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At least 703 records · Page 39

Discovery of nanopore filling by gypsum in wellbore cement exposed to 17 MPa CO 2 under geologic carbon storage conditions

Here, this study investigates the pore structure evolution of the reaction zones in wellbore cement samples exposed to a CO 2 -rich solution in equilibrium with 17 MPa supercritical CO 2 over 14 days. Through advanced characterization methods of field emission SEM, Quantitative Evaluation of Minerals by Scanning Electron Microscopy (QEMSCAN), and micro-CT, a new mechanism of CO 2 -cement reaction involving filling of nanopores in the interior of cement by gypsum was revealed. Gypsum was formed by the liberation of SO 4 2− from ettringite (AFt) and monosulfate (AFm) caused by a decrease in pH. Based on these experimental observations, a new CO 2 -cement reaction model that incorporates four distinct reaction zones is developed. This model provides a comprehensive framework for understanding the spatial and temporal distribution of minerals in cement due to high pressure CO 2 —cement reactions. This study demonstrates that the major damage induced by high pressure CO 2 alteration occurs in the most exterior region of the cement. The interior region of the cement maintains its integrity due to nanopore filling by gypsum.

54 ENVIRONMENTAL SCIENCES↗

Dehydration of Methyl Lactate on Alkali Cation-Exchanged Faujasite: Effects of Metal Cation Identity and Water Pressure

Turnover rates for the catalytic dehydration of methyl lactate (ML) over ion-exchanged faujasite (FAU) catalysts depend on the identity of alkali metal cations (Na + , K + , Cs + ) and local solvation effects. Analysis of rate measurements and in situ infrared spectroscopy gives evidence that the reaction involves kinetically relevant dissociation of adsorbed methyl lactate upon alkali metal cations. This process involves concerted methyl transfer to the surface and dissociation of the alkali metal from the framework, which occurs at cationic active sites that remain predominantly unoccupied under relevant conditions (0.5–10 kPa ML, 0.5–15 kPa H 2 O, 563–583 K). Despite the mechanistic similarities, apparent activation enthalpies (ΔH app ‡ ) decrease linearly (47 kJ mol –1 from Na + to Cs + ) with ionization energy and cationic radius, and apparent activation entropies (ΔS app ‡ ) decrease 74 J mol –1 K –1 . These trends reflect electrostatic interactions that stabilize the cations to the anionic sites on the zeolite: stronger association between these charges leads to increasingly endothermic processes to displace the alkali metal to form a cationic methoxy and an intrapore metal lactate intermediate. Water physisorption measurements suggest alkali metal ions bind superstoichiometric quantities of water within FAU pores, and in situ infrared spectra suggest the concerted adsorption of ML requires reorganization of this water. Consequently, these processes introduce entropic gains that partially offset entropy losses associated with ML adsorption. Hence, turnover rates differ only by a factor of 2 among Na-, K-, and Cs-FAU at 573 K (ΔΔG app ‡ = 5 kJ mol –1 ). These findings demonstrate the interplay of alkali metal ions with zeolite active sites and intrapore water clusters for ML dehydration, indicating that these interactions can be leveraged to deliver optimal performance under different reaction conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of High Mean Stress on High-cycle Fatigue Behavior of PWA 1480

PWA 1480 is a potential candidate material for use in the high-pressure fuel turbine blade of the space shuttle main engine. As an engine material it will be subjected to high-cycle fatigue loading superimposed on a high mean stress due to combined centrifugal and thermal loadings. The present paper describes the results obtained in an ongoing program at the Argonne National Laboratory, sponsored by NASA Lewis, to determine the effects of a high mean stress on the high-cycle fatigue behavior of this material. Straight-gauge high-cycle fatigue specimens, 0.2 inch in diameter and with the specimen axis in the 001 direction, were supplied by NASA Lewis. The nominal room temperature yield and ultimate strength of the material were 146 and 154 ksi, respectively. Each specimen was polished with 1-micron diamond paste prior to testing. However, the surface of each specimen contained many pores, some of which were as large as 50 micron. In the initial tests, specimens were subjected to axial-strain-controlled cycles. However, very little cyclic plasticity was observed.

