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At least 631 records · Page 35
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Bio-inspired alula-based winglet design for enhanced heat transfer in high temperature fin-and-tube heat exchangers

Fin-and-tube heat exchangers (FTHEs) are widely used for high-temperature flue-gas heat recovery, but their performance is often limited by wake regions and non-uniform fin-surface temperatures. This study proposes and numerically evaluates four bio-inspired longitudinal vortex generator (VG) configurations in a high-temperature FTHE with flue-gas inlet temperature ∼1230 K: double-delta, curved double-delta, alula, and a new curved-alula geometry. The reference fin is not hydraulically plain; it already incorporates leading-edge separation columns and convex protrusions, so the alula-type winglets are assessed as downstream add-ons acting on a strongly disturbed flow. In a second step, perforations (one, two and three circular holes) are introduced into the curved-alula VGs to further tailor the flow field. Three-dimensional simulations with the Shear Stress Transpor (SST) $k - ω$ model, temperature-dependent flue-gas properties and conjugate conduction are carried out for gas-side Reynolds numbers $Re_g ≈ 8.0$ x $10^2 - 3.6$ x $10^3$ (mass flow rates 0.5 – 2.5 g/s), and the designs are compared in terms of surface heat flux, Nusselt number, friction factor and hydrothermal performance factor (HTPF). For this already-promoted fin, the additional downstream winglets provide moderate, incremental hydrothermal gains. At the highest Reynolds number, the best non-perforated design (curved-alula) increases surface heat flux from 1630.9 to 1794.7 kW/m² (∼ 10 % gain) and the Nusselt number from 227.6 to 242.6 (∼ 7 % gain), while the friction factor rises from 0.26 to about 0.30, yielding HTPF values close to unity (∼ 0.9 – 1.0). Introducing circular perforations into the curved-alula winglets acts mainly as a wake-bleeding refinement: the three-hole configuration provides a heat flux of 1824.7 kW/m² and a pressure drop of 127.9 Pa, with HTPF in the range ∼ 1.03 – 1.14 and a small (∼ 1 – 3 %) improvement over the solid curved-alula design. Flow-field analysis shows that the perforated curved-alula VGs shrink tube-wake regions, thin the thermal boundary layer and homogenize the fin-surface temperature (outlet-gas temperature ∼ 510 – 520 K and fin-surface temperature ∼ 420 – 421 K for the three-hole case). An optimal flue-gas mass flow rate of ∼ 1 g/s ($Re_g ≈ 1.5$ x $10^3$) is identified, beyond which additional heat-transfer gains are offset by rapidly increasing pressure losses. Overall, the results highlight that initial fin geometry and VG placement are as important as VG shape: alula-based winglets are expected to yield larger relative gains on simpler flat-fin layouts or when positioned closer to the fin leading edge and tube

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2021

Sol-gel synthesis of nano-scale, end-member albite feldspar (NaAlSi 3 O 8 )

Feldspars are the most abundant minerals in the Earth’s crust, and are also important constituents of many lunar rocks and some stony meteorites. Albite (NaAlSi 3 O 8 ) makes up the sodium corner of the feldspar ternary diagram (KAlSi 3 O 8 - NaAlSi 3 O 8 – CaAl 2 Si 2 O 8 ) and connects the alkali-feldspar and plagioclase binary joins. Synthesis of albite, however, has long been a problem, even at high temperatures and even at high pressures when dry. In fact, most successful syntheses require the combination of high-pressure, high-temperature, and hydrothermal environments. Here, this paper presents a sol–gel method of albite synthesis that requires hydrothermal processing followed by high-temperature recrystallization, but no high-pressure environments. This has the advantage of allowing synthesis of relatively large amounts of material and controlled elemental substitutions.

