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Electronic structure calculations of twisted multi-layer graphene superlattices

Quantum confinement endows two-dimensional (2D) layered materials with exceptional physics and novel properties compared to their bulk counterparts. Although certain two- and few-layer configurations of graphene have been realized and studied, a systematic investigation of the properties of arbitrarily layered graphene assemblies is still lacking. We introduce theoretical concepts and methods for the processing of materials information, and as a case study, apply them to investigate the electronic structure of multi-layer graphene-based assemblies in a high-throughput fashion. We provide a critical discussion of patterns and trends in tight binding band structures and we identify specific layered assemblies using low-dispersion electronic bands as indicators of potentially interesting physics like strongly correlated behavior. A combination of data-driven models for visualization and prediction is used to intelligently explore the materials space. This work more generally aims to increase confidence in the combined use of physics-based and data-driven modeling for the systematic refinement of knowledge about 2D layered materials, with implications for the development of novel quantum devices.

36 MATERIALS SCIENCE↗

Nanostructure, structural stability, and diffusion characteristics of layered coatings for heat-assisted magnetic recording head media

The intense laser heating in heat-assisted magnetic recording (HAMR) has been a major hindrance to HAMR technology from becoming commercially viable. Thermal damage of the near-field transducer (NFT) and write pole (WP) embedded in the trailing edge of the magnetic head due to failure of the protective carbon overcoat after prolonged heating at an elevated temperature are major obstacles. Therefore, the main objective of this study was to develop an effective coating method for HAMR heads. This was accomplished by introducing a new class of layered coatings consisting of ultrathin amorphous carbon (a-C) overcoat, adhesion (SiN) layer, and buffer (NiCr or TaO x ) layer sequentially deposited onto Au and FeCo base layers to mimic the layer stacking of NFT and WP elements, respectively. The structural stability of the a-C overcoats and diffusion characteristics of each comprising layer under conditions of heating at 350°C for 30 min in an Ar atmosphere were investigated by high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM), and electron energy loss spectroscopy (EELS). For most stacking configurations the HRTEM/STEM and EELS results generally revealed some layer intermixing and minute carbon atom rehybridization in the heated a-C overcoats. The findings of this investigation suggest that further optimization of the developed layered coatings can provide a viable solution to thermal damage of HAMR heads.

Science & Technology - Other Topics↗

Investigation of Coincidence Counting for Improving Minimal Detectable Activity of 110m Ag in Single Particle Gamma Analysis

Post-irradiation examination (PIE) of fuel particles from the fourth Advanced Gas Reactor Fuel Development and Qualification (AGR) Program irradiation (AGR-5/6/7) is being performed at Oak Ridge National Laboratory (ORNL). Tristructural isotropic (TRISO)-coated particles and associated compacts for the AGR-5/6/7 experiment fabricated by BWX Technologies Nuclear Operations Group were formed into a graphite matrix compact and irradiated at the Advanced Test Reactor at Idaho National Laboratory. At ORNL, particles are deconsolidated from the graphite matrix compact and individually scanned for emitted gamma rays with the Irradiated Microsphere Gamma Analyzer (IMGA). The IMGA system comprises a single high purity germanium (HPGe) detector, an automated particle handling vacuum system, and an ORTEC DSPEC-50 digital spectrometer for gamma ray analysis. IMGA quantifies gamma ray-emitting fission product inventories of individual TRISO particles, and these inventories can be compared with the measured average inventories per particle and radionuclide inventories predicted by AGR-5/6/7 physics calculations to determine if a particle experienced radionuclide release. Details on IMGA data collection methods can be found in the literature. The TRISO particle’s SiC layer provides structural support, as well as a barrier for fission product release during irradiation or subsequent safety testing. A weakened or compromised SiC layer can be identified by the release of radionuclides, such as 137 Cs, which is detected by IMGA. However, select radionuclides, such as 90 Sr, 110 mAg, and 154 Eu have been shown to migrate through an intact SiC layer. Measurement of the radionuclide 110 mAg is significant as its release has been shown to be particularly sensitive to in-reactor conditions (e.g., temperature) with broad variable particle to-particle release behaviors observed within a single compact. As such, 110 mAg activity is often used for particle selection for comprehensive PIE as bounding 110 mAg retention particles are hypothesized to represent limits in particle behaviors within a compact. As TRISO particle fuel PIE activities continue over time, IMGA measurements of the 110 mAg inventory are eventually hindered because of its relatively short half-life (~250 days). As the fuel ages from its end of irradiation (EOI) date, the measurement uncertainty and minimum detectable activity (MDA) of 110m Ag increase because the detector background continuum begins to dominate. For particles from the second AGR irradiation experiment (AGR-2), the 110m Ag MDA was above 20% of the calculated average particle inventory after approximately five half-lives, and 110m Ag activity was no longer measurable with IMGA after approximately seven half-lives. Therefore, coincidence counting approaches have been explored to determine feasibility of leveraging new approaches to overcome limitations associated with increasing MDA over time.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Collapsible Cryogenic Storage Vessel Project

