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At least 1,027 records · Page 57

Structural crossover in a supercooled metallic liquid and the link to a liquid-to-liquid phase transition

Time-resolved synchrotron measurements were carried out to capture the structure evolution of an electrostatically levitated metallic-glass-forming liquid during free cooling. The experimental data shows a crossover in the liquid structure at ~1000 K, about 115 K below the melting temperature and 150 K above the crystallization temperature. The structure change is characterized by a dramatic growth in the extended-range order below the crossover temperature. Molecular dynamics simulations have identified that the growth of the extended-range order was due to an increased correlation between solute atoms. These results provide structural evidence for a liquid-to-liquid-phase-transition in the supercooled metallic liquid.

Glass transitions↗

A Composition-Based Approach for Predicting Hanford Tank Waste Liquid Viscosity

Liquid viscosity is an important Hanford waste physical property that governs, in part, the performance of key Hanford flowsheet unit operations and processes, including waste filtration, ion exchange, pumping and transport, and mixing. Evaluation and optimization of these processes rely on liquid viscosity correlations subject to substantial error (at least ±60%) that can lead to overly conservative, and sometimes physically unachievable, limits for validation and operation of these unit operations. The current liquid viscosity correlations used for the Hanford flowsheet attempt to capture the effects of specific waste chemistry (namely, the speciation of various salts) on liquid viscosity using liquid density alone. It is postulated that the ±60% or greater error associated with these “density-based” liquid viscosity predictions is driven in part by the inability of waste density to capture the full impact of waste chemistry on liquid viscosity, and that improved prediction accuracy could be achieved by implementing a composition-based approach to evaluating liquid viscosity for Hanford wastes. Recent publications, namely those of Lencka et al. (1998), Hu (2004), and Laliberté (2007a), provide correlations and comprehensive, consolidated databases of single-salt solution viscosity that enable composition-based predictions for Hanford-type liquids (i.e., concentrated multi-component aqueous electrolyte solutions). In the current study, the viscosities of Hanford wastes and waste simulants were predicted using a composition-based model developed by Laliberté (2007a) (hereafter referred to as the “Laliberté viscosity model”) to evaluate its accuracy relative to the current density-based models used to predict waste viscosity for engineering applications at the Hanford Site. A viscosity database that captured the composition and viscosity of wastes and waste simulants was developed to support this evaluation. To facilitate application of the Laliberté viscosity model, waste and waste simulant compositions were converted to an equivalent salt recipe composed of salts with known viscosity coefficients using a number of simplifying assumptions that have the potential to impact the fidelity of the model prediction. Despite these simplifications, the Laliberté viscosity model was able to predict viscosity more accurately than the density-based correlations currently available for Hanford flowsheet use, such as that proposed in RPP-RPT- 51652. The use of composition-based viscosity models, like that proposed by Laliberté (2007a), shows promise for leading to improved prediction of liquid waste viscosity. As implemented in this study, application of the Laliberté viscosity model could lead to a decrease in the uncertainty associated with liquid viscosity prediction by as much as a factor of two, allowing for reduction in unit operation design conservatism and for the more realistic selection of test simulants for flowsheet process evaluation and optimization, all of which could potentially reduce flowsheet design margins, lower costs and reduce duration of the Hanford mission, and reduce Hanford flowsheet risks.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Solution precursor plasma deposition of nanostructured ZnO coatings

