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Sorption Enhanced Mixed Matrix Membranes for Hydrogen (H 2 ) Purification and Carbon Dioxide (CO 2 ) Capture

The technical objective of this project was to develop sorption enhanced mixed matrix membranes with H 2 permeance of 500 gas permeance units (GPU) and H 2 /CO 2 selectivity of 30 at 150-200 °C. These membranes will be the central component in the design of membrane based systems for 90% capture of CO 2 from coal-derived syngas, with 95% CO 2 purity at a cost of electricity 30% less than baseline capture approaches. The unique approach in this proposal is to design crosslinked polymers containing Pd-based nanoparticles achieving strong H 2 sorption and size sieving ability and thus H 2 /CO 2 selectivity. The specific objectives for each budget period (BP) are described below. BP 1: Identify polymer matrix with strong size sieving ability and palladium (Pd)-containing nanomaterials to prepare freestanding mixed matrix films with H 2 permeability of 50 Barrer and H 2 /CO 2 selectivity of 30 at 150-200°C with simulated syngas. BP 2: Prepare and optimize thin film mixed matrix composite membranes materials with H 2 permeance of 500 GPU and H 2 /CO 2 selectivity of 30 at 150-200 °C, and complete the modification of the membrane test unit for the field test in the BP 3. BP 3: Conduct a 20-day field test of the membranes with real syngas at Center for Advanced Energy Research (CAER) of the University of Kentucky (UKy). During the BP2, we have successfully prepared thin-film composite (TFC) membranes based on mixed matrix materials (MMMs) containing Pd nanoparticles in polymers, and demonstrated their superior and robust performance for H 2 /CO 2 separation at 150 – 225 °C. (1) Production of the Pd based nanoparticles with a diameter of 4 nm has been scaled up to 200 mg/day. (2) We have prepared TFC membranes with H 2 permeance above 500 GPU and H 2 /CO 2 selectivity above 30 at temperatures up to 225 °C, which meet the targets for the BP2. (3) We have conducted parametric studies of TFC membranes with a mixed gas containing H 2 S and H 2 O and demonstrated the stability of the membranes. (4) We have established a new testing plan at the Center for Advanced Energy Studies (CAER) at the University of Kentucky because NCCC decided to shut down their gasifier. During this project, four Ph.D. students received the inter-disciplinary training and graduated, including Shailesh Konda, Maryam Omidvar, Deqiang Yin, and Lingxiang Zhu. One postdoctoral researcher (Dr. Liang Huang) and two Ph.D. students (Abhishek Kumar and Hien Nguyen) are involved in this project. The project leads to one provisional patent application, eight peer-reviewed articles, and one manuscript in preparation. The details are shown below.

01 COAL, LIGNITE, AND PEAT↗

Hanford Site Composite Analysis: Recharge and Inventory Sensitivity Analyses for the A Trenches, BC Cribs and Trenches, and PUREX Area Vadose Zone Models

The main objectives of the composite analysis (CA) compliance case vadose zone (VZ) facet are to simulate transport of radionuclide releases from the surface to the water table, and to provide radionuclide transfer rates to groundwater for inclusion into the Plateau-to-River (P2R) saturated zone (SZ) model (CP-57037, Model Package Report: Plateau to River Groundwater Model, Version 8.3). The CA compliance case approach to address the scale and distribution of contaminant sources in the VZ facet is to subdivide the Hanford Site Central Plateau into 26 models that contain contaminant sources and liquid discharges likely to commingle during migration through the VZ to the water table

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Composite Analysis Vadose Zone Transport of Selected Radionuclides Released from DOE O 435.1 Sources.

