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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.

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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Structural evolution of two-dimensional silicates using a “bond-switching” algorithm

Silicates are the most abundant materials in the earth's crust. In recent years, two-dimensional (2D) versions of them grown on metal supports (known as bilayer silicates) have allowed their study in detail down to the atomic scale. These structures are self-containing. Furthermore, they are not covalently bound to the metal support but interact with it through van der Waals forces. Like their three-dimensional counterparts, the 2D-silicates can form both crystalline and vitreous structures. Furthermore, the interconversion between vitreous to crystalline structures has been experimentally observed at the nanoscale. While theoretical work has been carried out to try to understand these transformations, a limitation for ab initio methods, and even molecular dynamics methods, is the computational cost of studying large systems and long timescales. In this work, we present a simple and computationally inexpensive approach, that can be used to represent the evolution of bilayer silicates using a bond-switching algorithm. This approach allows reaching equilibrium ring size distributions as a function of a parameter that can be related to the ratio between temperature and the energy required for the bond-switching event. The ring size distributions are compared to experimental data available in the literature.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Silicate minerals as a direct source of limiting nutrients: Siderophore synthesis and uptake promote ferric iron bioavailability from olivine and microbial growth

Iron is a micronutrient critical to fundamental biological processes including respiration and photosynthesis, and it can therefore impact primary and heterotrophic productivity. Yet in oxic environments, iron is highly insoluble, rendering it, in principle, unavailable as a nutrient for biological growth. Life has “solved” this problem via the invention of iron chelates, known as siderophores, that keep iron available for microbial productivity. In this work, we examined the impact of siderophore synthesis on the speciation, mobility, and bioavailability of iron from rock-forming silicate minerals—shedding new light on the mechanisms by which microbes use mineral substrates to support primary productivity, as well as the consequent effects on silicate dissolution. Growth experiments were performed with Shewanella oneidensis MR-1 in an oxic, iron-depleted minimal medium, amended with olivine minerals as the sole source of iron. Experiments included the wild-type strain MR-1, and a siderophore synthesis gene deletion mutant strain (ΔMR-1). Relative to MR-1, ΔMR-1 exhibited a very pronounced growth penalty and an extended lag phase. However, substantial growth of ΔMR-1, comparable to MR-1 growth, was observed when the mutant strain was provided with siderophores in the form of either filtrate from a well-grown MR-1 culture, or commercially available deferoxamine. These observations suggest that siderophores are critical for S. oneidensis to acquire iron from olivine. Growth-limiting concentrations of deferoxamine amendments were observed to be ≤5–10 µM, concentrations significantly lower than previously recorded as necessary to impact mineral dissolution rates. X-ray photoelectric spectroscopy analyses of the incubated olivine surfaces suggest that siderophores deplete mineral surface layers of ferric iron. Combined, these results demonstrate that low micromolar concentrations of siderophores can effectively mobilize iron bound within silicate minerals, supporting very significant biological growth in limiting environments. The specific mechanism would involve siderophores removing a protective layer of nanometer-thick iron oxides, enhancing silicate dissolution and nutrient bioavailability.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

29Si solid state NMR and Ti K-edge XAFS pre-edge spectroscopy reveal complex behavior of Ti in silicate melts