Highlights: {yields} The solution precursor route employed is an inexpensive process with capability to produce large scale coatings at fast rates on mass scale production. {yields} It is highly capable of developing tailorable nanostructures. {yields} This technique can be employed to spray the coatings on any kind of substrates including polymers. {yields} The ZnO coatings developed via solution precursor plasma spray process have good electrical conductivity and reflectivity properties in spite of possessing large amount of particulate boundaries, porosity and nanostructured grains. -- Abstract: Zinc oxide (ZnO) is a wide band gap semiconducting material that has various applications including optical, electronic, biomedical and corrosion protection. It is usually synthesized via processing routes, such as vapor deposition techniques, sol-gel, spray pyrolysis and thermal spray of pre-synthesized ZnO powders. Cheaper and faster synthesis techniques are of technological importance due to increased demand in alternative energy applications. Here, we report synthesis of nanostructured ZnO coatings directly from a solution precursor in a single step using plasma spray technique. Nanostructured ZnO coatings were deposited from the solution precursor prepared using zinc acetate and water/isopropanol. An axial liquid atomizer was employed in a DC plasma spray torch to create fine droplets of precursor for faster thermal treatment in the plasma plume to form ZnO. Microstructures of coatings revealed ultrafine particulate agglomerates. X-ray diffraction confirmed polycrystalline nature and hexagonal Wurtzite crystal structure of the coatings. Transmission electron microscopy studies showed fine grains in the range of 10-40 nm. Observed optical transmittance ({approx}65-80%) and reflectivity ({approx}65-70%) in the visible spectrum, and electrical resistivity (48.5-50.1 m{Omega} cm) of ZnO coatings are attributed to ultrafine particulate morphology of the coatings.

36 MATERIALS SCIENCE↗

Method for detecting coliform organisms

A method and apparatus are disclosed for determining the concentration of coliform bacteria in a sample. The sample containing the coliform bacteria is cultured in a liquid growth medium. The cultured bacteria produce hydrogen and the hydrogen is vented to a second cell containing a buffer solution in which the hydrogen dissolves. By measuring the potential change in the buffer solution caused by the hydrogen, as a function of time, the initial concentration of bacteria in the sample is determined. Alternatively, the potential change in the buffer solution can be compared with the potential change in the liquid growth medium to verify that the potential change in the liquid growth medium is produced primarily by the hydrogen gas produced by the coliform bacteria.

Nishioka, K.↗

Proven Technologies for the Solidification of Complex Liquid Radioactive Waste (LRW): Global Case Studies of Applications and Disposal Options - 20424

Legacy radioactive waste streams from the Cold War still exist and newly generated waste streams from nuclear power plants and research institutes go untreated and expose environmental hazards at many nuclear sites. The nature of the waste is diverse, depending upon the source or the process from which it originated. The most problematic waste streams include complex liquids such as organic (tri-butyl-phosphate TBP) solutions contaminated with Pu and U isotopes, mixed sludge types, high acid radioactive waste, H-3 contaminated organic and aqueous streams, etc. Technological, environmental and economic challenges exist for the treatment and disposal of such waste streams. A proven technology that has been applied to LRW on a global basis provides one option as a low-cost solution to legacy streams and small volume, highly complex LRW frequently found during decommissioning at nuclear power plants and weapons sites. The engineered polymer technology from Nochar, USA, is capable of solidifying standard and highly complex LLW and ILW waste streams for interim or final storage, or for incineration. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Time-resolved cryogenic electron tomography for the study of transient cellular processes

Cryogenic electron tomography (cryo-ET) is the highest resolution imaging technique applicable to the life sciences, enabling sub-nanometer visualization of specimens preserved in their near native states. The rapid plunge freezing process used to prepare samples lends itself to time-resolved studies, which researchers have pursued for in vitro samples for decades. Here, we focus on developing a freezing apparatus for time-resolved studies in situ. The device mixes cellular samples with solution-phase stimulants before spraying them directly onto an electron microscopy grid that is transiting into cryogenic liquid ethane. By varying the flow rates of cell and stimulant solutions within the device, we can control the reaction time from tens of milliseconds to over a second prior to freezing. In a proof-of-principle demonstration, the freezing method is applied to a model bacterium, Caulobacter crescentus, mixed with an acidic buffer. Through cryo-ET we resolved structural changes throughout the cell, including surface-layer protein dissolution, outer membrane deformation, and cytosolic rearrangement, all within 1.5 seconds of reaction time. This new approach, Time-Resolved cryo-ET (TR-cryo-ET), enhances the capabilities of cryo-ET by incorporating a sub-second temporal axis and enables the visualization of induced structural changes at the molecular, organelle, or cellular level.