The main objectives of the composite analysis (CA) compliance case vadose zone (VZ) facet are to simulate transport of radionuclide releases from the surface to the water table, and to provide radionuclide transfer rates to groundwater for inclusion into the Plateau-to-River (P2R) saturated zone (SZ) model (CP-57037, Model Package Report: Plateau to River Groundwater Model, Version 8.3). The parallel exascale version of the Subsurface Transport Over Multiple Phases (eSTOMP1) simulator is used to simulate flow and transport for the CA VZ models. The CA compliance case approach to address the scale and distribution of contaminant sources in the VZ facet is to subdivide the Hanford Site Central Plateau into 26 models that contain contaminant sources and liquid discharges likely to commingle during migration through the VZ to the water table.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Composite Analysis Vadose Zone Transport of Selected Hanford Site Composite Analysis: Vadose Zone Transport of Selected Radionuclides Released from DOE O 435.1 Waste Sites

The main objectives of the composite analysis (CA) compliance case vadose zone (VZ) facet are to simulate transport of radionuclide releases from the surface to the water table, and to provide radionuclide transfer rates to groundwater for inclusion into the Plateau-to-River (P2R) saturated zone (SZ) model (CP-57037, Model Package Report: Plateau to River Groundwater Model, Version 8.3). The parallel exascale version of the Subsurface Transport Over Multiple Phases (eSTOMP) simulator is used to simulate flow and transport for the CA VZ models. The CA compliance case approach to address the scale and distribution of contaminant sources in the VZ facet is to subdivide the Hanford Site Central Plateau into 26 models that contain contaminant sources and liquid discharges likely to commingle during migration through the VZ to the water table.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Adaptive Discovery and Mixed-Variable Optimization of Next Generation Synthesizable Microelectronic Materials

Design of new microelectronic materials is characterized by several challenges such as high-dimensionality of the atomic structure-composition variable space, formidable cost of directly using high-fidelity simulations for design optimization, dispersity in literature-reported similar materials and synthesis methods, complex physical mechanisms, and mixed qualitative and quantitative design variables that lead to a disjointed design space. Even though machine learning (ML) techniques have been employed to expedite materials innovation, existing methods treat ML and design optimization as two separate processes, failing to resolve the fundamental challenges associated with high dimensionality and mixed-variable complexity. We have developed a ML enhanced mixed-variable material design optimization framework to efficiently extract useful information from existing data in literature and physics-based simulations to guide the autonomous search for optimal materials. Our proposed framework is composed of four computational modules: (1) a natural language processing (NLP) based virtual screening module, (2) classification based concept exploration module, (3) a density functional theory (DFT)-based high-fidelity evaluation model, and (4) a novel latent-variable Gaussian process (LVGP) ML model for mixed-variable problems with uncertainty quantification, which seamlessly integrates with Bayesian Optimization (BO) and achieves superb efficiency through embedded physics-based dimension reduction. Our approach is demonstrated and validated using the testbed of functional materials exhibiting metal-insulation transitions (MITs), with the targeted reversible resistivity changes (∼10^5) near room temperature. At the end of the 30-month project, we have developed a series of new ML techniques using NLP, conditional variational autoencoders, active learning, latent-variable Gaussian processes, integrated with Bayesian optimization. Our project has resulted in new predicted MITs compounds and improved understanding of MITs microscopic mechanisms, which in turn will revolutionize microelectronics science to provide energy-saving solutions. Our research has improved both creativity and efficiency in transforming rare-event discoveries of new functional materials to persistent innovations. In addition to open-sourcing the online MIT database and the classification model, the LVGP open source code has been downloaded more than 15,000 times within two years. More than 40 MIT compounds have been identified and many have been pursued experimentally via collaborators. The research results are published in close to 20 collaborative papers in high-impact journals, such as Chem. Mater., Appl. Phys. Rev., Sci. Rep., among others of design space.

