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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 1,783 records · Page 99
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Thermodynamics and Kinetics of Phase Transformations in Energy Materials (Final Report)

The primary goal of this program is to develop computational tools and methodology for enabling a shift from empirical trial-and-error driven materials discovery towards data and information technology driven design of materials with targeted functional properties. Both thermodynamic and kinetic factors need to be taken into account when designing new materials. Thermodynamics sets the necessary-but-not-sufficient conditions for the suitability of a particular material in a given application, while the kinetics controls the rates of microscopic processes and hence the performance in energy applications (e.g., power in energy storage, conversion efficiencies in solar cells and thermoelectrics, chemical activity in catalysis). The complexity of these phenomena makes computational design difficult, not least due to the lack of suitable theoretical methods and computational tools. To address these needs, we develop systematic, quantitatively accurate first-principles methods to address two important problems: (i) predict and optimize the thermodynamics of materials over a large composition and structure space, and (ii) model kinetic processes such as mass and heat transport in crystalline solids under non-equilibrium conditions. These tasks are addressed by combining high-throughput computation with automatic construction of accurate lattice models using mathematically rigorous methods of information theory, such as compressive sensing and Bayesian inference.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Investigation of structural and electrochemical properties of LaSrCo{sub 1−x}Sb{sub x}O{sub 4} (0≤x≤0.20) as potential cathode materials in intermediate-temperature solid oxide fuel cells

The structural and electrochemical properties of the layered perovskite oxides LaSrCo{sub 1−x}Sb{sub x}O{sub 4} (0≤x≤0.20) were investigated to study the effects of substituting Sb for Co for application as cathode materials in intermediate temperature solid oxide fuel cells (IT-SOFCs). The results of crystal structure analyses show the maximum content of Sb in LaSrCo{sub 1−x}Sb{sub x}O{sub 4} to be 0.05 as a pure single phase. XPS shows that Co and Sb in LaSrCo{sub 0.95}Sb{sub 0.05}O{sub 4} may possess mixed-oxidation states. The electrical conductivity increased greatly after Sb substitution. An improvement in the cathode polarization (R{sub p}) values is observed from the Sb-doped sample with respect to the undoped samples. For example, R{sub p} of LaSrCo{sub 0.95}Sb{sub 0.05}O{sub 4} on LSGM was observed to be 0.16 Ω cm{sup 2} at 800 °C in air. The main rate-limiting step for LaSrCo{sub 0.95}Sb{sub 0.05}O{sub 4} cathode is charge transfer of oxygen atoms. These results indicate that Sb can be incorporated into LaSrCo{sub 1−x}Sb{sub x}O{sub 4} based materials and can have a beneficial effect on the performance, making them potentially suitable for use as cathode materials in IT-SOFCs. - Graphical abstract: The oxygen partial pressure dependence of polarization resistances for a new layered perovskite cathode LaSrCo{sub 0.95}Sb{sub 0.05}O{sub 4} at various temperatures was measured. - Highlights: • The maximum content of Sb was 0.05 mol in LaSrCo{sub 1−x}Sb{sub x}O{sub 4}. • The maximum electrical conductivity is 194 S cm{sup −1}for LaSrCo{sub 0.95}Sb{sub 0.05}O{sub 4} at 800 °C. • A rate-limiting process of charge transfer presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Experimental characterization and atomistic modeling of interfacial void formation and detachment in short pulse laser processing of metal surfaces covered by solid transparent overlayers

