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At least 1,387 records · Page 77

Development of neural network force fields for corrosion studies

To fully understand the chemistry and physics of corrosion, novel methods of simulation must be developed. One approach is designing machine learning (ML) algorithms integrated with density functional theory to develop adaptive force fields to gain insight into corrosion behavior namely at the surface of metal oxides. Current methods of modeling corrosion are slow due to the computational cost of resolving both reaction mechanics and mass transport processes. Machine learning methods can be implemented to obtain structure-activity relationships at both the molecular and bulk scale while still retaining the accuracy of density functional theory (DFT) and significantly decreasing the time needed for simulations of complex chemical processes in the various environments of corrosion. Multiscale models are needed for corrosion studies to fully understand its processes not only at the atomic length scale (chemical bonding, energies, and forces), but also at the nano and meso length scales (solid-state physics and material science processes). Current methods of study include DFT, molecular dynamics, and Monte Carlo. The limitation of DFT is that only a small number of atoms or molecules can be simulated at that level of theory. Density functional theory is used to study the electronic structure of atoms and molecules, and calculate the force component of each atom. However, these calculations are limited to about 1000 atoms. Custom periodic boundary conditions (PBC) can be used to describe the various environments and defects that affect the atomic forces to produce a large data set from which a training set can be derived. Machine learning can be utilized to overcome the barrier of modeling macroscopic and multi-scale processes from ab initio calculations through the development of adaptive force fields. Local environments determine the atomic forces of a given system, therefore adaptive force fields must be created to produce reliable quantum mechanical calculations. This can be achieved by developing a learning algorithm that uses the mapped atomic forces or fingerprint as an input to produce energies and magnetic moments as output. A systematic approach was used to begin to build a data set in order to accurately describe the atomic forces in various environments. In Figure 4 below, a simple PBC cell of Fe{sub 2}O{sub 3} was first optimized. A surface optimization was performed next, followed by a hydroxylated surface optimization. Once this calculation has converged, the adsorption of halide species to the hydroxylated surface will be investigated. TensorFlow is an open source platform for machine learning developed by Google. Using a high level application program interface (API) such as Keras allows for building and training ML models easily in a number of different environments and languages. For this project, a neural network was developed within Anaconda in Python. Future Work: Further development of reference data set; Refining neural network and learning algorithm; Fingerprinting atomic environment to enable mapping of atomic force components; Choosing appropriate training set from reference data; Learning from training set and enabling non-linear mapping of training set fingerprints and the atomic forces; Estimation of uncertainty to identify ranges of outside applicability; Testing and analysis of molecular dynamic simulations.

36 MATERIALS SCIENCE↗

Reactive, anomalous compression in shocked polyurethane foams

We present the results of plate impact experiments performed on 30%–75% porous, polymeric methylene diphenyl diisocyanate polyurethane foams. The combination of new data with those previously obtained on full-density material was used to calibrate complete equations-of-state under both inert and chemically reactive frameworks. Description of unreacted polyurethane was based on a combination of Hayes and P-α models, whereas its decomposition products were predicted via free energy minimization under the assumption of chemical and thermodynamic equilibrium. Correspondence of experiment and theory suggests that polyurethane at all densities decomposes when shocked above some threshold pressure, and that this threshold falls dramatically as a function of initial porosity. The shock locus of foams at 50% or less of theoretical maximum density was found “anomalous” in the sense that final volumes increased with pressure. We attribute this anomaly to chemical decomposition of the initial matrix to a mixture of small-molecule fluids and bulk carbon (graphite or diamond, depending on the initial density)

36 MATERIALS SCIENCE↗

Water Dissociates at the Aqueous Interface with Reduced Anatase TiO 2 (101)

Elucidating the structure of the interface between natural (reduced) anatase TiO 2 (101) and water is an essential step toward understanding the associated photoassisted water splitting mechanism. In this work we present surface X-ray diffraction results for the room temperature interface with ultrathin and bulk water, which we explain by reference to density functional theory calculations. We find that both interfaces contain a 25:75 mixture of molecular H 2 O and terminal OH bound to titanium atoms along with bridging OH species in the contact layer. This is in complete contrast to the inert character of room temperature anatase TiO 2 (101) in ultrahigh vacuum. A vital difference between the ultrathin and bulk water interfaces is that in the latter water in the second layer is also ordered. These molecules are hydrogen bonded to the contact layer, modifying the bond angles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spin transition of ferric iron in the calcium-ferrite type aluminous phase