59 BASIC BIOLOGICAL SCIENCES↗

Physics of lithium bromide (LiBr) solution dewatering through vapor venting membranes

The physics of water desorption from a lithium bromide (LiBr) solution flow through an array of microchannels capped by a porous membrane is studied. The membrane allows the vapor to exit the flow and retains the liquid. Effects of different parameters such as wall temperature, solution and vapor pressures, and solution mass flux on the desorption rate were studied. Two different mechanisms of desorption are analyzed. These mechanisms consisted of: (1) direct diffusion of water molecules out of the solution and their subsequent flow through the membrane and (2) formation of water vapor bubbles within the solution and their venting through the membrane. Direct diffusion was the dominant desorption mode at low surface temperatures and its magnitude was directly related to the vapor pressure, the solution concentration, and the heated wall temperature. Desorption at the boiling regime was predominantly controlled by the solution flow pressure and mass flux. Microscale visualization studies suggested that at a critical mass flux, some bubbles are carried out of the desorber through the solution microchannels rather than being vented through the membrane. Overall, an order of magnitude higher desorption rate compare to a previous study on a membrane-based desorber was achieved. Published by Elsevier Ltd.

Isfahani, RN↗

The lift force on a drop in unbounded plane Poiseuille flow

The lift force on a deformable liquid sphere moving in steady, plane Poiseuille-Stokes flow and subjected to an external body force is calculated. The results are obtained by seeking a solution to Stokes' equations for the motion of the liquids inside and outside the slightly perturbed sphere surface, as expansions valid for small values of the ratio of the Weber number to the Reynolds number. When the ratio of the drop and external fluid viscosities is small, the lift exerted on a neutrally buoyant drop is found to be approximately one-tenth of the magnitude of the force reported by Wohl and Rubinow acting on the same drop in unbounded Poiseuille flow in a tube. The resultant trajectory of the drop is calculated and displayed as a function of the external body force.

Wohl, P. R.↗

Numerical solution of 2D wet steam flow with non-equilibrium condensation and real thermodynamics

An approach to modeling of wet steam flow with non-equilibrium condensation phenomenon is presented. The first part of our flow model is homogeneous Euler system of transport equations for mass, momentum and total energy of wet steam (mixture). The additional second part describes liquid phase via non-homogeneous system of transport equations for moments of droplets number distribution function and relies on corrected classical nucleation theory. Moment equations are closed by linearization of droplet growth rate model. All necessary relations for thermodynamic properties of steam are provided by IAPWS set of equations. However, properties of condensate are simply modeled by liquid saturation data. Two real equations of state are implemented. Recently developed CFD formulation for entropy (does not require iteration process) and so-called IAPWS special gas equation for Helmholtz energy (one iteration loop is necessary). Flow model is validated on converging-diverging supersonic nozzle with Barschdorff geometry. Simulations were performed by in-house CFD code based on finite volume method and stiff character of equations was solved by symmetrical time operator splitting. Achieved results satisfactorily agreed with experimental data.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Kinetics of the Formation of a Disordered Crystal Structure during High-Speed Solidification

A phase–field description is given for the kinetic transition in the structure of a binary ordering crystal growing from a supercooled liquid. The results are interpreted on the basis of the solution of the phasefield dynamics equation and the relaxation equation for the long-range order parameter at the diffuse crystal–liquid interface and in the bulk of the crystal. The critical temperatures for the variation of the growth rate and the long-range order parameter of a growing A{sub 50}B{sub 50} crystal are determined. A qualitative difference and analogies are found between the processes of nonequilibrium impurity trapping and the formation of a disordered structure of rapidly growing crystals. The results of the study are analyzed in comparison with the results of the theory of kinetic phase transitions [A.A. Chernov, Sov. Phys. JETP 26, 1182 (1967)] and the experimental data on the high-speed solidification of congruently melting samples [H. Hartmann et al., Europhys. Lett. 87, 40007 (2009)].

