Publications

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Herein is presented the synthesis and characterization of copper-intercalated zirconium pentatelluride (ZrTe₅). ZrTe₅:Cu_0.05 crystals are synthesized by the chemical vapor transport method in a vacuum. X-ray diffraction and elemental analysis techniques are utilized to validate the synthesis. The results indicate that the intercalation of the layered Zr/Te structure with copper atoms causes the contraction of the unit cell along all three crystalline directions, the shrinkage of the overall volume of the unit cell, and the distortion of the unit cell. A single crystal was isolated, mechanically exfoliated, and used for the measurements of intercalation strains in a Hall bar device. Electronic transport studies indicate that an anomalous resistance drop is observed at T = 19 K. Furthermore, R_xx and R_xy results, respectively, indicate a probable disorder-induced localization effect and electron-type carriers.

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Acid gases (e.g., NO_x and SO_x), commonly found in complex chemical and petrochemical streams, require material development for their selective adsorption and removal. Here, we report the NO_x adsorption properties in a family of rare earth (RE) metal–organic frameworks (MOFs) materials. Fundamental understanding of the structure–property relationship of NO_x adsorption in the RE-DOBDC materials platform was sought via a combined experimental and molecular modeling study. No structural change was noted following humid NO_x exposure. Density functional theory (DFT) simulations indicated that H₂O has a stronger affinity to bind with the metal center than NO₂, while NO₂ preferentially binds with the DOBDC ligands. Further modeling results indicate no change in binding energy across the RE elements investigated. Also, stabilization of the NO₂ and H₂O molecules following adsorption was noted, predicted to be due to hydrogen bonding between the framework ligands and the molecules and nanoconfinement within the MOF structure. This interaction also caused distinct changes in emission spectra, identified experimentally. As a result, calculations indicated that this is due to the adsorption of NO₂ molecules onto the DOBDC ligand altering the electronic transitions and the resulting photoluminescent properties, a feature that has potential applications in future sensing technologies.

Recent years have seen an explosion in research efforts discovering and understanding novel electronic and optical properties of topological quantum materials (TQMs). In this LDRD, a synergistic effort of materials growth, characterization, electrical-magneto-optical measurements, combined with density functional theory and modeling has been established to address the unique properties of TQMs. Particularly, we have carried out extensive studies in search for Majorana fermions (MFs) in TQMs for topological quantum computation. Moreover, we have focused on three important science questions. 1) How can we controllably tune the properties of TQMs to make them suitable for quantum information applications? 2) What materials parameters are most important for successfully observing MFs in TQMs? 3) Can the physical properties of TQMs be tailored by topological band engineering? Results obtained in this LDRD not only deepen our current knowledge in fundamental quantum physics but also hold great promise for advanced electronic/photonic applications in information technologies.

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Iodine detection is crucial for nuclear waste clean-up and first responder activities. For ease of use and durability of response, robust active materials that enable the direct electrical detection of I2 are needed. Herein, a large reversible electrical response is demonstrated as I2 is controllably and repeatedly adsorbed and desorbed from a series of metal-organic frameworks (MOFs) MFM-300(X), each possessing a different metal center (X = Al, Fe, In, or Sc) bridged by biphenyl-3,3′,5,5′-tetracarboxylate linkers. Impedance spectroscopy is used to evaluate how the different metal centers influence the electrical response upon cycling of I2 gas, ranging from 10× to 106× decrease in resistance upon I2 adsorption in air. This large variation in electrical response is attributed not only to the differing structural characteristics of the MOFs but also to the differing MOF morphologies and how this influences the degree of reversibility of I2 adsorption. Interestingly, MFM-300(Al) and MFM-300(In) displayed the largest changes in resistance (up to 106×) yet lost much of their adsorption capacity after five I2 adsorption cycles in air. On the other hand, MFM-300(Fe) and MFM-300(Sc) revealed more moderate changes in resistance (10-100×), maintaining most of their original adsorption capacity after five cycles. This work demonstrates how changes in MOFs can profoundly affect the magnitude and reversibility of the electrical response of sensor materials. Tuning both the intrinsic (resistivity and adsorption capacity) and extrinsic (surface area and particle morphology) properties is necessary to develop highly reversible, large signal-generating MOF materials for direct electrical readout for I2 sensing.