We investigated Fe-free and Fe-bearing CF phases using nuclear forward scattering and X-ray diffraction coupled with diamond anvil cells up to 80 GPa at room temperature. Octahedral Fe 3+ ions in the Fe-bearing CF phase undergo a high-spin to low-spin transition at 25–35 GPa, accompanied by a volume reduction of ~2.0% and a softening of bulk sound velocity up to 17.6%. Based on the results of this study and our previous studies, both the NAL and CF phases, which account for 10–30 vol % of subducted MORB in the lower mantle, are predicted to undergo a spin transition of octahedral Fe 3+ at lower mantle pressures. Spin transitions in these two aluminous phases result in an increase of density of 0.24% and a pronounced softening of bulk sound velocity up to 2.3% for subducted MORB at 25–60 GPa and 300 K. The anomalous elasticity region expands and moves to 30–75 GPa at 1200 K and the maximum of the V Φ reduction decreases to ~1.8%. This anomalous elastic behavior of Fe-bearing aluminous phases across spin transition zones may be relevant in understanding the observed seismic signatures in the lower mantle.

58 GEOSCIENCES↗

Nucleation and Initial Stages of Growth during the Atomic Layer Deposition of Titanium Oxide on Mesoporous Silica

A chemical approach to the deposition of thin films on solid surfaces is highly desirable but prone to affect the final properties of the film. To better understand the origin of these complications, the initial stages of the atomic layer deposition of titania films on silica mesoporous materials were characterized. Adsorption-desorption measurements indicated that the films grow in a layer-by-layer fashion, as desired, but initially exhibit surprisingly low densities, about one-quarter of that of bulk titanium oxide. Electron microscopy, X-ray diffraction, UV/visible, and X-ray absorption spectroscopy data pointed to the amorphous nature of the first monolayers, and EXAFS and 29 Si CP/MAS NMR results to an initial growth via the formation of individual tetrahedral Ti-oxide units on isolated Si-OH surface groups with unusually long Ti-O bonds. Here, density functional theory calculations were used to propose a mechanism where the film growth starts at the nucleation centers to form an open 2D structure.

36 MATERIALS SCIENCE↗

Strain-induced modification in the magnetic properties of Mn{sub 5}Ge{sub 3} thin films

Epitaxial ferromagnetic Mn{sub 5}Ge{sub 3} thin films were stabilized on GaSb(001) and GaAs(001) substrates using molecular beam epitaxy. Compared to bulk Mn{sub 5}Ge{sub 3} materials, an enhancement of the Curie temperature above 350 K and about 320 K was observed for Mn{sub 5}Ge{sub 3}/GaAs(001) and Mn{sub 5}Ge{sub 3}/GaSb(001) heterostructures, respectively. The magnetization was found to decrease from 323 to 245 emu/cm{sup 3} for films grown on GaSb(001) and GaAs(001). Anomalous Hall effect measurements provide evidence of the strain-induced large spin polarization from density-functional study. Furthermore, our calculated results in bulk Mn{sub 5}Ge{sub 3} under strain indicate that the strain is the origin of different physical properties of Mn{sub 5}Ge{sub 3} grown on different substrates.

36 MATERIALS SCIENCE↗

Exploiting Symmetry Mismatch to Control Magnetism in a Ferroelastic Heterostructure

In the bulk, LaCoO 3 (LCO) is a paramagnet, yet the low-temperature ferromagnetism (FM) is observed in tensile strained thin films, and its origin remains unresolved. Here, we quantitatively measured the distribution of atomic density and magnetization in LCO films by polarized neutron reflectometry (PNR) and found that the LCO layers near the heterointerfaces exhibit a reduced magnetization but an enhanced atomic density, whereas the film's interior (i.e., its film bulk) shows the opposite trend. We attribute the nonuniformity to the symmetry mismatch at the interface, which induces a structural distortion related to the ferroelasticity of LCO. This assertion is tested by systematic application of hydrostatic pressure during the PNR experiments. The magnetization can be controlled at a rate of -20.4% per GPa. Here, these results provide unique insights into mechanisms driving FM in strained LCO films while offering a tantalizing observation that tunable deformation of the CoO 6 octahedra in combination with the ferroelastic order parameter.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Light propagation in stratified media with soft interfaces

The propagation of light through materials in which the density of charge carriers varies smoothly on a scale smaller than or comparable to the wavelength requires a description that goes beyond the commonly used Fresnel equations. We propose a method to solve Maxwell’s equations in such a way that any linear response theory for the bulk material can be combined with a given smooth density profile for the (free or bound) charge carriers. This method is implemented for linearly polarized monochromatic light impinging on inhomogeneous multilayer systems, leading to a fast algorithm that yields reflectance and transmittance for such systems. We apply our algorithm to investigate the difference in optical response between smooth interfaces and abrupt interfaces in stratified systems where the materials can have complex bulk permittivities, and find that the smoothening of the interface on a wavelength scale significantly reduces reflection in favor of absorption. This result is of importance to current experiments that aim to detect metallic hydrogen and deuterium films using their optical response. Furthermore, our results show that for a correct interpretation of these experiments it is important to consider the smoothness of the density profile of the metallic layer. Also, for nonabsorbing layers, a smooth, rather than abrupt transition, can have an important impact on the design of optical filters.

