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At least 307 records · Page 17

Understanding Biomass and Polymer Feedstock Variability Through Analytical Pyrolysis and Two Dimensional Gas Chromatography and Mass Spectrometry

Moving toward a circular carbon economy requires enabling reuse of carbon-based macromolecules like those in biomass and polymers. Meeting this goal requires increased upcycling of waste products into higher value products. For biomass waste such as corn stover, pine needles, or bark, one approach is using pyrolysis to convert these feedstocks into bio-oil that can be used for liquid fuel or transformed into other hydrocarbon based products, like bio-polymers. Waste plastics can be upcycled or recycled into new products, or alternatively converted into bio-oil by pyrolysis. Macromolecules from biomass and polymers are challenging to convert into liquid fuel or chemical feedstocks, due to large and sometimes heterogeneous networks of polymeric bonds. We work with the Idaho National Laboratory’s Biomass Feedstock National User Facility and Department of Energy’s Feedstock Conversion Interface Consortium to develop a molecular understanding of biomass variability that occurs naturally and as a result of storage or preprocessing techniques applied to feedstocks, to understand chemical reactions occurring during pyrolysis and other biomass or polymer conversion techniques. Using two dimensional gas chromatography mass spectrometry coupled to analytical pyrolysis provides insight into the molecular changes that occur during the pyrolysis event, and these insights can extend to bench or pilot scale pyrolysis conversions. Understanding pyrolysis of biomass and polymers at a molecular level contributes to development of new tools to predict and manipulate the optimum conditions and identify the best storage, preprocessing, and conversion techniques to maximize output of specific high-value chemical species in the conversion to fuels, or to characterize feedstocks for blending before pyrolysis. Identification and understanding of the molecular level changes resulting from novel preprocessing techniques that can be used to control and manipulate the chemical output of bench or pilot scale pyrolysis is another focus of investigation, including the use of gamma irradiation, acid, or enzyme pre-treatments. We also focus on the impacts of storage conditions and techniques, which can affect moisture levels, degradation, and impacts from naturally occurring microbes in the environment.

09 BIOMASS FUELS↗

Restraint of Liquid Jets by Surface Tension in Microgravity Modeled

Tension in Microgravity Modeled Microgravity poses many challenges to the designer of spacecraft tanks. Chief among these are the lack of phase separation and the need to supply vapor-free liquid or liquidfree vapor to the spacecraft processes that require fluid. One of the principal problems of phase separation is the creation of liquid jets. A jet can be created by liquid filling, settling of the fluid to one end of the tank, or even closing a valve to stop the liquid flow. Anyone who has seen a fountain knows that jets occur in normal gravity also. However, in normal gravity, the gravity controls and restricts the jet flow. In microgravity, with gravity largely absent, jets must be contained by surface tension forces. Recent NASA experiments in microgravity (Tank Pressure Control Experiment, TPCE, and Vented Tank Pressure Experiment, VTRE) resulted in a wealth of data about jet behavior in microgravity. VTRE was surprising in that, although it contained a complex geometry of baffles and vanes, the limit on liquid inflow was the emergence of a liquid jet from the top of the vane structure. Clearly understanding the restraint of liquid jets by surface tension is key to managing fluids in low gravity. To model this phenomenon, we need a numerical method that can track the fluid motion and the surface tension forces. The fluid motion is modeled with the Navier-Stokes equation formulated for low-speed incompressible flows. The quantities of velocity and pressure are placed on a staggered grid, with velocity being tracked at cell faces and pressure at cell centers. The free surface is tracked via the introduction of a color function that tracks liquid as 1/2 and gas as -1/2. A phase model developed by Jacqmin is used. This model converts the discrete surface tension force into a barrier function that peaks at the free surface and decays rapidly. Previous attempts at this formulation have been criticized for smearing the interface. However, by sharpening the phase function, double gridding the fluid function, and using a higher order solution for the fluid function, interface smearing is avoided. These equations can be rewritten as two coupled Poisson equations that also include the velocity. The method of solution is as follows: first, the phase equations are solved from this solution, a velocity field is generated, then a successive overrelaxation scheme is used to solve for a pressure field consistent with the velocity solution. After the code was implemented in axisymmetric form and verified by several test cases, the drop tower runs of Aydelott were modeled. The model handed the free-surface deformation quite nicely, even to the point of modeling geyser growth in the regime where the free surface was no longer restrained. A representative run is shown.

