The passivation of polycrystalline nickel surfaces against hydrogen uptake by oxygen is investigated experimentally with low energy ion scattering (LEIS), direct recoil spectroscopy (DRS), and thermal desorption spectroscopy (TDS). These techniques are highly sensitive to surface hydrogen, allowing the change in hydrogen adsorption in response to varying amounts of oxygen exposure to be measured. The chemical composition of a nickel surface during a mixed oxygen and hydrogen exposure was characterized with LEIS and DRS, while the uptake and activation energies of hydrogen on a nickel surface with preadsorbed oxygen were quantified with TDS. By and large, these measurements of how the oxygen and hydrogen surface coverage varied in response to oxygen exposure were found to be consistent with predictions of a simple site-blocking model. This finding suggests that, despite the complexities that arise due to polycrystallinity, the oxygen-induced passivation of a polycrystalline nickel surface against hydrogen uptake can be approximated by a simple site-blocking model.
Presented in this document are the theoretical aspects of capabilities contained in the Sierra/SM code. This manuscript serves as an ideal starting point for understanding the theoretical foundations of the code. For a comprehensive study of these capabilities, the reader is encouraged to explore the many references to scientific articles and textbooks contained in this manual. It is important to point out that some capabilities are still in development and may not be presented in this document. Further updates to this manuscript will be made as these capabilities come closer to production level.
Mishra, Lubhani; Jang, Taejin; Uppaluri, Maitri; Shah, Krishna; Roberts, Scott A.; Subramanian, Venkat R.
Electrochemical models at different scales and varying levels of complexity have been used in the literature to study the evolution of the anode surface in lithium metal batteries. This includes continuum, mesoscale (phase-field approaches), and multiscale models. In this paper, using a motivating example of a moving boundary model in one dimension, we show how battery models need proper formulation for mass conservation, especially when simulated over multiple charge and discharge cycles. The article concludes with some thoughts on mass conservation and proper formulation for multiscale models.
This report summarizes the current actives in FY21 related to the effort by Sandia National Laboratories to identify and test coating materials for the prevention, mitigation, and repair of spent nuclear fuel dry storage canisters against potential chloride-induced stress corrosion cracking. This work follows up on the details provided in Sandia National Laboratories FY20 report on the same topic, which provided a detailed description of the specific coating properties desired for application and implementation on spent nuclear fuel canisters, as well as provided detail into several different coatings and their applicability to coat spent nuclear fuel canisters. In FY21, Sandia National Laboratories has engaged with private industry to create a Memorandum of Understanding and established a collaborative R&D program building off the analytical and laboratory capabilities at Sandia National Laboratories and the material design and synthesis capabilities of private industry. The resulting Memorandum of Understanding included four companies to date (Oxford Performance Materials, White Horse R&D, Luna Innovations, and Flora Coating) proposing six different coating technologies (polyetherketoneketone, modified polyimide/polyurea, modified phenolic resin, silane-based polyurethane hybrid with and without a Znrich primer, and a quasi-ceramic sol-gel polyurethane hybrid) to be tested, evaluated, and optimized for their potential use for this application. This report provides a detailed description of each of the coating systems proposed by the participating industry partners. It also provides a description of the planned experimental actives to be performed by Sandia National Laboratories including physical tests, electrochemical tests, and characterization methods. These analyses will be used to identify specific ways to further improve coating technologies toward their application and implementation on spent nuclear fuel canisters. In FY21, Sandia National Laboratories began baseline testing of the base metal material in according with activities of the Memorandum of Understanding. In FY22, Sandia National Laboratories will receive coated coupons from each of the participating industry partners and begin characterization, physical, and electrochemical testing following the test plan described herein.
The finite element method is a scheme to discretize the infinite number of degrees of freedom in continuum-level problems down to a finite number of degrees of freedom. This discretization is done in conjunction with methods that also reduce the field differential equations to sets of algebraic ones that can be solved by arithmetical operations. Therefore, solutions attained by finite element models are approximations to the exact solutions of the field equations.
