection is yet undefined. In this study, we determine the contribution of anoxic microsites to soil C protection in soils of three distinct textures (clay loam, loam, sandy loam) across a range of soil moistures. We examined the influence of soil oxygen supply by increasing oxygen content in the incubation atmosphere (oxygen enrichment) and through disaggregation. We attributed increases in CO 2 efflux to the aeration of anoxic microsites. The contribution of anoxic microsites to soil C protection increased with decreasing clay content. Clay loam CO 2 efflux was relatively unaffected by aeration. Moderately moist, loam soils had CO 2 effluxes that did not increase with oxygen enrichment but increased by 375% upon disaggregation. Sandy loam soil CO 2 efflux increased by 50–75% with oxygen enrichment and 250% with disaggregation. Geochemical and microbial data reveal that anoxic microsite abundance also increased with decreasing clay content. The proportion of acid extractable Fe present as Fe(II) increased with decreasing clay content, and methanogens were more abundant in loam and sandy loam soils. Our results suggest that oxygen demand, rather than supply, can regulate anoxic microsite formation and that anoxic protection of soil C can be diminished through physical disruption of soil structure. Our findings further illustrate that anoxic microsites should be included in conceptual models of soil C protection to avoid soil C loss and improve predictions of soil C response to disturbance.

58 GEOSCIENCES↗
DOE OSTI2020

The passivity of low-temperature carburized austenitic stainless steel AISI-316L in a simulated boiling-water-reactor environment

The passive film on low-temperature-carburized AISI-316L austenitic stainless steel was studied in an oxygenated, simulated boiling-water-reactor environment with normal water chemistry. The microstructure was studied using scanning electron microscopy, grazing-incidence X-ray diffractometry, Auger electron spectroscopy, X-ray energy-dispersive spectroscopy, and transmission electron microscopy. For non-surface engineered AISI-316L, three distinct layers were observed after exposure: an outer layer of larger nickel-oxide enriched particles with the spinel structure, an intermediate layer of small Cr-oxide-enriched hematite particles, and a compact inner layer of Cr-enriched oxide also having the spinel structure. Exposure of low-temperature-carburized AISI-316L, in contrast, resulted in only two distinct layers. These layers did not include a compact Cr-rich inner layer. Instead, the innermost layer consisted of an oxide with the spinel structure that was a mixture of Fe, Cr and Ni oxide. The outer layer on the low-temperature-carburized specimen consisted of large loosely stacked particles with the spinel structure of mixed composition. In addition to passive-film characterization, the corrosion rate was studied by monitoring mass loss. Finally, after 500 h of immersion, the mass changes measured were relatively low for all specimens indicating good adhesion and low oxidation rates.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Effect of heat treatment on creep behavior of 316 L stainless steel manufactured by laser powder bed fusion

The objective of this study is to understand the thermal stability of microstructure and its effect on the creep behavior of additively-manufactured 316L stainless steel (AM 316L SS). Creep specimens were fabricated from rods printed by a laser powder bed fusion process. Six different heat treatments, namely 650 °C/1 h, 700 °C/1 h, 750 °C/1 h, 800 °C/1 h, 900 °C/1 h and 1050 °C/1 h were applied to the creep specimens. The heat-treated specimens were creep-tested under the same condition, 550 °C/275 MPa to evaluate the effect of post-build heat treatment on the creep behavior of AM 316L SS. In the temperature range of 650-750 °C, dislocation density within cells, and cell size and wall thickness were affected by the heat treatment, while elemental segregation at boundaries remained unchanged and Mn-enriched Si oxide particles remained stable. In the temperature range of 750-900 °C, concurrent changes were observed in dislocation cell structures, elemental segregation and oxide particles. The 1050 °C-heat treatment removed cell structures and boundary solute segregations, leading to formation of equiaxed grains; Mn-enriched Si oxide particles in the as-built specimen were replaced by more stable Mn-enriched Cr oxides. The creep life of AM 316L SS increased after the heat treatment at 650 °C and then decreased with increasing temperature up to 900 °C where cell/subgrain structures still existed. The creep rate and creep elongation followed an opposite trend. The creep rate can be correlated with the structural parameters of cell/subgrain size and cell wall/boundary thickness and can be rationalized by different strengthening mechanisms of dislocation cells and subgrains. The heat treatment affected strongly the primary and secondary creep but had a minimal effect on the tertiary creep of AM 316L SS.