Chato, David J.↗

Thermal Design, Analysis, and Testing of the Quench Module Insert Bread Board

The science requirements for materials processing is to provide the desired PI requirements of thermal gradient, solid/liquid interface front velocity for a given processing temperature desired by the PI. Processing is performed by translating the furnace with the sample in a stationary position to minimize any disturbances to the solid/liquid interface front during steady state processing. Typical sample materials for this metals and alloys furnace are lead-tin alloys, lead-antimony alloys, and aluminum alloys. Samples must be safe to process and therefore typically are contained with hermetically sealed cartridge tubes (gas tight) with inner ceramic liners (liquid tight) to prevent contamination and/or reaction of the sample material with the cartridge tube.

Breeding Shawn↗

MB-Fit: Software infrastructure for data-driven many-body potential energy functions

Many-body potential energy functions (MB-PEFs), which integrate data-driven representations of many-body short-range quantum mechanical interactions with physics-based representations of many-body polarization and long-range interactions, have recently been shown to provide high accuracy in the description of molecular interactions from the gas to the condensed phase. Here, we present MB-Fit, a software infrastructure for the automated development of MB-PEFs for generic molecules within the TTM-nrg (Thole-type model energy) and MB-nrg (many-body energy) theoretical frameworks. Besides providing all the necessary computational tools for generating TTM-nrg and MB-nrg PEFs, MB-Fit provides a seamless interface with the MBX software, a many-body energy and force calculator for computer simulations. Given the demonstrated accuracy of the MB-PEFs, particularly within the MB-nrg framework, we believe that MB-Fit will enable routine predictive computer simulations of generic (small) molecules in the gas, liquid, and solid phases, including, but not limited to, the modeling of quantum isomeric equilibria in molecular clusters, solvation processes, molecular crystals, and phase diagrams.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stabilizing Cathode–Electrolyte Interphase of Nickel-Rich Single-Crystal Cathodes for Lithium-Ion Batteries

Nickel-rich single-crystal (SC) layered oxides are promising cathode candidates for next-generation lithium-ion batteries (LIBs) owing to their high energy density and structural robustness against intergranular cracking. However, their intrinsic surface reactivity with liquid electrolytes accelerates parasitic reactions at the cathode–electrolyte interphase (CEI), leading to transition-metal dissolution, gas generation, and impedance buildup. In this work, we synthesized SC-Li x Ni 0.9 Mn 0.05 Co 0.05 O 2 (NMC9055, 1 ≤ x ≤ 1.2) using a eutectic-assisted method and investigated interface stabilization strategies. A nickel-deficient Li x Ni 0.6 Mn 0.2 Co 0.2 O 2 (NMC622, 1 ≤ x ≤ 1.2) coating was applied via evaporation-based deposition to suppress CEI degradation pathways. Structural and compositional analyses confirmed uniform shell formation and preserved particle integrity. Half-cell electrochemical testing against lithium metal revealed ∼10% higher capacity retention and improved reversibility compared with pristine SC NMC9055, particularly under high-voltage operation. In conclusion, these results highlight the critical role of controlled surface chemistry in mitigating CEI instability in nickel-rich SC cathodes, offering a pathway toward enabling durable high-energy LIBs.

