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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Quantitative assessment of soil CO 2 concentration and stable carbon isotope for leakage detection at geological carbon sequestration sites

This paper presents a quantitative method to evaluate CO 2 concentration ([CO 2 ]) and stable carbon isotope ratio (δ 13 C) as indicators for leakage detection at a geological carbon sequestration site by combining use of field release tests and a numerical modeling approach. A numerical model was developed to simulate CO 2 dynamics by considering diffusion, dissolution in soil water, and soil respiration. The numerical model fits the background dynamics of [CO 2 ] (360 to 550 ppm) and δ 13 C (-16‰ to -6‰) well and reproduces fairly the overall trend observed during the CO 2 release test. The model was further applied to assess detection probability (DP) of [CO 2 ] and δ 13 C for leakage detection in terms of various factors, such as CO 2 leakage rate, background variations, δ 13 C of the CO 2 leaked, and the threshold value of signal-to-noise ratio. Modeling results suggest that δ 13 C may have a higher DP than [CO 2 ]. This study also shows that DP of δ 13 C for the IEA Weyburn project is close to 0, implying δ 13 C is inappropriate to be an indicator for CO 2 leakage at the site. Finally, the quantitative method developed can also be used to design a monitoring plan or strategy in a near-surface environment for geological carbon sequestration.

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

Towards High Performance Oxide-Dispersion-Strengthened Alloys

The current first-generation candidate swelling-resistant alloys envisioned to replace austenitics are ferritic and ferritic-martensitic steels, with second-generation alloys being yttria dispersion-hardened variants of these steels. In ferritic-martensitic alloys, ferrite grains always swell earlier than martensite. Currently, most oxide dispersion-strengthened (ODS) alloys have only a ferrite matrix, thus giving up the first line of defense against swelling provided by tempered martensite. Towards development of better swelling-resistant ODS alloys, dual phase (ferrite + martensite) ODS alloys with oxide particles uniformly distributed in both ferrite and martensite phases is needed. Furthermore, fundamental understanding on mechanisms governing dispersoid stability and its correlation with void swelling is greatly needed. We reported here further alloy improvement by exploring new 9Cr ODS alloy with majority of oxide dispersoids uniformly distributed in tempered martensite grains. The alloy was irradiated by 3.5 MeV Fe self ions up to 600 dpa (displacements per atom) and at temperatures ranging from 325 to 625 deg. C. According to SRIM code, the dpa profile peaks at about 1000 nm. First of all, ion irradiation reduces the dispersoid sizes. The dispersoid sizes begin to increase beyond ∼1000 nm. Second, higher irradiation temperatures result in larger dispersoids on average. Third, there is no significant dispersoid size difference between 100 and 200 dpa irradiation. The equilibrium sizes are quickly saturated. Size and coherency of a dispersoid is closely related. In martensite grains, fine dispersoids tend to be coherent while coarse dispersoids tend to incoherent. We found that at a low irradiation temperature, coherent small dispersoids become smaller and their interface coherency remains. In a comparison, incoherent large dispersoids disappear after irradiation. At an intermediate irradiation temperature, the final equilibrium dispersoid sizes increase. At a high irradiation temperature, the final dispersoid sizes further increase and some large semi-coherent dispersoids survive. In ferrite grains, as-received dispersoids are relatively smaller in comparison with martensite grains. Their equilibrium size changes after irradiation follow a similar trend but large dispersoids completely disappear even under high temperature ion irradiation. We propose a model to explain the above dispersoid size changes under various irradiation conditions. The model considers the competing effects between ballistic-collision- assisted dispersoid dissolution into matrix and thermally driven back-diffusion for recovery. When the competing reaches a balance, an equilibrium size distribution curve is determined. For dispersoids smaller than the equilibrium size, they grow upon ion irradiation. Large dispersoids may shrink and reach the equilibrium size but ultra-large ones will completely disappear if they shrinkage paths are far away from the curve. The model further considers the complexity from the dpa rates, and damage cascade morphology.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Kinetic model for quartz and spinel dissolution during melting of high-level-waste glass batch

The dissolution of quartz particles and the growth and dissolution of crystalline phases during the conversion of batch to glass potentially affects both the glass melting process and product quality. Crystals of spinel exiting the cold cap to molten glass below can be troublesome during the vitrification of iron-containing high-level wastes. To estimate the distribution of quartz and spinel fractions within the cold cap, we used kinetic models that relate fractions of these phases to temperature and heating rate. Fitting the model equations to data showed that the heating rate, apart from affecting quartz and spinel behavior directly, also affects them indirectly via concurrent processes, such as the formation and motion of bubbles. Because of these indirect effects, it was necessary to allow one kinetic parameter (the pre-exponential factor) to vary with the heating rate. The resulting kinetic equations are sufficiently simple for the detailed modeling of batch-to-glass conversion as it occurs in glass melters. The estimated fractions and sizes of quartz and spinel particles as they leave the cold cap, determined in this study, will provide the source terms needed for modeling the behavior of these solid particles within the flow of molten glass in the melter.