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Detection of radiological iodine gas after nuclear accidents or in nuclear fuel reprocessing is necessary for the safety of human life and the environment. The development of sensors for the detection of iodine benefits from the incorporation of nanoporous materials with high selectivity for I2 from common competing gases in air. Silver mordenite zeolite (Ag-MOR) is widely-used material for capture of gaseous iodine (I2). Herein, thin film zeolite coatings were applied to Pt interdigitated electrodes (IEDs) to fabricate iodine gas sensors with direct electrical readout responses. Correlations between occluded ion, exposure to iodine gas, resultant AgI nanoparticle polymorphs and location in zeolite with resultant impedance spectroscopy (IS) properties are described. Furthermore, IS is leveraged to elucidate the changes in charge conduction pathways as determined by the cation-zeolite film incorporated in the sensor. Silver mordenite reveals a significant change in impedance upon exposure to gaseous I2 at 70 °C, and the magnitude and direction of the response is dependent on whether the Ag+-mordenite is reduced (Ag0) before I2 exposure. An equivalent circuit model is developed to describe the movement of charge along the surface and through the pores of the mordenite grains. Relative changes in the impedance of these conduction pathways are related to the chemical changes from Ag+ or Ag0 to resultant AgI polymorph phase. Together, these results inform design of a compact Ag-mordenite sensor for direct electrical detection of gaseous I2.

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In the past decade, basic physics, chemistry, and materials science research on topological quantum materials - and their potential use to implement reliable quantum computers - has rapidly expanded to become a major endeavor. A pivotal goal of this research has been to realize materials hosting Majorana quasiparticles, thereby making topological quantum computing a technological reality. While this goal remains elusive, recent data-mining studies, performed using topological quantum chemistry methodologies, have identified thousands of potential topological materials - some, and perhaps many, with potential for hosting Majoranas. We write this Review for advanced materials researchers who are interested in joining this expanding search, but who are not currently specialists in topology. The first half of the Review addresses, in readily understood terms, three main areas associated with topological sciences: (1) a description of topological quantum materials and how they enable quantum computing; (2) an explanation of Majorana quasiparticles, the important topologically endowed properties, and how it arises quantum mechanically; and (3) a description of the basic classes of topological materials where Majoranas might be found. The second half of the Review details selected materials systems where intense research efforts are underway to demonstrate nontrivial topological phenomena in the search for Majoranas. Specific materials reviewed include the groups II-V semiconductors (Cd3As2), the layered chalcogenides (MX2, ZrTe5), and the rare-earth pyrochlore iridates (A2Ir2O7, A = Eu, Pr). In each case, we describe crystallographic structures, bulk phase diagrams, materials synthesis methods (bulk, thin film, and/or nanowire forms), methods used to characterize topological phenomena, and potential evidence for the existence of Majorana quasiparticles.

Here, we apply density functional theory (DFT) to investigate rare-earth metal organic frameworks (RE-MOFs), RE12(μ3-OH)16(C8O6H4)8(C8O6H5)4 (RE = Y, Eu, Tb, Yb), and characterize the level of theory needed to accurately predict structural and electronic properties in MOF materials with 4f-electrons. A two-step calculation approach of geometry optimization with spin-restricted DFT and large core potential (LCPs), and detailed electronic structures with spin-unrestricted DFT with a full valence potential + Hubbard U correction is investigated. Spin-restricted DFT with LCPs resulted in good agreement between experimental lattice parameters and optimized geometries, while a full valence potential is necessary for accurate representation of the electronic structure. The electronic structure of Eu-DOBDC MOF indicated a strong dependence on the treatment of highly localized 4f-electrons and spin polarization, as well as variation within a range of Hubbard corrections (U = 1-9 eV). For Hubbard corrected spin-unrestricted calculations, a U value of 1-4 eV maintains the non-metallic character of the band gap with slight deviations in f-orbital energetics. When compared with experimentally reported results, the importance of the full valence calculation and the Hubbard correction in correctly predicting the electronic structure is highlighted.

