Search NASA⌕ Search

SEARCH · Search NASA

Results for “Structured packing”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,567 records · Page 87

Friction surfaced Stellite6 coatings

Solid state Stellite6 coatings were deposited on steel substrate by friction surfacing and compared with Stellite6 cast rod and coatings deposited by gas tungsten arc and plasma transferred arc welding processes. Friction surfaced coatings exhibited finer and uniformly distributed carbides and were characterized by the absence of solidification structure and compositional homogeneity compared to cast rod, gas tungsten arc and plasma transferred coatings. Friction surfaced coating showed relatively higher hardness. X-ray diffraction of samples showed only face centered cubic Co peaks while cold worked coating showed hexagonally close packed Co also. - Highlights: Black-Right-Pointing-Pointer Stellite6 used as coating material for friction surfacing. Black-Right-Pointing-Pointer Friction surfaced (FS) coatings compared with casting, GTA and PTA processes. Black-Right-Pointing-Pointer Finer and uniformly distributed carbides in friction surfaced coatings. Black-Right-Pointing-Pointer Absence of melting results compositional homogeneity in FS Stellite6 coatings.

36 MATERIALS SCIENCE↗

As–Se Pentagonal Linkers to Induce Chirality and Polarity in Mixed-Valent Fe–Se Tetrahedral Chains Resulting in Hidden Magnetic Ordering

A novel mixed-valent hybrid chiral and polar compound, Fe 7 As 3 Se 12 (en) 6 (H 2 O), has been synthesized by a single-step solvothermal method. The crystal structure consists of 1D [Fe 5 Se 9 ] chains connected via [As 3 Se 2 ]–Se pentagonal linkers and charge-balancing interstitial [Fe(en) 3 ] 2+ complexes (en = ethylenediamine). Neutron powder diffraction verified that interstitial water molecules participate in the crystal packing. Magnetic polarizability of the produced compound was confirmed by X-ray magnetic circular dichroism (XMCD) spectroscopy. X-ray absorption spectroscopy (XAS) and 57 Fe Mössbauer spectroscopy showed the presence of mixed-valent Fe 2+ /Fe 3+ in the Fe–Se chains. Magnetic susceptibility measurements reveal strong antiferromagnetic nearest neighbor interactions within the chains with no apparent magnetic ordering down to 2 K. Hidden short-range magnetic ordering below 70 K was found by 57 Fe Mössbauer spectroscopy, showing that a fraction of the Fe 3+ /Fe 2+ in the chains are magnetically ordered. Nevertheless, complete magnetic ordering is not achieved even at 6 K. Analysis of XAS spectra demonstrates that the fraction of Fe 3+ in the chain increases with decreasing temperature. Computational analysis points out several competing ferrimagnetic ordered models within a single chain. Here, this competition, together with variation in the Fe oxidation state and additional weak intrachain interactions, is hypothesized to prevent long-range magnetic ordering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical vapor infiltration of additively manufactured preforms: Pore-resolved simulations and experimental validation

The densification of additively manufactured porous preforms by chemical vapor infiltration (CVI) is studied using pore-resolved simulations and experiments. Experimentally, 3D printed silicon carbide (SiC) preforms are subject to CVI synthesis using methyltrichlorosilane (MTS) precursor to obtain high purity SiC/SiC composites. Optical images of the cross sections of the processed preforms are analyzed to obtain the spatial porosity distribution. The numerical method is based on a level set formulation to capture the spatial distribution and time evolution of the pore scale microstructural characteristics. The coupled transport and kinetic effects are represented using a dimensionless Thiele modulus. Simulations are initialized using representative synthetic preform geometries comprising of packed particles based on the size distribution of the powder used for 3D printing. The simulation results are validated against the experimental observations in terms of total density and the distribution of residual porosity. The densification characteristics, porosity classification, concentration profiles, and structure functions are analyzed as functions of processing temperature and Thiele modulus.