Collapsible cryogenic storage vessels may be useful for future space exploration missions by providing long-term storage capability using a lightweight system that can be compactly packaged for launch. Previous development efforts have identified an 'inflatable' concept as most promising. In the inflatable tank concept, the cryogen is contained within a flexible pressure wall comprised of a flexible bladder to contain the cryogen and a fabric reinforcement layer for structural strength. A flexible, high-performance insulation jacket surrounds the vessel. The weight of the tank and the cryogen is supported by rigid support structures. This design concept is developed through physical testing of a scaled pressure wall, and through development of tests for a flexible Layered Composite Insulation (LCI) insulation jacket. A demonstration pressure wall is fabricated using Spectra fabric for reinforcement, and burst tested under noncryogenic conditions. An insulation test specimens is prepared to demonstrate the effectiveness of the insulation when subject to folding effects, and to examine the effect of compression of the insulation under compressive loading to simulate the pressure effect in a nonrigid insulation blanket under the action atmospheric pressure, such as would be seen in application on the surface of Mars. Although pressure testing did not meet the design goals, the concept shows promise for the design. The testing program provides direction for future development of the collapsible cryogenic vessel concept.

Fleming, David C.↗

A Design Methodology for Optimizing and Integrating Composite Materials in Gear Structures

The application of composite materials to gear structures is complex because of the gear shape, the need for precise dimensional tolerances, and the complex dynamic load condition. Methods are presented in this work to design and optimize an integrated composite hub-web structure that can be used as part of a hybrid composite-steel gear. The composite hub-web structure is a planar structure with a large decrease in thickness from the hub to the rim. Methods for design and optimization of this variable-thickness structure are presented along with a method for forming braided prepreg material to conform to the shape of this structure. A layered approach is presented that integrates cut plies or filler materials for thickness buildup with continuous-fiber layers for the primary load path. An additional gear design concept is presented that has an axially extended continuous-fiber composite structure that can be combined with the planar structure. A proposed optimization methodology is introduced where an optimized design is output for each type of optimization simulation. Through this process, composite knowledge can be incorporated in the optimization, and more control is given over the design during the process. The methods in this study provide a tool for designing and optimizing composite structures for gears and other high-power-density applications.

optimization↗

Pressure‐Induced Structural and Magnetic Evolution in Layered Antiferromagnet YbMn 2 Sb 2

Electronic states under pressure exhibit unconventional spin and charge dynamics that provide a powerful route to uncover exotic phases in quantum materials. Here, we present the structural, magnetic, and electronic evolution of YbMn 2 Sb 2 under pressure. Single-crystal X-ray diffraction reveals a pressure-induced structural transition from the space group trigonal P$\overline{3}$m1 to the monoclinic P2 1 /m phase near 3.5 GPa, which remains stable up to 10 GPa. Magnetization measurements display an anomalously weak net magnetic moment and the absence of Curie–Weiss behavior up to 400 K, suggesting the formation of short-range Mn moment pairs that cancel macroscopically and subsequently evolve into long-range order upon cooling. Temperature-dependent resistivity shows semiconducting behavior with a transition at ∼119 K at ambient pressure, while pressure induces a dramatic suppression of resistance and the emergence of metallic-like temperature dependence, stabilized beyond 5 GPa. This pressure-driven semiconductor-metal transition is consistent with our density functional theory calculations, confirming the closing of the band gap under compression. Neutron diffraction under pressure identifies an incommensurate magnetic structure with antiparallel correlations between paired spins. Together, these results demonstrate how pressure-driven structural tuning and competing exchange interactions stabilize unconventional magnetic states in this low-dimensional magnetic semiconductor.

