Correlating surface stoichiometry and termination in SrTiO3 films grown by hybrid molecular beam epitaxy
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99 GENERAL AND MISCELLANEOUS↗
SEARCH · Engineering Papers
Results for “complex mixtures”
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Complex Relationship between Side-Chain Polarity, Conductivity, and Thermal Stability in Molecularly Doped Conjugated Polymers
Molecularly doped conjugated polymers with polar side chains are an emerging class of conducting materials exhibiting enhanced and thermally stable conductivity. In this work, we study the electronic conductivity (σ) and the corresponding thermal stability of two polythiophene derivatives comprising oligoethylene glycol side chains: one having oxygen attached to the thiophene ring (poly(3-(methoxyethoxyethoxy)thiophene) (P3MEET)) and the other having a methylene spacer between the oxygen and the thiophene ring (poly(3-(methoxyethoxyethoxymethyl)thiophene) (P3MEEMT)). Thin films were vapor-doped with fluorinated derivatives of tetracyanoquinodimethane (FnTCNQ, n = 4, 2, 1) to determine the role of dopant strength (electron affinity) in maximum achievable σ. Specifically, when vapor doping with F 4 TCNQ, P3MEET achieved a substantially higher σ of 37.1 ± 10.1 S/cm compared to a σ of 0.82 ± 0.06 S/cm for P3MEEMT. Structural characterization using a combination of X-ray and optical spectroscopy reveals that the higher degree of conformational order of polymer chains in the amorphous domain upon doping with F 4 TCNQ in P3MEET is a major contributing factor for the higher σ of P3MEET. Additionally, vapor-doped P3MEET exhibited superior thermal stability compared to P3MEEMT, highlighting that the presence of polar side chains alone does not ensure higher thermal stability. Molecular dynamics simulations indicate that the dopant–side-chain nonbond energy is lower in the P3MEET:F 4 TCNQ mixture, suggesting more favorable dopant–side-chain interaction, which is a factor in improving the thermal stability of a polymer/dopant pair. Our results reveal that additional factors such as polymer ionization energy and side-chain–dopant interaction should be taken into account for the design of thermally stable, highly conductive polymers.
36 MATERIALS SCIENCE↗
Adsorption and exchange reactions of iodine molecules at the alumina surface: modelling alumina-iodine reaction mechanisms
Harnessing aluminum oxidation energy requires navigating the particle's passivation shell composed of alumina. The shell is a barrier to aluminum oxidation but can also exothermically react with halogenated species and therefore contribute to the overall energy generated during aluminum particle combustion. Fluorination reactions with alumina have been studied because fluorine is abundant in binder formulations that commonly surround aluminum particles in an energetic mixture. However, iodine has emerged as an alternative halogenated-based binder or oxidizer because iodine gas provides ancillary benefits such as chemical neutralization of biological agents or sterilization of contaminated environments. Furthermore, this study used density functional theory (DFT) calculations to evaluate potential reaction pathways for aluminum–iodine combustion. Relative to fluorinated fragments such as HF and F – , the adsorption energies associated with HI and I– are nearly triple the exchange reaction energy available from fluorination reactions with alumina (–189 and –278 kJ mol –1 for HI and I – , respectively). However, exchange reactions between iodinated species and the alumina surface are energetically unfavorable. These results explain that through adsorption, alumina surface exothermic reactions with iodine are more energetic than with fluorine fragments. Experiments performed with differential scanning calorimetry (DSC) confirm the higher magnitude of energy generated for iodination compared with fluorination reactions with alumina. Additionally, strong adsorption energies can promote synthesis of new shell chemistries. Adsorption in solution will promote alumina dissolution and iodine precipitation reactions to produce hydroxyl complexes and iodinated species synthesized on the surface of the particle, thereby replacing alumina with alternative passivation shell chemistry.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Optimizing semi-hydrogenation of unsaturated hydrocarbons by electrolyte engineering approach
Electrochemical hydrogenation of unsaturated hydrocarbons, when powered by renewables, represents a unique opportunity to substitute current energy-intensive synthetic routes. Modulation of adsorption energies of the organic substrate and key intermediates of the reaction is critical for fine tuning of the yield, selectivity and kinetics of the reaction. Interestingly, mounting evidence exists regarding the role of electrolyte composition in the outcome of semi-hydrogenation reactions. Nevertheless, electrolyte optimization is a complex task, owing to its hybrid nature. Indeed, it is composed of water serving as a proton source, an organic solvent necessary to dissolve the organic substrate and a conducting salt. Herein, we demonstrate that varying conducting salt and organic solvent has a dramatic impact on the outcomes of semi-hydrogenation of alkynes. By varying salt and water concentrations, we demonstrate that water does not serve as a proton source, and instead addition of an acid is necessary. While increasing the acid concentration increases the yield of the reaction, at too large concentrations the hydrogen evolution reaction becomes predominant. Furthermore, by combining electrochemical measurements with spectroscopic techniques including Fourier transform infrared (FTIR) spectroscopy and small angle X-ray spectroscopy (SAXS), we demonstrate that the electrolyte solvation structure dramatically impacts the yield of the reaction. Organic solvents weakly interacting with water, including acetonitrile, form aqueous nanoheterogeneities that prevent the organic substrate from accessing the catalyst interface and thus lead to limited yields. Instead, solvents such as dimethylformamide form homogeneous mixtures with which all reactants can access the interface, leading to yields greater than 80% for optimized compositions.