Coating processes↗

Irradiation Effect on Noble Metal Particles in Water Using in situ Liquid Cell STEM Observation

During geologic disposal of spent nuclear fuel (SNF) in an engineered nuclear waste repository, once all other barriers have degraded, oxidizing may occur at the solid-water interface owing to a self-generated radiolytic field. The repository design includes large quantities of iron (Fe), that is anticipated to corrode under an anoxic environment, and generate hydrogen (H 2 ) gas. This H 2 gas is thought to be able to suppress the dissolution of SNF through a catalytic reaction with noble metal particles (NMP) that are pre-existing in the SNF. This interaction leads to the decomposition of the major oxidant, hydrogen peroxide (H 2 O 2 ). In conclusion, these processes are described in the Fuel Matrix Degradation (FMD) model that is being used to predict SNF degradation rates. The NMP, therefore, plays an important role within the FMD model.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Computational Methodology to Simulate Pyrometallurgical Processes in a Secondary Lead Furnace

Pyrometallurgical recovery of nonferrous metals involves a combination of thermally intensive transformations during exothermic gas-phase reactions, endothermic decomposition of solid charge, and melting of simpler solids. In the recovery of secondary lead, simultaneous thermal effects in a reverberatory-style furnace cause a melt pool to accumulate at the bottom, with lighter solids (slag) floating above and gaseous products from decomposition of the charge diffusing through the gas–slag interface. Species from oxy-fuel combustion of natural gas, species profiles from smelting reactions, and the formation of a melt pool consisting primarily of lead are simulated via a time-averaged formulation. Predictions of outflow are compared with preset inflow profiles to ensure conservation of mass. Thermal profiles for solid, liquid, and gas phases are presented by species. A novel method is implemented to model the latent heat of fusion using a heterogeneous chemical reaction. The simulation is conducted in Simcenter STAR-CCM+ v. 16.02.009-R8.

Rao, Vivek↗

A numerical study of an atomizing jet in a resonant acoustic field

By applying state-of-the-art, high-fidelity methods for compressible multiphase flows, this work features a parametric study of a turbulent liquid jet atomizing under the influence of standing acoustic waves with five different amplitude values. We perform these simulations in a semi-periodic domain to isolate interactions between acoustic and atomization processes and to emulate a pure liquid fuel spray placed at the pressure node of a resonant acoustic field. Characterization of the flow includes measurements of the mean dimensions, droplet number, and surface area of the liquid distribution, alongside qualitative depictions of the interface evolution, breakup events, and hydrodynamic fields. As acoustic forcing is provided to the flow, the added energy provokes atomization when shear would otherwise be insufficient for breakup. The magnitude of the forcing determines the rate of droplet production, which accelerates as the evolving liquid surface modifies the induced motion of the gas phase. At the nodal plane, the acoustic field produces an organizing effect on the liquid structures.

42 ENGINEERING↗

PTA1 Helium Pressurization System Model

A transient model of the Propulsion Test Article 1 (PTA1) Helium Pressurization System was developed using the Generalized Fluid System Simulation Program (GFSSP). The model included feed lines from the facility interface to the engine purge interface and Liquid Oxygen (LOX) and Rocket Propellant 1 (RP-1) tanks, the propellant tanks themselves including ullage space and propellant feed lines to their respective pump interfaces. GFSSPs capability was extended to model a control valve to maintain ullage pressure within a specified limit and pressurization processes such as heat transfer between ullage gas, propellant and the tank wall. The purpose of the model is to predict the flow system characteristics in the entire pressurization system during 80 seconds of pre-pressurization operation, 420 seconds of pressurization stand-by operation and 150 seconds of engine operation. Subsequent to the work presented here, the PTA1 model has been updated to include the LOX and RP-1 pumps, while the pressurization option itself has been modified to include the effects of mass transfer. This updated model will be compared with PTA1 test data as it becomes available.

Steadman, Todd↗

Numerical Modeling and Test Data Comparison of Propulsion Test Article Helium Pressurization System

A transient model of the propulsion test article (PTA) helium pressurization system was developed using the generalized fluid system simulation program (GFSSP). The model included pressurization lines from the facility interface to the engine purge interface and liquid oxygen (lox) and rocket propellant-1 (RP-1) tanks, the propellant tanks themselves including ullage space, and propellant feed lines to their respective pump interfaces. GFSSP's capability was extended to model a control valve to maintain ullage pressure within a specified limit and pressurization processes such as heat transfer between ullage gas, propellant, and the tank wall as well as conduction in the tank wall. The purpose of the model is to predict the flow system characteristics in the entire pressurization system during 80 sec of lower feed system priming, 420 sec of fuel and lox pump priming, and 150 sec of engine firing.

