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At least 1,459 records · Page 81
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Mechanisms and kinetics of citrate-promoted dissolution of a uranyl phosphate mineral

The formation of uranyl phosphate precipitates is a remediation strategy to limit the mobility of uranium in contaminated soils. However, exposure to organic ligands, like the plant exudate citrate, can remobilize the uranium. The purpose of this study is to provide a more thorough comprehension of citrate-promoted dissolution of a uranyl phosphate mineral, chernikovite [(H 3 O)(UO 2 )(PO 4 )·3H 2 O], by determining the extent of uranium release from chernikovite at a wide range of citrate concentrations. Here we have quantified the kinetics of dissolution and proposed potential mechanisms of chernikovite dissolution to gain a better understanding of the fate of uranyl phosphate precipitates in the environment. Batch dissolution and continuously stirred tank reactor (CSTR) experiments indicate that increasing citrate concentrations from 0.1 mM to 50 mM increases the concentration of dissolved uranium. However, at citrate concentrations of 10 mM and greater, the effectiveness of the ligand to enhance the dissolution decreases. Density functional theory modeling and Raman spectroscopy indicate a strong interaction between citrate and the uranyl ions at the surface of the uranyl phosphate. The interaction between citrate and uranyl suggests the formation of an alteration layer of uranyl-citrate surface complexes, which could impede uranium release at citrate concentrations of 10 mM or higher. Together, these results indicate that the citrate-promoted dissolution of chernikovite is a fast reaction that is hindered by a combination of surface saturation and a secondary-phase precipitation reaction at higher concentrations of citrate and reaction times greater than or equal to 72 min based on the hydraulic residence time of CSTR experiments. These findings improve our understanding of the stability of uranyl phosphate for use in sequestration of uranium groundwater plumes at contaminated sites.

58 GEOSCIENCES↗
DOE OSTI2024

Vivianite oxidation is not photocatalyzed

Vivianite is a hydrous Fe2+ phosphate mineral found in anoxic environments that plays an integral role in P cycling and environmental biogeochemistry. Imbued in the vivianite literature dating as far back as 1918 is the notion that vivianite is light-sensitive and susceptible to rapid photooxidation induced entirely by solar light. However, despite an exhaustive search, to our knowledge this conventionally accepted assumption has never been directly tested, nor has the band gap ever been measured. Resolving this question of photochemical control of vivianite redox chemistry is important for performing and interpreting experiments involving vivianite reactivity with contaminants, and potentially iron and phosphate cycling in the photic zone of aquatic systems. The present study was specifically designed to add¬ress this question. Pure synthetic vivianite samples were irradiated in aqueous suspensions with a Xe lamp at conditions mimicking the solar spectrum and compared to dark controls. Particles stirred in anoxic suspensions for up to 66 days showed no detectable oxidation irrespective of light exposure, according to colorimetric Fe2+/Fe3+ assays, micro X-ray diffraction, and Raman spectroscopy. In contrast, the same experiment performed using air-equilibrated suspensions showed systematic oxidation of up to ~80% mol% Fe(II) at 66 days, but again with no detectable light exposure effect. To test for UV reactivity, further experiments on vivianite powders under air versus N2 atmosphere were performed using a Hg lamp with a longpass filter. In contrast to oxidation in air where no effect of light was detected, after 24 hrs irradiation anoxically, 0.78% Fe was oxidized compared to dark controls, and after 13 days only an additional 0.3% Fe was oxidized. The band gap of pure vivianite was measured by the Tauc method to be 3.5 eV. Contrary to previous reports, solar light has minimal impact on the oxidation of pure vivianite, insignificant in particular when compared to its relatively fast oxidation by oxygen exposure. As such, light does not need to be excluded when running typical vivianite laboratory experiments. Long-term storage of natural vivianite in museums or private collections should continue protective measures given that a possible photocatalytic role of impurities cannot yet be ruled out. Nonetheless, at all depths in natural aquatic systems it appears that the primary abiotic control on the reactivity and half-life of vivianite particles should be the dissolved oxygen concentration, not light exposure.

