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At least 91 records · Page 5

Scalable in situ non-destructive evaluation of additively manufactured components using process monitoring, sensor fusion, and machine learning

Laser Powder Bed Fusion (L-PBF) Additive Manufacturing (AM) is among the metal 3D printing technologies most broadly adopted by the manufacturing industry. However, the current industry qualification paradigm for critical-application L-PBF parts relies heavily on expensive non-destructive inspection techniques, which significantly limits the use-cases of L-PBF. In situ monitoring of the process promises a less expensive alternative to ex situ testing, but existing sensor technologies and data analysis techniques struggle to detect sub-surface flaws (e.g., porosity and cracking) on production-scale L-PBF printers. In this work, an in situ NDE (INDE) system was engineered to detect subsurface flaws detected in X-Ray Computed Tomography (XCT) directly from process monitoring data. A multilayer, multimodal data input allowed the INDE system to detect numerous subsurface flaws in the size range of 200–1000µm using a novel human-in-the-loop annotation procedure. Furthermore, a framework was established for generating probability-of-detection (POD) and probability-of-false-alarm (PFA) curves compliant with NDE standards by systematically comparing instances of detected subsurface flaws to post-build XCT data. Here, we also introduce for the first time in the AM in situ sensing literature the a 90/95 – the flaw size corresponding to a 90% detection rate on the lower 95% confidence interval of the POD curve. The INDE system successfully demonstrated POD capabilities commensurate with traditional NDE methods. Traditional ML performance metrics were also shown to be inadequate for assessing the ability of the INDE system’s flaw detection performance. It is the hope of the authors that future studies will adopt the POD and PFA approach outlined here to provide better insight into the utility of process monitoring for AM.

36 MATERIALS SCIENCE↗

Custom-form iron trifluoride Li-batteries using material extrusion and electrolyte exchanged ionogels

Custom-form factor batteries fabricated in non-conventional shapes can maximize the overall energy density of the systems they power, particularly when used in conjunction with energy dense materials (e.g., Li metal anodes and conversion cathodes). Additive manufacturing (AM), and specifically material extrusion (ME), have been shown as effective methods for producing custom-form cell components, particularly electrodes. However, the AM of several promising energy dense materials (conversion electrodes such as iron trifluoride) have yet to be demonstrated or optimized. Furthermore, the integration of multiple AM produced cell components, such as electrodes and separators, along with a custom package remains largely unexplored. In this work, iron trifluoride (FeF 3 ) and ionogel (IG) separators are conformally printed using ME onto non-planar surfaces to enable the fabrication of custom-form Li-FeF 3 batteries. Further, to demonstrate printing on non-planar surfaces, cathodes and separators were deposited onto cylindrical rods using a 5-axis ME printer. ME printed FeF 3 was shown to have performance commensurate with FeF 3 cast using conventional means, both in coin cell and cylindrical rod formats, with capacities exceeding 700 mAh/g on the first cycle and ranging between 600 and 400 mAh/g over the next 50 cycles. Additionally, a ME process for printing polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) based IGs directly onto FeF 3 is developed and enabled using an electrolyte exchange process. In coin cells, this process is shown to produce cells with similar capacity to cells built with Celgard separators out to 50 cycles, with the exception that cycling instabilities are observed during cycles 8–20. When using printed and exchanged IGs in a custom cylindrical cell package, 6 stable high-capacity cycles are achieved. Overall, this work demonstrates approaches for producing high-energy-density Li-FeF 3 cells in coin and cylindrical rod formats, which are translatable to customized, arbitrary geometries compatible with ME printing and electrolyte exchange.