Holt, Kimberly↗

Numerical Modeling of Helium Pressurization System of Propulsion Test Article (PTA)

A transient model of the Propulsion Test Article (PTA) Helium Pressurization System was developed using the Generalized Fluid System Simulation Program (GFSSP). The model included feed lines from the facility interface to the engine purge interface and Liquid Oxygen (LOX) and Rocket Propellant 1 (RP-1) tanks, the propellant tanks themselves including ullage space and propellant feed lines to their respective pump interfaces. GFSSP's capability was extended to model a control valve to maintain ullage pressure within a specified limit and pressurization processes such as heat transfer between ullage gas, propellant and the tank wall. The purpose of the model is to predict the flow system characteristics in the entire pressurization system during 80 seconds of lower feed system priming, 420 seconds of fuel and LOX pump priming and 150 seconds of engine firing. Subsequent to the work presented here, the PTA model has been updated to include the LOX and RP-1 pumps, while the pressurization option itself has been modified to include the effects of mass transfer. This updated model will be compared with PTA test data as it becomes available.

Steadman, Todd↗

FaceSheet Push-off Tests to Determine Composite Sandwich Toughness at Cryogenic Temperatures

A new novel test method, associated analysis, and experimental procedures are developed to investigate the toughness of the facesheet-to-core interface of a sandwich material at cryogenic temperatures. The test method is designed to simulate the failure mode associated with facesheet debonding from high levels of gas pressure in the sandwich core. The effects of specimen orientation are considered, and the results of toughness measurements are presented. Comparisons are made between room and liquid nitrogen (-196 C) test temperatures. It was determined that the test method is insensitive to specimen facesheet orientation and strain energy release rate increases with a decrease in the test temperature.

Gates, Thomas S.↗

Hydrogen (H) Isotope Composition of Type II Kerogen Extracted by Pyrolysis-GC-MS-IRMS: Terrestrial Shale Deposits as Martian Analogs

Described here is a technique for H isotope analysis of organic compounds pyrolyzed from kerogens isolated from gas‐ and liquids‐rich shales. Application of this technique will progress the understanding of the use of H isotopes not only in potential kerogen occurrences on Mars, but also in terrestrial oil and gas resource plays. H isotope extraction and analyses were carried out utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC interfaced with a Thermo MAT 253 IRMS. Also, a split of GC‐separated products was sent to a DSQ II quadrupole MS to make qualitative and semi‐quantitative compositional measurements of these products. Kerogen samples from five different basins (type II and II‐S) were dehydrated (heated to 80 C overnight under vacuum) and analyzed for their H isotope compositions by Pyrolysis‐GC‐MS‐TC‐IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C), which quantitatively forms H2. Samples ranging from ~0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. and separated on a Poraplot Q GC column. H isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight. H2O average delta D = ‐215.2 per mille (V‐SMOW), ranging from ‐ 271.8 per mille for the Marcellus Shale to ‐51.9 per mille for a Polish shale. Higher molecular weight compounds like toluene (C7H8) have an average delta D of ‐89.7 per mille, ranging from ‐156.0 per mille for the Barnett Shale to ‐50.0 per mille for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during basin formation. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas‐water or oil‐water interaction in resource plays, and further as a possible indicator of paleoenvironmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analyses. Understanding the role that these H‐bearing compounds play in terrestrial shale paleo‐environmental reconstruction may also prove useful as analogs for understanding the interactions of water and potential kerogen/organic compounds on the planet Mars.

