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At least 217 records · Page 12

Size and Charge Effects on Crossover of Flow Battery Reactants Evaluated by Quinone Permeabilities Through Nafion

Organic reactants are promising candidates for long-lifetime redox flow batteries, and synthetic chemistry unlocks a wide design space for new molecules. Minimizing crossover of these molecules through ion exchange membranes is one important design consideration, but the ways in which the crossover rate depends on the structure of the crossing species remain unclear. Here, we contribute a systematic evaluation of size- and charge-based effects on dilute-solution small molecule permeability through the Nafion NR212 cation exchange membrane. We found that increasing the magnitude of charge number z with the same sign as membrane fixed charges, achieved here by successive sulfonation of quinone redox cores, results in more than an order of magnitude permeability reduction per sulfonate. Size-based effects, understood by comparing the Stokes radii of the quinones studied, also reduces permeability with increasing effective molecule size, but doubling the effective size of the redox reactants resulted in a permeability decrease of less than a factor of three.

25 ENERGY STORAGE↗

Crosslinked Polyethyleneimine Gel Polymer Interface to Improve Cycling Stability of RFBs

Redox flow batteries are considered a promising technology for grid energy storage. However, capacity decay caused by crossover of active materials is a universal challenge for many flow battery systems, which are based on various chemistries. In this paper, using the vanadium redox flow battery as an example, we demonstrate a new gel polymer interface (GPI) consisting of crosslinked polyethyleneimine with a large amount of amino and carboxylic acid groups introduced between the positive electrode and the membrane. The GPI functions as a key component to prevent vanadium ions from crossing the membrane, thus supporting stable long-term cycling. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were conducted to investigate the effect of GPI on the electrochemical properties of graphitic carbon electrodes (GCFs) and redox reaction of catholyte. X-ray photoelectron spectroscopy (XPS) and 1 H nuclear magnetic resonance (NMR) spectra demonstrated that the crosslinked GPI is chemically stable for 100 cycles without dissolution of polymers and swelling in the strong acidic electrolytes. Results from inductively coupled plasma mass spectrometry (ICP-MS), Fourier-transform infrared (FTIR) spectroscopy, and energy-dispersive X-ray (EDX) spectroscopy proved that the GPI is effective in maintaining the concentration of vanadium species in their respective half-cells, resulting in improved cycling stability because of it prevents active species from crossing the membrane and stabilizes the oxidation states of active species.

Lim, Hyung-Seok↗

Diurnal variations in the thermosphere. II - Temperature, composition, and winds

The fundamental diurnal component of temperature, composition and wind fields is discussed for the thermosphere, the results delineated in terms of energy sources in the lower atmosphere, mesosphere and thermosphere, illustrating their relative significance. The diurnal component in the composition of H, He, O, O2 and Ar has been analyzed in terms of effects from thermal expansion in diffusive equilibrium and transport processes associated with chemistry, wind circulation, exospheric flow and escape. Next to thermal expansion, wind-induced diffusion is the single most important process; it dominates the diurnal variations of He and prevails in the variations of O, O2 and Ar below 200 km.

Mayr, H. G.↗

Silicon production process evaluations

The chemical engineering analysis of the preliminary process design of a process for producing solar cell grade silicon from dichlorosilane is presented. A plant to produce 1,000 MT/yr of silicon is analyzed. Progress and status for the plant design are reported for the primary activities of base case conditions (60 percent), reaction chemistry (50 percent), process flow diagram (35 percent), energy balance (10 percent), property data (10 percent) and equipment design (5 percent).

Source record↗

Symposium (International) on Combustion, 19th, Technion Israel Institute of Technology, Haifa, Israel, August 8-13, 1982, Proceedings

Topics discussed are related to elementary reactions, reaction mechanisms and modeling, laminar flames, flame chemistry, turbulent reacting shear flows, turbulent premixed flames, turbulent combustion measurements, continuous combustors, detonation, detonation and explosion, heterogeneous detonation, propellant combustion, fire-ignition and thermal degradation, fire-flame spread and burning, fire-modeling, spray combustion, and droplet combustion. Coal combustion kinetics and mechanisms are considered along with coal combustion mechanisms and pyrolysis, coal combustion techniques, NOx in coal combustion, gaseous pollutants, soot and PAH, soot and inorganic pollutants, I.C. engine combustion, and ignition and extinction. Attention is given to intricate paths and simple steps in chemical kinetics and combustion, the formation of polycyclic aromatic hydrocarbons by combustion, turbulent flame structure and speed in spark ignition engines, and unresolved problems in SOx, NOx, and soot control in combustion.