The short pulse laser interaction with metal surfaces covered by solid transparent overlayers is investigated in experiments and atomistic simulations, with a particular aim of revealing the mechanisms responsible for structural modification of the metal–overlayer interfacial regions. Experimental characterization of Al–silica targets modified by single-pulse laser irradiation with the pulse duration of 10 ps reveals the transitions from the generation of extended interfacial voids with internal nanoscale surface roughness to the partial detachment of the overlayer from the metal substrate, and to the cracking/chipping or complete removal of the overlayer as the laser fluence increases. The mechanisms responsible for the appearance, growth, and percolation of the interfacial voids leading to the detachment of the overlayer from the metal substrate are investigated in a large-scale atomistic simulation. The results of the simulation demonstrate that the processes of nucleation and growth of the interfacial voids are driven by the dynamic relaxation of laser-induced stresses proceeding simultaneously with rapid phase transformations and temperature variation in the interfacial region. The growth and coalescence of the interfacial voids results in the formation of liquid bridges connecting the overlayer and the metal substrate, whereas solidification of the transient liquid structures produced by the breakup of the liquid bridges may be responsible for the formation of the nanoscale roughness of the interfacial voids observed in experiments. Computational analysis of the effect of preexisting interfacial voids reveals a complex dynamic picture of the initial expansion and subsequent compaction of the surface region of the metal substrate and suggests a possible scenario for the formation of voids below the metal–overlayer interface.

Materials Science↗
DOE OSTI2024

Moderate active Fe 3+ doping enables improved cationic and anionic redox reactions for wide-voltage-range sodium storage

Layered metal oxides are promising cathode materials for sodium-ion batteries (SIBs) due to their high theoretical specific capacity and wide Na + diffusion channels. However, the irreversible phase transitions and cationic/anionic redoxes cause fast capacity decay. Herein, P2-type Na 0.67 Mg 0.1 Mn 0.8 Fe 0.1 O 2 (NMMF-1) cathode material with moderate active Fe 3+ doping has been designed for sodium storage. Uneven Mn 3+ /Mn 4+ distribution is observed in NMMF-1 and the introduction of Fe 3+ is beneficial for reducing the Mn 3+ contents both at the surface and in the bulk to alleviate the Jahn–Teller effect. The moderate Fe 3+ /Fe 4+ redox can realize the best tradeoff between capacity and cyclability. Therefore, the NMMF-1 demonstrates a high capacity (174.7 mAh g -1 at 20 mA g -1 ) and improved cyclability (78.5% over 100 cycles) in a wide-voltage range of 1.5–4.5 V (vs. Na + /Na). In-situ X-ray diffraction reveals a complete solid-solution reaction with a small volume change of 1.7% during charge/discharge processes and the charge compensation is disclosed in detail. This study will provide new insights into designing high-capacity and stable layered oxide cathode materials for SIBs.

25 ENERGY STORAGE↗
DOE OSTI2020

Short-range order and its impact on the CrCoNi medium-entropy alloy

Traditional metallic alloys are mixtures of elements in which the atoms of minority species tend to be distributed randomly if they are below their solubility limit, or to form secondary phases if they are above it. The concept of multiple-principal-element alloys has recently expanded this view, as these materials are single-phase solid solutions of generally equiatomic mixtures of metallic elements. This group of materials has received much interest owing to their enhanced mechanical properties 1,2,3,4,5 . They are usually called medium-entropy alloys in ternary systems and high-entropy alloys in quaternary or quinary systems, alluding to their high degree of configurational entropy. However, the question has remained as to how random these solid solutions actually are, with the influence of short-range order being suggested in computational simulations but not seen experimentally 6,7 . In this paper we report the observation, using energy-filtered transmission electron microscopy, of structural features attributable to short-range order in the CrCoNi medium-entropy alloy. Increasing amounts of such order give rise to both higher stacking-fault energy and hardness. These findings suggest that the degree of local ordering at the nanometre scale can be tailored through thermomechanical processing, providing a new avenue for tuning the mechanical properties of medium- and high-entropy alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Mobile Sorption-based Thermal Battery for Harvesting Low-Temperature Geothermal Energy

