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At least 1,009 records · Page 56

Operational resilience of additively manufactured parts to stealthy cyberphysical attacks using geometric and process digital twins

Cyberphysical attacks on the digital backbone of Additive Manufacturing (AM) can compromise the printed part’s functionality. They can alter features in the digital geometry to introduce geometric defects (e.g., missing fillets) or alter process parameters to create local defects (e.g., voids). Addressing the downtime, waste, and quality deterioration associated with existing solutions requires operational resilience, i.e., rapid elimination or disruption of defect formation (to retain part function) without production stoppage or part disposal (to retain yield). This need is unmet due to the inherently unpredictable nature of attack-induced alterations, lack of access to the original geometric model for identification of altered geometric features, and in-process imposition of unknown process dynamics via attack-driven alteration of real-time-uncontrolled (or exogenous) parameters. This work establishes the above-mentioned operational resilience for the first time by creating two Digital Twins (DT). The Geometric DT (Geo-DT) is based on a unique physical-field-driven soft sensor and topology optimization method. The Process Digital Twin (Pro-DT) combines local defect quantification with a novel Reinforcement Learning formulation and training method. The importance of these methodological advances and the scalability of our approach are examined on a real AM testbed. It is shown that Geo-DT can correct geometric defects without access to the original digital geometry or explicit knowledge of attack-altered geometric features. Further, Pro-DT can accelerate real-time disruption of local defects despite attack-driven imposition of unknown process dynamics. We discuss how our framework goes beyond the contemporary focus on pre-attack security and in-attack detection towards resilience for AM and beyond.

Additive Manufacturing↗

Diagnosing collisionless energy transfer using field–particle correlations: Vlasov–Poisson plasmas

Turbulence plays a key role in the conversion of the energy of large-scale fields and flows to plasma heat, impacting the macroscopic evolution of the heliosphere and other astrophysical plasma systems. Although we have long been able to make direct spacecraft measurements of all aspects of the electromagnetic field and plasma fluctuations in near-Earth space, our understanding of the physical mechanisms responsible for the damping of the turbulent fluctuations in heliospheric plasmas remains incomplete. Here we propose an innovative field–particle correlation technique that can be used to measure directly the secular energy transfer from fields to particles associated with collisionless damping of the turbulent fluctuations. Furthermore, this novel procedure yields information about the collisionless energy transfer as a function of particle velocity, providing vital new information that can help to identify the dominant collisionless mechanism governing the damping of the turbulent fluctuations. Kinetic plasma theory is used to devise the appropriate correlation to diagnose Landau damping, and the field–particle correlation technique is thoroughly illustrated using the simplified case of the Landau damping of Langmuir waves in a 1D-1V (one dimension in physical space and one dimension in velocity space) Vlasov–Poisson plasma. Generalizations necessary to apply the field–particle correlation technique to diagnose the collisionless damping of turbulent fluctuations in the solar wind are discussed, highlighting several caveats. This novel field–particle correlation technique is intended to be used as a primary analysis tool for measurements from current, upcoming and proposed spacecraft missions that are focused on the kinetic microphysics of weakly collisional heliospheric plasmas, including the Magnetospheric Multiscale (MMS), Solar Probe Plus, Solar Orbiter and Turbulence Heating ObserveR (THOR) missions.

Physics↗

Chemically and Mechanically Recyclable Vitrimers from Carbon Dioxide-Based Polycarbonates

Designing thermoset materials with dynamic crosslinks is an important strategy to mitigate rising global carbon dioxide emission levels. The development of polymers from sustainable feedstocks, with efficient manufacturing methods, for high-value applications, and with circular end-of-use solutions is essential for advancing material technologies. One approach involves exploiting carbon dioxide itself as feedstock to create high performance, sustainable materials, by enchaining 50 mol% CO2 via copolymerization with epoxides to yield polycarbonates. This work describes the synthesis, end-functionalization, and curing of poly(propylene carbonate) (PPC) and poly(cyclohexene carbonate) (PCHC) into beta-hydroxy ester vitrimers. These vitrimers demonstrate the ability to be mechanically reprocessed up to 3 times with retention of the material’s properties through dynamic transesterification exchange reactions. The polycarbonate vitrimers with gel fractions exceeding 90 % exhibit high tensile strength (> 50 MPa) and Young’s modulus (> 2 GPa), achieved by varying repeat unit structure in the polymer backbone from the low Tg PPC to the more rigid high Tg PCHC structures. Owing to an entropically favorable chain back-biting mechanism, the network chains can be cleaved and depolymerized into cyclic small molecules. In the case of PCHC, this process enables repolymerization back to polycarbonates with 69 wt.% CO2 retention through life-cycles. The promising mechanical performance and recyclability of these CO2-based polycarbonate vitrimers indicate their potential for sustainable, high-performance materials, paving the way for future innovations in circular polymer technologies and carbon capture utilization.