316L stainless steel↗
DOE OSTI2021

Modernizing the active neutron collar poison rod correction using simulations to enhance PWR fresh fuel verification

The declared inventory of 235 U in fresh, low enriched uranium, nuclear fuel assemblies is routinely verified by nuclear safeguards inspectorates using the UNCL (Uranium Neutron Collar – Light Water Reactor Fuel) nondestructive assay instrument. The trend in modern fuels is towards higher initial enrichment, which in turn requires a larger number of burnable poison pins with higher Gadolinia concentration to hold down the initial reactivity. UNCL assay error for modern fuel assemblies typically exceeds 10%. The traditional algorithm used to correct the response for burnable poison content needs revision to achieve accuracy comparable to the $\sigma_\text{R}$ of 4.5% expected for poison-free assemblies. Here we review the problem and use a large set of 287 Monte Carlo simulations based on an experimentally benchmarked model corresponding to the 16×16 PWR array used in Brazilian Angra type II and III fuel. Simulated relative responses are used to evaluate the functional form of the poison correction and determine parameters optimal for 16×16 PWR assemblies. This update is conducted using between 4–24 Gadolinia pins ranging 2–11 wt% Gd 2 O 3 with assemblies having mean enrichments ranging 2.5%–5%. Experimental validation of the updated coefficients using seven measurements shows bias is reduced by an order of magnitude and $\sigma_\text{R}$R reduced from 10% to less than 2%. Two updated sets of coefficients are provided, the most accurate of which is directly useable in the existing analysis code (INCC) in use by inspectorate at fuel fabrication facilities.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2025

Multi-cycle reload analysis of a long cycle gas-cooled fast modular reactor

There is currently significant interest in deploying HALEU-fueled fast reactors, including the General Atomics (GA) Fast Modular Reactor (FMR). Such reactors can achieve very long fuel cycles, but with multi-batch loading will take decades to reach equilibrium. This motivates design and analysis of both the initial core and multi-cycle reload, which is typically performed using fast-running, deterministic fast reactor codes such as the Argonne Reactor Computation (ARC) codes. In this paper, multicycle reload of the GA FMR is analyzed using the ARC codes. The GA FMR utilizes 19.75 % enriched fuel in a 16 year cycle with a three-batch strategy, with twice-burned fuel placed on the core periphery. The GA FMR has a softened neutron spectrum due to reflecting elements in the core, so the neutronic solution is first benchmarked against the OpenMC Monte Carlo code. Discrepancy on k eff is 400–600 pcm, likely due to the softened neutron spectrum, heterogeneous fuel assembly design and central reflector. However, the rms discrepancy on the assembly power distribution is only 0.6 %, despite the presence of the central reflector. A reload strategy is devised for the first three cycles of such a reactor, ultimately spanning the first 45–48 years of its operation. The fresh core uses 19.75 %, 19.25 % and 16.75 % enriched fuel in place of fresh, once-burned and twice-burned and is then subsequently refueled with only 19.75 % enriched fuel. The cycle length is varied over 3 cycles of operation to balance fuel utilization and reactor availability, specifically with use of an extended 18-year Cycle 1, followed by a shortened 11-year Cycle 2. Cycle 3 is close to the target 16-year length. Finally, placing twice burned assemblies next to the GA FMR central reflector can reduce power peaking by 3 %, at the expense of slightly reducing the cycle length.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2025

Evidence for metal sources, fluid-mixing processes, and S isotope recycling within the feeder zone of an Irish type Zn-Pb deposit