36 MATERIALS SCIENCE↗

Modeling Rate Dependent Volume Change in Porous Electrodes in Lithium-Ion Batteries

Automotive manufacturers are working to improve individual cell, module, and overall pack design by increasing the performance, range, and durability, while reducing cost. One key piece to consider during the design process is the active material volume change, its linkage to the particle, electrode, and cell level volume changes, and the interplay with structural components in the rechargeable energy storage system. As the time from initial design to manufacture of electric vehicles decreases, design work needs to move to the virtual domain; therefore, a need for coupled electrochemical-mechanical models that take into account the active material volume change and the rate dependence of this volume change need to be considered. In this study, we illustrated the applicability of a coupled electrochemical-mechanical battery model considering multiple representative particles to capture experimentally measured rate dependent reversible volume change at the cell level through the use of an electrochemical-mechanical battery model that couples the particle, electrode, and cell level volume changes. By employing this coupled approach, the importance of considering multiple active material particle sizes representative of the distribution is demonstrated. The non-uniformity in utilization between two different size particles as well as the significant spatial non-uniformity in the radial direction of the larger particles is the primary driver of the rate dependent characteristics of the volume change at the electrode and cell level.

Electrochemistry↗

Carbon Nanotube – Polysiloxane Nanocomposites for Ablative Thermal Protection Systems

Ultra-high temperature resins (UHTR) such as polysiloxane possess excellent characteristics for ablation including low thermal conductivity, lightweight composition, high thermal resistance, and the ability to form a durable char layer. To enhance its mechanical strength, the aerospace industry utilizes fiber reinforcement, such as carbon fiber reinforced polysiloxane (CF-polysiloxane), due to its high strength-to-weight ratio. Carbon nanotubes (CNTs) have advantages over microfibers including higher specific strength, lower density, and customizable thermal conductivity. Their nano-scale dimensions allow for a more homogenous material compared to traditional microfibers. Conventional methods of incorporating CNTs into resins often have structural defects such as voids, CNT agglomerations, and randomly dispersed CNTs, resulting in marginal improvements in properties. A novel approach known as bulk nanocomposite laminating (BNL) has been introduced involving CNT densification, resin polymer infiltration, and pressurized curing to achieve a high packing density exceeding 35% by volume. Characterization and testing to simulate re-entry conditions is performed with a sample of CNT-polysiloxane nanocomposite cured onto a CF-polysiloxane backing. These samples are subjected to ablation by an oxyacetylene flame while collecting temperature data to evaluate thermal protection properties.

Palak B Patel↗

Dynamic imaging of metastable reaction pathways in lithiated cobalt oxide electrodes

Understanding how lithium-ion batteries function down to the atomic level during charge and discharge cycling can provide valuable guidance to optimize structure-property relationships and to design and understand new electrode materials. Lithium insertion and reactions with the electrodes during charge and discharge cycling can occur via metastable structures with complex ordering and related non-equilibrium phenomena. Remarkably, these processes remain still poorly understood despite their significance in the operation of lithium battery systems in critical technologies. In this communication, we present the dynamics of lithium insertion into Co3O4 and the evolution of metastable phases as probed by in-situ transmission electron microscopy, in concert with first principles density functional theory calculations. We show that the initial lithium intercalation reaction occurs with the formation of several metastable and intermediate phases, followed by a sequence of conversion reactions that perturb and expand the cubic-close-packed oxygen array, ultimately generating an end-product of finely dispersed cobalt metal clusters within a Li2O matrix. The calculated non-equilibrium lithiation pathways corroborate with the experimental lithiation voltages, and explain the significant hysteresis that occurs during electrochemical cycling. The data provide new insights into the complexity of solid state lithium electrochemistry in metal oxides that are relevant to advancing lithium battery technology.

conversion reaction electrode↗

Intermolecular Interactions and Electrostatic Properties of the [beta]-Hydroquinone Apohost: Implications for Supramolecular Chemistry