Albite↗
DOE OSTI2025

Process and environmental safety of thermochemical conversion of biomass

Biomass presents a promising opportunity for converting waste into valuable energy, fuels, and chemicals through various thermochemical processes, including hydrothermal carbonization, hydrothermal liquefaction, pyrolysis, gasification, and combustion. However, these processes operate under extreme conditions, introducing significant safety hazards that necessitate meticulous management to prevent accidents. This review discusses potential hazards, risk mitigation strategies, and safety management practices, emphasizing the importance of integrated safety measures into the design and operation of these processes. It also highlights the critical need for robust safety engineering and environmental management strategies tailored to each thermo-chemical process. As these processes transition from laboratory to industrial scale, there is an imperative to develop a clear and concise pathway for emerging industries to achieve regulatory compliance, achieve safety certification, and enable effective stewardship of potential fugitive emissions. By addressing safety and environmental concerns, stakeholders can optimize economic benefits, rural development, and achieve sustained domestic energy generation benefits offered by biomass conversion technologies. Further research on plant design optimization, operational safety, environmental evaluation standardization, and innovative waste management solutions will support the safe and effective scaling of these technologies, ultimately contributing to sustainable management and resource recovery.

09 - BIOMASS FUELS↗
DOE OSTI2021

Synthesis strategies toward improved ordering of [MnO 6 ] octahedra in tunnel structured 2 × 3 and 2 × 4 MnO 2

Improved homogeneity of tunnel size in Na-stabilized 2 × 3 and 2 × 4 MnO 2 structures was achieved by identifying and controlling critical synthesis parameters. 2 × 3 and 2 × 4 MnO 2 tunnel manganese oxide nanowires were obtained by hydrothermal treatment of Na-birnessite, a layered manganese oxide that undergoes a layer-to-tunnel transition under high pressure and temperature. Herein, the improved ordering of [MnO 6 ] octahedra is revealed via a combined analysis of X-ray diffraction patterns and scanning transmission electron microscopy images. Furthermore, we show that crystallinity of the Na-birnessite precursor and the chemical composition of the system during hydrothermal treatment are crucial for achieving the targeted size of the structural tunnels with adequate uniformity.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Tuning 3-D Nanomaterial Architectures Using Atomic Layer Deposition to Direct Solution Synthesis

The ability to synthesize nanoarchitected materials with tunable geometries provides a means to control their functional properties, with applications in biological, environmental, and energy fields. To this end, various bottom-up and top-down synthesis processes have been developed. However, many of these processes require prepatterning or etching steps, making them challenging to scale-up to complex, nonplanar substrates. Furthermore, the ability to integrate nanomaterials into hierarchical arrays with precise control of feature spacing and orientation remains a challenge. One approach to overcome these patterning challenges is the use of surface modification layers to guide the resulting geometry of nanomaterial architectures grown from the substrate. A powerful strategy to accomplish this is what we will refer to as “surface-directed assembly,” where the resulting geometric parameters (feature size, shape, orientation) are predetermined by the initial surface layer. In particular, the use of Atomic Layer Deposition (ALD) to form a surface layer, followed by solution-based growth processes, has the ability to synthesize architected structures with tunable geometries on complex, nonplanar surfaces. Over the past decade, we have reported a series of studies where surface-directed assembly is used to synthesize ZnO nanowires (NWs) on top of a variety of substrates. In this case, a thin film of ZnO is deposited onto the substrate using ALD, which can guide the NW diameter, spacing, and angular orientation with respect to the substrate by controlling epitaxial relationships. Furthermore, we have shown that by depositing a submonolayer overcoat of a secondary material (e.g., amorphous TiO 2 ), nucleation sites are partially blocked, which can further tune the spacing between nanowires while minimizing changes to their other geometric properties. This approach can be used to generate multilevel hierarchical structures, such as hyperbranched NW arrays with tunable control of each level of hierarchy using ALD. Finally, we have demonstrated that the tunable control of geometric parameters can be scaled-up to curved, nonplanar substrates. This highlights the power of ALD to conformally and uniformly deposit the seed layers on complex substrates with subnanometer precision. To complement these seeded hydrothermal approaches, we expanded this strategy to include conversion chemistry of the initial ALD seed layers. For example, by replacing ZnO with Al 2 O 3 as the seed layer without changing the hydrothermal growth conditions, Al–Zn layered-double hydroxide nanosheets can be formed instead of nanowires. In another example of conversion chemistry, a solution anion-exchange process was used to incorporate sulfur into ALD metal oxide films. In both of these conversion processes, the properties of the initial ALD film enabled tuning of the resulting nanostructure geometry. In this Account, we describe the use of ALD to guide the growth of diverse nanomaterial systems, with tunable control over their geometry and composition. We further show how these approaches can be used to tune functional properties for a range of applications, including superomniphobic surfaces, antibiofouling coatings, and photocatalysis. In conclusion, we conclude with an outlook on how the combination of ALD and solution synthesis can enable future directions in scalable nanomanufacturing to overcome the limitations of traditional top-down and bottom-up approaches.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

