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At least 1,765 records · Page 98

Crystal accumulation in the Hanford Waste Treatment Plant high level waste melter: Summary of 2017 experiments

A full-scale, transparent mock-up of the Hanford Tank Waste Treatment and Immobilization Project High Level Waste glass melter riser and pour spout has been constructed to allow for testing with visual feedback of particle settling, accumulation, and resuspension when operating with a controlled fraction of crystals in the glass melt. Room temperature operation with silicone oil and magnetite particles simulating molten glass and spinel crystals, respectively, allows for direct observation of flow patterns and settling patterns. The fluid and particle mixture is recycled within the system for each test.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

CFD Predictions of Boiling Regime Transitions during Line Chilldown validated against a 1G LN2 Experiment

Introduction Before filling a propellant tank on the ground or in Space, the transfer line between the donor and receiver tanks must be cooled down preferably by sacrificing a minimum amount of the cryogenic fluid. The cryogenic line chill-down process involves a transition between different flow boiling regimes, namely, film boiling, transition film boiling, and nucleate boiling which are complex and may be quite gravity-dependent. Capturing these boiling phenomena and predicting the transition between them in a CFD framework is new and challenging both for 1g and microgravity applications. Materials & Methods The present work addresses this challenge by employing a two-phase Eulerian approach in the context of a homogeneous fluid mixture together with the Lee phase change model to capture the film boiling regime of the chill-down process using ANSYS Fluent®. The nucleate boiling regime is predicted by incorporating an in-house developed sub-grid model that accounts for bubble nucleation, bubble growth, bubble departure diameter, and their shedding frequency. The sub-grid model is encoded and implemented into Fluent via a user-defined function for the wall-fluid heat flux calculations. The mathematical formulation and numerical implementation of the CFD model are described in detail. The coupled CFD-Subgrid model is validated against published experimental data for liquid nitrogen chill-down of a heated stainless-steel pipe in 1g. Results Numerical simulation results show good agreements between the CFD predictions of the wall temperature evolution, rewetting temperature, and transition between film and nucleate boiling, with the experimental measurements published by Darr et al [2] for several different LN2 flowrates in the vertical pipe orientation. The CFD predictions for the wall temperature distribution indicate a rapid quenching of the wall at two upstream and downstream temperature sensing locations as compared to the experimental measurement. The only tuning parameter in the CFD model is the Lee mass transfer coefficient. The CFD Model predicts the Liedenfrost rewetting temperature in close agreement with the experiment. This marks a transition between stable and transitionary flow boiling regimes. The CFD-predicted boiling curve for the downstream sensor location is also compared against its experimental counterpart and indicates that the model is able to predict all the key temperature and heat flux parameters during the transitions from stable to transitionary film boiling to nucleate boiling in close agreement with the experiment. A sequence of predicted volume fraction, and temperature contours depicting these transitions will be presented.

Evaporation Condensation↗

Influence of the double bond position in combustion chemistry of methyl butene isomers: A shock tube and laser absorption study

Shock tube experiments have been carried out on 2–methyl–1–butene (2M1B), 2–methyl–2–butene (2M2B), and 3–methyl–1–butene (3M1B)—the three isomers of methyl butene compound. Here, carbon monoxide (CO) time–histories and ignition delay times are obtained behind reflected shockwaves over the temperature range of 1350–1630 K and pressures of 8.3–10.5 atm with stoichiometric mixtures of 0.075% fuel in O 2 /Ar. Comparative ignition study reveals that 3M1B ignites significantly faster than the other two isomers, while 2M1B dissociates earlier but ignites later than 2M2B. Possible mechanisms for this behavior are discussed with ignition delay time sensitivity and reaction path analysis. In addition, time–resolved CO measurements are compared with three different reaction mechanisms from the literature. Sensitivity analyses have been carried out to identify important reactions that need attention to accurately predict the chemistry of these isomers. Further investigation into the rates of unimolecular fuel decomposition reactions and C 3 H 3 + O 2 = CH 2 CO + HCO reaction are suggested based on the current investigation.