Around 20% of the total primary energy in the United States is consumed for thermal demands of buildings such as space cooling, dehumidification, and space heating (EIA 2018). Low-temperature geothermal energy is abundant and can effectively satisfy buildings’ thermal demands. However, low-temperature geothermal energy is underutilized because the energy density of geothermal fluid is too low to justify the costs associated with transporting it between existing geothermal resources and buildings. The mobile sorption-based thermal battery (MSTB) system has been developed using three-phase (i.e., vapor–liquid, solution–solid, crystal) sorption technology to harvest low-temperature heat and store it with a much higher energy density than the geothermal fluid. The energy density of salt crystals is over six times higher than geothermal fluid, which makes long-distance transportation of salt crystals economically feasible. Salt crystals can be used to dehumidify air or provide space cooling in buildings, which alleviates peak demand on the electricity grid by offsetting electricity use for these end uses. This helps improve the grid’s stability and resilience. High-energy storage density, fast crystallization, and dissolution of salt crystals are all critical to the viability and performance of the MSTB system. Therefore, the design and operation of MSTB systems need to ensure effective generation and dissolution of salt crystals inside the MSTB. To achieve this target, this seedling project developed an experimental apparatus for characterizing the crystallization and dissolution processes. The energy density and potential latent cooling capacity of the MSTB are also evaluated based on lab test results. The crystallization results showed that the generated lithium chloride hydrate crystals are fluffy, the crystallization process lasts about 50 min, and the maximum crystal fraction (i.e., the ratio of crystal mass to the mass in the MSTB) can be up to 51.1% of the total mass in the MSTB at a solution flow rate of 1.58 g/s. The dissolution results show that the salt crystals in the MSTB can be fully dissolved within 15–28 min, based on different test conditions. Reducing solution flow rate and cooling water temperature can achieve increased energy storage density and crystal fraction. While the increase in the discharge rate (i.e., latent cooling capacity for dehumidifying air) is achieved by increasing flow rate and temperature of inlet diluted solution, as well as by using a pump for internal solution circulation, the discharge rate increases by 38%, from 0.95 kW to 1.31 kW. Compared with increasing the inlet solution flow rate, power consumption of salt solution transportation can be reduced by using a pump for internal solution circulation. The crystallization test results also showed that the maximum energy storage density is 981.8 kJ/kg, and the maximum discharge rate of the dissolution tests is ≤1.79 kW. Both are above the target values of 900 kJ/kg and 1.75 kW) for this project. The work reported here proves the feasibility and advancement of the MSTB system, which is helpful to the further study and improvement of the MSTB system.

15 GEOTHERMAL ENERGY↗
DOE OSTI2022

Preservation of high-pressure volatiles in nanostructured diamond capsules

High pressure induces dramatic changes and novel phenomena in condensed volatiles(1,2) that are usually not preserved after recovery from pressure vessels. In this study we report a process that pressurizes volatiles into nanopores of type 1 glassy carbon precursors, converts glassy carbon into nanocrystalline diamond by heating and synthesizes free-standing nanostructured diamond capsules (NDCs) capable of permanently preserving volatiles at high pressures, even after release back to ambient conditions for various vacuum-based diagnostic probes including electron microscopy. As a demonstration, we perform a comprehensive study of a high-pressure argon sample preserved in NDCs. Synchrotron X-ray diffraction and high-resolution transmission electron microscopy show nanometre-sized argon crystals at around 22.0 gigapascals embedded in nanocrystalline diamond, energy-dispersive X-ray spectroscopy provides quantitative compositional analysis and electron energy-loss spectroscopy details the chemical bonding nature of high-pressure argon. The preserved pressure of the argon sample inside NDCs can be tuned by controlling NDC synthesis pressure. To test the general applicability of the NDC process, we show that high-pressure neon can also be trapped in NDCs and that type 2 glassy carbon can be used as the precursor container material. Additional experiments on other volatiles and carbon allotropes open the possibility of bringing high-pressure explorations on a par with mainstream condensed-matter investigations and applications.

