Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Locking”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Prospects for carbon-negative biomanufacturing

Biomanufacturing has the potential to reduce demand for petrochemicals and mitigate climate change. Recent studies have also suggested that some of these products can be net carbon negative, effectively removing CO 2 from the atmosphere and locking it up in products. This review explores the magnitude of carbon removal achievable through biomanufacturing and discusses the likely fate of carbon in a range of target molecules. Solvents, cleaning agents, or food and pharmaceutical additives will likely re-release their carbon as CO 2 at the end of their functional lives, while carbon incorporated into non-compostable polymers can result in long-term sequestration. Future research can maximize its impact by focusing on reducing emissions, achieving performance advantages, and enabling a more circular carbon economy.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Stabilizing a strongly nonlinear structure through shaker dynamics in fixed frequency voltage control tests

Bifurcations are commonly encountered during force controlled swept and stepped sine testing of nonlinear structures, which generally leads to the so-called jump-down or jump-up phenomena between stable solutions. There are various experimental closed-loop control algorithms, such as control-based continuation and phase-locked loop, to stabilize dynamical systems through these bifurcations, but they generally rely on specialized control algorithms that are not readily available with many commercial data acquisition software packages. A recent method was developed to experimentally apply sequential continuation using the shaker voltage that can be readily deployed using commercially available software. By utilizing the stabilizing effects of electrodynamic shakers and the force dropout phenomena in fixed frequency voltage control sine tests, this approach has been demonstrated to stabilize the unstable branch of a nonlinear system with three branches, allowing for three multivalued solutions to be identified within a specific frequency bandwidth near resonance. Recent testing on a strongly nonlinear system with vibro-impact nonlinearity has revealed jumping behavior when performing sequential continuation along the voltage parameter, like the jump phenomena seen during more traditional force controlled swept and stepped sine testing. Here, this paper investigates the stabilizing effects of an electrodynamic shaker on strongly nonlinear structures in fixed frequency voltage control tests using both numerical and experimental methods. The harmonic balance method is applied to the coupled shaker-structure system with an electromechanical model to simulate the fixed voltage control tests and predict the stabilization for different parameters of the model. The simulated results are leveraged to inform the design of a set of experiments to demonstrate the stabilization characteristics on a fixture-pylon assembly with a vibro-impact nonlinearity. Through numerical simulation and experimental testing on two different strongly nonlinear systems, the various parameters that influence the stability of the coupled shaker-structure are revealed to better understand the performance of fixed frequency voltage control tests.

42 ENGINEERING↗
DOE OSTI2021

Precise Control of Noncovalent Interactions in Semiconducting Polymers for High-Performance Organic Field-Effect Transistors

Performed through side-chain engineering or by incorporating intramolecular locking units, the directionality and dynamic nature of noncovalent interactions are particularly attractive for the design of novel semiconducting materials in a wide variety of applications. This work investigates the nature and position of hydrogen bonding (intra- versus intermolecular), with the objective of developing a rational approach to the design of new semiconducting materials with improved properties in the solid state. To control the polymer chains’ self-assembly, a π-conjugated polymer incorporating a moiety capable of generating intramolecular hydrogen bonding is evaluated against a polymer that allows for intermolecular hydrogen bonding. Characterization through various techniques, optical spectroscopies, grazing incidence wide-angle x-ray scattering, and solution small-angle neutron scattering showed that intramolecular hydrogen bonds resulted in materials with improved crystallinity and higher effective conjugation in the solid state. Additionally, the effect of the noncovalent interaction configuration on the optoelectronic properties was analyzed in organic field-effect transistor fabrication. Devices prepared from the materials with intramolecular hydrogen bonds showed significantly higher performance, with three orders of magnitude higher charge mobility than their counterparts fabricated from polymers with intermolecular hydrogen bonds. These results confirm the importance of chemical design on polymer structures and offer a novel route for the design of high-efficiency semiconducting polymers for next-generation electronics.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Accelerating Quantum Materials Development with Advances in Transmission Electron Microscopy