An ordinary state-based peridynamic material model is proposed for single sheet graphene. The model is calibrated using coarse grained molecular dynamics simulations. The coarse graining method allows the dependence of bond force on bond length to be determined, including the horizon. The peridynamic model allows the horizon to be rescaled, providing a multiscale capability and allowing for substantial reductions in computational cost compared with molecular dynamics. The calibrated peridynamic model is compared to experimental data on the deflection and perforation of a graphene monolayer by an atomic force microscope probe.
Evstatiev, E.G.; Finn, J.M.; Shadwick, B.A.; Hengartner, N.
In this paper we analyze the noise in macro-particle methods used in plasma physics and fluid dynamics, leading to approaches for minimizing the total error, focusing on electrostatic models in one dimension. We begin by describing kernel density estimation for continuous values of the spatial variable x, expressing the kernel in a form in which its shape and width are represented separately. The covariance matrix C(x,y) of the noise in the density is computed, first for uniform true density. The bandwidth of the covariance matrix is related to the width of the kernel. A feature that stands out is the presence of constant negative terms in the elements of the covariance matrix both on and off-diagonal. These negative correlations are related to the fact that the total number of particles is fixed at each time step; they also lead to the property ∫C(x,y)dy=0. We investigate the effect of these negative correlations on the electric field computed by Gauss's law, finding that the noise in the electric field is related to a process called the Ornstein-Uhlenbeck bridge, leading to a covariance matrix of the electric field with variance significantly reduced relative to that of a Brownian process. For non-constant density, ρ(x), still with continuous x, we analyze the total error in the density estimation and discuss it in terms of bias-variance optimization (BVO). For some characteristic length l, determined by the density and its second derivative, and kernel width h, having too few particles within h leads to too much variance; for h that is large relative to l, there is too much smoothing of the density. The optimum between these two limits is found by BVO. For kernels of the same width, it is shown that this optimum (minimum) is weakly sensitive to the kernel shape. We repeat the analysis for x discretized on a grid. In this case the charge deposition rule is determined by a particle shape. An important property to be respected in the discrete system is the exact preservation of total charge on the grid; this property is necessary to ensure that the electric field is equal at both ends, consistent with periodic boundary conditions. We find that if the particle shapes satisfy a partition of unity property, the particle charge deposited on the grid is conserved exactly. Further, if the particle shape is expressed as the convolution of a kernel with another kernel that satisfies the partition of unity, then the particle shape obeys the partition of unity. This property holds for kernels of arbitrary width, including widths that are not integer multiples of the grid spacing. We show results relaxing the approximations used to do BVO optimization analytically, by doing numerical computations of the total error as a function of the kernel width, on a grid in x. The comparison between numerical and analytical results shows good agreement over a range of particle shapes. We discuss the practical implications of our results, including the criteria for design and implementation of computationally efficient particle shapes that take advantage of the developed theory.
A new generation of concentrating solar power (CSP) technologies is under development to provide dispatchable renewable power generation and reduce the levelized cost of electricity (LCOE) to 6 cents/kWh by leveraging heat transfer fluids (HTFs) capable of operation at higher temperatures and coupling with higher efficiency power conversion cycles. The U.S. Department of Energy (DOE) has funded three pathways for Generation 3 CSP (Gen3CSP) technology development to leverage solid, liquid, and gaseous HTFs to transfer heat to a supercritical carbon dioxide (sCO2) Brayton cycle. This paper presents the design and off-design capabilities of a 1 MWth sCO2 test system that can provide sCO2 coolant to the primary heat exchangers (PHX) coupling the high-Temperature HTFs to the sCO2 working fluid of the power cycle. This system will demonstrate design, performance, lifetime, and operability at a scale relevant to commercial CSP. A dense-phase high-pressure canned motor pump is used to supply up to 5.3 kg/s of sCO2 flow to the primary heat exchanger at pressures up to 250 bar and temperatures up to 715 °C with ambient air as the ultimate heat sink. Key component requirements for this system are presented in this paper.