Energy and cost efficient synthesis pathways are important for the production, processing, and recycling of rare earth metals necessary for a range of advanced energy and environmental applications. In this work, we present results of successful in situ liquid cell transmission electron microscopy production and imaging of rare earth element nanostructure synthesis, from aqueous salt solutions, via radiolysis due to exposure to a 200 keV electron beam. Nucleation, growth, and crystallization processes for nanostructures formed in yttrium(iii) nitrate hydrate (Y(NO3)3·4H2O), europium(iii) chloride hydrate (EuCl3·6H2O), and lanthanum(iii) chloride hydrate (LaCl3·7H2O) solutions are discussed. In situ electron diffraction analysis in a closed microfluidic configuration indicated that rare earth metal, salt, and metal oxide structures were synthesized. Real-time imaging of nanostructure formation was compared in closed cell and flow cell configurations. Notably, this work also includes the first known collection of automated crystal orientation mapping data through liquid using a microfluidic transmission electron microscope stage, which permits the deconvolution of amorphous and crystalline features (orientation and interfaces) inside the resulting nanostructures.

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This proposal is focused on the multidisciplinary, exploratory study of highly selective materials for distinguishing peaceful nuclear facilities from clandestine nuclear weapons development. In particular, we are focused on iodine fission off-gas species. This is a 1-year project; herein is the final FY18 report on the project. The project was divided into four Tasks: speciation, flowsheets, fission gas adsorption materials, and detection devices. We successfully addressed all four tasks and reported on them during this year's quarterly reports. This final report will serve as a summary of the accomplishments.

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Here, this Review Article focuses on the highly versatile and effective method of radiolysis for the synthesis of nanoparticles (NPs). In particular, the formation of bimetallic and alloyed nanoparticles (or nanoalloys), including both known super alloys and novel alloy NP compositions, is described. This Review Article discloses the synthesis techniques that rely on ionizing radiation sources to create metallic NPs. Then, alloy NPs formed from combinations of transition metals and noble metals with varied structures are described. Some of the advantages of radiolysis including exquisite control over the size, monodispersity, and alloying structure of NPs are discussed. Additionally, methodologies that facilitate the synthesis or deposition of NPs onto a range of supports under inert environments are described. Finally, applications of metallic NPs formed by radiolysis are summarized.

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High-fidelity detection of iodine species is of utmost importance to the safety of the population in cases of nuclear accidents or advanced nuclear fuel reprocessing. Herein, we describe the success at using impedance spectroscopy to directly detect the real-time adsorption of I2 by a metal-organic framework zeolitic imidazolate framework (ZIF)-8-based sensor. Methanolic suspensions of ZIF-8 were dropcast onto platinum interdigitated electrodes, dried, and exposed to gaseous I2 at 25, 40, or 70 °C. Using an unoptimized sensor geometry, I2 was readily detected at 25 °C in air within 720 s of exposure. The specific response is attributed to the chemical selectivity of the ZIF-8 toward I2. Furthermore, equivalent circuit modeling of the impedance data indicates a >105× decrease in ZIF-8 resistance when 116 wt % I2 is adsorbed by ZIF-8 at 70 °C in air. This irreversible decrease in resistance is accompanied by an irreversible loss in the long-range crystallinity, as evidenced by X-ray diffraction and infrared spectroscopy. Air, argon, methanol, and water were found to produce minimal changes in ZIF-8 impedance. This report demonstrates how selective I2 adsorption by ZIF-8 can be leveraged to create a highly selective sensor using >105× changes in impedance response to enable the direct electrical detection of environmentally relevant gaseous toxins.