The crystal structure of the {beta}-polymorph of hydroquinone ({beta}-HQ), the apohost of a large family of clathrates, is reported with a specific focus on intermolecular interactions and the electrostatic nature of its cavity. Hirshfeld surface analysis reveals subtle close contacts between two interconnecting HQ networks, and the local packing and related close contacts were examined by breakdown of the fingerprint plot. An experimental multipole model containing anisotropic thermal parameters for hydrogen atoms has been successfully refined against 15(2) K single microcrystal synchrotron X-ray diffraction data. The experimental electron density model has been compared with a theoretical electron density calculated with the molecule embedded in its own crystal field. Hirshfeld charges, interaction energies and the electrostatic potential calculated for both models are qualitatively in good agreement, but small differences in the electrostatic potential persist due to charge transfer from all hydrogen atoms to the oxygen atoms in the theoretical model. The electrostatic potential in the center of the cavity is positive, very shallow and highly symmetric, suggesting that the inclusion of polar molecules in the void will involve a balance between opposing effects. The electric field is by symmetry zero in the center of the cavity, increasing to a value of 0.0185 e/{angstrom}{sup 2} (0.27 V/{angstrom}) 1 {angstrom} along the 3-fold axis and 0.0105 e/{angstrom}{sup 2} (0.15 V/{angstrom}) 1 {angstrom} along the perpendicular direction. While these values are substantial in a macroscopic context, they are quite small for a molecular cavity and are not expected to strongly polarize a guest molecule.

08 HYDROGEN↗

Improvement of Photovoltaic Performance of Polymer Solar Cells by Rational Molecular Optimization of Organic Molecule Acceptors

Abstract Two n‐type organic semiconductor (n‐OS) small molecules m ‐ITIC‐2F and m ‐ITIC‐4F with fluorinated 2‐(2,3‐dihydro‐3‐oxo‐1H‐inden‐1‐ylidene)propanedinitrile (IC) terminal moieties are prepared, for the application as an acceptor in polymer solar cells (PSCs), to further improve the photovoltaic performance of the n‐OS acceptor 3,9‐bis(2‐methylene‐(3‐(1,1‐dicyanomethylene) indanone) ‐5,5,11,11‐tetrakis(3‐hexylphenyl)‐dithieno[2,3‐d:2′,3′‐d′]‐sindaceno[1,2‐b:5,6‐b′]‐dithiophene ( m ‐ITIC). Compared to m ‐ITIC, these two new acceptors show redshifted absorption, higher molecular packing order, and improved electron mobilities. The power conversion efficiencies (PCE) of the as‐cast PSCs with m ‐ITIC‐2F or m ‐ITIC‐4F as an acceptor and a low‐cost donor–acceptor (D–A) copolymer PTQ10 as a donor reach 11.57% and 11.64%, respectively, which are among the highest efficiency for the as‐cast PSCs so far. Furthermore, after thermal annealing treatment, improved molecular packing and enhanced phase separation are observed, and the higher PCE of 12.53% is achieved for both PSCs based on the two acceptors. The respective and unique advantage with the intrinsic high degree of order, molecular packing, and electron mobilities of these two acceptors will be suitable to match with different p‐type organic semiconductor donors for higher PCE values, which provide a great potential for the PSCs commercialization in the near future. These results indicate that rational molecular structure optimization is of great importance to further improve photovoltaic properties of the photovoltaic materials.

Li, Xiaojun↗

Benzimidazolone-Dioxazine Pigments-Based Conjugated Polymers for Organic Field-Effect Transistor

Molecules based on benzimidazolone-dioxazine are known as blue/violet pigments and have been commercialized for decades. However, unfavorable solubility limits the application of these structures as building blocks of conjugated polymers despite their low band gaps. Herein, a series of donor–acceptor conjugated polymers containing soluble benzimidazolone-dioxazine structures as the acceptors and oligothiophene as donors are synthesized and investigated. With increasing numbers of thiophene rings, the steric hindrance diminishes and high molecular weight polymers can be achieved, leading to an improved performance in organic field effect transistor devices. The hole mobility of polymers with three to six thiophene units is in the order of 10 -1 cm2 V -1 s -1 . Among all the polymers, polymer P3 with three thiophene units between benzimidazolone-dioxazine structures shows the best hole mobility of 0.4 cm2 V -1 s -1 . Grazing-incidence wide-angle X-ray scattering results reveal that the high mobility of organic field-effect transistors (OFETs) can be accredited by matched donor–acceptor packing in the solid thin films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of temperature on the microstructure of calcium silicate hydrate (C-S-H)

Temperature affects the properties of concrete through its effect on the hydration of cement and its associated microstructural development. This paper focuses on the modifications to C-S-H induced by isothermal curing between 5 and 60 °C. The results show that as the temperature increases (within the range studied) the C/S ratio of C-S-H changes only slightly, with a higher degree of polymerisation of silicate chains, but there is a significant decrease in its bound water content and an increase of apparent density of 25%. This increase seems to come from a different packing of C-S-H at the nanoscale. As a consequence of these changes, the microstructure of the cement paste is much coarser and porous, which explains the lower final strengths obtained by curing at elevated temperatures. -- Highlights: •C-S-H structure studied at the atomic level •Multiple analytical techniques used •Studies conducted at temperatures above and below normal temperatures.