The propagation of a wave pulse due to low-speed impact on a one-dimensional, heterogeneous bar is studied. Due to the dispersive character of the medium, the pulse attenuates as it propagates. This attenuation is studied over propagation distances that are much longer than the size of the microstructure. A homogenized peridynamic material model can be calibrated to reproduce the attenuation and spreading of the wave. The calibration consists of matching the dispersion curve for the heterogeneous material near the limit of long wavelengths. It is demonstrated that the peridynamic method reproduces the attenuation of wave pulses predicted by an exact microstructural model over large propagation distances.
Virtual prototyping in engineering design rely on modern numerical models of contacting structures with accurate resolution of interface mechanics, which strongly affect the system-level stiffness and energy dissipation due to frictional losses. High-fidelity modeling within the localized interfaces is required to resolve local quantities of interest that may drive design decisions. The high-resolution finite element meshes necessary to resolve inter-component stresses tend to be computationally expensive, particularly when the analyst is interested in response time histories. The Hurty/Craig-Bampton (HCB) transformation is a widely used method in structural dynamics for reducing the interior portion of a finite element model while having the ability to retain all nonlinear contact degrees of freedom (DOF) in physical coordinates. These models may still require many DOF to adequately resolve the kinematics of the interface, leading to inadequate reduction and computational savings. This study proposes a novel interface reduction method to overcome these challenges by means of system-level characteristic constraint (SCC) modes and properly orthogonal interface modal derivatives (POIMDs) for transient dynamic analyses. Both SCC modes and POIMDs are computed using the reduced HCB mass and stiffness matrices, which can be directly computed from many commercial finite element analysis software. Comparison of time history responses to an impulse-type load in a mechanical beam assembly indicate that the interface-reduced model correlates well with the HCB truth model. Localized features like slip and contact area are well-represented in the time domain when the beam assembly is loaded with a broadband excitation. The proposed method also yields reduced-order models with greater critical timestep lengths for explicit integration schemes.
Hypertriglyceridemia (HTG) is considered within the top 5 etiologies in acute pancreatitis (AP), but the association of serum triglyceride (TG) levels with the clinical course of AP remains controversial. This study aims to examine the effect of TG levels on severity of AP. Patients were enrolled prospectively through APPRENTICE. High TG levels were defined based on the Endocrine Society Clinical Practice Guidelines. HTG was categorized as mild (serum TG levels 150–199 mg/dL), moderate (200–999 mg/dL), severe (1,000–1,999 mg/dL), and very severe (≥2,000 mg/dL). Severity of AP was based on the revised Atlanta classification criteria. Additionally, early TG levels were measured in 764 subjects and found elevated in 342 (120 with mild; 176, moderate; and 46, severe/very severe HTG). Patients with increased TG levels were younger (age ≥60, 16.7 vs. 30.3%), more likely to be male (66.1 vs. 51.2%), with more frequent alcohol use (62.8 vs. 50.7%), and diabetes mellitus (30.2 vs. 12.3%; all p ≤ 0.005). Severe AP (24.9 vs. 10.0%), ICU admission (32.5 vs. 19.7%), and mortality (5.3 vs. 1.7%; all p ≤ 0.005) were more frequently seen in patients with elevated TG levels. Based on multivariable analysis, elevated TG levels were independently associated with severe AP (p < 0.05). This large multicenter study confirms that elevated TG levels are associated with severe disease regardless of AP etiology.
Barium titanate (BTO) is a ferroelectric perovskite material used in energy storage applications because of its high dielectric constant. A previous study showed that the dielectric constant for BTO nanoparticles drastically increases to over 15,000 at a particle size of 70 nm. This result is highly contested, but its implications to energy storage motivated our investigation into the dielectric constants of BTO nanoparticles that are incorporated into a polymer matrix. We developed a novel method of using image processing techniques on transmission electron microscope images of BTO-polymer nanocomposites. Data on the positions, shapes, sizes, and orientations of BTO nanoparticles were used to build more realistic computational models that simulate the dielectric behavior of the nanocomposites. Here, we investigate the relationship between regions of enhanced electric field and the composite dielectric constant.