08 HYDROGEN↗

Small-Scale Density Variations in the Lunar Crust Revealed by GRAIL

Data from the Gravity Recovery and Interior Laboratory (GRAIL) mission have revealed that approximately 98 percent of the power of the gravity signal of the Moon at high spherical harmonic degrees correlates with the topography. The remaining 2 percent of the signal, which cannot be explained by topography, contains information about density variations within the crust. These high-degree Bouguer gravity anomalies are likely caused by small-scale (10's of km) shallow density variations. Here we use gravity inversions to model the small-scale three-dimensional variations in the density of the lunar crust. Inversion results from three non-descript areas yield shallow density variations in the range of 100-200 kg/m3. Three end-member scenarios of variations in porosity, intrusions into the crust, and variations in bulk crustal composition were tested as possible sources of the density variations. We find that the density anomalies can be caused entirely by changes in porosity. Characteristics of density anomalies in the South Pole-Aitken basin also support porosity as a primary source of these variations. Mafic intrusions into the crust could explain many, but not all of the anomalies. Additionally, variations in crustal composition revealed by spectral data could only explain a small fraction of the density anomalies. Nevertheless, all three sources of density variations likely contribute. Collectively, results from this study of GRAIL gravity data, combined with other studies of remote sensing data and lunar samples, show that the lunar crust exhibits variations in density by plus or minus 10 percent over scales ranging from centimeters to 100’s of kilometers.

J C Jansen↗

Neutron activation diagnostics at the National Ignition Facility (invited)

Neutron yields are measured at the National Ignition Facility (NIF) by an extensive suite of neutron activation diagnostics. Neutrons interact with materials whose reaction cross sections threshold just below the fusion neutron production energy, providing an accurate measure of primary unscattered neutrons without contribution from lower-energy scattered neutrons. Indium samples are mounted on diagnostic instrument manipulators in the NIF target chamber, 25-50 cm from the source, to measure 2.45 MeV deuterium-deuterium fusion neutrons through the {sup 115}In(n,n'){sup 115m} In reaction. Outside the chamber, zirconium and copper are used to measure 14 MeV deuterium-tritium fusion neutrons via {sup 90}Zr(n,2n), {sup 63}Cu(n,2n), and {sup 65}Cu(n,2n) reactions. An array of 16 zirconium samples are located on port covers around the chamber to measure relative yield anisotropies, providing a global map of fuel areal density variation. Neutron yields are routinely measured with activation to an accuracy of 7% and are in excellent agreement both with each other and with neutron time-of-flight and magnetic recoil spectrometer measurements. Relative areal density anisotropies can be measured to a precision of less than 3%. These measurements reveal apparent bulk fuel velocities as high as 200 km/s in addition to large areal density variations between the pole and equator of the compressed fuel.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Clustering and pasta phases in nuclear density functional theory

Nuclear density functional theory is the tool of choice in describing properties of complex nuclei and intricate phases of bulk nucleonic matter. It is a microscopic approach based on an energy density functional representing the nuclear interaction. An attractive feature of nuclear DFT is that it can be applied to both finite nuclei and pasta phases appearing in the inner crust of neutron stars. While nuclear pasta clusters in a neutron star can be easily characterized through their density distributions, the level of clustering of nucleons in a nucleus can often be difficult to assess. To this end, we use the concept of nucleon localization. We demonstrate that the localization measure provides us with fingerprints of clusters in light and heavy nuclei, including fissioning systems. Furthermore we investigate the rod-like pasta phase using twist-averaged boundary conditions, which enable calculations in finite volumes accessible by state of the art DFT solvers.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Band structure, superconductivity, and polytypism in AuSn 4