36 MATERIALS SCIENCE↗

Precipitation hardening of laser powder bed fusion Ti-6Al-4V

Here, the laser powder bed fusion (PBF-L) additive manufacturing (AM) community has dedicated significant efforts into process optimization and control for defect-free Ti-6Al-4V. As defects become less of an issue for PBF-L Ti-6Al-4V, the processing-structure-properties (PSP) relationships between AM microstructures can now be explored to optimize mechanical properties. Lower temperature aging treatments around 550 °C in wrought Ti-6A-4V have been historically understood to precipitation harden the α phase with an ordered, hexagonal close packed (HCP) α 2 phase. The α 2 phase existed as nanoscale Ti 3 Al precipitates coherent with the parent α phase. The goal of the present investigation was to implement a vacuum heat treatment of 545 °C for 100 hours on PBF-L Ti-6Al-4V. This vacuum heat treatment took place after an initial hot isostatic pressure (HIP) treatment that decomposed the as-built, martensitic microstructure. The vacuum aging successfully produced nanoscale precipitates of α 2 phase within α-laths, confirmed via atom probe tomography (APT). Microstructural-length scale and quasi-static mechanical properties were investigated by nanoindentation and uniaxial tensile tests of miniaturized test specimens. Given the sensitivity of Ti-6Al-4V mechanical properties to small changes in chemistry, all test specimens originated from the same build. The α 2 precipitation resulted in significantly harder α-laths (≈ 2 GPa) as measured via nanoindentation, as well as a relative yield and ultimate tensile strength increase of 60 MPa and 38 MPa, respectively. Analysis of Variance (ANOVA) of the datasets revealed no statistical differences in total elongation between the HIPed and HIPed + aged specimens, indicative of the aging treatment producing a net benefit of strength with no loss in ductility.

36 MATERIALS SCIENCE↗

Real-time observations of TRIP-induced ultrahigh strain hardening in a dual-phase CrMnFeCoNi high-entropy alloy

Abstract Strategies involving metastable phases have been the basis of the design of numerous alloys, yet research on metastable high-entropy alloys is still in its infancy. In dual-phase high-entropy alloys, the combination of local chemical environments and loading-induced crystal structure changes suggests a relationship between deformation mechanisms and chemical atomic distribution, which we examine in here in a Cantor-like Cr 20 Mn 6 Fe 34 Co 34 Ni 6 alloy, comprising both face-centered cubic ( fcc ) and hexagonal closed packed ( hcp ) phases. We observe that partial dislocation activities result in stable three-dimensional stacking-fault networks. Additionally, the fraction of the stronger hcp phase progressively increases during plastic deformation by forming at the stacking-fault network boundaries in the fcc phase, serving as the major source of strain hardening. In this context, variations in local chemical composition promote a high density of Lomer-Cottrell locks, which facilitate the construction of the stacking-fault networks to provide nucleation sites for the hcp phase transformation.

36 MATERIALS SCIENCE↗

Structural analysis of polymer thin films using GISAXS in the tender X-ray region: Concept and design of GISAXS experiments using the tender X-ray energy at BL-15A2 at the Photon Factory