Majumdar, S.↗

Testing of electroformed deposited iridium/powder metallurgy rhenium rockets

High-temperature, oxidation-resistant chamber materials offer the thermal margin for high performance and extended lifetimes for radiation-cooled rockets. Rhenium (Re) coated with iridium (Ir) allow hours of operation at 2200 C on Earth-storable propellants. One process for manufacturing Ir/Re rocket chambers is the fabrication of Re substrates by powder metallurgy (PM) and the application of Ir coatings by using electroformed deposition (ED). ED Ir coatings, however, have been found to be porous and poorly adherent. The integrity of ED Ir coatings could be improved by densification after the electroforming process. This report summarizes the testing of two 22-N, ED Ir/PM Re rocket chambers that were subjected to post-deposition treatments in an effort to densify the Ir coating. One chamber was vacuum annealed, while the other chamber was subjected to hot isostatic pressure (HIP). The chambers were tested on gaseous oxygen/gaseous hydrogen propellants, at mixture ratios that simulated the oxidizing environments of Earth-storable propellants. ne annealed ED Ir/PM Re chamber was tested for a total of 24 firings and 4.58 hr at a mixture ratio of 4.2. After only 9 firings, the annealed ED Ir coating began to blister and spall upstream of the throat. The blistering and spalling were similar to what had been experienced with unannealed, as-deposited ED Ir coatings. The HIP ED Ir/PM Re chamber was tested for a total of 91 firings and 11.45 hr at mixture ratios of 3.2 and 4.2. The HIP ED Ir coating remained adherent to the Re substrate throughout testing; there were no visible signs of coating degradation. Metallography revealed, however, thinning of the HIP Ir coating and occasional pores in the Re layer upstream of the throat. Pinholes in the Ir coating may have provided a path for oxidation of the Re substrate at these locations. The HIP ED Ir coating proved to be more effective than vacuum annealed and as-deposited ED Ir. Further densification is still required to match the integrity of chemically vapor deposited Ir coatings. Despite this, the successful long duration testing of the HIP ED Ir chamber, in an oxidizing environment comparable to Earth-storable propellants, demonstrated the viability of this Ir/Re rocket fabrication process.

Reed, Brian D.↗

Confinement-Driven Heterogeneous Benzene Crystallization in Silica Nanopores

Nanoconfinement alters the thermodynamics, dynamics, and kinetics of fluids hosted in nanoscale solid nanopores to an extent that depends on the characteristics of the confining space and the chemistry of the confined fluids. Confinement-induced alterations in the phase behavior of confined energetic fluids under high pressure or low temperature are highly relevant to subsurface and subsea phenomena such as fluid flow in porous media, hydrate formation and dissociation, and gas storage capacity. Although extensive efforts have been directed toward understanding the phase behavior of confined fluids, the role of solid-liquid interfaces in the phase transitions of organic liquids has not been resolved yet. Here, we explore the onset and growth of benzene crystallization confined in 6 nm sized SBA-15 silica nanopores in the temperature range 300-200 K using in situ extended range small-angle and wide-angle X-ray scattering (SAXS/WAXS) measurements and atomistic classical molecular dynamics (MD) simulations. The crystallization onset of confined benzene depresses to 265 K compared to the freezing point of bulk benzene ( ~278 K), followed by the continuous growth of the emerged crystals in the pore space with complete crystallization at 200 K. The orientation of the emerged benzene crystals is dominated by parallel (π-π stacking) and perpendicular (T-shape stacking) orientations along the cylindrical pore radius and pore length, respectively. The onset of benzene crystals occurs heterogeneously on the pore surface and grows continuously toward the pore center. Further, confined benzene undergoes a dynamical crossover from fragile to strong dynamics behavior, inferred from the rotational and translational diffusion. The insights provided by this study have significant implications for the phase transitions of confined organic liquids that are relevant to a wide range of applications in the biological, geological, environmental, and chemical fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluating the Adsorptive Capabilites of Chemsorb 1000 and Chemsorb 1425