The removal of silica, ubiquitous in produced and industrial waters, by novel mixed oxides is investigated in this present study. We have combined the advantage of high selectivity hydrotalcite (HTC, (Mg6Al2(OH)16(CO3)·4H2O)), with large surface area of active alumina (AA, (Al2O3)) for effective removing of the dissolved silica from cooling tower water. The batch test results indicated the combined HTC/AA is a more effective method for removing silica from CTW than using each of HTC or AA separately. The silica uptake was confirmed by Fourier transform infrared (FTIR), and Energy dispersive spectroscopy (EDS). Results indicate HTC/AA effectively removes silica from cooling tower water (CTW), even in the presence of large concentrations of competing anions, such as Cl−, NO3− HCO3−, CO32− and SO42−. The Single Path Flow Through (SPFT) tests confirmed to rapid uptake of silica by combined HTC/AA during column filtration. The experimental data of silica adsorption fit best to Freundlich isotherm model.

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Silica is ubiquitous in produced and industrial waters, and plays a major disruptive role in water recycle. Herein we have investigated the use of mixed oxides for the removal of silica from these waters, and their incorporation into a low cost and low energy water purification process. High selectivity hydrotalcite (HTC, (Mg₆Al₂(OH)₁₆(CO₃)•4H₂O)), is combined in series with high surface area active alumina (AA, (Al₂O₃)) as the dissolved silica removal media. Batch test results indicated that combined HTC/AA is a more effective method for removing silica from industrial cooling tower wasters (CTW) than using HTC or AA separately. The silica uptake via ion exchange on the mixed oxides was confirmed by Fourier transform infrared (FTIR), and Energy dispersive spectroscopy (EDS). Furthermore, HTC/AA effectively removes silica from CTW even in the presence of large concentrations of competing anions, such as Cl^-, NO₃^- HCO₃^-, CO₃^2- and SO₄^2-. Similar to batch tests, Single Path Flow Through (SPFT) tests with sequential HTC/AA column filtration has very high silica removal too. Technoeconomic Analysis (TEA) was simultaneously performed for cost comparisons to existing silica removal technologies.

Securing additional water sources remains a primary concern for arid regions in both the developed and developing world. Climate change is causing fluctuations in the frequency and duration of precipitation, which can be can be seen as prolonged droughts in some arid areas. Droughts decrease the reliability of surface water supplies, which forces communities to find alternate primary water sources. In many cases, ground water can supplement the use of surface supplies during periods of drought, reducing the need for above-ground storage without sacrificing reliability objectives. Unfortunately, accessible ground waters are often brackish, requiring desalination prior to use, and underdeveloped infrastructure and inconsistent electrical grid access can create obstacles to groundwater desalination in developing regions. The objectives of the proposed project are to (i) mathematically simulate the operation of hollow fiber membrane distillation systems and (ii) optimize system design for off-grid treatment of brackish water. It is anticipated that methods developed here can be used to supply potable water at many off-grid locations in semi-arid regions including parts of the Navajo Reservation. This research is a collaborative project between Sandia and the University of Arizona.

Impedance spectroscopy was leveraged to directly detect the sorption of I 2 by selective adsorption into nanoporous metal organic frameworks (MOF). Films of three different types of MOF frameworks, respectively, were drop cast onto platinum interdigitated electrodes, dried, and exposed to gaseous I 2 at 25, 40, or 70 C. The MOF frameworks varied in topology from small pores (equivalent to I 2 diameter) to large pore frameworks. The combination of the chemistry of the framework and pore size dictated quantity and kinetics of I 2 adsorption. Air, argon, methanol, and water were found to produce minimal changes in ZIF-8 impedance. Independent of MOF framework characteristics, all resultant sensors showed high response to I 2 in air. As an example of sensor output, I 2 was readily detected at 25 C in air within 720 s of exposure, using an un-optimized sensor geometry with a small pored MOF. Further optimization of sensor geometry, decreasing MOF film thicknesses and maximizing sensor capacitance, will enable faster detection of trace I 2 .