Source record↗

Fact Sheet: Range Complex

NASA Ames has a long tradition in leadership with the use of ballistic ranges and shock tubes for the purpose of studying the physics and phenomena associated with hypervelocity flight. Cutting-edge areas of research run the gamut from aerodynamics, to impact physics, to flow-field structure and chemistry. This legacy of testing began in the NACA era of the 1940's with the Supersonic Free Flight Tunnel, and evolved dramatically up through the late 1950s with the pioneering work in the Ames Hypersonic Ballistic Range. The tradition continued in the mid-60s with the commissioning of the three newest facilities: the Ames Vertical Gun Range (AVGR) in 1964, the Hypervelocity Free Flight Facility (HFFF) in 1965 and the Electric Arc Shock Tube (EAST) in 1966. Today the Range Complex continues to provide unique and critical testing in support of the Nation's programs for planetary geology and geophysics; exobiology; solar system origins; earth atmospheric entry, planetary entry, and aerobraking vehicles; and various configurations for supersonic and hypersonic aircraft.

Cornelson, C.↗

Numerical Simulation of Vitiation Effects on a Hydrogen-Fueled Dual-Mode Scramjet

The Wind-US computational fluid dynamics (CFD) flow solver was used to simulate dual-mode direct-connect ramjet/scramjet engine flowpath tests conducted in the University of Virginia (UVa) Supersonic Combustion Facility (SCF). The objective was to develop a computational capability within Wind-US to aid current hypersonic research and provide insight to flow as well as chemistry details that are not resolved by instruments available. Computational results are compared with experimental data to validate the accuracy of the numerical modeling. These results include two fuel-off non-reacting and eight fuel-on reacting cases with different equivalence ratios, split between one set with a clean (non-vitiated) air supply and the other set with a vitiated air supply (12 percent H2O vapor). The Peters and Rogg hydrogen-air chemical kinetics model was selected for the scramjet simulations. A limited sensitivity study was done to investigate the choice of turbulence model and inviscid flux scheme and led to the selection of the k-epsilon model and Harten, Lax and van Leer (for contact waves) (HLLC) scheme for general use. Simulation results show reasonably good agreement with experimental data and the overall vitiation effects were captured.

Vyas, Manan A.↗

Slag Management of Carbon Feedstock Used in Gasification FY17 TCF between Eastman Chemical and NETL (Final Report)

NETL, in collaboration with Eastman Chemical Corp (Kingsport, TN), targeted the joint evaluation and refinement of a slag management program developed by NETL (NETL IP, patent applied for) to control gasifier slag properties formed from ash in individual or combinations of different coal-based carbon feedstock materials and specific slag modifiers used in gasification. Slag forms from mineral or organic-metallic impurities in the carbon feedstock that melt at the high temperatures of gasification, coalescing to form a liquid (slag) that must flow from the gasifier. Slag additives, also known as slag modifiers, are often added to the carbon feedstock to modify the ash chemistry and achieve desired slag flow properties at target temperatures used in gasification. If slag does not flow from a gasifier, its buildup within the gasification chamber will cause either gasifier shutdown to physically remove the slag (consuming time and damaging the protective refractory lining), or the gasification temperature must be increased to lower slag viscosity so it can flow from the gasifier, leading to greater refractory wear/corrosion, along with increased fouling and downstream component wear. Because of these issues, gasification is typically targeted at the lowest temperature possible where slag will flow in a controlled manner (a temperature range called T100 for the lowest temperature, with T250 being the highest temperature where the slag has achieved the desired fluidity). That temperature range also needs to yield a desired syngas composition, highlighting the importance of knowing and being able to control carbon feedstock slag viscosity and the temperature of thermal breakdown of the carbon feedstock. Slag viscosity varies with changes in the gasification chamber temperature, oxygen partial pressure, and slag chemistry. The slag model work with Eastman Chemical targeted predicting and controlling molten coal ash slag behavior at specific gasification conditions. The final goal of the refined model was to develop/refine the NETL slag model so a gasifier operator would be able to predict slag behavior prior to purchasing or using a carbon feedstock and control slag properties once a carbon feedstock is being gasified, allowing a gasifier user to determine what mineral additives or blends of different carbon materials would be needed to achieve desired slag properties at targeted gasification conditions. For a given carbon feedstock and desired gasification condition, the actual gasification cost and slag behavior would be able to be predicted using the slag management program in advance of purchasing or using the carbon feedstock – allowing accurate control of slag ash behavior in real time. As part of the TCF project work with Eastman Chemical, the viscosity of several ash compositions of interest to them would be measured and used to populate the slag model, along with a large database of historical slag temperature, chemistry, and viscosity information they possess – information that would in-crease the predictive accuracy of the slag management model with slag ash chemistry of interest to them. As part of the model evaluation and refinement, the predictive model and its database will be installed on computers at Eastman Chemical and used to manage slag properties in a gasifier during real-time operation of their gasifier. In summary, success of the slag management program at Eastman Chemical would support its use by other gasifier operators to manage slag chemistry and properties over other desired gasification temperature ranges, allowing greater process control and efficiency of their carbon feedstock conversion during gasification.