Batch melting, Cold cap, Quartz, Spinel, Waste gla↗
DOE OSTI2017

Microbial community response and SDS-PAGE reveal possible mechanism of waste activated sludge acidification enhanced by microaeration coupled thermophilic pretreatment

Aiming to strengthen the performance of waste activated sludge digestion, pretreatment is a prerequisite for keeping operations within an industrially acceptable time- frame. The performance of microaeration coupled with thermophilic (MT) pretreatment on waste activated sludge solubilization and acidification was investigated. The results showed that the maximum soluble organics concentrations, including soluble proteins and carbohydrates, reached 2290 mg COD/L in 24 h when the ventilation rate and temperature were 0.05 vvm and 70 °C. SDS-polyacrylamide gel electrophoresis (SDS-PAGE) test on pure-culture (E.coli) and scanning electron microscopy analysis indicated that MT pretreatment effectively destroyed microbial cell wall and resulted in an increase in soluble proteins. Polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) analysis revealed that MT pretreatment reduced the diversity of the bacterial community during pretreatment. Along with the dissolution of a large quantity of organic matter, microbial species such as Lactococcus and Methyloversatilis bloomed at the end of acidification period, which contributed to SCFAs production. Finally, this study revealed that MT pretreatment facilitated the WAS hydrolysis efficiency and enhanced SCFAs (3149 mg COD/L with fermentation for 96 h) production, especially for acetic acid (50%) accumulation, which provides a new perspective for the application and recovery of sludge resources.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Simulating Droplet-Resolved Haze and Cloud Chemistry Forming Secondary Organic Aerosols in Turbulent Conditions within Laboratory and Cloud Parcels

Most of our existing knowledge of cloud chemistry in regards to forming secondary organic aerosols (SOA) is based on measurements in bulk aqueous solutions. However, SOA reaction kinetics derived from bulk solution measurements might differ from the kinetics in actual cloud droplets, since turbulent mixing and ionic strengths, and ratio of surface area to volume in individual cloud droplets might vary substantially from bulk solutions in the real atmosphere. Three-dimensional models at various scales have been used to simulate aqueous chemistry. However, most of these models do not resolve turbulence down to the smallest length scales of 1 mm and do not simulate cloud chemistry in individual cloud droplets due to large computational costs. Here we incorporate the formation of isoprene epoxydiol SOA (IEPOX-SOA) in individual droplets within a one-dimensional explicit mixing parcel model (EMPM-Chem). We apply EMPM-Chem to simulate turbulence and droplet-resolved IEPOX-SOA formation using a configuration based on the Michigan Tech Pi chamber. We find that the dissolution of IEPOX gases is weighted more towards larger cloud droplets due to their large liquid water content (compared to smaller droplets), while the conversion of dissolved IEPOX to IEPOX-SOA is much greater within smaller deliquesced haze particles due to their higher acidity and ionic strengths compared to cloud droplets. We also find that as droplet residence times increase in the chamber, e.g., due to increasing ammonium bisulfate seed aerosol injection rates and/or increasing heights of the chamber, formation of IEPOX-SOA increases substantially. Thus, our EMPM-Chem model could be used to design future cloud chambers to maximize SOA production from cloud chemistry. We also apply the EMPM-Chem model to simulate how IEPOX-SOA formation evolves in individual cloud droplets within rising cloudy parcels in the atmosphere. We find that as subsaturated air is entrained into and turbulently mixed with the cloud parcel, evaporation causes a reduction in droplet sizes, which leads to corresponding increases in per droplet ionic strength and acidity. Increased droplet acidity in turn greatly accelerates the kinetics of IEPOX-SOA formation. In conclusion, our results provide key insights into single-cloud-droplet chemistry, suggesting that entrainment mixing may be an important process that increases SOA formation in the real atmosphere.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Improved Application of Local Models to Steel Corrosion in Lead-Bismuth Loops