09 BIOMASS FUELS↗

Quantifying Dynamic Processes in Reactive Materials: An Extended Burn Tube Test

Abstract A common method for measuring the reactivity of rapidly deflagrating materials has been to loosely pack a desired mixture into an approx. 10 cm long×3 mm diameter acrylic tube, ignite the material on one end, and report the observed self‐propagating flame velocity through the material. While this method can yield qualitative information, linking this to quantitative intrinsic properties, such as particle burn time, has remained challenging. In this work, we significantly redesign the traditional burn tube experiment. Between 25 and 250 mg of nanocomposite aluminum/copper oxide (Al/CuO) thermite is loosely packed into the capped end of a 1.8 m long tube, and the remainder of the tube is left unfilled. The material is ignited using a hot wire, resulting in a steadily‐propagating luminous front, which extends part, or all, of the way down the length of the tube. We suggest the behavior is a result of “reactive entrainment”, which occurs when the reaction time scale becomes longer than the characteristic momentum relaxation time scale. When this criterion is met, and when there are significant pressure gradients present or produced during the reaction, material will be entrained by the gases before and/or during the reaction; a behavior very different from conventional thermites, which use larger particle sizes. The effect of sample mass and tube diameter on propagation velocity is investigated, and we find a linear scaling with mass and a power law scaling with tube radius ( r −1.3 ) between 1.56 and 4.76 mm radii. For several conditions, we observe the reaction complete; defined by the distance where the propagation velocity decreases to a fixed fraction of its steady value. The ratio of quench distance to propagation velocity was found to approach a constant value of 3.29±0.70 ms, which we suggest is the burn time of the Material. For the range of masses studied in this work, the burn time was found to be independent of mass, implying that it is an intrinsic particle burn time. We expect other quantitative information can be deduced from this experiment, so long as the chosen sample mass and tube dimensions allow one to observe the full extent of reaction.

Sullivan, Kyle T.↗

A novel process for separation of polycarbonate, polyvinyl chloride and polymethyl methacrylate waste plastics by froth flotation

Highlights: • KMnO{sub 4} treatment changes selectively flotation behavior of PC, PVC and PMMA plastics. • Ternary waste plastics are separated efficiently by froth flotation. • Recycling of KMnO{sub 4} solutions is conducted to make the process green. • A novel process is proposed for separation of waste plastics by froth flotation. - Abstract: A novel process was proposed for separation of ternary waste plastics by froth flotation. Pretreatment of plastics with potassium permanganate (KMnO{sub 4}) solution was conducted to aid flotation separation of polycarbonate (PC), polyvinyl chloride (PVC) and polymethyl methacrylate (PMMA) plastics. The effect of pretreatment parameters including KMnO{sub 4} concentration, treatment time, temperature and stirring rate on flotation recovery were investigated by single factor experiments. Surface treatment with KMnO{sub 4} changes selectively the flotation behavior of PC, PVC and PMMA, enabling separation of the plastics by froth flotation. Mechanism of surface treatment was studied by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and X-ray photoelectron spectrum (XPS). Effect of frother concentration and flotation time on flotation behavior of plastic mixtures was further studied for flotation separation. The optimized conditions for separation of PC are KMnO{sub 4} concentration 2 mmol L{sup −1}, treatment time 10 min, temperature 60 °C, stirring rate 300 rpm, flotation time 1 min and frother concentration 17.5 mg L{sup −1}. Under optimum conditions, PVC and PMMA mixtures are also separated efficiently by froth flotation associated with KMnO{sub 4} treatment. The purity of PC, PVC and PMMA is up to 100%, 98.41% and 98.68%, while the recovery reaches 96.82%, 98.71% and 98.38%, respectively. Economic analysis manifests remarkable profits of the developed process. Reusing KMnO{sub 4} solution is feasible, enabling the process greener.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Pressure Vapor-Liquid Equilibria of 1-Alkyl-1-Methylpyrrolidinium Bis(trifluoromethylsulfonyl)imide Ionic Liquids and CO 2

