In this work, medium scale (30 cm diameter) methanol pool fires were simulated using the latest fire modeling suite implemented in Sierra/Fuego, a low Mach number multiphysics reacting flow code. The sensitivity of model outputs to various model parameters was studied with the objective of providing model validation. This work also assesses model performance relative to other recently published large eddy simulations (LES) of the same validation case. Two pool surface boundary conditions were simulated. The first was a prescribed fuel mass flux and the second used an algorithm to predict mass flux based on a mass and energy balance at the fuel surface. Gray gas radiation model parameters (absorption coefficients and gas radiation sources) were varied to assess radiant heat losses to the surroundings and pool surface. The radiation model was calibrated by comparing the simulated radiant fraction of the plume to experimental data. The effects of mesh resolution were also quantified starting with a grid resolution representative of engineering type fire calculations and then uniformly refining that mesh in the plume region. Simulation data were compared to experimental data collected at the University of Waterloo and the National Institute of Standards and Technology (NIST). Validation data included plume temperature, radial and axial velocities, velocity temperature turbulent correlations, velocity velocity turbulent correlations, radiant and convective heat fluxes to the pool surface, and plume radiant fraction. Additional analyses were performed in the pool boundary layer to assess simulated flame anchoring and the effect on convective heat fluxes. This work assesses the capability of the latest Fuego physics and chemistry model suite and provides additional insight into pool fire modeling for nonluminous, non-sooting flames.
Depleted uranium hexafluoride (UF6), a stockpiled byproduct of the nuclear fuel cycle, reacts readily with atmospheric humidity, but the mechanism is poorly understood. Here we compare several potential initiation steps at a consistent level of theory, generating underlying structures and vibrational modes using hybrid density functional theory (DFT) and computing relative energies of stationary points with double-hybrid (DH) DFT. A benchmark comparison is performed to assess the quality of DH-DFT data using reference energy differences obtained using a complete-basis-limit coupled-cluster (CC) composite method. The associated large-basis CC computations were enabled by a new general-purpose pseudopotential capability implemented as part of this work. Dispersion-corrected parameter-free DH-DFT methods, namely PBE0-DH-D3(BJ) and PBE-QIDH-D3(BJ), provided mean unsigned errors within chemical accuracy (1 kcal mol-1) for a set of barrier heights corresponding to the most energetically favorable initiation steps. The hydrolysis mechanism is found to proceed via intermolecular hydrogen transfer within van der Waals complexes involving UF6, UF5OH, and UOF4, in agreement with previous studies, followed by the formation of a previously unappreciated dihydroxide intermediate, UF4(OH)2. The dihydroxide is predicted to form under both kinetic and thermodynamic control, and, unlike the alternate pathway leading to the UO2F2 monomer, its reaction energy is exothermic, in agreement with observation. Finally, harmonic and anharmonic vibrational simulations are performed to reinterpret literature infrared spectroscopy in light of this newly identified species.
As part of the Advanced Simulation and Computing Verification and Validation (ASCVV) program, a 0.3-m diameter hydrocarbon pool fire with multiple fuels was modeled and simulated. In the study described in this report, systematic examination was performed on the radiation model used in a series of coupled Fuego/Nalu simulations. A calibration study was done with a medium-scale methanol pool fire and the effect of calibration traced throughout the radiation model. This analysis provided a more detailed understanding of the effect of radiation model parameters on each other and on other quantities in the simulations. Heptane simulation results were also examined using this approach and possible areas for further improvement of the models were identified. The effect of soot on radiative losses was examined by comparing heptane and methanol results.
In response to the global SARS-CoV-2 transmission pandemic, Sandia National Laboratories Rapid Lab-Directed Research and Development COVID-19 initiative has deployed a multi-physics, droplet-laden, turbulent low-Mach simulation tool to model pathogen-containing water droplets that emanate from synthetic human coughing and breathing. The low-Mach turbulent large-eddy simulation-based Eulerian/point-particle Lagrangian methodology directly couples mass, momentum, energy, and species to capture droplet evaporation physics that supports the ability to distinguish between droplets that deposit and those that persist in the environment. The cough mechanism is modeled as a pulsed spray with a prescribed log-normal droplet size distribution. Simulations demonstrate direct droplet deposition lengths in excess of three meters while the persistence of droplet nuclei entrained within a buoyant plume is noted. Including the effect of protective barriers demonstrates effective mitigation of large-droplet transport. For coughs into a protective barrier, jet impingement and large-scale recirculation can drive droplets vertically and back toward the subject while supporting persistence of droplet nuclei. Simulations in quiescent conditions demonstrate droplet preferential concentrations due to the coupling between vortex ring shedding and the subsequent advection of a series of three-dimensional rings that tilt and rise vertically due to a misalignment between the initial principle vortex trajectory and gravity. These resolved coughing simulations note vortex ring formation, roll-up and breakdown, while entraining droplet nuclei for large distances and time scales.