The corrosion of steels exposed to flowing liquid metals is influenced by local and global conditions of flow systems. The present study improves the previous local models when applied to closed loops by incorporating some global condition effects. In particular the bulk corrosion product concentration is calculated based on balancing the dissolution and precipitation in the entire closed loop. Mass transfer expressions developed in aqueous medium and an analytical expression are tested in the liquid-metal environments. The improved model is applied to a pure lead loop and produces results closer to the experimental data than the previous local models do. The model is also applied to a lead-bismuth eutectic (LBE) test loop. Systematic studies illustrate the effects of the flow rate, the oxygen concentration in LBE, and the temperature profile on the corrosion rate.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Atomic-scale constituting stable interface for improved LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathodes of lithium-ion batteries

Ascribed to their higher capacity and lower cost compared to conventional LiCoO 2 , the Ni-rich layered LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) is now considered as one promising cathode for lithium-ion batteries (LIBs). However, it still suffers from some evident performance degradation, especially under high cutoff voltages (i.e., >4.3 V versus Li/Li + ). The performance degradation typically is exhibited as capacity fading and voltage drop, mainly originating from an instable interface between the NMC622 and electrolyte as well as the evolution of the NMC structure. To improve the interfacial and structural stability of NMC cathodes, herein we deposited an ultrathin layer of Al 2 O 3 coatings (<5 nm) conformally over NMC622 composite electrodes directly using atomic layer deposition (ALD). It was found that, under different upper cutoff voltages (4.3, 4.5, and 4.7 V), the ALD Al 2 O 3 coatings enable enhanced performance of NMC622 cathodes with better cyclability and higher capacity. Particularly, the beneficial effects of the ALD Al 2 O 3 coatings are more remarkable at higher upper cutoff voltages (4.5 and 4.7 V). Furthermore, the ALD coatings can significantly improve the rate capability of NMC622. To this end, we utilized a suite of characterization tools and performed a series of electrochemical tests to clarify the effects of the ALD Al 2 O 3 coatings. This study revealed that the beneficial effects of the Al 2 O 3 ALD coatings are multiple: (i) serving as an artificial layer of solid electrolyte interphase to mitigate undesirable interfacial reactions; (ii) acting as a physical barrier to inhibit metal dissolution of NMC; and (iii) forming a reinforced networked overcoating to boost the mechanical integrity of NMC cathodes. This study is favorable for designing high-performance NMC cathodes.

25 ENERGY STORAGE↗
DOE OSTI2025

On the Source of Conductivity in Alkaline Zn Anodes: Zn Percolation and ZnO Bridging

Alkaline Zn anodes are fundamental to commercial Zn-MnO 2 batteries as well as emerging rechargeable designs. In these electrodes, Zn particles are both the active material and source of electronic conduction. However, there are known cases in which electronic connectivity between Zn particles or the current collecting pin is lost even though the battery continues to function. Here we use X-ray computed tomography (CT) of AA batteries to demonstrate several examples of Zn particle-to-particle connectivity breakdown, which is observed even in cases at relatively high discharge rate. This indicates maintenance of the electronic network through the less-conductive ZnO discharge product. We introduce a new equation for electronic conductivity maintained through bridges of ZnO formed between percolating Zn particles. This necessitates discarding the Bruggeman correlation and instead redefining effective electronic conductivity using percolation theory. We demonstrate that such a model for conduction enables prediction of an inverted reaction zone, which is an experimentally observed case in which significant Zn dissolution and ZnO formation occurs heavily near the current collecting pin. Current computational Zn-MnO 2 models never predict an inverted reaction zone, and thus the updated conductivity enables models to accurately explain a wider range of experimental conditions.

Guida, Dominick P. [Northeastern Univ., Boston, MA↗
DOE OSTI2016

Design Optimization of Liquid Fueled High Velocity Oxy- Fuel Thermal Spraying Technique for Durable Coating for Fossil Power Systems