The high-pressure vapor-liquid equilibrium for the binary systems of carbon dioxide (CO 2 ) and a series of 1-alkyl-1-methyl pyrrolidinium bis(trifluoromethylsulfonyl)amide ionic liquids ([C n C 1 pyr][NTf 2 ] ( n = 3,4,6)) are reported at 298.15, 318.15 and 338.15 K and at pressures up to 20 MPa. Experiments were conducted using gravimetric (IGA and XEMIS microbalances) and a volumetric method (high-pressure view cell). The solubility of CO 2 in pyrrolidinium ionic liquids increases with decreasing temperature and increasing pressure. The CO 2 solubility also slightly increases with increase in alkyl chain length on the pyrrolidinium cation. Molar volume and volume expansion of CO 2 + IL mixtures are also reported. The Fickian diffusion of CO 2 in pyrrolidinium based ionic liquids (~10 -10 m 2 ·s -1 ) was calculated at pressures of up to 2 MPa and found to be at the same order of magnitude but slightly lower than the diffusivity of CO 2 in imidazolium based ionic liquid with the [NTf 2 ] anion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Facile, ethylene glycol-promoted microwave-assisted solvothermal synthesis of high-performance LiCoPO 4 as a high-voltage cathode material for lithium-ion batteries

Olivine-type LiCoPO 4 is considered a promising high-voltage cathode material for next-generation lithium-ion batteries. However, preparing high-performance LiCoPO 4 by a simple approach has been challenging. Herein, we present a facile and rapid (30 min) one-step microwave-assisted solvothermal synthesis route using a 1 : 1 (v/v) water/ethylene glycol (EG) binary solvent mixture and a temperature of 250 °C. Here, the technique delivers high-performance LiCoPO4nanoparticles without additional post-annealing or carbon coating steps. The as-prepared powder consists of single crystalline LiCoPO 4 and features a hexagonal platelet-like morphology with dimensions of 700-800 nm × 400-600 nm × 100-220 nm. Selected area electron diffraction (SAED) experiments reveal that the platelets show the smallest dimension along [010], which is the direction of the lithium diffusion pathways in the olivine crystal structure. Furthermore, the results indicate that the EG co-solvent plays an important role in tailoring the particle size, morphology, and crystal orientation of the material. Co L-edge soft X-ray absorption spectroscopy (XAS) of LiCoPO 4 are presented for the first time and confirm that the material only consists of Co 2+ . Benefiting from the unique morphology, which facilitates Li-ion conduction, electrochemical measurements deliver an initial discharge capacity of 137 mA h g -1 at 0.1 C, a remarkably stable capacity retention of 68% after 100 cycles at 0.5 C, and a specific energy density of 658 W h kg -1 based on its capacity and voltage, which is the best performance of LiCoPO 4 obtained from microwave-assisted solvothermal synthesis to date.

36 MATERIALS SCIENCE↗

High pressure neutron diffraction on WAND 2 with a Paris-Edinburgh press

The Paris-Edinburgh press is a widely available, highly adaptable pressure cell commonly used while collecting neutron scattering data. Here, we detail the use of the VX3 and VX5 Paris-Edinburgh presses on the Wide-Angle Neutron Diffractometer (WAND 2 ) at the High Flux Isotope Reactor at Oak Ridge National Laboratory. We first give a detailed overview of the instrument setup and alignment capabilities used at WAND 2 . We then demonstrate the high pressure capabilities through three examples. In this work, the first example focuses on diffraction data obtained from a lithium-diamond mixture to 10 GPa with the use of single toroidal cubic boron nitride anvils. Other examples include the room temperature compressions of germanium (up to 16 GPa) and the mineral malachite with double toroidal sintered diamond anvils. This work thereby represents the first studies above 10 GPa at the High Flux Isotope Reactor and opens the door for future user experiments at these elevated pressures.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Compatibility of FeCrAlMo in Flowing Pb-Li at 600°C to 700°C