Abstract An understanding of the mechanisms of Ti is incorporation into silicate glasses and melts is critical for the field of petrology. Trace-element thermobarometry, high-field-strength element partitioning, and the physical properties of magmas are all be influenced by Ti incorporation into glasses and changes therein in response to changes in composition and temperature. In this study, we combine 29 Si solid state NMR and Ti K -edge XAFS spectroscopy to investigate how Ti is incorporated into quenched Na-silicate glasses, and the influence of Ti on the structure of silicate species in these glasses. 29 Si NMR shows that in both Ti-bearing Na 2 O•4SiO 2 (NS4) and Na 2 O•8SiO 2 (NS8) glasses, increasing the amount of Ti in the melt results in a shift of Si Q 4 peak in the 29 Si NMR spectra reflecting Ti nearest neighbors for Si in Q 4 speciation. The Ti XAFS results from NS8 glass indicate that Ti is primarily incorporated in [5]-fold coordination. At higher Ti content, there is a shift of the XAFS pre-edge feature suggesting mixing of [4]-fold Ti into the spectra. Combined, the 29 Si NMR and XAFS pre-edge data are consistent with Ti incorporation as isolated [5] Ti atoms and the formation of [5] Ti clusters at relatively low Ti concentrations, with no evidence for Ti–Na interactions as suggested by previous studies. As the Ti content increases, the Ti atoms begin to occupy 4-fold coordinated sites interacting primarily with Si in Q 4 speciation (no significant Na– [4] Ti bonding). The internal consistency of these two techniques provides a uniquely complete snapshot of the complexity of Ti incorporation in silicate melts and underlies the importance of understanding Ti incorporation mechanisms in natural magmatic systems.

Ackerson, Michael R.↗
DOE OSTI2020

Carbonation of metal silicates for long-term CO2 sequestration

In a preferred embodiment, the invention relates to a process of sequestering carbon dioxide. The process comprises the steps of: (a) reacting a metal silicate with a caustic alkali-metal hydroxide to produce a hydroxide of the metal formerly contained in the silicate; (b) reacting carbon dioxide with at least one of a caustic alkali-metal hydroxide and an alkali-metal silicate to produce at least one of an alkali-metal carbonate and an alkali-metal bicarbonate; and (c) reacting the metal hydroxide product of step (a) with at least one of the alkali-metal carbonate and the alkali-metal bicarbonate produced in step (b) to produce a carbonate of the metal formerly contained in the metal silicate of step (a).

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

Effect of second Si–O vibrational overtones/combinations on quantifying water in silicate and silica minerals using infrared spectroscopy, and an experimental method for its removal

Infrared spectroscopy (IR) is the most widely used analytical tool to quantify trace water in silicate and silica minerals. A prerequisite for highly accurate IR measurements of trace water is a good understanding of the effect of the second Si–O vibrational overtones/combination bands (2nd Si–O VOCBs) on the water peaks. Silicate and silica minerals can be divided as isolated (Q 0 ), paired (Q 1 ), ring (Q 2 ), chain (Q 1 or Q 2 ), sheet (Q 3 ) and framework (Q 4 ) structures according to the polymerization of their SiO 4 tetrahedral units, and the 2nd Si–O VOCBs of these different structural types attain different vibrational features which are expected to affect the water peaks to different extents. Here, we selected olivine (Q 0 ) and α-quartz (Q 4 ) as two endmember-like structural examples, performed extensive IR measurements on both pristine and heat-treated thin sections prepared for these two minerals, and explored the vibrational features of the 2nd Si–O VOCBs. In this work, we have found that the 2nd Si–O VOCBs are well separated from the water peaks in olivine, but severely overlap with the water peaks in α-quartz, confirming the different roles that the 2nd Si–O VOCBs play in quantifying trace water in silicate and silica minerals with different structural polymerizations. To remove the influence of the 2nd Si–O VOCBs (or any other species rather than water), an experimental protocol has been successfully developed, as approved by some fundamental equations and verified by the data of α-quartz in the literature. This development should lead to significant accuracy improvement in quantifying trace amounts of water in Earth and planetary materials.

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

Iron incorporation in synthetic precipitated calcium silicate hydrates

Effect of Fe{sup 3+} on the precipitation of synthetic calcium silicate hydrates (C-S-H) under controlled conditions has been evaluated. Using extremely basic either initial calcium nitrate or sodium silicate solutions (pH > 11), incipient formation of ferrihydrite in both solutions was observed. In this case both C-S-H and iron-containing siliceous hydrogarnet are formed. For pH < 11, ferrihydrite was absent. Only C-S-H is formed. The presence of magnetically dilute Fe{sup 3+} in the C-S-H was shown by EPR and the atomic Fe/Si ratio of the C-S-H phase was shown to be between 0.01% and 0.1% by measuring and modelling the {sup 29}Si spin-lattice relaxation in NMR experiments. A uniform distribution of Fe{sup 3+} when C-S-H precipitates in the absence of initial ferrihydrite is obtained. When initial ferrihydrite is present, a non-uniform distribution of Fe{sup 3+} is found and the concentration of Fe{sup 3+} in the C-S-H is merely 3% of the overall iron concentration, suggesting the initial formation of ferrihydrite restricts the incorporation of iron into C-S-H.