Quantum materials are driving a technology revolution in sensing, communication, and computing, while simultaneously testing many core theories of the past century. Materials such as topological insulators, complex oxides, superconductors, quantum dots, color center-hosting semiconductors, and other types of strongly correlated materials can exhibit exotic properties such as edge conductivity, multiferroicity, magnetoresistance, superconductivity, single photon emission, and optical-spin locking. These emergent properties arise and depend strongly on the material’s detailed atomic-scale structure, including atomic defects, dopants, and lattice stacking. In this review, we describe how progress in the field of electron microscopy (EM), including in situ and in operando EM, can accelerate advances in quantum materials and quantum excitations. We begin by describing fundamental EM principles and operation modes. We then discuss various EM methods such as (i) EM spectroscopies, including electron energy loss spectroscopy (EELS), cathodoluminescence (CL), and electron energy gain spectroscopy (EEGS); (ii) four-dimensional scanning transmission electron microscopy (4D-STEM); (iii) dynamic and ultrafast EM (UEM); (iv) complementary ultrafast spectroscopies (UED, XFEL); and (v) atomic electron tomography (AET). We describe how these methods could inform structure–function relations in quantum materials down to the picometer scale and femtosecond time resolution, and how they enable precision positioning of atomic defects and high-resolution manipulation of quantum materials. For each method, we also describe existing limitations to solve open quantum mechanical questions, and how they might be addressed to accelerate progress. Among numerous notable results, our review highlights how EM is enabling identification of the 3D structure of quantum defects; measuring reversible and metastable dynamics of quantum excitations; mapping exciton states and single photon emission; measuring nanoscale thermal transport and coupled excitation dynamics; and measuring the internal electric field and charge density distribution of quantum heterointerfaces- all at the quantum materials’ intrinsic atomic and near atomic-length scale. Finally, we conclude by describing open challenges for the future, including achieving stable sample holders for ultralow temperature (below 10K) atomic-scale spatial resolution, stable spectrometers that enable meV energy resolution, and high-resolution, dynamic mapping of magnetic and spin fields. With atomic manipulation and ultrafast characterization enabled by EM, quantum materials will be poised to integrate into many of the sustainable and energy-efficient technologies needed for the 21st century.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Influence of Rare-Earth Ion Radius on Metal–Metal Charge Transfer in Trinuclear Mixed-Valent Complexes

We report the synthesis and characterization of a highly conjugated bisferrocenyl pyrrolediimine ligand, Fc 2 PyrDIH (1), and its trinuclear complexes with rare earth ions—(Fc 2 PyrDI)M(N(TMS) 2 ) 2 (2-M, M = Sc, Y, Lu, La). Crystal structures, NMR spectra, and UV/Vis-NIR data are presented. The latter are in good agreement with DFT calculations, illuminating the impact of the rare earth ionic radius on NIR charge transfer excitations. For [2-Sc] + , the charge transfer is at 11500 cm -1 , while for [2-Y] + only a d-d transition at 8000 cm -1 is observed. Lu has an ionic radius in between Sc and Y, and the [2-Lu] + complex exhibits both transitions. From TDDFT analysis we assign the 11500 cm -1 transition as a mixture of MLCT and MMCT, rather than pure metal-to-metal CT, because it has significant ligand character. Typically, the ferrocenes have high rotational freedom in bis-ferrocenyl mixed valent complexes. However, in the present (Fc 2 PyrDI)M(N(TMS) 2 ) 2 complexes, ligand-ligand repulsions lock the rotational freedom, so that rare earth ionic radius-dependent geometric differences increasingly influence orbital overlap as the ionic radius falls. The Marcus-Hush coupling constant HAB trends as: [2-Sc] + >[2-Lu] + >[2-Y] +

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Orientational Disorder of NH3 in Hexammine Magnesium Borohydride

Hexammine magnesium borohydride, Mg(NH3)6(BH4)2, consists of adducted NH3 molecules locked in a matrix of Mg cations and borohydride anions. It is a candidate material for hydrogen storage, with 16.8 wt % hydrogen stored in both the NH3 and borohydride anions. It may also be of interest as an Mg2+-conducting electrolyte in solid-state batteries. Its crystal structure has, until now, eluded a proper structural solution due to ambiguity regarding the NH3 position and behavior. In this work, we show using synchrotron X-ray diffraction that the room-temperature structure can be solved only with a model assuming the orientational disorder of ammonia molecules within the crystal structure. Cooling the sample to 120 K yields additional Bragg peaks, which can be solved only with a unit cell expansion consistent with the freezing of the orientational freedom of ammonia molecules. Using this insight from the structure solution, we performed a full assignment of the vibrational modes in the room-temperature infrared spectrum.