Vivianite, photochemistry, oxidation↗
DOE OSTI2025

Distributed Fiber Optic Sensing for in-well hydraulic fracture monitoring

This study presents the results from in-well hydraulic fracture monitoring within a horizontal well in an unconventional reservoir utilizing Distributed Fiber Optic Sensing (DFOS). An in-house-developed Brillouin-based Distributed Strain Sensing (DSS) interrogator was deployed to obtain strain measurements, complemented by a commercial Raman-based Distributed Temperature Sensing (DTS) interrogator for temperature measurements and a commercial Rayleigh-based Low-Frequency Distributed Acoustic Sensing (LF-DAS) interrogator for strain-rate measurements. Examined over a ten-day period, the spatio-temporal distribution of temperature-compensated strain obtained from DSS and DTS revealed distinct signatures of the multi-stage hydraulic fracturing process. These signatures were analyzed with respect to fracture width growth and closure, residual strain effects, and fracture conductivity near the wellbore. Fracture widths within the fracture zone were estimated for individual stages. The findings were assessed with LF-DAS measurements for further evaluation. This work integrates DFOS-measured strain, temperature, and strain-rate data for monitoring in-well hydraulic fracturing, with the goal of supporting future studies in interpreting DFOS measurements for improved understanding of hydraulic fracturing in unconventional reservoirs.

58 GEOSCIENCES↗
DOE OSTI2023

Differential multi-probe thermal transport measurements of multi-walled carbon nanotubes grown by chemical vapor deposition

Carbon nanotubes (CNTs) are quasi-one dimensional nanostructures that display both high thermal conductivity for potential thermal management applications and intriguing low-dimensional phonon transport phenomena. In comparison to the advances made in the theoretical calculation of the lattice thermal conductivity of CNTs, thermal transport measurements of CNTs have been limited by either the poor temperature sensitivity of Raman thermometry technique or the presence of contact thermal resistance errors in sensitive two-probe resistance thermometry measurements. Here we report advances in a multi-probe measurement of the intrinsic thermal conductivity of individual multi-walled CNT samples that are transferred from the growth substrate onto the measurement device. The sample-thermometer thermal interface resistance is directly measured by this multi-probe method and used to model the temperature distribution along the contacted sample segment. The detailed temperature profile helps to eliminate the contact thermal resistance error in the obtained thermal conductivity of the suspended sample segment. A differential electro-thermal bridge measurement method is established to enhance the signal-to-noise ratio and reduce the measurement uncertainty by over 40%. The obtained thermal resistances of multiple suspended segments of the same MWCNT samples increase nearly linearly with increasing length, revealing diffusive phonon transport as a result of phonon-defect scattering in these MWCNT samples. The measured thermal conductivity increases with temperature and reaches up to 390 ± 20 W m –1 K –1 at room temperature for a 9-walled MWCNT. In conclusion, theoretical analysis of the measurement results suggests submicron phonon mean free paths due to extrinsic phonon scattering by extended defects such as grain boundaries. The obtained thermal conductivity is decreased by a factor of 3 upon electron beam damage and surface contamination of the CNT sample.