The removal of trace contaminants from spacecraft cabin air is necessary for crew health and comfort during long duration space exploration missions. The air revitalization technologies used in these future exploration missions will evolve from current ISS ISS State-of-Art (SOA) and is being designed and tested by the Advanced Exploration Systems (AES) Program's Atmosphere Resource Recovery and Environmental Monitoring (ARREM) project. The ARREM project is working to mature optimum atmosphere revitalization and environmental monitoring system architectures to enable exploration beyond Lower Earth Orbit (LEO). The Air Revitalization Lab at KSC is one of six NASA field centers participating in the ARREM that specializes in adsorbent and catalyst characterization with simulated spacecraft gas streams using combinations of pressure, O2 partial pressure, CO2 partial pressure, and humidity that are representative of a range of anticipated cabin atmospheric conditions and loads. On board ISS, the Trace Contaminant Control Subassembly (TCCS) provides active control of trace contaminants from the cabin atmosphere utilizing physical adsorption, thermal catalytic oxidation, and chemical adsorption processes. High molecular weight contaminants and ammonia (NH3) are removed a granular activated carbon treated with approx. 10% by weight phosphoric acid (H3PO4) (B-S Type 3032 4×6 mesh), which is expendable and is periodically refurbished. The Type 3032 granular activated carbon bed is no longer commercially available and therefore it is important to characterize the efficiency and capacity of commercially available NH3 sorbents. This paper describes the characterization of two Molecular Products LTD activated carbons: Chemsorb 1000 and Chemsorb 1425. Untreated activated carbons (e.g. Chemsorb 1000) remove contaminants by physisorption, which concentrates the contaminant within the pores of the carbon while letting air to pass through the sorbent4. Low molecular weight or polar gases (e.g. HCl, SO2, formaldehyde, and NH3) are not removed by physisorption and typically require chemisorption for removal. Treated activated carbons (e.g. Chemsorb 1425) are impregnated with a a chemical agent (e.g. phosphoric acid) that reacts with those gases, converting them to solids or salts within the carbon and removes them from the air stream. This process occurs via neutralization or catalysis reactions and adsorption capacity is exhaustedwhen the available impregnated chemicals are consumed. Moisture affects removal performance since adsorption sites within the pores are filled with water. The performance of impregnated carbons may be enhanced by moisture content because the mechanisms of contaminant removal are chemical reactions that occur in reagents contained within the pores. The adsorptive capacity data (mol/kg) of Chemsorb 1000 and 1425 for gas mixtures (ethanol, acetone, toluene, acetaldehyde, dichloromethane, and xylene) was measured with 40% relative humidity at 23 deg C air temperature. The adsorptive capacity data (mol/kg) of Chemsorb 1425 was measured using NH3 gas streams.

adsorptive capacities↗

Pore-scale simulation of gas flow in microscopic permeable media with complex geometries

Lattice Boltzmann method (LBM) is an efficient tool to perform direct numerical simulation of gas flow in micro-size pores. Despite great advances in LBM and its use in describing gas flow in micro-size channels in slip and transitional flow regimes, exploring formulations that are able to capture flow behavior in domains with complex boundary geometries remains a challenging task. As a result, the impact of complexities in pore structures on gas flow may not be fully explored using LBM. In this study, we propose to use the combined bounce-back and Maxwellian diffusive reflection scheme to capture the slip velocity with a new set of slip coefficients. Optimal values of slip coefficients are determined using a gradient based method, where the results from the linearized Boltzmann equation is used as the reference solution. The proposed formulation is further validated against predictions from molecular dynamics simulation in the presence of complex geometries by introducing obstacles of different shapes in straight channels. LBM with the proposed boundary treatment is then used to investigate gas flow in a synthetic microscopic permeable medium. Here, results indicate that gas exhibits different flow configurations as Knudsen number varies, and apparent gas permeability appears to have up to a second-order dependency on the reciprocal mean pressure in slip and transitional flow regimes.

03 NATURAL GAS↗

Substituted ALPO-5 Zeolites as Promising O 2 Sorption Pump Materials: A Density Functional Theory Study

Many chemical processes depend on having an environment that is low in oxygen partial pressure (P O2 < 100 Pa); sorption pumps are a promising route to establishing that environment by either oxygen pumping or oxygen separation from an inert gas. Near ambient sorption-based processes rely on either pressure or thermal swings, requiring no moving parts, no electricity, and neither very high nor very low temperatures. In this work, we use ab initio calculations to explore zeolites as a class of materials for sorption based oxygen pumping/separation. Our calculations indicate that while the neat ALPO-5 zeolite does not adsorb O 2 , O 2 does adsorb on zeolites selectively substituted with transition metals and metalloids and hence, can enable separation and pumping. ALPO-5 substituted with Si, Ge, Sn, Pd, Pt, Ti, V, Cr, Mn, Zr, Mo, Hf, W, Ce, and Pr provides adsorption energies ranging from -0.19 to -3.92 eV, (-) indicates exothermic process. Additionally, we provide a comprehensive understanding of what controls the adsorption energy: 1) the substi-tutions must be able to adopt an oxidation state that is more positive than the cation it replaces, and 2) the size of the pore into which the O 2 adsorbs to the wall. Additionally, we conduct a ther-modynamic analysis of a thermal swing cycle to approximate the optimal O 2 binding energy for 2 low energy O 2 pumping/separation. We find that the minimum energy cost likely occurs when the adsorption energy is in the range of 0.75 – 1.00 eV (72 – 97 kJ·mol -1 ), which corresponds to Ge, V, Pt, or Ce substituted ALPO-5.