36 MATERIALS SCIENCE↗
DOE OSTI2014

COLLABORATIVE RESEARCH: Study of Aerosol Sources and Processing at the GVAX Pantnagar Supersite

This project funded the participation of scientists from seven research groups, running more than thirty instruments, in the Winter Intensive Operating Period (January-February 2012) of the Clean Air for London (ClearfLo) campaign at a rural site in Detling, UK, 45 km southeast of central London. The primary science questions for the ClearfLo Winter IOP were, 1) what is the urban increment of particulate matter (PM) and other pollutants in the greater London area, and, 2) what is the contribution of solid fuel use for home heating to wintertime PM? An additional motivation for the Detling measurements was the question of whether coatings on black carbon particles enhance absorption. The following four key accomplishments have been identified so far: 1) Chemical, physical and optical characterization of PM from local and regional sources (Figures 2, 4, 5 and 6). 2) Measurement of urban increment in particulate matter and gases in London (Figure 3). 3) Measurement of optical properties and chemical composition of coatings on black carbon containing particles indicates absorption enhancement. 4) First deployment of chemical ionization instrument (MOVI-CI-TOFMS) to measure both particle-phase and gas-phase organic acids. (See final report from Joel Thornton, University of Washington, for details.) Analysis of the large dataset acquired in Detling is ongoing and will yield further key accomplishments. These measurements of urban and rural aerosol properties will contribute to improved modeling of regional aerosol emissions, and of atmospheric aging and removal. The measurement of absorption enhancement by coatings on black carbon will contribute to improved modeling of the direct radiative properties of PM.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Viscosity of TiO{sub 2}-FeO-Ti{sub 2}O{sub 3}-SiO{sub 2}-MgO-CaO-Al{sub 2}O{sub 3} for High-Titania Slag Smelting Process

The present study demonstrates the dependence of viscosity on chemical composition and temperature of high-titania slag, a very important raw material for producing titanium dioxide. The results indicated that completely molten high-titania slag exhibits a viscosity of less than 1 dPa s with negligible dependence on temperature. However, it increases dramatically with decreasing temperature slightly below the critical temperature, i.e., the solidus temperature of the slag. Above the critical temperature, the slag samples displayed the same order of viscosity at 0.6 dPa s, regardless of their compositional variation. However, the FeO, CaO, and MgO were confirmed to decrease viscosity, while SiO{sub 2} and Ti{sub 2}O{sub 3} increase it. The apparent activation energy for viscosity-temperature relation and liquidus temperature based on experiments and thermodynamic calculations are also presented. Conclusively, the critical temperatures of the slags are on average 15 K below their corresponding calculated liquidus temperatures. The increase in FeO content was found to considerably lower the critical temperature, while the increase in both Ti{sub 2}O{sub 3} and TiO{sub 2} contents increases it. The main phases of the slag in solid state, as indicated by X-ray diffraction, are (Fe, Mg){sub x}Ti{sub y}O{sub 5} (x + y = 3, pseudobrookite) and rutile.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Preparation and thermophysical properties of (Sm{sub 1−x}Er{sub x}){sub 2}Ce{sub 2}O{sub 7} oxides for thermal barrier coatings

Graphical abstract: - Highlights: • These ceramic materials with fluorite structure were synthesized. • Defect points lead to their lower thermal conductivities. • The lower ionic radius of Er{sup 3+} ion leads to the reduction of thermal expansion coefficient of (Sm{sub 1−x}Er{sub x}){sub 2}Ce{sub 2}O{sub 7} oxides. - Abstract: (Sm{sub 1−x}Er{sub x}){sub 2}Ce{sub 2}O{sub 7} ceramics were synthesized by sol–gel method and sintered at 1600 °C for 10 h in air. The influence of Er{sub 2}O{sub 3}-substitution on the phase structure and thermophysical properties of Sm{sub 2}Ce{sub 2}O{sub 7} was investigated. The phase structures of these ceramics were identified by X-ray diffraction showing that all synthesized ceramics have fluorite-type structure. The measurements for thermophysical properties of these ceramics show that their thermal conductivities and thermal expansion coefficients remarkably decreased through Er-substitution. However, the thermal expansion coefficients were higher than that of YSZ and their thermal conductivities were much lower than that of 8YSZ. The excellent thermophysical property implies that these solid solutions are potential materials for the ceramics layer in thermal barrier coatings.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Immobilizing Pertechnetate in Ettringite via Sulfate Substitution