Zhang, Rongyu↗
Localized High-Concentration Electrolytes Get More Localized
Liquid electrolytes in batteries are typically treated as macroscopically homogeneous ionic transport media, despite having complex chemical composition and atomistic solvation structures, thus leaving a knowledge gap of microstructural characteristics. A promising electrolyte system design has recently been developed with the title of a localized high-concentration electrolyte (LHCE). These electrolytes are a summation of three components – a charge-carrying salt, a solvent that solvates the salt, and a diluent that is sparingly interactive with the salt in terms of ion solvation. This creates the perception of a high-concentration electrolyte (HCE) with high anion-cation interactions that supports a salt-derived, stable solid-electrolyte interphase, while an LHCE improves bulk electrolyte properties, such as ionic conductivity and viscosity, when compared to an HCE. Much trial by error design of this LHCE concept has been supported by simulations to confirm ionic interactions, cycling data to confirm cell stability, and post-mortem analysis to provide evidence of mechanisms. However, a systematic design to extend the capabilities of LHCEs is still to be desired. Here, we analyzed a specific LHCE mixture to dictate the best viable mixture that extends the localization of solvation structures while maintaining viable cell-level capabilities. We seek to observe and understand solvent-to-salt interactions that impact electrolyte performance. These interactions range from single-ion solvation, multidentate interactions (i.e., solvation-driven clustering), to more widespread network-level interactions. With the support of both experimental and computational analysis of different electrolyte features, we have begun a methodology of formulating the most ideal LHCE mixtures for improving the cyclability of high-capacity battery chemistries.
25 ENERGY STORAGE↗
Pathways for Sustainable Reaction Kinetics in Li-CO2 Batteries
Lithium-carbon dioxide (Li-CO2) batteries hold great promise for high-energy-density storage applications. However, advancing this technology as a sustainable alternative to Li-ion systems requires a deeper understanding of the underlying reaction mechanisms, which remain elusive. A key challenge stems from the added complexity introduced by the presence of oxygen (O2) in CO2 environment. In this study, we employed a stable Cu3(VBi)0.5Se4 mid-entropy catalyst and conducted a comprehensive investigation to uncover the underlying reaction mechanisms in Li-CO2 batteries under varying CO2/O2 ratios. Under pure CO2 conditions, the battery exhibits excellent rechargeability, sustaining up to 1200 cycles. However, at high current densities, the discharge potential drops significantly (below 2.0 V), primarily due to sluggish reaction kinetics caused by solid carbon formation. Interestingly, introducing O2 mitigates this limitation, leading to a 58% increase of the discharge potential (from 1.7 V to 2.7 V) at the high current density of 0.8 mA/cm2, signifying a substantial boost in energy output. Our results reveal that the reactions follow distinct pathways, shifting from surface- to solution-based mechanism, and may even exhibit coexistence of both mechanisms, depending on the CO2/O2 ratio. These findings offer new insights for designing high-performance and sustainable Li-gas batteries utilizing CO2 and O2 mixtures.