42 ENGINEERING↗
DOE OSTI2020

Hydrogen wide area monitoring of LH2 releases

The characterization of liquid hydrogen (LH2) releases has been identified as an international research priority to expand the safe use of hydrogen as an energy carrier. The elucidation of LH2 release behavior will require the development of dispersion and other models, guided and validated by empirical field measurements such as those afforded by Hydrogen Wide Area Monitoring (HyWAM). HyWAM can be defined as the quantitative spatial and temporal three-dimensional monitoring of planned or unintentional hydrogen releases. With support provided through the FCH JU Prenormative Research for the Safe Use of Liquid Hydrogen (PRESLHY) program, HSE performed a series of LH2 releases to characterize the dispersion and pooling behavior of cold hydrogen releases. The NREL Sensor Laboratory developed a HyWAM system based upon a distributed array of point sensors that is amenable for profiling cold hydrogen plumes. The NREL Sensor Laboratory and HSE formally committed to collaborate on profiling the LH2 releases. This collaboration included the integration of the NREL HyWAM into the HSE LH2 release hardware. This was achieved through a deployment plan jointly developed by the NREL and HSE personnel. Under this plan, the NREL Sensor Laboratory provided multiple HyWAM modules that accommodated 32 sampling points for near-field hydrogen profiling during the HSE PRESLHY LH2 releases. The NREL HyWAM would be utilized throughout the LH2 release study performed under PRESLHY by HSE, including Work Package 3 (WP3—Release and Mixing--Rainout) and subsequent work packages (WP4—Ignition and WP5—Combustion). Under the auspices of the PRESLHY WP6 (Implementation), data and findings from the HSE LH2 Releases are to be made available to stakeholders in the hydrogen community. Comprehensive data analysis and dissemination is ongoing, but the integration of the NREL HyWAM into the HSE LH2 Release Apparatus and its performance as well as some key outcomes of the LH2 releases in WP3 are presented.

08 HYDROGEN↗
DOE OSTI2020

Dispersion of cryogenic hydrogen through high-aspect ratio nozzles

Liquid hydrogen is increasingly being used as a delivery and storage medium for stations that provide compressed gaseous hydrogen for fuel cell electric vehicles. In efforts to provide scientific justification for separation distances for liquid hydrogen infrastructure in fire codes, the dispersion characteristics of cryogenic hydrogen jets (50–64 K) from high aspect ratio nozzles have been measured at 3 and 5 bar abs stagnation pressures. These nozzles are more characteristic of unintended leaks, which would be expected to be cracks, rather than conventional round nozzles. Spontaneous Raman scattering was used to measure the concentration and temperature field along the major and minor axes. Within the field of interrogation, the axis-switching phenomena was not observed, but rather a self-similar Gaussian-profile flow regime similar to room temperature or cryogenic hydrogen releases through round nozzles. The concentration decay rate and half-widths for the planar cryogenic jets were found to be nominally equivalent to that of round nozzle cryogenic hydrogen jets indicating a similar flammable envelope. The results from these experiments will be used to validate models for cryogenic hydrogen dispersion that will be used for simulations of alternative scenarios and quantitative risk assessment.

08 HYDROGEN↗
DOE OSTI2023

Investigation of methane and ethane pyrolysis with highly active and durable iron-alumina catalyst to produce hydrogen and valuable nano carbons: Continuous fluidized bed tests and reaction rate analysis

The goal of this research work was to evaluate a novel iron-alumina catalyst for methane and ethane pyrolysis with high conversion rates to H 2 with a long life time to address two major issues reported with previous catalysts. Fluidized bed tests demonstrated continuous hydrogen production while collecting carbon containing fines. During the 230 h fluid bed test the methane conversion rate to hydrogen at 700 °C remained above 80% for 160 h while creating valuable nano carbons. Similarly high catalyst lifetimes with high methane conversions have not been reported before. Ethane was more active than methane for pyrolysis with 100% conversion to H 2 . Transmission electron microscopy and Raman analysis of the carbon showed single and multiwall nanotubes and conglomerate nano-fibers. Ethane did not impact the allotrope of carbon formed. TGA was used to create a data array that was used for kinetic analysis and reaction model parametric regressions. Ethane had a higher rate of pyrolysis that was 2.3–2.8 times that of methane. Ethane pyrolysis was found to be more sensitive to temperature with a higher activation energy of 62 kJ/mol as compared to methane at 43 kJ/mol. The frequency factor, A i , was significantly higher for ethane at 0.73 [[kmol/m 3 -sec]/[N/m2] n ] compared to 0.03 for methane on the same basis. Both gases had a functional partial pressure order dependence of ~0.6 based on the regression analysis.