The Role of Water and Hydroxyl Groups in the Structures of Stetindite and Coffinite, MSiO 4 (M = Ce, U)

Orthosilicates adopt the zircon structure types ( I 4 1 /amd ), consisting of isolated SiO 4 tetrahedra joined by A-site metal cations, such as Ce and U. They are of significant interest in the fields of geochemistry, mineralogy, nuclear waste form development, and material science. Stetindite (CeSiO 4 ) and coffinite (USiO 4 ) can be formed under hydrothermal conditions despite both being thermodynamically metastable. Water has been hypothesized to play a significant role in stabilizing and forming these orthosilicate phases, though little experimental evidence exists. To understand the effects of hydration or hydroxylation on these orthosilicates, in situ high-temperature synchrotron and laboratory-based X-ray diffraction was conducted from 25 to ~850 °C. Stetindite maintains its I 4 1 /amd symmetry with increasing temperature but exhibits a discontinuous expansion along the a- axis during heating, presumably due to the removal of water confined in the [001] channels, which shrink against thermal expansion along the a -axis. Furthermore, additional in situ high-temperature Raman and Fourier transform infrared spectroscopy also confirmed the presence of the confined water. Coffinite was also found to expand nonlinearly up to 600 °C and then thermally decompose into a mixture of UO 2 and SiO 2 . A combination of dehydration and dehydroxylation is proposed for explaining the thermal behavior of coffinite synthesized hydrothermally. Additionally, we investigated high-temperature structures of two coffinite-thorite solid solutions, uranothorite (U x Th 1– x SiO 4 ), which displayed complex variations in composition during heating that was attributed to the negative enthalpy of mixing. Lastly, for the first time, the coefficients of thermal expansion of CeSiO 4 , USiO 4 , U 0.46 Th 0.54 SiO 4 , and U 0.9 Th 0.1 SiO 4 were determined to be α V = 14.49 × 10 –6 , 14.29 × 10 –6 , 17.21 × 10 –6 , and 17.23 × 10 –6 °C –1 , respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Improving Electronic Conductivity of Layered Oxides through the Formation of Two-Dimensional Heterointerface for Intercalation Batteries

Synthetic strategies for the improvement in electronic conductivities and electrochemical stabilities of transition metal oxide cathodes, which are limiting factors in the performance of commercial intercalation batteries, are required for next-generation, high-performance battery systems. Furthermore, the chemical preintercalation approach, consisting of a combined sequence of a sol–gel process, extended aging, and a hydrothermal treatment, is a versatile, wet synthesis technique that allows for the incorporation of a polar species between the layers of transition metal oxides. Here, formation of a layered 2D δ-C x V 2 O 5 · n H 2 O heterostructure occurs via chemical preintercalation of dopamine molecules between bilayers of vanadium oxide followed by the hydrothermal treatment of the precipitate, leading to carbonization of the organic molecules. The presence of carbon layers within the structure has been confirmed via a combined analysis of scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, Raman spectroscopy, X-ray photoelectron spectroscopy, electrochemical impedance spectroscopy, four-probe conductivity measurements, and scanning transmission electron microscopy characterization. 2D δ-C x V 2 O 5 · n H 2 O heterostructure electrodes demonstrated significantly improved electrochemical performance, particularly at higher current densities, in Li-ion cells. The heterostructure electrodes exhibited 75% of the capacity retention when the current was changed from 20 mA g –1 (206 mAh g –1 ) to 300 mA g –1 (155 mAh g –1 ), while the reference δ-V 2 O 5 · n H 2 O electrodes exhibited only 10% capacity retention in the same experiment. Remarkably, 2D δ-C x V 2 O 5 · n H 2 O heterostructure electrodes demonstrated significantly improved capacity retention (94% after 30 cycles) for bilayered vanadium oxide electrodes in Li-ion cells during galvanostatic cycling at 20 mA g –1 . The improved electrochemical performance, in both extended cycling and rate capability studies, of the 2D δ-C x V 2 O 5 · n H 2 O heterostructure electrodes in the Li-ion system is ascribed to the intermittent formation of carbon layers within the bilayered structure, which leads to increased electronic conductivity and improved structural stability of the heterostructure compared to the reference δ-V 2 O 5 · n H 2 O electrodes.