36 MATERIALS SCIENCE↗

CORRELATIONS BETWEEN COMPOSITIONS AND ORBITS ESTABLISHED BY THE GIANT IMPACT ERA OF PLANET FORMATION

The giant impact phase of terrestrial planet formation establishes connections between super-Earths’ orbital properties (semimajor axis spacings, eccentricities, mutual inclinations) and interior compositions (the presence or absence of gaseous envelopes). Using N -body simulations and analytic arguments, we show that spacings derive not only from eccentricities, but also from inclinations. Flatter systems attain tighter spacings, a consequence of an eccentricity equilibrium between gravitational scatterings, which increase eccentricities, and mergers, which damp them. Dynamical friction by residual disk gas plays a critical role in regulating mergers and in damping inclinations and eccentricities. Systems with moderate gas damping and high solid surface density spawn gas-enveloped super-Earths with tight spacings, small eccentricities, and small inclinations. Systems in which super-Earths coagulate without as much ambient gas, in disks with low solid surface density, produce rocky planets with wider spacings, larger eccentricities, and larger mutual inclinations. A combination of both populations can reproduce the observed distributions of spacings, period ratios, transiting planet multiplicities, and transit duration ratios exhibited by Kepler super-Earths. The two populations, both formed in situ, also help to explain observed trends of eccentricity versus planet size, and bulk density versus method of mass measurement (radial velocities versus transit timing variations). Simplifications made in this study—including the limited time span of the simulations, and the approximate treatments of gas dynamical friction and gas depletion history—should be improved on in future work to enable a detailed quantitative comparison to the observations.

79 ASTRONOMY AND ASTROPHYSICS↗

The impact of hurricane disturbances on a tropical forest: implementing a palm plant functional type and hurricane disturbance module in ED2-HuDi V1.0

Hurricanes commonly disturb and damage tropical forests. Hurricane frequency and intensity are predicted to change under the changing climate. The short-term impacts of hurricane disturbances to tropical forests have been widely studied, but the long-term impacts are rarely investigated. Modeling is critical to investigate the potential response of forests to future disturbances, particularly if the nature of the disturbances is changing with climate. Unfortunately, existing models of forest dynamics are not presently able to account for hurricane disturbances. Therefore, we implement the Hurricane Disturbance in the Ecosystem Demography model (ED2) (ED2-HuDi). The hurricane disturbance includes hurricane-induced immediate mortality and subsequent recovery modules. The parameterizations are based on observations at the Bisley Experimental Watersheds (BEW) in the Luquillo Experimental Forest in Puerto Rico. We add one new plant functional type (PFT) to the model – Palm, as palms cannot be categorized into one of the current existing PFTs and are known to be an abundant component of tropical forests worldwide. The model is calibrated with observations at BEW using the generalized likelihood uncertainty estimation (GLUE) approach. The optimal simulation obtained from GLUE has a mean relative error of –21 %, –12 %, and –15 % for stem density, basal area, and aboveground biomass, respectively. The optimal simulation also agrees well with the observation in terms of PFT composition (+1 %, –8 %, –2 %, and +9 % differences in the percentages of “Early”, “Mid”, “Late”, and “Palm” PFTs, respectively) and size structure of the forest (+0.8 % differences in the percentage of large stems). Lastly, using the optimal parameter set, we study the impact of forest initial condition on the recovery of the forest from a single hurricane disturbance. The results indicate that, compared to a no-hurricane scenario, a single hurricane disturbance has little impact on forest structure (+1 % change in the percentage of large stems) and composition (<1 % change in the percentage of each of the four PFTs) but leads to 5 % higher aboveground biomass after 80 years of succession. The assumption of a less severe hurricane disturbance leads to a 4 % increase in aboveground biomass.

54 ENVIRONMENTAL SCIENCES↗

Impact of Nuclear Data Uncertainties on Calculated Spent Fuel Nuclide Inventories and Advanced NDA Instrument Response

The U.S. Department of Energy’s Next Generation Safeguards Initiative Spent Fuel (NGSI-SF) project is nearing the final phase of developing several advanced nondestructive assay (NDA) instruments designed to measure spent nuclear fuel assemblies for the purpose of improving nuclear safeguards. Current efforts are focusing on calibrating several of these instruments with spent fuel assemblies at two international spent fuel facilities. Modelling and simulation is expected to play an important role in predicting nuclide compositions, neutron and gamma source terms, and instrument responses in order to inform the instrument calibration procedures. As part of NGSI-SF project, this work was carried out to assess the impacts of uncertainties in the nuclear data used in the calculations of spent fuel content, radiation emissions and instrument responses. Nuclear data is an essential part of nuclear fuel burnup and decay codes and nuclear transport codes. Such codes are routinely used for analysis of spent fuel and NDA safeguards instruments. Hence, the uncertainties existing in the nuclear data used in these codes affect the accuracies of such analysis. In addition, nuclear data uncertainties represent the limiting (smallest) uncertainties that can be expected from nuclear code predictions, and therefore define the highest attainable accuracy of the NDA instrument. This work studies the impacts of nuclear data uncertainties on calculated spent fuel nuclide inventories and the associated NDA instrument response. Recently developed methods within the SCALE code system are applied in this study. The Californium Interrogation with Prompt Neutron instrument was selected to illustrate the impact of these uncertainties on NDA instrument response.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Composition Measurements of the LAW ML1 Glasses