The Chemkin-Pro Application Programming Interface (API) was used to implement surface-kinetics user-routines to expand current aerosol dynamics models. Phase change mechanisms were expanded to include homogeneous nucleation in supersaturated environments, and particle size-dependent vapor condensation and evaporation. Homogeneous nucleation of water droplets was modeled with classical nucleation theory (CNT) and a modified form of nucleation theory published by Dillmann, A., and Meier, G. E. A. (1991, "A Refined Droplet Approach to the Problem of Homogeneous Nucleation From the Vapor-Phase,"J. Chem. Phys., 94(5), pp. 3872-3884). The Chemkin-Pro homogeneous nucleation module, developed in this work, was validated against published data for nucleation fluxes at varying pressures, temperatures, and vapor concentrations. A newly released feature in Chemkin-Pro enabled particle size-dependent surface reaction rates. A Chemkin-Pro vapor condensation and evaporation module was written and verified with the formulation published in Hinds, W. C. (1999, Aerosol Technology: Properties, Behavior, and Measurement of Airborne Particles, Wiley, New York). Lastly, Chemkin-Pro results for coagulation in the transition regime were verified with the semi-implicit method developed by Jacobson, M. Z. (1999, Fundamentals of Atmospheric Modeling, Cambridge University Press, New York, NY). Good performance was observed for all three Chemkin-Pro modules. This work illustrates the utility of the Chemkin-Pro API, and the flexibility with which models can be developed using surface-kinetics user-routines. This paper illustrates that Chemkin-Pro can be developed to include more physically representative aerosol dynamics processes where rates are defined based on physical and chemical parameters rather than Arrhenius rates. The methods and modules developed in this work can be applied to industrial problems like material synthesis (e.g., powder production), processes involving phase change like heat exchangers, as well as more fundamental scientific processes like cloud physics.
Pressure losses and aerosol collection efficiencies were measured for fibrous filter materials at air-flow rates consistent with high efficiency filtration (hundreds of cubic feet per minute). Microfiber filters coated with nanofibers were purchased and fabricated into test assemblies for a 12-inch duct system designed to mimic high efficiency filtration testing of commercial and industrial processes. Standards and specifications for high efficiency filtration were studied from a variety of institutions to assess protocols for design, testing, operations and maintenance, and quality assurance (e.g., DOE, ASHRAE, ASME). Three materials with varying Minimum Efficiency Reporting Values (MERV) were challenged with sodium chloride aerosol. Substantial filter loading was observed where aerosol collection efficiencies and pressure losses increased during experiments. Filter designs will be optimized and characterized in subsequent years of this study. Additional testing will be performed with higher hazard aerosols at Oak Ridge National Laboratory.
A simple aerosol transport model was developed for a multi-compartmented cleanroom. Each compartment was treated as a well-mixed volume with ventilating supply and return air. Gravitational settling, intercompartment transport, and leakage of exterior air into the system were included in the model. A set of first order, coupled, ordinary differential equations was derived from the conservation equations of aerosol mass and air mass. The system of ODEs was then solved in MATLAB using pre-existing numerical methods. The model was verified against cases of (1) constant inlet-duct concentration, and (2) exponentially decaying inlet-duct concentration. Numerical methods resulted in normalized error of less than 10 -9 when model solutions were compared to analytical solutions. The model was validated against experimental measurements from a single field test and showed good agreement in the shape and magnitude of the aerosol concentration profile with time.
An electrostatic size classification technique was used to segregate particles of known composition prior to being injected into an inductively coupled plasma mass spectrometer (ICP-MS). Size-segregated particles were counted with a condensation nuclei counter as well as sampled with an ICP-MS. By injecting particles of known size, composition, and aerosol concentration into the ICP-MS, efficiencies of the order of magnitude aerosol detection were calculated, and the particle size dependencies for volatile and refractory species were quantified. Similar to laser ablation ICP-MS, aerosol detection efficiency was defined as the rate at which atoms were detected in the ICP-MS normalized by the rate at which atoms were injected in the form of particles. This method adds valuable insight into the development of technologies like laser ablation ICP-MS where aerosol particles (of relatively unknown size and gas concentration) are generated during ablation and then transported into the plasma of an ICP-MS. In this study, we characterized aerosol detection efficiencies of volatile species gold and silver along with refractory species aluminum oxide, cerium oxide, and yttrium oxide. Aerosols were generated with electrical mobility diameters ranging from 100 to 1000 nm. In general, it was observed that refractory species had lower aerosol detection efficiencies than volatile species, and there were strong dependencies on particle size and plasma torch residence time. Volatile species showed a distinct transition point at which aerosol detection efficiency began decreasing with increasing particle size. This critical diameter indicated the largest particle size for which complete particle detection should be expected and agreed with theories published in other works. Aerosol detection efficiencies also displayed power law dependencies on particle size. Aerosol detection efficiencies ranged from 10- 5 to 10- 11. Free molecular heat and mass transfer theory was applied, but evaporative phenomena were not sufficient to explain the dependence of aerosol detection on particle diameter. Additional work is needed to correlate experimental data with theory for metal-oxides where thermodynamic property data are sparse relative to pure elements. Lastly, when matrix effects and the diffusion of ions inside the plasma were considered, mass loading was concluded to have had an effect on the dependence of detection efficiency on particle diameter.
A laboratory system was constructed that allows the super-micron particles to be aged for long periods of time under conditions that can simulate a range of natural environments and conditions, including relative humidity, oxidizing chemicals, organics and simulated solar radiation. Two proof-of-concept experiments using a non-biological simulant for biological particles and a biological simulant demonstrate the utility of these types of aging experiments. Green Visolite®, which is often used as a tracer material for model validation experiments, does not degrade with exposure to simulated solar radiation, the actual biological material does. This would indicate that Visolite® should be a good tracer compound for mapping the extent of a biological release using fluorescence as an indicator, but that it should not be used to simulate the decay of a biological particle when exposed to sunlight. The decay in the fluorescence measured for B. thurengiensis is similar to what has been previously observed in outdoor environments.