The origin and evolution of fluids in Irish-type Zn-Pb deposits remains debated, particularly regarding the mobility of metals such as Cu and Ni, sources of sulphur, and the role of fluid mixing and replacement. The Lisheen Zn-Pb deposit, Ireland, offers a well-defined natural laboratory to investigate these questions. While most studies have focused on the Waulsortian Limestone Formation, the primary sulphide host, less is known about mineralisation in underlying units, such as the Lisduff Oolite Member (LOM). The LOM displays enrichment in Cu and Ni and displays intense replacement textures compared to other hosts at Lisheen, making it an ideal target for studying metal mobility and sulphur recycling in carbonate-hosted systems. Through characterising and studying LOM-hosted sulphides, valuable insights into mineralisation processes, especially related to Cu-Ni metals, can be defined. This study integrates petrography, EMPA, and in situ sulphur isotope (δ 34 S) analysis to investigate sulphide paragenesis, mineral chemistry, and fluid evolution across LOM ore zones. Results reveal a multistage mineralising system involving extensive replacement of early pyrite (Py0, δ 34 S = −28.4 to −21.9 ‰) by sphalerite and galena, with zoned pyrite (Py1) enriched in As-Cu-Ni-Tl. The δ 34 S values and trace element trends indicate mixing between hydrothermal and bacteriogenic sulphur-rich fluids, with evidence for sulphur recycling during replacement. Pyrite textures and compositions capture this evolving fluid regime, with trace element enrichment linked to paragenetic stage. The steel ore region, adjacent to major fault intersections, records intense hydrothermal fluid interaction, hosting Ni- and As-rich phases such as nickeline, gersdorffite, and arsenopyrite. These findings highlight the importance of structural controls and fluid mixing in metal transport and deposition, positioning the LOM as a key stratigraphic unit for understanding ore-forming processes in Irish-type systems. These results have implications for targeting similar carbonate-hosted systems globally, especially where deeper or structurally complex ore zones remain underexplored.

58 - GEOSCIENCES↗
DOE OSTI2022

Preliminary conceptual design of fast neutron spectrum nuclear thermal rocket cores using monolithic uranium nitride fuel

This paper presents a few nuclear thermal rocket (NTR) reactor core preliminary conceptual designs based on the use of monolithic uranium nitride (UN) fuel plates or pins clad with tungsten (W), alloyed or unalloyed as needed. High-assay low-enriched uranium (HALEU) as well as high-enriched uranium (HEU) are considered. Nominal core thermal powers are between 300 and 1100 MW corresponding to thrusts between 66 kN and 240 kN. The estimated thrust-to-reactor-weight ratios (T/WRx) achievable with the HEU plate and pin configurations are between 3.8 and 10.9. The T/WRx achievable with the HALEU plate and pin configurations are lower, 1.9–4.0, than those achievable with HEU. It is noteworthy that even a relatively modest increase in fuel enrichment above the HALEU limit enables a significant increase in T/WRx. It must be emphasized that these results do not yet account for uncertainties and that the appropriateness of the assumed fuel thermal design limits for normal operation (i.e., peak centerline temperature of 3100 K) will need to be confirmed. Finally, just like for the other UN-based fuels currently considered for NTR applications (i.e., CERMET and CERCER), the proposed UN fuel systems need significant testing in prototypic conditions to confirm the appropriate performance for safe NTR applications. However, the monolithic fuel systems may have, overall, a higher technology readiness level (TRL), and, consequently, shorter fuel development and validation time may result.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2023

Protein-based approach for high-purity Sc, Y, and grouped lanthanide separation

Rare earth elements (REEs: Sc, Y, La- Lu) are irreplaceable components in many clean energy and consumer technologies. However, the extraction and subsequent separation of individual REEs from ore-based feedstocks remains a significant economic and environmental challenge. Here in this work, we investigated the intra-REE separation potential of lanmodulin (LanM), a natural protein from Methylorubrum extorquens that has emerged as a sustainable potential alternative to conventional solvent extraction-based separation. By determining the intra-REE selectivity of immobilized LanM and systematically testing pH-based and small chelator-based (i.e., citrate and malonate) desorption processes, we established the framework and methodology for achieving select individual and grouped REE separations from a mixed REE feedstock. We show that Sc forms the tightest complex with LanM among REEs but can be readily and selectively desorbed using malonate to generate high-purity Sc (>99 % purity, >99 % yield) in a single adsorption/desorption cycle. We further show that the intrinsic REE selectivity of LanM is sufficient to achieve heavy REE (HREE) separation from light and middle REEs (L-MREEs), yielding an yttrium-enriched product. This separation effect is further magnified by pairing LanM’s unique M-LREE preference with a HREE-preferring chelator in the desorption process, which enriches HREE and MREE fractions relative to low value, abundant La/Ce. Finally, by combining pH- and citrate-based desorption processes in a two-cycle separation scheme, we demonstrate the generation of fractions highly enriched in Y, Gd-Lu, Pr-Eu, and La-Ce. Collectively, these data support the application of a LanM-based approach for achieving impactful REE separations from mixed REE feedstocks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Rapid isotopic analysis of uranium microparticles via SP-ICP-TOF-MS