36 MATERIALS SCIENCE↗
DOE OSTI2023

The effect of composition, temperature and pressure on the oxidation state and coordination environment of copper in silicate melts

Copper is a redox variable element that may occur as Cu 0 , Cu + , and Cu 2+ in the Earth’s crust. The oxidation state will affect its partitioning between coexisting minerals, melts and fluids and hence its behaviour in magmatic processes. Copper bearing silicate glasses were quenched from melts with 23 synthetic compositions (19 CaO-Na 2 O-MgO-Al 2 O 3 -SiO 2 (CNMAS), two “granites” containing K 2 O ± H 2 O, and Fe-bearing “MORB” and “andesite”) equilibrated at oxygen fugacities (fO 2 ), expressed in log units relative to the fayalite-magnetite-quartz (FMQ) buffer, ranging from −0.7 to 14, temperatures from 900 to 1500 °C and pressures from 0 to 2.5 GPa. Cu K-edge X-ray absorption near edge structure (XANES) spectra were recorded from the glasses and a pre-edge feature in the XANES spectra was found to scale with the proportion of Cu + . Cu + /ΣCu (where ΣCu = Cu + + Cu 2+ ) was quantified by fitting the intensity of the pre-edge feature as a function of fO 2 to the thermodynamically expected relationship. Cu + /ΣCu was found to only weakly depend on melt composition, with more basic melts (e.g., basalts rather than granites) preferentially stabilising Cu 2+ . Increasing temperature stabilises Cu + , while increasing pressure had little effect on Cu + /ΣCu in CNMAS melts but preferentially stabilised Cu 2+ in granite melts. Cu + /ΣCu can be predicted in silicate melts by the empirical equation: log(Cu 2+ /Cu + ) = 0.25(ΔFMQ + 8.58 − 25050/T + 940P/T – 0.02P) − 4.73 + 5400/T + 1.99Λ + (280P – 90P2) where T is temperature in K, P is pressure in GPa and is the optical basicity of the composition. The effects of fO 2 , melt composition, temperature and pressure on Cu + /ΣCu indicate that Cu + will be the dominant oxidation state in terrestrial silicate melts (e.g., Cu + /ΣCu = 99% in an andesitic melt at 900 °C, 1 GPa and ΔFMQ = 1). The electron exchange reaction Cu 2+ + Fe 2+ → Cu + + Fe 3+ occurs on cooling and, given the abundance of Fe in natural melts, the oxidation state of Cu in natural glasses is unlikely to correspond to that in the original melt.

Copper↗
DOE OSTI2020

Feasibility of using reactive silicate particles with temperature-responsive coatings to enhance the security of geologic carbon storage

The large-scale deployment of geologic carbon storage will require minimizing the risk of CO 2 leakage. Here we report on a novel strategy to seal leakage pathways by injecting functionalized reactive calcium silicate (CaSiO 3 ) particles. The particles consist of a mineral silicate core within a temperature-sensitive Poly(N,N-dimethylaminoethyl methacrylate) coating that limits contact between the core and the surrounding CO 2 (aq) above a switching temperature making them relatively unreactive deep in the subsurface. If the CO 2 leaks to shallower depths and cooler temperatures, the coatings would extend and enable the silicate core to react with CO 2(aq) to form solid carbonate precipitates that reduce the permeability of the fracture or flow path. A combined laboratory- and simulation-based investigation was conducted to explore key early-stage research questions related to the feasibility of this leakage management strategy. Sand columns were injected with either coated or uncoated CaSiO 3 particles and the permeability was measured before and after exposure to CO 2 . Experiments were conducted at 35 °C and 70 °C, a range that spans the switching temperature for the coatings. Results show that at the cooler temperature the coating effectively enabled reaction and permeability reduction. At higher temperatures, the coated particles limited mineral carbonation and the permeability decrease was minimal compared to columns with uncoated particles. Here, the morphology and location of the precipitates provides insight about permeability evolution. Model simulations of 2D radial particle transport from an injection point provided insight into the effects of particle size, coating properties, and concentrations of particles in several representative rock formations.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Electrochemical Reduction Pathways from Goethite to Green Iron in Alkaline Solution with Silicate Additive