01 COAL, LIGNITE, AND PEAT↗

Numerical investigation of chemically reacting flows in ramjet dump combustors

The time-dependent Navier-Stokes equations, including second-order turbulence model, are numerically integrated by using four-stage Runge-Kutta scheme to predict the steady-state supersonic flow structures in ramjet dump combustors. The formulation is derived for reacting flows with finite-rate chemistry. In the present study, it is firstly attempted to assess the accuracy of existing high-order turbulence model in supersonic flows. The comparison shows reasonable agreement between calculated and measured data in terms of velocity distributions. It is indicated that a modified constant C-mu for calculating turbulent eddy viscosity is needed in the supersonic flow regime and the adaptive meshing is preferred to capture the recirculation zone. In the reacting flow calculation, the results from a test case of hydrogen and air combustion at premixed conditon show that the rearward facing step is able to increase flow residence time and stabilize the flame in supersonic flows.

Hsieh, Kwang-Chung↗

An improved PNS scheme for predicting complex three-dimensional hypersonic flows

Upwinding is incorporated into a numerical technique for predicting hypersonic viscous flows over lifting configurations at moderate angles of attack. A general real-gas flux-vector-splitting technique based on Van Leer's (1982) approach is employed to model upwinding, and three techniques are examined for flux-vector differencing. The three methods are evaluated by applying them to an axisymmetric configuration with a 10-deg afterbody flare. The results indicate that an oscillation-free shock front can be described by using first-order full upwinding across the embedded shock and central-differencing for the other zones. This combined approach is found to be highly convergent for the near-wall region, and its performance is examined for predicting a Mach 15 flow over a finned missile. Attention is given to the effects of gas chemistry which can significantly affect the flows over the missile configurations.

Bhutta, Bilal A.↗

The NATA code; theory and analysis. Volume 2: User's manual

The NATA code is a computer program for calculating quasi-one-dimensional gas flow in axisymmetric nozzles and rectangular channels, primarily to describe conditions in electric archeated wind tunnels. The program provides solutions based on frozen chemistry, chemical equilibrium, and nonequilibrium flow with finite reaction rates. The shear and heat flux on the nozzle wall are calculated and boundary layer displacement effects on the inviscid flow are taken into account. The program contains compiled-in thermochemical, chemical kinetic and transport cross section data for high-temperature air, CO2-N2-Ar mixtures, helium, and argon. It calculates stagnation conditions on axisymmetric or two-dimensional models and conditions on the flat surface of a blunt wedge. Included in the report are: definitions of the inputs and outputs; precoded data on gas models, reactions, thermodynamic and transport properties of species, and nozzle geometries; explanations of diagnostic outputs and code abort conditions; test problems; and a user's manual for an auxiliary program (NOZFIT) used to set up analytical curvefits to nozzle profiles.