A series of monometallic thermal convection loops (TCLs) has been conducted to determine the maximum temperature where FeCrAl alloys have compatibility with eutectic lead lithium (Pb-Li) for a dual-coolant fusion blanket. Pre-oxidizing commercial alloy APMT (Fe-21Cr-5Al-3Mo) for 2 h at 1000°C to form a surface α-Al 2 O 3 layer was very effective in reducing the mass loss of specimens in the hot and cold legs of the most recent TCL that was operated for 1000 h with a peak temperature of 700°C. However, unlike previous experiments, the postexposure room temperature ductility of many of the APMT specimens was degraded to <10% total elongation, and many of the specimens at the highest temperature (>680°C) were severely damaged or were not recovered. Furthermore, wide-angle X-ray scattering found that the pre-formed α-Al 2 O 3 scale transformed to a mixture of trigonal and tetragonal LiAlO 2 . The overall results suggest that the maximum temperature for FeCrAl is limited to <700°C.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Chemistry of the CO dimer at low temperatures

Researchers conducted a series of experiments on the chlorine-catalyzed photodecomposition of O sub 3 both in the gas and in inert solvents such as CF sub 4 and CO sub 2 in the temperature range about 190 to 225 K. The liquid medium was chosen in order to minimize possible surface loss of long-lived ClO dimer, and to aid in the stabilization of transient excited intermediates. The mechanism of dimer formation was as follows: (1) Cl sub 2 + hv yields Cl + Cl; (2) Cl + O sub 3 yields ClO + O sub 2; (3) ClO + ClO yields Cl sub 2 O sub 2. The experiments were done in cooled low temperature cells, with irradiation from an Osram high pressure mercury arc, filtered to remove radiation below 325 nm. Spectral analysis was by means of a Cary Model 2200 UV spectrometer. The principal objectives were: (1) to determine the lifetime of the dimer as a function of temperature; (2) to observe spectral changes in the mixtures which could be attributed to dimer or related products; and (3) to observe chemical or photochemical reactions of the dimer.

Demore, W. B.↗

High spatial resolution measurements in a single stage ram accelerator

High spatial resolution experimental tube wall pressure measurements of ram accelerator gas dynamic phenomena are presented in this paper. The ram accelerator is a ramjet-in-tube device which operates in a manner similar to that of a conventional ramjet. The projectile resembles the centerbody of a ramjet and travels supersonically through a tube filled with a combustible gaseous mixture, with the tube acting as the outer cowling. Pressure data are recorded as the projectile passes by sensors mounted in the tube wall at various locations along the tube. Utilization of special highly instrumented sections of tube has allowed the recording of gas dynamic phenomena with high resolution. High spatial resolution tube wall pressure data from the three regimes of propulsion studied to date (subdetonative, transdetonative, and superdetonative) in a single stage gas mixture are presented and reveal the three-dimensional character of the flow field induced by projectile fins and the canting of the fins and the canting of the projectile body relative to the tube wall. Also presented for comparison to the experimental data are calculations made with an inviscid, three-dimensional CFD code. The knowledge gained from these experiments and simulations is useful in understanding the underlying nature of ram accelerator propulsive regimes, as well as assisting in the validation of three-dimensional CFD coded which model unsteady, chemically reactive flows.

Hinkey, J. B.↗

Numerical Analysis of an Impinging Jet Reactor for the CVD and Gas-Phase Nucleation of Titania

We model a cold-wall atmospheric pressure impinging jet reactor to study the CVD and gas-phase nucleation of TiO2 from a titanium tetra-iso-propoxide (TTIP)/oxygen dilute source gas mixture in nitrogen. The mathematical model uses the computational code FIDAP and complements our recent asymptotic theory for high activation energy gas-phase reactions in thin chemically reacting sublayers. The numerical predictions highlight deviations from ideality in various regions inside the experimental reactor. Model predictions of deposition rates and the onset of gas-phase nucleation compare favorably with experiments. Although variable property effects on deposition rates are not significant (approximately 11 percent at 1000 K), the reduction rates due to Soret transport is substantial (approximately 75 percent at 1000 K).