08 HYDROGEN↗
DOE OSTI2024

Microwave-assisted catalytic gasification of mixed plastics and corn stover for low tar, hydrogen-rich syngas production

The challenge for efficient management of post-consumer plastic and biomass waste has grown over the past few decades due to their dramatic increases. In comparison to conventional gasification, microwave-assisted co-gasification of plastics and corn stover offers many benefits, including increased H 2 yield and gas components compared to unfavorable char/tar. Nonetheless, for future commercialization of the process and ease of product separation, further reduction of the undesirable tar is necessary, which can be achieved over the catalytic route. Here, in this work, we studied the catalytic effect of magnetite for microwave-assisted co-gasification of corn stover and plastic to make syngas with higher H 2 and lower tar selectivity over non-catalytic conditions. A 1:1:1 ratio of plastic-corn stover-magnetite was used to evaluate the reaction parameters such as temperature, space velocity, heating media, and catalytic cycles under gasification conditions. In comparison with the microwave non-catalytic route, a 100% increase in the total H 2 yield with 76% higher H 2 production efficiency (mmol/kWh) was achieved in the presence of the magnetite catalyst, while reducing the overall tar formation from 9% to 2%. When magnetite was reduced in situ during the reaction, it coupled with microwave and delivered oxygen radicals that cracked down plastic and corn stover intermediates generated from the synergistic effect under microwave heating. Soon after the oxygen transfer process initiated, magnetite reached its final oxidation state consisting of microwave-active Fe and Fe 3 C phases that continued coupling with microwaves along with the generated graphitic carbon to maintain the heat necessary to further reduce the generated tar and make additional gaseous products, as confirmed by XRD, Raman, and TGA analyses.

08 HYDROGEN↗
DOE OSTI2020

Facile All-Optical Method for In Situ Detection of Low Amounts of Ammonia

As a key precursor for nitrogenous compounds and fertilizer, ammonia affects our lives in numerous ways. Rapid and sensitive detection of ammonia is essential, both in environmental monitoring and in process control for industrial production. Here we report a novel and nonperturbative method that allows rapid detection of ammonia at low concentrations, based on the all-optical detection of surface-enhanced Raman signals. We show that this simple and affordable approach enables ammonia probing at selected regions of interest with high spatial resolution, making in situ and operando observations possible.

09 BIOMASS FUELS↗
DOE OSTI2024

Optically induced quantum transitions in direct probed mesoscopic NbSe 2 for prototypical bolometers

Superconducting transition-edge sensors (TES) have emerged as fascinating devices to detect broadband electromagnetic radiation with low thermal noise. The advent of metallic transition metal dichalcogenides, such as NbSe 2 , has also created an impetus to understand their low-temperature properties, including superconductivity. Interestingly, NbSe 2 -based sensor within the TES framework remains unexplored. In this work, direct-probed superconducting NbSe 2 absorbers led to a proof-of-concept demonstration for the transduction of incoming light to heat, where a thermodynamic superconducting phase transition in NbSe 2 was evident to switch it to the normal-state, when biased below its superconducting transition temperature. A wavelength-dependent response of its optical absorption properties was observed, based on the incident optical excitation source used. Furthermore, extensive optical characterization studies were conducted using Raman spectroscopy, where the in-plane and out-of-plane thermal conductivity was empirically determined. Our results open new possibilities for the use of NbSe 2 in superconducting radiation detectors, including in a TES framework