If small angle X-ray scattering (SAXS) utilizing the soft X-ray region is available, advanced and unique experiments, which differ from traditional SAXS methods, can be realized. For example, grazing-incidence small angle X-ray scattering (GISAXS) using hard X-ray is a powerful tool for understanding the nanostructure in both vertical and lateral directions of thin films, while GISAXS utilizing the tender X-ray region (SX-GISAXS) enables depth-resolved analysis as well as a standard GISAXS analysis in thin films. Thus, at BL-15A2 at the Photon Factory, a dedicated diffractometer for SX-GISAXS (above 2.1 keV) was constructed. This diffractometer is composed of four vacuum chambers and can be converted into the vacuum state from the sample chamber in front of the detector surface. Diffractions are clearly observed until 12th peak when measuring collagen by SAXS with an X-ray energy of 2.40 keV and a camera length of 825 mm. Additionally, we conducted the model experiment using SX-GISAXS with an X-ray energy of 2.40 keV to confirm that a poly(methyl methacrylate)-poly(n-butyl acrylate) block copolymer thin film has a microphase-separated structure in the thin film, which is composed of lamellae aligned both parallel and perpendicular to the substrate surface. Similarly, in a polystyrene-poly(methyl methacrylate) block copolymer thin film, SX-GISAXS with 3.60 keV and 5.73 keV revealed that hexagonally packed cylinders are aligned parallel to the substrate surface. The incident angle dependence of the first order peak position of the q{sub z} direction obtained from experiments at various incident X-ray energies agrees very well with the theoretical one calculated from the distorted wave Born approximation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Pseudorotational epitaxy of self-assembled octadecyltrichlorosilane monolayers on sapphire (0001)

The structure of octadecyltrichlorosilane self-assembled monolayers (SAMs) on sapphire (0001) was studied by Å-resolution surface-specific x-ray scattering methods. The monolayer was found to consist of three sublayers where the outermost layer corresponds to vertically oriented, closely packed alkyl tails. Laterally, the monolayer is hexagonally packed and exhibits pseudorotational epitaxy to the sapphire, manifested by a broad scattering peak at zero relative azimuthal rotation, with long powderlike tails. The lattice mismatch of ~1% – 3% to the sapphire’s and the different length scale introduced by the lateral Si-O-Si bonding prohibit positional epitaxy. However, the substrate induces an intriguing increase in the crystalline coherence length of the SAM’s powderlike crystallites when rotationally aligned with the sapphire’s lattice. As a result, the increase correlates well with the rotational dependence of the separation of corresponding substrate-monolayer lattice sites.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Low-Earth Orbit Flight Test of an Inflatable Decelerator (LOFTID) Mission Overview, Science Return, and Future Applications of This Technology

The Low-Earth Orbit (LEO) Flight Test of an Inflatable Decelerator (LOFTID) mission was the culmination of two decades of research and development for Hyper-sonic Inflatable Aerodynamic Decelerator (HIAD) technology. LOFTID was a project overseen by the Technology Demonstration Mission (TDM) program within NASA’s Space Technology Mission Directorate. The success of the LOFTID mission could enable new NASA missions to Mars, Venus, and most solar-system destinations with atmospheres, as well as cost-effective payload returns to Earth, including in-space manufactured materials and launch vehicle asset recovery. LOFTID, with its unique inflatable heat shield, was the first-of-a-kind orbital reentry flight, and the largest blunt body atmospheric entry of any kind. On November 10, 2022, just over 10 years since the previous flight test of the smaller sub-orbital Inflatable Reentry Vehicle Experiment-3 (IRVE-3) [1], NASA Langley Research Center, with partner United Launch Alliance (ULA), successfully launched and achieved reentry and recovery of the LOFTID Reentry Vehicle (RV), further demonstrating the viability of the HIAD technology for large-diameter, inflatable heat shields to safely and accurately deliver large payloads through an atmosphere via a controlled descent and landing. Launching as a secondary payload with the Joint Polar Satellite System 2 (JPSS-2) from Vandenberg Space Force Base, California, stowed inside an ex-tended payload adapter of the Atlas V 401 launch vehicle, the LOFTID mission officially began after the JPSS-2 payload was delivered to its orbit by the Centaur second stage. The LOFTID RV was flying solo on its spin-stabilized ballistic reentry trajectory about one hour after launch, and the flight ended approximately one hour later with a gentle splashdown under parachute in the Pacific Ocean off the east coast of Hawaii, where the RV was recovered and later shipped back to NASA Langley. LOFTID endured the harsh environments of atmospheric reentry while demonstrating stable aerodynamics through the entire spectrum of hypersonic, supersonic, transonic, and subsonic flight. The LOFTID RV was exposed to an aeroheating environment representative of many Mars and LEO HIAD applications, while successfully demonstrating the ability of the heat-affected inflatable structure to with-stand aerodynamic forces that exceeded those expected at Mars. This flight demonstration of a 6m diameter HIAD confirmed the technology structural and thermal performance as it protected the 1100kg RV entering Earth’s atmosphere at 8 km/s, reaching Mach 30, and experiencing 9g deceleration before deploying parachutes and splashing down in the Pacific Ocean. HIAD technology involves an aeroshell that can be hard packed into a small volume for launch and then deployed prior to atmospheric entry for a controlled deceleration through the atmosphere. Large deployable heat shields enable spacecraft to carry bigger, heavier payloads, including scientific instruments and human support systems for planetary landing and exploration. Much larger than traditional fixed diameter aeroshells that are constrained by the size of launch vehicle shrouds, inflatable decelerators create more drag and start the deceleration process in the upper reaches of the atmosphere with greater efficiency and stability. LOFTID’s successful demonstration of the HIAD technology has greatly expanded NASA’s options for future planetary missions and opened new commercial opportunities for lower-cost mission pay-load recovery including recovery of launch vehicle assets, or as a delivery system to return cargo from the International Space Station or cislunar space. The developments for some of these applications are al-ready underway. While LOFTID was indeed a first-of-a-kind flight for an inflatable heatshield, the largest blunt-body entry ever, its remarkable performance assured that it will not be the last of its kind.

