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Microstructural and infiltration properties of woven preforms during chemical vapor infiltration

Interface-resolved direct numerical simulations (DNSs) of chemical vapor infiltration (CVI) have been performed over a range of furnace-operating conditions (Thiele moduli) and for practical woven preform geometries. A level-set method is used to resolve the geometry of the initial preform at tow scale. The interface between the vapor and solid phase is then evolved in time through the entire CVI densification cycle, fully resolving the time-varying topology between the two phases. In contrast to previous level-set methods for CVI simulation, the physical reaction and diffusion processes govern the level-set movement in the current approach. The surface deposition kinetics is described by the usual one-step model. In this paper, the DNS data are used to study the evolving porosity, surface-to-volume ratio, and flow infiltration properties (permeability and effective diffusivities). Additionally, comparisons are made to popularly-assumed structure functions and the standard, Kozeny–Carmen porous media model commonly employed in modeled CFD simulations of CVI. The virtual DNS experiments reveal a Thiele modulus and preform geometry (fabric layup) dependence which the existing microstructural and infiltration models are not able to describe throughout the entire densification process. The DNS-based, woven geometry-specific correlations can be applied directly to mean-field, furnace-scale CFD simulations.

36 MATERIALS SCIENCE↗

Laser Ablation Plasmas and Spectroscopy for Nuclear Applications

The development of measurement methodologies to detect and monitor nuclear-relevant materials remains a consistent and significant interest across the nuclear energy, nonproliferation, safeguards, and forensics communities. Optical spectroscopy of laser-produced plasmas is becoming an increasingly popular diagnostic technique to measure radiological and nuclear materials in the field without sample preparation, where current capabilities encompass the standoff, isotopically resolved and phase-identifiable (e.g., UO and UO[Formula: see text]) detection of elements across the periodic table. These methods rely on the process of laser ablation (LA), where a high-powered pulsed laser is used to excite a sample (solid, liquid, or gas) into a luminous microplasma that rapidly undergoes de-excitation through the emission of electromagnetic radiation, which serves as a spectroscopic fingerprint for that sample. This review focuses on LA plasmas and spectroscopy for nuclear applications, covering topics from the wide-area environmental sampling and atmospheric sensing of radionuclides to recent implementations of multivariate machine learning methods that work to enable the real-time analysis of spectrochemical measurements with an emphasis on fundamental research and development activities over the past two decades. Background on the physical breakdown mechanisms and interactions of matter with nanosecond and ultrafast laser pulses that lead to the generation of laser-produced microplasmas is provided, followed by a description of the transient spatiotemporal plasma conditions that control the behavior of spectroscopic signatures recorded by analytical methods in atomic and molecular spectroscopy. High-temperature chemical and thermodynamic processes governing reactive LA plasmas are also examined alongside investigations into the condensation pathways of the plasma, which are believed to serve as chemical surrogates for fallout particles formed in nuclear fireballs. Laser-supported absorption waves and laser-induced shockwaves that accompany LA plasmas are also discussed, which could provide insights into atmospheric ionization phenomena from strong shocks following nuclear detonations. Furthermore, the standoff detection of trace radioactive aerosols and fission gases is reviewed in the context of monitoring atmospheric radiation plumes and off-gas streams of molten salt reactors. Finally, concluding remarks will present future outlooks on the role of LA plasma spectroscopy in the nuclear community.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Synthesis and characterization of polylactic acid microspheres via emulsion-based processing

Polylactic acid (PLA) microspheres are primarily used in drug delivery applications and rarely manufactured commercially. In encapsulation, the drug encapsulation and microsphere synthesis process happen simultaneously. Simultaneous synthesis necessitates conditions that ensure the drugs to be encapsulated remain viable in the synthesis process. Here, in the present work, solid pure PLA microspheres are prepared using a repeatable centrifugal mixing method to create a single emulsion system. A planetary thinky mixer is used to achieve centrifugal mixing. PLA acts as the dispersed phase of the emulsion, whereas Polyvinyl alcohol (emulsifier) dissolved in deionized water serves as the bulk phase. The emulsions are stirred for about 4 min at 2000 rpm. Microspheres prepared by mechanical mixing are compared with microspheres prepared by centrifugal mixing. The microspheres prepared by centrifugal mixing proved to be narrower and closer to a normal distribution with a mean size (D x 50) of 30 microns. The size distribution of planetary mixed microspheres did not change from one batch to another.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Collaborative Research: failure of RockMasses from Nucleation and Growth of Microscopic Defects and Disorder