The orthorhombic compound AuSn 4 is compositionally similar to the Dirac node arc semimetal PtSn 4 . AuSn 4 is, contrary to PtSn 4 , superconducting with a critical temperature of T c = 2.35 K. Recent measurements present indications for quasi-two-dimensional superconducting behavior in AuSn 4 . Here we present measurements of the superconducting density of states and the band structure of AuSn 4 through scanning tunneling microscopy and angular resolved photoemission spectroscopy (ARPES). The superconducting gap values in different portions of the Fermi surface are spread around Δ 0 = 0.4 meV, which is close to but somewhat larger than Δ = 1.76k B T c expected from BCS theory. We observe superconducting features in the tunneling conductance at the surface up to temperatures about 20% larger than bulk T c . The band structure calculated with density functional theory follows well the results of ARPES. The crystal structure presents two possible stackings of Sn layers, giving two nearly degenerate polytypes. This makes AuSn 4 a rather unique case with a three-dimensional electronic band structure but properties ressembling those of low-dimensional layered compounds.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Quantum Ornstein-Zernike theory for two-temperature two-component plasmas

Laboratory plasma production almost always preferentially heats either the ions or electrons, leading to a two-temperature state. In this state, density functional theory molecular dynamic simulation is the state of the art for modeling bulk material properties. We construct a statistical mechanics model for the two temperature limit that is theoretically consistent with the molecular dynamics method. We proceed to derive the electron-ion multi-temperature quantum Ornstein-Zernike equations for the first time. This allows the construction of a two-temperature two-component plasma model using the average atom from which we can compute bulk material properties at a fraction of the computation time of the two-temperature density functional theory simulation. The accuracy of the model is benchmarked against ion pair correlation and self-diffusion results from ab initio simulation. Here, we proceed to compute the viscosity and ion thermal conductivity as a function of both ion and electron temperature.

Ab initio molecular dynamics↗

Tailoring Interfaces in Solid-State Batteries Using Interfacial Thermochemistry and Band Alignment

Solid-state lithium ion batteries have enhanced thermal stability compared to batteries using liquid electrolytes. Although their practical implementation is limited by undesired side reactions between the electrode and electrolyte, different modification strategies have been proposed to stabilize these reactive interfaces. These approaches have been primarily based upon bulk materials properties, however, which may not necessarily be representative of the chemistry at the solid/solid interface. In this work, first principles calculations and X-ray scattering experiments are used to elucidate molecular-level reactivity and develop design principles for tailored interfaces based on surface and interfacial properties. Because of its well-known instability, the interface between the Li metal anode and the lithium lanthanum titanate (LLTO) solid electrolyte is applied as a model system. Density functional theory calculations are used to describe bulk, surface, and interfacial thermochemistry of the Li/LLTO system, and interfacial reconstruction is probed using ab initio molecular dynamics. These simulations of the Li/LLTO interface demonstrate facile decomposition concomitant with reduction of Ti 4+ ions. Based on further insights from computational analysis of the surface band edge positions, La 2 O 3 is proposed as an interlayer coating and is shown to provide an energetic barrier for interfacial charge transfer and decomposition reactions from X-ray reflectivity measurements and theoretical calculations. The findings in this work suggest that design strategies based on surface and interfacial properties can be used to kinetically stabilize electrode/electrolyte interfaces in solid-state batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Incorporating Electrochemical Halide Oxidation into Drift-Diffusion Models to Explain Performance Losses in Perovskite Solar Cells under Prolonged Reverse Bias

Partial shading of a solar module can induce a set of cells within the module to operate under reverse bias. Studies have shown that metal halide perovskite solar cells with a wide variety of compositions and contacts exhibit interesting behavior in reverse bias that includes both reversible performance loss and non-reversible degradation. In this paper, an advanced drift-diffusion approach incorporating an electrochemical term to explain the short-circuit, open circuit and fill factor losses that are experimentally measured after prolonged reverse bias is used. It is shown that holes can tunnel into the perovskite due to sharp band bending near the contact, accumulate within the bulk of the perovskite absorber, and trigger the oxidation of halides to form neutral halogens. The density of neutral halogens is much higher in reverse bias because there are hardly any electrons available to reduce the iodine. The resulting halogens act as bulk recombination centers. While the interstitial halogen density does decay when the cell is operated in forward bias, permanent degradation can occur if the iodine diffuses out of the perovskite layer. Finally, the ways in which changing parameters such as the mobile ion density or the series resistance at the contact can influence device performance and stability are discussed.

degradation↗

Emergence of charge density waves and a pseudogap in single-layer TiTe 2

Two-dimensional materials constitute a promising platform for developing nanoscale devices and systems. Their physical properties can be very different from those of the corresponding three-dimensional materials because of extreme quantum confinement and dimensional reduction. Here in this paper we report a study of TiTe 2 from the single-layer to the bulk limit. Using angle-resolved photoemission spectroscopy and scanning tunneling microscopy and spectroscopy, we observed the emergence of a (2 × 2) charge density wave order in single-layer TiTe 2 with a transition temperature of 92 ± 3 K. Also observed was a pseudogap of about 28 meV at the Fermi level at 4.2 K. Surprisingly, no charge density wave transitions were observed in two-layer and multi-layer TiTe 2 , despite the quasi-two-dimensional nature of the material in the bulk. The unique charge density wave phenomenon in the single layer raises intriguing questions that challenge the prevailing thinking about the mechanisms of charge density wave formation.