25 ENERGY STORAGE↗
DOE OSTI2021

Nanoscale Interfacial Smoothing and Dissolution during Unconventional Reservoir Stimulation Implications for Hydrocarbon Mobilization and Transport

Hydraulic fracturing of low-permeability rocks significantly enhances hydrocarbon production from unconventional reservoirs. However, fluid transport through low-permeability rocks, and the influence of geochemical transformations on pore networks, are poorly constrained. Mineral reactivity during interactions with injected water may alter the physical nature of the rock, which may affect hydrocarbon mobility. To assess alteration to the rock, we previously conducted a hydrothermal experiment that reacted cubed rock samples (1 cm3) with synthetic hydraulic fracturing fluid to simulate physicochemical reactivity during hydraulic fracturing. We analyzed unreacted and reacted rocks by small-angle neutron scattering and high-pressure mercury intrusion to determine how nanoscale (~1-1400 nm) pore networks of unconventional reservoir rocks are influenced by reaction with hydraulic fracturing injectates. We show that fluid-rock interactions have a two-fold influence on hydrocarbon recovery, promoting both hydrocarbon mobilization and transport. Pore-matrix interfaces smooth via removal of clay mineral surface asperities, reducing available surface area for hydrocarbon adsorption by ca. 12-75%. Additionally, hydraulic fracturing fluid-induced dissolution creates new pores with diameters ranging in size from 800-1400 nm, increasing the permeability of the rocks by a factor of 5-10. These two consequences of mineral dissolution act in concert to release hydrocarbons from the host rock and facilitate transport through the rock during unconventional reservoir production.

Herz-Thyhsen, Ryan↗
DOE OSTI2021

Atomic Layer Deposition with TiO2 for Enhanced Reactivity and Stability of Aromatic Hydrogenation Catalysts

Hydrogenation of aromatic molecules in fossil- and bio-derived fuels is essential for decreasing emissions of harmful combustion products and addressing growing concerns around urban air pollution. In this work, we used atomic layer deposition to significantly enhance the hydrogenation performance of a conventional supported Pd catalyst by applying an ultrathin coating of TiO2 in a scalable powder coating process. The TiO2-coated catalyst showed substantial gains in the conversion of multiple aromatic molecules, including a 5-fold improvement in turnover frequency versus the uncoated catalyst in the hydrogenation of naphthalene. This activity enhancement was maintained upon scaling the coating synthesis process from 3 to 100 g. Based on the results from Xray photoelectron spectroscopy, X-ray absorption spectroscopy, and computational modeling, the activity enhancement was attributed to ensemble effects resulting from partial TiO2 coverage of the Pd surface rather than fundamental changes to the Pd electronic structure. Additional durability testing confirmed that the TiO2 coating improved the thermal and hydrothermal stability of the catalyst as well as tolerance toward sulfur impurities in the reactant stream. Using an economic model of an industrial deep hydrogenation process, we found that an increase in catalyst activity or lifetime of 2× would justify even a relatively high estimate for the cost of TiO2 atomic layer deposition coatings at scale

atomic layer↗
DOE OSTI2022

Direct Synthesis of Highly Siliceous ZnO-FAU Zeolite with Enhanced Performance in Hydrocarbon Cracking Reactions

The hydrothermal stability and catalytic activity of zeolite Y (faujasite, FAU) is highly dependent on its composition. High silicon content is often desirable for catalytic applications; however, direct synthesis of faujasite with high silicon content (Si/Al > 2.5) is nontrivial. Here, we present an organic-free synthesis of FAU-type zeolite with Si/Al = 3.4 using zinc oxide as a modifier. A combination of spectroscopy and microscopy confirm that ZnO is well-distributed within zeolite pores as extra-framework species, and the nature of these species differs from bulk ZnO and framework zinc in Zn-FAU crystals. We demonstrate that the increased Si/Al ratio leads to improved hydrothermal stability, while catalytic cracking of 1-hexene and cumene show that ZnO-FAU exhibits significantly longer lifetime compared to in-house and commercial zeolite Y. Collectively, this study presents a facile and efficient method to prepare more siliceous FAU with enhanced catalytic performance.