25 ENERGY STORAGE↗

Topological approach to electron correlations at fractional quantum Hall effect

Highlights: • Braids in 2D electron systems in magnetic field acquire a cyclotron metrics. • Commensurability of 2D braids with Wigner crystal of electrons leads to FQHE. • Homotopy invariants define the hierarchy of FQHE universal in all 2D Hall systems. • Composite fermions illustrate multiloop braids in the simplest homotopy case. • Correlations in FQHE reveal long-range quantum entanglement of all electrons. The classification of homotopy invariants in interacting multi-electron 2D systems at quantizing magnetic fields is presented, explaining the topologically protected correlations occurring at integer and fractional quantum Hall effects. The long-range quantum entanglement is essential for homotopy correlated phases in contrast to the binary entanglement for conventional phases with local order parameters. The classification of homotopy long-range correlated phases induced by the Coulomb interaction of electrons has been derived in terms of homotopy invariants, which are universal and robust against local disorder and single-particle crystal field, as illustrated by experimental observations in various materials with different microscopic structure, like GaAs 2DES, graphene monolayer and bilayer and in Chern topological insulators. The homotopy phases are demonstrated to be topologically protected and immune to single-particle perturbations, temperature chaos and variation of the electron interaction strength. The nonzero repulsive interaction between electrons is shown, however, to be essential for the definition of the homotopy invariants, which disappear in gaseous systems.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Competing conduction mechanisms in high performance carbon nanotube fibers

The performance of carbon nanotube (CNT) cables, a contender for copper-wire replacement, is tied to its metallic and semi-conducting-like conductivity responses with temperature; the origin of the semi-conducting-like response however is an underappreciated incongruity in literature. With controlled aspect-ratio and doping-degree, over 61 unique cryogenic experiments including anisotropy and Hall measurements, CNT cable performance is explored at extreme temperatures (65 mK) and magnetic-fields (60 T). A semi-conducting-like conductivity response with temperature becomes temperature-independent approaching absolute-zero, uniquely demonstrating for the first time the necessity of heterogeneous fluctuation induced tunneling; complete de-doping leads to localized hopping, contrasting graphite's pure metallic-like response. High-field magneto-resistance (including novel +22 % longitudinal magneto-resistance near room-temperature) is analyzed with hopping and classical two-band models, both yielding a similar parameter useful for conductor development. Varying field-orientation angle uncovers significant two- and four-fold symmetries that are shown to be from Aharonov-Bohm-like corrections to the curvature-induced bandgap, a first for macroscale CNT fibers. Tight-binding calculations using Green's Function formalism model the largest, coherent transport to-date in commensurate CNT bundles in magnetic-field, revealing non-uniform transmission across bundle cross-sections with doping restoring uniformity; independent of doping, transport in bundle-junction-bundle systems are predominantly from CNTs adjacent to the other bundle—demonstrating that smaller bundles are more efficient for electronic transport. The final impact is predicting the ultimate conductivity of heterogeneous CNT cables using temperature and field-dependent transport, surpassing conductivity of traditional metals.

36 MATERIALS SCIENCE↗

Temperature transformation of blended magnesium potassium phosphate cement binders

In this study, a multi-technique approach was utilised to determine the high temperature performance of magnesium potassium phosphate cement (MKPC) blended with fly ash (FA) or ground granulated blast furnace slag (GBFS) with respect to nuclear waste immobilisation applications. Conceptual fire conditions were employed (up to 1200 °C, 30 min) to simulate scenarios that could occur during interim storage, transportation or within a final geological disposal facility. After exposure up to 400 °C, the main crystalline phase, struvite-K (MgKPO{sub 4}·6H{sub 2}O), was dehydrated to poorly crystalline MgKPO{sub 4} (with corresponding volumetric and mass changes), with MgKPO{sub 4} recrystallisation achieved by 800 °C. XRD and SEM/EDX analysis revealed reaction occurred between the MgKPO{sub 4} and FA/GBFS components after exposure to 1000–1200 °C, with the formation of potassium aluminosilicate phases, leucite and kalsilite (KAlSi{sub 2}O{sub 6} and KAlSiO{sub 4}), commensurate with a reduced relative intensity (or complete elimination) of the dehydrated struvite-K phase, MgKPO{sub 4.} This was further supported by solid-state NMR ({sup 27}Al and {sup 29}Si MAS), where only residual features associated with the raw FA/GBFS components were observable at 1200 °C. The high temperature phase transformation of blended MKPC binders resulted in the development of a glass/ceramic matrix with all existing porosity infilled via sintering and the formation of a vitreous phase, whilst the physical integrity was retained (no cracking or spalling). This study demonstrates that, based on small-scaled specimens, blended MKPC binders should perform satisfactorily under fire performance parameters relevant to the operation of a geological disposal facility, up to at least 1200 °C.