Ngo, Anh [University of illinois Chicago]↗
Designing Peptide Fossils That Model the Evolution of the Bacterial Ferredoxin Fold
Electron transfer coupled to redox chemistry is at the heart of metabolism. The proteins responsible for moving electrons (protein electron carriers) must have emerged at the origin of life. The small iron–sulfur-binding bacterial ferredoxins were likely among these first proteins. Embedded within the ferredoxin sequence and structure is a symmetry that points to an ancient gene duplication event. Little is understood about the nature of ferredoxins prior to this duplication event or what environmental factors may have driven the selection for more complex forms. The deep-time molecular history of ferredoxins goes back billions of years and cannot be reconstructed by phylogenetic analyses based on amino acid sequences. Here, we use structure-guided protein design to model a fossil half-ferredoxin stage in the evolution of this fold, the semidoxins, and their symmetric full-length counterparts, the symdoxins. Semidoxin designs homodimerize, exhibiting structural, thermodynamic, and electrochemical behaviors in most cases identical to cognate symdoxins. However, the semi- and symdoxin fossil stages behave differently when incorporated into an in vivo electron transfer complementation assay. Both can support bacterial growth dependent on protein expression. Growth rates of bacteria expressing the semidoxins are much more sensitive to oxygen than those of bacteria expressing symdoxins. Motivated by the in vivo functionality of designed semidoxins, we identified putative naturally occurring semidoxins in extant anaerobic microorganisms. This is consistent with the observed in vivo oxygen sensitivity of the semidoxin designs. One natural semidoxin is shown to be folded and redox active. However, it exists as a mixture of monomers and dimers, suggesting a potential connection between semidoxins and even simpler single iron–sulfur cluster-binding peptides.
59 BASIC BIOLOGICAL SCIENCES↗
The Power of Many: An Ensemble Approach to Spectral Similarity
Quantifying the similarity between two mass spectra─a known reference mass spectrum and an unidentified sample mass spectrum─is at the heart of compound identification workflows in gas chromatography–mass spectrometry (GC-MS). The reference spectrum most like the sample is assigned as its identification (provided some quantitative similarity threshold is met, e.g., 80%) and thus accurately measuring similarity is essential. Significant research has gone toward developing metrics for this purpose, each of which has attempted to improve upon existing methods by incorporating GC-MS-specific information (e.g., peak ratios or retention times) or adopting various statistical and algorithmic frameworks. While this active development has led to a plethora of similarity metrics with demonstrated value across different contexts, the unfortunate consequence has been confusion surrounding which metric should be used as a global standard. No such metric is currently accepted as the standard method because different metrics have demonstrated optimal performance in different contexts. In this work, we propose an ensemble approach to spectral similarity scoring that combines the collective information from across existing similarity metrics to form an improved, globally representative similarity metric as a step toward establishing a global standard method. In conclusion, the resulting ensemble metrics are evaluated on over 88,000 spectra of varying complexity and demonstrate improved abilities to accurately rank the correct reference spectrum as the top-matching candidate for a sample relative to the rankings generated by individual similarity scores.
Carbohydrates↗
World Congress on High Entropy Alloys (HEA 2019) (Final Technical Report)
The World Congress on High Entropy Alloys (HEA 2019) was a new, cross-disciplinary technical forum designed to share the latest research advances in materials with high configurational entropy, including both single-phase and multiphase (compositionally complex) alloys. This inaugural World Congress on High Entropy Alloys (HEA 2019) was held in Seattle, Washington from November 17-20, 2019 with the goal of HEA 2019 to assemble the international community of HEA stakeholders – including researchers, educators, and engineers – to capture the current state-of-the-art, identify current gaps in HEA efforts, and to set the stage for the future growth and application of HEAs worldwide. HEA 2019 was the environment for leaders in this field to showcase their researc, and network with their peers to informally discuss the latest developments in high entropy alloys, while also making valuable professional connections. The goal of the organizers was to ensure a high-quality conference that held a strong international presence and aimed to highlight the important advances in HEA research on a global scale. Student participation was greatly encouraged in order to give students exposure to recent advances in this field. This meeting was open to all interested individuals and attempted to provide the most advanced technical meeting possible, with a mixture of attendees from research and development, industry, and education.