High-velocity oxy–fuel (HVOF) thermal spraying was developed in 1930 and has been commercially available for twenty-five years. HVOF thermal spraying has several benefits over the more conventional plasma spray technique including a faster deposition rate which leads to quicker turn-around, with more durable coatings and higher bond strength, hardness and wear resistance due to a homogeneous distribution of the sprayed particles. HVOF thermal spraying is frequently used in engineering to deposit cermets, metallic alloys, composites and polymers, to enhance product life and performance. HVOF thermal spraying system is a highly promising technique for applying durable coatings on structural materials for corrosive and high temperature environments in advanced ultra-supercritical coal- fired (AUSC) boilers, steam turbines and gas turbines. HVOF thermal spraying is the preferred method for producing coatings with low porosity and high adhesion. HVOF thermal spray process has been shown to be one of the most efficient techniques to deposit high performance coatings at moderate cost. Variables affecting the deposit formation and coating properties include hardware characteristics such as nozzle geometry and spraying distance and process parameters such as equivalence ratio, gas flow density, and powder feedstock. In the spray process, the powder particles experience very high speeds combined with fast heating to the powder material melting point or above. This high temperature causes evaporation of the powder, dissolution, and phase transformations. Due to the complex nature of the HVOF technique, the control and optimization of the process is difficult. In general, good coating quality with suitable properties and required performance for specific applications is the goal in producing thermal spray coatings. In order to reach this goal, a deeper understanding of the spray process as a whole is needed. Although many researchers studied commercial HVOF thermal spray systems, there exists a lack of fundamental understanding of the effect of hardware characteristics and operating parameters on HVOF thermally sprayed coatings. Motivated by these issues, this study is devoted to investigate the effect of hardware characteristics (e.g. spraying distance) and operating parameters (e.g. combustion chamber pressure, equivalence ratio, and total gas flow rate) on HVOF sprayed coatings using Inconel 718 alloy. The current study provides extensive understanding of several key operating and process parameters to optimize the next generation of HVOF thermally sprayed coatings for high temperature and harsh environment applications. A facility was developed to support this endeavor in a safe and efficient way, including a HVOF thermal spray system with a Data Acquisition and Remote Controls system (DARCS). The coatings microstructure and morphology were examined using X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM) and Nanoindentation.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2018

Investigation on Microstructural Evolutions and Mechanical Properties of P92 Steel During Thermal Processing

The evolution of the microstructure of P92 steel during heat processing has a significant effect on the final performance of steel products and is thus an area of critical interest. Accordingly, the grain growth behavior of austenite and δ-ferrite changes in P92 steel is comprehensively investigated in this study through thermodynamic calculations and physical simulation. The results show that the A{sub C1}, A{sub C3} and γ–δ transformation temperatures of P92 steel are 841 °C, 878 °C and 1095 °C, respectively, which are comparable to the measured values of 850 °C, 879 °C and 1175 °C, respectively. When the temperature exceeds the A{sub C1} temperature, the austenite grain size increases with increasing temperature and longer holding times, and the growth rate of austenite grains increases with higher temperatures but decreases with holding time at a certain temperature. A model that shows the austenite grain growth kinetics is established: D{sup n} − D{sub 0}{sup n} = 2.03 × 10{sup 16}exp(− 498,770/RT)t, in which the time exponent n decreases from 4.52 to 2.11 with an increase in temperature from 1000 °C to 1200 °C due to the reduced pinning effect resultant of the dissolution of precipitates, M{sub 23}C{sub 6}, VX and NbX at 887 °C, 1073 °C and 1200 °C, respectively. The formation of δ-ferrite at 1200 °C when held for 600 s and 1300 °C when held for 60 ~ 600 s causes a smaller austenite grain size. The relationship between the evolution of the microstructure of P92 steel and the mechanical properties is also studied. The results show that the prior austenite grain size has an inverse relationship with impact energy and ultimate tensile strength at 620 °C, while the presence of soft δ-ferrite leads to a reduction in the microhardness, impact energy and ultimate tensile strength at 620 °C.

36 MATERIALS SCIENCE↗
DOE OSTI2017

A New Lamination and doping Concepts for Enhanced Li – S Battery Performance

Lithium ion batteries (LIBs) clearly dominated the area of high-energy storage systems for the past decade with significant research and development activity focused on the development of cathode and anode materials to maximize the specific energy storage, stability, and cycle life of the batteries. However, with the increasing demand in the EV industry for low cost, low weight, and high-energy storage batteries to meet the EV everywhere grand challenge, the current focus of research has shifted towards the development of lithium sulfur batteries (LSB) owing to the high theoretical specific capacity exhibited by sulfur compared to other cathode materials currently available. Li–S battery shows a theoretical capacity of 1675 mAh/g corresponding to the formation of Li2S which makes sulfur a promising electrode to replace the layered transition metal oxides (~150 mAh/g) and LiFePO4 (~170 mAh/g) hitherto deployed in present LIB systems. Moreover, the abundance of sulfur in the earth’s crust makes it a more economical and highly attractive proposition compared to currently existing cathodes. Despite advantages of sulfur, the existing Li-S battery technology display poor cyclability, low coulombic efficiency (CE) and very low cycle life due to the following issues: 1. Polysulfide (PS) dissolution; 2. Sluggish kinetics of PS to Li2S conversion; 3. High PS diffusivity in the electrolyte; 4. Insulating nature or poor conductivity of sulfur/Li2S; 5. Volumetric expansion/contraction of sulfur; 6. Shuttling of PS along with Li+. These issues result in loss of sulfur causing mechanical disintegration, surface passivation of both anode and cathode, thereby decreasing the specific capacity and columbic efficiency (CE). Present generation sulfur cathodes also show low specific storage capacity, very poor charging rates and low loading densities. Research is needed to overcome the issues impeding Li-S battery technology development.