Bade, W. L.↗

Radiative interactions in a hydrogen-fueled supersonic combustor

The two-dimensional, elliptic Navier-Stokes equations are used to investigate supersonic flows with finite-rate chemistry and radiation, for hydrogen-air systems. The chemistry source term in the species equation is treated implicitly to alleviate the stiffness associated with fast reactions. The explicit, unsplit MacCormack finite-difference scheme is used to advance the governing equations in time, until convergence is achieved. The specific problem considered is the premixed flow in a channel with a 10-deg compression ramp. Three different chemistry models are used, accounting for increasing number of reactions and participating species. Two chemistry models assume nitrogen as inert, while the third model accounts for nitrogen reactions and NO(x) formation. The tangent slab approximation is used in the radiative flux formulation. A pseudogray model is used to represent the absorption-emission characteristics of the participating species. Results otained for specific conditions indicate that the radiative interactions vary substantially, depending on reactions involving HO2 and NO species, and that this can have a significant influence on the flowfield.

Chandrasekhar, R.↗

Radiative interactions in chemically reacting supersonic internal flows

The two-dimensional, elliptic Navier-Stokes equations are used to investigate supersonic flows with finite-rate chemistry and radiation for hydrogen-air systems. The chemistry source terms in the species equation is treated implicitly to alleviate the stiffness associated with fast reactions. The explicit, unsplit MacCormack finite-difference scheme is used to advance the governing equations in time, until convergence is achieved. The specific problem considered is the premixed flow in a channel with a ten-degree compression ramp. Three different chemistry models are used, accounting for increasing number of reactions and participating species. Two chemistry models assure nitrogen as inert, while the third model accounts for nitrogen reactions and NO(x) formation. The tangent slab approximation is used in the radiative flux formulation. A pseudo-gray model is used to represent the absorption-emission characteristics of the participating species. Results obtained for specific conditions indicate that the radiative interactions vary substantially, depending on reactions involving HO2 and NO species and that this can have a significant influence on the flowfield.

Tiwari, S. N.↗

Discovery of Energy Storage Molecular Materials Using Quantum Chemistry-Guided Multiobjective Bayesian Optimization

Redox flow batteries (RFBs) are a promising technology for stationary energy storage applications due to their flexible design, scalability, and low cost. In RFBs, energy is carried in flowable redoxactive materials (redoxmers) which are stored externally and pumped to the cell during operation. Further improvements in the energy density of RFBs necessitates redoxmer designs with wider redox potential windows and higher solubility. Additionally, designing redoxmers with a fluorescence-enabled self-reporting functionality allows monitoring of the state of health of RFBs. To accelerate the discovery of redoxmers with desired properties, state-of-the- art machine learning ( ML) methods, such as multiobjective Bayesian optimization (MBO), are useful. Here, we first employed density functional theory calculations to generate a database of reduction potentials, solvation free energies, and absorption wavelengths for 1400 redoxmer molecules based on a 2,1,3-benzothiadiazole (BzNSN) core structure. From the computed properties, we identified 22 Pareto-optimal molecules that represent best trade-off among all of the desired properties. We further utilized these data to develop and benchmark an MBO approach to identify candidates quickly and efficiently with multiple targeted properties. With MBO, optimal candidates from the 1400-molecule data set can be identified at least 15 times more efficiently compared to the brute force or random selection approach. Importantly, we utilized this approach for discovering promising redoxmers from an unseen database of 1 million BzNSN-based molecules, where we discovered 16 new Pareto-optimal molecules with significant improvements in properties over the initial 1400 molecules. Furthermore, we anticipate that this active learning technique is general and can be utilized for the discovery of any class of functional materials that satisfies multiple desired property criteria.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Boost-phase discrimination research activities

Theoretical research in two areas was performed. The aerothermodynamics research focused on the hard-body and rocket plume flows. Analytical real gas models to describe finite rate chemistry were developed and incorporated into the three-dimensional flow codes. New numerical algorithms capable of treating multi-species reacting gas equations and treating flows with large gradients were also developed. The computational chemistry research focused on the determination of spectral radiative intensity factors, transport properties and reaction rates. Ab initio solutions to the Schrodinger equation provided potential energy curves transition moments (radiative probabilities and strengths) and potential energy surfaces. These surfaces were then coupled with classical particle reactive trajectories to compute reaction cross-sections and rates.

Cooper, David M.↗