Inductively coupled plasma – time-of-flight – mass spectrometry (ICP-TOF-MS) was employed for the isotopic analysis of uranium particles of varying 235 U enrichment levels. Here, a single particle (SP)-based introduction scheme was employed such that individual particles, in a suspension, were analyzed. The uranium oxide microparticles were comprised of depleted uranium (DU, 235 U/ 238 U of 0.0017316(14)), natural uranium (NU, 235 U/ 238 U of 0.0072614(39)), and low enriched uranium (LEU, 235 U/ 238 U of 0.051025(15)). The percent relative difference of the SP-ICP-TOF-MS measured isotopic ratios compared to the expected values for the DU, NU, and LEU particle populations were 8.75, 0.12, and 1.23 %, respectively. After characterization, the DU and NU particles were doped within a complex sample matrix (Arizona Test Dust) containing Fe, Ti, Al, and Si particles, among others. Then, the suspension was analyzed via SP-ICP-TOF-MS and the detected particles were classified as DU or NU based on their measured 235 U/ 238 U ratio. In the same analysis, the matrix particles (i.e., Al, Fe, and Ti) were detected, demonstrating the simultaneous nuclide detection provided by the measurement platform. The presented SP-ICP-TOF-MS methodology for uranium particle characterization proved to be a high throughput method for detecting and isotopically discerning uranium particles with varying enrichment levels, in a complex matrix.

Stanberry, Jordan S. [Oak Ridge National Laborator↗
DOE OSTI2026

Power and particle exhaust for the ARC fusion power plant

To successfully show that fusion is an attractive energy source, the ARCTM fusion power plant will need to operate with a robust, integrated power and particle exhaust solution. To maximise ARC’s fusion power output while avoiding excessive erosion of the plasma-facing components, we will need to radiatively dissipate most of the power crossing the last-closed flux surface, injecting radiating impurities such as argon or neon to access divertor detachment. Divertor detachment will need to be integrated with a high-performance core plasma, and with efficient impurity pumping to prevent the accumulation of helium ash in the core. To access and control detachment in high-performance plasmas, we have designed ARC with up–down-symmetric divertors, with secondary X-points in long, tightly baffled outer legs. Using a core-edge modelling workflow, we predict that with this divertor design, ARC will access detachment with modest argon seeding in the divertor (c Ar,div ∼0.9%), which should have minimal impact on the core ( Z eff,core <0.5) for reasonable argon enrichment (c Ar,div /c Ar,core =6). Due to the high predicted divertor neutral pressure (p div ∼20 Pa), we predict that ARC will sufficiently pump helium to limit ash accumulation in the core (c He,core <2%) for a helium enrichment of c He,div /c He,core =0.4. ARC’s divertor design is expected to increase the stability of a detachment front in the outer divertor leg, helping to prevent divertor reattachment during smaller heat-flux transients such as scrape-off-layer filaments associated with the quasi-continuous exhaust regime. However, this buffering will not be sufficient to prevent divertor reattachment during large type-I edge-localised modes (ELMs), and as such these will need to be avoided on ARC. Experiments on SPARC will be used to select an integrated scenario which avoids or mitigates type-I-ELMs while maintaining access to detachment, good core fusion performance and sufficient impurity exhaust. SPARC experiments will also be used to finalise ARC’s divertor design, by studying the impact of magnetic and first-wall geometry on detachment stability, impurity enrichment and neutral baffling under conditions similar to those expected for ARC. In conclusion, our analysis finds that ARC will have a viable power and particle exhaust solution which is compatible with high-power operations, and this solution will be validated in experiments on SPARC.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Isotopic Heterogeneity Imaged in a Uranium Fuel Pellet with Extreme Ultraviolet Laser Ablation and Ionization Time-of-Flight Mass Spectrometry

We use extreme ultraviolet laser ablation and ionization time-of-flight mass spectrometry (EUV TOF) to map uranium isotopic heterogeneity at the nanoscale (=100 nm). Using low-enriched uranium fuel pellets that were made by blending two isotopically distinct feedstocks, we show that EUV TOF can map the 235U/238U content in 100 nm-sized pixels. The two-dimensional (2D) isotope maps reveal U ratio variations in sub-microscale to =1 µm areas of the pellet that had not been fully exposed by microscale or bulk mass spectrometry analyses. Compared to the ratio distribution measured in a homogeneous U reference material, the ratios in the enriched pellet follow a ~3× wider distribution. These results indicate U heterogeneity in the fuel pellet from incomplete blending of the different source materials. EUV TOF results agree well with those obtained on the same enriched pellets by nanoscale secondary ionization mass spectrometry (NanoSIMS), which reveals a comparable U isotope ratio distribution at the same spatial scale. EUV TOF’s ability to assess and map isotopic heterogeneity at the nanoscale makes it a promising tool in fields such as nuclear forensics, geochemistry, and biology that could benefit from uncovering sub-microscale sources of chemical modifications.