36 MATERIALS SCIENCE↗

Development and Testing of an ISRU Soil Mechanics Vacuum Test Facility

For extraterrestrial missions, earth based testing in relevant environments is key to successful hardware development. This is true for both early component level development and system level integration. For In-Situ Resource Utilization (ISRU) on the moon, hardware must interface with the surface material, or regolith, in a vacuum environment. A relevant test environment will therefore involve a vacuum chamber with a controlled, properly conditioned bed of lunar regolith simulant. However, in earth-based granular media, such as lunar regolith simulant, gases trapped within the material pore structures and water adsorbed to all particle surfaces will release when exposed to vacuum. Early vacuum testing has shown that this gas release can occur violently, which loosens and weakens the simulant, altering the consolidation state. A mid-size chamber (3.66 m tall, 1.5 m inner diameter) at the NASA Glenn Research Center has been modified to create a soil mechanics test facility. A 0.64 m deep by 0.914 m square metric ton bed of lunar simulant was placed under vacuum using a variety of pumping techniques. Both GRC-3 and LHT-3M simulant types were used. Data obtained from an electric cone penetrometer can be used to determine strength properties at vacuum including: cohesion, friction angle, bulk density and shear modulus. Simulant disruptions, caused by off-gassing, affected the strength properties, but could be mitigated by reducing pump rate. No disruptions were observed at pressures below 2.5 Torr, regardless of the pump rate. The slow off-gassing of the soil at low pressure lead to long test times; a full week to reach 10(exp -5) Torr. Robotic soil manipulation would enable multiple ISRU hardware test within the same vacuum cycle. The feasibility of a robotically controlled auger and tamper was explored at vacuum conditions.

lunar regolith↗

ISRU Soil Mechanics Vacuum Facility: Soil Bin Preparation and Simulant Strength Characterization

Testing in relevant environments is key to exploration mission hardware development. This is true on both the component level (in early development) and system level (in late development stages). During ISRU missions the hardware will interface with the soil (digging, roving, etc) in a vacuum environment. A relevant test environment will therefore involve a vacuum chamber with a controlled, conditioned simulant bed. However, in earth-based granular media, such as lunar soil simulant, gases trapped within the material pore structures and water adsorbed to all particle surfaces will release when exposed to vacuum. Early vacuum testing has shown that this gas release can occur violently, which loosens and weakens the simulant, altering the consolidation state. The Vacuum Facility #13, a mid-size chamber (3.66m tall, 1.5m inner diameter) at the NASA Glenn Research Center has been modified to create a soil mechanics test facility. A 0.64m deep by 0.914m square metric ton bed of lunar simulant was placed under vacuum using a variety of pumping techniques. Both GRC-3 and LHT-3M simulant types have been used. An electric cone penetrometer was used to measure simulant strength properties at vacuum including: cohesion, friction angle, bulk density and shear modulus. Simulant disruptions, caused by off gassing, affected the strength properties, but could be mitigated by reducing pump rate. No disruptions were observed at pressures below 2.5Torr, regardless of the pump rate. However, slow off gassing of the soil lead to long test times, a full week, to reach 10-5Torr. This work highlights the need for robotic machine-simulant hardware and operations in vacuum to expeditiously perform (sub-)systems tests.