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Liquid-Air Interface Corrosion Testing Simulating The Environment Of Hanford Double Shell Tanks

Coupon tests on A537 carbon steel materials were conducted to evaluate the Liquid-Air Interface (LAI) corrosion susceptibility in a series of solutions designed to simulate conditions in the radioactive waste tanks located at the Hanford Nuclear Facility. The new stress corrosion cracking requirements and the impact of ammonia on LAI corrosion were the primary focus. The minimum R value (i.e., molar ratio of nitrite to nitrate) of 0.15 specified by the new stress corrosion cracking requirements was found to be insufficient to prevent pitting corrosion at the LAI. The pH of the test solutions was 10, which was actually less than the required pH 11 defined by the new requirements. These tests examined the effect of the variation of the pH due to hydroxide depletion at the liquid air interface. The pits from the current testing ranged from 0.001 to 0.008 inch in solutions with nitrate concentrations of 0.4 M and 2.0 M. The pitting and general attack that occurred progressed over the four-months. No significant pitting was observed, however, for a solution with a nitrate concentration of 4.5 M. The pitting depths observed in these partial immersion tests in unevaporated condensates ranged from 0.001 to 0.005 inch after 4 months. The deeper pits were in simulants with low R values. Simulants with R values of approximately 0.6 to 0.8 appeared to significantly reduce the degree of attack. Although, the ammonia did not completely eliminate attack at the LAI, the amount of corrosion in an extremely corrosive solution was significantly reduced. Only light general attack (< 1 mil) occurred on the coupon in the vicinity of the LAI. The concentration of ammonia (i.e., 50 ppm or 500 ppm) did not have a strong effect.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Specific physical and chemical properties of two modifications of poly(N-vinylcaprolcatam)

Two modifications of poly(N-vinylcaprolactam)—PVCL25 and PVCL40 (drying of a PVCL solution at 25 and 40°C, respectively)—as powdered films and their solutions were systematically investigated for the first time. Powders were studied by X-ray diffraction, IR spectroscopy, scanning electron microscopy, low-temperature krypton adsorption, and differential scanning calorimetry. Solutions were studied by smallangle X-ray scattering and dynamic light scattering. It was demonstrated that powders of PVCL25 and PVCL40 differ in the characteristics of the sub- and microstructure and in the water content and the solutions differ in the particle size. The relationships between the characteristics of the systems in the solid and liquid state and between the hydrodynamic diameter of PVCL particles in solution and their coagulation time were found.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Synthesis of rock-salt type lithium borohydride and its peculiar Li{sup +} ion conduction properties

The high energy density and excellent cycle performance of lithium ion batteries makes them superior to all other secondary batteries and explains why they are widely used in portable devices. However, because organic liquid electrolytes have a higher operating voltage than aqueous solution, they are used in lithium ion batteries. This comes with the risk of fire due to their flammability. Solid electrolytes are being investigated to find an alternative to organic liquid. However, the nature of the solid-solid point contact at the interface between the electrolyte and electrode or between the electrolyte grains is such that high power density has proven difficult to attain. We develop a new method for the fabrication of a solid electrolyte using LiBH{sub 4,} known for its super Li{sup +} ion conduction without any grain boundary contribution. The modifications to the conduction pathway achieved by stabilizing the high pressure form of this material provided a new structure with some LiBH{sub 4}, more suitable to the high rate condition. We synthesized the H.P. form of LiBH{sub 4} under ambient pressure by doping LiBH{sub 4} with the KI lattice by sintering. The formation of a KI - LiBH{sub 4} solid solution was confirmed both macroscopically and microscopically. The obtained sample was shown to be a pure Li{sup +} conductor despite its small Li{sup +} content. This conduction mechanism, where the light doping cation played a major role in ion conduction, was termed the “Parasitic Conduction Mechanism.” This mechanism made it possible to synthesize a new ion conductor and is expected to have enormous potential in the search for new battery materials.