Energy-efficient and low-temperature iron electrolysis in alkaline solutions is a low-cost and sustainable ironmaking process with zero-carbon emissions when renewable electrical sources are involved. However, its implementation is hindered by electrochemically inert Fe 3 O 4 and parasitic H 2 gas formation during the electrochemical reduction process, resulting in the low energy efficiency of iron electrolysis. Here, we further explore the potential of electrochemical reduction of goethite (FeOOH) by employing a low concentration of silicate additive in an alkaline solution to mitigate Fe 3 O 4 accumulation and H 2 generation. Electrochemical measurements coupled with operando X-ray diffraction and X-ray absorption spectroscopy suggested FeOOH → Fe 3 O 4 → Fe(OH) 2 → Fe reduction pathways. Interestingly, a poorly crystalline or amorphous Fe(OH) 2 phase formed in the NaOH/silicate mixed electrolyte, possibly due to the inhibitive effect of silicate on water and ion transport, which eventually contributed to the improved reduction of Fe 3 O 4 , also supported by atomistic simulations. This work demonstrates the potential for silicate as a low-cost and effective electrolyte additive to improve room-temperature green iron formation via electrolysis.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Nanoconfinement matters in humidified CO 2 interaction with metal silicates

With enigmatic observations of enhanced reactivity of wet CO 2 -rich fluids with metal silicates, the mechanistic understanding of molecular processes governing carbonation proves critical in designing secure geological carbon sequestration and economical carbonated concrete technologies. Here, we use the first principle and classical molecular simulations to probe the impact of nanoconfinement on physicochemical processes at the rock–water–CO 2 interface. We choose nanoporous calcium–silicate–hydrate (C–S–H) and forsterite (Mg 2 SiO 4 ) as model metal silicate surfaces that are of significance in cement chemistry and geochemistry communities, respectively. We show that while a nanometer-thick interfacial water film persists at unsaturated conditions consistent with in situ infrared spectroscopy, the phase behavior of the water–CO 2 mixture changes from its bulk counterpart depending on the surface chemistry and nanoconfinement. We also observe enhanced solubility at the interface of water and CO 2 phases, which could amplify the CO 2 speciation rate. Additionally, through free energy calculations, we show that CO 2 could be found in a metastable state near the C–S–H surface, which can potentially react with surface water and hydroxyl groups to form carbonic acid and bicarbonate. These findings support the explicit consideration of nanoconfinement effects in reactive and non-reactive pore-scale processes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Noble gas incorporation into silicate glasses: implications for planetary volatile storage

Incorporation of small molecules in silicate melts may provide an important mechanism for storing noble gases in the deep Earth, yet the means by which chemically inert noble gases enter and are retained in silica-based materials is not understood. High pressure, room temperature sound velocity measurements on silica and natural basalt glasses in different pressure-transmitting media reveal that neon enters the structure of silicate glasses and enhances their elastic strengths, whereas an ethanol-methanol mixture does not. Combined with literature data, we found the incorporation of small molecules into silica and basalt glasses is controlled by the void size distribution of the glass and size of the molecules. Pressure primarily reduces the size of noble gases, thereby increasing their solubilities in silicate melts and glasses.