36 MATERIALS SCIENCE↗

Understanding Heterolytic H2 Cleavage and Water-Assisted Hydrogen Spillover on Fe3O4(001)-Supported Single Palladium Atoms

The high specific activity, novel properties, and cost effectiveness of single-atom catalysts (SAC) hold great promise and allow for new chemistry in numerous reactions. Here, we focus on fundamental understanding of the critical step in hydrogenation reactions, H2 activation, on a model SAC catalyst comprised of single Pd atoms on reconstructed Fe3O4(001). Using a combination of scanning tunneling microscopy and density functional theory we demonstrate that H2 dissociates heterolytically, ultimately yielding hydroxyls on, and excess charge in, the Fe3O4 support. The hydrogenation can be carried out to high coverages and ultimately leads to lifting of the Fe3O4 reconstruction and Pd reduction and destabilization. Water plays an important role in reduction of the hydrogen diffusion barrier, thereby facilitating redistribution of hydroxyls away from Pd. Our study demonstrates a distinct H2 activation mechanism on single Pd atoms and shows the importance of a reducible support that can facilitate charge transport away from the active site.

Doudin, Nassar M.↗

Inverted organic solar cells with non-clustering bathocuproine (BCP) cathode interlayers obtained by fullerene doping

Bathocuproine (BCP) is a well-studied cathode interlayer in organic photovoltaic (OPV) devices, where it for standard device configurations has demonstrated improved electron extraction as well as exciton blocking properties, leading to high device efficiencies. For inverted devices, however, BCP interlayers has shown to lead to device failure, mainly due to the clustering of BCP molecules on indium tin oxide (ITO) surfaces, which is a significant problem during scale-up of the OPV devices. In this work, we introduce C70 doped BCP thin films as cathode interlayers in inverted OPV devices. We demonstrate that the interlayer forms smooth films on ITO surfaces, resulting from the introduction of C70 molecules into the BCP film, and that these films possess both improved electron extraction as well exciton blocking properties, as evidenced by electron-only devices and photoluminescence studies, respectively. Importantly, the improved cathode interlayers leads to well-functioning large area (100 mm2) devices, showing a device yield of 100%. This is in strong contrast to inverted devices based on pure BCP layers. These results are founded by the effective suppression of BCP clustering from C70, along with the electron transport and exciton blocking properties of the two materials, which thus presents a route for its integration as an interlayer material towards up-scaled inverted OPV devices.

36 MATERIALS SCIENCE↗

Universal scaling of weak localization in graphene due to bias-induced dispersion decoherence

The differential conductance of graphene is shown to exhibit a zero-bias anomaly at low temperatures, arising from a suppression of the quantum corrections due to weak localization and electron interactions. A simple rescaling of these data, free of any adjustable parameters, shows that this anomaly exhibits a universal, temperature- (T) independent form. According to this, the differential conductance is approximately constant at small voltages (V < kBT/e), while at larger voltages it increases logarithmically with the applied bias. For theoretical insight into the origins of this behaviour, which is inconsistent with electron heating, we formulate a model for weak-localization in the presence of nonequilibrium transport. According to this model, the applied voltage causes unavoidable dispersion decoherence, which arises as diffusing electron partial waves, with a spread of energies defined by the value of the applied voltage, gradually decohere with one another as they diffuse through the system. The decoherence yields a universal scaling of the conductance as a function of eV/kBT, with a logarithmic variation for eV/kBT > 1, variations in accordance with the results of experiment. Our theoretical description of nonequilibrium transport in the presence of this source of decoherence exhibits strong similarities with the results of experiment, including the aforementioned rescaling of the conductance and its logarithmic variation as a function of the applied voltage.