antiferromagnetic semiconductor↗

Wall turbulence control

A variety of wall turbulence control devices which were experimentally investigated are discussed; these include devices for burst control, alteration of outer flow structures, large eddy substitution, increased heat transfer efficiency, and reduction of wall pressure fluctuations. Control of pre-burst flow was demonstrated with a single, traveling surface depression which is phase-locked to elements of the burst production process. Another approach to wall turbulence control is to interfere with the outer layer coherent structures. A device in the outer part of a boundary layer was shown to suppress turbulence and reduce drag by opposing both the mean and unsteady vorticity in the boundary layer. Large eddy substitution is a method in which streamline curvature is introduced into the boundary layer in the form of streamwise vortices. Riblets, which were already shown to reduce turbulent drag, were also shown to exhibit superior heat transfer characteristics. Heat transfer efficiency as measured by the Reynolds Analogy Factor was shown to be as much as 36 percent greater than a smooth flat plate in a turbulent boundary layer. Large Eddy Break-Up (LEBU) which are also known to reduce turbulent drag were shown to reduce turbulent wall pressure fluctuation.

Wilkinson, Stephen P.↗

Dimensionally driven crossover from semimetal to direct semiconductor in layered SbAs

Two-dimensional (2D) materials have attracted a great deal of attention because they exhibit intriguing physical and chemical properties with great potential applications in electronic and optoelectronic devices, and even energy conversion. Due to the high anisotropy and unique crystal structure of layered materials, the properties can be effectively tuned by simply reducing dimensions to 2D. In this work, a unique 2D semiconductor, namely, monolayered SbAs, with high stability and indirect band gap, is predicted on the basis of first-principles calculations together with cluster expansion and Monte Carlo simulations. Interestingly, although the bulk antimony arsenide compound SbAs is known to exhibit semimetallic behavior, our calculations find that it is transformed into a direct semiconductor with a band gap of 1.28 eV when thinned down to a single atomic layer. The monolayer with antisite defects is transformed from indirect into a direct band-gap semiconductor. Such dramatic changes in the electronic structure could pave the way for SbAs to play a role in electronic device applications. Moreover, we find that the interlayer interactions in SbAs lead to a higher exfoliation energy than typical transition metal dichalcogenides such as MoS 2 , and hence we suggest that chemical deposition methods might be better than mechanical exfoliation methods for obtaining monolayer samples.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High Resolution Multimodal Chemical Imaging Platform for Organics and Inorganics

Chemical analysis at the nanoscale is critical to advance our understanding of materials and systems from medicine and biology to material science and computing. Macroscale-observed phenomena in these systems are in the large part driven by processes that take place at the nanoscale and are highly heterogeneous. Therefore, there is a clear need to develop a new technology that enables correlative imaging of material functionalities with nanoscale spatial and chemical resolutions that will enable us to untangle the structure–function relationship of functional materials. As such, here, we report on the analytical figures of merit of the newly developed correlative chemical imaging technique of helium ion microscopy coupled with secondary ion mass spectrometry (HIM-SIMS) that enables multimodal topographical/chemical imaging of organic and inorganic materials at the nanoscale. In HIM-SIMS, a focused ion beam acts as a sputtering and ionization source for chemical analysis along with simultaneous high-resolution surface imaging, providing an unprecedented level of spatial resolution for gathering chemical information on organic and inorganic materials. In this work, we demonstrate HIM-SIMS as a platform for a next-generation tool for an in situ material design and analysis capable of down to 8 nm spatial resolution chemical imaging, layered metal structure imaging in depth profiling, single graphene layer detection, and spectral analysis of metals, metal oxides, and polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Porous but Mechanically Robust All-Inorganic Antireflective Coatings Synthesized using Polymers of Intrinsic Microporosity

Herein, we introduce polymer of intrinsic microporosity 1 (PIM-1) to design single-layer and multilayered all-inorganic antireflective coatings (ARCs) with excellent mechanical properties. Using PIM-1 as a template in sequential infiltration synthesis (SIS), we can fabricate highly uniform, mechanically stable conformal coatings of AlO x with porosities of ~50% and a refractive index of 1.41 compared to 1.76 for nonporous AlO x that is perfectly suited for substrates commonly used in high-end optical systems or touch screens (e.g., sapphire, conductive glass, bendable glass, etc.). We show that such films can be used as a single-layer ARC capable of reduction of the Fresnel reflections of sapphire to as low as 0.1% at 500 nm being deposited only on one side of the substrate. We also demonstrate that deposition of the second layer with higher porosity using block copolymers enables the design of graded-index double-layered coatings. AlO x structures with just two layers and a total thickness of less than 200 nm are capable of reduction of Fresnel reflections under normal illumination to below 0.5% in a broad spectral range with 0.1% reflection at 700 nm. Additionally, and most importantly, we show that highly porous single-layer and graded-index double-layered ARCs are characterized by high hardness and scratch resistivity. The hardness and the maximum reached load were 7.5 GPa and 13 mN with a scratch depth of about 130 nm, respectively, that is very promising for the structures consisting of two porous AlO x layers with 50% and 85% porosities, correspondingly. Such mechanical properties of coatings can also allow their application as protective layers for other optical coatings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Creating Zipper‐Like van der Waals Gap Discontinuity in Low‐Temperature‐Processed Nanostructured PbBi 2 n Te 1+3 n : Enhanced Phonon Scattering and Improved Thermoelectric Performance