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

Overview of the Morphology and Chemistry of Diagenetic Features in the Clay-Rich Glen Torridon Unit of Gale Crater, Mars

The clay-rich Glen Torridon region of Gale crater, Mars, was explored between sols 2300 and 3007. Here, we analyzed the diagenetic features observed by Curiosity, including veins, cements, nodules, and nodular bedrock, using the ChemCam, Mastcam, and Mars Hand Lens Imager instruments. We discovered many diagenetic features in Glen Torridon, including dark-toned iron- and manganese-rich veins, magnesium- and fluorine-rich linear features, Ca-sulfate cemented bedrock, manganese-rich nodules, and iron-rich strata. We have characterized the chemistry and morphology of these features, which are most widespread in the higher stratigraphic members in Glen Torridon, and exhibit a wide range of chemistries. These discoveries are strong evidence for multiple generations of fluids from multiple chemical endmembers that likely underwent redox reactions to form some of these features. In a few cases, we may be able to use mineralogy and chemistry to constrain formation conditions of the diagenetic features. For example, the dark-toned veins likely formed in warmer, highly alkaline, and highly reducing conditions, while manganese-rich nodules likely formed in oxidizing and circumneutral conditions. We also hypothesize that an initial enrichment of soluble elements, including fluorine, occurred during hydrothermal alteration early in Gale crater history to account for elemental enrichment in nodules and veins. The presence of redox-active elements, including Fe and Mn, and elements required for life, including P and S, in these fluids is strong evidence for habitability of Gale crater groundwater. Hydrothermal alteration also has interesting implications for prebiotic chemistry during the earliest stages of the crater’s evolution and early Mars.

58 GEOSCIENCES↗
DOE OSTI2023

Using Dark Fiber and Distributed Acoustic Sensing to Characterize a Geothermal System in the Imperial Valley, Southern California

The Imperial Valley, CA, is a tectonically active transtensional basin located south of the Salton Sea; the area hosts numerous geothermal fields, including significant hidden hydrothermal resources without surface manifestations. Development of inexpensive, rugged, and highly sensitive exploration techniques for undiscovered geothermal systems is critical for accelerating geothermal power deployment as well as unlocking a low-carbon energy future. We present a case study utilizing distributed acoustic sensing (DAS) and ambient noise interferometry for geothermal reservoir imaging, utilizing unlit fiber-optic telecommunication infrastructure (dark fiber). The study exploits two days of passive DAS data acquired in early November 2020 over a ~28-km section of fiber from Calipatria, CA to Imperial, CA. We apply ambient noise interferometry to retrieve coherent signals from DAS records and develop a bin stacking technique to attenuate the effects from persistent localized noise sources and to enhance retrieval of coherent surface waves. As a result, we are able to obtain high-resolution two-dimensional (2D) S wave velocity ($V_s$) structure to 3 km depth, based on joint inversion of both the fundamental and higher overtones. We observe a previously unmapped high $V_s$ and low $V_p$/$V_s$ ratio feature beneath the Brawley geothermal system, which we interpret to be a zone of hydrothermal mineralization and lower porosity. This interpretation is consistent with a host of other measurements including surface heat flow, gravity anomalies, and available borehole wireline data. These results demonstrate the potential utility of DAS deployed on dark fiber for geothermal system exploration and characterization in the appropriate geological settings.