Gokoglu, Suleyman A.↗

Influence of flow on interface shape stability in low gravity

The objectives are to: (1) Understand the influence in low gravity of flow on interface shape. For example, document and control the influence of axial flow on the Plateau-Rayleigh instability of a liquid bridge; and (2) Extend the ground-based density-matching technique of low gravity simulation to situations with flow; that is, develop Plateau chamber experiments for which flow can be controlled. Containerless containment of liquid by surface tension has broad importance in low gravity. For space vehicles, the behavior of liquid/gas interfaces is crucial to successful liquid management systems. In microgravity science, free interfaces are exploited in various applications. Examples include float-zone crystal growth, phase separation near the critical point of liquid mixtures (spinoidal decomposition) and quenching of miscibility gap molten metal alloys. In some cases, it is desired to stabilize the capillary instability while in others it is desired to induce capillary breakup. In all cases, understanding the stability of interface shape in the presence of liquid motion is central.

Steen, Paul H.↗

Search for life on Mars: Evaluation of techniques

An important question for exobiology is, did life evolve on Mars? To answer this question, experiments must be conducted on the martian surface. Given current mission constraints on mass, power, and volume, these experiments can only be performed using proposed analytical techniques such as: electron microscopy, X-ray fluorescence, X-ray diffraction, a-proton backscatter, g-ray spectrometry, differential thermal analysis, differential scanning calorimetry, pyrolysis gas chromatography, mass spectrometry, and specific element detectors. Using prepared test samples consisting of 1% organic matter (bovine serum albumin) in palagonite and a mixture of palagonite, clays, iron oxides, and evaporites, it was determined that a combination of X-ray diffraction and differential thermal analysis coupled with gas chromatography provides the best insight into the chemistry, mineralogy, and geological history of the samples.

Schwartz, D. E.↗

Premixed Gas Combustion: An Excitable System

Rotating spiral and target patterns have been observed experimentally on freely-propagating premixed gas flames in large diameter tubes at normal gravity (1-g). These modes of propagation occur in near-limit mixtures which have a Lewis number (Le, defined as the ratio of the thermal diffusivity of the cold mixture to the mass diffusivity of the scarce component into the mixture) sufficiently greater than one. However, at 1-g, buoyant flows strongly distort the flame curvature, hydrodynamics (thus stretch) and convective transport of species and heat. In turn, these alter the critical Le required for onset of instability. To isolate and better understand the mechanisms which drive the observed patterns and their dynamics, 1-g and microgravity (micro-g) experiments are being conducted to determine: (1) the structure and dynamics of the patterns, (2) a map of the critical Le and heat loss for their occurrence, (3) the relative significance of the chemical kinetics, and (4) the effect of curvature (local wave and global flame front) on wave propagation. With this in hand, we will be better prepared to discuss an additional mode, a state of 'chemical turbulence,' which seems to be the ultimate fate of many of these near-limit flames prior to extinction.

Pearlman, Howard↗

Carbon Isotope Characterization of Organic Intermediaries in Hydrothermal Hydrocarbon Synthesis by Pyrolysis-GC-MS-C-IRMS

We report results of experiments designed to characterize the carbon isotope composition of intermediate organic compounds produced as a result of mineral surface catalyzed reactions. The impetus for this work stems from recently reported detection of methane in the Martian atmosphere coupled with evidence showing extensive water-rock interaction during Martian history. Abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions may be one possible process responsible for methane generation on Mars, and measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible isotope measurements. Our isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-Combustion-Isotope Ratio Mass Specrometry (Py-GC-MS-C-IRMS). Others have conducted similar pyrolysis-IRMS experiments on low molecular weight organic acids (Dias, et al, Organic Geochemistry, 33 [2002]). Our technique differs in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of the organic compounds. A sample of carboxylic acid (mixture of C1 through C6) was pyrolyzed at 100 XC and passed through the GC-MS-C-IRMS (combusted at 940 XC). In order to test the reliability of our technique we compared the _13C composition of different molecular weight organic acids (from C1 through C6) extracted individually by the traditional sealed-tube cupric oxide combustion (940 XC) method with the _13C produced by our pyrolysis technique. Our data indicate that an average 4.3. +/-0.5. (V-PDB) apparent isotopic fractionation accompanies the pyrolysis extractions. We postulate that this isotope offset could be the result of incomplete thermal desorption during pyrolysis. We are continuing to investigate the reliability of this pyrolysis technique for correcting carbon isotope measurements of mineral surface catalyzed organic compounds.