08 HYDROGEN↗
DOE OSTI2026

Tetrel Bond-Mediated Photophysical Modulation and Fluoride Recognition in Carbazole-Organosilanes

Silicon-centered orbitals are typically regarded as electronically inert in donor–acceptor systems. Here, we show that silole-based carbazole–silane architectures can render these orbitals electronically relevant, enabling modulation of excited-state behavior and anion-responsive photophysics. Two carbazole–Dipp–silanes exhibit identical carbazole-localized LE singlet emission in solution yet diverge markedly in the solid state: one compound displays a broad long-wavelength emission band in the prompt spectrum and enhanced long-lived emission consistent with a triplet-derived excited state, likely arising from a combination of intramolecular structural locking and solid-state packing effects, whereas the more flexible analogue remains predominantly LE-emissive. Fluoride coordination further differentiates the two systems, producing ratiometric red-shifted emission in one case and fluorescence quenching in the other through a fully reversible coordination process. These results identify σ*(Si–Ar) orbitals as tunable contributors to excited-state landscapes in organosilane luminophores and suggest a broader design strategy for controlling excited-state behavior in tetrel-based photofunctional systems.

Haque, Md Hasanul↗
DOE OSTI2024

Eliminating Imaginary Vibrational Frequencies in Quantum-Chemical Cluster Models of Enzymatic Active Sites

In constructing finite models of enzyme active sites for quantum-chemical calculations, atoms at the periphery of the model must be constrained to stop unphysical rearrangements during geometry relaxation. A simple fixed-atom or “coordinate-lock” approach is commonly employed but leads to undesirable artifacts in the form of small imaginary frequencies. These preclude evaluation of finite-temperature free-energy corrections, limiting thermochemical calculations to enthalpies only. Full-dimensional vibrational frequency calculations are possible by replacing the fixed-atom constraints with harmonic confining potentials. Here, we compare that approach to an alternative strategy in which fixed-atom contributions to the Hessian are simply omitted. While the latter strategy does eliminate imaginary frequencies, it tends to underestimate both the zero-point energy and the vibrational entropy while introducing artificial rigidity. Harmonic confining potentials eliminate imaginary frequencies and provide a flexible means to construct active-site models that can be used in unconstrained geometry relaxations, affording better convergence of reaction energies and barrier heights with respect to the model size, as compared to models with fixed-atom constraints.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Zero-Field NMR and Millitesla-SLIC Spectra for >200 Molecules from Density Functional Theory and Spin Dynamics

NMR is usually performed at magnetic fields of 1 T and above to obtain sufficient sensitivity and spectral dispersion to identify chemicals based on chemical shifts and J couplings. At lower fields, the advent of hyperpolarization technologies and sensitive detectors can address sensitivity concerns. However, it remains disputed whether spectral signatures at zero and ultra-low fields are sufficient for chemical identification. Here, we report an all–electron DFT-based batch calculation of J-coupling constants, which are used to generate J coupling NMR spectra at zero field and 6.5 mT for over 200 small molecules. In the developed computational tool chain, we first used the all-electron FHI-aims code to calculate the molecular J couplings and chemical shifts. We then fed the calculated NMR parameters into the NMR simulation package SPINACH to simulate both heteronuclear J coupling spectra at zero-field, and homonuclear J coupling spectra as spin-lock induced crossing (SLIC) spectra at ultra-low field (6.5 mT). The resulting spectra demonstrate that zero and ultra-low field NMR spectra can represent unique identifiers of chemical structure for small molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Stacking Faults and Topological Properties in MnBi 2 Te 4 : Reconciling Gapped and Gapless States