Water shortages are a growing global problem. Reclamation of industrial and municipal wastewater will be necessary in order to mitigate water scarcity. However, many operational challenges, such as silica scaling, prevent large scale water reuse. Previously, our team at Sandia has demonstrated the use of selective ion exchange materials, such as calcinated hydrotalcite (HTC, (Mg ₆ Al ₂ (OH) ₁₆ (CO ₃ )*4H ₂ O)), for the low cost removal of silica from synthetic cooling tower water. However, it is not currently know if calcinated HTC has similar capabilities in realistic applications. The purpose of this study was to investigate the ability of calcinated HTC to remove silica from real cooling tower water. This was investigated under both batch and continuous conditions, and in the presence of competing ions. It was determined that calcinated HTC behaved similarly in real and synthetic cooling tower water; the HTC is highly selective for the silica even in the presence of competing cations. Therefore, the data concludes that calcinated HTC is a viable anti-scaling pretreatment for the reuse of industrial wastewaters.

Significant quantities of water are produced during enhanced oil recovery making these “produced water” streams attractive candidates for treatment and reuse. However, high concentrations of dissolved silica raise the propensity for fouling. In this paper, we report the design and economic analysis for a new ion exchange process using calcined hydrotalcite (HTC) to remove silica from water. This process improves upon known technologies by minimizing sludge product, reducing process fouling, and lowering energy use. Process modeling outputs included raw material requirements, energy use, and the minimum water treatment price (MWTP). Monte Carlo simulations quantified the impact of uncertainty and variability in process inputs on MWTP. These analyses showed that cost can be significantly reduced if the HTC materials are optimized. Specifically, R&D improving HTC reusability, silica binding capacity, and raw material price can reduce MWTP by 40%, 13%, and 20%, respectively. Optimizing geographic deployment further improves cost competitiveness.

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On August 15, 2016, Sandia hosted a visit by Professor Venkatesh Narayanamurti. Prof Narayanamurti (Benjamin Peirce Research Professor of Technology and Public Policy at Harvard, Board Member of the Belfer Center for Science and International Affairs, former Dean of the School of Engineering and Applied Science at Harvard, former Dean of Engineering at UC Santa Barbara, and former Vice President of Division 1000 at Sandia). During the visit, a small, informal, all-day idea exploration session on "Towards an Engineering and Applied Science of Research" was conducted. This document is a brief synopsis or "footprint" of the presentations and discussions at this Idea Exploration Session. The intent of this document is to stimulate further discussion about pathways Sandia can take to improve its Research practices.

Fresh water scarcity is going to be a global great challenge in the near future because of the increasing population. Our water resources are limited and, hence, water treatment and recycling methods are the only alternatives for fresh water procurement in the upcoming decades. Water treatment and recycling methods serve to remove harmful or problematic constituents from ground, surface and waste waters prior to its consumption, industrial supply, or other uses. Scale formation in industrial and domestic installations is still an important problem during water treatment. In water treatment, silica scaling is a real and constant concern for plant operations. The focus of this study is on the viability of using a combination of catechol and active carbon to remove dissolved silica from concentrated cooling tower water (CCTW). Various analytical methods, such as ICP-MS and UV-vis, were used to understand the structure-property relationship between the material and the silica removal results. UV-Vis indicates that catechol can react with silica ions and form a silica-catecholate complex. The speciation calculation of catechol and silica shows that catechol and silica bind in the pH range of 8 – 10; there is no evidence of linkage between them in neutral and acidic pHs. The silica removal results indicate that using ~4g/L of catechol and 10g/L active carbon removes up to 50% of the dissolved silica from the CCTW.