Socki, Richard A.↗

Urethane/Silicone Adhesives for Bonding Flexing Metal Parts

Adhesives that are blends of commercially available urethane and silicone adhesives have been found to be useful for bonding metal parts that flex somewhat during use. These urethane/silicone adhesives are formulated for the specific metal parts to be bonded. The bonds formed by these adhesives have peel and shear strengths greater than those of bonds formed by double-sided tapes and by other adhesives, including epoxies and neat silicones. In addition, unlike the bonds formed by epoxies, the bonds formed by these adhesives retain flexibility. In the initial application for which the urethane/silicone adhesives were devised, there was a need to bond spring rings, which provide longitudinal rigidity for inflatable satellite booms, with the blades that provide the booms axial strength. The problem was to make the bonds withstand the stresses, associated with differences in curvature between the bonded parts, that arose when the booms were deflated and the springs were compressed. In experiments using single adhesives (that is, not the urethane/ silicone blends), the bonds were broken and, in each experiment, it was found that the adhesive bonded well with either the ring or with the blade, but not both. After numerous experiments, the adhesive that bonded best with the rings and the adhesive that bonded best with the blades were identified. These adhesives were then blended and, as expected, the blend bonded well with both the rings and the blades. The two adhesives are Kalex (or equivalent) high-shear-strength urethane and Dow Corning 732 (or equivalent) silicone. The nominal mixture ratio is 5 volume parts of the urethane per 1 volume part of the silicone. Increasing the proportion of silicone makes the bond weaker but more flexible, and decreasing the proportion of silicone makes the bond stronger but more brittle. The urethane/silicone blend must be prepared and used quickly because of the limited working time of the urethane: The precursor of the urethane adhesive is supplied in a two-part form, comprising a resin and a hardener that must be mixed. The resulting urethane adhesive has a working time of 3 to 5 minutes. To prepare the urethane/silicone blend, one must quickly add the silicone to the urethane adhesive and mix it in thoroughly within the working time of the urethane. Once the urethane/silicone blend has been mixed and applied to the bond surfaces, it takes about 2 hours for the adhesive to cure under pressure. However, it takes about 24 hours for the adhesive to reach full strength.

Edwards, Paul D.↗

Role of the Tenax® Adsorbent in the Interpretation of the EGA and GC‐MS Analyses Performed With the Sample Analysis at Mars in Gale Crater

The Sample Analysis at Mars (SAM) experiment on the National Aeronautics and Space Administration Curiosity rover seeks evidence of organic compounds on the surface of Mars. Since the beginning of the mission, various organic molecules have been detected and identified. While several have been demonstrated to be indigenous to the Martian soil and rocks analyzed, others appear to have been produced from sources internal to the experiment. The objective of this study is to build an exhaustive molecular database to support the interpretation of SAM results by identifying all the chemical species produced from Tenax® adsorbents, by determining (1) the thermal degradation by‐products of Tenax®, (2) the effect of Tenax® conditioning on the formation of Tenax® by‐products, (3) the impact of MTBSTFA or a mixture of MTBSTFA and DMF on Tenax® decomposition, and (4) the reaction between Tenax® and calcium perchlorate. Our results indicate that the by‐products of the SAM trap are due to the impact of trap heating, the impact of the derivatization reagent (MTBSTFA) and the presence of perchlorate in Martian soil. Some of these by‐products are observed in the SAM gas chromatograph mass spectrometer data from Mars.

Buch, A.↗