36 MATERIALS SCIENCE↗

A multi-center quadrature scheme for the molecular continuum

We report a common way to evaluate electronic integrals for polyatomic molecules is to use Becke’s partitioning scheme (Becke and Chem, 1988) in conjunction with overlapping grids centered at each atomic site. The Becke scheme was designed for integrands that fall off rapidly at large distances, such as those approximating bound electronic states. When applied to states in the electronic continuum, however, Becke scheme exhibits slow convergence and it is highly redundant. Here, we present a modified version of Becke scheme that is applicable to functions of the electronic continuum, such as those involved in molecular photoionization and electron–molecule scattering, and which ensures convergence and efficiency comparable to those realized in the calculation of bound states. In this modified scheme, the atomic weights already present in Becke’s partition are smoothly switched off within a range of few bond lengths from their respective nuclei, and complemented by an asymptotically unitary weight. The atomic integrals are evaluated on small spherical grids, centered on each atom, with size commensurate to the support of the corresponding atomic weight. The residual integral of the interstitial and long-range region is evaluated with a central master grid. The accuracy of the method is demonstrated by evaluating integrals involving integrands containing Gaussian Type Orbitals and Yukawa potentials, on the atomic sites, as well as spherical Bessel functions centered on the master grid. These functions are representative of those encountered in realistic electron-scattering and photoionization calculations in polyatomic molecules.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Advocating for view and daylight in buildings: Next steps

With the exponential growth in population and commensurate increased density in urban cities, access to daylight and views to nature is being severely curtailed in buildings. In parallel, increasingly urgent demands to sharply reduce building energy use and associated greenhouse gas emissions are being made to mitigate climate change. There are many challenges and performance tradeoffs associated with the building facade (i.e., daylight and view versus solar and glare control); increased prioritization of health and well-being as a fundamental human requirement could adversely affect building energy-efficiency. Given the current state of knowledge on the effects of daylight and view on health and well-being in buildings, we identify critical needs in research, tools and technologies that if satisfied may enable more effective use of daylight and view in buildings within the constraints of climate change. Lack of knowledge regarding the complex causal mechanisms of window views on human factors is a severely limiting factor in forward progress. Current models and methods to derive bidirectional scattering distribution functions (BSDFs) will need to be modified. Developers of energy-efficient window technologies will need more guidance to shape product development. Advanced window technologies and integrated design can enable attainment of both health and well-being and net zero energy goals, but considerable work will be needed to make such options turnkey and broadly available.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Common risk segment mapping: Streamlining exploration for carbon storage sites, with application to coastal Texas and Louisiana

Large-scale deployment of Carbon Capture and Storage (CCS) will require a commensurately large number of sites. Efficient screening methods are needed to create investment assurance and focus efforts on the most promising sites. The problem is similar to petroleum exploration, for which there are well-developed (though seldom published) workflows, including Common Risk Segment (CRS) mapping. In brief, the process requires 1) defining the key play elements; 2) identifying candidate geologic intervals for each; 3) creating fact-based maps for those intervals; 4) determining minimum criteria for the success of each element; 5) reinterpreting the fact-based maps in terms of chance of success; and 6) combining the individual maps to form a composite, basin-scale view of prospectivity. We adapt the CRS process to screening for CO 2 storage sites. Critically, we redefine the process in terms of cost of characterization and development, rather than chance of success. For illustration, we apply the process to the example of the Lower Miocene on the Texas and Louisiana Gulf Coast. We show that the predictions are consistent with historic hydrocarbon production volumes and rates. The power of the CRS method is that it creates a systematic approach to geologic evaluation and translates complex, multidimensional analysis into clear, graphical and easily comprehended business inputs. The results highlight sweet spots and identifies critical risks, suggesting a focus for further data collection and analysis. Furthermore, the method developed here can be applied to both surface and subsurface factors anywhere that there is interest in geologic storage of CO 2 .