Kleinhenz, Julie↗

Microgravity Passive Phase Separator

A new invention disclosure discusses a structure and process for separating gas from liquids in microgravity. The Microgravity Passive Phase Separator consists of two concentric, pleated, woven stainless- steel screens (25-micrometer nominal pore) with an axial inlet, and an annular outlet between both screens (see figure). Water enters at one end of the center screen at high velocity, eventually passing through the inner screen and out through the annular exit. As gas is introduced into the flow stream, the drag force exerted on the bubble pushes it downstream until flow stagnation or until it reaches an equilibrium point between the surface tension holding bubble to the screen and the drag force. Gas bubbles of a given size will form a front that is moved further down the length of the inner screen with increasing velocity. As more bubbles are added, the front location will remain fixed, but additional bubbles will move to the end of the unit, eventually coming to rest in the large cavity between the unit housing and the outer screen (storage area). Owing to the small size of the pores and the hydrophilic nature of the screen material, gas does not pass through the screen and is retained within the unit for emptying during ground processing. If debris is picked up on the screen, the area closest to the inlet will become clogged, so high-velocity flow will persist farther down the length of the center screen, pushing the bubble front further from the inlet of the inner screen. It is desired to keep the velocity high enough so that, for any bubble size, an area of clean screen exists between the bubbles and the debris. The primary benefits of this innovation are the lack of any need for additional power, strip gas, or location for venting the separated gas. As the unit contains no membrane, the transport fluid will not be lost due to evaporation in the process of gas separation. Separation is performed with relatively low pressure drop based on the large surface area of the separating screen. Additionally, there are no moving parts, and there are no failure modes that involve fluid loss. A patent application has been filed.

Paragano, Matthew↗

Measured CO 2 sorption isotherms with 25 Bakken Petroleum System rock samples from the Lower and Upper Shales, Middle Bakken, and Three Forks formations

Isotherms were measured with 25 Bakken Petroleum System (BPS) rock samples using a magnetic suspension balance at reservoir conditions of 110 °C and pressures up to 345 bar. Samples from four wells represented the Middle Bakken (MB) and Three Forks (TF) production zones, and the Upper Bakken Shale (UBS) and Lower Bakken Shale (LBS) source shales. UBS and LBS CO 2 sorption capacities at 345 bar averaged 12–14 g/kg rock compared to 1.3 to 2.5 g/kg rock for MB and TF. Increasing pressure from 150 to 345 bar resulted in only small increases in CO 2 sorption for all lithofacies. For the UBS and LBS source shales, the higher average total organic carbon (TOC) values (14.7 and 11.4 wt.%) and clay values (25 and 28 wt.%) corresponded to their higher CO 2 sorption values while for the MB and TF samples, lower TOCs (0.3 and 0.5 wt.%) and clay values (8.2 and 18.2 wt.%) corresponded to lower CO 2 sorption values. Here, when all 25 samples (from all lithofacies) were evaluated as a group, sorption capacities were highly correlated with TOC (Spearman's rho values +0.84 to +0.85), with rock density (rho values -0.75 to -0.76), and clay content (rho values +0.66). However, correlations with porosity and thermal maturity (Tmax) were weak. Measured sorption capacities and rock porosities showed that sorption accounted for about 10-times as much CO 2 storage as the available pore space for the UBS and LBS lithofacies. In contrast, the pore space dominated the storage resource of the TF and MB lithofacies.

54 ENVIRONMENTAL SCIENCES↗

Mineral and fluid transformation of hydraulically fractured shale: case study of Caney Shale in Southern Oklahoma

This study explores the geochemical reactions that can cause permeability loss in hydraulically fractured reservoirs. The experiments involved the reaction of powdered-rock samples with produced brines in batch reactor system at temperature of 95 °C and atmospheric pressure for 7-days and 30-days respectively. Results show changes in mineralogy and chemistry of rock and fluid samples respectively, therefore confirming chemical reactions between the two during the experiments. The mineralogical changes of the rock included decreases of pyrite and feldspar content, whilst carbonate and illite content showed an initial stability and increase respectively before decreasing. Results from analyses of post-reaction fluids generally corroborate the results obtained from mineralogical analyses. Integrating the results obtained from both rocks and fluids reveal a complex trend of reactions between rock and fluid samples which is summarized as follows. Dissolution of pyrite by oxygenated fluid causes transient and localized acidity which triggers the dissolution of feldspar, carbonates, and other minerals susceptible to dissolution under acidic conditions. The dissolution of minerals releases high concentrations of ions, some of which subsequently precipitate secondary minerals. On the field scale, the formation of secondary minerals in the pores and flow paths of hydrocarbons can cause significant reduction in the permeability of the reservoir, which will culminate in rapid productivity decline. This study provides an understanding of the geochemical rock–fluid reactions that impact long term permeability of shale reservoirs.