Over the 21 years of funding we have pursued several projects related to earthquakes, damage and nucleation. We developed simple models of earthquake faults which we studied to understand Gutenburg-Richter scaling, foreshocks and aftershocks, the effect of spatial structure of the faults and its interaction with underlying self organization and phase transitions. In addition we studied the formation of amorphous solids via the glass transition. We have also studied nucleation with a particular concentration on transitions in systems with a spatial symmetry change. In addition we investigated the nucleation process in models that mimic rock masses. We obtained the structure of the droplet in both homogeneous and heterogeneous nucleation. We also investigated the effect of defects or asperities on the nucleation of failure in simple models of earthquake faults.

58 GEOSCIENCES↗

Vadose Zone Model for A Trenches Area for Composite Analysis

The objectives of the vadose modeling for the updated Hanford Site composite analysis (CA) are to simulate the flow and transport of water and radionuclide releases from the surface to the water table and to provide radionuclide transfer rates for the plateau to river (P2R) model, version 8.3. Water additions include natural recharge and water discharged to the ground as a result of industrial processes associated with Hanford Site operations. Contaminant sources include radionuclides in water discharged to the ground during operations and radionuclides disposed “dry” in solid waste burial grounds or other means. The parallel version of the Subsurface Transport Over Multiple Phases (STOMP) simulator, officially named the exascale Subsurface Transport Over Multiple Phases (eSTOMP), is used to simulate flow and transport for the vadose models. The scope of this ECF is to document the development and results of the A Trenches Area vadose zone model. The A Trenches Area model covers the region between the 200 East Area and southwest of the 216-B-3 Pond. The primary waste sites in this area are cribs associated with PUREX Plant (202-A).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A Common Origin of Magnetism from Planets to White Dwarfs

Isolated magnetic white dwarfs have field strengths ranging from kilogauss to gigagauss. However, the origin of the magnetic field has not been hitherto elucidated. Whether these fields are fossil, hence the remnants of original weak magnetic fields amplified during the course of the evolution of their progenitor stars, or are the result of binary interactions, or, finally, they are produced by other internal physical mechanisms during the cooling of the white dwarf itself, remains a mystery. At sufficiently low temperatures, white dwarfs crystallize. Upon solidification, phase separation of its main constituents, {sup 12}C and {sup 16}O, and of the impurities left by previous evolution occurs. This process leads to the formation of a Rayleigh–Taylor unstable liquid mantle on top of a solid core. This convective region, as it occurs in solar system planets like the Earth and Jupiter, can produce a dynamo able to yield magnetic fields of strengths of up to 0.1 MG, thus providing a mechanism that could explain magnetism in single white dwarfs.

79 ASTRONOMY AND ASTROPHYSICS↗

Sorption Behavior of Iodate Ions on Calcium Silicate Hydrate under a High Saline Condition - 18176