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

Methane pyrolysis by Joule heating for graphitic carbon and hydrogen production

The global energy transition toward sustainability requires technologies that can decarbonize energy carriers and fuels while producing valuable materials. Methane, a primary component of natural gas, is both a high-energy-density fuel and a significant greenhouse gas. This study reports an approach for methane pyrolysis utilizing Joule heating within the deposition substrate to drive the endothermic reaction. With electric current passing through a resistive porous carbon cloth, heat is generated to break C-H bonds of methane molecules. Here, the decomposition of methane as it flows through the cloth results in hydrogen production and the formation of conformally layered graphite around the carbon fibers. The effects of input power, chamber pressure, feedstock flow rate, and process duration on hydrogen and graphite production are characterized via in situ mass spectrometry and laser absorption spectroscopy, resulting in methane conversion rates up to 88%, with hydrogen and carbon yields of 82% and 72%, respectively. Material characterization verifies uniform high-quality graphite deposition, with a Raman I D /I G ratio of 0.1 and 3.38 Å d-spacing. This Joule heating method for catalyst-free methane pyrolysis offers the potential for advancing hydrogen production technology by simultaneously producing valuable materials such as solid graphite, thus enhancing the economic viability of the fuel decarbonization process.

Energy Resources↗
DOE OSTI2019

Effect of high temperature preoxidation treatment on the oxidation behavior of MoSi 2 - and WSi 2 –Al 2 O 3 composites

Composites of 30 vol% MoSi 2 -70 vol% Al 2 O 3 and 30 vol% WSi 2 -70 vol% Al 2 O 3 were prepared via sintering at 1600 °C in argon. The high-temperature preoxidation treatments were applied at 1000°-1200 °C for 10–120 min in air. The non-isothermal oxidation tests were conducted in air at temperatures ranging between 50° and 870 °C to study and understand the influence of the alumina phase and preoxidation process on the low-temperature oxidation behavior. The optical and scanning electron microscopy, X-ray diffraction, X-ray photoelectron and Raman spectroscopy were used to characterize the surface layers formed. The oxidation-induced mass gains were substantially reduced by 82.1–99.8%, implying their enhanced oxidation resistance. This was due to the formation of highly dense, protective surface layers with a sufficient thickness (3.1–14.2 μm). The structural and surface analyses revealed their complex chemistries, since the ternary (Mo–Si–Al, W–Si–Al) intermetallic, mullite, alumina and silica phases with high oxidation resistances were identified within these surface features. In addition, the high-temperature electrical properties of the composites were highly preserved after the preoxidation treatment, and their electrical conductivities were measured as 45.1–78.6 S/cm at 800 °C and 40.1–69.1 S/cm at 900 °C.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Monitoring structural variation on Gd ratio of La modified bismuth ferrite ceramics with enhanced magnetization

Critical structural variation and dielectric properties were investigated in Lanthanum and Gadolinium co-substituted bismuth ferrite (Bi 0.9 La 0.1 Fe 1-x Gd x O 3 (x = 0.01, 0.03, 0.05, 0.07, 0.1, and 0.15). Conventional solid state reaction technique was used to synthesize ceramic samples. To investigate the influence of co-substitution on the phase formation and crystal structure, X-ray diffraction method (XRD), Scanning electron microscopy (SEM) and Raman spectroscopy were utilized. Probing the structural properties by changing Gd ratio was carried out to ensure single phase of rhombohedral R3c structure. Hence, the exploration of dielectric properties of single phase modified BiFeO 3 (BFO) ceramic was executed by room temperature capacitance and loss tangent measurements. It was found that by substitution of 10 mol% La for Bi and up to 5 mol% Gd for Bi, perovskite structure of rhombohedral symmetry and R3c space group were formed. This possessed enhanced magnetization and reduced dielectric loss compared to pure BFO.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Boron carbide amorphous solid with tunable band gap

Boron carbide B x C (x = 1/6 – 10) powders were synthesized through a microwave-assisted carbothermic reduction reaction as a potential clean energy material. Their crystallographic structures and optical properties were characterized. X-ray diffraction and electron diffraction indicated that the synthesized B x C powders were amorphous. Electron energy-loss spectroscopy demonstrated that the composition of boron and carbon was in amorphous materials, and their chemical bonding were disclosed from Raman scattering spectroscopy. Here, UV-vis absorption spectroscopy indicated that the bandgap of the bulks varied from 2.30 eV to 3.90 eV, tuned by the boron/carbon element ratio.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Phase stabilization and oxidation of a continuous composition spread multi-principal element (AlFeNiTiVZr) 1-x Cr x alloy