Despite theoretical predictions of a gapped surface state for the magnetic topological insulator MnBi 2 Te 4 (MBT), there has been a series of experimental evidence pointing toward gapless states. Here, we theoretically explore how stacking faults could influence the topological characteristics of MBT. We envisage a scenario that a stacking fault exists at the surface of MBT, causing the uppermost layer to deviate from the ground state and its interlayer separation to be expanded. This stacking fault with modulated interlayer couplings hosts a nearly gapless state within the topmost layer due to charge redistribution as the outermost layer recedes. Furthermore, we find evidence of spin-momentum locking and preservation of weak band inversion in the gapless surface state, suggesting the nontrivial topological surface states in the presence of the stacking fault. In conclusion, our findings provide a plausible elucidation to the long-standing conundrum of reconciling the observation of gapped and gapless states on MBT surfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Creation of Single-Photon Emitters in WSe 2 Monolayers Using Nanometer-Sized Gold Tips

Due to their tunable bandgaps and strong spin-valley locking, transition metal dichalcogenides constitute a unique platform for hosting single-photon emitters. Here, we present a versatile approach for creating bright single-photon emitters in WSe 2 monolayers by the deposition of gold nanostars. Our molecular dynamics simulations reveal that the formation of the quantum emitters is likely caused by the highly localized strain fields created by the sharp tips of the gold nanostars. The surface plasmon modes supported by the gold nanostars can change the local electromagnetic fields in the vicinity of the quantum emitters, leading to their enhanced emission intensities. Moreover, by correlating the emission energies and intensities of the quantum emitters, we are able to associate them with two types of strain fields and derive the existence of a low-lying dark state in their electronic structures. The findings here are highly relevant for the development and understanding of single-photon emitters in transition metal dichalcogenide materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Multiterminal Inverse AC Josephson Effect

When a Josephson junction is exposed to microwave radiation, it undergoes the inverse AC Josephson effect–the phase of the junction locks to the drive frequency. As a result, the I–V curves of the junction acquire “Shapiro steps” of quantized voltage. If the junction has three or more superconducting contacts, coupling between different pairs of terminals must be taken into account and the state of the junction evolves in a phase space of higher dimensionality. Here, we study the multiterminal inverse AC Josephson effect in a graphene sample with three superconducting terminals. We observe robust fractional Shapiro steps and correlated switching events, which can only be explained by considering the device as a completely connected Josephson network. We successfully simulate the observed behaviors using a modified two-dimensional RCSJ model. Our results suggest that multiterminal Josephson junctions are a playground to study highly connected nonlinear networks with novel topologies.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2022

Direct Observation of the Pressure-Induced Structural Variation in Gold Nanoclusters and the Correlated Optical Response

The ability to gradually modify the atomic structures of nanomaterials and directly identify such structural variation is important in nanoscience research. Here, we present the first example of a high-pressure single-crystal X-ray diffraction analysis of atomically precise metal nanoclusters. The pressure-dependent, subangstrom structural evolution of an ultrasmall gold nanoparticle, Au 25 S 18 , has been directly identified. We found that a 0.1 Å decrease of the Au–Au bond length could induce a blue-shift of 30 nm in the photoluminescence spectra of gold nanoclusters. From theoretical calculations, the origins of the blue-shift and enhanced photoluminescence under pressure are investigated, which are ascribed to molecular orbital symmetry and conformational locking, respectively. Here, the combination of the high-pressure in situ X-ray results with both theoretical and experimental optical spectra provides a direct and generalizable avenue to unveil the underlying structure–property relations for nanoclusters and nanoparticles which cannot be obtained through traditional physical chemistry measurements.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Delamination-Assisted Ultrafast Wrinkle Formation in a Freestanding Film

Freestanding films provide a versatile platform for materials engineering thanks to additional structural motifs not found in films with a substrate. A ubiquitous example is wrinkles, yet little is known about how they can develop over as fast as a few picoseconds due to a lack of experimental probes to visualize their dynamics in real time on the nanoscopic scale. Here, we use time-resolved electron diffraction to directly observe light-activated wrinkling formation in freestanding La 2/3 Ca 1/3 MnO 3 films. Via a “lock-in” analysis of oscillations in the diffraction peak position, intensity, and width, we quantitatively reconstructed how wrinkles develop on the time scale of lattice vibration. Contrary to the common assumption of fixed boundary conditions, we found that wrinkle development is associated with ultrafast delamination at the film boundaries. Finally, our work provides a generic protocol to quantify wrinkling dynamics in freestanding films and highlights the importance of the film–substrate interaction in determining the properties of freestanding structures.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Deriving Material Properties from Feedback Error Signals in Scanning Tunneling Microscopy