Socki, Richard A.↗

Mathematical Modeling of Hydroxide-Exchange-Membrane Water Electrolyzer

Water electrolyzers can transform intermittent renewable energy like solar energy and wind energy into the chemical energy of hydrogen with zero greenhouse-gas emissions. The hydroxide-exchange membrane electrolyzer (HEME) combines the capability to produce pressurized hydrogen with the advantage of being able to use low or non-platinum group metal (PGM) electrocatalysts in the alkaline environment.1 Hydroxide salts, for example, KOH, are added to the HEME water feed on both anode and cathode to improve its performance. However, the specific mechanism of performance improvement still needs to be further understood. In addition, at high current densities, bubble evolution can result in mass-transport limitations, a less well studied phenomena. Mathematical modeling is ideal to explore these issues as it is cost and time efficient and can deconvolute the physics, processes, and observed phenomena and study the applied-voltage breakdown. In this work, we extend our previously developed 1D two-phase continuum model2 to study the varies processes in the HEME and provide insights on performance optimizations. First, the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) kinetics at different hydroxide concentrations have been studied by rotating disk electrodes (RDE) and implemented in the model. Then, the model is calibrated and validated against experimental HEME polarization curves for different KOH concentrations as a liquid electrolyte. The model clearly shows a performance increase with increasing KOH concentrations, which is consistent with the experimental results. The reduced ohmic resistance and increased electrochemical active surface area (ECSA) are the two main reasons for performance increase. The large amount of hydroxide in the liquid electrolyte not only helps to distribute the reactant hydroxide throughout the catalyst layer (CL), which reduces ohmic loss, but also enables reaction at the interface between the liquid electrolyte and electrocatalyst, which increases the ECSA. Applied-voltage breakdown demonstrates that the electrolyzer performance is dominated by anode kinetics and ohmic loss. A comparison with the DI water feed shows a more uniform current distribution in the anode CL when KOH is added, which indicates a higher utilization of the CL. Second, we present modeling on the effects of bubble coverage. As gas evolves, part of the ECSA is minimized due to bubble coverage. To account for this effect, an empirical relationship between the fractional bubble coverage and the current density is implemented in the model.3 The model shows this bubble coverage effect is more pronounced at large current densities with DI water feed. Acknowledgements This work was funded under the HydroGEN Consortium by the Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office, of the U. S. Department of Energy under contract number DE-AC02-05CH11231. References R. Abbasi, B. P. Setzler, S. Lin, J. Wang, Y. Zhao, H. Xu, B. Pivovar, B. Tian, X. Chen, G. Wu and Y. Yan, 31, 1805876 (2019). L. N. Stanislaw, M. R. Gerhardt and A. Z. Weber, ECS Transactions, 92, 767 (2019). H. Vogt and R. J. Balzer, Electrochimica Acta, 50, 2073 (2005).

Liu, Jiangjin↗

Behavior of Particle Depots in Molten Silicon During Float-Zone Growth in Strong Static Magnetic Fields

In the photovoltaics industry, the largest market share is represented by solar cells made from multicrystalline silicon, which is grown by directional solidification. During the growth process, the silicon melt is in contact with the silicon nitride coated crucible walls and the furnace atmosphere which contains carbon monoxide. The dissolution of the crucible coating, the carbon bearing gas, and the carbon already present in the feedstock, lead to the precipitation of silicon carbide, and silicon nitride, at later stages of the growth process. The precipitation of Si3N4 and SiC particles of up to several hundred micrometers in diameter leads to severe problems during the wire sawing process for wafering the ingots. Furthermore the growth of the silicon grains can be negatively influenced by the presence of particles, which act as nucleation sources and lead to a grit structure of small grains and are sources for dislocations. If doped with Nitrogen from the dissolved crucible coating, SiC is a semi conductive material, and can act as a shunt, short circuiting parts of the solar cell. For these reasons, the incorporation of such particles needs to be avoided. In this contribution we performed model experiments in which the transport of intentionally added SiC particles and their interaction with the solid-liquid interface during float zone growth of silicon in strong steady magnetic fields was investigated. SiC particles of 7μm and 60μm size are placed in single crystal silicon [100] and [111] rods of 8mm diameter. This is achieved by drilling a hole of 2mm diameter, filling in the particles and closing the hole by melting the surface of the rod until a film of silicon covers the hole. The samples are processed under a vacuum of 1x10(exp -5) mbar or better, to prevent gas inclusions. An oxide layer to suppress Marangoni convection is applied by wet oxidation. Experiments without and with static magnetic field are carried out to investigate the influence of melt convection on the distribution of particles and their incorporation into the crystal. The field strengths applied by a superconducting magnet are 1T, 3T, 4.5T, and 5T. The increase in field strength dampens the melt flow, and so this study provides comparative data to the crystal growth experiment to be carried out onboard the sounding rocket mission TEXUS 51, where purely diffusive growth condition will be achieved under microgravity conditions.