Ultra-low voltage drop tunnel junctions (TJs) were utilized to enable multi-active region blue light emitting diodes (LEDs) with up to three active regions in a single device. The multi-active region blue LEDs were grown monolithically by metal-organic chemical vapor deposition (MOCVD) without growth interruption. This is the first demonstration of a MOCVD grown triple-junction LED. Optimized TJ design enabled near-ideal voltage and EQE scaling close to the number of junctions. This work demonstrates that with proper TJ design, improvements in wall-plug efficiency at high output power operation are possible by cascading multiple III-nitride based LEDs.
Upon extraction/injection of a large quantity of gas from/into a subsurface system in shale gas production or carbon sequestration, the gas pressure varies remarkably, which may significantly change the wettability of porous media involved. Mechanistic understanding of such changes is critical for designing and optimizing a related subsurface engineering process. Using molecular dynamics simulations, we have calculated the contact angle of a water droplet on various solid surfaces (kerogen, pyrophyllite, calcite, gibbsite, and montmorillonite) as a function of CO2 or CH4 gas pressure up to 200 atm at a temperature of 300 K. The calculation reveals a complex behavior of surface wettability alteration by gas pressure variation depending on surface chemistry and structure, and molecular interactions of fluid molecules with surfaces. As the CO2 gas pressure increases, a partially hydrophilic kerogen surface becomes highly hydrophobic, while a calcite surface becomes more hydrophilic. Considering kerogen and calcite being the major components of a shale formation, we postulate that the wettability alteration of a solid surface induced by a gas pressure change may play an important role in fluid flows in shale gas production and geological carbon sequestration.
The quantum k-Local Hamiltonian problem is a natural generalization of classical constraint satisfaction problems (k-CSP) and is complete for QMA, a quantum analog of NP. Although the complexity of k-Local Hamiltonian problems has been well studied, only a handful of approximation results are known. For Max 2-Local Hamiltonian where each term is a rank 3 projector, a natural quantum generalization of classical Max 2-SAT, the best known approximation algorithm was the trivial random assignment, yielding a 0.75-approximation. We present the first approximation algorithm beating this bound, a classical polynomial-time 0.764-approximation. For strictly quadratic instances, which are maximally entangled instances, we provide a 0.801 approximation algorithm, and numerically demonstrate that our algorithm is likely a 0.821-approximation. We conjecture these are the hardest instances to approximate. We also give improved approximations for quantum generalizations of other related classical 2-CSPs. Finally, we exploit quantum connections to a generalization of the Grothendieck problem to obtain a classical constant-factor approximation for the physically relevant special case of strictly quadratic traceless 2-Local Hamiltonians on bipartite interaction graphs, where a inverse logarithmic approximation was the best previously known (for general interaction graphs). Our work employs recently developed techniques for analyzing classical approximations of CSPs and is intended to be accessible to both quantum information scientists and classical computer scientists.
Seismic source modeling allows researchers both to simulate how a source that induces seismic waves interacts with the Earth to produce observed seismograms and, inversely, to infer what the time histories, sizes, and force distributions were for a seismic source given observed seismograms. In this report, we discuss improvements made in FY21 to our software as applies to both the forward and inverse seismic source modeling problems. For the forward portion of the problem, we have added the ability to use full 3-D nonlinear simulations by implementing 3-D time varying boundary conditions within Sandia’s linear seismic code Parelasti. Secondly, on the inverse source modeling side, we have developed software that allows us to invert seismic gradiometer-derived observations in conjunction with standard translational motion seismic data to infer properties of the source that may improve characterization in certain circumstances. First, we describe the basic theory behind each software enhancement and then demonstrate the software in action with some simple examples.