58 GEOSCIENCES↗
DOE OSTI2023

Multi–Step Nucleation of a Crystalline Silicate Framework via a Structurally Precise Prenucleation Cluster

Hierarchical nucleation pathways are ubiquitous in the synthesis of minerals and materials. In the case of zeolites and metal–organic frameworks, pre-organized multi-ion “secondary building units” (SBUs) have been proposed as fundamental building blocks. However, detailing the progress of multi-step reaction mechanisms from monomeric species to stable crystals and defining the structures of the SBUs remains an unmet challenge. Furthermore, combining in situ nuclear magnetic resonance, small-angle X-ray scattering, and atomic force microscopy, we show that crystallization of the framework silicate, cyclosilicate hydrate, occurs through an assembly of cubic octameric Q 3 8 polyanions formed through cross-linking and polymerization of smaller silicate monomers and other oligomers. These Q 3 8 are stabilized by hydrogen bonds with surrounding H 2 O and tetramethylammonium ions (TMA + ). When Q 3 8 levels reach a threshold of ≈32 % of the total silicate species, nucleation occurs. Further growth proceeds through the incorporation of [(TMA) x (Q 3 8 )•n H 2 O] (x–8) clathrate complexes into step edges on the crystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

A silicate dynamo in the early Earth

The Earth’s magnetic field has operated for at least 3.4 billion years, yet how the ancient field was produced is still unknown. The core in the early Earth was surrounded by a molten silicate layer, a basal magma ocean that may have survived for more than one billion years. Here we use density functional theory-based molecular dynamics simulations to predict the electrical conductivity of silicate liquid at the conditions of the basal magma ocean: 100–140 GPa, and 4000–6000 K. We find that the electrical conductivity exceeds 10,000 S/m, more than 100 times that measured in silicate liquids at low pressure and temperature. The magnetic Reynolds number computed from our results exceeds the threshold for dynamo activity and the magnetic field strength is similar to that observed in the Archean paleomagnetic record. We therefore conclude that the Archean field was produced by the basal magma ocean.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Silicon ion radiation as a viable surrogate for emulating neutron radiation damage in silicates

Abstract Nuclear power plants are aging around the world, and a precise assessment of irradiation damage in their components is needed. One key component, concrete, and specifically the silicates in its aggregates, can undergo significant expansion upon neutron radiation, which can lead to cracking and, ultimately, structural failure. However, assessing and predicting the extent of damage via neutron radiation is challenging due to reasons such as residual radioactivity and, most importantly, the high time involved. Here, we evaluate whether ion radiation can be a viable surrogate. Specifically, by employing Si 2+ ion radiations and a comprehensive multi-modal imaging protocol, we report mineral-specific responses for key silicates such as quartz, albite, anorthite, and microcline. We find that 10 MeV Si 2+ ions result in mineral expansions that are remarkably comparable to neutron radiation equivalent expansions (R 2 = 0.86, RMSE = 1.29%), opening up pathways towards rapid assessment of silicates subject to irradiation.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Radiation damages the silicates present in polyphasic mineral aggregates causing concrete’s degradation

While many U.S. nuclear power plants have submitted Subsequent License Renewal Application to operate beyond 60 years, others are already considering Operations Beyond Eighty years. In such cases, concrete biological shields are exposed to neutron and gamma radiation exceeding prescribed thresholds. Radiation-induced volumetric expansion (RIVE), extensively studied in single crystals, may also contribute to the degradation of polycrystalline aggregates. Since minerals differ in atomic structure and chemistry, radiation can affect them in distinct ways. This study examines quartzite, marble, and limestone to evaluate how irradiation affects their physical attributes and chemical reactivity. Results show crystalline silicates experience significant RIVE damage and enhanced reactivity in alkaline solutions compared to non-irradiated phases. Enhanced intra- and inter-granular dissolution could compromise aggregate integrity. An empirical correlation links silicate dissolution rate to atomic constraints (density, rigidity) and radiation dose, providing a predictive framework for estimating changes in silicate aggregate properties within radiation-exposed concrete.