36 MATERIALS SCIENCE↗
Implementation of a Drift Flux Model into SAM with Development of a Verification and Validation Test Suite for Modeling of Noncondensable Gas Mixtures
The advanced thermal-hydraulic system code, System Analysis Module (SAM), was originally developed for the modeling of single-phase flow in advanced reactors. It has since been expanded to include a four-equation drift flux model for the modeling of two-phase flows containing a noncondensable gas. The model was expanded to support the modeling of molten salt reactor (MSR) designs in which the fuel is directly dissolved in the circulating coolant. These designs have shown that circulating gas bubbles can play an important role in the management of fission products and the operational behavior of the reactor. A drift flux model was implemented to more accurately capture the localized behavior of the void in the core and its impact on the mass transfer of fission products. A thorough assessment of the new model was performed by developing a verification and validation test suite. Verification problems were designed to test all major terms in the new governing equations. The new model converged to the correct solution at the expected order of accuracy for all verification cases. The validation cases included a wide range of flow and void conditions in different pipe geometries. Although higher void experiments show a slight underprediction of void by the drift flux model, experiments that aim to reproduce Molten Salt Reactor Experiment (MSRE) experimental conditions show good agreement with the model. The gas transport model was activated for a SAM model of the MSRE to demonstrate that it can be used in a more complex model. Finally, this gas transport model will be used along with an interfacial area transport equation being implemented in SAM for the prediction of mass transport behavior in MSR conditions.
21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
PFSA-Ionomer Adsorption to C and Pt/C Particles in Fuel-Cell Inks
Catalyst inks used to make fuel-cell electrodes consist of Pt/C catalyst particles and a perfluorosulfonic acid (PFSA) ionomer dispersed in water/alcohol solvent mixtures. PFSA ionomer in the ink adsorbs to the surface of the catalyst particles, dictating the dispersion colloid properties. Following adsorption, the subsequent distribution of excess nonadsorbed ionomer in the ink then governs the final structure of the electrode. Here, we characterize the adsorption of the PFSA ionomer onto Pt/C catalyst particles. PFSA adsorption is largely irreversible. Adsorbed sulfonic-acid moieties impart a negative charge on the catalyst surface, causing electrostatic repulsion between the free ionomer in solution and the ionomer-covered Pt/C particle surface. The amount of adsorption is limited by the resulting electrostatic charge that grows as more ionomer adsorbs, and the catalyst surface becomes more negatively charged. Attenuating electrostatic repulsion by increasing the ink ionic strength promotes ionomer adsorption. Electrostatically limited adsorption is observed, irrespective of the solvent water/n-propanol ratio or the catalyst particle porosity and Pt loading. Experimentally measured ionomer adsorption isotherms are well predicted by a Smoluchowski-based kinetic adsorption model, in which the electrostatic energy barrier for adsorption is predicted from DLVO theory. These findings help to unravel the complex phenomena within these colloidal dispersions, allowing for subsequent tailoring of inks to optimize fuel-cell electrode structure and performance.
Adsorption↗
Assessment of Impurities in Neptunium Metal Using Double-Focusing SF-ICP-MS
In the transmutation process, minor actinides such as neptunium, americium and curium obtained from spent nuclear fuel are incorporated into new fuel that can be placed into a fast reactor, where these elements fission into products with shorter half-lives which reduces the health and safety hazards. In order to better understand the all the involved processes, fundamental physical properties of actinides should be investigated, and for that reason, high-purity materials need to be produced. One of the main challenges in characterizing these materials is the lack of pure metal available for study, and lack of analytical methods to determine the purity. Trans-uranic elements are challenging to study because of the need to be handled in specialized facilities, safeguards concerns and they are not easily purchased and/or produced. High-purity Np metal is being produced at the Materials and Fuels Complex (MFC) of Idaho National Laboratory (INL), in a process of direct oxide reduction developed by Squires and Lessing, with a target purity of 99.999%. The goal of this research is to develop methods to determine the impurities in the Np metal, with detection limits low enough to achieve this purity level. In this work, we have used several ICP-MS and ICP OES techniques, but the focus was the method development using a recently acquired Double-Focusing Sector Field Inductively Coupled Plasma Mass