This report provides the results from the chemical analyses of the glass compositions of the quenched Low Activity Waste Machine Learning study glasses, a series of simulated nuclear waste glasses designed and fabricated at Pacific Northwest National Laboratory. These data will be used in the development, validation, and implementation of enhanced property/composition models for waste glass vitrification at Hanford. Chemical analyses were performed on a representative sample of each of the quenched glasses to allow for comparisons with target compositions. The relative differences between the target and measured concentrations of F - for one glass, P 2 O 5 for two glasses, SO 3 for three glasses, and ZrO 2 for two of the glasses were greater than 10%. These results can be used in further characterization of this series of glasses, including the normalization of Product Consistency Test results.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mining for dust in type 1 quasars

We explore the extinction/reddening of ∼35,000 uniformly selected quasars with 0 0.1 and 0.1% (1.3%) with E(B−V)>0.2. Simulations show both populations of quasars are intrinsically bluer than the mean composite, with a mean spectral index (α{sub λ}) of −1.79 (−1.83). The emission and absorption-line properties of both samples reveal that quasars with intrinsically red continua have narrower Balmer lines and stronger high-ionization emission lines, the latter indicating a harder continuum in the extreme-UV and the former pointing to differences in black hole mass and/or orientation.

79 ASTRONOMY AND ASTROPHYSICS↗

Chemical Composition Measurements of LAWA44 Glass Samples

DOE is building the Hanford Tank Waste Treatment and Immobilization Plant (WTP) at the Hanford Site in Washington to remediate 55 million gallons of radioactive waste that is temporarily stored in 177 underground tanks. Both low-activity and high-level wastes will then be vitrified into borosilicate glass using Joule-heated ceramic melters. Efforts are being made to increase the loading of Hanford tank wastes in the glass. One area of work is enhancing waste glass composition/property models and broadening the compositional regions over which those models are applicable. In this report, the Savannah River National Laboratory provides chemical analysis results for several samples of a simulated low-activity waste glass, LAWA44, provided by the Pacific Northwest National Laboratory as part of an ongoing development task. The measured chemical composition data are reported and compared with the targeted values for each component for each glass. A detailed review showed no indications of errors in the preparation or measurement of the study glasses. All of the measured sums of oxides for the study glasses fell within the interval of 97.9 to 102.6 wt %, indicating acceptable recovery of the glass components. Comparisons of the targeted and measured chemical compositions showed that the measured values for the glasses met the targeted concentrations within 10% for those components present at more than 5 wt %. It was noted that the measured B 2 O 3 concentrations are somewhat above the targeted values for the study glasses. No obvious trends were observed with regard to the multiple melting steps used to prepare the study glasses, indicating that any potential effects of volatility were below measurable thresholds.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Active Mixing of Disparate Inks for Multimaterial 3D Printing

3D printing of multimaterial parts relies upon efficient mixing of the ink components and a rapid response to composition changes. However, at low Reynolds numbers and large Peclet numbers, mixing disparate viscosity and density inks poses a challenge. In this study, the performance of active micromixers for disparate non-Newtonian inks is evaluated using both experiments and computational fluid dynamics simulations. The mixing efficiencies are compared with scaling relationships for active micromixers. Using detailed simulation results, multiple factors are identified that can impact the micromixer response time during a composition change. Finally, an active micromixer is proposed and evaluated to efficiently mix arbitrary multimaterial ink compositions and produce fine composition gradients within printed parts.

