Publications

Abstract not provided.

Abstract not provided.

Abstract not provided.

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. In this paper, 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. Finally, 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.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

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.

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 .

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

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.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

An open pored metal-organic framework (MOF) with oxygen selectivity at exceptionally high temperatures is confirmed by synthesis, sorption, and synchrotron structural analyses. The large-pore MIL-100 framework with access to the metal center (e.g., Sc and Fe) resulted in preferential O2 over N2 gas uptake at temperatures ranging from 77 K to ambient temperatures (258, 298, and 313 K). Most notably, Sc-MIL-100 shows exceptional O2 sorption; pair distribution function analyses indicate that this is due to distortions in the framework owing to the size of Sc atoms, in particular in the trimer metal cluster. Experimental studies also correlate very well with GCMC simulations, confirming more favorable O2-framework interactions at pressures up to 1 bar, due to the close proximity of O2 to the high density of metal centers in the small tetrahedral cages. Both materials maintain their crystallinity upon gas adsorption cycling, are regenerable, and show exceptional promise for use in energy efficient oxygen purification processes, such as Pressure Swing Adsorption.

Abstract not provided.

Abstract not provided.

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. 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.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

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.

Abstract not provided.

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.

Abstract not provided.

Abstract not provided.

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.