Bouissonnié, Arnaud [Univ. of California, Los Ange↗
DOE OSTI2022

Incorporation of 16 O-rich anhydrous silicates in the protolith of highly hydrated asteroid Ryugu

The abundant phyllosilicate and carbonate minerals characterizing most of the returned particles from asteroid Ryugu suggest a history of extensive aqueous alteration on its parent body, similar to the rare mineralogically altered, but chemically primitive, CI (Ivuna-type) chondrite meteorites. Particle C0009 differs mineralogically from other Ryugu particles examined so far by containing anhydrous silicates at a level of ~0.5 vol%, and thus can help shed light on the unaltered original materials that constituted Ryugu’s protolith. In situ oxygen isotope measurements of the most Mg-rich olivine and pyroxene in C0009 reveal two populations of Δ 17 O: –25‰ to –15‰ and –8‰ to –3‰. The former and the latter populations correlate well with silicate morphologies similar to those seen in amoeboid olivine aggregates and chondrule phenocrysts, respectively, both of which are abundant in less aqueously altered carbonaceous chondrites. Here, this result also highlights the presence of olivine with Δ 17 O close to the solar value in either a CI chondrite or an asteroid with CI-chondrite characteristics, and provides strong evidence that amoeboid olivine aggregates and Mg-rich chondrules accreted into Ryugu’s protolith. Our data also raise the possibility that the protoliths of CI and other carbonaceous chondrites incorporated similar anhydrous silicates.

58 GEOSCIENCES↗
DOE OSTI2023

Spectroscopic identification of Ca-bearing uranyl silicates formed in C–S–H systems

Portland cement-based grouts used for radioactive waste immobilisation contain a Ca- and Si-rich binder phase, known as calcium–silicate–hydrate (C–S–H). Depending on the blend of cement used, the Ca/Si ratio can vary considerably. A range of C–S–H minerals with Ca/Si ratios from 0.6 to 1.6 were synthesised and contacted with aqueous U(VI) at 0.5 mM and 10 mM concentrations. Solid-state 29 Si MAS-NMR spectroscopy was applied to probe the Si coordination environment in U(VI)-contacted C–S–H minerals and, in conjunction with U L III -edge X-ray absorption spectroscopy analysis, inferences of the fate of U(VI) in these systems were made. At moderate or high Ca/Si ratios, uranophane-type uranyl silicates or Ca-uranates dominated, while at the lowest Ca/Si ratios, the formation of a Ca-bearing uranyl silicate mineral, similar to haiweeite (Ca[(UO 2 ) 2 Si 5 O 12 (OH) 2 ]·3H 2 O) or Ca-bearing weeksite (Ca 2 (UO 2 ) 2 Si 6 O 15 ·10H 2 O) was identified. This study highlights the influence of Ca/Si ratio on uranyl sequestration, of interest in the development of post-closure safety models for U-bearing radioactive waste disposal.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Behavior of soda-lime silicate glass under laser-driven shock compression up to 315 GPa

Shock experiments give a unique insight into the behavior of matter subjected to extremely high pressures and temperatures. Understanding the behavior of materials under such extreme conditions is key to modeling material failure and deformation dynamics under impact. While studies on pure silica are extensive, the shock behavior of other commercial silicates that contain additional oxides has not been systematically investigated. To better understand the role of composition in the dynamic behavior of silicates, we performed laser-driven dynamic compression experiments on soda-lime glass (SLG) up to 315 GPa. Using the accurate pulse shaping offered by the long pulse laser system at the Matter in Extreme Conditions end-station at the Linac Coherent Light Source, SLG was shock compressed along the Hugoniot to multiple pressure-temperature points. Velocity Interferometer System for Any Reflector was used to measure the velocity and determine the pressure inside the SLG. The U s –u p relationship obtained agrees well with the previous parallel plate impact studies. Within the error bars, no transformation to the crystalline phase was observed up to 70 GPa, which is in contrast to the behavior of pure silica under shock compression. Our studies show that the glass composition strongly influences the shock compression behavior of the silicate glasses.

36 MATERIALS SCIENCE↗