The sorption behavior of iodate ions on calcium-silicate hydrate (CSH) gel under high saline condition was examined by monitoring the concentrations of iodate ions and chloride ions using ion chromatography and Raman spectroscopy, without drying process. In the sorption experiments, a stable isotope I-127 was used as an alternative of I-129 which is radioactive one. Each sample was synthesized with mixing CaO powder, SiO{sub 2} as fumed silica and NaCl solution. Ca/Si molar ratios of CSH gel were set to 0.4, 0.8, 1.2 and 1.6 (add 0.2, 0.6, 1.0 and 1.4 only L/S = 20), and the concentration of NaCl solution was set to 0 M or 0.6 M for simulating the condition of fresh or saline groundwater. The liquid/solid (L/S) ratios of CSH gel were set to 10, 15 and 20, and the total weight of solid phase was 1.5 g. At the same time, NaIO{sub 3} solution was added to the sample in order to adjust its concentration to 1.0 mM, 0.67 mM and 0.5 mM for each L/S ratios. The synthesis procedure for all samples was conducted in a glove bag filled with nitrogen gas. The curing period was 7, 14, 30, and 60 days at a room temperature (298 K) with shaking at 120 strokes/min. As a results, the concentration of iodate ions in the liquid phase decreased for all samples under experimental conditions. Besides, the sorption behavior of iodate ions were hardly changed by the concentration of NaCl. That is, iodate ions migrated to solid phase in spite of the high concentration of NaCl. The distribution coefficients, Kd, increased as Ca/Si ratio increased, and hardly depended on NaCl concentration. The results of Raman analysis shows that the structure of CSH gel was almost not changed with or without NaCl from the viewpoint of the silicate chain under this condition. These results suggest that a sorption process except for the electrostatic process such as an ion exchange and a complexation exists between CSH gel and iodate ions. Besides, CSH gel might be able to contribute the retardation for the migration of iodate ions without changing its structure, even if the disposal environment are saturated by a high saline groundwater. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Solid state amorphization in the Al-Fe binary system during high energy milling

In the present study, mechanical alloying (MA) of Al75Fe25 elemental powders mixture was carried out in argon atmosphere, using a high energy attritor ball mill. The microstructure of the milled products at different stages of milling was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). The results showed that the amorphous phase content increased by increasing the milling time, and after 50 hours the amorphization process became complete. Heating the samples resulted in the crystallization of the synthesized amorphous alloys and the appearance of the equilibrium intermetallic compounds Al{sub 5}Fe{sub 2}.

36 MATERIALS SCIENCE↗

A first-principles study of cementite (Fe{sub 3}C) and its alloyed counterparts: Elastic constants, elastic anisotropies, and isotropic elastic moduli

A comprehensive computational study of elastic properties of cementite (Fe{sub 3}C) and its alloyed counterparts (M{sub 3}C (M = Al, Co, Cr, Cu, Fe, Hf, Mn, Mo, Nb, Ni, Si, Ta, Ti, V, W, Zr, Cr{sub 2}FeC and CrFe{sub 2}C) having the crystal structure of Fe{sub 3}C is carried out employing electronic density-functional theory (DFT), all-electron PAW pseudopotentials and the generalized gradient approximation for the exchange-correlation energy (GGA). Specifically, as a part of our systematic study of cohesive properties of solids and in the spirit of materials genome, following properties are calculated: (i) single-crystal elastic constants, C{sub ij}, of above M{sub 3}Cs; (ii) anisotropies of bulk, Young’s and shear moduli, and Poisson’s ratio based on calculated C{sub ij}s, demonstrating their extreme anisotropies; (iii) isotropic (polycrystalline) elastic moduli (bulk, shear, Young’s moduli and Poisson’s ratio) of M{sub 3}Cs by homogenization of calculated C{sub ij}s; and (iv) acoustic Debye temperature, θ{sub D}, of M{sub 3}Cs based on calculated C{sub ij}s. We provide a critical appraisal of available data of polycrystalline elastic properties of alloyed cementite. Calculated single crystal properties may be incorporated in anisotropic constitutive models to develop and test microstructure-processing-property-performance links in multi-phase materials where cementite is a constituent phase.