3D printing↗

Production of Secondary Organic Aerosol During Aging of Biomass Burning Smoke From Fresh Fuels and Its Relationship to VOC Precursors

After smoke from burning biomass is emitted into the atmosphere, chemical and physical processes change the composition and amount of organic aerosol present in the aged, diluted plume. During the fourth Fire Lab at Missoula Experiment, we performed smog-chamber experiments to investigate formation of secondary organic aerosol (SOA) and multiphase oxidation of primary organic aerosol (POA). We simulated atmospheric aging of diluted smoke from a variety of biomass fuels while measuring particle composition using high-resolution aerosol mass spectrometry. We quantified SOA formation using a tracer ion for low-volatility POA as a reference standard (akin to a naturally occurring internal standard). We report these smoke aging experiments revealed variable organic aerosol (OA) enhancements, even for smoke from similar fuels and aging mechanisms. This variable OA enhancement correlated well with measured differences in the amounts of emitted volatile organic compounds (VOCs) that could subsequently be oxidized to form SOA. For some aging experiments, we were able to predict the SOA production to within a factor of 2 using a fuel-specific VOC emission inventory that was scaled by burn-specific toluene measurements. For fires of coniferous fuels that were dominated by needle burning, volatile biogenic compounds were the dominant precursor class. For wiregrass fires, furans were the dominant SOA precursors. We used a POA tracer ion to calculate the amount of mass lost due to gas-phase oxidation and subsequent volatilization of semivolatile POA. Less than 5% of the POA mass was lost via multiphase oxidation-driven evaporation during up to 2 hr of equivalent atmospheric oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pore size effect on selective gas transport in shale nanopores

In shale gas production, gas composition may vary over time. To understand this phenomenon, we use molecular dynamics simulations to study the permeation of CH 4 , C 2 H 6 and their mixture from a source container through a pyrophyllite nanopore driven by a pressure gradient. For a pure gas, the flow rate of CH 4 is always higher than that of C 2 H 6 , regardless of pore size. For a 1:1 C 2 H 6 : CH 4 mixture, however, C 2 H 6 :CH 4 flow rate ratio is higher than the compositional ratio in the container (i.e., 1:1) when the pore size is smaller than ~1.8 nm. The selective transport is caused by the competitive adsorption of C 2 H 6 over CH 4 in the nanopore. The selectivity is also determined by the interplay between the surface diffusion of the adsorbed molecules and the viscous flow in the center of the pore, and it diminishes as the viscous flow becomes to dominate the surface diffusion when the pore size becomes larger than 1.8 nm. Our work shows that compositional differentiation of shale gas in production is a consequence of nanopore confinement and therefore a key characteristic of an unconventional reservoir. Finally, the related compositional information can potentially be used for monitoring the status of a production well such as its recovery rate.

03 NATURAL GAS↗

Relativistic MHD simulations of collision-induced magnetic dissipation in Poynting-flux-dominated jets/outflows

The question of the energy composition of the jets/outflows in high-energy astrophysical systems, e.g. GRBs, AGNs, is taken up first: Matter-flux-dominated (MFD), σ < 1, and/or Poynting-flux-dominated (PFD), σ >1? The standard fireball IS model and dissipative photosphere model are MFD, while the ICMART (Internal-Collision-induced MAgnetic Reconnection and Turbulence) model is PFD. Motivated by ICMART model and other relevant problems, such as “jets in a jet” model of AGNs, the author investigates the models from the EMF energy dissipation efficiency, relativistic outflow generation, and σ evolution points of view, and simulates collisions between high-σ blobs to mimic the situation of the interactions inside the PFD jets/outflows by using a 3D SRMHD code which solves the conservative form of the ideal MHD equations. σ b,f is calculated from the simulation results (threshold = 1). The efficiency obtained from this hybrid method is similar to the efficiency got from the energy evolution of the simulations (35.2%). Efficiency is nearly σ independent, which is also confirmed by the hybrid method. σ b,i - σ b,f provides an interesting linear relationship. Results of several parameter studies of EMF energy dissipation efficiency are shown.