58 GEOSCIENCES↗

Investigation of Advanced Processed Single-Crystal Turbine Blade Alloys

This investigation studied the influence of thermal processing and microstructure on the mechanical properties of the single-crystal, nickel-based superalloys PWA 1482 and PWA 1484. The objective of the program was to develop an improved single-crystal turbine blade alloy that is specifically tailored for use in hydrogen fueled rocket engine turbopumps. High-gradient casting, hot isostatic pressing (HIP), and alternate heat treatment (HT) processing parameters were developed to produce pore-free, eutectic-free microstructures with different (gamma)' precipitate morphologies. Test materials were cast in high thermal gradient solidification (greater than 30 C/cm (137 F/in.)) casting furnaces for reduced dendrite arm spacing, improved chemical homogeneity, and reduced interdendritic pore size. The HIP processing was conducted in 40 cm (15.7 in.) diameter production furnaces using a set of parameters selected from a trial matrix study. Metallography was conducted on test samples taken from each respective trial run to characterize the as-HIP microstructure. Post-HIP alternate HT processes were developed for each of the two alloys. The goal of the alternate HT processing was to fully solution the eutectic gamma/(gamma)' phase islands and to develop a series of modified (gamma)' morphologies for subsequent characterization testing. This was accomplished by slow cooling through the (gamma)' solvus at controlled rates to precipitate volume fractions of large (gamma)'. Post-solution alternate HT parameters were established for each alloy providing additional volume fractions of finer precipitates. Screening tests included tensile, high-cycle fatigue (HCF), smooth and notched low-cycle fatigue (LCF), creep, and fatigue crack growth evaluations performed in air and high pressure (34.5 MPa (5 ksi)) hydrogen at room and elevated temperature. Under the most severe embrittling conditions (HCF and smooth and notched LCF in 34.5 MPa (5 ksi) hydrogen at 20 C (68 F), screening test results showed increases in fatigue life typically on the order of 1OX, when compared to the current Space Shuttle Main Engine (SSME) Alternate Turbopump (AT) blade alloy (PWA 1480).

Peters, B. J.↗

Wash Penalty Factors: Insight into the Effects of Water Wash Down of Building Materials for Radionuclide/Nuclear (Rn) Decontamination - 20153

The release of radiological material to the urban environment can have a devastating socio-economic impact. In an urban release scenario, areas around the dispersal epicenter and any areas contaminated via atmospheric deposition may require extensive decontamination. Most recently, our group reported the decontamination efficacy of pressurized water washing of common porous building materials, and compared the penetration depth of the contaminations before and after exposure to pressurized tap water. Here, we continue evaluation of the decontamination efficacy of wash solutions based on potassium (K{sup +}) salt for cesium (Cs), strontium (Sr), and europium (Eu) contaminations on common building surfaces. The surfaces included: the cement used in concrete, the aggregate used in concrete, intact concrete, roadway asphalt, asphalt shingles, and latex paint. We deposited solutions of {sup 137}Cs, {sup 85}Sr, and {sup 152}Eu onto numerous common building materials and exposed these materials to a static bath or low-pressure flow of tap water, 0.1 M potassium chloride (KCl), and 0.5 M KCl. The decontamination efficacy and the depth profile for residual contamination were measured to determine the conditions under which applying a wash solution has benefit compared to physically removing the surface material. To aid in these analyses, we introduced a 'wash penalty factor' to quantify the degree to which contamination migrated into the bulk material by the action of the wash method. On asphalt, 70-80% of the radionuclides were found to be within 0.02 mm of the surface. Cs{sup +} bonded to negative charge sites on the surface of the mineral aggregate (used in concrete) so decontamination was improved by ion exchange with K{sup +}. Sr{sup 2+} is soluble and removed by water, while not bonding to aggregate or demonstrating solubility in the liquid asphalt. Eu{sup 3+} is precipitated and not removed in gentle wash but displays mobility within the pore space that suggests its presence as a colloid. Concrete is more porous than asphalt, and 80% of the radionuclides were within 0.2 mm of the surface for {sup 137}Cs and {sup 152}Eu and 50- 80% for {sup 85}Sr. On concrete, Cs{sup +} bonds similarly to asphalt. Sr{sup 2+} bonds to the cement or precipitates from the alkaline pore water. Eu{sup 3+} sorbs to the cement and then precipitates. In brick, the results for Cs{sup +} and Sr{sup 2+} suggested that diffusion of ions from deeper in the coupon was important. Eu{sup 3+} is removed poorly due to precipitation. We will explain and report example wash penalty factors that vary from 0 to > 1 for the various methods and the implications for deciding when to implement wash down methods. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Viewing is understanding: Graphite microstructure effects on infiltrated molten salt distribution revealed by 3D neutron tomography