36 MATERIALS SCIENCE↗

Nanostructured Ni—Cd powders

Nanostructured powders of the Ni—Cd system containing 0–50 mol.% Cd obtained by co-reduction of metal salts from aqueous solutions by hydrazine were studied by X-ray diffraction, optical emission spectroscopy and electron microscopy. The reduction leads to formation of polycrystalline particles of 100–350 nm size, consisting of 10–20 nm crystallites. Phase composition of the powders is substantially different from that predicted by equilibrium on the phase diagram. Instead of a two-phase area consisting of Ni—NiCd intermetallide, other phase states are observed. If the system contains up to 6% Cd, the XRD data indicates the presence of a single-phase solid solution with a face centred cubic (fcc)-structure. The increase in the Cd content to ~40% is accompanied by formation of the NiCd{sub 5} intermetallide phase, along with a solid solution. In the 40–50% Cd content range, the main phases are NiCd{sub 5}, as well as a fcc-phase containing up to 18% Cd and characterized by a strong broadening of the diffraction maxima caused by the presence of 2–3 nm crystallites. Furthermore, the system of such composition contains a previously unknown non-stoichiometric phase based on Ni{sub 3}Cd, having a similar to Cu{sub 3}Au structure. The results serve to clarify compositions of reduction products and the character of the structural-phase transformations of the intermediate hydroxides and metal products during the reduction process. Based on the obtained data, we proposed a formation scheme for the phases that are unconventional for the studied composition region of the Ni-Cd system. It has been concluded that the main factors determining formation of the reduction products are particle nanoscale dimensionality and occurrence of the reduction process far from equilibrium.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Ligand-Free Processable Perovskite Semiconductor Ink

We report traditional covalent semiconductors require complex processing methods for device fabrication due to their high cohesive energies. Here, we develop a stable, ligand-free perovskite semiconductor ink that can be used to make patterned semiconductor-based optoelectronics in one step. The perovskite ink is formed via the dissolution of crystals of vacancy-ordered double perovskite Cs 2 TeX 6 (X = Cl - , Br - , I - ) in polar aprotic solvents, leading to the stabilization of isolated [TeX 6 ] 2- octahedral anions and free Cs + cations without the presence of ligands. The stabilization of the fundamental perovskite ionic octahedral building blocks in solution creates multifunctional inks with the ability to reversibly transform between the liquid ink and the solid-state perovskite crystalline system in air within minutes. These easily processable inks can be patterned onto various materials via dropcasting, spraying or painting, and stamping, highlighting the crucial role of solvated octahedral complexes toward the rapid formation of phase-pure perovskite structures in ambient conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A new approach for simulating inhomogeneous chemical kinetics

Abstract In this paper, inhomogeneous chemical kinetics are simulated by describing the concentrations of interacting chemical species by a linear expansion of basis functions in such a manner that the coupled reaction and diffusion processes are propagated through time efficiently by tailor-made numerical methods. The approach is illustrated through modelling $$\alpha$$ α - and $$\gamma$$ γ -radiolysis in thin layers of water and at their solid interfaces from the start of the chemical phase until equilibrium was established. The method’s efficiency is such that hundreds of such systems can be modelled in a few hours using a single core of a typical laptop, allowing the investigation of the effects of the underlying parameter space. Illustrative calculations showing the effects of changing dose-rate and water-layer thickness are presented. Other simulations are presented which show the approach’s capability to solve problems with spherical symmetry (an approximation to an isolated radiolytic spur), where the hollowing out of an initial Gaussian distribution is observed, in line with previous calculations. These illustrative simulations show the generality and the computational efficiency of this approach to solving reaction-diffusion problems. Furthermore, these example simulations illustrate the method’s suitability for simulating solid-fluid interfaces, which have received a lot of experimental attention in contrast to the lack of computational studies.

97 MATHEMATICS AND COMPUTING↗

Crystallization and thermophysical properties of Cu{sub 46}Zr{sub 47}Al{sub 6}Co{sub 1} bulk metallic glass

Phase evolution of two-step crystallization and the subsequent B2-phase transformation was presented in Cu{sub 46}Zr{sub 47}Al{sub 6}Co{sub 1} bulk metallic glass (BMG) during heating process. Thermophysical properties, i.e. the thermal diffusivity and the specific heat capacity, of the BMG in amorphous solid state and supercooled liquid state as well as its crystalline counterparts were measured from room temperature to 1070 K. The thermal conductivity was also calculated through combination of the data of the thermal diffusivity and the specific heat capacity. The possible influence of the crystallization on the thermophysical properties was discussed.