79 ASTRONOMY AND ASTROPHYSICS↗

Composition and grain size effects on the structural and mechanical properties of CuZr nanoglasses

Nanoglasses (NGs), metallic glasses (MGs) with a nanoscale grain structure, have the potential to considerably increase the ductility of traditional MGs while retaining their outstanding mechanical properties. We investigated the effects of composition on the structural and mechanical properties of CuZr NG films with grain sizes between 3 to 15 nm using molecular dynamics simulations. Results indicate a transition from localized shear banding to homogeneous superplastic flow with decreasing grain size, although the critical average grain size depends on composition: 5 nm for Cu{sub 36}Zr{sub 64} and 3 nm for Cu{sub 64}Zr{sub 36}. The flow stress of the superplastic NG at different compositions follows the trend of the yield stress of the parent MG, i.e., Cu{sub 36}Zr{sub 64} yield/flow stress: 2.54 GPa/1.29 GPa and Cu{sub 64}Zr{sub 36} yield/flow stress: 3.57 GPa /1.58 GPa. Structural analysis indicates that the differences in mechanical behavior as a function of composition are rooted at the distinct statistics of prominent atomic Voronoi polyhedra. The mechanical behavior of NGs is also affected by the grain boundary thickness and the fraction of atoms at interfaces for a given average grain size. The results suggest that the composition dependence of the mechanical behavior of NGs follows that of their parent MGs, e.g., a stronger MG will generate a stronger NG, while the intrinsic tendency for homogeneous deformation occurring at small grain size is not affected by composition.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Investigating old-growth ponderosa pine physiology using tree-rings, δ 13 C, δ 18 O, and a process-based model

In dealing with predicted changes in environmental conditions outside those experienced today, forest managers and researchers rely on process-based models to inform physiological processes and predict future forest growth responses. The carbon and oxygen isotope ratios of tree-ring cellulose (d13Ccell, d18Ocell) reveal long-term, integrated physiological responses to environmental conditions. We incorporated a submodel of d18Ocell into the widely used Physiological Principles in Predicting Growth (3-PG) model for the first time, to complement a recently added d13Ccell submodel. We parameterized the model using previously reported stand characteristics and long-term trajectories of tree-ring growth, d13Ccell, and d18Ocell collected from the Metolius AmeriFlux site in central Oregon (upland trees). We then applied the parameterized model to a nearby set of riparian trees to investigate the physiological drivers of differences in observed basal area increment (BAI) and d13Ccell trajectories between upland and riparian trees. The model showed that greater available soil water and maximum canopy conductance likely explain the greater observed BAI and lower d13Ccell of riparian trees. Unexpectedly, both observed and simulated d18Ocell trajectories did not differ between the upland and riparian trees, likely due to similar d18O of source water isotope composition. The d18Ocell submodel with a Peclet effect improved model estimates of d18Ocell because its calculation utilizes 3-PG growth and allocation processes. Because simulated stand-level transpiration (E) is used in the d18O submodel, aspects of leaf-level anatomy such as the effective path length for transport of water from the xylem to the sites of evaporation could be estimated.

54 ENVIRONMENTAL SCIENCES↗

Effect of Tapering on Morphology and Interfacial Behavior of Diblock Copolymers from Molecular Dynamics Simulations

Tapered diblock copolymers are AB diblock copolymers modified by adding a gradient region between the blocks in which composition varies smoothly from one species to the other. This gives additional control parameters, the length of the taper and its direction, to control the microphase separation behavior. Using tapers can also increase the accessibility of the bicontinuous gyroid phase, potentially of interest in transport applications. Recently, the phase diagram of these systems was predicted using self-consistent field theory (SCFT). Here, we perform coarse-grained molecular dynamics (MD) simulations to investigate both the structural and dynamic properties of tapered diblock copolymers. The MD results are consistent with the SCFT phase diagram, and the density profiles are also similar as a function of taper length and direction. We additionally compute mean-squared displacements and end-to-end relaxation times of lamellar systems and observe individual polymer conformations. Increasing taper length effectively lowers segregation strength and leads to a smaller domain spacing; the changes in dynamics are also discussed. The short (30%) inverse taper has a significantly shorter domain spacing than the diblock and qualitatively different polymer conformations (chains can fold back and forth across the interface).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