Spectrometer (SF-ICP-MS). To produce the Np metal, approximately 20 g of the neptunium oxide powder was calcined at 800 oC for 6 h in a magnesium oxide crucible, which is placed inside a stainless steel crucible, that goes into the Hot Uniaxial Press (HUP) furnace insert. After the calcining step, the Np oxide was mixed with approximately 9 g of calcium metal and 100 g of ultra-dry calcium chloride. The HUP furnace was heated in a ramp rate of 50 oC min -1 up to 1000 oC. When the reaction mixture reached 850 oC, a tantalum stirrer was activated at 100 rpm. After the tantalum stirrer was removed and the mixture cooled overnight, the MgO crucible was opened with a hammer and chisel to retrieve the Np metal button at the bottom of the reaction mixture. Prior to the dissolution process, the surface contaminants of the sample were removed. The Np button was washed in 10 mL of ultra-pure water for 1 min, with a faint reaction observed on the surface, indicating the presence of Ca metal. The water-washed sample was placed in a tube with 2 M HCl for only 3 s, as a vigorous reaction in the button surface was observed. The leachates were saved for further analysis. The sample was then rinsed with ultra-pure water and air-dried prior to dissolution. The cleaned sample was placed in a PTFE beaker and 25 mL of 6 M HCl and 150 µL of 24 M HF were added. After 10 minutes of reaction, the beaker was placed on a hot plate for 1 h and 30 min, followed by the addition of 1 mL of 16 M HNO3 and allowed to react for a further 1 h and 20 min. The sample was removed from heat and 10 mL of HNO3 16 M was added to react with the HCl. The beaker was covered and left for overnight reaction, producing a solution with approximately 20 mL of final volume. A Quadrupole Inductively Coupled Plasma Mass Spectrometer (Q-ICP-MS, Perkin Elmer ELAN DRC II Q-ICP-MS) was used to obtain qualitative mass spectra for the dissolution blank, each of the leachates and the dissolved sample. In the water leachate spectrum mainly Ca and Mg were observed, while the acid wash had a similar peak pattern to the one observed for the Np metal sample, indicating that the process not only removed surface contamination, but also reacted with the sample itself. In the Np material spectrum, Ta and actinides were identified as candidates for major contaminants, as the most intense peaks corresponded to the mass-to-charge ratios of these elements. Minor contaminants included Al, Au, Ca, Cr, Fe, I, Na, Nb, Pb, Sn, Ti, Tl, V, Y. The presence of impurities in the material could have originated from several sources, such as the materials used for the casting process, the use of impure NpO2 or contamination of reagents and materials used for the analysis. Some of the isotopes listed as potential contaminants are susceptible to spectral interferences, so Double-Focusing SF-ICP-MS (Nu Instruments Attom ES HR-ICP-MS) was used for the quantitative analysis. For each isotope determined, several items were evaluated: raw signal of a blank solution, sensitivity and determination coefficient of calibration curves, possibility of interferences and comparison of results obtained for at least two resolving powers (RP): 300 and 4000. The evaluation of the signal in a blank solution can indicate if a spectral interference from the plasma gas and/or the solvent was successfully resolved (commonly observed for 52Cr+/40Ar12C+, for example). It is important to highlight that a signal reduction is expected when a higher RP is used, as the ion beam transmission is decreased by the use of narrower slits
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Modeling and optimization of steady flow of natural gas and hydrogen mixtures in pipeline networks
Here, we extend the canonical problems of simulation and optimization of steady-state gas flows in pipeline networks with compressors to the transport of mixtures of highly heterogeneous gases injected throughout a network. Our study is motivated by proposed projects to blend hydrogen generated using clean energy into existing natural gas pipeline systems as part of efforts to reduce the reliance of energy systems on fossil fuels. Flow in a pipe is related to endpoint pressures by a basic Weymouth equation model, with an ideal gas equation of state, where the wave speed depends on the hydrogen concentration. At vertices, in addition to mass balance, we also consider mixing of incoming flows of varying hydrogen concentrations. The problems of interest are the heterogeneous gas flow simulation (HGFS), which determines system pressures and flows given fixed boundary conditions and compressor settings, as well as the heterogeneous gas flow optimization (HGFO), which extremizes an objective by determining optimal boundary conditions and compressor settings. We examine conditions for uniqueness of solutions to the HGFS, as well as compare and contrast mixed-integer and continuous nonlinear programming formulations for the HGFO. We develop computational methods to solve both problems, and examine their performance using four test networks of increasing complexity.