36 MATERIALS SCIENCE↗

Low temperature dielectric and impedance studies on magnetoelectric Pb(Fe{sub 0.5}Nb{sub 0.5})O{sub 3} ceramic

The structural, microstructural, low temperature dielectric and impedance properties of Pb(Fe{sub 0.5}Nb{sub 0.5})O{sub 3} (PFN) ceramic prepared by single step solid-state reaction method have been investigated. Processing parameters such as calcination, sintering temperature and sintering durations were optimized to get better dielectric properties. It was found that the above ceramics sintered at 1050 °C for 4 hr exhibited single phase, maximum density and uniform microstructure. X-ray diffraction (XRD) and neutron diffraction (ND) reveals that the system exhibit single phase without any kind of secondary phases at room temperature (RT) with monoclinic crystal structure (Cm). Surface morphology of the compounds was studied by Scanning electron microscope (SEM). Impedance spectroscopy is used to study the electrical behaviour of PFN in the frequency range from 100Hz to 1MHz and in the temperature range from 120 to 293 K. The frequency-dependent electrical data are analyzed by impedance formalisms. The complex impedance shows the relaxation (conduction) mechanism in the sample.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

ECO2N V. 2.0: A New TOUGH2 Fluid Property Module for Mixtures of Water, NaCl, and CO 2

ECO2N V2.0 is a fluid property module for the TOUGH2 simulator (Version 2.1) that was designed for applications to geologic sequestration of CO 2 in saline aquifers and enhanced geothermal reservoirs. ECO2N V2.0 is an enhanced version of the previous ECO2N V1.0 module (Pruess, 2005). It expands the temperature range up to about 300°C whereas V1.0 can only be used for temperatures below about 110°C. V2.0 includes a comprehensive description of the thermodynamics and thermophysical properties of H 2 O - NaCl -CO 2 mixtures, that reproduces fluid properties largely within experimental error for the temperature, pressure and salinity conditions of interest (10 °C < T < 300 °C; P < 600 bar; salinity up to halite saturation). This includes density, viscosity, and specific enthalpy of fluid phases as functions of temperature, pressure, and composition, as well as partitioning of mass components H 2 O, NaCl and CO 2 among the different phases. In particular, V2.0 accounts for the effects of water on the thermophysical properties of the CO 2 -rich phase, which was ignored in V1.0, using a model consistent with the solubility models developed by Spycher and Pruess (2005, 2010). In terms of solubility models, V2.0 uses the same model for partitioning of mass components among the different phases (Spycher and Pruess, 2005) as V1.0 for the low temperature range (<99°C) but uses a new model (Spycher and Pruess, 2010) for the high temperature range (>109°C). In the transition range (99-109°C), a smooth interpolation is applied to estimate the partitioning as a function of the temperature. Flow processes can be modeled isothermally or non-isothermally, and phase conditions represented may include a single (aqueous or CO 2 -rich) phase, as well as two-phase mixtures. Fluid phases may appear or disappear in the course of a simulation, and solid salt may precipitate or dissolve. This report gives technical specifications of ECO2N V2.0 and includes instructions for preparing input data

15 GEOTHERMAL ENERGY↗

Experimental and Computational Investigation of High Entropy Alloys for Elevated-Temperature Applications