Jauss, T.↗

Vapor-Gas Bubble Evolution and Growth in Extremely Viscous Fluids Under Vacuum

Formation of vapor and gas bubbles and voids is normal and expected in flow processes involving extremely viscous fluids in normal gravity. Practical examples of extremely viscous fluids are epoxy-like filler materials before the epoxy fluids cure to their permanent form to create a mechanical bond between two substrates. When these fluids flow with a free liquid interface exposed to vacuum, rapid bubble expansion process may ensue. Bubble expansion might compromise the mechanical bond strength. The potential sources for the origin of the gases might be incomplete out-gassing process prior to filler application; regasification due to seal leakage in the filler applicator; and/or volatiles evolved from cure reaction products formed in the hardening process. We embarked on a study that involved conducting laboratory experiments with imaging diagnostics in order to deduce the seriousness of bubbling caused by entrained air and volatile fluids under space vacuum and low gravity environment. We used clear fluids with the similar physical properties as the epoxy-like filler material to mimic the dynamics of bubbles. Another aspect of the present study was to determine the likelihood of bubbling resulting from dissolved gases nucleating from solution. These experimental studies of the bubble expansion are compared with predictions using a modified Rayleigh- Plesset equation, which models the bubble expansion.

Kizito, John↗

Risk Assessment and Scaling for the SLS LH2 ET

In this report the main physics processes in LH2 tank during prepress and rocket flight are studied. The goal of this investigation is to analyze possible hazards and to make risk assessment in proposed LH2 tank designs for SLS with 5 engines (the situation with 4 engines is less critical). For analysis we use the multinode model (MNM) developed by us and presented in a separate report and also 3D ANSYS simulations. We carry out simulation and theoretical analysis the physics processes such as (i) accumulation of bubbles in LH2 during replenish stage and their collapsing in the liquid during the prepress; (ii) condensation-evaporation at the liquid-vapor interface and tank wall, (iv) heating the liquid near the interface and wall due to condensation and environment heat, (v) injection of hot He during prepress and of hot GH2 during flight, (vi) mixing and cooling of the injected gases due to heat transfer between the gases, liquid and the tank wall. We analyze the effects of these physical processes on the thermo- and fluid gas dynamics in the ullage and on the stratification of temperature in the liquid and assess the associated hazards. A special emphasize is put on the scaling predictions for the larger SLS LH2 tank.

Hafiychuk, Halyna↗

On the nature of droplet production in DC glows with a liquid anode: mechanisms and potential applications

The interactions between plasma and liquid solutions give rise to the formation of chemically reactive species useful for many applications, but the mass transport in the interfacial region is usually limited and not fully understood. In this work, we report on the observation and explanation of droplet ejection at the plasma–liquid interface of a one-atmosphere glow discharge with the liquid anode. The impact of droplets emission on plasma properties is also analyzed by spectroscopy. The process, which is an efficient mass and charge transport mechanism, apparently occurs during discharge operation and thus constitutes a feedback vehicle between the discharge and the liquid. Distinctive from the well-known Talyor cone droplets associated with liquid cathodes, the observed droplets originate from the bubbles due to electrolysis and solvated air which does not require strong electric field at liquid surface. Instead, the droplets are ejected by bubble cavity rupture at the plasma–liquid interface and their size, initial speed are strongly dependent on the gravity, inertia and capillarity. Further, the droplets emerge near the plasma attachment and are subsequently vaporized, emitting intense UV and visible light, which originated from excited OH radicals and sodium derived from the liquid electrolyte. Spectroscopy analysis confirmed that the bursting droplets generally reduce the gas temperature while their effects on electron density depend on the composition of the liquid anode. Results also show that droplets from NaCl solution increase the plasma electron density due to the lower ionization potential of sodium. These findings reveal a new mechanism for discharge maintenance and mass transport as well as suggest a simple approach to dispersing plasma-activated liquid into the gas phase and thus enhancing plasma–liquid interaction.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