25 ENERGY STORAGE↗
DOE OSTI2020

Consolidating Lithiothermic-Ready Transition Metals for Li2S-Based Cathodes

Li 2 S holds a promising role as a high-capacity Li-containing cathode, circumventing use of metallic lithium in constructing next-generation batteries to replace current Li-ion batteries. However, progress of Li 2 S cathode has been plagued by its intrinsic drawbacks, including high activation potentials, poor rate performance, and rapid capacity fading during long cycling. In this work, a series of Li 2 S/transition metal (TM) nanocomposites are synthesized via a lithiothermic reduction reaction, and it is realized that the presence of TMs in Li 2 S matrix can transform electrochemical behaviors of Li 2 S. On the one hand, the incorporation of W, Mo, or Ti greatly increases electronic and ionic conductivity of Li 2 S composites and inhibits the polysulfide dissolution via the TM—S bond, effectively addressing the drawbacks of Li 2 S cathodes. In particular, Li 2 S/W and Li 2 S/Mo exhibit the highest ionic conductivity of solid-phase Li-ion conductors ever-reported: 5.44 × 10 –2 and 3.62 × 10 –2 S m –1 , respectively. On the other hand, integrating Co, Mn, and Zn turns Li 2 S into a prelithiation agent, forming metal sulfides rather than S 8 after the full charge. These interesting findings may shed light on the design of Li 2 S-based cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2014

MODELING POTENTIAL IMPACTS OF SO2 CO-INJECTED WITH CO2 ON THE KNOX GROUP, WESTERN KENTUCKY

Understanding potential long-term impacts of CO2 impurities, such as sulfur and nitrogen compounds, on deep carbon storage reservoirs is of considerable interest because co-injection of the impurities with CO2 can bring significant economic and environmental benefits. The Cambrian–Ordovician Knox Group, a thick sequence of dolostone (Beekmantown Dolomite) with minor dolomitic sandstone (Gunter Sandstone), in western Kentucky, USA, has been evaluated as a prospective CO2 sequestration target. In this study, TOUGHREACT was used to build 1-D radial models to simulate the potential impacts of co-injected CO2 and SO2 on minerals, pore fluids, and porosity and permeability in the Beekmantown Dolomite and the Gunter Sandstone. Co-injection of a mass ratio of 2.5 percent SO2 and 97.5 percent CO2, representative of flue gas from coal-fired plants, was simulated and the co-injection simulations were compared to models with CO2 only injections. The model results suggest that the major impacts of added SO2 for both the Beekmantown and the Gunter rocks were significant enhancement of dissolution of dolomite and precipitation of anhydrite, leading to noticeable increases in porosity and permeability. The Gunter Sandstone appeared to be more active with SO2 than the Beekmantown Dolomite. More dolomite was dissolved in the Gunter than in the Beekmantown with the same SO2 impurity. Consequently, porosity was raised more in the Gunter than in the Beekmantown. On the other hand, the impacts on aluminosilicate minerals appeared to be insignificant in both reservoirs, slightly changing the rates of precipitation/dissolution but the overall reaction paths remained the same.

Zhu, Junfeng↗
DOE OSTI2020

Copper Electrodeposition from Deep Eutectic Solvents—Voltammetric Studies Providing Insights into the Role of Substrate: Platinum vs Glassy Carbon

We report on the effect of the substrate on electrochemical deposition of Cu from deep eutectic solvent ethaline. We investigated the polarization behavior during electrodeposition of Cu on Pt and glassy carbon (GC) from both Cu 2+ and Cu + containing ethaline using cyclic voltammetry (CV). Formation of bulk Cu deposits on both substrates underwent nucleation and growth processes; however, the nucleation was considerably sluggish on GC compared to Pt. While experiments in Cu+ solutions indicated that coalescence of Cu islands on Pt is a slow process and that its surface may not be fully covered by Cu, such determination of Cu coverage could not be made on GC. Cu dissolution is also slower from GC than from Pt. It was observed that CV of Cu deposition on GC is influenced by the surface preparation method. Since ethaline has high chloride concentration, a parallel study in aqueous 3 M NaCl solution was conducted in order to examine the influence of the chloride medium on the electrodeposition process. Lastly, this revealed that electrodeposition in both media occurred in the same manner but with different charge and mass transfer rates caused by the differences in viscosity and chloride concentrations of the two solutions.