To create and design novel structural materials with enhanced creep-resistance, fundamental studies have been conducted on high-entropy alloys (HEAs), using (1) thermodynamic calculations, (2) mechanical tests, (3) neutron diffraction, (4) characterization techniques, and (5) crystal-plasticity finite-element modeling (CPFEM), to explore future candidates for next-generation power plants. All the constituent binary and ternary systems of the Al-Cr-Cu-Fe-Mn-Ni and Al-Co-Cr-Fe-Ni systems were thermodynamically modeled within the whole composition range. Comparisons between the calculated phase diagrams and literature data are in good agreement. Seven types of HEAs were fabricated from Al-Cr-Cu-Fe-Mn-Ni and Al-Co-Cr-Fe-Ni systems. The Al x CrCuFeMnNi HEAs have disordered [face-centered cubic (FCC) + body-centered cubic (BCC)] crystal structures, not FCC or BCC single structure. Excessive alloying of the Al element results in the change of both microstructural and mechanical properties in Al x CoCrFeNi HEAs. There are mainly three structural features in Al x CoCrFeNi: (1) the morphology, (2) the volume fractions of the constitute phases, and (3) existing temperatures of all six phases. After homogenization, the Al 0.3 CoCrFeNi material is a pure FCC solid solution. After aging at 700 °C for 500 hours, the optimal microstructure combinations, the FCC matrix, needle-like B2 phase within grains, and granular σ phase along grain boundary, is achieved for Al 0.3 CoCrFeNi. The cold-rolling process is utilized to reduce the grain size of Al 0.1 CoCrFeNi and Al 0.3 CoCrFeNi. The chemical elemental partitioning of FCC, BCC, B2, and σphases at different temperatures, before and after mechanical tests, in Al-Cr-Cu-Fe-Mn-Ni and Al-Co-Cr-Fe-Ni systems are quantitatively characterized by both synchrotron X-ray diffraction, neutron diffraction with levitation, scanning electron microscopy (SEM), advanced atom probe tomography (APT), and transmission electron microscopy (TEM). In-situ neutron diffraction experiments were conducted to study the strengthening effect of B2 phase on tensile properties of Al 0.3 CoCrFeNi HEAs directly. The results shows the creep behavior of Al 0.3 CoCrFeNi is superior to conventional alloys, and the heat treatment introduces secondary B2 phase into the FCC matrix, which increase the yielding strength, decrease the ductility, diminish the serrated flow during compression tests at high temperatures. In summary, the outcomes of the development of the HEAs with creep resistance include: (1) Suitable candidates, for the application to boilers and steam and gas turbines at temperatures above 760 °C and a stress of 35 MPa. (2) Fundamental understanding on the precipitate stability and deformation mechanisms of both single-phase and precipitate-strengthened alloys at room and elevated temperatures, and (3) The demonstration of an integrated approach, coupling modeling [thermodynamic calculations and crystal-plasticity finite-element modeling (CPFEM)] and focused experiments, to identify HEAs that outperform conventional alloys for high-temperature applications, which will be applicable for the discovery and development of other high-temperature materials in the power-generating industry.

36 MATERIALS SCIENCE↗

Granular Temperature Modeling with Large-Scale CFD-DEM Data

The granular temperature is a measure of solids-phase fluctuating kinetic energy in particle-laden gas-solid flows. This report focuses on reduced-order models of granular temperature in triply-periodic cluster induced turbulent flow. The granular temperature data was generated by post-processing large-scale CFD-DEM simulations that were carried out as part of an ALCC awarded study. The algebraic model of Tang et al, originally fit to DNS data, was found to be amenable to the present data. The results of several regression analyses are presented building on the original expression. This work was performed in part through the National Nuclear Security Administration (NNSA) Minority Serving Institutions Internship Program (MSIIP).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Leaching of Rare Earth Elements from Central Appalachian Coal Seam Underclays

Rare earth elements (REE) are necessary for advanced technological and energy applications. To support the emerging need, it is necessary to identify new domestic sources of REE and technologies to separate and recover saleable REE product in a safe and economical manner. Underclay rock associated with Central Appalachian coal seams and prevalent in coal utilization waste products is an alternative source of REE to hard rock ores that are mainly composed of highly refractory REE-bearing minerals. This study utilizes a suite of analytical techniques and benchtop leaching tests to characterize the properties and leachability of the coal seam underclays sampled. Laboratory bench-top and flow-through reactor leaching experiments were conducted on underclay rock powders to produce a pregnant leach solution (PLS) that has relatively low concentrations of gangue elements Al, Si, Fe, and Th and is amenable to further processing steps to recover and produce purified REE product. The leaching method described here uses a chelating agent, the citrate anion, to solubilize elements that are adsorbed, or weakly bonded to the surface of clay minerals or other mineral solid phases in the rock. The citrate PLS produced from leaching specific underclay powders contains relatively higher concentrations of REE and lower concentrations of gangue elements compared to PLS produced from sequential digestion using ammonium sulfate and mineral acids. Citrate solution leaching of underclay produces a PLS with lower concentrations of gangue elements and higher concentrations of REE than achieved with hydrochloric acid or sulfuric acid. The results provide a preliminary assessment of the types of REE-bearing minerals and potential leachability of coal seam underclays from the Central Appalachian basin.

58 GEOSCIENCES↗