42 ENGINEERING↗

Processes setting the structure of the electron distribution function within the exhausts of anti-parallel reconnection

In situ spacecraft observations within the exhausts of magnetic reconnection document a large variation in the velocity space structure of the electron distribution function. Multiple mechanisms help govern the underlying electron dynamics, yielding a range of signatures for collisionless reconnection. These signatures include passing beams of electrons separated by well-defined boundaries from betatron heated/cooled trapped electrons. The present study emphasizes how localized regions of non-adiabatic electron dynamics can mix electrons across the trapped/passing boundaries and impact the form of the electron distributions in the full width of the exhaust. Here, while our study is based on 2D simulations, the described principles shaping the velocity space distributions also apply to 3D geometries making our findings relevant to spacecraft observation of reconnection in the Earth's magnetosphere.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Quasi-equilibrium predictions of water desorption kinetics from rapidly-heated metal oxide surfaces

Controlling sub-microsecond desorption of water and other impurities from electrode surfaces at high heating rates is crucial for pulsed power applications. Despite the short time scales involved, quasi-equilibrium ideas based on transition state theory (TST) and Arrhenius temperature dependence have been widely applied to fit desorption activation free energies. Here, we apply molecular dynamics (MD) simulations in conjunction with equilibrium potential-of-mean-force (PMF) techniques to directly compute the activation free energies (ΔG*) associated with desorption of intact water molecules from Fe 2 O 3 and Cr 2 O 3 (0001) surfaces. The desorption free energy profiles are diffuse, without maxima, and have substantial dependences on temperature and surface water coverage. Incorporating the predicted ΔG* into an analytical form gives rate equations that are in reasonable agreement with non-equilibrium molecular dynamics desorption simulations. We also show that different ΔG* analytical functional forms which give similar predictions at a particular heating rate can yield desorption times that differ by up to a factor of four or more when the ramp rate is extrapolated by 8 orders of magnitude. This highlights the importance of constructing a physically-motivated ΔG* functional form to predict fast desorption kinetics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Including massive neutrinos in thermal Sunyaev Zeldovich power spectrum and cluster counts analyses

We consistently include the effect of massive neutrinos in the thermal Sunyaev Zeldovich (SZ) power spectrum and cluster counts analyses, highlighting subtle dependencies on the total neutrino mass and data combination. In particular, we find that using the transfer functions for cold dark matter (CDM) + baryons in the computation of the halo mass function, instead of the transfer functions including neutrino perturbations, as prescribed in recent work, yields an ≈0.25 percent downward shift of the σ 8 constraint from tSZ power spectrum data, with a fiducial neutrino mass Σm ν = 0.06 eV. In ΛCDM, with an X-ray mass bias corresponding to the expected hydrostatic mass bias, i.e. (1 - b) ≃ 0.8, our constraints from Planck SZ data are consistent with the latest results from SPT, DES-Y1, and KiDS+VIKING-450. In νΛCDM, our joint analyses of Planck SZ with Planck 2015 primary CMB yield a small improvement on the total neutrino mass bound compared to the Planck 2015 primary CMB constraint, as well as (1 - b) = 0.64 ± 0.04 (68 percent CL). For forecasts, we find that competitive neutrino mass measurements using cosmic variance limited SZ power spectrum require masking the heaviest clusters and probing the small-scale SZ power spectrum up to ℓ max ≈ 10 4 . Although this is challenging, we find that SZ power spectrum can realistically be used to tightly constrain intracluster medium properties: we forecast a 2 percent determination of the X-ray mass bias by combining CMB-S4 and our mock SZ power spectrum with ℓ max = 10 3 .

Astronomy & Astrophysics↗

Magnetic fields in the formation of the first stars – II. Results

ABSTRACT Beginning with cosmological initial conditions at z = 100, we simulate the effects of magnetic fields on the formation of Population III stars and compare our results with the predictions of Paper I. We use gadget-2 to follow the evolution of the system while the field is weak. We introduce a new method for treating kinematic fields by tracking the evolution of the deformation tensor. The growth rate in this stage of the simulation is lower than expected for diffuse astrophysical plasmas, which have a very low resistivity (high magnetic Prandtl number); we attribute this to the large numerical resistivity in simulations, corresponding to a magnetic Prandtl number of order unity. When the magnetic field begins to be dynamically significant in the core of the minihalo at z = 27, we map it on to a uniform grid and follow the evolution in an adaptive mesh refinement, MHD simulation in orion2. The non-linear evolution of the field in the orion2 simulation violates flux-freezing and is consistent with the theory proposed by Xu & Lazarian. The fields approach equipartition with kinetic energy at densities ∼1010–1012 cm−3. When the same calculation is carried out in orion2 with no magnetic fields, several protostars form, ranging in mass from ∼1 to 30 M⊙; with magnetic fields, only a single ∼30 M⊙ protostar forms by the end of the simulation. Magnetic fields thus suppress the formation of low-mass Pop III stars, yielding a top-heavy Pop III initial mass function and contributing to the absence of observed Pop III stars.