Molten salt infiltration in the pore network of nuclear graphite may cause unwanted changes to graphite's local structure and mechanical and thermal properties. A detailed and comprehensive understanding of molten salt intrusion (distribution across sample cross section and penetration depth) is needed to assess its effects. Here, in this work, we report on an improved methodology for the use of neutron imaging (computed tomography) to evaluate salt penetration and distribution of a wide range of graphite grades with diverse microstructures. Neutron tomography data were acquired on the same graphite sample before and after salt intrusion; the 3D reconstructed volumes were digitally co-registered and subtracted. The difference in neutron attenuation coefficient represents direct visualization of FLiNaK (LiF–NaF–KF) salt distribution in the salt-impregnated graphite samples. This improved methodology was applied to investigate the effect of exposure times (12 h and 336 h) and of graphite microstructure when exposed to FLiNaK at 750 °C and 3 bar (gauge) pressure, starting from flowing argon at near atmospheric pressure. The results show that medium-grained and fine-grained graphites evolve to equilibrium at significantly different rates: fast salt uptake in medium-grained graphites produces salt deposits throughout the volume of graphite specimens, whereas salt infiltration in fine-grained graphites is much slower and limited to exposed surfaces.

FLiNaK infiltration↗

Design optimization of gap distance for the capillary limitation of a heat pipe with annular-type wick structure

In this study, an experimental investigation was conducted on the rising height and contact angle of fluid in an annular wick-type heat pipe. The annular wick-type heat pipe was characterized by a small gap between the wick structure and tube wall, which compensated for the pressure drop along the porous media and created additional capillary force. To describe and model the advantage of this gap, the rising of a wetting liquid in the gap between a vertical solid plate and a mesh (with a small angle between them) was experimentally measured and analyzed. An additional experiment was performed to investigate the effect of curvature on the capillary rise using tubes and meshes of varying radii. Resultantly, we confirmed that the linear combination of the contact angles of the solid plate and mesh could be applied to calculate the rising height from the Laplace–Young equation. Furthermore, the effect of curvature on the rising height of the liquid was negligible. These results were extended to the investigation of finding the optimal gap distance for the annular wick-type heat pipe by referring to previous studies. We observed that a gap distance of 1.27 mm provided the largest permeability (K) over the effective pore radius (r eff ) value for a heat pipe with ethanol, which in turn resulted in the highest capillary limitation. For a sodium heat pipe, a gap distance of 0.84 mm resulted in the highest capillary limitation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Quantifying Drivers of Methane Hydrobiogeochemistry in a Tidal River Floodplain System

The influence of coastal ecosystems on global greenhouse gas (GHG) budgets and their response to increasing inundation and salinization remains poorly constrained. In this study, we have integrated an uncertainty quantification (UQ) and ensemble machine learning (ML) framework to identify and rank the most influential processes, properties, and conditions controlling methane behavior in a freshwater floodplain responding to recently restored seawater inundation. Our unique multivariate, multiyear, and multi-site dataset comprises tidal creek and floodplain porewater observations encompassing water level, salinity, pH, temperature, dissolved oxygen (DO), dissolved organic carbon (DOC), total dissolved nitrogen (TDN), partial pressure of carbon dioxide (pCO 2 ), nitrous oxide (pN 2 O), methane (pCH 4 ), and the stable isotopic composition of methane (δ 13 CH 4 ). Additionally, we incorporated topographical data, soil porosity, hydraulic conductivity, and water retention parameters for UQ analysis using a previously developed 3D variably saturated flow and transport floodplain model for a physical mechanistic understanding of factors influencing groundwater levels and salinity and, therefore, CH 4 . Principal component analysis revealed that groundwater level and salinity are the most significant predictors of overall biogeochemical variability. The ensemble ML models and UQ analyses identified DO, water level, salinity, and temperature as the most influential factors for porewater methane levels and indicated that approximately 80% of the total variability in hourly water levels and around 60% of the total variability in hourly salinity can be explained by permeability, creek water level, and two van Genuchten water retention function parameters: the air-entry suction parameter α and the pore size distribution parameter m. These findings provide insights on the physicochemical factors in methane behavior in coastal ecosystems and their representation in local- to global-scale Earth system models.

54 ENVIRONMENTAL SCIENCES↗