54 ENVIRONMENTAL SCIENCES↗

Microstructure refinement of hot deformed Dy-free NdFeB magnets through a novel cold sintering approach by pressure-assisted spark plasma sintering

Anisotropic fine-grained Dy-free NdFeB high-performance magnets were produced using a novel cold sintering approach by pressure-assisted spark plasma sintering (SPS). The NdFeB nanocrystalline ribbon powders were subjected to cold sintering below 450 °C using pressure-assisted SPS, followed by hot deformation at 710 °C and 810 °C via SPS. Results indicate that cold sintering below 450 °C effectively restricts grain growth in the NdFeB magnets, yielding sub-100 nm scale grains across both fine-grained regions and most coarse-grained regions. The refined grain structure achieved through cold sintering allows for a lower hot deformation temperature as compared with the magnet by conventional sintering, as finer grains allow easier deformation and grain sliding/rotation. This process produces a highly fine-grained and anisotropic microstructure to achieve high magnetic performance (i.e., high intrinsic coercivity, remanence, and maximum energy product) in the magnets. The cold sintering (at 350 °C) and lower hot deformation temperatures required (e.g., 710 °C) help control grain coarsening and limit grain size that is commensurate with the size of a single magnetic domain of the Nd 2 Fe 14 B magnetic matrix phase, resulting in high intrinsic coercivity (H ci =11.4 kOe). Furthermore, the reduced hot deformation temperature mitigates the formation of coarse grain bands, leading to improved magnetic properties, specifically an increased remanence (B r = 14.3 kGs) and a high maximum energy product ((BH) max = 48 MGOe). In conclusion, cold sintered hot deformed NdFeB magnet also shows good thermal stability with reversible temperature coefficient α(B r )= -0.097 %/K and α(H ci )= -0.616 %/K at elevated temperatures up to 400 K.

Cold Sintering↗

Neutron diffraction study of magnetic ordering in high pressure phases of rare earth metal holmium

The magnetic ordering in rare earth metals is well established for ambient pressure crystal structures, however, little is known about the magnetic ordering in their corresponding high-pressure crystalline modifications. Holmium (Ho) was studied in a large-volume diamond anvil cell at the Spallation Neutron Source to high-pressure up to 20 GPa and to low-temperature to 10 K. We have conducted two independent high-pressure low-temperature experiments under non-hydrostatic and quasi-hydrostatic pressure conditions respectively. The ambient pressure hexagonal close packed (hcp) phase of holmium shows two magnetic transitions below 10 GPa one to an incommensurate Antiferromagnetic (AFM) phase and another to a conical-Ferromagnetic (c-FM) phase. In contrast, alpha-Samarium-type (α-Sm) phase above 10 GPa and the double hexagonal close packed (dhcp) phase above 19 GPa show only one FM transition marked by the appearance of a magnetic peak at 3 Å and the concurrent enhancement of nuclear peaks below 30 K. Finally, these new transitions observed by neutron diffraction can be accounted by a commensurate superlattice formation along c-axis in both the α-Sm-type phase and the dhcp phase.

36 MATERIALS SCIENCE↗

An examination of the precipitation behavior of proton irradiated dual phase 308L weldment filler materials

Voids, G phase particles, and Ni-Si rich clusters in proton irradiated dual phase 308L groove filler of a SA508–304 L dissimilar metal weldment are analyzed using advanced characterization techniques. These weldments are often used in light water nuclear reactors and are subject to enhanced corrosion and associated stress corrosion cracking (SCC). Radiation damage is known to accelerate SCC. Ni-Si enriched clusters were observed in proton irradiated γ austenite, while G phase M 6 Ni 16 Si 7 (where M transition metal element) precipitates were observed in proton irradiated δ ferrite. Compositional analysis of the G phase precipitates and Ni-Si clusters from STEM-EDS and APT are compared. Unlike G phase particles in proton irradiated δ ferrite, Ni-Si clusters in proton irradiated γ austenite are not rich in Mn. Both STEM-EDS and APT line-scan profiles of the Ni-Si clusters show that the Fe and Cr concentration gradient between matrix γ austenite and the Ni-Si clusters is not as sharp as those between matrix δ ferrite and G phase. Further, HR-STEM imaging indicates that the lattice parameter of the Ni-Si clusters is commensurate with γ austenite and the clusters do not represent the precipitation of a second phase. Finally, our analysis demonstrates the density and volume fraction of G phase particles and the density of voids scales with proton irradiation damage and the energy to recoils.