The localized corrosion of laser surface melted (LSM) 316L stainless steel is investigated by a combination of potentiodynamic anodic polarization in 0.1 M HCl and microscopic investigation of the initiation and propagation of localized corrosion. The pitting potential of LSM 316L is significantly lower than the pitting potential of wrought 316L. The LSM microstructure is highly banded as a consequence of the high laser power density and high linear energy density. The bands are composed of zones of changing modes of solidification, cycling between very narrow regions of primary austenite solidification and very wide regions of primary ferrite solidification. Pits initiate in the outer edge of each band where the mode of solidification is primary austenite plane front solidification and primary austenite cellular solidification. The primary austenite regions have low chromium concentration (and possibly low molybdenum concentration), which explains their susceptibility to pitting corrosion. The ferrite is enriched in chromium, which explains the absence of pitting in the primary ferrite regions. The presence of the low chromium regions of primary austenite solidification explains the lower pitting resistance of LSM 316L relative to wrought 316L. The influence of banding on localized corrosion is applicable to other rapidly solidified processes such as additive manufacturing.
We present a novel definition of variable-order fractional Laplacian on Rn based on a natural generalization of the standard Riesz potential. Our definition holds for values of the fractional parameter spanning the entire open set (0, n/2). We then discuss some properties of the fractional Poisson’s equation involving this operator and we compute the corresponding Green’s function, for which we provide some instructive examples for specific problems.
Sandia National Laboratories has performed testing on several Hyperion 5313A infrasound sensors in order to determine the length of time it takes for the sensors to thermally equilibrate under a variety of environmental conditions. The motivation for performing these tests is to aid in determining suitable procedures for station operators to follow when installing these sensors. The desired outcome is for the station operators to be able to determine more quickly and reliably whether the sensors are performing correctly at the time of installation.
This report summarizes work completed under the Laboratory Directed Research and Development (LDRD) project "Uncertainty Quantification of Geophysical Inversion Using Stochastic Differential Equations." Geophysical inversions often require computationally expensive algorithms to find even one solution, let alone propagating uncertainties through to the solution domain. The primary purpose of this project was to find more computationally efficient means to approximate solution uncertainty in geophysical inversions. We found multiple computationally efficient methods of propagating Earth model uncertainty into uncertainties in solutions of full waveform seismic moment tensor inversions. However, the optimum method of approximating the uncertainty in these seismic source solutions was to use the Karhunen-Love theorem with data misfit residuals. This method was orders of magnitude more computationally efficient than traditional Monte Carlo methods and yielded estimates of uncertainty that closely approximated those of Monte Carlo. We will summarize the various methods we evaluated for estimating uncertainty in seismic source inversions as well as work toward this goal in the realm of 3-D seismic tomographic inversion uncertainty.
Microstructures and corresponding properties of compacted powders ultimately depend on the mechanical response of individual particles. In principle, computational simulations can predict the results of powder compaction processes, but the selection of appropriate models for both particle–particle interactions and particle deformations across all relevant length scales remain nontrivial tasks, especially in material systems lacking detailed mechanical property information. The work presented here addresses these issues by conducting uniaxial compressions in situ inside of a scanning electron microscope to characterize the mechanical response of individual micron-sized particles of a molecular crystal, hexanitrohexaazaisowurtzitane (CL-20). This experimental approach enabled the collection of quantitative force and displacement data alongside simultaneous imaging to capture morphology changes. The results reveal information about elastic deformation, yield, plastic deformation, creep, and fracture phenomena. Accordingly, this work demonstrates a generalizable approach for assessing the mechanical response of individual micron-sized molecular crystal particles and utilizing those responses in particle-level models. Graphic abstract: [Figure not available: see fulltext.].
We present an experimental and numerical study of a terahertz metamaterial with a nonlinear response that is controllable via the relative structural arrangement of two stacked split ring resonator arrays. The first array is fabricated on an n-doped GaAs substrate, and the second array is fabricated vertically above the first using a polyimide spacer layer. Due to GaAs carrier dynamics, the on-resonance terahertz transmission at 0.4 THz varies in a nonlinear manner with incident terahertz power. The second resonator layer dampens this nonlinear response. In samples where the two layers are aligned, the resonance disappears, and the total nonlinear modulation of the on-resonance transmission decreases. The nonlinear modulation is restored in samples where an alignment offset is imposed between the two resonator arrays. Structurally tunable metamaterials and metasurfaces can therefore act as a design template for tunable nonlinear THz devices by controlling the coupling of confined electric fields to nonlinear phenomena in a complex material substrate or inclusion.