Vp/Vs imaging↗
DOE OSTI2023

Thermally Significant Fluid Seepage Through Thick Sediment on the Juan de Fuca Plate Entering the Cascadia Subduction Zone

We use heat flux measurements colocated with seismic reflection profiles over a buried basement high on the Juan de Fuca plate ∼25 km seaward of the deformation front offshore Oregon to test for the presence of hydrothermal circulation in the oceanic crust. We also revisit heat flux data crossing a buried basement high ∼25 km seaward of the deformation front ∼150 km north, offshore Washington. Seafloor heat flux is inversely correlated with sediment thickness, consistent with vigorous hydrothermal circulation in the basement aquifer homogenizing temperatures at the top of the basement. Heat flux immediately above the summit of the basement highs is greater than expected solely from conduction. Fluid seepage at rates of ∼2.6–5.4 cm yr −1 in a 1–1.5 km-wide conduit through ∼800–1,300 m thick sediment sections above these basement highs can explain these observations. Observations of thermally significant fluid seepage through sediment >225 m thick on oceanic crust are unprecedented. High sediment permeability, high fluid overpressure in the basement, or a combination of both is required to drive fluid seepage at the observed rates. We infer that rapid seepage occurs because the basement highs rise above the low permeability basal sediment with their tops protruding into the base of high permeability Nitinat or Astoria Fan sediment. Seepage from basement highs penetrating into the submarine fans can affect the thermal state of crust entering the subduction zone.

58 GEOSCIENCES↗
DOE OSTI2023

The Thermal Plumbing System of Stromboli Volcano, Aeolian Islands (Italy) Inferred From Electrical Conductivity and Induced Polarization Tomography

Abstract We performed the first 3D island‐scale tomography of the electrical conductivity of Stromboli volcano (Aeolian Islands, Italy) using 2D acquisition lines (37.2 km) and a total of 18,880 measurements and 2,402 unique electrode locations. This 3D data set was inverted using a Gauss‐Newton algorithm, parallel‐processing on an unstructured tetrahedral mesh containing 678,420 finite‐element nodes and 3,580,145 elements to account for the topography of the volcanic island. The tomogram exhibits a conductive body (10 −2 –1.0 S m −1 ) consistent with the location of CO 2 and temperature anomalies observed at the ground surface. It corresponds to the hydrothermal system with high electrical conductivity associated with alteration. In order to confirm this interpretation, a 2.5D large‐scale induced polarization tomography was performed crossing the volcano. The joint interpretation of the conductivity and normalized chargeability is done with a petrophysical model previously tested and verified at both shield‐ and strato‐volcanoes. This model implies that alteration (through the effect of the cation exchange capacity associated with clay minerals and zeolites) plays a strong role in both controlling the electrical conductivity and normalized chargeability at Stromboli volcano. A temperature tomogram, derived from the geoelectrical measurements, is consistent with surface temperature anomalies and the Very Long Period (VLP) seismicity related to the mild‐explosive activity. This survey displays at 600 m a.s.l. a lateral shift in the highest temperature location, also corresponding to the source of VLP seismicity. Structural boundaries have a major role in the hottest hydrothermal fluids rising below the active crater terrace of Stromboli volcano.

58 GEOSCIENCES↗
DOE OSTI2024

Formation of a Large Cold Groundwater Mantle Helium Anomaly and High Temperature Geothermal Resources in Response to Bimodal Magmatism Near Roosevelt Hot Springs and Utah FORGE, Milford Valley, Southwest Utah

Abstract A large mantle helium anomaly and separate domains of high heat flow are the predominant manifestations of bimodal magmatic activity in the Milford valley. The mantle helium anomaly (1.9–2.6 R/Ra) covers 270 km 2 and is subdivided into two separated domains: a cold shallow groundwater regime and high temperature hydrothermal activity. The zone of anomalous heat flow covers >100 km 2 and is also subdivided into two adjacent domains, comprising hydrothermal activity at Roosevelt Hot Springs (RHS) (3–7 W/m 2 ) and conductive heat flow (100–180 mW/m 2 ). While the transfer of heat and mantle helium at RHS are coupled, heat and helium transfer are decoupled in the adjacent cold groundwater regime to the west. Both the mantle helium and geothermal anomalies are attributed to recent mafic‐felsic magmatic intrusions of >400 km 3 , however, the absence of volcanic eruptions <500,000 years indicates magmas stall before rising to shallow crustal level <10 km depth. Deep level magmatism produces a felsic composition melt, which is inferred to be responsible for the widespread and near uniform range of diluted mantle helium values. A thick and impermeable mass of crystalline granitic basement rock at the mid‐crustal level divides the ascent of mantle helium into separate flow paths. It may also impede the rise of buoyant magma trapping thermal energy that facilitates partial melting, slow cooling, and development of a thick thermal aureole. Partitioning of convective and conductive thermal regimes and independent flow paths supplying deeply derived helium characterize the development of a large long‐lived magma‐related geothermal system.