308L groove filler↗

Compact ammonia reforming at low temperature using catalytic membrane reactors

Ammonia is a leading carrier for the storage and transport of renewable hydrogen, but its deployment requires scalable technologies for efficient decomposition and purification. In this work, we report on the efficient delivery of high purity hydrogen from ammonia decomposition using a catalytic membrane reactor (CMR). Improvements to the electroless plating process reduced the Pd membrane thickness by >35%, resulting in commensurate increases in hydrogen permeance without sacrificing selectivity. To increase throughput a commercial Ru/Al 2 O 3 catalyst was added to the lumen, and the CMR could process ammonia flowrates 10–50 times higher than an equivalent packed bed reactor while maintaining the same level of conversion. It is shown that the earth-abundant zeolite clinoptilolite could reduce ammonia impurities in the permeated H 2 to the levels required by PEM fuel cells (<25 ppb). Performance increased significantly across a >500-h durability test due to improvements in membrane permeability. Finally, the results show that CMRs are a viable technology for distributed production of hydrogen from ammonia.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solvation dynamics of choline fluoride in ethylene glycol – Water mixtures

Due to their favorable physical properties, deep eutectic solvents (DESs) have been of interest in many applications in the energy and industry sectors. In this study, we investigate the new deep eutectic solvent ethalineF (a 1:2 M ratio of choline fluoride:ethylene glycol) and the effect of water addition on the solvation dynamics compared to the better known ethaline (a 1:2 M ratio of choline chloride:ethylene glycol). Femtosecond transient absorption spectroscopy and NMR diffusometry were used to study the solvation dynamics. 19 F NMR spectra were obtained for ethalineF solutions with different water additions. The 19 F NMR spectra show two fluorine signals; one can be assigned to fluoride anions solvated by EG and the other signal to fluoride anions associated with the much heavier and less mobile choline cation. Density, viscosity, conductivity, and E T (30) polarity measurements are also provided for ethalineF. The nuclear spin nature of fluorine atom permits to measure the self-diffusion coefficient of the negative ion in addition of the cation diffusion in a choline halide based deep eutectic solvent system. This allows to calculate the NMR-predicted conductivities σ NMR . The obtained ion dissociation coefficients α D at different water concentrations suggest a partial ion dissociation which was commensurate with the relatively low ion conductivity. Furthermore, the observed modest conductivity of ethalineF is explained in terms of ion association as well as the gradual increase in conductivity caused by the addition of water.

19F NMR↗

The incommensurate modulation of tetragonal tungsten bronze quantified by high resolution 4D STEM

Many members of the tetragonal tungsten bronze (TTB) family of oxides display an incommensurate periodic lattice distortion, the nature of which has been the subject of some controversy. Here we present a study of this structural modulation in the relaxor ferroelectric Ba 5 SmSn 3 Nb 7 O 30 (BSSN) by quantitative scanning transmission electron microscopy (STEM). Additionally, we characterize the modulation in BSSN by employing a fast, pixelated direct electron detector to perform high resolution phase contrast STEM imaging of the crystalline lattice. By quantitatively analyzing the images, we visualize the atomic structural correlations present in the material on both the cation and anion sublattices. This analysis reveals the incommensurate structure to have an octahedral tilting pattern and cooperative A2 site cation displacements, analogous to an Ama2 commensurate cell. Finally, we show that the modulation is composed of a structural motif with a period of 3 x $d_{1\bar{1}0}$ and modified by discommensurations, likely arise from frustrated octahedral tilting in the odd-valued periodicity.