Until recently, a nuclear waste form did not exist for the immobilization and long-term storage of the anionic form of radionuclide technetium-99 (99Tc), pertechnetate (TcO 4 - ). Across international nuclear waste sites, the inability to capture TcO 4 - poses a threat to the local environment due to the anion’s long half-life and environmental mobility under environmentally oxic conditions. To combat this challenge, most waste forms would capture 99Tc using materials that reduce TcO 4 - to Tc(IV) species, e.g. 99Tc oxides or 99Tc sulfides. However, this is a short-lived solution unless reducing capacities can be regenerated to last over the long life expectancy of some nuclear waste forms (~10,000 years). In light of recent experimental observations gained from the development of cementitious waste forms and unconfirmed hypotheses from the literature, this work explores how ettringite, a common mineral formed in cementitious materials with demonstrated success in incorporating oxyanions, may be used to immobilize TcO 4 - directly and over the life-time of the waste form. Using batch precipitation experiments, solid phase characterization techniques, and ab initio molecular dynamics simulations, we demonstrate herein successful incorporation of TcO 4 - into ettringite via substitution for SO 4 2- within the ettringite crystal structure. Here, these results are first of their kind and confirm the hypothesis that ettringite acts as an immobilizing mineral within cementitious waste forms for the highly mobile TcO 4 - oxyanion, enhancing the overall performance of these waste forms over time.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Characterization of Interaction between Fe‐Infiltrates and LSM Backbone in Solid Oxide Fuel Cells

In this paper, detailed materials characterization analyses on the interaction between FeO x nanoparticles infiltrated onto a La 0.8 Sr 0.2 MnO 3 (LSM) backbone cathode in a solid oxide fuel cell (SOFC) are reported. The infiltration process leads to an increase of 3.4% in cell performance. X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) as well as energy dispersive X‐ray spectroscopy (EDS) and electron energy loss spectroscopy (EELS) are utilized to perform a comprehensive examination of the microstructure and chemical properties at the interface of the infiltrate and backbone materials. Mn from the LSM backbone diffuses into the FeO x infiltrate and forms a Fe‐Mn‐O spinel. A small amount of Fe also diffuses into the LSM backbone, which could partially be responsible for the enhanced performance of the cell. The valence state of Mn increases from the surface of the Fe‐Mn‐O particle into bulk LSM, with the highest value being at the interface of the Fe‐Mn‐O/LSM backbone. Possible mechanisms are discussed for the change in Mn valence state within the LSM phase. Trace amounts of Mn and La are found in the YSZ phase, as a result of interdiffusion between LSM and YSZ.

Yu, Yang↗
DOE OSTI2015

Precipitation pathways for ferrihydrite formation in acidic solutions

In this study, iron oxides and oxyhydroxides form via Fe 3+ hydrolysis and polymerization in many aqueous environments, but the pathway from Fe 3+ monomers to oligomers and then to solid phase nuclei is unknown. In this work, using combined X-ray, UV–vis, and Mössbauer spectroscopic approaches, we were able to identify and quantify the long-time sought ferric speciation over time during ferric oxyhydroxide formation in partially-neutralized ferric nitrate solutions ([Fe 3+ ] = 0.2 M, 1.8 < pH < 3). Results demonstrate that Fe exists mainly as Fe(H 2 O) 6 3+ , μ-oxo aquo dimers and ferrihydrite, and that with time, the μ-oxo dimer decreases while the other two species increase in their concentrations. No larger Fe oligomers were detected. Given that the structure of the μ-oxo dimer is incompatible with those of all Fe oxides and oxyhydroxides, our results suggest that reconfiguration of the μ-oxo dimer structure occurs prior to further condensation leading up to the nucleation of ferrihydrite. The structural reconfiguration is likely the rate-limiting step involved in the nucleation process.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Recovery Act : Heterogeneous Feed Biorefinery Project