08 HYDROGEN↗
Sponge exhalent metabolites influence coral reef picoplankton dynamics
Coral reef sponges efficiently take up particulate and dissolved organic matter (DOM) from the water column and release compounds such as nucleosides, amino acids, and other dissolved metabolites to the surrounding reef via their exhalent seawater, but the influence of this process on reef picoplankton and nutrient processing is relatively unexplored. Here we examined the impact of sponge exhalent on the reef picoplankon community and subsequent alterations to the reef dissolved metabolite pool. We exposed reef picoplankton communities to a sponge exhalent water mixture (Niphates digitalis and Xestospongia muta) or filtered reef seawater (control) in closed, container-based dark incubations. We used 16S rRNA gene sequencing and flow cytometry-based cell counts to examine the picoplankton community and metabolomics and other analyses to examine the dissolved metabolite pool. The initial sponge exhalent was enriched in adenosine, inosine, chorismate, humic-like and amino acid-like components, and ammonium. Following 48 h of exposure to sponge exhalent, the picoplankton differed in composition, were reduced in diversity, showed doubled (or higher) growth efficiencies, and harbored increased copiotrophic and denitrifying taxa (Marinomonas, Pontibacterium, Aliiroseovarius) compared to control, reef-water based incubations. Alongside these picoplankton alterations, the sponge treatments, relative to seawater controls, had decreased adenosine, inosine, tryptophan, and ammonium, metabolites that may support the observed higher picoplankton growth efficiencies. Sponge treatments also had a net increase in several monosaccharides and other metabolites including anthranilate, riboflavin, nitrite, and nitrate. Our work demonstrates a link between sponge exhalent-associated metabolites and the picoplankton community, with exhalent water supporting an increased abundance of efficient, copiotrophic taxa that catabolize complex nutrients. The copiotrophic taxa were often different from those observed in previous algae and coral studies. These results have implications for better understanding the multifaceted role of sponges on picoplankton biomass with subsequent potential impacts to coral and other planktonic feeders in oligotrophic reef environments.
59 BASIC BIOLOGICAL SCIENCES↗
Current status of biogas upgrading for direct biomethane use: A review
Anaerobic digestion produces biogas, a mixture of CH 4 and CO 2 , where CH 4 is a low cost, environmentally friendly, and renewable energy source. The application of biogas production is increasing rapidly as a means of reducing the pollution impact of organic biomasses. However, biogas contains unwanted elements such as hydrogen sulfide, carbon monoxide, siloxanes, and carbon dioxide. To remove these elements, several biogas upgrading technologies like water scrubbing, amine scrubbing, pressure swing adsorption, and membrane separation have been developed and are being used at various commercial scales. Problems with these methods are high energy consumption, the use of expensive chemicals, and high operating cost. Therefore, a major effort is currently underway to improve the design of existing methods as well as developing innovative new upgrading technologies such as cryogenic separation and biological upgrading. Here, this review intends to provide a comprehensive overview of the limitations with the existing upgrading technologies along with recent advances in physical, chemical, and biological biogas upgrading technologies (e.g., pressure swing adsorption, membrane separation, biochar adsorption and CO 2 conversion by biological organisms) and further into possible future solutions, such as hybrid systems. Comparative studies of process complexities and associated economic concerns are also provided, and future perspectives that may facilitate research into sustainable biogas upgrading technologies are discussed, focusing in particular on cryogenic separation, novel biological techniques, biochar based upgrading and hybrid technologies incorporating two or more different methods seamlessly integrated.