79 ASTRONOMY AND ASTROPHYSICS↗

Interplay between electron localization, magnetic order, and Jahn-Teller distortion dictates LiMnO2 phase stability

The development of manganese (Mn)-rich cathodes for Li-ion batteries promises to alleviate potential supply chain bottlenecks in battery manufacturing. Fundamental challenges in Mn-rich cathodes arise from phenomena such as structural changes due to cooperative Jahn-Teller (JT) distortions of in octahedral environments, Mn migration, and phase transformations to spinel-like order, all of which affect the electrochemical performance. These physically complex phenomena motivate an re-examination of the Li-Mn-O rock-salt space, with a focus on the thermodynamics of the prototypical, polymorphs. It is found that the generalized gradient approximation (GGA-PBEsol) and meta-GGA ( ) density functionals with empirically fitted on-site Hubbard corrections yield spurious stable phases for , such as predicting a phase with -like order ( ) to be the ground state instead of the orthorhombic (Pmmn) phase, which is the experimentally known ground state. Accounting for antiferromagnetic order in each structure is shown to have a substantial effect on the total energies and resulting phase stability. By using hybrid-GGA (HSE06) and GGA with self-consistent Hubbard parameters (on-site and inter-site ) calculated from linear response theory, the experimentally observed phase stability trends are recovered. The calculated on-site between Mn- states in the experimentally observed orthorhombic, layered, and spinel phases are significantly smaller than in and disordered layered structures, by within GGA. The smaller values of are shown to be correlated with a collinear ordering of JT distortions, in which all orbitals are oriented in the same direction. This cooperative JT effect can lead to greater electron delocalization from Mn along the states due to increased Mn-O covalency, which contributes to the greater electronic stability compared to the phases with noncollinear JT arrangements. The structures with collinear ordering of JT distortions also generate greater vibrational entropy, which helps stabilize these phases at high temperature. These phases are shown to be strongly insulating with large calculated band gaps , which are computed using HSE06 and .

Kam, Ronald L↗

Cross sections for photoionization of fullerene molecular ions C n + with n = 40, 50, 70, 76, 78, and 84

Absolute cross-section measurements are reported for single photoionization of C n + fullerene molecular ions (n=40, 50, 70, 76, 78, and 84) in the photon-energy range 18-70 eV. The experiments were performed by merging a mass and charge selected beam of C n + molecular ions with a beam of monochromatized synchrotron radiation and measuring the yield of C n 2+ product ions as a function of the photon energy. Oscillator strengths determined by integrating the measured cross sections over this energy range exhibit a linear dependence on n. The cross sections are parametrized by fits to three Lorentzian functions to represent plasmon excitations and a linear function for direct ionization. Finally, the highest-energy resonance in the data near 46 eV is similar to that previously observed in single photoionization of C 60 and may be attributable to a harmonic of the dominant surface-plasmon resonance near 23 eV.

74 ATOMIC AND MOLECULAR PHYSICS↗

Resistivity anisotropy of quantum Hall stripe phases

In this work, quantum Hall stripe phases near half-integer filling factors $\nu$ $\geqslant$ 9/2 were predicted by Hartree-Fock (HF) theory and confirmed by discoveries of giant resistance anisotropies in high-mobility two dimensional electron gases. A theory of such anisotropy was proposed by MacDonald and Fisher, although they used parameters whose dependencies on the filling factor, electron density, and mobility remained unspecified. Here, we fill this void by calculating the hard-to-easy resistivity ratio as a function of these three variables. Quantitative comparison with experiment yields very good agreement, which we view as evidence for the “plain vanilla” smectic stripe HF phases

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Topological superconductivity in Landau levels

The intense search for topological superconductivity is inspired by the prospect that it hosts Majorana quasiparticles. We explore in this work the optimal design for producing topological superconductivity by combining a quantum Hall state with an ordinary superconductor. To this end, we consider a microscopic model for a topologically trivial two-dimensional p-wave superconductor exposed to a magnetic field, and find that the interplay of superconductivity and Landau level physics yields a rich phase diagram of states as a function of μ/t and Δ/t, where μ, t and Δ are the chemical potential, hopping strength, and the amplitude of the superconducting gap. In addition to quantum Hall states and topologically trivial p-wave superconductor, the phase diagram also accommodates regions of topological superconductivity. Most importantly, we find that application of a non-uniform, periodic magnetic field produced by a square or a hexagonal lattice of h/e fluxoids greatly facilitates regions of topological superconductivity in the limit of Δ/t → 0. In contrast, a uniform magnetic field, a hexagonal Abrikosov lattice of h/2e fluxoids, or a one dimensional lattice of stripes produces topological superconductivity only for sufficiently large Δ/t.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Systematic Construction of Scarred Many-Body Dynamics in 1D Lattice Models