To overcome the hurdles associated with introducing a new technology, Enerkem applied to the US DOE for grant assistance with its Pontotoc, Mississippi, biorefinery under the DOE’s Demonstration of Integrated Biorefinery Operations FOA. Consistent with Enerkem’s strategic approach, the project proposed uses post sorted municipal solid waste blended with other forest residue. The proposed biorefinery is to be located within the boundaries of a working landfill, thus simplifying many aspects of environmental permitting while also reducing feedstock acquisition and transportation costs. An economic impact analysis was conducted using an adaptation of the US Department of Energy’s JEDI (Jobs and Economic Development Impact) model for an ethanol-producing biorefinery. The JEDI model, which does not have a thermochemical processing option, had to be configured to reflect a biomass feedstock and was thus adapted by Enerkem to account for the unique feedstock requirements and operations of the Project. According to this model, development, construction, and 2 years of operation of the biorefinery require an investment of approximately $140 million. Also, a construction period of 18 months will create significant direct and indirect employment. Indirect employment includes steel manufacturers, construction materials manufacturers, material shipping, equipment manufacturers and fabrication, etc. During the construction phase of the Project, 210 total jobs are expected to be created, including 145 direct jobs and 72 indirect or induced jobs. During the operating period, 131 jobs would be created, 95 of which are direct. It is anticipated that the project will create at least 10 new jobs (included in the above figures and in addition to the JEDI data) in the sorting and recycling sector, since the project will require operations in sorting MSW since valuable ferrous, nonferrous and recyclable plastic materials will be sorted from MSW as part of the process that isolates MSW-derived biomass.

09 BIOMASS FUELS↗
DOE OSTI2025

DOE SCGSR Final Report - Project Accomplishments and Additional Materials

The major accomplishments of my project were successfully developing and testing the laser interferometry diagnostic on the Plasma Liner Experiment (PLX) at Los Alamos National Laboratory (LANL). This diagnostic helped advance my research by providing a simpler way to obtain electron density measurements of magnetized plasmas compared to other electron density diagnostics such as triple Langmuir probes. The laser used was a 561 nm continuous wave (CW) diode-pumped solid state (DPSS) laser. The PLX laser interferometry diagnostic consists of two parts. These include the launching and receiving sides of the laser diagnostic. The launching side consists of the main laser beam from the DPSS laser being split into five chords(probe beams) and a reference beam which are then directed with fiber optic couplers into fiber optic cables which transmit the probe beamsto the PLX vacuum chamber. The probe beams then pass through the plasma in the chamber and into the receiving side optics where they are again directed through fiber optic cables to be combined with the reference beam. The combined beams are transmitted via multi-mode fiber optic cables to photodiodes to convert the light signals into electrical signals. Before the electrical signals get digitized, they pass through bandpass and low pass filters to eliminate electromagnetic noise and unwanted frequencies. The electrical signals are then processed by IQ demodulators to determine phase angle difference between the probe and reference beams for each chord in order to calculate line-integrated electron density.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Thermal Diffusivity Measurement of Irradiated SiC-SiC Composite Material

Silicon Carbide fiber and matrix composite (SiC-SiC) is being considered as a fuel cladding candidate because of its high melting point, low susceptibility to corrosion, good thermal and mechanical shock resistance, and low degradation of mechanical properties under irradiation. The thermal properties of SiC-SiC composite depend heavily on the fabrication process, thus cannot be simply referenced from available database. Similarly, the influence of irradiation on SiC-SiC composite thermal properties needs to be measured to provide general trends of property degradation. For ion irradiated samples, the damaged layer is only a few to a few tens of micrometers. It is impossible to directly measure the bulk property change of a SiC-SiC composite because of the thin, damaged layer. This paper focuses on a methodology that is based on microscale measurement of fiber and matrix properties to determine the overall bulk property change due to ion irradiation. Laser-based photothermal reflectance technique is one of the ideal methods to measure local thermal conductivity and diffusivity with high spatial resolution. The main principle of this technique is to heat the solid sample using an intensity-modulated laser, and scan the sample with a constant intensity continuous-wave (CW) laser to detect the phase lag of the thermal wave propagation. On bulk, isotropic material, if the heating laser intensity is modulated as a sine wave, thermal diffusivity of the sample can be derived from the phase lag, scan distance and modulation frequency in a straight forward manner. By using more specific analytical models, thermal conductivity and diffusivity in complicated cases, such as layered structure materials, composite materials, and/or anisotropic materials, are measurable as well. In this work, a new measurement approach of SiC-SiC composite thermal diffusivity is presented. Due to the micrometer spatial resolution of the photothermal reflectance technique, the measurements are performed locally on fibers along both radial and axial directions, and on the matrix. The influence of Silicon ion irradiation (75 MeV, 10 dpa) is then examined by comparing the experimental results of samples before and after irradiation. (authors)