Water is the backbone of our economy - safe and adequate supplies of water are vital for agriculture, industry, recreation, and human consumption. While our supply of water today is largely safe and adequate, we as a nation face increasing water supply challenges in the form of extended droughts, demand growth due to population increase, more stringent health-based regulation, and competing demands from a variety of users. To meet these challenges in the coming decades, water treatment technologies, including desalination, will contribute substantially to ensuring a safe, sustainable, affordable, and adequate water supply for the United States. This overview documents Sandia National Laboratories' (SNL, or Sandia) Water Treatment Program which focused on the development and demonstration of advanced water purification technologies as part of the larger Sandia Water Initiative. Projects under the Water Treatment Program include: (1) the development of desalination research roadmaps (2) our efforts to accelerate the commercialization of new desalination and water treatment technologies (known as the 'Jump-Start Program),' (3) long range (high risk, early stage) desalination research (known as the 'Long Range Research Program'), (4) treatment research projects under the Joint Water Reuse & Desalination Task Force, (5) the Arsenic Water Technology Partnership Program, (6) water treatment projects funded under the New Mexico Small Business Administration, (7) water treatment projects for the National Energy Technology Laboratory (NETL) and the National Renewable Energy Laboratory (NREL), (8) Sandia- developed contaminant-selective treatment technologies, and finally (9) current Laboratory Directed Research and Development (LDRD) funded desalination projects.

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In this study, oxygen selectivity in metal-organic frameworks (MOFs) at exceptionally high temperatures originally predicted by Density Functional Theory (DFT) and Grand Canonical Monte Carlo (GCMC) modeling is now confirmed by synthesis, sorption metal center access, in particular Sc and Fe. Based on DFT M-O₂ binding energies, we chose the large pored MIL-100 framework for metal center access, in particular Sc and Fe. Both resulted in preferential O₂ and N₂ gas uptake at temperatures ranging from 77 K to ambient temperatures (258 K, 298 K and 313 K).

The separation of oxygen from nitrogen using metal–organic frameworks (MOFs) is of great interest for potential pressure-swing adsorption processes for the generation of purified O₂ on industrial scales. This study uses ab initio molecular dynamics (AIMD) simulations to examine for the first time the pure-gas and competitive gas adsorption of O₂ and N₂ in the M₂(dobdc) (M = Cr, Mn, Fe) MOF series with coordinatively unsaturated metal centers. Effects of metal, temperature, and gas composition are explored. Lastly, this unique application of AIMD allows us to study in detail the adsorption/desorption processes and to visualize the process of multiple guests competitively binding to coordinatively unsaturated metal sites of a MOF.

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This study is focused on describing the desorbed off gases due to heating of the AgIMordenite (MOR) produced at ORNL for iodine (I₂) gas capture from nuclear fuel aqueous reprocessing. In particular, the interest is for the incorporation of the AgI-MOR into a waste form, which might be the Sandia developed, low temperature sintering, Bi-Si oxide based, Glass Composite Material (GCM). The GCM has been developed as a waste form for the incorporation any oxide based getter material. In the case where iodine may be released during the sintering process of the GCM, additional Ag flake is added as further insurance in total iodine capture and retention. This has been the case for the incorporated ORNL developed AgIMOR. Thermal analysis studies were carried out to determine off gasing processes of ORNL AgIMOR. Independent of sample size, ~7wt% of total water is desorbed by 225°C. This includes both bulk surface and occluded water, and are monitored as H2O and OH. Of that total, ~5.5wt% is surface water which is removed by 125°C, and 1.5wt% is occluded (in zeolite pore) water. Less than ~1 wt% total water continues to desorb, but is completely removed by 500°C. Above 300°C, the detectable remaining desorbing species observed are iodine containing compounds, including I and I₂.