Abstract Nanoengineered materials can embody distinct atomic structures which deviate from that of the bulk‐grain counterpart and induce significantly modified electronic structures and physical/chemical properties. The phonon structure and thermal properties, which can also be potentially modulated by the modified atomic structure in nanostructured materials, however, are seldom investigated. Employed here is a mild approach to fabricate nanostructured PbBi 2 n Te 1+3 n using a solution‐synthesized PbTe‐Bi 2 Te 3 nano‐heterostructure as a precursor. The as‐obtained monoliths have unprecedented atomic structure, differing from that of the bulk counterpart, especially the zipper‐like van der Waals gap discontinuity and the random arrangement of septuple‐quintuple layers. These structural motifs break the lattice periodicity and coherence of phonon transport, leading to ultralow thermal conductivity and excellent thermoelectric z T .

Xu, Biao↗

Pressure effect on the electronic, structural, and vibrational properties of layered 2 H - MoTe 2

Layered molybdenum dichalchogenides differ from the classic example of bilayer graphene with their unique electronic properties: the application of pressure can continuously tune electronic structure since the band gap is controlled by delicate interlayer interaction. In this work, we have performed measurements of Raman scattering, synchrotron x-ray diffraction, electrical conductivity, and Hall coefficient combined with density functional theory calculations to synthetically study the pressure effect on $2H$-MoTe 2 . Both the experiments and calculations consistently demonstrate that MoTe2 undergoes a semiconductor-to-metallic (S-M) transition above 10 GPa. Unlike MoS 2 , the S-M transition is driven by the gradual tunability of electric structure and band gap without structural transition. The applied pressure also effectively enhances conductivity and carrier concentration while reducing the mobility, which makes MoTe 2 more suitable for applications than most other transition-metal dichalchogenides and allows it to be applied in strain-modulated optoelectronic devices.

36 MATERIALS SCIENCE↗

Study on Application of Geopolymer to the Retrieval of Fuel Debris in Fukushima Dai-ichi NPP

In order to retrieve fuel debris in Fukushima Dai-ichi NPP, many retrieval methods are proposed. Geopolymer is the candidate material applied for an alternative retrieval method. In this concept, Geopolymer can be used to stabilize fuel debris and suppress the diffusion of radioactive materials. Objective: Evaluation of geopolymer applied for retrieving fuel debris. Slump Flow Test: Slump flow values decreased as the test temperature increased. In air condition, water molecules evaporated from geopolymer and the viscosity of geopolymer increased. In water condition, the same trends as in air condition were observed. Slump flow values of geopolymer also depended on the elapsed time after mixing. By adding water, the slump flow values of geopolymer became higher (Even at 80 deg. C). It is possible to adjust the solidification time (Setting time) of geopolymer. Solidification Process of Geopolymer: After the first layer solidified, the second layer was injected. At 300 deg. C, porous structure was observed in the first layer, while the second layer structure was intact. In the actual application, multilayered geopolymer may be used to stabilize fuel debris. Conclusion: Fluidity of geopolymer decreased with raising temperature. Setting time can be adjusted by adding water. Geopolymer may be applied by injecting multiple times on high temperature materials above 100 deg. C.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Integral analysis of the effect of material dimension and composition on tokamak neutronics *

Abstract The neutronics performance of a tokamak has been identified as an important factor in designing a fusion power plant. The design of the tokamak should not only meet operational parameters such as sufficient tritium breeding, but also safety parameters such as low structural material activation. This paper investigates the impacts of the neutronics metrics for the ARC-class tokamak, a compact tokamak with an immersion blanket, by perturbing the first five layers of structural material—first wall, inner vacuum vessel, coolant salt channel, neutron multiplier, and outer vacuum vessel. The goal of this work is to provide insight into shaping and scaling the flux on each layer to obtain optimized operational and safety metrics through quantification of the responses from each perturbation. Results show that increased first wall thickness can increase the tritium breeding ratio (TBR) in specific configurations with high 6 Li enrichments and that vacuum vessels decrease TBR for low- 6 Li enrichment configurations. It was also found that the neutron multiplier can either increase or decrease TBR depending on the configuration. The response of metrics to the change in layer thickness and enrichment also varies depending on the vacuum vessel material. The integral impacts of 6 Li enrichment, layer thicknesses, and vacuum vessel material choice are investigated and presented in this paper.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Microstructural, Chemical and Mechanical Characterization of Polymer-Derived Hi-Nicalon Fibers with Surface Coatings