25 ENERGY STORAGE↗
DOE OSTI2021

In Situ Polymerization of Polypyrrole and Polyaniline on the Surface of Magnetic Molybdenum Trioxide Nanoparticles: Implications for Water Treatment

Photocatalyst dissolution greatly diminishes the usability of photocatalysts in water treatments. Coating conductive polymers on the surface of photocatalysts can reduce dissolution without compromising the photocatalytic properties of the material. In this investigation, polypyrrole (PPy) and polyaniline (PANI) were used to coat two magnetic MoO 3 nanoparticles with different surface chemistries. The polymer-coated MoO 3 @Fe 3 O 4 nanoparticles were synthesized by optimizing the mole fractions of PPy or PANI, MoO 3 , and Fe 3 O 4 . The optimized PPy@ MoO 3 @Fe 3 O 4 (PMF1) and PANI@MoO 3 @Fe 3 O 4 (PMF2) resulted in 95.39 and 75.98% methylene blue dye removal, respectively. MoO 3 dissolutions of 4.12 and 5.6% were obtained for PMF1 and PMF2, respectively, demonstrating the reduced solubility of the coated nanoparticles as compared to their uncoated counterparts (7.87% for MF1 and 18.1% for MF2). In situ small-angle neutron scattering (SANS) was utilized to investigate the polymerization kinetics of PPy and PANI on nanoparticles. The results revealed that an increase in base material oxygen vacancies resulted in the reduction of both the polymer size and the polymerization rate. Furthermore, this study demonstrated that SANS provides valuable insights into the polymer growth mechanisms on nanoparticle surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Effects of Aging on PuO2∙xH2O Particle Size in Alkaline Solution

Between 1944 and 1989, 54.5 metric tons of the United States’ weapons-grade plutonium and an additional 12.9 metric tons of fuel-grade plutonium were produced and separated from irradiated fuel at the Hanford Site. Acidic high-activity wastes containing around 600 kg of plutonium were made alkaline and discharged to underground storage tanks from separations, isolation, and recycle processes to yield average plutonium concentration of about 0.003 grams per liter (or ~0.0002 wt%) in the ~200 million liter tank waste volume. The plutonium is largely associated with low-solubility metal hydroxide/oxide sludges where its low concentration and intimate mixture with neutron-absorbing elements (e.g., iron) are credited in nuclear criticality safety. However, concerns have been expressed that plutonium, in the form of plutonium hydrous oxide, PuO2∙xH2O, could undergo sufficient crystal growth through dissolution and reprecipitation in the alkaline tank waste to potentially become separable from neutron absorbing constituents by settling or sedimentation. Thermodynamic considerations and laboratory studies of systems chemically analogous to tank waste show that the plutonium formed in the alkaline tank waste by precipitation through neutralization from acid solution probably entered as 2–4-nm PuO2∙xH2O crystallite particles that, because of their low solubility and opposition from radiolytic processes, grow from that point at exceedingly slow rates, thus posing no risk of physical segregation.

aging↗
DOE OSTI2018

The Development of Wormholes in Laboratory-Scale Fractures: Perspectives From Three-Dimensional Simulations

Here, we investigate the development of wormholes in laboratory–scale fractures using three–dimensional numerical simulations. Well–controlled initial conditions, involving a small perturbation near the inlet of an otherwise flat fracture aperture field, were used to make a systematic study of the effects of flow rate and reaction rate on the aperture evolution. We find at least two characteristic wormhole shapes, which can be grouped within a phase diagram in the space of Péclet and Damköhler numbers. We investigate how this phase diagram depends on fracture geometry, specifically the length ( L ) and width ( W ) in comparison to the initial aperture ( h 0 ). This information is used to determine an effective Damköhler number that leads to a Péclet and length–independent phase boundary between wormholes and uniform dissolution. We relate these observations to experimental studies of wormhole formation in dissolving fractures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