John DiNonno↗

Determining the Role of Synthesis and Reaction Conditions on the Exposed Surface and Shape of ..beta..-Mo2C Catalysts

The production of drop-in quality biofuels typically can be achieved through catalytic fast pyrolysis (CFP) of biomass, followed by hydrodeoxygenation (HDO) of the vapor-phase product to reduce the oxygen content and stabilize the bio-oil product. To favor selectivity toward desired deoxygenation products, bifunctional catalysts with both acidic and hydrogenation sites are often employed. Due to both its oxophilicity and its ability to promote hydrogenation reactions, molybdenum carbide catalysts have shown promise for promoting the HDO of CFP vapors. However, the surface structure and composition of carbide catalyst particles are not well understood, precluding the establishment of fundamental structure-function relationships needed for the rational development of molybdedum carbide for HDO, as well as other reactions. For orthorhombic ..beta..-Mo2C, the (100) facet is largely studied for computational surface-reaction analyses, possibly due to its similarities with the close-packed (111) facet of noble-metal catalysts. However, it has previously been postulated through ab initio thermodynamic studies that the (111), (110), and (011) facets are most stable, though there is no consensus. Furthermore, while a majority of previous surface stability analyses of ..beta..-Mo2C focus on bulk terminations, the highly carburizing synthesis conditions and the use of ..beta..-Mo2C in carbon-containing reaction applications could introduce non-stoichiometric coverages of surface carbon. As such, this study uses ab initio thermodynamics calculations to assess the relative surface stability of the low-index facets of ..beta..-Mo2C, including consideration of varying the coverage of surface carbon. From this information, Wulff constructions are utilized to predict the synthesis and reaction condition-dependent shape and surface carbon composition of ..beta..-Mo2C catalyst particles.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗

THREE-DIMENSIONAL THERMAL MODELING ANALYSIS OF CST MEDIA FOR THE SMALL ION EXCHANGE PROJECT

The Small Column Ion Exchange (SCIX) project is designed to accelerate closure of High Level Waste (HLW) tanks at the Savannah River Site (SRS). The SRS tanks store HLW in three forms: sludge, saltcake, and supernate. An in-tank ion exchange process is being designed to treat supernate and dissolved saltcake waste. Through this process, radioactive cesium from the salt solution is adsorbed into Crystalline Silicotitanate (CST) ion exchange media packed within a flow-through column. A packed column loaded with radioactive cesium generates significant heat from radiolytic decay. The waste supernate solution within the ion exchange bed will boil around 120 C. Solution superheating above the boiling point within the column could lead to violent hazardous energy releases. System heating from loaded CST is also of concern in other process modules, such as the waste tank. Due to tank structural integrity concerns, the wall temperature limit for the SRS waste tanks is 100 C. The transfer of cesium-loaded CST to the tank could result in localized hot spots on the tank floor and walls which may exceed this limit. As a result, thermal modeling calculations have been conducted to predict the maximum temperatures achievable both in the column and in the waste tank. As specified in the associated Technical Task Plan, one objective of the present work was to compute temperature distributions within the ion exchange column module under accident scenarios including loss of salt solution flow through the bed and loss of coolant system flow. The column modeling domain and the scope of the calculations in this case were broadened relative to previous two-dimensional calculations to include vertical temperature distributions within the packed bed of ion exchange media as well as the upper column plenum region containing only fluid. The baseline design conditions and in-column modeling domain for the ion-exchange column module are shown in Figure 1. These evaluations assumed the maximum bounding cesium loading considered possible based on current knowledge regarding CST media and the anticipated feed compositions. Since this cesium loading was considerably higher than the nominal loading conditions in SRS waste, cases with lower loading were also evaluated. Modeling parameters were the same as those used previously unless otherwise indicated. The current model does not capture multi-phase cooling mechanisms operative when solution boiling occurs. This feature is conservative in the sense that it does not account for the large cooling effects associated with phase transfer. However, the potential transfer of heat to the plenum region associated with vertical bubble ascension through the column during boiling is also neglected. Thermal modeling calculations were also performed for the entire waste storage tank for the case where loaded and ground CST was transferred to the tank. The modeling domain used for the in-tank calculations is provided in Figure 2. The in-tank domain is based on SRS Tank 41, which is a Type-IIIA tank. Temperature distributions were evaluated for cylindrical, ground CST mounds located on the tank floor. Media grinding is required prior to vitrification processing of the CST in the SRS Defense Waste Processing Facility (DWPF). The location of the heat source region on the tank floor due to the accumulation of CST material was assumed to be just under the grinder. The shape of the CST mound was assumed to be cylindrical. This shape is believed to be most representative of the actual mound shape formed in the tank, given that submersible mixing pumps will be available for media dispersion. Alternative configurations involving other geometrical shapes for the CST mound were evaluated in the previous work. Sensitivity analysis for the in-tank region was performed for different amounts of CST media. As was the case for the in-column model, the in-tank model does not include multi-phase cooling mechanisms operative when solution boiling occurs. The in-column and the in-tank evaluations incorporated recently updated maximum cesium loading levels calculated using the current SCIX feed compositions, which resulted in significantly higher cesium loading than previously calculated. The calculations were conducted to ensure conservative predictions for the maximum temperatures achievable using the current baseline design. The degree of conservatism was reduced for in-column calculations relative to the previous work by using a three-dimensional modeling approach and selecting parameters which were nearer to expected conditions. The degree of conservatism for the in-tank calculations was also reduced by lowering the soil penetration depth below the tank from 150 to 20 feet. The primary goals of the extended thermal modeling effort were to determine whether fluid boiling or superheating are possible within the column module and to determine the maximum floor temperatures within the tank loaded with spent CST.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Molecular Dynamics Simulation Study of Solvent and State of Charge Effects on Solid-Phase Structure and Counterion Binding in a Nitroxide Radical Containing Polymer Energy Storage Material

Here we performed molecular dynamics simulations to understand the effects of solvent swelling and state of charge (SOC) on the redox active, organic radical cathode material poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate) (PTMA). We show that the polar solvent acetonitrile primarily solvates the nitroxide radical without disrupting the packing of the (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) pendant groups of PTMA. We also simulated bulk PTMA in different SOC, 25%, 50%, 75%, and 100%, by converting the appropriate number of TEMPO groups to the cation charge state and adding BF 4 - counterions to the simulation. At each SOC the packing of PTMA, the solvent, and the counterions were examined. The binding of the anion to the nitroxide cation site was examined using the potential of mean force and found to be on the order of tens of meV, with a binding energy that decreased with increasing SOC. Additionally, we found that the cation state is stabilized by the presence of a nearby anion by more than 1 eV, and the implications of this stabilization on charge transport are discussed. Finally, we describe the implications of our results for how the SOC of an organic electrode affects electron and anion charge transport during the charging and discharging processes.

36 MATERIALS SCIENCE↗