Room temperature tensile strengths of as-received Hi-Nicalon fibers and those having BN/SiC, p-BN/SiC, and p-B(Si)N/SiC surface coatings, deposited by chemical vapor deposition, were measured using an average fiber diameter of 13.5 microns. The Weibull statistical parameters were determined for each fiber. The average tensile strength of uncoated Hi-Nicalon on was 3.19 +/- 0.73 GPa with a Weibull modulus of 5.41. Strength of fibers coated with BN/SiC did not change. However, coat with p-BN/SiC and p-B(Si)N/SiC surface layers showed strength loss of approx. 10 and 35 percent, respectively, compared with as-received fibers. The elemental compositions of the fibers and the coatings were analyzed using scanning Auger microprobe and energy dispersive x-ray spectroscopy. The BN coating was contaminated with a large concentration of carbon and some oxygen. In contrast, p-BN, p-B(Si)N, and SiC coatings did not show any contamination. Microstructural analyses of the fibers and the coatings were done by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected area electron diffraction. Hi-Nicalon fiber consists of the P-SIC nanocrystals ranging in size from 1 to 30 nm embedded in an amorphous matrix. TEM analysis of the BN coating revealed four distinct layers with turbostatic structure. The p-BN layer was turbostratic and showed considerable preferred orientation. The p-B(Si)N was glassy and the silicon and boron were uniformly distributed. The silicon carbide coating was polycrystalline with a columnar structure along the growth direction. The p-B(Si)N/SiC coatings were more uniform, less defective and of better quality than the BN/SiC or the p-BN/SiC coatings.

Bansal, Narottam P.↗

Regulation of Surface Defect Chemistry toward Stable Ni-Rich Cathodes

Surface reconstruction of Ni-rich layered oxides (NLO) degrades the cycling stability and safety of high-energy-density lithium-ion batteries (LIBs), which challenges typical surface-modification approaches to build a robust interface with electrochemical activity. Here, a strategy of leveraging the low-strain analogues of Li- and Mn-rich layered oxides (LMR) to reconstruct a stable surface on the Ni-rich layered cathodes is proposed. The new surface structure not only consists of a gradient chemical composition but also contains a defect-rich structure regarding the formation of oxygen vacancies and cationic ordering, which can simultaneously facilitate lithium diffusion and stabilize the crystal structure during the (de)lithiation. These features in the NLO lead to a dramatic improvement in electrochemical properties, especially the cyclability under high voltage cycling, exhibiting the 30% increase in capacity retention after 200 cycles at the current density of 1 C (3.0-4.6 V). We report the findings offer a facile and effective way to regulate defect chemistry and surface structure in parallel on Ni-rich layered structure cathodes to achieve high-energy density LIBs.

25 ENERGY STORAGE↗

Collapse of LiNi 1– x–y Co x Mn y O 2 Lattice at Deep Charge Irrespective of Nickel Content in Lithium-Ion Batteries

Volume variation and the associated mechanical fracture of electrode materials upon Li extraction/insertion are a main cause limiting lifetime performance of lithium-ion batteries. For LiNi 1-x-y Co x Mn y O 2 (NCM) cathodes, abrupt anisotropic collapse of the layered lattice structure at deep charge is generally considered characteristic to high Ni content and can be effectively suppressed by elemental substitution. Herein, we demonstrate the lattice collapse is a universal phenomenon almost entirely dependent on Li utilization, and not Ni content, of NCM cathodes upon delithiation. With Li removal nearing 80 mol%, very similar c-axis lattice shrinkage of around 5% occurs concurrently for NCMs synthesized in-house regardless of nickel content (90, 70, 50, or 33 mol%); meanwhile, the a-axis lattice contracts for high-Ni NCM, but it expands for low-Ni NCM. We further reveal Co-Mn co-substitution in NCM barely, if at all, affects several key structural aspects governing the lattice distortion upon delithiation. Finally, our results highlight the importance of evaluating true implications of compositional tuning on high-Ni layered oxide cathode materials to maximize their charge-storage capacities for next-generation high-energy Li-ion batteries.

25 ENERGY STORAGE↗