36 MATERIALS SCIENCE↗
DOE OSTI2016

Sorption testing and generalized composite surface complexation models for determining uranium sorption parameters at a proposed in-situ recovery site

Solid-phase iron concentrations and generalized composite surface complexation models were used to evaluate procedures in determining uranium sorption on oxidized aquifer material at a proposed U in situ recovery (ISR) site. At the proposed Dewey Burdock ISR site in South Dakota, USA, oxidized aquifer material occurs downgradient of the U ore zones. Solid-phase Fe concentrations did not explain our batch sorption test results,though total extracted Fe appeared to be positively correlated with overall measured U sorption. Batch sorption test results were used to develop generalized composite surface complexation models that incorporated the full genericsorption potential of each sample, without detailed mineralogiccharacterization. The resultant models provide U sorption parameters (site densities and equilibrium constants) for reactive transport modeling. The generalized composite surface complexation sorption models were calibrated to batch sorption data from three oxidized core samples using inverse modeling, and gave larger sorption parameters than just U sorption on the measured solidphase Fe. These larger sorption parameters can significantly influence reactive transport modeling, potentially increasing U attenuation. Because of the limited number of calibration points, inverse modeling required the reduction of estimated parameters by fixing two parameters. The best-fit models used fixed values for equilibrium constants, with the sorption site densities being estimated by the inversion process. While these inverse routines did provide best-fit sorption parameters, local minima and correlated parameters might require further evaluation. Despite our limited number of proxy samples, the procedures presented provide a valuable methodology to consider for sites where metal sorption parameters are required. Furthermore, these sorption parameters can be used in reactive transport modeling to assess downgradient metal attenuation, especially when no other calibration data are available, such as at proposed U ISR sites.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Kinetic analyses for solid-state phase transition of metastable amorphous-AlO x (2.5 < x ≤ 3.0) nanostructures into crystalline alumina polymorphs

Solid-solid phase change materials (SS-PCMs) hold promise for energy storage/dissipation in batteries and energetic materials. Yet, phase change kinetics for SS-PCMs undergoing metastable to semi-stable/stable phase transformations remain relatively ill-studied because trapping metastable phases remain challenging. Recently, we demonstrated the kinetic entrapment and stabilization of a highly disordered and amorphous Al-oxide phase m-AlO x @C (x~2.5-3.0) via laser ablation synthesis in solution (LASiS). We report here, to our knowledge, the first chemical kinetics analysis for S-S phase transition of the m-AlO 3 @C nanocomposites (< 5–8 nm sizes) into semi-stable equilibrium alumina phases (θ/γ-Al 2 O 3 ) via disproportionation reaction, while releasing excess trapped gases. Our results indicate the atomic density of the AlO 3 structures to be ~5–10 times less than that of the final Al 2 O 3 phases, which led to the hypothesis of a volume shrinkage process during their phase transition. Temperature-dependent X-ray diffraction studies reveal the high-temperature phase transition for m-AlO 3 → θ/γ-Al 2 O 3 to follow contracting volume kinetics model, thereby validating our earlier hypothesis. Using the geometric volume contraction model, reaction kinetics analyses from Arrhenius plots reveal the activation energy barrier for the phase transition to be ~270±11 kJ/mol. This makes the activation energy barrier nearly identical to the oxidation of micron-sized Al particles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