In this paper, we introduce a family of nonintegrable 1D lattice models that feature robust periodic revivals under a global quench from certain initial product states, thus generalizing the phenomenon of many-body scarring recently observed in Rydberg atom quantum simulators. Our construction is based on a systematic embedding of the single-site unitary dynamics into a kinetically constrained many-body system. We numerically demonstrate that this construction yields new families of models with robust wave-function revivals, and it includes kinetically constrained quantum clock models as a special case. We show that scarring dynamics in these models can be decomposed into a period of nearly free clock precession and an interacting bottleneck, shedding light on their anomalously slow thermalization when quenched from special initial states.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The role of oxygen in stimulating methane production in wetlands

Methane (CH 4 ), a potent greenhouse gas, is the second most important greenhouse gas contributor to climate change after carbon dioxide (CO 2 ). The biological emissions of CH 4 from wetlands are a major uncertainty in CH 4 budgets. Microbial methanogenesis by Archaea is an anaerobic process accounting for most biological CH 4 production in nature, yet recent observations indicate that large emissions can originate from oxygenated or frequently oxygenated wetland soil layers. To determine how oxygen (O 2 ) can stimulate CH 4 emissions, we used incubations of Sphagnum peat to demonstrate that the temporary exposure of peat to O 2 can increase CH 4 yields up to 2000-fold during subsequent anoxic conditions relative to peat without O 2 exposure. Geochemical (including ion cyclotron resonance mass spectrometry, X-ray absorbance spectroscopy) and microbiome (16S rDNA amplicons, metagenomics) analyses of peat showed that higher CH 4 yields of redox-oscillated peat were due to functional shifts in the peat microbiome arising during redox oscillation that enhanced peat carbon (C) degradation. Novosphingobium species with O 2 -dependent aromatic oxygenase genes increased greatly in relative abundance during the oxygenation period in redox-oscillated peat compared to anoxic controls. Acidobacteria species were particularly important for anaerobic processing of peat C, including in the production of methanogenic substrates H 2 and CO 2 . Higher CO 2 production during the anoxic phase of redox-oscillated peat stimulated hydrogenotrophic CH 4 production by Methanobacterium species. The persistence of reduced iron (Fe(II)) during prolonged oxygenation in redox-oscillated peat may further enhance C degradation through abiotic mechanisms (e.g., Fenton reactions). The results indicate that specific functional shifts in the peat microbiome underlie O 2 enhancement of CH 4 production in acidic, Sphagnum-rich wetland soils. They also imply that understanding microbial dynamics spanning temporal and spatial redox transitions in peatlands is critical for constraining CH 4 budgets; predicting feedbacks between climate change, hydrologic variability, and wetland CH 4 emissions; and guiding wetland C management strategies.

54 ENVIRONMENTAL SCIENCES↗

Measurement of O and Ti atom displacements in TiO 2 during flash sintering experiments

In-situ flash experiments on rutile TiO 2 were performed at the synchrotron at the Brookhaven National Laboratory. Pair distribution function analysis of total X-ray scattering measurements yielded mean-square atomic displacements of oxygen and titanium atoms during the progression of the 3 stages of flash. The displacements are measured to be far greater for oxygen atoms than for titanium atoms. Thus, these large displacements may signal an “elastic softening” of the lattice, which, recently, has been predicted as a precursor to the onset of flash.

36 MATERIALS SCIENCE↗

Diffusion power spectra as a window into dynamic materials architecture

Chemical recycling of commodity and specialty polymers presents a multifaceted challenge for industrial societies. On one hand, macromolecular architectures must be engineered to yield durable products that, on the other hand, rapidly deconstruct to recyclable monomers under pre-determined conditions. Polymer deconstruction is a chemical process that requires deep understanding of molecular reactivity in heterogeneous media, where porous material architectures evolve in both space and time. To build this understanding, we develop herein experimental and analytical methods describing sets of diffusive eigenmodes that exist within time-varying, non-Euclidean boundary conditions, a situation commonly encountered in the reactive deconstruction of polymers where chain fragments splay, alter their local dynamics, and evolve in their confinement of reacting media. Diffusion power spectra, discerned experimentally by NMR, yield polymer and solvent frequency-domain velocity autocorrelation functions that are analyzed in the context of physical models for chemical reactions parameterized with fractal mathematics. The results connect local motion in polymers to chemical reactivity during acidolysis of circular elastomers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