Geochemistry & Geophysics↗
DOE OSTI2021

Uranium carbonate complexes demonstrate drastic decrease in stability at elevated temperatures

Quantitative understanding of uranium transport by high temperature fluids is crucial for confident assessment of its migration in a number of natural and artificially induced contexts, such as hydrothermal uranium ore deposits and nuclear waste stored in geological repositories. An additional recent and atypical context would be the seawater inundated fuel of the Fukushima Daiichi Nuclear Power Plant. Given its wide applicability, understanding uranium transport will be useful regardless of whether nuclear power finds increased or decreased adoption in the future. The amount of uranium that can be carried by geofluids is enhanced by the formation of complexes with inorganic ligands. Carbonate has long been touted as a critical transporting ligand for uranium in both ore deposit and waste repository contexts. However, this paradigm has only been supported by experiments conducted at ambient conditions. We have experimentally evaluated the ability of carbonate-bearing fluids to dissolve (and therefore transport) uranium at high temperature, and discovered that in fact, at temperatures above 100 °C, carbonate becomes almost completely irrelevant as a transporting ligand. This demands a re-evaluation of a number of hydrothermal uranium transport models, as carbonate can no longer be considered key to the formation of uranium ore deposits or as an enabler of uranium transport from nuclear waste repositories at elevated temperatures.

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

Barrierless nucleation in glassy precursors drives zeolite formation

Zeolites are crystalline, microporous silicates widely used in catalysis and separations, yet the molecular mechanisms of their formation remain unresolved. Experiments indicate that hydrothermal synthesis of silica zeolites from clear solution proceeds through amorphous nanoaggregates that gradually develop zeolite order in an apparently continuous amorphous to crystal transformation. Here, we combine molecular simulations with advanced algorithms that identify zeolite order and computer vision to elucidate the pathway from clear solution to zeolite nanocrystal. We show that at conditions of hydrothermal synthesis of silica zeolites, the transformation of precursor aggregate into zeolite is not limited by nucleation barriers but by the slow dynamics of reorganization in the glassy precursor matrix. The negligible nucleation barriers result in spinodal-like crystallization that leads to a gradual formation of a mosaic of small crystallites that explain the seemingly continuous character of zeolite crystallization and the catalytic activity of X-ray amorphous, protozeolites and embryonic zeolites. We find that zeolite-like porosity and short-range order emerge early within glassy precursors, well before crystallinity is detected in transmission electron microscopy (TEM) images or X-ray diffraction. The nanoaggregate’s temperature-size phase diagram reveals a convergence of the zeolite–amorphous equilibrium and maximum crystallization rate at ~3 nm diameter nanoparticle diameters and ~200 °C. This convergence signals the termination of the first-order amorphous-to-zeolite transition. Our results provide a unifying framework for understanding nucleation of silica zeolites from solution and suggest that barrierless nucleation may govern the formation of other nanoparticle systems, including minerals and oxides synthesized far below their bulk melting points.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Water Migration and Swelling in Engineered Barrier Materials for Radioactive Waste Disposal

Deep, underground repositories are needed to isolate radioactive waste from the biosphere. Because bentonite is an integral component of many multibarrier repository systems, information on the hydraulic behavior of bentonite is crucial for modeling the long-term viability of such systems. In this paper the hydraulic behavior of bentonite samples was analyzed as a function of aggregate size, and samples were subjected to hydrothermal treatments involving contact with NaCl, KCl, and deionized water. Neutron and X-ray imaging were used to quantify water sorption into packed bentonite samples and bentonite swelling into the water column. The distance between the original clay-water interface and the wetting front was determined as a function of time. Average water uptake exhibited a square-root-of-time dependence in freshly prepared samples, but more variable rates were observed for samples previously in contact with water. The radiography was supported by small-angle neutron scattering analysis and ultra-small-angle neutron scattering analysis of aggregate size distributions and by inelastic neutron scattering to understand the physicochemical environment of the sorbed water. Results showed that hydrothermal treatment with KCl had the greatest effect of increased water transport in the bentonite, possibly as a result of the interaction of K + with smectite layers in the clay.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