Imperfections in measurements, e.g., deviations and broadening, are not devoid of information; rather, they can reveal valuable physical properties and processes. Scanning tunneling microscopy leverages a negative feedback loop to regulate the tunneling current. Practically, current fluctuates around its set point, and such deviations are considered insignificant and ignored. Here, in this study, we investigate the information embedded in these deviations. In the constant-current mode with an active feedback loop, we observe an unexpected persistent DC current offset from its set point when the tunneling junction is periodically perturbed. We demonstrate both experimentally and theoretically that such error signals encode local tunneling barrier heights and the square of local differential conductance as a consequence of the interplay between rectification and active feedback compensation. We provide evidence on the generalizability of this phenomenology to other negative feedback systems. This new approach has the potential to broadly impact physical sciences by allowing rapid measurements without lock-in amplifiers.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Beyond Epitaxy: Ion Implantation as a Tool for Orbital Engineering

Manipulating electronic orbital states in quantum materials provides a powerful means of controlling their physical properties and technological functionality. Here, we demonstrate that orbital populations in strongly correlated oxide thin films can be continuously and reversibly tuned through postsynthesis He ion implantation. Using LaNiO 3 as a model system, we show that the orbital preference can be systematically adjusted from favoring in-plane d x 2 –y 2 occupation toward out-of-plane d z 2 states through precise control of ion fluence. Unlike conventional heteroepitaxial approaches that lock in orbital configurations during growth, this strain-doping technique enables continuous orbital tuning and the selective modification of specific film regions after device fabrication. We demonstrate the practical impact of this control by achieving a 7-fold enhancement in oxygen reduction reaction catalysis. This work establishes ion implantation as a powerful approach for orbital engineering that complements existing synthesis-based strategies while offering unique advantages for both basic research and device development.

Doping↗
DOE OSTI2020

Reconfigurable Liquids Stabilized by DNA Surfactants

Polyelectrolyte microcapsules can be produced either by the layer-by-layer assembly technique or the formation of polyelectrolyte complexes at the liquid-liquid interface. In this work, we describe the design and construction of DNA microcapsules using the cooperative assembly of DNA and amine-functionalized polyhedral oligomeric silsesquioxane (POSS-NH 2 ) at the oil-water interface. "Janus-like" DNA surfactants (DNASs) assemble in situ at the interface, forming an elastic film. By controlling the jamming and unjamming behavior of DNASs, the interfacial assemblies can assume three different physical states: solid-like, elastomer-like, and liquid-like, similar to that seen with thermoplastics upon heating, that change from a glassy to a rubbery state, and then to a viscous liquid. By the interfacial jamming of DNASs, the liquid structures can be locked-in and reconfigured, showing promising potentials for drug delivery, biphasic reactors, and programmable liquid constructs.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Exploring Domain-Wall Pinning in Ferroelectrics via Automated High-Throughput Atomic Force Microscopy

Domain-wall dynamics in ferroelectric materials are strongly position-dependent, since each polar interface is locked into a unique local microstructure. This necessitates spatially resolved studies of wall pinning using scanning-probe microscopy techniques. The pinning centers and pre-existing domain walls are usually sparse within the image plane, precluding the use of dense hyperspectral imaging modes and requiring time-consuming human experimentation. Here, a large-area epitaxial PbTiO 3 film on cubic KTaO 3 was investigated to quantify the electric-field-driven dynamics of the polar–strain domain structures using ML-controlled automated piezoresponse force microscopy. Analysis of 1500 switching events reveals that domain-wall displacement depends not only on field parameters but also on the local ferroelectric–ferroelastic configuration. For example, twin boundaries in polydomains regions, like a 1 – /c+ ∥ a 2 – /c – , stay pinned up to a certain level of bias magnitude and change only marginally as the bias increases from 20 to 30 V, whereas single-variant boundaries, like the a 2 + /c + ∥ a 2 – /c – stack, are already activated at 20 V. These statistics on the possible ferroelectric and ferroelastic wall orientations, together with the automated high-throughput AFM workflow, can be distilled into a predictive map that links domain configurations to pulse parameters. Here, this microstructure-specific rule set forms the foundation for the design of ferroelectric memories.

automated scanning probe microscopy↗