36 MATERIALS SCIENCE↗

Using earth abundant materials for long duration energy storage: electro-chemical and thermo-chemical cycling of bicarbonate/formate

Using hydrogen to store energy in chemical bonds is a key component of the global strategy to achieving a sustainable future and ameliorating climate change. The challenges associated with handling molecular hydrogen can be solved by using liquid hydrogen carriers. In this perspective, we discuss the concept of bicarbonate–formate cycle, where aqueous solutions of formate ions (HCO 2 – ) are used as hydrogen and energy carriers. Such solutions are composed by earth abundant elements and, in contrast to common liquid organic carriers, are non-flammable, and readily convert to the oxide forms (HCO 3 – ) under reaction with water to release hydrogen, or electrons, at moderate temperatures. We discuss thermodynamic aspects of the bicarbonate–formate cycle and show how it offers the opportunity of combining electrochemical and thermochemical operations, as well as of coupling CO 2 capture with energy/hydrogen storage. We emphasize the potential role of electrochemistry in the generation of formate and in the release of energy in the form of electricity. At present, more information on both the fundamental and systems level, is needed to identify the feasible scenarios for using formate/bicarbonate salts for hydrogen/energy storage. It is likely, however, that several strategies, including hybrid electrochemical–thermochemical approaches, will suit different applications. It is also clear that more integration between the disciplines of electrochemistry and heterogeneous catalysis is needed to overcome the challenges for advancing the HCO 3 – –HCO 2 – system as a feasible green alternative for storing and transporting energy.

08 HYDROGEN↗

Tank 9H Salt Solution Supernatant Characterization in Support of Potential Operating Strategies of Tank 9H Supernatant Through the Tank Closure Cesium Removal System

Savannah River Remediation (SRR) recently initiated an ion exchange process to remove radioactive cesium from dissolved salt solution in Tank 10H, known as Tank Closure Cesium Removal (TCCR). As part of that ongoing campaign, the salt in Tank 9H will be dissolved and transferred to Tank 10H for processing through the TCCR system, and SRR requested the characterization of the dissolved salt solution in Tank 9H prior to the transfer to Tank 10H. On July 18, 2019, Savannah River Remediation Engineering (SRR-E) delivered two variable depth Tank 9H salt solution samples, identified as samples HTF-9-19-74 and HTF-9-19-75 (combined total sample volume of about 400 mL) to the Savannah River National Laboratory (SRNL) for characterization. These two Tank 9H variable depth samples (HTF-9-19-74 and HTF-9-19-75 taken at ~180” and 42”, respectively) were retrieved from Riser 7 after hydro-lancing activities were complete. Approximately 4200 gallons of water were added to the tank during this activity. This report presents the analytical characterization results for the Tank 9H salt solution variable depth samples HTF-9-19-74 and HTF-9-19-75 and contains mainly the filtrate analytical results for anions, elements, mass spectral data, total cesium characterization results and select radionuclide results, along with the X-ray diffraction characterization of the solid fractions from the liquid /solid separation of the variable depth salt solutions. Most of these analyses were performed in duplicate with the percent relative standard deviation (%RSD), a measure of the variability between each duplicate data set expressed as a percentage, used to estimate the analytical result quality for each analyte.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Melting and crystallization peculiarities in Cd0.50Mn0.50Te solid solutions

We investigated melting and crystallization processes of Cd0.50Mn0.50Te. Using differential thermal analysis (DTA) we studied the solid-liquid equilibrium temperature range, the temperature dependence of the volume fraction of the solid phase in the melt, and crystallization peculiarities. We observed that changing a dwell temperature from 1346 to 1354 K results in an increase of the crystallization temperature of the Cd0.50Mn0.50Te melt. Since the melt is in a semi-liquid state, its crystallization occurs over a solid-phase domain. It was found that a slightly overheated Cd0.50Mn0.50Te melt (up to 10 K) crystallizes more slowly than more overheated melts, and that the Cd0.50Mn0.50Te solid solutions are in a semi-liquid state in the temperature range of 1338 – 1354 K.

Kopach, Oleh↗