36 MATERIALS SCIENCE↗

Development of Bulk Nanocrystalline Tungsten Alloys for Fusion Reactor Structures

This project developed a technology for manufacturing bulk ultrafine tungsten materials that are at or near full density for fusion reactor structural applications, aiming to improve ductility and toughness of tungsten before and after irradiation. The project involved the development of fabrication processes for making bulk ultrafine grained W, the development of new alloys of ultrafine grained W and evaluations of properties of these specific materials. The goal of this fabrication process is to produce fully dense bulk W with ultrafine grain sizes, with uniform distributions of grain size and additives. To date there is no known process that could be used to make ultrafine grained tungsten in a fully dense state and in a cost-acceptable fashion. The specific technology described in this proposal for making ultrafine grained tungsten involves a suite of nano-particle processing and sintering techniques. The program also developed new alloys of ultrafine grained W, e.g. W-(Ta,V,Ti)-TiC alloys to improve ductility and toughness before and after irradiation. By completing this project, we achieved the following objectives: • Demonstrated experimentally the feasibility of producing bulk ultrafine grained tungsten alloys (at or near 100% dense, <1000 nm grain size) using the proposed process • Demonstrated the proposed ultrafine grained W alloys, namely, W-(Ta, V, Ti)-TiC, can indeed be made using the proposed process • Demonstrated that the properties of nano tungsten alloys meet the requirements for fusion reactor applications. The overall goal was to harness the potential of ultrafine grained W produced using the proposed processes as the core structural materials for future fusion reactors. The project was very successful overall, meeting all milestones and surpassing project goals in terms of process development and material’s blistering resistance properties. A novel process similar to the conventional press-and-sinter powder metallurgy method was developed for producing ultrafine grain tungsten from nanosize tungsten powders. Grain growth was significantly controlled during sintering by certain alloy compositions, particularly Ti, and most compositions sintered to maximum densification. To optimize this process, the effect of processing parameters on the densification and grain growth of nano-W powders was investigated. Near-fully densified tungsten was obtained at sintering temperatures between 1100 and 1300 °C, and both Ar and H2 sintering atmospheres were investigated. The Ar sintering atmosphere was determined to more favorably promote densification and minimize grain growth. The nanosized tungsten powder compacts were subjected to reduction in H2 as a part of the sintering cycle. The reduction temperature was found to have significant effects on the sintering of nano-W powder, primarily as a result of grain coarsening, which was seen at temperatures as low as 700 °C. In an effort to inhibit grain growth, the effect of Ti-based additives on the densification and grain growth of nano-W powders was investigated in this project. The addition of 1 wt.% Ti into tungsten led to more than a 63% decrease in average grain size of sintered samples at comparable density levels. Compared to conventional high temperature sintering, a lower temperature sintering cycle for a longer hold time resulted in both near-full density and fine grain size. The roles of the Ti additives include not only the inhibition of grain growth, but also the potential absorption of oxygen from W particles. The project has resulted in the publication; thus far, of six peer reviewed journal articles and seven conference presentations, as well as a master’s thesis. Two additional journal articles are currently in preparation. Presentations and articles were a particular focus of the second half of the project, once significant experimentation had been performed and analyzed. As part of our efforts to disseminate information of our results, the W research teams with Prof. Fang had a strong presence at multiple international conferences during 2015 and 2016. Several research groups in the US are now performing experiments using the ultrafine grained W materials.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Adsorption of simple square-well fluids in slit nanopores: Modeling based on Generalized van der Waals partition function and Monte Carlo simulation

A model based on the Generalized van der Waals partition function is derived to predict the adsorption of square-well fluid in slit pores of any size, the walls of which also have square-well potential. The space inside the pore is divided into several regions based on the extent of the attractive regions generated by the walls. Closed-form expressions of the chemical potentials of the confined fluid in different regions in the pore are obtained. The densities of fluid in different regions are calculated by equalizing the chemical potentials of fluid in those regions to that of the bulk phase. To examine the accuracy of the model, the Grand Canonical Monte Carlo (GCMC) simulation is also conducted. Here we find that the model well captures the effects of the bulk conditions and the properties of adsorbate and pore on the density of adsorbate in the pore. The model is also shown to be able to predict the adsorption of real gases in various activated carbons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