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The study of mineral-water interfaces is of great importance to a variety of applications including oil and gas extraction, gas subsurface storage, environmental contaminant treatment, and nuclear waste repositories. Understanding the fundamentals of that interface is key to the success of those applications. Confinement of water in the interlayer of smectite clay minerals provides a unique environment to examine the interactions among water molecules, interlayer cations, and clay mineral surfaces. Smectite minerals are characterized by a relatively low layer charge that allows the clay to swell with increasing water content. Montmorillonite and beidellite varieties of smectite were investigated to compare the impact of the location of layer charge on the interlayer structure and dynamics. Inelastic neutron scattering of hydrated and dehydrated cation-exchanged smectites was used to probe the dynamics of the interlayer water (200-900 cm-1 spectral region) and identify the shift in the librational edge as a function of the interlayer cation. Molecular dynamics simulations of equivalent phases and power spectra, derived from the resulting molecular trajectories, indicate a general shift in the librational behavior with interlayer cation that is generally consistent with the neutron scattering results for the monolayer hydrates. Both neutron scattering and power spectra exhibit librational structures affected by the location of layer charge and by the charge of the interlayer cation. Divalent cations (Ba2+ and Mg2+) characterized by large hydration enthalpies typically exhibit multiple broad librational peaks compared to monovalent cations (Cs+ and Na+), which have relatively small hydration enthalpies.

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Oxy-fuel combustion is a well-known approach to improve the heat transfer associated with stationary energy processes. Its overall penetration into industrial and power markets is constrained by the high cost of existing air separation technologies for generating oxygen. Cryogenic air separation is the most widely used technology for generating oxygen but is complex and expensive. Pressure swing adsorption is a competing technology that uses activated carbon, zeolites and polymer membranes for gas separations. However, it is expensive and limited to moderate purity O₂ . MOFs are cutting edge materials for gas separations at ambient pressure and room temperature, potentially revolutionizing the PSA process and providing dramatic process efficiency improvements through oxy-fuel combustion. This LDRD combined (1) MOF synthesis, (2) gas sorption testing, (3) MD simulations and crystallography of gas siting in pores for structure-property relationship, (4) combustion testing and (5) technoeconomic analysis to aid in real-world implementation.

This milestone is focused on developing a plan for the analysis of the effluent from the Sandia low temperature sintering Bi-Si-Zn oxide glass composite material (GCM) waste form for the long term storage of iodine and its capture materials.

This program at Sandia is focused on Iodine waste form development for Fuel Cycle R&D needs. Our research has a general theme of “Capture and Storage of Iodine Fission Gas “ in which we are focused on silver loaded zeolite waste forms, evaluation of iodine loaded getter materials (eg., mordenite zeolite), and the development of low temperature glass waste forms that successfully incorporate iodine loaded getter materials from I₂, organic iodide, etc. containing off-gas streams.

This study encompasses initial scoping tests on the incorporation of a novel iodine loaded getter material into the Sandia developed low temperature sintering glass ceramic material (GCM) waste form. In particular, we studied the PNNL Ag-I-Aerogel. Optical microscopy indicates inhomogenous samples based on particle sizes and variations in color (AgI vs Ag/AgO on silica). TGA/MS data when heated in air indicates loss of iodine and organics (CO2) between 250-450°C a total of ~15wt% loss, with additional / small iodine loss when during 550°C hold for 1 hr. TGA/MS data when heated in N2 indicates less organic and slightly less iodine loss below 550°C, with no loss of iodine in 550°C 1 hour hold. Furthermore, a substantial mass loss of sulfur containing compounds is observed (m/e of 34 and 36) between 150 – 550°C in both air and N2 sintering atmospheres. In an effort to capture iodine lost to volatilization during heating (at temps below glass sintering temperature of 550°C), we added 5 wt% Ag flake to the AgIaerogel. Resulting data indicates the iodine is retained with the addition of the Ag flake, resulting in only a small iodine loss (< 1wt%) at ~350°C. No method of curtailing loss of sulfur containing compounds due to heating was successful in this scoping study.

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