Rush, Lydia A.↗
DOE OSTI2020

Selective One-Dimensional 13 C– 13 C Spin-Diffusion Solid-State Nuclear Magnetic Resonance Methods to Probe Spatial Arrangements in Biopolymers Including Plant Cell Walls, Peptides, and Spider Silk

Two-dimensional (2D) and 3D through-space 13 C– 13 C homonuclear spin-diffusion techniques are powerful solid-state nuclear magnetic resonance (NMR) tools for extracting structural information from 13 C-enriched biomolecules, but necessarily long acquisition times restrict their applications. In this work, we explore the broad utility and underutilized power of a chemical shift-selective one-dimensional (1D) version of a 2D 13 C– 13 C spin-diffusion solid-state NMR technique. The method, which is called 1D dipolar-assisted rotational resonance (DARR) difference, is applied to a variety of biomaterials including lignocellulosic plant cell walls, microcrystalline peptide fMLF, and black widow dragline spider silk. 1D 13 C– 13 C spin-diffusion methods described here apply in select cases in which the 1D 13 C solid-state NMR spectrum displays chemical shift-resolved moieties. Furthermore, this is analogous to the selective 1D nuclear Overhauser effect spectroscopy (NOESY) experiment utilized in liquid-state NMR as a faster (1D instead of 2D) and often less ambiguous (direct sampling of the time domain data, coupled with increased signal averaging) alternative to 2D NOESY. Selective 1D 13 C– 13 C spin-diffusion methods are more time-efficient than their 2D counterparts such as proton-driven spin diffusion (PDSD) and dipolar-assisted rotational resonance. The additional time gained enables measurements of 13 C– 13 C spin-diffusion buildup curves and extraction of spin-diffusion time constants TSD, yielding detailed structural information. Specifically, selective 1D DARR difference buildup curves applied to 13 C-enriched hybrid poplar woody stems confirm strong spatial interaction between lignin and acetylated xylan polymers within poplar plant secondary cell walls, and an interpolymer distance of ~0.45–0.5 nm was estimated. Additionally, Tyr/Gly long-range correlations were observed on isotopically enriched black widow spider dragline silks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Dipolar Heteronuclear Correlation Solid-State NMR Experiments between Half-Integer Quadrupolar Nuclei: The Case of 11 B– 17 O

With 73% of all NMR-active nuclei being quadrupolar, there is great interest in the development of NMR experiments that can probe the proximity of quadrupolar spins. Here, pulse sequences for magic-angle spinning (MAS) 11 B– 17 O resonance-echo saturation-pulse double-resonance (RESPDOR) and dipolar heteronuclear multiple quantum correlation (D-HMQC) solid-state NMR experiments were investigated. In these pulse sequences, rotational-echo double-resonance (REDOR) recoupling was used with central transition (CT)-selective π-pulses applied to either the 11 B or 17 O spins to recouple 11 B– 17 O dipolar interactions. 11 B{ 17 O} RESPDOR experiments on 17 O-enriched boric acid and benzene diboronic acid showed that application of dipolar recoupling on the 11 B channel yielded more signal dephasing than when recoupling is applied on the 17 O channel; however, short effective 11 B transverse relaxation time constants (T 2 ') hinder the acquisition of dephasing curves out to long recoupling durations. Application of REDOR recoupling to 17 O spins was found to produce significant dephasing without compromising the 11 B T 2 '. Comparison of experimental 11 B{ 17 O} RESPDOR curves to those of numerical simulations enabled the 17 O isotopic enrichment to be estimated. 2D 11 B{ 17 O} D-HMQC spectra were recorded with either 11 B or 17 O REDOR recoupling under a variety of radio frequency field conditions. Lastly, 2D 11 B{ 17 O} and 23 Na{ 17 O} D-HMQC spectra of an 17 O-enriched sodium borate glass were acquired to demonstrate the practical application of these heteronuclear correlation experiments to probe structural connectivity between two quadrupolar spins. Importantly, the high-field 2D 11 B– 17 O D-HMQC NMR spectrum revealed two unique 17 O sites correlating to 4-coordinate BO 4 ( [4] B), which were attributed to the [3] B–O– [4] B and [4] B–O– [4] B bridging O atoms. Furthermore, the heteronuclear correlation experiments outlined here should be applicable to a variety of quadrupolar spin pairs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