Differential phase contrast↗

Non-stationary historical trends in wave energy climate for coastal waters of the United States

The thirty-year non-stationary historical trends in the wave energy climate for United States coastal waters between 1980 and 2009 are investigated using spectral partitioned wave data generated from a WaveWatch III® (version 5.05) hindcast. In addition to historical trends in the omni-directional wave power, frequency and directionally resolved wave power, frequency and directional spreading, and seasonal variability, are examined for the first time, including their geographical distribution. These historical wave energy climate trends are linked to changes to the dominant wave systems and commensurate trends in the historical wind climate. Total wave power trends are consistent with other studies, but the present study identifies regions, and specific frequency and direction bands, where significant wave energy climate changes have occurred. For some regions, changes to wave climate parameters exceeded one-percent annually, more than thirty-percent over the study period. In conclusion, non-stationary trends of this magnitude have significant implications for ocean and coastal engineering projects designed assuming wave climates are stationary and warran

16 TIDAL AND WAVE POWER↗

Zr 3 Mn 3 Sn 4 Ga: A new hetero-kagome bilayer antiferromagnet

Here, we report the magnetic and electrical transport properties of single-crystalline Zr 3 Mn 3 Sn 4 Ga, featuring two distinct kagome lattices: a non-magnetic breathing Zr 3 Sn 4 lattice and a magnetic intact Mn 3 Ga lattice. The material undergoes an antiferromagnetic phase transition at T N = 87 K, with neutron diffraction confirming commensurate ordering characterized by k = (1/3,1/3,0). Transport measurements show metallic behavior, a resistivity anomaly near T N , and 12% magnetoresistance at 2 K under 9 T. Deviations from the conventional second-order power law, along with negative magnetoresistance and nonlinear Hall slope variations near T N , suggest strong magneto-electronic coupling. Resonant photoemission spectroscopy identifies Zr 4d and Mn 3d orbitals as dominant contributors to the valence band, linking the material’s unique electronic properties to its kagome layers. Zr 3 Mn 3 Sn 4 Ga offers a valuable platform to study interactions between magnetism and topological electronic bands in hetero-kagome systems using the co- existence of magnetic and non-magnetic kagome layers and its tunable electronic structure.

Crystal structure↗

Single Entity Electrochemistry in Nanopore Electrode Arrays: Ion Transport Meets Electron Transfer in Confined Geometries

Electrochemical measurements conducted in confined volumes provide a powerful and direct means to address scientific questions at the nexus of nanoscience, biotechnology, and chemical analysis. How are electron transfer and ion transport coupled in confined volumes and how does understanding them require moving beyond macroscopic theories? Also, how do these coupled processes impact electrochemical detection and processing? We address these questions by studying a special type of confined-volume architecture, the nanopore electrode array, or NEA, which is designed to be commensurate in size with physical scaling lengths, such as the Debye length, a concordance that offers performance characteristics not available in larger scale structures. The experiments described here depend critically on carefully constructed nanoscale architectures that can usefully control molecular transport and electrochemical reactivity. We begin by considering the experimental constraints that guide the design and fabrication of zero-dimensional nanopore arrays with multiple embedded electrodes. These zero-dimensional structures are nearly ideal for exploring how permselectivity and unscreened ion migration can be combined to amplify signals and improve selectivity by enabling highly efficient redox cycling. Our studies also highlight the benefits of arrays, in that molecules escaping from a single nanopore are efficiently captured by neighboring pores and returned to the population of active redox species being measured, benefits that arise from coupling ion accumulation and migration. These tools for manipulating redox species are well-positioned to explore single molecule and single particle electron transfer events through spectroelectrochemistry, studies which are enabled by the electrochemical zero-mode waveguide (ZMW), a special hybrid nanophotonic/nanoelectronic architecture in which the lower ring electrode of an NEA nanopore functions both as a working electrode to initiate electron transfer reactions and as the optical cladding layer of a ZMW. Furthermore, while the work described here is largely exploratory and fundamental, we believe that the development of NEAs will enable important applications that emerge directly from the unique coupled transport and electron-transfer capabilities of NEAs, including in situ molecular separation and detection with external stimuli, redox-based electrochemical rectification in individually encapsulated nanopores, and coupled sorters and analyzers for nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