Multi-Principal Element Alloys (MPEA) have been hypothesized to maintain a stable single alloy phase and resist corrosion at high temperatures, which are desirable in various functional applications, including material of turbine blades. However, studies into oxidation resistant alloys have been constrained to individual MPEA systems or a limited selection of compositions within those systems. Here, High-Throughput Experimental (HTE) techniques were utilized to rapidly assess phase stability and resistance to oxidation of an (AlFeNiTiVZr) 1-x Cr x continuous composition spread (CCS) thin-film alloy system. High-throughput synchrotron diffraction and Raman spectroscopy were used to identify phases, especially high symmetry structures and oxides, as a function of annealing time and composition. The formation of two distinct phase regions, R 1 and R 2 , across the CCS was observed. One of these phase regions, R 2 , exhibited a stable high symmetry BCC-like phase at Cr concentrations greater than 25.4 at%, and grew a passivating mixed metal surface oxide; whereas, the R 1 phase region, decomposed on oxidation to multiple oxides and reacted with the substrate to form silicides. The passivating mixed metal oxide layer appears to prevent destabilization of the (AlFeNiTiVZr) 1-x Cr x MPEA BCC solid solution. Furthermore, at longer annealing times the passivating phase was seen only above 29.2 at% Cr. High Cr-doped (AlFeNiTiVZr) 1-x Cr x appear to be a good candidate for high temperature, oxidation-resistant structural alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The orbital effect on the anomalous magnetism and evolution in La $x$ Y 1-$x$ VO 3 (0 ≤ $x$ ≤ 0.2) single crystals

The orbital effect on the anomalous magnetism and evolution of single crystals with low La doping, La $x$ Y 1-$x$ VO 3 ($x$ = 0, 0.1, and 0.2), has been studied using single-crystal X-ray diffraction, specific heat, magnetization, and Raman-scattering techniques. It is found that substituting Y 3+ by La 3+ increases the degeneracy of the $yz/zx$ orbitals and decreases the Jahn-Teller distortion. These weakens the G-type (antiphase ordering along the c axis) orbital ordering phase. Meanwhile, the substituting decreases the magnetism entropy, indicating the shrinking of the t 2g and e g orbital hybridization, eventually destabilizing the C-type (in-phase ordering along the c axis) antiferromagnetic ordering phase. In addition, the mechanism for the shrinking of the diamagnetism with increasing $x$ is analyzed. In conclusion, it may attribute to the competition between the antisymmetric Dzyaloshinsky–Moriya interaction and the single-ion anisotropy.

36 MATERIALS SCIENCE↗
DOE OSTI2021

In-operando surface-sensitive probing of electrochemical reactions on nanoparticle electrocatalysts: Spectroscopic characterization of reaction intermediates and elementary steps of oxygen reduction reaction on Pt

In this paper we present an in-operando spectroscopic study of the reaction intermediates involved in ORR on electrified Pt nanoparticle electrocatalysts. To accomplish this, we have synthesized Ag-Pt core–shell nanoparticles, that contain a thin shell of Pt (~1 nm) uniformly deposited on a larger Ag core (~60 nm). We show that these nanostructures are ideal platforms for in-operando Plasmon Enhanced Raman Spectroscopy (PERS) of ORR on Pt. We combined these PERS studies with DFT calculations to assign the measured vibrational spectra to relevant surface intermediates as a function of electrocatalyst potential. Overall, these vibrational assignments were further verified and validated by performing PERS measurements using de-oxygenated and heavy oxygen (O 2 -18) saturated electrolyte. These studies allowed us to identity the presence of critical reaction intermediates (OH, O 2 , OOH, and H 2 O) as the function of operating voltage on the Pt surface and derive voltage-dependent elementary step mechanisms of the reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