ZeroCAL: Eliminating Carbon Dioxide Emissions from Limestone’s Decomposition to Decarbonize Cement Production

Limestone (calcite, CaCO 3 ) is an abundant and cost-effective source of calcium oxide (CaO) for cement and lime production. However, the thermochemical decomposition of limestone (~800 °C, 1 bar) to produce lime (CaO) results in substantial carbon dioxide (CO 2(g) ) emissions and energy use, i.e., ~1 tonne [t] of CO 2 and ~1.4 MWh per t of CaO produced. Here, we describe a new pathway to use CaCO 3 as a Ca source to make hydrated lime (portlandite, Ca(OH) 2 ) at ambient conditions (p, T) while nearly eliminating process CO 2(g) emissions (as low as 1.5 mol. % of the CO 2 in the precursor CaCO 3 , equivalent to 9 kg of CO 2(g) per t of Ca(OH) 2 ) within an aqueous flowelectrolysis/ pH-swing process that coproduces hydrogen (H 2(g) ) and oxygen (O 2(g) ). Because Ca(OH) 2 is a zero-carbon precursor for cement and lime production, this approach represents a significant advancement in the production of zero-carbon cement. The Zero CArbon Lime (ZeroCAL) process includes dissolution, separation/recovery, and electrolysis stages according to the following steps: (Step 1) chelator (e.g., ethylenediaminetetraacetic acid, EDTA)-promoted dissolution of CaCO 3 and complexation of Ca 2+ under basic (>pH 9) conditions, (Step 2a) Ca enrichment and separation using nanofiltration (NF), which allows separation of the Ca-EDTA complex from the accompanying bicarbonate (HCO 3 – ) species, (Step 2b) acidity-promoted decomplexation of Ca from EDTA, which allows near-complete chelator recovery and the formation of a Ca-enriched stream, and (Step 3) rapid precipitation of Ca(OH) 2 from the Ca-enriched stream using electrolytically produced alkalinity. These reactions can be conducted in a seawater matrix yielding coproducts including hydrochloric acid (HCl) and sodium bicarbonate (NaHCO 3 ), resulting from electrolysis and limestone dissolution, respectively. Careful analysis of the reaction stoichiometries and energy balances indicates that approximately 1.35 t of CaCO 3 , 1.09 t of water, 0.79 t of sodium chloride (NaCl), and ~2 MWh of electrical energy are required to produce 1 t of Ca(OH) 2 , with significant opportunity for process intensification. This approach has major implications for decarbonizing cement production within a paradigm that emphasizes the use of existing cement plants and electrification of industrial operations, while also creating approaches for alkalinity production that enable cost-effective and scalable CO 2 mineralization via Ca(OH) 2 carbonation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Pressurized Gas-Driven Elemental Redistribution Enables Ultrastable PtNi Catalysts for Heavy-Duty Vehicles

Gas-driven element redistribution, characterized by the preferential enrichment of one element at the surface relative to the bulk, is frequently observed in multicomponent alloys. Using L1 0 -ordered PtNi as a model system, we reveal that gas pressure plays a critical role in governing adsorption-driven surface composition during annealing in reducing gases: low pressure favors Pt surface segregation, while high pressure facilitates Ni surface enrichment. In this study, we developed a high-pressure nitriding (HPN) strategy that modulates the surface structure and composition of PtNi catalysts. The resulting HPN-PtNi exhibits enhanced performance and durability in membrane electrode assemblies for heavy-duty fuel cell applications, maintaining a high current density of 1.19 A cm −2 at 0.7 V after 90,000 voltage cycles. Through a combination of experimental and theoretical analyses, we reveal that the HPN process forms additional stabilizing Ni−N bonds and induces elemental redistribution with Ni surface enrichment and a Ni-deficient Pt subsurface. These modifications alter the atomic coordination environment of the ordered PtNi phase. This work presents a generalizable strategy to design robust and high-performing Pt-based catalysts by controlling gas-pressure-driven elemental redistribution and dopant incorporation.

30 DIRECT ENERGY CONVERSION↗