09 BIOMASS FUELS↗
Constant-potential molecular dynamics simulations of molten salt double layers for FLiBe and FLiNaK
We report the results of constant-potential molecular dynamics simulations of the double layer interface between molten 2LiF–BeF 2 (FLiBe) and 23LiF–6NaF–21KF (FLiNaK) fluoride mixtures and idealized solid electrodes. Employing methods similar to those used in studies of chloride double layers, we compute the structure and differential capacitance of molten fluoride electric double layers as a function of applied voltage. The role of molten salt structure is probed through comparisons between FLiBe and FLiNaK, which serve as models for strong and weak associate-forming salts, respectively. In FLiBe, screening involves changes in Be–F–Be angles and alignment of the oligomers parallel to the electrode, while in FLiNaK, the electric field is screened mainly by rearrangement of individual ions, predominantly the polarizable potassium cation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Development of Methods for In-line Monitoring of Yield Stress During the Transfer of Radioactive Waste - 20435
Radioactive waste slurries at the Savannah River Site (SRS) and Hanford often behave as non-Newtonian fluids with a yield stress. The yield stress increases the size of equipment needed to transport or mix these slurries and can increase the risk of process upsets. This property is often measured by collection of samples and transportation to a laboratory, which can increase the risk of personnel exposure and even change the rheology. In addition, slurry rheology has been observed to change with time. Real-time in-line monitoring (RTIM) of rheological properties of slurries can have substantial benefits to critical processes which are currently in operation or will be part of future plans in Department of Energy (DOE) complex processes. The need for an appropriate RTIM technology that can potentially minimize or eliminate numerous sampling operations was recently identified. This research at Florida International University focuses on addressing the need for a reliable RTIM technology at US Department of Energy sites. The objective of this work is to investigate and develop appropriate and reliable technologies that can perform accurate and easy measurements of yield stress with minimal changes to the flow conditions at US Department of Energy sites. Use of ultrasound in longitudinal and shear modes was considered as a method for monitoring of yield stress variations with no disturbance to the flow. Measurement of shear wave velocity (in shear mode) and monitoring of sound velocity variations with start of flow from rest (longitudinal mode) are the underlying principles. Measurement of pressure loss and liquid rise (due to static differential pressure) during flow of slurries were two other methods that were considered and investigated. In addition, analysis of stability depth of a penetrometer in slurry medium (penetrometer method) revealed a potential suitability. This paper presents efforts associated with investigation of different methods mentioned earlier for kaolin-water mixtures at different concentrations. Theoretical analysis showed that all methods under investigation were capable of monitoring yield stress in a desirable range of 0 to 70 pascal. A bench scale test setup was constructed for investigation of pressure loss and liquid rise methods. Simulants at different concentrations were created for initial testing campaigns. For ultrasonic testing, effects of yield stress on sound propagation speed in longitudinal and shear modes were investigated for simulants placed inside PVC pipes. Parameters such as simulant concentration and pipe diameter were varied to find optimal values. It was found that spacing (or medium thickness) of 1/8 inch or less was necessary to observe echoes with sufficient strength. In addition, a significant effect of yield stress on sound propagation velocity was observed. For the liquid rise method, kaolin-water simulant at 1.17 specific gravity was pumped through a 1/4 inch pipe and liquid height was measured in a vertical riser branching off a three-way connection. Static gauge pressure was varied within [0.3 to 1.1] psi range by increase of pumping pressure and flow. Results showed consistent yield stress data within 10% deviation from values reported by a rheometer. (authors)
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Infrared Optical Constants from Pressed Pellets of Powders: I. Improved n and k Values of (NH4)(2)SO(4)from Single-Angle Reflectance
In combination with other parameters, the real, n(?), and imaginary, k(?), components of the complex refractive index, = n + ik, can be used to simulate the optical properties of a material in different forms, e.g. its infrared spectra. But obtaining reliable values of the optical constants n/k for solid materials is challenging due to the lack of optical quality specimens, usually crystals, large enough to measure. An alternative to crystals is to press the powder into a uniform disk. We have produced pellets from ammonium sulfate, (NH4)2SO4, powder and derived the pellets’ n and k values via single-angle reflectance using a specular reflectance device in combination with a Fourier transform infrared spectrometer. The single-angle technique measures amplitude of light reflected from the material as a function of wavelength over a wide spectral domain; the optical constants are determined from the reflectance data using the Kramers-Kronig relationship. We investigate several parameters associated with the pellets and pellet formation and their effects upon delivering the most reliable n/k values. Parameters studied include pellet diameter, mass and density (void space), drying, grinding, sieving and particle size in the pellet formation, as well as pressing pressure and duration. Of these parameters, using size-selected mixtures of dried, small (< 100 µm) particles and pressing at = 10 tons for at least 30 minutes were found key to forming highly reflective samples. Comparison to two sets of previous literature n(?) and k(?) values obtained from crystalline (NH4)2SO4 both as crystal reflectance as well as extinction spectra of aerosols measured in a flow tube show reasonable agreement, but suggests the present values, as confirmed from two independent techniques, represent a substantial improvement for n/k values for (NH4)2SO4, also demonstrating promise to measure the optical constants of other materials.
Optical constants, index of refraction, single-ang↗